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WO2015146673A1 - Film hautement transparent durable en termes de lumière du soleil, film de régulation de la lumière du soleil, film réfléchissant dans l'infrarouge et miroir à film - Google Patents

Film hautement transparent durable en termes de lumière du soleil, film de régulation de la lumière du soleil, film réfléchissant dans l'infrarouge et miroir à film Download PDF

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Publication number
WO2015146673A1
WO2015146673A1 PCT/JP2015/057685 JP2015057685W WO2015146673A1 WO 2015146673 A1 WO2015146673 A1 WO 2015146673A1 JP 2015057685 W JP2015057685 W JP 2015057685W WO 2015146673 A1 WO2015146673 A1 WO 2015146673A1
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Prior art keywords
film
group
layer
refractive index
polymer component
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Ceased
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English (en)
Japanese (ja)
Inventor
一成 中原
宏佳 木内
福坂　潔
鈴木　隆嗣
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Konica Minolta Inc
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Konica Minolta Inc
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Priority to JP2016510253A priority Critical patent/JP6597598B2/ja
Publication of WO2015146673A1 publication Critical patent/WO2015146673A1/fr
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B23/00—Layered products comprising a layer of cellulosic plastic substances, i.e. substances obtained by chemical modification of cellulose, e.g. cellulose ethers, cellulose esters, viscose
    • B32B23/04—Layered products comprising a layer of cellulosic plastic substances, i.e. substances obtained by chemical modification of cellulose, e.g. cellulose ethers, cellulose esters, viscose comprising such cellulosic plastic substance as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
    • B32B7/02—Physical, chemical or physicochemical properties
    • B32B7/022—Mechanical properties
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
    • B32B7/02—Physical, chemical or physicochemical properties
    • B32B7/023—Optical properties
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/18—Manufacture of films or sheets
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L1/00—Compositions of cellulose, modified cellulose or cellulose derivatives
    • C08L1/08—Cellulose derivatives
    • C08L1/10—Esters of organic acids, i.e. acylates
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L1/00—Compositions of cellulose, modified cellulose or cellulose derivatives
    • C08L1/08—Cellulose derivatives
    • C08L1/10—Esters of organic acids, i.e. acylates
    • C08L1/12—Cellulose acetate
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L1/00—Compositions of cellulose, modified cellulose or cellulose derivatives
    • C08L1/08—Cellulose derivatives
    • C08L1/10—Esters of organic acids, i.e. acylates
    • C08L1/14—Mixed esters, e.g. cellulose acetate-butyrate
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/08—Mirrors
    • G02B5/0808—Mirrors having a single reflecting layer
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/20—Filters
    • G02B5/208—Filters for use with infrared or ultraviolet radiation, e.g. for separating visible light from infrared and/or ultraviolet radiation
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2264/00—Composition or properties of particles which form a particulate layer or are present as additives
    • B32B2264/10—Inorganic particles
    • B32B2264/102—Oxide or hydroxide
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/30—Properties of the layers or laminate having particular thermal properties
    • B32B2307/306—Resistant to heat
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/40—Properties of the layers or laminate having particular optical properties
    • B32B2307/412—Transparent
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/40—Properties of the layers or laminate having particular optical properties
    • B32B2307/416—Reflective
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/50—Properties of the layers or laminate having particular mechanical properties
    • B32B2307/584—Scratch resistance
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/70—Other properties
    • B32B2307/71—Resistive to light or to UV
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/70—Other properties
    • B32B2307/718—Weight, e.g. weight per square meter
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2419/00—Buildings or parts thereof
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2457/00—Electrical equipment
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2605/00—Vehicles
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2301/00—Characterised by the use of cellulose, modified cellulose or cellulose derivatives
    • C08J2301/08—Cellulose derivatives
    • C08J2301/10—Esters of organic acids
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2467/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
    • C08J2467/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2471/00—Characterised by the use of polyethers obtained by reactions forming an ether link in the main chain; Derivatives of such polymers
    • C08J2471/02—Polyalkylene oxides

Definitions

  • the present invention relates to a sunlight-resistant highly transparent film, a sunlight control film, an infrared reflection film, and a film mirror.
  • Plastic films are widely used in various applications such as food packaging, building materials, display films, and substrate films.
  • a film having high transparency, high heat resistance, and high durability has a high need for a display application or an application used under sunlight exposure.
  • polymers that satisfy these performances such as polyethersulfone (PES) and alicyclic polyimide, which are very expensive and cannot be used for general purposes.
  • PES polyethersulfone
  • alicyclic polyimide which are very expensive and cannot be used for general purposes.
  • a film used under sunlight exposure needs light transmittance and durability against sunlight. Accordingly, those having an aromatic group in the main chain or side chain are substantially difficult to use because they are decomposed by long-term exposure to ultraviolet rays. Moreover, since the influence of infrared rays is large, high heat resistance is also required.
  • the curl recoverability and shear processability are also problems with respect to the film processability. Since such properties are caused by the hardness of the film, there is a problem that if the hardness of the film is increased in order to improve the scratch resistance, the workability deteriorates.
  • a film that can be used under exposure to sunlight and is suitable for processing needs to have light transmittance, ultraviolet resistance, heat resistance, scratch resistance, and cutting processability. However, no transparent film satisfying such performance has been reported so far.
  • the resin used is a non-aromatic polymer (ultraviolet light resistance), has a rigid main chain structure (heat resistance), and the film has an appropriate flexibility. It is considered necessary to have toughness (scratch resistance and cutting workability).
  • toughness shock resistance and cutting workability.
  • many resins having a rigid main chain structure have low flexibility and low toughness, and it has been difficult to satisfy all of these performances.
  • Patent Document 2 a technique for improving mechanical properties by mixing a cellulose derivative advantageous for carbon offset and a high molecular weight aliphatic polyester for the purpose of use in an electric / electronic housing is disclosed (for example, see Patent Document 2).
  • Patent Document 2 the technique described in Patent Document 2 is only a technique for imparting thermoplasticity and impact resistance to a cellulose derivative, and requires light transmission, ultraviolet resistance, and scratch resistance required for a film used under sunlight exposure. There is no description that realizes all of the properties and cutting processability at a high level.
  • a technique for mixing a cellulose ester and an aliphatic polyester to form a display film is disclosed (for example, see Patent Documents 4 and 5).
  • aliphatic polyester is used as a plasticizer having thermoplasticity, low moisture permeability, and bleed-out resistance, and specifically described are relatively low molecular weight polymers. Therefore, even if two types of polymers, a low molecular weight polymer and a high molecular weight cellulose ester, are combined, there is little entanglement between the molecular chains, resulting in greater strain between the molecular chains and improved toughness. I can't.
  • the present invention has been made in view of the above-mentioned problems and situations, and the solution to the problem is cutting workability and toughness (tear strength and resistance) in addition to light transmittance, ultraviolet resistance, heat resistance, transparency, and scratch resistance. It is to provide a sunlight-resistant highly transparent film, a sunlight control film, an infrared reflection film and a film mirror excellent in breaking elongation).
  • the present inventor thought that it can be solved by separating and fusing the required functions in the process of examining the cause of the above-mentioned problems. That is, the first function is to suppress decomposition by ultraviolet rays and to impart heat resistance by having a rigid main chain structure having no aromatic group as a polymer component. Another function is to impart flexibility and toughness to the polymer component. It was thought that light transmittance, ultraviolet resistance, heat resistance, scratch resistance and cutting processability could be improved by giving these two functions to separate polymers and highly combining them.
  • FIG. 1 is a conceptual diagram showing the relationship between the interaction point of each polymer component and entropy. As shown in B, the number of interaction points of the second polymer component with respect to the first polymer component is increased. (Interaction A ⁇ B) and thermodynamically stabilized (entropy relationship A ⁇ B).
  • a first polymer component which is a non-aromatic polymer component having a rigid main chain structure
  • a second polymer component having a soft segment and having a weight average molecular weight in the range of 4000 to 500,000 It has been found that a film satisfying light transmittance, ultraviolet resistance, heat resistance, scratch resistance and cutting processability can be obtained by compatibilizing the above.
  • a window film infrared reflective film
  • a solar reflective film that is used when solar power is generated by reflecting and concentrating sunlight.
  • a solar-resistant highly transparent film containing at least two compatible polymer components The first polymer component is a non-aromatic polymer component having a rigid main chain structure;
  • the content of the second polymer component is in the range of 5 to 50% by mass with respect to the first polymer component, according to any one of items 1 to 8, Solar durable high transparent film.
  • the tear strength is in the range of 60 to 350 mN, and the elongation at break is in the range of 60 to 200%. Any one of items 1 to 9, Solar durable high transparent film.
  • a solar control film wherein at least a solar control layer is formed on the solar durable highly transparent film according to any one of items 1 to 10.
  • the solar control layer is a low refractive index layer containing a first water-soluble binder resin and first metal oxide particles, and a low refractive index layer containing a second water-soluble binder resin and second metal oxide particles.
  • An infrared reflection layer wherein a layer that reflects infrared rays is formed as at least a sunlight control layer on the sunlight durable highly transparent film according to any one of items 1 to 10. the film.
  • a film mirror wherein a silver reflective layer is formed at least as a sunlight control layer on the sunlight-resistant highly transparent film according to any one of items 1 to 10.
  • a sunlight-resistant highly transparent film excellent in light transmission, ultraviolet resistance, heat resistance, scratch resistance, cutting processability and toughness (tear strength and elongation at break), solar control film, Infrared reflective films and film mirrors can be provided.
  • the expression mechanism or action mechanism of the effect of the present invention is not clear, but is presumed as follows.
  • thermodynamic stabilization entropy effect stabilizes the different polymers of the first polymer component and the second polymer component, and can be highly compatible. As a result, it is speculated that a highly durable solar transparent film satisfying light transmittance, ultraviolet resistance, heat resistance, scratch resistance, cutting workability and toughness (tear strength and elongation at break) can be obtained.
  • the schematic diagram which shows the procedure of an internal haze measurement (b) The state which put the sample film on glycerol is shown.
  • the schematic diagram which shows the procedure of an internal haze measurement (c) The state which dripped glycerol on the sample film is shown.
  • the schematic diagram which shows the procedure of an internal haze measurement (d) The state which put the cover glass on glycerol is shown.
  • the sunlight-resistant highly transparent film of the present invention is a sunlight-resistant highly transparent film containing at least two compatible polymer components, wherein the first polymer component has a rigid main chain structure.
  • This feature is a technical feature common to the inventions according to claims 1 to 14.
  • the weight average molecular weight of the second polymer component is within the range of 30,000 to 400,000 when interacting with the first polymer component. Is more preferable than the self-cohesion force of the second polymer component, and the transparency, breaking elongation and tear strength are improved.
  • the first polymer component and the second polymer component have an interaction point with the first polymer component per polymer chain of the second polymer component in the range of 1500 to 15000. This is preferable in that the system in which these interact with each other is greatly stabilized, and as a result, highly compatible.
  • the first polymer component is preferably a natural polymer from the viewpoint of light resistance and heat resistance.
  • the first polymer component is preferably a cellulose ester in terms of transparency, light resistance, heat resistance, and processability.
  • the second polymer component is preferably an aliphatic polyester or a polyalkylene oxide from the viewpoint of transparency, tear strength, and elongation at break.
  • the second polymer component is preferably an aliphatic polyester having a structure represented by the general formula (1) in terms of transparency, tear strength, and scratch resistance.
  • the content of the second polymer component is within the range of 5 to 50% by mass with respect to the first polymer component, in terms of transparency, tear strength, elongation at break, and scratch resistance. Is preferable.
  • the tear strength is in the range of 60 to 350 mN and the elongation at break is in the range of 60 to 200% from the viewpoint of excellent scratch resistance, cutting workability, and toughness.
  • the solar control film of the present invention is characterized in that at least a solar control layer is formed on the solar durable highly transparent film.
  • the sunlight control film excellent in light transmittance, ultraviolet-ray resistance, heat resistance, transparency, scratch resistance, cutting workability, and toughness can be obtained.
  • the said sunlight durability highly transparent film of this invention can be used suitably for an infrared reflective film.
  • the sunlight-resistant highly transparent film of the present invention can be suitably used for a film mirror.
  • ⁇ is used to mean that the numerical values described before and after it are included as a lower limit value and an upper limit value.
  • the sunlight-resistant highly transparent film in the present invention is a film that is used in applications that are always exposed to sunlight, and is distinguished from a display film.
  • the film is excellent in durability against long-term exposure to ultraviolet rays, heat resistance, scratch resistance due to sand, dust, and the like, and has high light transmittance in the visible range.
  • Such a film can be suitably used for applications (for example, a window film (infrared reflective film) or a solar reflective film (film mirror)) used in a state exposed to sunlight.
  • the sunlight-resistant highly transparent film of the present invention is a sunlight-resistant highly transparent film containing at least two compatible polymer components, wherein the first polymer component has a rigid main chain structure. An aromatic polymer component, wherein the second polymer component has a soft segment and has a weight average molecular weight in the range of 4,000 to 500,000.
  • the first polymer component in the present invention is a non-aromatic polymer component having a rigid main chain structure.
  • “Non-aromatic” in the present invention means that an aromatic ring or a heteroaromatic ring is not included, and the first polymer component of the present invention is composed of a non-aromatic group or the like in the main chain and the side chain. Is done.
  • the “rigid main chain structure” in the present invention refers to a structure in which the rotation of the main chain itself is suppressed, a main chain including a ring structure, a main chain that has a large steric hindrance and is difficult to rotate, a highly three-dimensional structure.
  • non-aromatic polymers having a rigid main chain structure include cellulose derivatives, chitin derivatives, chitosan derivatives, natural polymers such as polylactic acid and proteins, acrylic resins, sterically regulated polypropylene, and polyvinyl.
  • polymers containing a cyclic structure in the main chain such as butyral, polyvinyl acetal, maleimide, glutarimide, and maleic anhydride.
  • the first polymer in the present invention is preferably a natural polymer such as a cellulose derivative, a chitin derivative, or a chitosan derivative, and a cellulose derivative is particularly preferable.
  • a cellulose derivative is particularly preferable.
  • cellulose derivatives cellulose ester or cellulose ether is preferable, and cellulose ester is particularly preferable.
  • the cellulose ester will be described in detail below.
  • the total acyl group substitution degree of the cellulose ester is preferably in the range of 1.5 to 3.0, more preferably in the range of 2.5 to 2.95, from the viewpoint of transparency.
  • the method for measuring the substitution degree of the acyl group can be measured according to ASTM-D817-96.
  • Preferred examples of the cellulose ester include cellulose acetate, cellulose acetate propionate, cellulose acetate butyrate, cellulose acetate propionate butyrate and the like. Among these, cellulose acetate and cellulose acetate propionate are particularly preferable.
  • the cellulose ester may contain a plurality of cellulose esters having different degrees of substitution in order to obtain desired characteristics.
  • the mixing ratio thereof is in the range of 10:90 to 90:10 by mass ratio.
  • the number average molecular weight of the cellulose ester is preferably in the range of 6 ⁇ 10 4 to 3 ⁇ 10 5 and preferably in the range of 7 ⁇ 10 4 to 2 ⁇ 10 5 because the mechanical strength of the resulting film is high. It is more preferable that
  • the weight average molecular weight Mw and the number average molecular weight Mn of the cellulose ester can be measured by gel permeation chromatography (GPC).
  • GPC gel permeation chromatography
  • the cellulose ester can be produced by a known method. Specifically, it can be synthesized with reference to the method described in JP-A-10-45804.
  • the cellulose used as a raw material is not particularly limited, but may be cotton linter, wood pulp, kenaf, and the like.
  • the cellulose ester obtained from them can each be mixed and used for arbitrary ratios.
  • the substituent that can be substituted for the first polymer component in the present invention is not particularly limited as long as it is a non-aromatic group.
  • a halogen atom fluorine atom, chlorine atom, bromine atom, iodine atom, etc.
  • alkyl group etc.
  • the second polymer component in the present invention has a soft segment and has a weight average molecular weight in the range of 4000 to 500,000.
  • the soft segment in the present invention refers to a linking group capable of imparting stretchability and rotation to the main chain, and is not particularly limited as long as it has a structure satisfying them. Specifically, —O— , —COO—, OCOO—, —S—, —SOO—, —OSOO—, —OSiO—, —OSi—, an alkylene group, and the like.
  • the weight average molecular weight of the second polymer component is in the range of 4,000 to 500,000, preferably in the range of 30,000 to 400,000, and particularly preferably in the range of 50,000 to 300,000. If the molecular weight of the second polymer component is within the range of 4,000 to 500,000, the stabilization energy when interacting with the first polymer component is greater than the self-cohesion force of the second polymer component, and transparency , Elongation at break and tear strength are improved.
  • the weight average molecular weight is a weight average molecular weight measured by gel permeation chromatography (GPC). More specifically, N-methylpyrrolidone is used as a solvent, a polystyrene gel is used, and the molecular weight is obtained from a standard monodisperse polystyrene constituent curve using a conversion molecular weight calibration curve obtained in advance.
  • GPC apparatus HLC-8220 GPC (manufactured by Tosoh Corporation) can be used.
  • the high molecular weight second polymer component has many points of interaction with the first polymer component per main chain and interacts with the first polymer component at a plurality of locations. It is.
  • the second polymer component can interact with the first polymer component at a plurality of locations, the number of possible states increases exponentially and entropy increases, so that the free energy of the cast increases negatively. As a result of greatly stabilizing the system in which the first polymer component and the second polymer component interact with each other, it becomes possible to achieve high compatibility.
  • the term “compatible” in the present invention means that the first polymer component and the second polymer component are mixed and transparent. Whether or not the first polymer component and the second polymer component are compatible can be determined by, for example, the glass transition temperature Tg.
  • the two polymers when the two polymers have different glass transition temperatures, when the two polymers are mixed, there are two or more glass transition temperatures of the mixture because there is a glass transition temperature of each polymer. When they are compatible, the glass transition temperature specific to each polymer disappears and becomes one glass transition temperature, which is the glass transition temperature of the compatible polymer.
  • the glass transition temperature referred to here is a temperature increase rate of 20 ° C. using a differential scanning calorimeter (for example, DSC-7 model manufactured by PerkinElmer, differential scanning calorimeter DSC220 manufactured by Seiko Instruments Inc.).
  • the intermediate glass transition temperature (Tmg) determined in accordance with JIS K7121 (1987).
  • Examples of the interaction in the present invention include hydrogen bond, dipole-dipole interaction, intermolecular force, CH- ⁇ interaction, and the like.
  • Such a site capable of interaction is called an interaction point, and the interaction point may be included in the main chain, may be included in the side chain, and is included in the soft segment described later. It may be.
  • the number of interaction points is determined by the following formula from the weight average molecular weight of the polymer component, the molecular weight of each monomer, and the composition ratio. Divide the weight average molecular weight by the composition ratio (molar fraction) of each monomer unit x the sum of molecular weights and multiply the number of interaction points in each monomer unit by the composition ratio (molar fraction) for all monomer types. It is expressed as the sum of numbers.
  • Interaction point ⁇ ⁇ (monomer interaction point ⁇ monomer composition ratio ⁇ polymer component Mw / ( ⁇ monomer composition ratio ⁇ monomer molecular weight)) Adjacent interaction points are counted separately.
  • the interaction point is counted as 2.
  • the hydroxyl group is counted as 2 because there is one oxygen atom and one hydrogen capable of hydrogen bonding.
  • the above “interaction point in the monomer unit” refers to the interaction point of the monomer structure contained in the polymer structure, not the structure of the monomer alone.
  • the structure of the monomer alone includes hydrogen of the hydroxyl group of alcohol and hydrogen atom of the carboxy group of carboxylic acid as the interaction point.
  • Polyesters do not count as interaction points because there are no hydrogen atoms.
  • the oxygen atom at the time of polycondensation is shared by alcohol and carboxylic acid, it counts as an interaction point number in both an alcohol site and a carboxylic acid site.
  • the first polymer component needs to have an interaction point in the main chain or side chain.
  • the interaction point of the first polymer component is not particularly limited as long as it is non-aromatic, but for example, cyano group, hydroxy group, nitro group, carboxy group, alkoxy group (methoxy group, ethoxy group, isopropoxy group) Tert-butoxy group, n-octyloxy group, 2-methoxyethoxy group, etc.), acyl group (acetyl group etc.), acyloxy group (formyloxy group, acetyloxy group, pivaloyloxy group, stearoyloxy group etc.), amino group (Amino group, methylamino group, dimethylamino group, etc.), acylamino group (formylamino group, acetylamino group, pivaloylamino group, lauroylamino group, etc.), alkylsulfonylamino group (methyls),
  • the point of interaction of the second polymer component with the first polymer component per polymer chain is preferably in the range of 1500 to 15000, and preferably in the range of 2000 to 10,000. Further preferred. If the interaction point is 1500 or more, it can interact with the first polymer to obtain great stabilization by entropy. If it is 15000 or less, it interacts with the first polymer component rather than its own cohesive energy. The entropy stabilization increases the compatibility, and the film has excellent light transmittance, tear strength, and elongation at break.
  • the second polymer component in the present invention is polyester or polyalkylene oxide, more preferably aliphatic polyester or polyalkylene oxide, and particularly preferably aliphatic polyester.
  • the polyalkylene oxide that can be used as the second polymer component in the present invention is not particularly limited, and examples thereof include those containing ethylene oxide as one component, such as polyethylene oxide that is an ethylene oxide homopolymer; ethylene oxide and other Examples include copolymers with alkylene oxides.
  • Examples of the other alkylene oxides include propylene oxide, 1,2-epoxybutane, 2,3-epoxybutane, epichlorohydrin, epibromohydrin, trifluoromethylethylene oxide, cyclohexene oxide, styrene oxide, methyl glycidyl ether, and allyl.
  • Examples thereof include glycidyl ether, phenyl glycidyl ether, glycidol, glycidyl acrylate, butadiene monooxide, and butadiene dioxide.
  • polyethylene oxide or polypropylene oxide is preferable, and polyethylene oxide is more preferable.
  • a commercially available product may be used as the alkylene oxide in the present invention.
  • the aliphatic polyester that can be used as the second polymer component in the present invention will be described.
  • the aliphatic polyester referred to in the present invention is not particularly limited as long as it is an aliphatic polyester having a weight average molecular weight in the range of 4,000 to 500,000.
  • the aliphatic polyester in the present invention is a polyester obtained by a condensation reaction of an aliphatic polyhydric alcohol and an aliphatic polybasic acid (or an ester thereof), or an aliphatic polyester obtained by ring-opening polymerization of a cyclic ester. preferable.
  • the aliphatic polyester in the present invention may be an aliphatic polyester as a main component, and may contain an aromatic moiety as long as the effect of the present invention is not affected. This is because heat resistance and ultraviolet light resistance can be imparted by the first polymer component, and even if a small amount of aromatic sites are contained in the second polymer component, the performance is not greatly affected.
  • the aromatic moiety that may be contained in the second polymer component is preferably a terephthalic acid derivative, an isophthalic acid derivative, or a bisphenol derivative from the viewpoint of scratch resistance, and more preferably a terephthalic acid derivative or an isophthalic acid derivative.
  • the ratio of the aromatic moiety that may be contained in the second polymer component is preferably in the range of 1 to 20%, more preferably in the range of 5 to 10%, in terms of the molar ratio of the constituent monomers.
  • the aliphatic polyester in the present invention is preferably an aliphatic polyester having a structure represented by the following general formula (1).
  • R 1 to R 6 each represent a hydrogen atom or a substituent, and are substituents that may be substituted with a second polymer component described later.
  • formula (1) in the present invention is a soft segment -CO- and the substituents R 1 ⁇ R 6 since the connecting group is in many -O- is the effect of the present invention is intended Any substituent may be introduced as long as it is not blocked.
  • i represents an integer of 0 to 2, preferably 0 to 1, and more preferably 1.
  • j represents an integer of 0 to 10, preferably 0 to 5, and more preferably 1 to 3.
  • k represents an integer of 3 to 10, preferably 3 to 8, more preferably 3 to 5, and particularly preferably 3.
  • a, b and c each represent a constituent ratio (molar fraction), and the sum of a, b and c is 1.
  • a / b / c 0.20 to 0.35 / 0.50 / 0.15 to 0.25 is most preferable.
  • the balance of interaction is excellent, and the transparency is improved.
  • transparency, elongation at break, and tear strength are improved.
  • Examples of the aliphatic polyester having the structure represented by the general formula (1) in the present invention include polyethylene adipate, polyethylene succinate, polybutylene adipate, polybutylene succinate, polybutylene succinate adipate, and the like. Polyethylene succinate, polybutylene succinate, or polybutylene succinate adipate is preferred.
  • Examples of the aliphatic polybasic acid used in the condensation reaction of an aliphatic polyhydric alcohol and an aliphatic polybasic acid (or an ester thereof) include succinic acid, oxalic acid, malonic acid, glutaric acid, adipic acid, and pimelic acid. , Suberic acid, sebacic acid, azelaic acid, decanedicarboxylic acid, octadecanedicarboxylic acid, cyclohexanedicarboxylic acid, dimer acid undecanedioic acid, dodecanedioic acid, and their anhydrides or esters thereof.
  • Examples of the aliphatic polyhydric alcohol include ethylene glycol, diethylene glycol, triethylene glycol, polyethylene glycol, propylene glycol, dipropylene glycol, 3-methyl-1,5-pentanediol, 1,3-propanediol, 1,4 -Butanediol, 1,9-nonanediol, neopentyl glycol, 1,5-pentanediol, 1,6-hexanediol, decamethylene glycol, cyclohexanedimethanol, polytetramethylene glycol 1,4-cyclohexanedimethanol, etc. .
  • polyoxyalkylene glycol as a part of the aliphatic polyhydric alcohol, and examples thereof include polyoxyethylene glycol, polyoxypropylene glycol, polyoxytetramethylene glycol and copolymers thereof. Is done.
  • the aliphatic polyester can be used alone or in combination of two or more.
  • any of D-form, L-form, and racemate may be used, and the form may be any of solid, liquid, or aqueous solution.
  • the aliphatic polyhydric alcohol is ethylene glycol, diethylene glycol, triethylene glycol, polyethylene glycol, propylene glycol, dipropylene glycol, 1,3-butanediol, 1,4-butanediol, 3-methyl-1 , 5-pentanediol, 1,6-hexanediol, 1,9-nonanediol, neopentyl glycol, polytetramethylene glycol 1,4-cyclohexanedimethanol, and the aliphatic polybasic acid is , Succinic acid, oxalic acid, malonic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, undecanedioic acid, dodecanedioic acid, and anhydrides thereof.
  • a basic acid there.
  • the aliphatic polyhydric alcohol is at least one selected from diethylene glycol, triethylene glycol, polyethylene glycol, propylene glycol, 1,3-butanediol, 1,4-butanediol, neopentyl glycol, and the aliphatic More preferably, the polybasic acid is at least one aliphatic polybasic acid selected from succinic acid, oxalic acid, malonic acid, glutaric acid, adipic acid, sebacic acid, dodecanedioic acid, and anhydrides thereof.
  • the total amount of the aliphatic polybasic acid (or its ester) component and the aliphatic polyhydric alcohol component may be initially mixed and reacted, or added in portions as the reaction proceeds. It's okay.
  • the polycondensation reaction it is possible to use a normal transesterification method or esterification method, or a combination of both, and if necessary, the degree of polymerization can be increased by increasing the pressure in the reaction vessel or reducing the pressure. .
  • Examples of the cyclic ester used in the method for ring-opening polymerization of a cyclic ester include ⁇ -propiolactone, ⁇ -methyl- ⁇ -propiolactone, ⁇ -valerolactone, and ⁇ -caprolactone. Of these, ⁇ -caprolactone is particularly preferred.
  • the ring-opening polymerization can be performed by a method such as polymerization in a solvent or bulk polymerization using a known ring-opening polymerization catalyst.
  • hydroxyalkanoic acid used in the method of condensation reaction of hydroxyalkanoic acid known compounds can be used, such as 3-hydroxybutyric acid, 4-hydroxybutyric acid, glycolic acid, lactic acid, hydroxyvaleric acid, 3-hydroxyhexanoic acid, etc. Is mentioned.
  • a divalent carboxylic acid or divalent alcohol may be used in combination.
  • the aliphatic polyester used in the present invention can be produced by a known method.
  • a general method of melt polymerization in which an esterification reaction and / or a transesterification reaction between the aliphatic dicarboxylic acid component and the aliphatic diol component is performed, followed by a polycondensation reaction under reduced pressure, It can also be produced by a known solution heating dehydration condensation method using a solvent.
  • a method of producing a polyester by melt polymerization performed in the absence of a solvent is preferable.
  • the polycondensation reaction is preferably performed in the presence of a polymerization catalyst.
  • the addition timing of the polymerization catalyst is not particularly limited as long as it is before the polycondensation reaction, and it may be added when the raw materials are charged, or may be added at the start of pressure reduction.
  • the polymerization catalyst is generally a compound containing a group 1 to group 14 metal element excluding hydrogen and carbon in the periodic table.
  • esterification catalyst As esterification catalyst, ring-opening polymerization catalyst and deglycolization catalyst in condensation and polymerization reactions, lithium, sodium, potassium, cesium, magnesium, calcium, barium, strontium, zinc, aluminum, titanium, cobalt, germanium, tin, lead And metals such as antimony, cadmium, manganese, iron, zirconium, vanadium, iridium, lanthanum, and selenium, and organic metal compounds thereof, salts of organic acids, metal alkoxides, and metal oxides. If necessary, it can be used in combination with a promoter such as phosphoric acid.
  • a promoter such as phosphoric acid.
  • These catalysts can be used singly or in combination of two or more, and the addition amount is preferably 0.1 mol or less, more preferably 0.8 mol or less, more preferably 100 mol per 100 mol of all dicarboxylic acids. 0.6 mol or less.
  • the amount of catalyst added in the case of using a metal compound as these catalysts is such that the lower limit is usually 5 ppm or more, preferably 10 ppm or more, and the upper limit is usually 30000 ppm or less, preferably 1000 ppm or less, as the amount of metal relative to the produced polyester. More preferably, it is 250 ppm or less, and particularly preferably 130 ppm or less.
  • the reason why the upper limit of the amount of catalyst to be used is in the above range is economically preferable and because the thermal stability of the polymer is increased.
  • the lower limit of the amount of catalyst in the above range the polymerization activity is increased. This is because the decomposition of the polymer during the production of the polymer can be suppressed accordingly.
  • the molecular weight can be increased using a chain extender.
  • chain extender include bifunctional or higher functional isocyanate compounds, epoxy compounds, aziridine compounds, oxazoline compounds, and polyvalent metal compounds, polyfunctional acid anhydrides, phosphate esters, phosphites, and the like. Two or more kinds may be combined.
  • the lower limit of the esterification reaction and / or transesterification reaction temperature between the dicarboxylic acid component and the diol component is usually 150 ° C or higher, preferably 180 ° C or higher, and the upper limit is usually 260 ° C or lower, preferably 250 ° C or lower.
  • the reaction atmosphere is usually an inert gas atmosphere such as nitrogen or argon.
  • the reaction pressure is usually from normal pressure to 10 kPa, but normal pressure is preferred.
  • the reaction time is usually 1 hour or longer, and the upper limit is usually 10 hours or shorter, preferably 4 hours or shorter.
  • the lower limit of the pressure is usually 0.001 ⁇ 10 3 Pa or more, preferably 0.01 ⁇ 10 3 Pa or more, and the upper limit is usually 1.4 ⁇ 10 3 Pa or less, preferably 0.
  • the degree of vacuum is 4 ⁇ 10 3 Pa or less.
  • the lower limit of the reaction temperature is usually 150 ° C. or higher, preferably 180 ° C. or higher, and the upper limit is usually 260 ° C. or lower, preferably 250 ° C. or lower.
  • the lower limit of the reaction time is usually 2 hours or more, and the upper limit is usually 15 hours or less, preferably 10 hours or less.
  • reaction apparatus for producing the aliphatic polyester in the present invention a known vertical type or horizontal type stirred tank type reactor, a batch type reactor, a twin screw extruder, or the like is used. It is preferred that the reaction is carried out. For example, melt polymerization is performed in two stages of esterification and / or transesterification and reduced pressure polycondensation using the same or different reactors, and a vacuum pump and a reactor are used as the reduced pressure polycondensation reactor. The method of using the stirring tank type reactor provided with the exhaust pipe for pressure reduction to tie is mentioned. In addition, a condenser is connected between the vacuum exhaust pipe connecting the vacuum pump and the reactor, and the volatile components and unreacted monomers generated during the condensation polymerization reaction are recovered by the condenser. Is preferred.
  • the molar ratio of the diol component to the dicarboxylic acid component for obtaining the aliphatic polyester having the desired degree of polymerization differs in a preferable range depending on the purpose and the kind of raw material, but the diol component relative to 1 mol of the acid component.
  • the lower limit of the amount is usually 0.8 mol or more, preferably 0.9 mol or more, and the upper limit is usually 1.5 mol or less, preferably 1.3 mol or less, particularly preferably 1.2 mol or less.
  • a urethane bond, an amide bond, a carbonate bond, an ether bond, or the like can be introduced as long as the biodegradability is not affected.
  • additives such as a heat stabilizer, an antioxidant, a crystal nucleating agent, a flame retardant, an antistatic agent, and a release agent may be added to the polyester in the course of the production method of the present invention or within the range where the properties are not impaired. Further, an ultraviolet absorber or the like may be added at the time of polymerization.
  • the polymer terminal may be controlled.
  • the charging ratio of the dicarboxylic acid component and the dialcohol component needs to be equimolar, so if the terminal is not controlled, the terminal is a carboxylic acid or alcohol. .
  • the terminal can be controlled by adding a carboxylic acid component or an alcohol component. It is also possible to modify functional molecules at the ends. In the case where the terminal is not controlled, a complicated manufacturing operation is not necessary, so that the manufacturing aptitude is excellent. Moreover, since it is a reaction of only normal polymerization, it is excellent in uniformity. When the end is controlled, desired performance can be imparted uniformly.
  • aliphatic polyester in the present invention commercially available products may be used.
  • the substituent that can be substituted for the second polymer component in the present invention is not particularly limited, and examples thereof include halogen atoms (fluorine atom, chlorine atom, bromine atom, iodine atom, etc.), alkyl groups (methyl group, ethyl group, n-propyl group, isopropyl group, tert-butyl group, n-octyl group, 2-ethylhexyl group, etc.), cycloalkyl group (cyclohexyl group, cyclopentyl group, 4-n-dodecylcyclohexyl group etc.), alkenyl group (vinyl group) Allyl group, etc.), cycloalkenyl group (2-cyclopenten-1-yl, 2-cyclohexen-1-yl group, etc.), alkynyl group (ethynyl group, propargyl group, etc.), aryl group (phenyl group, p
  • the second polymer component in the present invention is preferably composed of a non-aromatic polymer component, like the first polymer component. However, unlike the first polymer component, it may have an aromatic group and a heteroaromatic group. This is because the first polymer component imparts heat resistance and ultraviolet resistance as a film, and the second component imparts flexibility and toughness. This is because even if destroyed, the film performance is not greatly affected.
  • the first polymer component and the second polymer component may be crosslinked by a covalent bond or may not be crosslinked. Also, the first polymer components and the second polymer components may be crosslinked by a covalent bond, or may not be crosslinked.
  • the polymer component crosslinked by a covalent bond means, for example, a crosslinking agent having at least two functional groups capable of reacting with the hydroxy group remaining in the first polymer component or the second polymer component, or By the cross-linking agent having a vinyl group, the residual hydroxy groups of the first polymer component or the second polymer component, or the carbon atoms contained in the first polymer component or the second polymer component are partially It is cross-linked by a covalent bond.
  • a radical is generated by cleavage of the vinyl group by heating and / or ultraviolet irradiation, and this radical converts a hydrogen atom of the first polymer component or the second polymer component.
  • the first polymer component or the second polymer component can be partially crosslinked by a covalent bond through the radical sites generated by the partial extraction or the crosslinking agent having a vinyl group.
  • the polymers to be crosslinked may be the first polymer components, the second polymer components, or the first polymer component and the second polymer component.
  • Examples of the functional group capable of reacting with the residual hydroxy group of the first polymer component or the second polymer component include, for example, formyl group, isocyanate group, thioisocyanate group, carboxy group, chlorocarbonyl group, and acid anhydride group.
  • Examples thereof include salts, phosphates, and phosphonates.
  • An epoxy group, an ester group, a formyl group, an isocyanate group, a thioisocyanate group, and a carboxy group are preferable, and an epoxy group, an isocyanate group, or a thioisocyanate group is more preferable.
  • These crosslinking agents having a functional group may be used alone or in combination of two or more.
  • a compound having a functional group capable of reacting with the residual hydroxy group of the first polymer component or the second polymer component and having a polymerizable group is used.
  • the first polymer component or the second polymer component may be crosslinked with a covalent bond by polymerizing the polymerizable groups after reacting with the residual hydroxy group of the first polymer component or the second polymer component. good.
  • the functional group capable of reacting with the residual hydroxy group of the first polymer component or the second polymer component is as described above, and examples thereof include a formyl group, an isocyanate group, a thioisocyanate group, a carboxy group, a chlorocarbonyl group, Acid anhydride group, sulfonic acid group, chlorosulfonyl group, sulfinic acid group, chlorosulfinyl group, epoxy group, glycidyl group, vinyl group, halogen atom, ester group, sulfonic acid ester group, carbonate ester group, amide group, imide group , Carboxylate, sulfonate, phosphate, or phosphonate.
  • a chlorocarbonyl group, an acid anhydride group, an isocyanate group, a thioisocyanate group, a glycidyl group, or an epoxy group is preferable.
  • Examples of the polymerizable group include groups such as a styryl group, an allyl group, a vinylbenzyl group, a vinyl ether group, a vinyl ketone group, a vinyl group, an isopropenyl group, an acryloyl group, a methacryloyl group, a glycidyl group, and an epoxy group.
  • crosslinking agent in the present invention examples include (meth) acrylic acid esters of polyester resins, (meth) acrylic acid esters of polyether resins such as polyethylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, and divinyl compounds.
  • Aldehyde compounds such as formaldehyde, monoaldehyde, dialdehyde, 2- (meth) acryloyloxyethyl isocyanate, tolylene diisocyanate, 4,4'-diphenylmethane diisocyanate, hexamethylene diisocyanate, xylylene diisocyanate, metaxylylene diisocyanate 1, 5-naphthalene diisocyanate, hydrogenated diphenylmethane diisocyanate, hydrogenated tolylene diisocyanate, hydrogenated xylylene diiso Isocyanate compounds such as cyanate and isophorone diisocyanate; Bullet polyisocyanate compounds such as Sumidur N (manufactured by Sumika Bayer Urethane Co., Ltd.); Desmodur IL, HL (manufactured by Bayer AG), Coronate EH (Nippon Polyurethane Industry ( Polyisocyanate compounds having an iso
  • metal oxides such as inorganic cross-linking agents such as aluminum oxide, boron compounds, cobalt oxide, phosphoric acid, monomethyl phosphate, monoethyl phosphate, monobutyl phosphate, monooctyl phosphate, monodecyl phosphate, dimethyl phosphate, diethyl phosphate, Phosphoric acid or phosphate esters such as dibutyl phosphate, dioctyl phosphate, didecyl phosphate; propylene oxide, butylene oxide, cyclohexene oxide, glycidyl methacrylate, glycidol, acrylic glycidyl ether, ⁇ -glycidoxypropyltrimethoxysilane, ⁇ -glycol Sidoxypropyltriethoxysilane, ⁇ -glycidoxypropylmethyldimethoxysilane, (3,4-epoxy
  • Epicoat 152 and Epicoat 154 (above, trade name made by Yuka Shell Epoxy Co., Ltd.), DEN438 and DEN448 (above, trade name made by Dow Chemical Company), Araldite EPN1138 and Araldite EPN1139 (above, As commercial products of epoxy cresol novolak, such as BASF Japan Co., Ltd., Araldite ECN1235, Araldite ECN1273, Araldite ECN1280 (above, product name of BASF Japan), etc., Epicoat 5050 (oil)
  • BREN trade name, manufactured by Nippon Kayaku Co., Ltd.
  • Diglycidyl ether of bisphenol F diglycidyl ester obtained by reaction of dibasic acid such as phthalic acid, dihydrophthalic acid and tetrahydrophthalic acid with epihalohydrin
  • the crosslinking agent used in the present invention is preferably a (meth) acrylic ester of a polyester resin, a (meth) acrylic ester of a polyether resin, an isocyanate compound, or a blocked isocyanate compound. Furthermore, (meth) acrylic acid ester, (meth) acrylic acid ester of polyether resin, and (meth) acrylic acid ester of polyether resin are particularly preferable.
  • the (meth) acrylic acid ester of the polyether resin include polyethylene glycol (meth) acrylate (manufactured by Shin-Nakamura Chemical Co., Ltd .: A-200, A-400, A-600, A-1000, 1G, 2G, 3G.
  • polypropylene glycol (meth) acrylate manufactured by Shin-Nakamura Chemical Co., Ltd .: APG-100, APG-200, APG-400, APG-700, 3PG, 9PG, etc.
  • polyethylene glycol and Polypropylene glycol (meth) acrylate block type) (manufactured by Shin-Nakamura Chemical Co., Ltd .: A-1206PE, A-0612PE, A-0412PE, 1206PE, etc.)
  • polyethylene glycol and polypropylene glycol (meth) acrylate random type
  • Shin-Nakamura Chemical industry: -1000PER, A-3000PER, etc. 1000PER
  • the addition amount of these crosslinking agents is not particularly limited, but is preferably in the range of 0.01 to 30% by mass, more preferably 0.1 to 10% by mass with respect to the cellulose derivative from the viewpoint of film strength and flatness. %.
  • the addition amount 0.01% by mass or more the cellulose derivative can be sufficiently crosslinked, and sufficient heat resistance and mechanical strength can be obtained.
  • the addition amount 30% by mass or less toughness is improved, and in handling Generation
  • the crosslinking may be carried out by using heat, ultraviolet rays or the like without using an initiator serving as a catalyst.
  • a radical polymerization catalyst such as azobisisobutyronitrile (AIBN) or benzoyl peroxide (BPO), an anionic polymerization catalyst, or a cationic polymerization catalyst may be used.
  • a photopolymerization initiator When a photopolymerization initiator is used, preferred examples include benzoin derivatives, benzyl ketal derivatives such as Irgacure 651, ⁇ -hydroxyacetophenone derivatives such as 1-hydroxycyclohexyl phenyl ketone (Irgacure 184), and Irgacure 907. And such ⁇ -aminoacetophenone derivatives.
  • a crosslinking agent containing no aromatic ring is particularly preferred from the viewpoint of durability against sunlight.
  • the content of the second polymer component in the present invention is preferably in the range of 5 to 50% by mass with respect to the first polymer component. By setting it within this range, transparency, tear strength, breaking elongation, and scratch resistance can be improved.
  • additives can be added to the sunlight-resistant highly transparent film of the present invention as long as the intended function is not deteriorated.
  • the additive include at least one or more selected from the group consisting of sugar esters, plasticizers, ultraviolet absorbers, antioxidants, hydrolysis inhibitors, and fine particles.
  • these additives will be described.
  • sugar ester From the viewpoint of improving the plasticity of the sunlight-resistant highly transparent film in the present invention, a sugar ester can be further contained.
  • the sugar ester is a compound having 1 to 12 furanose structures or pyranose structures, and all or part of the hydroxy groups in the compound are esterified.
  • sugar esters include sucrose esters having a structure represented by the following general formula (FA).
  • R 1 to R 8 each represent a hydrogen atom, a substituted or unsubstituted alkylcarbonyl group, or a substituted or unsubstituted arylcarbonyl group.
  • R 1 to R 8 may be the same as or different from each other.
  • the substituted or unsubstituted alkylcarbonyl group is preferably a substituted or unsubstituted alkylcarbonyl group having 2 or more carbon atoms.
  • Examples of the substituted or unsubstituted alkylcarbonyl group include a methylcarbonyl group (acetyl group).
  • aryl groups such as a phenyl group, are mentioned.
  • the substituted or unsubstituted arylcarbonyl group is preferably a substituted or unsubstituted arylcarbonyl group having 7 or more carbon atoms.
  • a phenylcarbonyl group is mentioned as an arylcarbonyl group.
  • Examples of the substituent that the aryl group has include an alkyl group such as a methyl group, or an alkoxyl group such as a methoxy group.
  • the average substitution degree of the acyl group of the sucrose ester is preferably in the range of 3.0 to 7.5.
  • the average substitution degree of the acyl group is within the above range, sufficient compatibility is easily obtained.
  • cellulose ester is used as the first polymer component, it is preferable in terms of increasing compatibility.
  • sucrose ester having the structure represented by the general formula (FA) include the following exemplified compounds (FA-1) to (FA-24).
  • the following table shows R 1 to R 8 in the general formula (FA) of the exemplary compounds (FA-1) to (FA-24) and the average substitution degree of the acyl group.
  • sugar esters examples include the compounds described in JP-A Nos. 62-42996 and 10-237084.
  • the content of the sugar ester is preferably in the range of 0.5 to 35.0% by mass with respect to the total amount of the first polymer component and the second polymer component, and is preferably 5.0 to 30.0% by mass. It is more preferable to be within the range.
  • the sunlight-resistant highly transparent film of the present invention may further contain a plasticizer in order to improve the fluidity of the composition during film production and the flexibility of the film.
  • plasticizers include polyester plasticizers, polyhydric alcohol ester plasticizers, polycarboxylic acid ester plasticizers (including phthalate ester plasticizers), glycolate plasticizers, and ester plasticizers (quenches). Acid ester plasticizers, fatty acid ester plasticizers, phosphate ester plasticizers, trimellitic acid ester plasticizers, and the like). Of these, polyester plasticizers and phosphate ester plasticizers are preferred. These may be used alone or in combination of two or more.
  • the polyester plasticizer is a compound obtained by reacting a monovalent to tetravalent carboxylic acid with a monovalent to hexavalent alcohol, and preferably obtained by reacting a divalent carboxylic acid with a glycol. A compound.
  • divalent carboxylic acid examples include glutaric acid, itaconic acid, adipic acid, phthalic acid, azelaic acid, and sebacic acid.
  • a compound using adipic acid, phthalic acid, or the like as the divalent carboxylic acid is preferable in that it can impart good plasticity.
  • glycol examples include ethylene glycol, propylene glycol, 1,3-butylene glycol, 1,4-butylene glycol, 1,6-hexamethylene glycol, neopentylene glycol, diethylene glycol, triethylene glycol, or dipropylene glycol. It is done.
  • One kind of divalent carboxylic acid and glycol may be used, respectively, or two or more kinds may be used in combination.
  • the polyester plasticizer may be any of ester, oligoester, or polyester.
  • the weight average molecular weight of the polyester plasticizer is preferably in the range of 100 to 10,000, and more preferably in the range of 600 to 3,000 because the effect of imparting plasticity is great.
  • the viscosity of the polyester plasticizer depends on the molecular structure and molecular weight, but in the case of an adipic acid plasticizer, it is in the range of 200 to 5000 MPa ⁇ s (25 ° C.) because of its high effect of imparting plasticity. It is preferable.
  • One type of polyester plasticizer may be used, or two or more types may be used in combination.
  • phosphate ester plasticizer examples include triphenyl phosphate, tricresyl phosphate, cresyl diphenyl phosphate, octyl diphenyl phosphate, diphenyl biphenyl phosphate, trioctyl phosphate, and tributyl phosphate.
  • the plasticizer content is preferably in the range of 0.5 to 30.0% by mass with respect to the first polymer component. If the content of the plasticizer is within the above range, the sunlight-resistant highly transparent film is less likely to cause bleed out.
  • the sunlight-resistant highly transparent film of the present invention may further contain an ultraviolet absorber.
  • the ultraviolet absorber include benzotriazole, 2-hydroxybenzophenone, and salicylic acid phenyl ester.
  • an ultraviolet absorber having a molecular weight of 400 or more is difficult to volatilize at a high boiling point, and is not easily scattered during high temperature molding. Therefore, even if the addition amount is relatively small, weather resistance can be imparted to the obtained film.
  • Examples of the ultraviolet absorber having a molecular weight of 400 or more include 2- [2-hydroxy-3,5-bis ( ⁇ , ⁇ -dimethylbenzyl) phenyl] -2-benzotriazole, 2,2-methylenebis [4- (1 , 1,3,3-tetrabutyl) -6- (2H-benzotriazol-2-yl) phenol] and the like; Hindered amines such as bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate, bis (1,2,2,6,6-pentamethyl-4-piperidyl) sebacate; 2- (3,5-di-t-butyl-4-hydroxybenzyl) -2-n-butylmalonate bis (1,2,2,6,6-pentamethyl-4-piperidyl), 1- [2- [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionyloxy] ethyl] -4- [3- (3,5-di-ter
  • 2- [2-hydroxy-3,5-bis ( ⁇ , ⁇ -dimethylbenzyl) phenyl] -2-benzotriazole or 2,2-methylenebis [4- (1,1,3,3-tetrabutyl) -6- (2H-benzotriazol-2-yl) phenol may be used alone or in combination of two or more.
  • antioxidant A well-known thing can be used for antioxidant, A lactone type compound, a sulfur type compound, a phenol type compound, a double bond type compound, a hindered amine type compound, or a phosphorus type compound etc. are mentioned.
  • lactone compound examples include Irgafos XP40 and Irgafos XP60 (BASF Japan Ltd.).
  • sulfur compounds examples include Sumilizer TPL-R or Sumilizer. TP-D (Sumitomo Chemical Co., Ltd.).
  • phenolic compound those having a 2,6-dialkylphenol structure are preferable, and examples thereof include Irganox 1076, Irganox 1010 (BASF Japan Ltd.), ADK STAB AO-50 (ADEKA) and the like.
  • Examples of the double bond compound include Sumilizer GM or Sumilizer GS (Sumitomo Chemical Co., Ltd.).
  • Examples of the hindered amine compound include Tinuvin 144, Tinuvin 770 (BASF Japan Ltd.), or ADK STAB LA-52 (ADEKA Corporation).
  • Examples of phosphorus compounds include Sumizer GP (Sumitomo Chemical Co., Ltd.), ADK STAB PEP-24G, ADK STAB PEP-36, ADK STAB 3010 (ADEKA), IRGAFOS P-EPQ (BASF Japan Ltd.), or GSY-P101. (Sakai Chemical Industry Co., Ltd.).
  • the content of the antioxidant can be in the range of 0.05 to 5% by mass, preferably 0.1 to 4% by mass, based on the total amount of the first polymer component and the second polymer component described above. %.
  • the sunlight-resistant highly transparent film of the present invention may contain fine particles made of an inorganic compound or an organic compound.
  • Inorganic compounds include silicon dioxide, titanium dioxide, aluminum oxide, zirconium oxide, calcium carbonate, calcium carbonate, talc, clay, calcined kaolin, calcined calcium silicate, hydrated calcium silicate, aluminum silicate, magnesium silicate, or Examples thereof include calcium phosphate.
  • organic compound examples include polytetrafluoroethylene, polystyrene, polymethyl methacrylate, polypropyl methacrylate, polymethyl acrylate, polyethylene carbonate, acrylic styrene resin, or silicone resin.
  • fine particles of silicon dioxide are preferable because the haze of the obtained film is difficult to increase.
  • the fine particles of silicon dioxide include Aerosil R972, R972V, R974, R812, 200, 200V, 300, R202, OX50, or TT600 (manufactured by Nippon Aerosil Co., Ltd.).
  • Aerosil 200V or Aerosil R972V is particularly preferable because it can easily increase the slipperiness of the film surface while keeping the haze of the solar durable high transparent film low.
  • the average primary particle diameter of the fine particles is preferably in the range of 5 to 400 nm, more preferably in the range of 10 to 300 nm.
  • the fine particles may form secondary aggregates mainly having a particle size in the range of 0.05 to 0.30 ⁇ m. If the average particle size of the fine particles is in the range of 100 to 400 nm, they can exist as primary particles without agglomeration.
  • the content of the fine particles is preferably in the range of 0.01 to 1.00% by mass with respect to the total amount of the first polymer component and the second polymer component, and is preferably 0.05 to 0.50% by mass. More preferably within the range.
  • the solar highly durable highly transparent film of the present invention may contain a hydrolysis inhibitor.
  • the hydrolysis inhibitor include carbodiimide compounds such as polycarbodiimide compounds and monocarbodiimide compounds.
  • Polycarbodiimide compounds are preferable from the viewpoint of tear strength and elongation at break, and monocarbodiimide compounds are preferable from the viewpoint of shear processability.
  • polycarbodiimide compound examples include poly (4,4′-diphenylmethanecarbodiimide), poly (4,4′-dicyclohexylmethanecarbodiimide), poly (1,3,5-triisopropylbenzene) polycarbodiimide, poly (1,3,3). 5-triisopropylbenzene, or 1,5-diisopropylbenzene) polycarbodiimide.
  • Examples of the monocarbodiimide compound examples include N, N′-di-2,6-diisopropylphenylcarbodiimide.
  • the carbodiimide compounds may be used alone or in combination of two or more.
  • poly (4,4′-dicyclohexylmethanecarbodiimide) is obtained by converting carbodilite LA-1 (manufactured by Nisshinbo Chemical Co., Ltd.), poly (1,3,5-triisopropylbenzene) polycarbodiimide and poly (1,3,5- Triisopropylbenzene and 1,5-diisopropylbenzene) polycarbodiimide are stabuxol P and stabaxol P-100 (manufactured by Rhein Chemie), and N, N′-di-2,6-diisopropylphenylcarbodiimide is stabuxol I (Rhein).
  • Chemie can be used.
  • poly (4,4′-dicyclohexylmethanecarbodiimide) product name: Carbodilite LA-1, manufactured by Nisshinbo Chemical Co., Ltd.
  • the content of the hydrolysis inhibitor is based on 100 parts by mass of the total amount of the first polymer component and the second polymer component from the viewpoint of improving the light transmittance and the cutting processability of the sunlight-durable highly transparent film. Is preferably in the range of 0.05 to 3 parts by mass, more preferably in the range of 0.10 to 2 parts by mass, and still more preferably in the range of 0.2 to 1 part by mass.
  • the sunlight-resistant highly transparent film in the present invention preferably has a tear strength in the range of 60 to 350 mN.
  • the tear strength of the solar-resistant highly transparent film according to the present invention is in accordance with JIS K 7128-2: 1998 (Plastics-Test method for tear strength of films and sheets-Part 2: Elmendorf tear method).
  • JIS K 7128-2 1998
  • Elmendorf tear method By measuring the tear load of the support in the direction perpendicular to the transport direction (TD direction) or the transport direction (MD direction) by the Elmendorf tear method with a light load tear tester manufactured by Toyo Seiki Seisakusho Co., Ltd. Desired.
  • the tear strength is measured under a constant temperature and humidity condition (in the present invention, a temperature of 23 ° C. and a relative humidity of 55%).
  • the tear length and thickness of the sample are the same conditions, and the average value in the direction orthogonal to the transport direction (TD direction) and the transport direction (MD direction) is determined as the tear strength
  • the sunlight-resistant highly transparent film of the present invention preferably has a breaking elongation in the range of 60 to 200% from the viewpoint of the effect of means for enhancing the breaking elongation and productivity.
  • the elongation at break represents the maximum force (tensile strength) that can be withstanded when the film is pulled and how much the film has stretched (tensile elongation). Specifically, it refers to the elongation immediately before breakage between the determined marks of the test piece in the tensile test. After rupture, some recover as elastic strain, while others remain in the material as permanent or residual strain. The unit is expressed in%.
  • the measuring method conforms to JIS K 7127.
  • the elongation at break according to the present invention is obtained, for example, by casting a dope obtained by dissolving the first polymer component and the second polymer component in a solvent so as to obtain a dry film thickness suitable for measurement.
  • the sample film can be used to measure using a commercially available tensile tester.
  • the sunlight-resistant highly transparent film of the present invention can be produced by a solution casting method or a melt casting method. From the viewpoint of suppressing the optical defects such as coloring and foreign matter defects, die line, etc. of the sunlight durable highly transparent film, the solution casting method is preferable, and from the viewpoint of suppressing the solvent remaining in the sunlight durable highly transparent film, The melt casting method is preferred. When a cellulose derivative is used as the first polymer component, a solution casting method is preferable.
  • a method for producing a sunlight-resistant highly transparent film by the solution casting method is as follows: A1) Step of obtaining a dope by dissolving at least a first polymer component and a second polymer component in a solvent A2) casting the dope onto an endless metal support, A3) evaporating the solvent from the cast dope to obtain a web, A4) peeling the web from the metal support, and A5) web. A step of drying to obtain a film. If necessary, the film may be stretched during or after drying.
  • Step of obtaining a dope A dope is prepared by dissolving a first polymer component, a second polymer component, and, if necessary, other additives in a solvent in a dissolution vessel.
  • the solvent can be used without limitation as long as it dissolves the first polymer component, the second polymer component, and other additives.
  • a chlorinated organic solvent methylene chloride
  • a non-chlorinated organic solvent methyl acetate, ethyl acetate, amyl acetate, acetone, tetrahydrofuran, 1,3-dioxolane, 1,4-dioxane, cyclohexanone, ethyl formate, 2,2,2-trifluoroethanol, 2,2,3,3-hexafluoro-1-propanol, 1,3-difluoro-2-propanol, 1,1,1,3,3,3-hexafluoro- Examples include 2-methyl-2-propanol, 1,1,1,3,3,3-hexafluoro-2-propanol, 2,2,3,3,3-pentafluoro-1-propanol, or nitroethane.
  • methylene chloride and as a non-ch
  • the dope preferably further contains a linear or branched aliphatic alcohol having 1 to 4 carbon atoms in the range of 1 to 40% by mass.
  • a linear or branched aliphatic alcohol having 1 to 4 carbon atoms in the range of 1 to 40% by mass.
  • linear or branched aliphatic alcohol having 1 to 4 carbon atoms examples include methanol, ethanol, n-propanol, iso-propanol, n-butanol, sec-butanol, and tert-butanol.
  • ethanol is preferable because of high dope stability, relatively low boiling point, and high drying property.
  • the dope preferably contains a solvent, methylene chloride, and a linear or branched aliphatic alcohol having 1 to 4 carbon atoms.
  • the concentration of the first polymer component and the second polymer component in the dope is preferably high in order to reduce the drying load, but if the concentration of the first polymer component and the second polymer component is too high, the dope is filtered. Hateful. Therefore, the concentration of the first polymer component and the second polymer component in the dope is preferably in the range of 10 to 35% by mass, more preferably in the range of 15 to 25% by mass.
  • Examples of the method of dissolving the first polymer component and the second polymer component in a solvent include a method of dissolving under heating and pressure.
  • a higher heating temperature is preferable from the viewpoint of increasing the solubility of the first polymer component and the second polymer component.
  • the heating temperature is preferably in the range of 45 to 120 ° C. without increasing the pressure and from the viewpoint of improving productivity.
  • the additive may be added batchwise to the dope, or an additive solution may be separately prepared and added inline.
  • an additive solution may be separately prepared and added inline.
  • the additive solution When the additive solution is added in-line, it is preferable to dissolve a small amount of the first polymer component or the second polymer component in order to facilitate mixing with the dope.
  • the content of the first polymer component or the second polymer component is preferably in the range of 1 to 10 parts by mass, more preferably in the range of 3 to 5 parts by mass with respect to 100 parts by mass of the solvent.
  • an in-line mixer such as a static mixer (manufactured by Toray Engineering) or SWJ (Toray static type in-tube mixer Hi-Mixer) is preferably used.
  • the obtained dope may contain, for example, insoluble matters such as impurities contained in the first polymer component and the second polymer component. Such an insoluble matter can become a bright spot foreign material in the obtained film. In order to remove insoluble matter, it is preferable to further filter the obtained dope.
  • the dope filtration is preferably performed so that the number of bright spot foreign substances in the obtained film is a certain value or less.
  • the number of bright spot foreign matters having a diameter of 0.01 mm or more is 200 / cm 2 or less, preferably 100 / cm 2 or less, more preferably 50 / cm 2 or less, and still more preferably 30 Filtration is performed so that the number of particles / cm 2 or less, particularly preferably 10 / cm 2 or less.
  • the bright spot foreign matter having a diameter of 0.01 mm or less is also preferably 200 pieces / cm 2 or less, more preferably 100 pieces / cm 2 or less, and further preferably 50 pieces / cm 2 or less. 30 / cm 2 or less is more preferable, 10 / cm 2 or less is particularly preferable, and none is most preferable.
  • the number of bright spot foreign matter on the film can be measured by the following procedure. 1) Two polarizing plates are arranged in a crossed Nicol state, and the obtained film is arranged between them. 2) When light is applied from the side of one polarizing plate and observed from the side of the other polarizing plate, the number where the light appears to leak is counted as a foreign object.
  • A2) Casting step The dope is cast on the endless metal support from the slit of the pressure die.
  • the metal support a stainless steel belt or a drum whose surface is plated with a casting is preferably used.
  • the surface of the metal support is preferably mirror-finished.
  • the width of the cast can be in the range of 1 to 4 m.
  • the surface temperature of the metal support in the casting process is set to ⁇ 50 ° C. or more and below the temperature at which the solvent boils and does not foam. A higher temperature is preferable because the web can be dried at a higher speed, but it is within a temperature range in which foaming of the web and deterioration of flatness can be prevented.
  • the surface temperature of the metal support is preferably in the range of 0 to 100 ° C., more preferably in the range of 5 to 30 ° C.
  • the metal support may be cooled so that the web is gelled and can be peeled off from the drum in a state containing a large amount of residual solvent.
  • the method for adjusting the temperature of the metal support is not particularly limited, and there are a method of blowing hot air or cold air, and a method of contacting hot water with the back side of the metal support. It is preferable to use warm water because heat transfer is performed efficiently, so that the time until the temperature of the metal support becomes constant is short.
  • A3) Solvent evaporation step The dope film cast on the metal support is heated on the metal support to evaporate the solvent to obtain a film.
  • the drying method and drying conditions of the dope film can be the same as in the above-described A2) casting step.
  • the film obtained by evaporating the solvent on the metal support is peeled off at the peeling position on the metal support.
  • the residual solvent amount of the film at the time of peeling at the peeling position on the metal support is preferably in the range of 10 to 150% by mass, 20 to 40% by mass or 60% in order to improve the flatness of the film. More preferably, it is in the range of ⁇ 130% by mass, and further preferably in the range of 20-30% by mass or 70-120% by mass.
  • the film peeled off from the metal support can be stretched after drying as necessary.
  • the stretching method may be any method such as uniaxial stretching, biaxial stretching, or oblique stretching.
  • the film may be dried while being transported by a number of rollers arranged above and below, or may be dried while being transported while fixing both ends of the film with clips.
  • the method for drying the film may be a method of drying with hot air, infrared rays, a heating roller, or a microwave, and a method of drying with hot air is preferable because it is simple.
  • a film having a desired retardation, shrinkage, and film width is obtained.
  • the phase difference, shrinkage, and width of the film can be controlled by adjusting the magnitude of the web tension and the draw ratio.
  • stretching a sunlight durability highly transparent film may be arbitrary directions.
  • the width direction (or transport direction) of the film it can also be stretched in an oblique direction (stretched obliquely).
  • the oblique direction can be adjusted in any direction.
  • the draw ratio is represented by the ratio W / W0 of the width of the film before and after stretching (W is before stretching, W0 is the width after stretching), and the film thickness of the obtained optical film and the required level.
  • W is before stretching
  • W0 is the width after stretching
  • the film thickness of the obtained optical film and the required level is preferably in the range of 1.3 to 3.0 times, more preferably in the range of 1.5 to 2.8 times.
  • the stretching temperature is preferably in the range of 80 to 230 ° C., more preferably in the range of 100 to 220 ° C., and even more preferably greater than 110 ° C. and 210 ° C. or less.
  • the stretching operation may be performed in multiple stages. Moreover, when performing biaxial stretching, simultaneous biaxial stretching may be performed and you may implement in steps.
  • stepwise means that, for example, stretching in different stretching directions can be sequentially performed, stretching in the same direction is divided into multiple stages, and stretching in different directions is added to any one of the stages. Is also possible.
  • the residual solvent of the film at the start of stretching is preferably 20% by mass or less, more preferably 15% by mass or less. If the amount of the residual solvent is 2% by mass or more, the film thickness deviation is small and preferable from the viewpoint of flatness, and if it is within 15% by mass, the unevenness of the surface is reduced, and the flatness is improved.
  • the sunlight-resistant highly transparent film according to the present invention is preferably stretched in a temperature range of (Tg + 15) to (Tg + 50) ° C. when the glass transition temperature is Tg.
  • the stretching temperature is preferably in the range of (Tg + 20) to (Tg + 40) ° C.
  • the glass transition temperature Tg referred to here is a midpoint glass transition temperature (Tmg) measured according to JIS K7121 (1987) using a commercially available differential scanning calorimeter with a heating rate of 20 ° C./min. ).
  • Tmg midpoint glass transition temperature
  • a specific method for measuring the glass transition temperature Tg of a highly durable solar transparent film is measured using a differential scanning calorimeter DSC220 manufactured by Seiko Instruments Inc. according to JIS K7121 (1987).
  • B) Melt Casting Method The method for producing the solar durable high transparent film of the present invention by the melt casting method is as follows: B1) Step for producing molten pellets (pelletizing step), B2) After melt kneading the molten pellets , An extruding step (melt extrusion step), B3) a step of cooling and solidifying the molten resin to obtain a film (cooling solidification step), and B4) a step of stretching the film (stretching step).
  • the resin composition containing the first polymer component and the second polymer component of the solar durable highly transparent film is preferably kneaded and pelletized in advance.
  • the pelletization can be performed by a known method.
  • a resin composition containing the first polymer component and the second polymer component described above and, if necessary, an additive such as a plasticizer is extruded into an extruder. After kneading and kneading in, it is extruded in a strand form from the die.
  • the molten resin extruded in a strand form can be cooled with water or air, and then cut to obtain pellets.
  • the raw material of the pellet is preferably dried before being supplied to the extruder in order to prevent decomposition.
  • the antioxidant, the first polymer component, and the second polymer component may be performed by mixing solids with each other, or the antioxidant dissolved in the solvent may be mixed with the first polymer component and the second polymer component.
  • the first polymer component and the second polymer component may be sprayed and mixed with the antioxidant.
  • the atmosphere around the feeder portion of the extruder and the outlet portion of the die is preferably an atmosphere of dehumidified air or nitrogen gas in order to prevent deterioration of the raw material of the pellet.
  • an extruder it is preferable to knead at a low shearing force or at a low temperature so that the resin does not deteriorate (decrease in molecular weight, coloring, gel formation, etc.).
  • a twin screw extruder it is preferable to use a deep groove type screw and to rotate the two screws in the same direction.
  • two screw shapes mesh with each other.
  • the resin composition containing the first polymer component and the second polymer component is not pelletized, and the first polymer component and the second polymer component that are not melt-kneaded are melt-kneaded in an extruder as raw materials.
  • a sunlight-resistant highly transparent film may be produced.
  • the obtained molten pellets and other additives as required are supplied from the hopper to the extruder.
  • the supply of pellets is preferably performed under vacuum, reduced pressure, or an inert gas atmosphere in order to prevent oxidative decomposition of the pellets. And it melt-kneads the melt pellet which is a film material, and another additive as needed with an extruder.
  • the melting temperature of the film material in the extruder is preferably in the range of Tg to (Tg + 100) ° C., more preferably when the glass transition temperature of the film is Tg (° C.), although it depends on the type of film material. Is in the range of (Tg + 10) to (Tg + 90) ° C.
  • a mixing device such as a static mixer is further arranged on the downstream side of the extruder to uniformly mix these components. May be.
  • the molten resin extruded from the extruder is filtered with a leaf disc filter or the like as necessary, and further mixed with a static mixer or the like, and extruded from a die into a film.
  • the extrusion flow rate is preferably stabilized using a gear pump.
  • the leaf disk filter used for removal of a foreign material is a stainless fiber sintered filter.
  • the stainless steel fiber sintered filter is an integrated, intricately intertwined stainless steel fiber body that is compressed and sintered by integrating the contact points. The density is changed according to the thickness of the fiber and the amount of compression, and the filtration accuracy is adjusted. it can.
  • the melting temperature of the resin at the exit of the die can be in the range of about 200-300 ° C.
  • Cooling and solidifying step The resin extruded from the die is nipped between the cooling roller and the elastic touch roller to make the film-like molten resin a predetermined thickness. Then, the film-like molten resin is cooled and solidified stepwise by a plurality of cooling rollers.
  • the surface temperature of a cooling roller can be made into Tg (degreeC) or less, when the glass transition temperature of a film is set to Tg (degreeC).
  • the surface temperatures of the plurality of cooling rollers may be different.
  • the elastic touch roller is also called a pinching rotator.
  • a commercially available elastic touch roller can also be used.
  • the film surface temperature on the elastic touch roller side can be in the range of Tg to (Tg + 110) ° C. of the film.
  • the film-like molten resin solidified from the cooling roller is peeled off with a peeling roller or the like to obtain a film.
  • a peeling roller or the like When peeling the film-like molten resin, it is preferable to adjust the tension in order to prevent deformation of the obtained film.
  • Stretching step Similarly to the solution casting method, the film being cooled or the obtained film can be stretched with a stretching machine to obtain a film.
  • the stretching method, stretching ratio, and stretching temperature of the film can be the same as in the solution casting method.
  • the solar control film according to the present invention is a film in which at least a solar control layer is formed on the above-described solar durable highly transparent film.
  • the solar control film in the present invention is a film having a function of absorbing or reflecting light of all wavelengths of sunlight or a part of wavelengths, a function of collecting light, and a function of changing the direction of light.
  • means for absorbing sunlight include a method for uniformly dissolving or dyeing a dye in a film, a method for uniformly dispersing a pigment, and a method using metal plasmon absorption.
  • Examples of the method for reflecting sunlight include a method of reflecting sunlight by a metal film or the like, and a method of reflecting sunlight by selective reflection by a resin thin film multilayer film or an array of fine particles.
  • the solar control layer according to the present invention is a functional layer laminated on the above-mentioned solar durable high transparent film, and is not particularly limited as long as it has a function of controlling optical characteristics.
  • Examples thereof include a layer that controls reflectance and transmittance, a layer that changes the direction of light, such as a microlens, a microprism, and a scattering layer, or that collects light.
  • a layer that reflects light of all wavelengths of sunlight for example, a silver reflection layer
  • an optical reflection layer that selectively transmits or shields light of a specific wavelength (for example, an infrared reflection layer or an infrared absorption layer) It is preferable to do.
  • a film in which the sunlight control layer is an infrared reflection layer is an infrared reflection film
  • a film in which the sunlight control layer is a silver reflection layer is a film mirror in the present invention.
  • a layer that selectively transmits or blocks light of a specific wavelength a layer that absorbs a specific wavelength by a dye or pigment, a layer that provides a metal thin film to reflect infrared light (infrared reflective layer), and a low refractive index
  • a layer that absorbs a specific wavelength by a dye or pigment a layer that provides a metal thin film to reflect infrared light (infrared reflective layer)
  • a low refractive index Examples include a layer (multilayer light reflection layer: infrared reflection layer) that alternately layers layers and high refractive index layers and reflects only light having a wavelength corresponding to the film thickness.
  • a high refractive index layer including the first water-soluble binder resin and the first metal oxide particles, and a low refractive index layer including the second water-soluble binder resin and the second metal oxide particles are alternately arranged. It is preferable to use a layer that selectively reflects light of a specific wavelength laminated on the substrate.
  • the cellulose derivative is used as a support (solar durability). Highly transparent film), the cellulose derivative absorbs the solvent at the time of coating, and the solvent volatilizes not only from the upper surface (air side) of the coating layer but also from the support side (sunlight-resistant highly transparent film side). Therefore, the coating layer is quickly solidified, the interface mixing between the low refractive index layer and the high refractive index layer is reduced, and a high reflectance is obtained. From this point, it is preferable to apply the cellulose derivative to a support (sunlight-resistant highly transparent film). On the other hand, since the layer structure is complicated and the effect of deterioration during storage is likely to occur, the present invention is very useful. It can be preferably applied.
  • the infrared reflective film according to the present invention is a film in which at least an infrared reflective layer is formed as a solar control layer on the sunlight-resistant highly transparent film of the present invention.
  • the infrared reflection layer include (1) an optical reflection layer having a multilayer structure shown below, and (3) a layer that provides infrared rays by providing a metal thin film.
  • the multi-layer optical reflection layer expresses a function of reflecting and blocking sunlight rays, for example, infrared components, and is composed of a plurality of refractive index layers having different refractive indexes. . Specifically, a high refractive index layer and a low refractive index layer are laminated.
  • the optical reflection layer used in the present invention may have any structure including at least one laminate (unit) composed of a high refractive index layer and a low refractive index layer. It is preferable to have a configuration in which two or more of the above laminates composed of refractive index layers are laminated.
  • the uppermost layer and the lowermost layer of the optical reflection layer may be either a high refractive index layer or a low refractive index layer, but it is preferable that both the uppermost layer and the lowermost layer are low refractive index layers.
  • the uppermost layer is a low refractive index layer, the coating property is improved, and when the lowermost layer is a low refractive index layer, it is preferable from the viewpoint of improving adhesion.
  • an arbitrary refractive index layer of the optical reflection layer is a high refractive index layer or a low refractive index layer is determined by comparing the refractive index with an adjacent refractive index layer. Specifically, when a refractive index layer is used as a reference layer, if the refractive index layer adjacent to the reference layer has a lower refractive index than the reference layer, the reference layer is a high refractive index layer (the adjacent layer is a low refractive index layer). It is judged to be a rate layer.) On the other hand, if the refractive index of the adjacent layer is higher than that of the reference layer, it is determined that the reference layer is a low refractive index layer (the adjacent layer is a high refractive index layer).
  • the refractive index layer is a high refractive index layer or a low refractive index layer is a relative one determined by the relationship with the refractive index of the adjacent layer. Depending on the relationship, it can be a high refractive index layer or a low refractive index layer.
  • high refractive index layer component there are two components constituting the high refractive index layer
  • low refractive index layer component components constituting the low refractive index layer
  • a layer is formed that is mixed at the interface of two layers and includes a high refractive index layer component and a low refractive index layer component.
  • a set of portions where the high refractive index layer component is 50% by mass or more is defined as a high refractive index layer
  • a set of portions where the low refractive index layer component exceeds 50% by mass is defined as a low refractive index layer.
  • the concentration profile of the metal oxide particles in the layer thickness direction in these laminated films can determine whether the mixed layer that can be formed is a high refractive index layer or a low refractive index layer.
  • the concentration profile of the metal oxide particles in the laminated film is sputtered at a rate of 0.5 nm / min using the XPS surface analyzer, etching from the surface to the depth direction, with the outermost surface being 0 nm. It can be observed by measuring the atomic composition ratio. Further, even when the metal oxide particles are not contained in the low refractive index component or the high refractive index component and are formed only from the water-soluble resin, similarly, in the concentration profile of the water-soluble resin, for example, Then, it is confirmed that the mixed region exists by measuring the carbon concentration in the layer thickness direction, and further, its composition is measured by EDX (energy dispersive X-ray spectroscopy), so that it is etched by sputtering. Each layer can be regarded as a high refractive index layer or a low refractive index layer.
  • the XPS surface analyzer is not particularly limited, and any model can be used, but ESCALAB-200R manufactured by VG Scientific Fix Co. was used. Mg is used for the X-ray anode, and measurement is performed at an output of 600 W (acceleration voltage: 15 kV, emission current: 40 mA).
  • the difference in refractive index between the adjacent low refractive index layer and high refractive index layer is 0.1 or more.
  • it is 0.3 or more, more preferably 0.35 or more, and particularly preferably more than 0.4.
  • the optical reflection layer has a plurality of laminates (units) of two or more high refractive index layers and low refractive index layers, the refraction of the high refractive index layer and the low refractive index layer in all the laminates (units). It is preferable that the rate difference is within the preferable range. However, even in this case, the refractive index layer constituting the uppermost layer or the lowermost layer of the optical reflection layer may have a configuration outside the above preferred range.
  • the number of refractive index layers of the optical reflection layer (units of high refractive index layer and low refractive index layer) is preferably 100 layers or less, that is, 50 units or less, and 40 layers (20 units). ) Or less, more preferably 20 layers (10 units) or less.
  • n ⁇ d wavelength / 4 when viewed with a single layer film
  • the reflected light is strengthened by the phase difference. It can be controlled and the reflectance can be increased.
  • n is the refractive index
  • d is the physical film thickness of the layer
  • n ⁇ d is the optical film thickness.
  • the reflectance in a specific wavelength region can be increased by the refractive index of each layer, the film thickness of each layer, and the way of stacking each layer.
  • the optical reflection layer used in the present invention can be made into an ultraviolet reflection film, a visible light reflection film, or a near-infrared light reflection film by changing a specific wavelength region for increasing the reflectance. That is, if the specific wavelength region that increases the reflectance is set in the ultraviolet region, it becomes an ultraviolet reflecting film, if it is set in the visible light region, it becomes a visible light reflecting film, and if it is set in the near infrared region, the near infrared light reflecting film It becomes.
  • the high refractive index layer contains the first water-soluble binder resin and the first metal oxide particles, and may contain a curing agent, other binder resin, a surfactant, and various additives as necessary. Good.
  • the refractive index of the high refractive index layer according to the present invention is preferably in the range of 1.80 to 2.50, more preferably in the range of 1.90 to 2.20.
  • the first water-soluble binder resin according to the present invention has a G2 glass filter (maximum pores of 40 to 50 ⁇ m) when dissolved in water at a concentration of 0.5% by mass at the temperature at which the water-soluble binder resin is most dissolved.
  • the mass of the insoluble matter that is filtered off when filtered in ()) is within 50 mass% of the added water-soluble binder resin.
  • the weight average molecular weight of the first water-soluble binder resin according to the present invention is preferably in the range of 1,000 to 200,000. Further, it is more preferably within the range of 3000 to 40000.
  • the weight average molecular weight can be measured by a known method, such as static light scattering, gel permeation chromatography (GPC), or time-of-flight mass spectrometry (TOF-MASS).
  • GPC gel permeation chromatography
  • TOF-MASS time-of-flight mass spectrometry
  • it is measured by a gel permeation chromatography method which is a generally known method.
  • the content of the first water-soluble binder resin in the high refractive index layer is preferably within the range of 5 to 50% by mass with respect to the solid content of 100% by mass of the high refractive index layer. It is more preferable to be within the range.
  • the first water-soluble binder resin applied to the high refractive index layer is preferably polyvinyl alcohol.
  • the water-soluble binder resin which exists in the low-refractive-index layer mentioned later is also polyvinyl alcohol. Therefore, in the following, polyvinyl alcohol contained in the high refractive index layer and the low refractive index layer will be described together.
  • the high refractive index layer and the low refractive index layer preferably contain two or more types of polyvinyl alcohol having different saponification degrees.
  • polyvinyl alcohol as a water-soluble binder resin used in the high refractive index layer is polyvinyl alcohol (A)
  • polyvinyl alcohol as a water-soluble binder resin used in the low refractive index layer is polyvinyl alcohol (B). That's it.
  • each refractive index layer contains a plurality of polyvinyl alcohols having different saponification degrees and polymerization degrees
  • the polyvinyl alcohol having the highest content in each refractive index layer is changed to polyvinyl alcohol (A ) And polyvinyl alcohol (B) in the low refractive index layer.
  • the “degree of saponification” is the ratio of hydroxy groups to the total number of acetyloxy groups (derived from the starting vinyl acetate) and hydroxy groups in polyvinyl alcohol.
  • the degree of polymerization is calculated assuming that the polyvinyl alcohol having a saponification degree difference of 3 mol% or less is the same polyvinyl alcohol. .
  • a low polymerization degree polyvinyl alcohol having a polymerization degree of 1000 or less is a different polyvinyl alcohol (even if there is a polyvinyl alcohol having a saponification degree difference of 3 mol% or less, it is not regarded as the same polyvinyl alcohol).
  • polyvinyl alcohol having a saponification degree of 90 mol%, a saponification degree of 91 mol%, and a saponification degree of 93 mol% is contained in the same layer by 10 mass%, 40 mass%, and 50 mass%, respectively.
  • These three polyvinyl alcohols are the same polyvinyl alcohol, and these three mixtures are polyvinyl alcohol (A) or (B).
  • the above-mentioned “polyvinyl alcohol having a saponification degree difference of 3 mol% or less” suffices to be within 3 mol% when attention is paid to any polyvinyl alcohol.
  • polyvinyl alcohol having a saponification degree different by 3 mol% or more is contained in the same layer, it is regarded as a mixture of different polyvinyl alcohols, and the polymerization degree and the saponification degree are calculated for each.
  • PVA203 5% by mass
  • PVA117 25% by mass
  • PVA217 10% by mass
  • PVA220 10% by mass
  • PVA224 10% by mass
  • PVA235 20% by mass
  • PVA245 20% by mass
  • most contained A large amount of PVA (polyvinyl alcohol) is a mixture of PVA 217 to 245 (the difference in the degree of saponification of PVA 217 to 245 is within 3 mol%, and thus is the same polyvinyl alcohol), and this mixture is polyvinyl alcohol (A) or ( B).
  • the difference in the absolute value of the degree of saponification between the polyvinyl alcohol (A) and the polyvinyl alcohol (B) is preferably 3 mol% or more, and more preferably 5 mol% or more. If it is such a range, since the interlayer mixing state of a high refractive index layer and a low refractive index layer will become a preferable level, it is preferable. Moreover, although the difference of the saponification degree of polyvinyl alcohol (A) and polyvinyl alcohol (B) is so preferable that it is separated, it is 20 mol% or less from the viewpoint of the solubility to water of polyvinyl alcohol. It is preferable.
  • the saponification degree of polyvinyl alcohol (A) and polyvinyl alcohol (B) is 75 mol% or more from a soluble viewpoint to water. Furthermore, the intermixed state of the high refractive index layer and the low refractive index layer is that one of the polyvinyl alcohol (A) and the polyvinyl alcohol (B) has a saponification degree of 90 mol% or more and the other is 90 mol% or less. Is preferable for achieving a preferable level. It is more preferable that one of the polyvinyl alcohol (A) and the polyvinyl alcohol (B) has a saponification degree of 95 mol% or more and the other is 90 mol% or less. In addition, although the upper limit of the saponification degree of polyvinyl alcohol is not specifically limited, Usually, it is less than 100 mol% and is about 99.9 mol% or less.
  • the polymerization degree of the two types of polyvinyl alcohols having different saponification degrees is preferably 1000 or more, particularly preferably those having a polymerization degree in the range of 1500 to 5000, more preferably in the range of 2000 to 5000. Those are more preferably used. This is because when the polymerization degree of polyvinyl alcohol is 1000 or more, there is no cracking of the coating film, and when it is 5000 or less, the coating solution is stabilized. In the present specification, “the coating solution is stable” means that the coating solution is stable over time.
  • the degree of polymerization of at least one of the polyvinyl alcohol (A) and the polyvinyl alcohol (B) is in the range of 2000 to 5000, it is preferable because cracks of the coating film are reduced and the reflectance at a specific wavelength is improved. It is preferable that both the polyvinyl alcohol (A) and the polyvinyl alcohol (B) are in the range of 2,000 to 5,000 because the above effects can be more remarkably exhibited.
  • Polymerization degree P in the present specification refers to a viscosity average degree of polymerization, measured according to JIS K6726 (1994), and measured in water at 30 ° C. after completely re-saponifying and purifying PVA. From the intrinsic viscosity [ ⁇ ] (dl / g), it is obtained by the following formula (a).
  • the polyvinyl alcohol (B) contained in the low refractive index layer preferably has a saponification degree in the range of 75 to 90 mol% and a polymerization degree in the range of 2000 to 5000.
  • polyvinyl alcohol having such characteristics is contained in the low refractive index layer, it is preferable in that interfacial mixing is further suppressed. This is considered to be because there are few cracks of a coating film and set property improves.
  • the polyvinyl alcohol (A) and (B) used in the present invention may be a synthetic product or a commercially available product.
  • Examples of commercially available products used as the polyvinyl alcohol (A) and (B) include, for example, PVA-102, PVA-103, PVA-105, PVA-110, PVA-117, PVA-120, PVA-124, PVA -203, PVA-205, PVA-210, PVA-217, PVA-220, PVA-224, PVA-235 (manufactured by Kuraray Co., Ltd.), JC-25, JC-33, JF-03, JF-04 , JF-05, JP-03, JP-04JP-05, JP-45 (above, manufactured by Nihon Vinegar Pover Co., Ltd.) and the like.
  • modified polyvinyl alcohol partially modified May be included.
  • modified polyvinyl alcohol include cation-modified polyvinyl alcohol, anion-modified polyvinyl alcohol, nonionic-modified polyvinyl alcohol, and vinyl alcohol-based polymers.
  • Examples of the cation-modified polyvinyl alcohol include primary to tertiary amino groups and quaternary ammonium groups in the main chain or side chain of the polyvinyl alcohol as described in JP-A-61-10383. It is obtained by saponifying a copolymer of an ethylenically unsaturated monomer having a cationic group and vinyl acetate.
  • Examples of the ethylenically unsaturated monomer having a cationic group include trimethyl- (2-acrylamido-2,2-dimethylethyl) ammonium chloride and trimethyl- (3-acrylamido-3,3-dimethylpropyl) ammonium chloride.
  • the ratio of the cation-modified group-containing monomer in the cation-modified polyvinyl alcohol is in the range of 0.1 to 10 mol%, preferably in the range of 0.2 to 5 mol%, relative to vinyl acetate.
  • Anion-modified polyvinyl alcohol is described in, for example, polyvinyl alcohol having an anionic group as described in JP-A-1-206088, JP-A-61-237681 and JP-A-63-307979.
  • examples thereof include a copolymer of vinyl alcohol and a vinyl compound having a water-soluble group, and a modified polyvinyl alcohol having a water-soluble group as described in JP-A-7-285265.
  • Nonionic modified polyvinyl alcohols include, for example, polyvinyl alcohol derivatives obtained by adding a polyalkylene oxide group to a part of vinyl alcohol as described in JP-A-7-9758, and JP-A-8-2595.
  • Polyvinyl alcohol etc. are mentioned.
  • vinyl alcohol polymers examples include EXEVAL (registered trademark, manufactured by Kuraray Co., Ltd.) and Nichigo G polymer (registered trademark, manufactured by Nippon Synthetic Chemical Industry Co., Ltd.).
  • Modified polyvinyl alcohol can be used in combination of two or more, such as the degree of polymerization and the type of modification.
  • the content of the modified polyvinyl alcohol is not particularly limited, but is preferably in the range of 1 to 30% by mass with respect to the total mass (solid content) of each refractive index. If it is in such a range, the said effect will be exhibited more.
  • polyvinyl alcohols having different saponification degrees are used between layers having different refractive indexes.
  • the polyvinyl alcohol (A) having a low saponification degree is used for the high refractive index layer and polyvinyl alcohol (B) having a high saponification degree is used for the low refractive index layer
  • the polyvinyl alcohol ( A) is preferably contained within a range of 40 to 100% by mass, and more preferably within a range of 60 to 95% by mass with respect to the total mass of all polyvinyl alcohols in the layer.
  • the polyvinyl alcohol (B) in the low refractive index layer is preferably contained in the range of 40 to 100% by mass with respect to the total mass of all polyvinyl alcohols in the low refractive index layer, and is preferably 60 to 95% by mass. % Is more preferable.
  • the polyvinyl alcohol (A) having a high saponification degree is used for the high refractive index layer and polyvinyl alcohol (B) having a low saponification degree is used for the low refractive index layer
  • the polyvinyl alcohol ( A) is preferably contained within a range of 40 to 100% by mass, more preferably within a range of 60 to 95% by mass, based on the total mass of all polyvinyl alcohols in the layer.
  • the polyvinyl alcohol (B) in the low refractive index layer is preferably contained in the range of 40 to 100% by mass with respect to the total mass of all polyvinyl alcohols in the low refractive index layer, and is preferably 60 to 95% by mass. % Is more preferable.
  • the content is 40% by mass or more, interlayer mixing is suppressed, and the effect of less disturbance of the interface appears remarkably. On the other hand, if content is 100 mass% or less, stability of a coating liquid will improve.
  • the first water-soluble binder resin other than polyvinyl alcohol in the high refractive index layer, is not limited as long as the high refractive index layer containing the first metal oxide particles can form a coating film. But it can be used without restriction.
  • the second water-soluble binder resin other than the polyvinyl alcohol (B) the low refractive index layer containing the second metal oxide particles is coated as described above. Any device can be used without limitation as long as it can be formed. However, in view of environmental problems and flexibility of the coating film, water-soluble polymers (particularly gelatin, thickening polysaccharides, polymers having reactive functional groups) are preferable. These water-soluble polymers may be used alone or in combination of two or more.
  • the content of other binder resin used together with polyvinyl alcohol preferably used as the water-soluble binder resin is in the range of 5 to 50% by mass with respect to 100% by mass of the solid content of the high refractive index layer. It can also be used within.
  • the binder resin is preferably composed of a water-soluble polymer. That is, in the present invention, a water-soluble polymer other than polyvinyl alcohol and modified polyvinyl alcohol may be used as the binder resin in addition to the polyvinyl alcohol and modified polyvinyl alcohol as long as the effect is not impaired.
  • the water-soluble polymer is a temperature at which the water-soluble polymer is most dissolved, and when dissolved in water at a concentration of 0.5% by mass, a G2 glass filter (within a maximum pore range of 40 to 50 ⁇ m).
  • the mass of the insoluble matter that is filtered off when filtered is within 50 mass% of the added water-soluble polymer.
  • water-soluble polymers gelatin, celluloses, thickening polysaccharides, or polymers having reactive functional groups are particularly preferable. These water-soluble polymers may be used alone or in combination of two or more.
  • the first metal oxide particles applicable to the high refractive index layer are preferably metal oxide particles having a refractive index in the range of 2.0 to 3.0. More specifically, for example, titanium oxide, zirconium oxide, zinc oxide, synthetic amorphous silica, colloidal silica, alumina, colloidal alumina, lead titanate, red lead, yellow lead, zinc yellow, chromium oxide, oxidized oxide Examples thereof include ferric iron, iron black, copper oxide, magnesium oxide, magnesium hydroxide, strontium titanate, yttrium oxide, niobium oxide, europium oxide, lanthanum oxide, zircon, and tin oxide. In addition, composite oxide particles composed of a plurality of metals, core / shell particles whose metal structure changes into a core / shell shape, and the like can also be used.
  • the high refractive index layer includes metal oxide fine particles having a high refractive index such as titanium and zirconium, that is, titanium oxide fine particles and / or zirconia oxide. It is preferable to contain fine particles.
  • titanium oxide is more preferable from the viewpoint of the stability of the coating liquid for forming the high refractive index layer.
  • the rutile type tetragonal type
  • the weather resistance of the high refractive index layer and adjacent layers is higher, and the refractive index is higher. Is more preferable.
  • core / shell particles are used as the first metal oxide particles in the high refractive index layer, due to the interaction between the silicon-containing hydrated oxide of the shell layer and the first water-soluble binder resin, From the effect of suppressing interlayer mixing between the high refractive index layer and the adjacent layer, core / shell particles in which titanium oxide particles are coated with a silicon-containing hydrated oxide are more preferable.
  • the aqueous solution containing titanium oxide particles used in the core of the core / shell particles used in the present invention has a pH measured in the range of 1.0 to 3.0 at 25 ° C., and the titanium particles have a positive zeta potential. It is preferable to use a water-based titanium oxide sol having a surface that is made hydrophobic and dispersible in an organic solvent.
  • the content of the first metal oxide particles according to the present invention is in the range of 15 to 80% by mass with respect to 100% by mass of the solid content of the high refractive index layer, the refractive index with the low refractive index layer This is preferable from the viewpoint of providing a difference. Further, it is more preferably in the range of 20 to 77% by mass, and further preferably in the range of 30 to 75% by mass.
  • content in case metal oxide particles other than the said core-shell particle are contained in a high refractive index layer will not be specifically limited if it is a range which can have the effect of this invention.
  • the volume average particle size of the first metal oxide particles applied to the high refractive index layer is preferably 30 nm or less, more preferably in the range of 1 to 30 nm, and more preferably in the range of 5 to 15 nm. More preferably, it is in the range.
  • a volume average particle size in the range of 1 to 30 nm is preferable from the viewpoint of low visible light transmittance and low haze.
  • the first metal oxide particles according to the present invention are preferably monodispersed.
  • the monodispersion here means that the monodispersity obtained by the following formula (b) is 40% or less. This monodispersity is more preferably 30% or less, and particularly preferably in the range of 0.1 to 20%.
  • titanium oxide particles surface-treated with a silicon-containing hydrated oxide is preferably used.
  • the titanium particles may be referred to as “core / shell particles” or “Si-coated TiO 2 ”.
  • the titanium oxide particles are coated with a silicon-containing hydrated oxide, and the average particle diameter which is preferably a core portion is in the range of 1 to 30 nm, more preferably the average
  • the surface of the titanium oxide particles having a particle size in the range of 4 to 30 nm has a coating amount of silicon-containing hydrated oxide in the range of 3 to 30% by mass as SiO 2 with respect to the titanium oxide as the core. In this way, a shell made of a silicon-containing hydrated oxide is coated.
  • the interaction between the silicon-containing hydrated oxide of the shell layer and the first water-soluble binder resin causes the high refractive index layer and the low refractive index layer to The effect of suppressing the intermixing between the layers and the effect of preventing the deterioration of the binder and choking due to the photocatalytic activity of titanium oxide when titanium oxide is used as the core are exhibited.
  • the core / shell particles preferably have a silicon-containing hydrated oxide coating amount in the range of 3 to 30% by mass as SiO 2 with respect to titanium oxide as the core, more preferably 3 It is in the range of ⁇ 10% by mass, more preferably in the range of 3 to 8% by mass. If the coating amount is 30% by mass or less, a high refractive index layer can be made to have a high refractive index, and if the coating amount is 3% by mass or more, core / shell particle particles can be stably formed. can do.
  • the average particle diameter of the core / shell particles is preferably in the range of 1 to 30 nm, more preferably in the range of 5 to 20 nm, and still more preferably in the range of 5 to 15 nm.
  • optical properties such as near infrared reflectance, transparency, and haze can be further improved.
  • the average particle diameter as used in the field of this invention means a primary average particle diameter, and can be measured from the electron micrograph by a transmission electron microscope (TEM) etc. You may measure by the particle size distribution meter etc. which utilize a dynamic light scattering method, a static light scattering method, etc.
  • TEM transmission electron microscope
  • the average particle size of primary particles is determined by observing particles themselves or particles appearing on the cross section or surface of the refractive index layer with an electron microscope and measuring the particle size of 1000 arbitrary particles.
  • the simple average value (number average) is obtained.
  • the particle size of each particle is represented by a diameter assuming a circle equal to the projected area.
  • JP-A-10-158015 JP-A-2000-053421, JP-A-2000-063119.
  • the silicon-containing hydrated oxide applied to the core / shell particles may be either a hydrate of an inorganic silicon compound, a hydrolyzate or a condensate of an organosilicon compound.
  • silanol A compound having a group is preferable.
  • the high refractive index layer according to the present invention may contain other metal oxide particles in addition to the core / shell particles.
  • various ionic dispersants and protective agents can be used so that the core and shell particles described above do not aggregate in a chargeable manner.
  • metal oxide particles that can be used in addition to the core / shell particles include titanium dioxide, zirconium oxide, zinc oxide, synthetic amorphous silica, colloidal silica, alumina, colloidal alumina, lead titanate, red lead, and yellow lead.
  • Zinc yellow Zinc yellow, chromium oxide, ferric oxide, iron black, copper oxide, magnesium oxide, magnesium hydroxide, strontium titanate, yttrium oxide, niobium oxide, europium oxide, lanthanum oxide, zircon, tin oxide and the like.
  • the core / shell particles used in the present invention may be those in which the entire surface of the titanium oxide particles that are the core is coated with a silicon-containing hydrated oxide, or part of the surface of the titanium oxide particles that are the core. It may be coated with a silicon hydrated oxide.
  • a curing agent can also be used to cure the first water-soluble binder resin applied to the high refractive index layer.
  • the curing agent that can be used together with the first water-soluble binder resin is not particularly limited as long as it causes a curing reaction with the water-soluble binder resin.
  • boric acid and its salt are preferable as the curing agent.
  • known ones can be used, and in general, a compound having a group capable of reacting with polyvinyl alcohol or a compound that promotes the reaction between different groups possessed by polyvinyl alcohol. Select and use.
  • the curing agent include, for example, epoxy curing agents (diglycidyl ethyl ether, ethylene glycol diglycidyl ether, 1,4-butanediol diglycidyl ether, 1,6-diglycidyl cyclohexane, N, N-diglycidyl- 4-glycidyloxyaniline, sorbitol polyglycidyl ether, glycerol polyglycidyl ether, etc.), aldehyde curing agents (formaldehyde, glioxal, etc.), active halogen curing agents (2,4-dichloro-4-hydroxy-1,3,5) , -S-triazine, etc.), active vinyl compounds (1,3,5-trisacryloyl-hexahydro-s-triazine, bisvinylsulfonylmethyl ether, etc.), aluminum alum and the like.
  • epoxy curing agents diglycidyl ethyl
  • Boric acid and its salts refer to oxygen acids and their salts having a boron atom as a central atom, specifically, orthoboric acid, diboric acid, metaboric acid, tetraboric acid, pentaboric acid and octabored acid. Examples include acids and their salts.
  • Boric acid having a boron atom and a salt thereof as a curing agent may be used alone or in a mixture of two or more. Particularly preferred is a mixed aqueous solution of boric acid and borax.
  • aqueous solutions of boric acid and borax can be added only in relatively dilute aqueous solutions, respectively, but by mixing them both can be made into a concentrated aqueous solution and the coating solution can be concentrated. Further, there is an advantage that the pH of the aqueous solution to be added can be controlled relatively freely.
  • boric acid and a salt thereof, or borax it is more preferable to use boric acid and a salt thereof, or borax to obtain the effects of the present invention.
  • boric acid and its salt, or borax are used, metal oxide particles and water-soluble binder resin polyvinyl alcohol OH groups and hydrogen bond network are more easily formed, as a result, high refractive index layer and It is considered that interlayer mixing with the low refractive index layer is suppressed, and preferable near-infrared blocking characteristics are achieved.
  • the film surface temperature of the coating film is once cooled to about 15 ° C., and then the film surface is dried.
  • the effect can be expressed more preferably.
  • the content of the curing agent in the high refractive index layer is preferably in the range of 1 to 10% by mass, preferably in the range of 2 to 6% by mass with respect to 100% by mass of the solid content of the high refractive index layer. It is more preferable.
  • the total amount of the curing agent used is preferably in the range of 1 to 600 mg per gram of polyvinyl alcohol, and in the range of 100 to 600 mg per gram of polyvinyl alcohol. Is more preferable.
  • the low refractive index layer according to the present invention includes a second water-soluble binder resin and second metal oxide particles, and further includes a curing agent, a surface coating component, a particle surface protective agent, a binder resin, a surfactant, Various additives may be included.
  • the refractive index of the low refractive index layer according to the present invention is preferably in the range of 1.10 to 1.60, more preferably 1.30 to 1.50.
  • Polyvinyl alcohol is preferably used as the second water-soluble binder resin applied to the low refractive index layer according to the present invention. Furthermore, it is more preferable that polyvinyl alcohol (B) different from the saponification degree of polyvinyl alcohol (A) present in the high refractive index layer is used in the low refractive index layer according to the present invention.
  • polyvinyl alcohol (A) and polyvinyl alcohol (B), such as a preferable weight average molecular weight of 2nd water-soluble binder resin here is demonstrated by the water-soluble binder resin of the said high refractive index layer. The description is omitted here.
  • the content of the second water-soluble binder resin in the low refractive index layer is preferably within a range of 20 to 99.9% by mass with respect to a solid content of 100% by mass of the low refractive index layer. More preferably, it is in the range of 25 to 80% by mass.
  • any method can be used as long as the low refractive index layer containing the second metal oxide particles can form a coating film. Anything can be used without limitation.
  • water-soluble polymers particularly gelatin, thickening polysaccharides, polymers having reactive functional groups
  • These water-soluble polymers may be used alone or in combination of two or more.
  • the content of the other binder resin used together with polyvinyl alcohol preferably used as the second water-soluble binder resin is 0 to 10 mass with respect to 100 mass% of the solid content of the low refractive index layer. % Can also be used.
  • the low refractive index layer according to the present invention may contain water-soluble polymers such as celluloses, thickening polysaccharides and polymers having reactive functional groups. These water-soluble polymers such as celluloses, thickening polysaccharides and polymers having reactive functional groups are the same as the water-soluble polymers described in the high refractive index layer described above. Is omitted.
  • silica As the second metal oxide particles applied to the low refractive index layer according to the present invention, silica (silicon dioxide) is preferably used, and specific examples thereof include synthetic amorphous silica and colloidal silica. Of these, acidic colloidal silica sol is more preferably used, and colloidal silica sol dispersed in an organic solvent is more preferably used. Further, in order to further reduce the refractive index, hollow fine particles having pores inside the particles can be used as the second metal oxide particles applied to the low refractive index layer, particularly silica (silicon dioxide). The hollow fine particles are preferred.
  • the second metal oxide particles (preferably silicon dioxide) applied to the low refractive index layer preferably have an average particle size in the range of 3 to 100 nm.
  • the average particle size of primary particles of silicon dioxide dispersed in a primary particle state is more preferably in the range of 3 to 50 nm, and in the range of 3 to 40 nm. Is more preferably 3 to 20 nm, and most preferably 4 to 10 nm.
  • grains it is preferable from a viewpoint with few hazes and excellent visible light transmittance
  • the average particle size of the metal oxide particles applied to the low refractive index layer is determined by observing the particles themselves or the particles appearing on the cross section or surface of the refractive index layer with an electron microscope and measuring the particle size of 1000 arbitrary particles.
  • the simple average value (number average) is obtained.
  • the particle diameter of each particle is represented by a diameter assuming a circle equal to the projected area.
  • the colloidal silica used in the present invention is obtained by heating and aging a silica sol obtained by metathesis with an acid of sodium silicate or the like and passing through an ion exchange resin layer.
  • colloidal silica may be a synthetic product or a commercially available product.
  • the surface of the colloidal silica may be cation-modified, or may be treated with Al, Ca, Mg, Ba or the like.
  • Hollow particles can also be used as the second metal oxide particles applied to the low refractive index layer.
  • the average particle pore diameter is preferably within the range of 3 to 70 nm, more preferably within the range of 5 to 50 nm, and even more preferably within the range of 5 to 45 nm.
  • the average particle pore diameter of the hollow particles is the average value of the inner diameters of the hollow particles.
  • the refractive index of the low refractive index layer is sufficiently lowered.
  • the average particle diameter is 50 or more at random, which can be observed as an ellipse in a circular, elliptical or substantially circular shape by electron microscope observation. Is obtained.
  • the average particle hole diameter means the smallest distance among the distances between the outer edges of the hole diameter that can be observed as a circle, an ellipse, or a substantially circle or ellipse, between two parallel lines.
  • the second metal oxide particles according to the present invention may be surface-coated with a surface coating component.
  • a surface coating component such as polyaluminum chloride. It becomes difficult to aggregate with the first metal oxide particles.
  • the content of the second metal oxide particles in the low refractive index layer is preferably within the range of 0.1 to 70% by mass with respect to 100% by mass of the solid content of the low refractive index layer, and preferably 30 to 70%. It is more preferably in the range of mass%, more preferably in the range of 45 to 65 mass%.
  • the low refractive index layer according to the present invention may further include a curing agent.
  • a curing agent there is no particular limitation as long as it causes a curing reaction with the second water-soluble binder resin contained in the low refractive index layer.
  • boric acid and its salt and / or borax are preferred as the curing agent when polyvinyl alcohol is used as the second water-soluble binder resin applied to the low refractive index layer.
  • boric acid and its salts known ones can be used.
  • the content of the curing agent in the low refractive index layer is preferably in the range of 1 to 10% by mass and preferably in the range of 2 to 6% by mass with respect to 100% by mass of the solid content of the low refractive index layer. It is more preferable.
  • the total amount of the curing agent used is preferably in the range of 1 to 600 mg per gram of polyvinyl alcohol, and in the range of 100 to 600 mg per gram of polyvinyl alcohol. More preferred.
  • additives for each refractive index layer In the high refractive index layer and the low refractive index layer according to the present invention, various additives can be used as necessary.
  • the content of the additive in the high refractive index layer is preferably in the range of 0 to 20% by mass with respect to 100% by mass of the solid content of the high refractive index layer. Examples of such additives are described below.
  • At least one of the high refractive index layer and the low refractive index layer may further contain a surfactant.
  • a surfactant any of zwitterionic, cationic, anionic, and nonionic types can be used. More preferably, a betaine zwitterionic surfactant, a quaternary ammonium salt cationic surfactant, a dialkylsulfosuccinate anionic surfactant, an acetylene glycol nonionic surfactant, or a fluorine cationic interface Activators are preferred.
  • the addition amount of the surfactant used in the present invention is 0.005 to 0.30 mass% when the total mass of the coating liquid for high refractive index layer or the coating liquid for low refractive index layer is 100 mass%. It is preferably within the range, and more preferably within the range of 0.01 to 0.10% by mass.
  • the high refractive index layer or the low refractive index layer may contain an amino acid having an isoelectric point of 6.5 or less.
  • an amino acid By including an amino acid, the dispersibility of the metal oxide particles in the high refractive index layer or the low refractive index layer can be improved.
  • an amino acid is a compound having an amino group and a carboxy group in the same molecule, and may be any type of amino acid such as ⁇ -, ⁇ -, and ⁇ -.
  • Some amino acids have optical isomers, but in the present invention, there is no difference in effect due to optical isomers, and any isomer can be used alone or in racemic form.
  • preferred amino acids include aspartic acid, glutamic acid, glycine, serine, and the like, with glycine and serine being particularly preferred.
  • the isoelectric point of an amino acid refers to this pH value because an amino acid balances the positive and negative charges in the molecule at a specific pH and the overall charge is zero.
  • the isoelectric point of each amino acid can be determined by isoelectric focusing at a low ionic strength.
  • the high refractive index layer or the low refractive index layer according to the present invention may further contain an emulsion resin.
  • an emulsion resin By including the emulsion resin, the flexibility of the film is increased and the workability such as sticking to glass is improved.
  • the emulsion resin is a resin in which fine resin particles having an average particle diameter of about 0.01 to 2.0 ⁇ m, for example, are dispersed in an emulsion state in an aqueous medium.
  • the oil-soluble monomer has a hydroxy group. It can be obtained by emulsion polymerization using a polymer dispersant. There is no fundamental difference in the polymer component of the resulting emulsion resin depending on the type of dispersant used.
  • dispersant used in the polymerization of the emulsion examples include polyoxyethylene nonylphenyl ether in addition to low molecular weight dispersants such as alkylsulfonate, alkylbenzenesulfonate, diethylamine, ethylenediamine, and quaternary ammonium salt.
  • Polymer dispersing agents such as polyoxyethylene lauryl ether, hydroxyethyl cellulose, and polyvinylpyrrolidone.
  • emulsion polymerization is performed using a polymer dispersant having hydroxy groups
  • the presence of hydroxy groups is estimated on at least the surface of fine particles
  • emulsion resins polymerized using other dispersants are the chemical and physical properties of emulsions. The nature is different.
  • the polymer dispersant containing a hydroxy group is a polymer dispersant having a weight average molecular weight of 10,000 or more and having a hydroxy group substituted on the side chain or terminal, such as sodium polyacrylate and polyacrylamide.
  • examples of such an acrylic polymer include 2-ethylhexyl acrylate copolymerized and polyethers such as polyethylene glycol and polypropylene glycol.
  • At least one of the high refractive index layer and the low refractive index layer may further contain a lithium compound.
  • the coating liquid for the high refractive index layer or the coating liquid for the low refractive index layer containing the lithium compound makes it easier to control the viscosity, and as a result, the production stability when adding the solar control film of the present invention to glass. Will be improved.
  • the lithium compound applicable to the present invention is not particularly limited.
  • lithium lithium hypochlorite, lithium oxide, lithium carbide, lithium nitride, lithium niobate, lithium sulfide, lithium borate, LiBF 4 , LiClO 4 , LiPF 4 , LiCF 3 SO 3 and the like.
  • These lithium compounds can be used alone or in combination of two or more.
  • lithium hydroxide is preferable from the viewpoint of sufficiently exerting the effects of the present invention.
  • the addition amount of the lithium compound is preferably in the range of 0.005 to 0.05 g, more preferably in the range of 0.01 to 0.03 g, per 1 g of the metal oxide particles present in the refractive index layer.
  • additives Various additives applicable to the high refractive index layer and the low refractive index layer according to the present invention are listed below.
  • ultraviolet absorbers described in JP-A-57-74193, JP-A-57-87988, and JP-A-62-261476, JP-A-57-74192, and JP-A-57-87989.
  • JP-A-60-127785 JP-A-61-146591, JP-A-1-95091, JP-A-3-13376, etc.
  • nonionic surfactants JP-A-59-42993, JP-A-59-52689, JP-A-62-280069, JP-A-61-242871, and JP-A-4-219266.
  • Optical brighteners sulfuric acid, phosphoric acid, acetic acid, citric acid, sodium hydroxide, potassium hydroxide, potassium carbonate, etc.
  • Lubricants such as tylene glycol, antiseptics, antifungal agents, antistatic agents, matting agents, heat stabilizers, antioxidants, flame retardants, crystal nucleating agents, inorganic particles, organic particles, thickeners, lubricants, infrared absorption Examples include various known additives such as agents, dyes, and pigments.
  • the method of forming the optical reflective layer group used in the present invention is preferably formed by applying a wet coating method. Furthermore, the coating liquid for high refractive index layer containing the first water-soluble binder resin and the first metal oxide particles on the support (sunlight durability highly transparent film) according to the present invention, and the second A production method including a step of wet-coating a coating solution for a low refractive index layer containing a water-soluble binder resin and second metal oxide particles is preferable.
  • the wet coating method is not particularly limited.
  • a sequential multilayer application method or a simultaneous multilayer application method may be used as a method of applying a plurality of layers in a multilayer manner.
  • the solvent applicable for preparing the coating solution for the high refractive index layer and the coating solution for the low refractive index layer is not particularly limited, but water, an organic solvent, or a mixed solvent thereof is preferable.
  • organic solvent examples include alcohols such as methanol, ethanol, 2-propanol and 1-butanol, esters such as ethyl acetate, butyl acetate, propylene glycol monomethyl ether acetate and propylene glycol monoethyl ether acetate, diethyl ether and propylene.
  • examples include ethers such as glycol monomethyl ether and ethylene glycol monoethyl ether, amides such as dimethylformamide and N-methylpyrrolidone, and ketones such as acetone, methyl ethyl ketone, acetylacetone and cyclohexanone. These organic solvents may be used alone or in combination of two or more.
  • the solvent of the coating solution is particularly preferably water or a mixed solvent of water and methanol, ethanol, or ethyl acetate.
  • the concentration of the water-soluble binder resin in the coating solution for the high refractive index layer is preferably in the range of 1 to 10% by mass.
  • concentration of the metal oxide particles in the coating solution for the high refractive index layer is preferably in the range of 1 to 50% by mass.
  • the concentration of the water-soluble binder resin in the coating solution for the low refractive index layer is preferably in the range of 1 to 10% by mass.
  • the concentration of the metal oxide particles in the coating solution for the low refractive index layer is preferably in the range of 1 to 50% by mass.
  • the method for preparing the coating solution for the high refractive index layer and the coating solution for the low refractive index layer is not particularly limited.
  • a water-soluble binder resin, metal oxide particles, and other additives added as necessary The method of adding and stirring and mixing is mentioned.
  • the order of addition of the water-soluble binder resin, the metal oxide particles, and other additives used as necessary is not particularly limited, and each component may be added and mixed sequentially while stirring. However, they may be added and mixed at once. If necessary, it is further adjusted to an appropriate viscosity using a solvent.
  • a high refractive index layer using an aqueous high refractive index coating solution prepared by adding and dispersing core / shell particles.
  • the core / shell particles are added to the coating solution for the high refractive index layer as a sol having a pH measured in the range of 5.0 to 7.5 at 25 ° C. and a negative zeta potential of the particles. It is preferable to prepare it.
  • the viscosity at 40 to 45 ° C. of the coating solution for the high refractive index layer and the coating solution for the low refractive index layer is preferably within the range of 5 to 150 mPa ⁇ s. More preferably within the range of 100 mPa ⁇ s.
  • the viscosity at 40 to 45 ° C. of the coating solution for the high refractive index layer and the coating solution for the low refractive index layer when performing simultaneous multilayer coating by the slide curtain coating method is preferably within the range of 5 to 1200 mPa ⁇ s. A range of 25 to 500 mPa ⁇ s is more preferable.
  • the viscosity at 15 ° C. of the coating solution for the high refractive index layer and the coating solution for the low refractive index layer is preferably 100 mPa ⁇ s or more, more preferably in the range of 100 to 30000 mPa ⁇ s, and in the range of 3000 to 30000 mPa ⁇ s.
  • the inside is more preferable, and the inside of the range of 10,000 to 30,000 mPa ⁇ s is particularly preferable.
  • the coating and drying method is not particularly limited, but the coating liquid for high refractive index layer and the coating liquid for low refractive index layer are heated to 30 ° C. or higher, and high on the support (solar durability durable transparent film).
  • the temperature of the formed coating film is preferably cooled (set) preferably within the range of 1 to 15 ° C.
  • it is preferable to dry at 10 degreeC or more. More preferable drying conditions are conditions in which the wet bulb temperature is in the range of 5 to 50 ° C. and the film surface temperature is in the range of 10 to 50 ° C.
  • a horizontal set system from a viewpoint of the uniformity improvement of the formed coating film.
  • the set means a step of increasing the viscosity of the coating composition and reducing the fluidity of substances in each layer and in each layer by means such as applying cold air to the coating to lower the temperature.
  • a state in which the cold air is applied to the coating film from the surface and the finger is pressed against the surface of the coating film is defined as a set completion state.
  • the time from application of cold air to completion of setting is preferably within 5 minutes, and preferably within 2 minutes.
  • the lower limit time is not particularly limited, but it is preferable to take 45 seconds or more.
  • the components in the layer are sufficiently mixed.
  • by setting the set time within 5 minutes it is possible to prevent the difference in refractive index between the high refractive index layer and the low refractive index layer from becoming insufficient due to the progress of interlayer diffusion of the metal oxide particles. .
  • the setting step may not be provided.
  • the set time is adjusted by adjusting the concentration of the water-soluble binder resin and the metal oxide particles, and adding other components such as various known gelling agents such as gelatin, pectin, agar, carrageenan and gellan gum. Can be adjusted. *
  • the temperature of the cold air is preferably in the range of 0 to 25 ° C, more preferably in the range of 5 to 10 ° C. Further, the time for which the coating film is exposed to the cold air is preferably in the range of 10 to 120 seconds, although it depends on the transport speed of the coating film.
  • FIG. 2 is an infrared reflecting film of the present invention having a multilayer light reflecting layer, and has a structure including a reflecting layer unit having a reflecting layer group on one surface side of a solar durable high transparent film as a support. It is a schematic sectional drawing shown.
  • the infrared reflective film 1 a of the present invention has a reflective layer unit U.
  • the reflective layer unit U includes, as an example, a high refractive index reflective layer containing a first water-soluble binder resin and first metal oxide particles on a support (sunlight-resistant highly transparent film) 2a.
  • a reflective layer group ML in which a second water-soluble binder resin and a low refractive index reflective layer containing second metal oxide particles are alternately laminated.
  • the reflective layer group ML is composed of n layers of reflective layers T 1 to T n , for example, T 1 , T 3 , T 5 , (omitted), T n ⁇ 2 , T n with a refractive index of 1.10 to It is composed of a low refractive index layer in the range of 1.60, and T 2 , T 4 , T 6 , (omitted), and T n-1 are high in the refractive index range of 1.80 to 2.50.
  • An example of the configuration is a refractive index layer.
  • the refractive index referred to in the present invention is a value measured at a measurement light wavelength of 550 nm in an environment of 25 ° C.
  • a hard coat layer for improving scratch resistance on the outermost layer of the reflective layer unit.
  • an adhesive layer or a pressure-sensitive adhesive layer that bonds the durable highly transparent film to another substrate.
  • FIG. 3 is a schematic cross-sectional view showing another configuration of the infrared reflecting film of the present invention having a multilayer light reflecting layer, in which a reflecting layer unit having a reflecting layer group is provided on both sides of a support.
  • the ultraviolet curable resin which is a binder component, a photoinitiator, an infrared absorber, etc. are mentioned. It is preferable that the binder component contained in the infrared absorption layer is cured.
  • the curing means that the reaction proceeds and cures by active energy rays such as ultraviolet rays or heat.
  • the ultraviolet curable resin is more excellent in hardness and smoothness than other resins, and is also advantageous from the viewpoint of dispersibility of ITO, ATO, and thermally conductive metal oxide.
  • the ultraviolet curable resin can be used without particular limitation as long as it forms a transparent layer by curing, and examples thereof include silicon resin, epoxy resin, vinyl ester resin, acrylic resin, and allyl ester resin. More preferred is an acrylic resin from the viewpoint of hardness, smoothness and transparency.
  • the acrylic resin is a reactive silica particle in which a photosensitive group having photopolymerization reactivity is introduced on the surface as described in International Publication No. 2008/035669.
  • a photosensitive group having photopolymerization reactivity is introduced on the surface as described in International Publication No. 2008/035669.
  • examples of the photopolymerizable photosensitive group include polymerizable unsaturated groups represented by a (meth) acryloyloxy group.
  • the ultraviolet curable resin contains a photopolymerizable photosensitive group introduced on the surface of the reactive silica particles and a compound capable of photopolymerization, for example, an organic compound having a polymerizable unsaturated group. There may be.
  • the polymerizable unsaturated group-modified hydrolyzable silane is chemically bonded to the silica particles by generating a silyloxy group by a hydrolysis reaction of the hydrolyzable silyl group. It can be used as reactive silica particles.
  • the average particle diameter of the reactive silica particles is preferably in the range of 0.001 to 0.1 ⁇ m. By setting the average particle diameter in such a range, transparency, smoothness, and hardness can be satisfied in a well-balanced manner.
  • the acrylic resin preferably contains fluorine from the viewpoint of adjusting the refractive index. That is, the infrared absorption layer preferably contains fluorine.
  • examples of such an acrylic resin include an acrylic resin containing a structural unit derived from a fluorine-containing vinyl monomer.
  • fluorine-containing vinyl monomer examples include fluoroolefins (for example, fluoroethylene, vinylidene fluoride, tetrafluoroethylene, hexafluoropropylene, etc.), (meth) acrylic acid partial or fully fluorinated alkyl ester derivatives (for example, biscoat 6FM (commodity) Name, manufactured by Osaka Organic Chemical Industry Co., Ltd.) and R-2020 (trade name, manufactured by Daikin Industries, Ltd.)), and fully or partially fluorinated vinyl ethers.
  • fluoroolefins for example, fluoroethylene, vinylidene fluoride, tetrafluoroethylene, hexafluoropropylene, etc.
  • acrylic acid partial or fully fluorinated alkyl ester derivatives for example, biscoat 6FM (commodity) Name, manufactured by Osaka Organic Chemical Industry Co., Ltd.) and R-2020 (trade name, manufactured by Daikin Industries, Ltd.)
  • photopolymerization initiator known ones can be used, and they can be used alone or in combination of two or more.
  • Inorganic infrared absorbers that can be contained in the infrared absorbing layer include tin-doped indium oxide (ITO), antimony-doped tin oxide (ATO), from the viewpoints of visible light transmittance, infrared absorptivity, suitability for dispersion in resin, and the like.
  • ITO tin-doped indium oxide
  • ATO antimony-doped tin oxide
  • Zinc antimonate, lanthanum hexaboride (LaB 6 ), cesium-containing tungsten oxide (Cs 0.33 WO 3 ) and the like are preferable. These may be used alone or in combination of two or more.
  • the average particle size of the inorganic infrared absorber is preferably in the range of 5 to 100 nm, more preferably in the range of 10 to 50 nm.
  • the thickness By setting the thickness to 5 nm or more, there are places where dispersibility in the resin and infrared absorptivity are improved. Moreover, there exists a place which visible light transmittance improves by setting it as 100 nm or less.
  • the average particle size is measured by taking an image with a transmission electron microscope, randomly extracting, for example, 50 particles, measuring the particle size, and averaging the results. Moreover, when the shape of particle
  • the content of the inorganic infrared absorber in the infrared absorption layer is preferably in the range of 1 to 80% by mass, more preferably in the range of 5 to 50% by mass with respect to the total mass of the infrared absorption layer. preferable. If the content is 1% or more, a sufficient infrared absorption effect appears, and if it is 80% or less, a sufficient amount of visible light can be transmitted.
  • Organic infrared absorbing materials include polymethine, phthalocyanine, naphthalocyanine, metal complex, aminium, imonium, diimonium, anthraquinone, dithiol metal complex, naphthoquinone, indolephenol, azo And triallylmethane compounds.
  • metal complex compounds aminium compounds (aminium derivatives), phthalocyanine compounds (phthalocyanine derivatives), naphthalocyanine compounds (naphthalocyanine derivatives), diimonium compounds (diimonium derivatives), squalium compounds (squarium derivatives), and the like. Used.
  • the infrared absorption layer may contain other infrared absorbers such as metal oxides other than those described above, organic infrared absorbers, metal complexes, and the like within the scope of the effects of the present invention.
  • specific examples of such other infrared absorbers include, for example, diimonium compounds, aluminum compounds, phthalocyanine compounds, organometallic complexes, cyanine compounds, azo compounds, polymethine compounds, quinone compounds, diphenylmethane compounds. And triphenylmethane compounds.
  • the thickness of the infrared absorbing layer is preferably in the range of 0.1 to 50 ⁇ m, and more preferably in the range of 1 to 20 ⁇ m. If it is 0.1 ⁇ m or more, the infrared absorption ability tends to be improved, while if it is 50 ⁇ m or less, the crack resistance of the coating film is improved.
  • the method for forming the infrared absorbing layer is not particularly limited.
  • the metal thin film is preferably composed of a metal layer, or a metal layer and a metal oxide layer and / or a metal nitride layer.
  • the metal layer containing a metal exhibits an infrared reflection function, and although not essential, the visible light transmittance can be increased by using a metal oxide layer and / or a metal nitride layer in combination.
  • the metal layer used in the present invention preferably contains silver having excellent infrared reflection performance as a main component, and contains at least gold and / or palladium in the range of 2 to 5% by mass as the total of gold atoms and palladium atoms. If the content of these metals is within the above range, the effect of suppressing corrosion and cracking of silver due to sulfuration is exhibited, and it is advantageous from the viewpoint of the balance between the cost and the improvement effect. Furthermore, gold and palladium are not preferable because they absorb a large amount of visible light as compared with silver, and the visible light transmission performance as a laminated film decreases as the amount added increases.
  • the metal layer may be a single silver alloy layer to which gold and palladium are added in the above-described ratio, or a multilayer structure in which two or more silver alloys having different gold and palladium ratios are stacked.
  • the total thickness of the metal layer is not particularly limited, but is preferably selected appropriately within a range of 5 to 20 nm in consideration of necessary infrared reflection performance and visible light transmission performance. If the thickness is thin, the transparency is excellent, but the infrared reflection performance is degraded. On the other hand, if it is too thick, the transparency is lowered, the amount of metal used is increased, and this is not preferable economically.
  • the metal composition of the metal layer described above can be quantified using a known analysis method such as ICP emission, XPS, or XRF.
  • ICP emission analysis because the composition of each metal can be accurately analyzed even when a protective layer such as a hard coat layer is provided on the metal layer.
  • the metal oxide layer and / or the metal nitride layer may be stacked on the metal layer described above, or the metal layer may be sandwiched between the metal oxide layer and / or the metal nitride layer.
  • the refractive index of silver alone is as low as 0.3 or less, interface reflection occurs between other layers, and the visible light transmission performance is deteriorated, whereas the metal oxide having a refractive index of about 1.5 to 3
  • these substances include metal oxides such as titanium oxide, zinc oxide, and tin-doped indium oxide (ITO), and metal nitrides such as silicon nitride, which can be appropriately selected and used.
  • the thickness of the layer is preferably within a range of 10 to 100 nm, and more preferably within a range of 30 to 60 nm.
  • the solar durable highly transparent film according to the present invention is preferably provided with an easy adhesion layer.
  • the resin forming the easy-adhesion layer is not particularly limited as long as it is highly transparent and durable.
  • acrylic resins, urethane resins, fluorine resins, silicon resins and the like can be used alone or as a mixture.
  • These easy-adhesion layers are coated with a resin or resin composition solution by a known technique such as a gravure coating method, a reverse roll coating method, a roll coating method, or a dip coating method, dried, and then UV, if necessary. It can be formed by irradiating and curing with an electron beam.
  • the thickness of the easy-adhesion layer is preferably in the range of 0.5 to 5 ⁇ m, more preferably in the range of 1 to 3 ⁇ m. If the thickness of the easy-adhesion layer is thin, the surface of the substrate cannot be uniformly coated, and the effect of improving the corrosion resistance tends to be insufficient. On the contrary, even if it is formed too thick, no further improvement in scratch resistance is observed.
  • the easily adhesive layer is made of gelatin, polyvinyl alcohol, partially acetalized polyvinyl alcohol, vinyl acetate-maleic anhydride copolymer or other hydrophilic resin, cellulose diacetate.
  • Cellulose ester resins such as cellulose nitrate are preferable, and these may be used alone or in combination.
  • Effective solvents for the coating solution for the easy adhesion layer include acetone, methyl ethyl ketone, methanol, isopropanol, methylene chloride, ethylene chloride, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, 1-methoxy-2-propanol, ethyl acetate, dimethyl Formamide or the like can be used, and these may be mixed and used as necessary.
  • Adhesive layer The adhesive used for the adhesive layer is selected from adhesives such as rubber, acrylic, silicon, and urethane. Acrylic and silicon-based materials are preferable because they do not yellow over time, and acrylic-based materials are most preferable in that a general-purpose release sheet can be used.
  • the thickness of the adhesive layer is preferably in the range of 5 ⁇ m to 30 ⁇ m. When the thickness is 5 ⁇ m or more, the adhesiveness is stable, and when the thickness is 30 ⁇ m or less, the pressure-sensitive adhesive does not protrude from the side of the film, and there is no inconvenience in handling.
  • the type of separator (release sheet) to be bonded to the adhesive layer it is possible to use a substrate such as polyester, polyethylene, polypropylene, paper, etc., which is coated with silicon, polyalkylene, or fluororesin.
  • a polyester film coated with silicon is particularly preferred.
  • the thickness of the separator is preferably in the range of 10 to 100 ⁇ m, more preferably in the range of 20 to 60 ⁇ m. By setting the thickness to 10 ⁇ m or more, wrinkles in the film do not occur due to a thermal picture during coating and drying. Moreover, it is preferable from a viewpoint of economical efficiency to set it as 100 micrometers or less.
  • the infrared reflective film of the present invention has a conductive layer, an antistatic layer, a gas barrier layer, an antifouling layer, and a deodorant for the purpose of adding further functions on a highly durable solar transparent film.
  • a layer, a droplet layer, a slippery layer, a hard coat layer, an abrasion-resistant layer, an electromagnetic wave shielding layer, an ultraviolet absorption layer, a printing layer, a fluorescent light emitting layer, a hologram layer, a release layer, an adhesive layer, and the like may be provided.
  • the film mirror which concerns on this invention has a silver reflection layer on a support body, and may also have a resin film layer also on the sunlight incident surface side.
  • the support or the resin film layer on the sunlight incident surface side is a sunlight-resistant highly transparent film in the present invention.
  • the sunlight-resistant highly transparent film is located on the light incident surface side with respect to the silver reflective layer, and has a gas barrier layer on the opposite side to the light incident surface with respect to the silver reflective layer.
  • the sunlight-resistant highly transparent film is located on the light incident surface side with respect to the silver reflective layer, and contains a corrosion inhibitor in an adjacent layer opposite to the light incident surface with respect to the silver reflective layer. It is preferable to have a layer.
  • FIGS. 4A, 4B, 5A, and 5B show the configurations of the film mirror and the solar power generation reflection device of the present invention.
  • the film mirror 20 for solar power generation shown in FIG. 4A includes at least a polymer film (for example, a sunlight-durable highly transparent film) 2 as a protective layer, an adhesive layer 3, and a silver reflective layer 5 as constituent layers. Yes. Further, a corrosion prevention layer 4 is provided between the adhesive layer 3 and the silver reflection layer 5. An anchor layer 6 and a support as a support are provided on the opposite side of the silver reflection layer 5 from the light reflection side.
  • a polymer film (for example, a sunlight-resistant highly transparent film) 7 and an adhesive layer 8 are provided, and a release sheet 9 is provided on the outermost layer so as to be peelable.
  • the hard coat layer 1 is formed on the outermost layer of the polymer film 2 as the protective layer on the light reflecting side of the silver reflecting layer 5 as another constituent layer. It is good also to prepare.
  • the film mirror main body is the one obtained by peeling the release sheet 9 from the film mirrors 20 and 21.
  • the film mirrors 20 and 21 not including the adhesive layer 8 and the release sheet 9 and the metal support 10 may be attached using an adhesive.
  • the silver reflection layer 5 is a sunlight reflection layer containing metallic silver as a main component (pure silver or an alloy containing 60 mass% or more of silver), and reflects incident sunlight with high reflectance. To do.
  • a method for forming the silver reflective layer 5 any of a wet method (plating method) and a dry method (vacuum film forming method) can be applied.
  • the wet method is a method for forming a silver film by depositing a metal from a solution. Specific examples of this wet method include silver mirror reaction. Moreover, as one of the wet methods, there is a method of forming a silver reflective layer by applying a solution containing an organic silver complex compound to a film and baking it. By firing the organic silver complex compound, the ligand forming the organic silver complex compound is decomposed, desorbed and vaporized, and metallic silver is precipitated.
  • a specific method of the dry method for example, resistance heating type vacuum deposition method, electron beam heating type vacuum deposition method, ion plating method, ion beam assisted vacuum deposition method, sputtering method, etc. Is mentioned.
  • a vapor deposition method capable of applying a roll-to-roll method of continuously forming a film is preferably used.
  • the thickness of the silver reflective layer 5 according to the present invention is preferably in the range of 10 to 200 nm, more preferably in the range of 30 to 150 nm from the viewpoint of reflectivity and the like.
  • the corrosion prevention layer 4 is a layer for preventing the silver reflection layer 5 from corroding silver, and is a film-like resin coat layer containing a corrosion inhibitor.
  • corrosion refers to a phenomenon in which silver (metal) is chemically or electrochemically eroded by the surrounding environmental material or deteriorated in material quality (see JIS Z0103-2004). .
  • the corrosion prevention layer 4 is preferably provided adjacent to the silver reflection layer 5.
  • the molecular weight of the corrosion inhibitor contained in the corrosion prevention layer 4 is preferably 800 or less. By adding such a low molecular weight corrosion inhibitor, the corrosion inhibitor can easily move to the interface with the silver reflective layer 5, thereby improving the corrosion prevention function and suppressing the deterioration of the silver reflective layer 5. It is thought that it is done.
  • the content of the corrosion inhibitor varies depending on the compound used, but is preferably in the range of 0.01 to 1.0 g / m 2 .
  • the corrosion inhibitor preferably has an adsorptive group for silver.
  • Corrosion inhibitors having an adsorptive group for silver include amines and derivatives thereof, compounds having a pyrrole ring, compounds having a triazole ring, compounds having a pyrazole ring, compounds having a thiazole ring, compounds having an imidazole ring, indazole
  • the compound is selected from a compound having a ring, copper chelate compounds, thioureas, a compound having a mercapto group, at least one naphthalene-based compound, or a mixture thereof.
  • Polymer film for protective layer As the polymer film 2 used as the protective layer, various conventionally known resin films can be used.
  • the solar durable high transparent film of the present invention cellulose ester film, polyester film, polycarbonate film, polyarylate film, polysulfone (including polyethersulfone) film, polyethylene terephthalate, polyethylene naphthalate, etc.
  • Polyester film polyethylene film, polypropylene film, cellophane, cellulose diacetate film, cellulose triacetate film, cellulose acetate propionate film, cellulose acetate butyrate film, polyvinylidene chloride film, polyvinyl alcohol film, ethylene vinyl alcohol film, syndiotactic Polystyrene film, polycarbonate film, norbornene A resin film, a polymethylpentene film, a polyether ketone film, polyether ketone imide film, a polyamide film, a fluororesin film, a nylon film, polymethyl methacrylate film, and acrylic films.
  • the solar durable high transparent film, polycarbonate film, polyester film, norbornene resin film, and cellulose ester film of the present invention are preferable, and the solar durable highly transparent film of the present invention is particularly used.
  • the polymer film 2 may be a film manufactured by melt casting or a film manufactured by solution casting.
  • the thickness of the polymer film 2 is preferably in the range of 10 to 125 ⁇ m. If the polymer film 2 is 10 ⁇ m or more, the tensile strength and tear strength tend to be strong, and if it is 125 ⁇ m or less, the average reflectance for light (infrared rays) in the wavelength range of 1600 nm to 2500 nm exceeds 80%.
  • the surface of the protective layer polymer film 2 may be subjected to corona discharge treatment, plasma treatment, or the like in order to improve adhesion to the hard coat layer 1.
  • the polymer film 2 preferably contains any one of benzotriazole, benzophenone, triazine, cyanoacrylate, and polymer type ultraviolet absorbers.
  • this polymer film 2 it is preferable to use what was manufactured using the solution casting method (casting method).
  • the polymer film 2 produced by using this solution casting method the thickness accuracy and smoothness can be improved as compared with the conventionally used polymer film 2 by the melt casting method.
  • Adhesive Layer 3 is made of a resin (also referred to as “polymer”), and adheres the corrosion prevention layer 4 and the protective layer polymer film 2 containing an ultraviolet absorber. Therefore, the adhesive layer 3 is required to have adhesiveness for bringing the corrosion prevention layer 4 and the polymer film 2 into close contact with each other, and smoothness and transparency for drawing out the high reflection performance inherent to the silver reflection layer 5.
  • the resin used for the adhesive layer 3 is not particularly limited as long as it satisfies the above conditions of adhesion, heat resistance, and smoothness.
  • Polyamide resins, vinyl chloride resins, vinyl chloride vinyl acetate copolymer resins, or the like, or a mixed resin thereof can be used.
  • a mixed resin of a polyester resin and a melamine resin is particularly preferable, and a thermosetting resin in which a curing agent such as isocyanate is further mixed is more preferable.
  • the thickness of the adhesive layer 3 is preferably in the range of 0.05 to 3 ⁇ m, more preferably in the range of 0.1 to 1 ⁇ m. When the thickness of the adhesive layer 3 is within the above range, the adhesion is improved and the effect of forming the adhesive layer is increased, and the unevenness existing on the surface of the polymer film 2 can be covered, and the smoothness is improved. .
  • Polymer film for support As the polymer film 7 used as a support, various conventionally known polymer films can be used.
  • the solar durable high transparent film of the present invention cellulose ester film, polyester film, polycarbonate film, polyarylate film, polysulfone (including polyethersulfone) film, polyethylene terephthalate, polyethylene naphthalate, etc.
  • Polyester film polyethylene film, polypropylene film, cellophane, cellulose diacetate film, cellulose triacetate film, cellulose acetate propionate film, cellulose acetate butyrate film, polyvinylidene chloride film, polyvinyl alcohol film, ethylene vinyl alcohol film, syndiotactic Polystyrene film, polycarbonate film, norbornene A resin film, a polymethylpentene film, a polyether ketone film, polyether ketone imide film, a polyamide film, a fluororesin film, a nylon film, polymethyl methacrylate film, and acrylic films.
  • the solar durable high transparent film, polycarbonate film, polyester film, norbornene resin film, and cellulose ester film of the present invention are preferable, and the solar durable highly transparent film of the present invention is particularly used. preferable.
  • the support polymer film 7 may be a film manufactured by melt casting or a film manufactured by solution casting.
  • the thickness of the polymer film for support 7 is preferably set to an appropriate thickness depending on the type of polymer (resin). For example, it is generally in the range of 10 to 300 ⁇ m. Preferably it is in the range of 20 to 200 ⁇ m, more preferably in the range of 30 to 100 ⁇ m.
  • the polymer film 7 may be a film manufactured by melt casting or a film manufactured by solution casting.
  • Anchor layer 6 that adheres the silver reflective layer 5 and the support polymer film 7 has an adhesive property that allows the silver reflective layer 5 and the polymer film 7 to adhere to each other.
  • the heat resistance that can withstand the heat in the case of forming the film and the smoothness for drawing out the high reflection performance that the silver reflection layer 5 originally has are required.
  • the material of the anchor layer 6 is not particularly limited as long as it satisfies these conditions, but is preferably made of a resin, for example, a polyester resin, an acrylic resin, a melamine resin, an epoxy resin, a polyamide resin Resins, vinyl chloride resins, vinyl chloride vinyl acetate copolymer resins and the like can be used alone or in combination.
  • a mixed resin of a polyester-based resin and a melamine-based resin is preferable from the viewpoint of weather resistance, and a thermosetting resin in which a curing agent such as isocyanate is further mixed is more preferable.
  • the thickness of the anchor layer 6 is preferably in the range of 0.01 to 3 ⁇ m, more preferably in the range of 0.1 to 1 ⁇ m, from the viewpoints of adhesion, smoothness, reflectance of the silver reflective layer 5 and the like. Within range.
  • a method for forming the anchor layer 6 a conventionally known coating method such as a gravure coating method, a reverse coating method, a die coating method or the like can be used.
  • Adhesive layer 8 is a layer for adhering the film mirror main body provided with the silver reflective layer 5 to the metal support 10 when the solar power generation reflective device (30, 31) described later is manufactured. It is provided on the back side (surface opposite to the anchor layer 6) of the polymer film 7 for support.
  • the material of the adhesive layer 8 is not particularly limited, and for example, a dry laminating agent, a wet laminating agent, an adhesive, a heat seal agent, a hot melt agent, and the like can be used. Further, a polyester resin, a urethane resin, a polyvinyl acetate resin, an acrylic resin, a nitrile rubber, or the like may be used.
  • Specific materials for the adhesive layer 8 include, for example, “SK Dyne Series” manufactured by Soken Chemical Co., Ltd. “Oribain BPW Series, BPS Series” manufactured by Toyo Ink Co., Ltd., “Arcon” “Superester” “High Pale” manufactured by Arakawa Chemical Co., Ltd. Etc. can be suitably used.
  • the thickness of the pressure-sensitive adhesive layer 8 is usually preferably in the range of about 1 to 50 ⁇ m from the viewpoint of the pressure-sensitive adhesive effect, the drying speed, and the like.
  • the method of providing the adhesive layer 8 on the film mirror is not particularly limited, but for example, a laminating method that is continuously performed in a roll manner is preferable from the viewpoints of economy and productivity. Or you may provide so that the adhesion layer 8 laminated
  • the release sheet 9 is a polymer film containing a predetermined amount (for example, in the range of 20 to 50% by mass) of fine particles, and is a film layer having a thickness in the range of 75 to 125 ⁇ m. is there. More preferably, the release sheet 9 has a thickness in the range of 100 to 125 ⁇ m.
  • the resin film constituting the release sheet 9 includes various conventionally known film materials (sheet materials) such as an acrylic film or sheet, a polycarbonate film or sheet, a polyarylate film or sheet, a polyethylene naphthalate film or sheet, A polyethylene terephthalate film or sheet, a plastic film or sheet such as a fluororesin, or the like can be used.
  • Specific materials that can be used for the release sheet 9 include, for example, “Separator SP-PET” manufactured by Mitsui Chemicals, Inc., Otac Tack Co., Ltd., Lintec Co., Ltd. release film, and the like.
  • the hard coat layer 1 is provided on the outermost layer of the film mirror in order to prevent damage on the surface of the film mirror.
  • a material for forming the hard coat layer 1 acrylic resin, urethane resin, melamine resin, epoxy resin, organic silicate compound, silicon resin, and the like can be used.
  • a silicon resin or an acrylic resin it is preferable to use a silicon resin or an acrylic resin.
  • an active energy ray-curable acrylic resin or a thermosetting acrylic resin it is preferable to use an active energy ray-curable acrylic resin or a thermosetting acrylic resin.
  • the active energy ray-curable acrylic resin or the thermosetting acrylic resin is a composition containing a polyfunctional acrylate, an acrylic oligomer, or a reactive diluent as a polymerization curing component.
  • Acrylic oligomers include polyester acrylates, urethane acrylates, epoxy acrylates, polyether acrylates, etc., including those in which a reactive acrylic group is bonded to an acrylic resin skeleton, and rigid materials such as melamine and isocyanuric acid. Those having an acrylic group bonded to a simple skeleton can also be used.
  • the reactive diluent has a function of a solvent in the coating process as a coating agent medium, and has a group that itself reacts with a monofunctional or polyfunctional acrylic oligomer. It becomes a copolymerization component.
  • polyfunctional acrylic cured paints include Mitsubishi Rayon Co., Ltd. (trade name “Diabeam (registered trademark)” series, etc.), Nagase Sangyo Co., Ltd. (trade name “Denacol (registered trademark)”).
  • a coating layer 1 can be formed.
  • various additives can be further blended as necessary within the range where the effects of the present invention are not impaired.
  • an antioxidant a light stabilizer, a surfactant, a leveling agent, an antistatic agent, and the like are used in addition to the corrosion inhibitor used for the corrosion prevention layer 4 and the ultraviolet absorber used for the acrylic film 2.
  • an antioxidant a light stabilizer, a surfactant, a leveling agent, an antistatic agent, and the like are used in addition to the corrosion inhibitor used for the corrosion prevention layer 4 and the ultraviolet absorber used for the acrylic film 2.
  • Reflector 30 for Solar Power Generation As shown in FIG. 4B, the reflector 30 for solar power generation is affixed to the metal support 10 with the adhesive layer 8 that is peeled off and exposed from the release sheet 9 of the film mirror 20. Can be manufactured. Similarly, as shown in FIG. 5B, the solar power generation reflecting device 31 can be manufactured by attaching the adhesive layer 8 that is peeled and exposed to the release sheet 9 of the film mirror 21 to the metal support 10.
  • the solar power generation reflector for example, a bowl-shaped (semi-cylindrical) shape can be mentioned.
  • the inside of this semi-cylindrical shape is the reflective surface side, and a cylindrical member having fluid inside is provided at the axial position of the semi-cylindrical, and sunlight is condensed on the cylindrical member to heat the fluid. Then, power is generated by converting the heat energy of the heated fluid into electric energy.
  • flat plate solar power generation reflection devices are installed at a plurality of locations, and sunlight reflected by each reflection device is reflected by a single reflection mirror (central reflection mirror). ), And further, the heat energy obtained by being reflected by the reflecting mirror is converted into electric energy by the power generation unit to generate power.
  • a steel plate, a copper plate, an aluminum plate, an aluminum plated steel plate, an aluminum alloy plated steel plate, a copper plated steel plate, a tin plated steel plate, a chrome plated steel plate, a stainless steel plate, etc. have high thermal conductivity.
  • a metal material or a steel plate in which a resin and a metal plate are combined can be used.
  • the film mirrors 20 and 21 according to the present invention since the film made by the solution casting method is used as the acrylic film 2, a film having a good regular reflectance with respect to sunlight. A mirror can be manufactured.
  • the adhesiveness and smoothness between the acrylic film 2 and the silver reflective layer 5 are set by setting the thickness of the adhesive layer 3 within a range of 0.05 ⁇ m to 3 ⁇ m, more preferably within a range of 0.1 ⁇ m to 1 ⁇ m.
  • the film mirror which has a favorable regular reflectance with respect to sunlight can be manufactured.
  • the silver reflective layer can be easily and stably formed by using silver having a high reflectance as the reflective layer and using a vapor deposition method or a method of firing an organic silver complex compound.
  • the film mirrors 20 and 21 manufactured as described above are bonded to the metal support 10 to manufacture the solar power generation reflection devices 30 and 31, so that the regular reflectance is high, that is, the light collection efficiency is high. A good solar power generation reflector can be obtained.
  • Example 1 [Preparation of high durability sunlight transparent film]
  • First polymer component As the first polymer component, the following cellulose esters A to E, polyethylene terephthalate (PET), cyclic acrylate and maleimide / isobutene copolymer were prepared.
  • Cellulose ester E Acetoxypropylmethylacetylcellulose polyethylene terephthalate described in Synthesis Example 1 of JP 2011-148976 A: Polyethylene tere
  • the amount of resin is added to a vent type screw twin screw extruder equipped with a leaf disk type polymer filter (5 inches, 5 sheets, manufactured by Nagase Sangyo) with a filtration accuracy of 5 ⁇ m and 1 rear vent and 4 fore vents.
  • the polymer (thermoplastic resin) solution (A-1) was introduced at a treatment rate of 2.0 kg / h in terms of conversion, and a polymer filter treatment was performed simultaneously with a deaeration treatment.
  • zinc octylate 18% Nikka octix zinc, manufactured by Nippon Chemical Industry Co., Ltd.
  • deactivator a foaming inhibitor
  • the toluene solution was injected so that zinc octylate was 700 ppm by weight with respect to the obtained thermoplastic resin composition.
  • the temperature in the polymer filter at this time was 280 ° C., and the resin melt viscosity at a shear rate of 100 / sec was 400 Pa ⁇ sec.
  • After passing through a die provided at the tip of the twin-screw extruder filtered with a filter having a pore size of 1 ⁇ m (manufactured by Organo, product name: Micropore filter 1EU), and the cooling water maintained at a temperature in the range of 60 ⁇ 5 ° C.
  • the strand was cooled by a filled water bath.
  • pellets of the thermoplastic resin composition (A-2) (cyclic acrylate) were obtained by introduction into a cutting machine (pelletizer). During the production of pellets, a clean space was provided so that the environmental cleanliness from the die to the cutting machine was 5000 or less (US federal standard FED-STD-209E).
  • ⁇ Second polymer component> The following aliphatic polyesters were prepared as the second polymer component.
  • the weight average molecular weight of each aliphatic polyester and the content of the aliphatic polyester with respect to the cellulose ester are shown in Tables 1 and 2 below.
  • the interaction points are shown in Table 2 below.
  • reaction temperature was raised to 200 ° C., and the pressure in the reaction system was reduced.
  • the reaction was continued until the weight average molecular weight of the reaction product reached 47000, and at the end of the reaction, the melt was discharged into a SUS vat to obtain PES-1.
  • Production Example 5 Synthesis of aliphatic polyester: PBS-2 to PBS-8, PES-2, and PESA-2.
  • the reaction time and degree of vacuum were adjusted in the same manner as in Production Examples 1 to 4 to obtain aliphatic polyesters PBS-2 to PBS-8, PES-2 and PESA-2 having the weight average molecular weights shown in Table 1. .
  • reaction temperature was raised to 200 ° C., and the pressure in the reaction system was reduced.
  • the reaction was continued until the weight average molecular weight of the reaction product reached 70000, and at the end of the reaction, the melt was discharged into a SUS vat to obtain PHBV-1.
  • Fine particles (Aerosil R972V manufactured by Nippon Aerosil Co., Ltd.) 9 parts by mass Ethanol 89 parts by mass Fine particles and ethanol are mixed in the above ratio with stirring using a dissolver for 50 minutes, and then dispersed with Manton Gorin to prepare a fine particle dispersion. did.
  • Fine particle additive solution Methylene chloride 100 parts by weight Fine particle dispersion 4.3 parts by weight Methylene chloride was charged into a dissolution tank, and the prepared fine particle dispersion was slowly added in the above addition amount with sufficient stirring. Subsequently, after being dispersed with an attritor so that the particle size of the secondary particles of the fine particles becomes a predetermined size, the fine particles are filtered through Finemet NF (manufactured by Nippon Seisen Co., Ltd.) to obtain a fine particle additive solution. .
  • Finemet NF manufactured by Nippon Seisen Co., Ltd.
  • the obtained main dope was uniformly cast on a stainless belt support using an endless belt casting apparatus.
  • the solvent in the cast main dope film was evaporated until the residual solvent amount became 75%, and the obtained web was peeled off from the stainless steel belt support.
  • the peeled web was conveyed while being gripped by a clip of a tenter stretching apparatus.
  • the obtained film was dried while being conveyed by a number of rollers in a drying zone.
  • film 101 unsunlight-resistant highly transparent film 101 (hereinafter simply referred to as “film 101”)) was taken up. Obtained.
  • the film thickness was 55 ⁇ m.
  • the first polymer component and the second polymer component shown in Tables 1 and 2 below are the cellulose ester C as the first polymer component and the PBS-1 as the second polymer component.
  • Films 102 to 138 were produced in the same manner except that the content of the second polymer component was changed to that shown in Tables 1 and 2 below.
  • a commercially available film (thickness 50 ⁇ m, manufactured by Teijin DuPont, Teijin Tetron film highly transparent grade) was used as the PET film 130 of the comparative example.
  • a film 139 was produced in the same manner as described above except that the cyclic acrylate was used as the first polymer component.
  • a film 140 was produced in the same manner as described above except that the N-cyclohexylmaleimide / isobutene copolymer was used as the first polymer component in the production of the film 101.
  • Haze meter (turbidity meter): Model NDH 2000, manufactured by Nippon Denshoku Co., Ltd.
  • Light source 5V9W halogen bulb
  • light receiving part is a silicon photocell (with a relative sensitivity filter)
  • the solar durable high transparent film of the present invention has a value of 0.05 or less in the haze measurement of the film when a solvent having a refractive index of ⁇ 0.05 is dropped on the film with this apparatus. Preferably there is.
  • the measurement was performed according to JIS K-7136.
  • the blank haze 1 of a measuring instrument other than a film is measured.
  • the haze 2 including the sample film is measured by the following procedure. 4).
  • 0.05 ml of glycerin 41 is dropped on the slide glass 40 (see FIG. 6A). 5.
  • a sample film 42 to be measured is placed thereon so that air bubbles do not enter (see FIG. 6B).
  • 0.05 ml of glycerin 43 is dropped on the sample film 42 (see FIG. 6C). 7).
  • a cover glass 44 is placed thereon (see FIG. 6D). 8).
  • the laminate produced as described above from above, cover glass 44 / glycerin 43 / sample film 42 / glycerin 41 / slide glass 40) is set in a haze meter, and haze 2 is measured. 9.
  • (Haze 2) ⁇ (Haze 1) (Internal haze of sample film) is calculated.
  • a to C were determined to be acceptable.
  • ⁇ Tear strength> In accordance with JIS K 7128-2 (1998), it was measured by the Elmendorf tearing method using the light load tear tester manufactured by Toyo Seiki Seisakusho Co., Ltd. under the following conditions. A sample was cut out of 63 mm ⁇ 75 mm, left for 1 day under the conditions of a temperature of 23 ° C. and a relative humidity of 55%, and then measured under the same conditions. The sample was measured for a total of 10 tear loads (mN), 5 in each of the direction orthogonal to the transport direction (TD direction) and the transport direction (MD direction). (Converted) was determined as the tear strength.
  • Tg glass transition temperature
  • DSC apparatus differential scanning calorimeter
  • DSC220 Differential scanning calorimeter manufactured by Seiko Instruments Inc.
  • the measured glass transition temperature was evaluated according to the following criteria, and A to C were regarded as acceptable. It was confirmed that the first polymer component and the second polymer component were compatible.
  • C Tg is 80 ° C. or more and less than 100 ° C.
  • D Tg is less than 80 ° C.
  • ⁇ UV resistance> The produced film was put into a light resistance evaluation tester manufactured by Suga Corporation for 500 hours, the light transmittance at 380 nm before and after the turn-on was measured, and the attenuation rate ⁇ T (%) was evaluated. Evaluation was made according to the following criteria, and A to C were set to a level causing no practical problem. A: Decay rate ⁇ T is less than 2% B: Decay rate ⁇ T is 2% or more and less than 10% C: Decay rate ⁇ T is 10% or more and less than 20% D: Decay rate ⁇ T is 20% or more
  • ⁇ Cutability> A film sample cut to a size of 20 cm ⁇ 20 cm is folded into 10 equal parts to 20 cm ⁇ 2.0 cm, and cut into 10 cm ⁇ 2.0 cm with a push-cut paper cutter DN-3 (manufactured by KOKUYO Corporation). The cross section was evaluated. Further, this operation was repeated 1000 times to visually evaluate the scratches on the cutter blade. The evaluation results were divided into the following levels. If it is level B or higher, it is a practically usable level. A: The cut surface is transparent, there is no roughness when touched with a finger, and there is no scratch on the cutter visually after cutting 1000 times. B: The cut surface is transparent and does not feel rough even when touched with a finger, and the cutter is slightly scratched visually after cutting 1000 times.
  • C The cut surface is transparent, but feels somewhat rough when touched with a finger, and the cutter is not scratched visually after cutting 1000 times.
  • D The cut surface is transparent, but feels somewhat rough when touched with a finger, and the cutter is slightly scratched visually after cutting 1000 times.
  • ⁇ Scratch resistance> The prepared A4 size films were attached to glass, and the total haze after 10 g of dried sea sand was sprayed 1000 times at a wind speed of 10 m / S was measured. The measurement was performed according to JIS K7136 using NDH2000 of Nippon Denshoku Industries. This is a three-sheet value measurement. Scratch resistance was calculated from the following formula using the obtained value. The obtained values were ranked A to D, and A to C were accepted.
  • Scratch resistance 100 ⁇ total haze after durability test / total haze before durability test A: Scratch resistance is 95 or more and 100 or less B: Scratch resistance is 90 or more and less than 95 C: Scratch resistance is 85 or more and less than 90 D: Scratch resistance is less than 85
  • the films 101 to 129 and 135 to 138 are light transmissive, tear strength, elongation at break, heat resistance, ultraviolet resistance, and cutting as compared with the films 130 to 134. It is recognized that it is excellent in terms of workability and scratch resistance.
  • the films 133 to 134 of the comparative example are comparative examples in which rigid polymer components are mixed, but the effect of improving the tear strength and the breaking elongation as in the present invention was not obtained.
  • the films 139 and 140 also have light transmittance, tear strength, elongation at break, heat resistance, ultraviolet resistance, cutting processability and scratch resistance as compared with the films 130 to 134. It was excellent at.
  • Example 2 The dope used in the production of the films 101 to 138 in Example 1 was uniformly cast on a stainless steel band support using a belt casting apparatus. With the stainless steel band support, the solvent was evaporated until the residual solvent amount reached 100%, and the stainless steel band support was peeled off. Cellulose ester film web was evaporated at 38 ° C, slitted to 1.65m width, stretched in the TD direction (film width direction) 1.17 times, MD direction (film longitudinal direction) with a tenter Was dried at a drying temperature of 162 ° C. while being stretched by 1.02. The residual solvent amount at the start of drying was 22%. Then, after drying for 15 minutes while transporting the inside of a drying device at 120 ° C.
  • the undercoat layer coating solution 1 was applied to each support 101 to 138 with an extrusion coater so as to be 16 ml / m 2 , passed through a 50 ° C. no-air zone (1 second), and then dried at 122 ° C. for 30 seconds. As a result, a substrate coated with an undercoat layer was obtained.
  • ⁇ Preparation of deionized gelatin> Ocein from which lime was removed by lime treatment, water washing, and neutralization treatment was extracted in hot water at 55 to 60 ° C. to obtain ossein gelatin.
  • the obtained ossein gelatin aqueous solution was subjected to both ion exchanges in a mixed bed of anion exchange resin (Diaion PA-31G) and cation exchange resin (Diaion PK-218).
  • the coating solution L1 for the low refractive index layer and the coating solution H1 for the high refractive index layer shown below are heated to 43 ° C while being kept at 43 ° C.
  • Six layers of the low refractive index layer and the high refractive index layer 5 are provided on the above-mentioned support with the undercoat layer applied thereon so that the film thickness of each of the high refractive index layer and the low refractive index layer when dried is 130 nm. A total of 11 layers were alternately layered alternately.
  • HC layer 1 was formed on the infrared reflective layer to obtain multilayer infrared reflective films 101 to 138.
  • the obtained colloidal silica dispersion L1 was heated to 45 ° C., and 4.0% by mass of polyvinyl alcohol (B) as a polyvinyl alcohol (manufactured by Nippon Vinyl Bipo-Poval Co., Ltd., JP-45: polymerization) 4500, saponification degree 86.5 to 89.5 mol%) and 760 parts of an aqueous solution were sequentially added with stirring. Thereafter, 40 parts of a 1% by weight betaine surfactant (manufactured by Kawaken Fine Chemical Co., Ltd., Sofazoline (registered trademark) LSB-R) aqueous solution was added to prepare a coating solution L1 for a low refractive index layer.
  • B polyvinyl alcohol
  • betaine surfactant manufactured by Kawaken Fine Chemical Co., Ltd., Sofazoline (registered trademark) LSB-R
  • the raw material titanium oxide hydrate is obtained by thermal hydrolysis of an aqueous titanium sulfate solution according to a known method.
  • the base-treated titanium compound was suspended in pure water so that the concentration when converted to TiO 2 was 20 g / L. Therein, it was added with TiO 2 amount to stirring 0.4 mole% citric acid. Then, when the temperature of the mixed sol liquid reaches 92 ° C., concentrated hydrochloric acid was added so that the hydrochloric acid concentration was 31 g / L, and the liquid temperature was maintained at 95 ° C., and the mixture was stirred for 3 hours. A liquid was prepared.
  • the pH and zeta potential of the obtained titanium oxide sol solution were measured, the pH was 1.4 and the zeta potential was +39 mV. Further, when the particle size was measured with a Zetasizer Nano manufactured by Malvern, the monodispersity was 17%.
  • titanium oxide sol solution was dried at 105 ° C. for 3 hours to obtain titanium oxide powder fine particles.
  • the powder fine particles were subjected to X-ray diffraction measurement using JDX-3530 type manufactured by JEOL Datum Co., Ltd. and confirmed to be rutile titanium oxide fine particles.
  • the volume average particle diameter of the fine particles was 10 nm.
  • a 20.0 mass% titanium oxide sol aqueous dispersion containing rutile-type titanium oxide fine particles having a volume average particle diameter of 10 nm was added to 4 kg of pure water to obtain a sol solution serving as core particles.
  • Preparation of coating liquid H1 for high refractive index layer 28.9 parts of a sol solution containing core / shell particles as the first metal oxide particles having a solid content concentration of 20.0% by mass obtained above, and 10.5 parts of a 1.92% by mass citric acid aqueous solution. And 2.0 parts of an aqueous solution of 10% by weight polyvinyl alcohol (manufactured by Kuraray Co., Ltd., PVA-103: polymerization degree 300, saponification degree 98.5 mol%) and 9.0 parts of a 3% by weight aqueous boric acid solution. By mixing, a core-shell particle dispersion H1 was prepared.
  • HC layer 1 ⁇ Formation of hard coat layer (HC layer 1)> Beam set 577 (Arakawa Chemical Industries, Ltd.) was used as an ultraviolet curable resin, and methyl ethyl ketone was added as a solvent. Furthermore, 0.08% by mass of a fluorosurfactant (trade name: Footage (registered trademark) 650A, manufactured by Neos Co., Ltd.) was added, and the total solid content was adjusted to 40 parts by mass. A coating layer coating solution A was prepared.
  • a fluorosurfactant trade name: Footage (registered trademark) 650A, manufactured by Neos Co., Ltd.
  • the coating liquid A for hard coat layer prepared above is coated on the infrared reflective layer with a gravure coater under the condition that the dry layer thickness is 5 ⁇ m, dried at a drying zone temperature of 90 ° C. for 1 minute, and then using an ultraviolet lamp.
  • the hard coat layer was cured by setting the illuminance of the irradiated portion to 100 mW / cm 2 and the irradiation amount to 0.5 J / cm 2 to form a hard coat layer.
  • Example 3 [Solar control film: production of Ag thin film infrared reflective film] As a sunlight control layer, an Ag thin film infrared reflective film having an infrared reflective layer provided with a metal thin film and reflecting infrared light was prepared as follows.
  • the undercoat layer coating solution 2 shown below is filtered through a polypropylene filter having a pore diameter of 0.4 ⁇ m on the supports (sunlight-resistant highly transparent film) 101 to 138 used in Example 2, and the undercoat layer coating solution 2 is obtained.
  • a heat ray reflective layer having a thickness of 14 nm was formed on the undercoat layer using a sputtering target material containing 2% by mass of gold in silver. Further, an acrylic resin “OPSTAR Z7535 (manufactured by JSR Co., Ltd.)” was applied on the heat ray reflective layer using a micro gravure coater, dried at 90 ° C., and then irradiated with an ultraviolet lamp at an illuminance of the irradiated part of 100 mW / cm. 2 , the coating layer was cured with an irradiation amount of 100 mJ / cm 2 to form a hard coat layer having a thickness of 0.8 ⁇ m, and Ag thin-film infrared reflective films 101 to 138 were produced.
  • Acrylic monomer KAYARAD DPHA (dipentaerythritol hexaacrylate, Nippon Kayaku) 201 parts by mass Irgacure 184 (manufactured by BASF Japan) 19 parts by mass Propylene glycol monomethyl ether 115 parts by mass Ethyl acetate 105 parts by mass
  • thermo-machines prepare three thermo-machines, adjust each to 90 ° C (no humidification), -25 ° C, 60 ° C-80% relative humidity, and set each sample to (90 ° C-1 hour) ⁇ (-35 ° C-1 Time) ⁇ (60 ° C.—80% relative humidity—1 hour), this is repeated three times (the movement between thermostats should be within one minute). Thereafter, light with an irradiance of 1 kW / m 2 is irradiated for 15 hours by a metal halide lamp type weather resistance tester (M6T manufactured by Suga Test Instruments). Using this as one cycle, a three-cycle storage acceleration test was performed, and then the haze and near-infrared reflectance of each sample were measured again, and changes before and after the storage acceleration test were evaluated using the following indices.
  • M6T metal halide lamp type weather resistance tester
  • ⁇ Measurement of haze value> The haze value (%) after light irradiation was measured at 10 points at equal intervals in the width direction of the film with a haze meter (Nippon Denshoku Industries Co., Ltd., NDH2000) in an environment of 23 ° C. and 50% RH. The average value was obtained.
  • Haze change width ( ⁇ haze; unit%); haze value after storage acceleration test ⁇ haze value C before storage acceleration test was regarded as acceptable as practicality.
  • Near-infrared reflectivity change width ( ⁇ near-infrared reflectivity; unit%); near-infrared reflectivity before storage acceleration test ⁇ near-infrared reflectivity after storage acceleration test C or higher was regarded as acceptable.
  • the above evaluation results are shown in Table 3 and Table 4 .
  • Tables 3 and 4 the results of the haze change width and near-infrared reflectivity change width are shown as AD.
  • the multilayer thin film infrared film and the Ag thin film infrared reflective film of the present invention have good tear strength, breaking elongation and cutting workability of the solar durable high transparent film as the support. It was excellent in workability without breaking when it was applied as a film to an automobile or indoor window.
  • Example 4 [Production of Film Mirror 101]
  • the film 101 of Example 1 was used as a polymer film for a support of a solar power generation mirror.
  • Esper 9940A made by Hitachi Chemical Co., Ltd.
  • TDI tolylene diisocyanate
  • HMDI hexamethylene diisocyanate
  • a resin dispersion mixed at a mass ratio of 19.5: 1.0: 1.0: 2.5 is coated by a gravure coating method to form an anchor layer having a thickness of 0.1 ⁇ m, and further silver reflection As a layer, a silver reflective layer having a thickness of 80 nm was formed by vacuum deposition.
  • Tinuvin 234 manufactured by Ciba Japan Co., Ltd.
  • Esper 9940A and tolylene diisocyanate were mixed at a resin solid content ratio (mass ratio) of 8.2: 1.8 on the silver reflective layer.
  • vinylol 92T (acrylic resin adhesive; manufactured by Showa Polymer Co., Ltd.) was coated with a thickness of 0.1 ⁇ m, and the film 101 of Example 1 was laminated as a protective layer to produce a film mirror.
  • the film mirrors 102 to 138 were produced in the same manner as the production of the film mirror 101 except that the film 101 of Example 1 was changed to the films 102 to 138 of Example 1.
  • the solar power generation reflecting devices 102 to 138 were produced in the same manner as the solar power generation reflecting device 101 except that the film mirror 101 was changed to the film mirrors 102 to 138.
  • the solar power generation reflectors 101 to 129 and 135 to 138 provided with the film mirrors using the solar durable highly transparent film of the present invention are solar thermal power generations that are comparative examples. It is recognized that the regular reflection rate and durability are excellent as compared with the reflectors 130 to 134 for use.
  • the film mirror of the present invention uses the sunlight-resistant highly transparent film of the present invention as a support or a resin film on the surface on which sunlight is incident, the tear strength, elongation at break and cutting Excellent workability. For this reason, even when the film mirror was applied to a curved solar power generation reflecting device, the workability was satisfactory without breaking.
  • the solar power generation reflecting device was regularly washed with water, and was excellent in scratch resistance.
  • Example 5 When the solar-resistant highly transparent film of the present invention used in Example 1 was buried in soil for 1 year, biodegradability was observed. Therefore, if the first polymer component is a natural polymer and the second polymer component is a biodegradable polymer such as polyester, it is used outdoors and has scratch resistance, durability, ultraviolet resistance, and processability. It can also be used for agricultural films, agricultural light reflecting films, medical films to be affixed on skin and medical supplies, and medical transparent tape substrates that are required and biodegradable.
  • the sunlight-durable highly transparent film of the present invention is highly transparent from the results of Example 1 and has scratch resistance, so that the transparency can be maintained even after long-term use.
  • the solar durable high transparent film of the present invention is excellent in light transmittance, ultraviolet resistance, heat resistance, scratch resistance, cutting workability and toughness (tear strength and breaking elongation), solar control film, infrared reflective film And it can utilize suitably for a film mirror.

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Abstract

La présente invention concerne un film hautement transparent durable en termes de lumière du soleil, qui présente d'excellentes propriétés d'aptitude au façonnage par découpage et de solidité (résistance à la déchirure et allongement à la rupture) en plus de propriétés de transmittance de la lumière, de résistance à la lumière ultraviolette, de résistance à la chaleur, de transparence et de résistance aux rayures; un film de régulation de la lumière du soleil; un film réfléchissant dans l'infrarouge; et un miroir à film. Un film hautement transparent durable en termes de lumière du soleil selon la présente invention contient au moins deux constituants polymères compatibles, et est caractérisé en ce que : un premier constituant polymère est un constituant polymère non aromatique présentant une structure de chaîne principale rigide; et un second constituant polymère comprend un segment souple et présente une masse moléculaire moyenne en poids située dans la plage allant de 4 000 à 500 000.
PCT/JP2015/057685 2014-03-26 2015-03-16 Film hautement transparent durable en termes de lumière du soleil, film de régulation de la lumière du soleil, film réfléchissant dans l'infrarouge et miroir à film Ceased WO2015146673A1 (fr)

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Cited By (14)

* Cited by examiner, † Cited by third party
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CN106443853A (zh) * 2016-11-25 2017-02-22 中国科学院上海技术物理研究所 一种可见光近红外透射中长波红外反射的宽光谱分色片
JP2017194563A (ja) * 2016-04-20 2017-10-26 コニカミノルタ株式会社 光学反射フィルム、光学反射フィルムの製造方法、及び、光学反射体
WO2019004199A1 (fr) * 2017-06-28 2019-01-03 マクセルホールディングス株式会社 Élément à écran thermique/thermo-isolant transparent et son procédé de fabrication
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EP3733555A4 (fr) * 2017-12-27 2020-11-04 Fujifilm Corporation Contenant pour produit agricole
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JP2021518863A (ja) * 2018-04-23 2021-08-05 ウッドリー オイ 均一なポリマー混合物、それに関連する方法、およびその使用
WO2021187524A1 (fr) * 2020-03-19 2021-09-23 出光興産株式会社 Film de résine, matériau de base en résine renforcé par des fibres, corps multicouche, corps composite et leurs procédés de production
US20220363847A1 (en) * 2019-10-22 2022-11-17 Woodly Oy Oriented film of binary polymer composition
WO2023047988A1 (fr) * 2021-09-27 2023-03-30 富士フイルム株式会社 Film d'acylate de cellulose, matériau d'emballage alimentaire, matériau agricole et film pour plaque polarisante
JP2023055686A (ja) * 2021-10-06 2023-04-18 三菱ケミカル株式会社 生分解性樹脂組成物及び成形体
JPWO2023095293A1 (fr) * 2021-11-26 2023-06-01
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CN106443853B (zh) * 2016-11-25 2019-01-25 中国科学院上海技术物理研究所 一种可见光近红外透射中长波红外反射的宽光谱分色片
CN106443853A (zh) * 2016-11-25 2017-02-22 中国科学院上海技术物理研究所 一种可见光近红外透射中长波红外反射的宽光谱分色片
WO2019004199A1 (fr) * 2017-06-28 2019-01-03 マクセルホールディングス株式会社 Élément à écran thermique/thermo-isolant transparent et son procédé de fabrication
JPWO2019004199A1 (ja) * 2017-06-28 2020-04-30 マクセルホールディングス株式会社 透明遮熱断熱部材及びその製造方法
JPWO2019130829A1 (ja) * 2017-12-27 2020-11-19 富士フイルム株式会社 農産容器
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JP2023179493A (ja) * 2018-02-13 2023-12-19 イーストマン ケミカル カンパニー セルロースエステル及びポリマー脂肪族ポリエステルの組成物並びに物品
JP7702458B2 (ja) 2018-02-13 2025-07-03 イーストマン ケミカル カンパニー セルロースエステル及びポリマー脂肪族ポリエステルの組成物並びに物品
JP7702457B2 (ja) 2018-02-13 2025-07-03 イーストマン ケミカル カンパニー セルロースエステル及びポリマー脂肪族ポリエステルの組成物並びに物品
JP2023179492A (ja) * 2018-02-13 2023-12-19 イーストマン ケミカル カンパニー セルロースエステル及びポリマー脂肪族ポリエステルの組成物並びに物品
JP2021518863A (ja) * 2018-04-23 2021-08-05 ウッドリー オイ 均一なポリマー混合物、それに関連する方法、およびその使用
JP7434162B2 (ja) 2018-04-23 2024-02-20 ウッドリー オイ 均一なポリマー混合物、それに関連する方法、およびその使用
JP2019197172A (ja) * 2018-05-10 2019-11-14 マクセルホールディングス株式会社 透明遮熱断熱部材及びその製造方法
JP7057714B2 (ja) 2018-05-10 2022-04-20 マクセル株式会社 透明遮熱断熱部材及びその製造方法
WO2019216318A1 (fr) * 2018-05-10 2019-11-14 マクセルホールディングス株式会社 Élément transparent de protection thermique/isolation thermique et son procédé de fabrication
CN112123684A (zh) * 2019-06-25 2020-12-25 江苏想靓眼镜有限公司 一种多种变色太阳镜加工工艺
US20220363847A1 (en) * 2019-10-22 2022-11-17 Woodly Oy Oriented film of binary polymer composition
WO2021187524A1 (fr) * 2020-03-19 2021-09-23 出光興産株式会社 Film de résine, matériau de base en résine renforcé par des fibres, corps multicouche, corps composite et leurs procédés de production
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JP2023055686A (ja) * 2021-10-06 2023-04-18 三菱ケミカル株式会社 生分解性樹脂組成物及び成形体
JP7750213B2 (ja) 2021-10-06 2025-10-07 三菱ケミカル株式会社 生分解性樹脂組成物及び成形体
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