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WO2015146674A1 - Film optique et film de fenêtre l'employant - Google Patents

Film optique et film de fenêtre l'employant Download PDF

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Publication number
WO2015146674A1
WO2015146674A1 PCT/JP2015/057703 JP2015057703W WO2015146674A1 WO 2015146674 A1 WO2015146674 A1 WO 2015146674A1 JP 2015057703 W JP2015057703 W JP 2015057703W WO 2015146674 A1 WO2015146674 A1 WO 2015146674A1
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WIPO (PCT)
Prior art keywords
layer
refractive index
group
mass
film
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Ceased
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PCT/JP2015/057703
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English (en)
Japanese (ja)
Inventor
仁 安達
博和 小山
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Konica Minolta Inc
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Konica Minolta Inc
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Filing date
Publication date
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Publication of WO2015146674A1 publication Critical patent/WO2015146674A1/fr
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    • 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
    • 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
    • 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
    • B32B23/20—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 esters
    • 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
    • B32B7/04—Interconnection of layers
    • B32B7/12—Interconnection of layers using interposed adhesives or interposed materials with bonding properties
    • 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
    • C08L71/00—Compositions of polyethers obtained by reactions forming an ether link in the main chain; Compositions of derivatives of such polymers
    • C08L71/02—Polyalkylene oxides
    • 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
    • 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
    • B32B2307/70—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
    • B32B2551/00—Optical elements

Definitions

  • the present invention relates to an optical film and a window film using the same. More specifically, the present invention relates to an optical film excellent in curl recovery and tear strength, and a window film excellent in water sticking workability and finished quality using the optical film.
  • a polyethylene terephthalate (PET) film is generally used as a support for optical films such as window films.
  • the product form is often wound into a roll with a narrow diameter.
  • a wound mold is attached (also referred to as a curl), and it returns to a wound state even if it is spread in a sheet form. For this reason, an optical film with a curl is stuck on a window, and handling properties when processing the product into an object are extremely deteriorated. In particular, in the work of attaching a window film to a window, this curl greatly reduced the handleability.
  • a cellulose triacetate (TAC) film used as a cellulose-based support for example, as a support for a photographic photosensitive material, recovers its curl by water treatment such as development.
  • the film is immersed in a developing solution, whereas when the window film is attached with water, water is sprayed by spraying or the like, and the behavior at that time is not well understood. Furthermore, it has been found that when a cellulosic support is applied to a window film support, troubles in which the squeegee catches and the film tears when water is applied.
  • 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 (see Patent Document 2).
  • Patent Document 2 describes that a cellulose derivative is imparted with thermoplasticity and impact resistance, but it does not completely describe the improvement of the problem during water pasting due to winding when storing a window film. There is no suggestion.
  • the present invention has been made in view of the above problems and situations, and a solution to that problem is to provide an optical film excellent in curl recovery and tear strength. Another object of the present invention is to provide a window film excellent in water pasting workability and finished quality using the same.
  • the present inventor has incorporated an optical film with a polyester or polyalkylene oxide that is highly compatible with a cellulose derivative, thereby providing a tear strength.
  • a support containing a cellulose derivative which has been greatly improved, and has led to the present invention.
  • An optical film having at least an optical functional layer and an adhesive layer on a film-like support, wherein the support contains 30% by mass or more of a cellulose derivative, and a curl recovery rate is 20% or more, An optical film that is adjusted to have a strength of 150 mN or more.
  • optical film according to item 1 wherein the support contains an aliphatic polyester or a polyalkylene oxide as a second polymer component in addition to the cellulose derivative.
  • R 1 to R 6 each represents a hydrogen atom or a substituent.
  • I represents an integer of 0 to 2.
  • j represents an integer of 0 to 10.
  • k represents an integer of 3 to 10.
  • A, b, and c represent constituent ratios (molar fractions), and the sum of a, b, and c is 1.) 8).
  • the optical functional layer has a high refractive index layer containing a first water-soluble binder resin and first metal oxide particles, and a low refractive index containing a second water-soluble binder resin and second metal oxide particles.
  • the optical film according to item 8 wherein the optical film is a layer that selectively reflects light of a specific wavelength in which rate layers are alternately laminated.
  • a window film comprising the optical film according to any one of items 1 to 9.
  • the above-described means of the present invention can provide an optical film excellent in curl recovery and tear strength.
  • the window film used under sunlight exposure needs to have light transmission, UV resistance, heat resistance, scratch resistance, workability, and curl recovery. However, no transparent film satisfying such performance has been reported so far.
  • the polymer (resin) used is a non-aromatic polymer (UV resistance), has a rigid main chain structure (heat resistance), and the film is moderate It is considered necessary to have excellent flexibility and toughness (toughness) (scratch resistance, workability).
  • resins with a rigid main chain structure are difficult to remove once the curl is attached, and there are many polymers (resins) with low flexibility and low toughness, and it is difficult to satisfy all these performances.
  • the first function is to suppress decomposition by ultraviolet rays and to impart heat resistance by having a rigid main chain structure that does not contain an aromatic group as a polymer component.
  • Another function is to impart flexibility and toughness to the polymer.
  • Yet another function is to impart curl recovery to the polymer.
  • the stabilization energy when interacting between different polymers needs to be larger than the stabilization energy when interacting with each other.
  • a cellulose derivative that is a natural polymer-modified polymer as a rigid main chain structure that does not contain an aromatic group, and a high molecular weight aliphatic polyester or polyethylene oxide that has a soft segment and can interact with the natural polymer.
  • High compatibility makes it possible to greatly improve the toughness and flexibility of cellulose derivative-containing films, satisfying UV resistance, heat resistance, transparency, scratch resistance, workability and curl recovery.
  • a support could be obtained. Therefore, using this support, it is possible to realize a support having both good curl recovery properties of conventional cellulose derivative films and high strength comparable to PET films, and an optical film suitable as a window film can be obtained. It is inferred that
  • the optical film of the present invention is an optical film having at least an optical functional layer and an adhesive layer on a film-like support, and the support contains 30% by mass or more of a cellulose derivative, and a curl recovery rate Is 20% or more, and the tear strength is adjusted to be 150 mN or more.
  • This feature is a technical feature common to the inventions according to claims 1 to 10.
  • the support is made of an aliphatic polyester or polyalkylene oxide in addition to the cellulose derivative (also referred to as the first polymer component). It is preferable to contain as a component. Further, the support preferably contains 5% by mass or more of the second polymer component having a weight average molecular weight in the range of 4000 to 500,000 with respect to the cellulose derivative. It is preferable that the support contains 5% by mass or more of the second polymer component having a weight average molecular weight in the range of 30,000 to 400,000 with respect to the cellulose derivative because high toughness can be imparted to the support. Furthermore, the cellulose derivative is preferably a cellulose ester.
  • the acetyl group substitution degree X of the cellulose ester and the total substitution degree Y of propionyl group and butyryl group preferably satisfy the above formulas (I) and (II). Thereby, a high toughness can be imparted to the support.
  • the second polymer component is preferably an aliphatic polyester having a structure represented by the general formula (1).
  • the optical functional layer has a layer that selectively transmits or shields light of a specific wavelength, it can be preferably applied because it is easily damaged by stick-slip-like unevenness or squeeze work when water is applied.
  • the optical functional layer has a high refractive index layer containing the first water-soluble binder resin and the first metal oxide particles, and the second water-soluble binder resin and the second metal oxide.
  • permeability is high, it is excellent in heat-shielding performance, and the window film more excellent in curl recovery property can be provided.
  • the optical film of the present invention can be suitably provided for a window film.
  • ⁇ 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 optical film of the present invention is an optical film having at least an optical functional layer and an adhesive layer on a film-like support, and the support contains 30% by mass or more of a cellulose derivative, and a curl recovery rate Is 20% or more, and the tear strength is adjusted to be 150 mN or more.
  • the support according to the present invention includes, in addition to the cellulose derivative, a polyester or polyalkylene oxide having a weight average molecular weight in the range of 4,000 to 500,000 as the second polymer component. On the other hand, it contains 5 mass% or more.
  • an optical film having a sufficient strength as a window film can be provided by taking advantage of the excellent characteristics of the cellulose derivative as a support.
  • FIG. 1A to 1G are examples of the layer structure of the optical film of the present invention.
  • FIG. 1A includes an optical functional layer 3, an adhesive layer 2 and a separator 1 on one side of a support 4 according to the present invention, and a hard coat layer 7 on the opposite side of the support.
  • This optical film can be used as a window film by peeling off the separator 1 and attaching the adhesive layer 2 to a window glass.
  • FIG. 1B is an example in which the optical functional layer 3 is provided on the opposite side of the support 4, and an additional support 6 is provided via the adhesive layer 5.
  • FIG. 1C is an example of a configuration in which the support 4 according to the present invention is used instead of the additional support in the example shown in FIG. 1B and the optical functional layer 3 is sandwiched between the supports 6 according to the present invention.
  • FIG. 1D is an example in which the support 4 and the additional support 6 according to the present invention are replaced with the example shown in FIG. 1B.
  • 1E to 1G are examples in which the support 4 or the additional support 6 according to the present invention is further used with respect to FIG. 1A.
  • the optical functional layer and the adhesive layer may be provided on one side of the support, or may be separately provided on the opposite side of the support via the support.
  • the optical film of the present invention is an optical film having at least an optical functional layer and an adhesive layer on a film-like support, and the support contains 30% by mass or more of a cellulose derivative, and a curl recovery rate Is 20% or more, and the tear strength is adjusted to be 150 mN or more.
  • the support according to the present invention is adjusted so as to contain 30% by mass or more of a cellulose derivative, a curl recovery rate of 20% or more, and a tear strength of 150 mN or more.
  • the support preferably contains 5% by mass or more of the second polymer component having a weight average molecular weight in the range of 4000 to 500,000 with respect to the cellulose derivative.
  • the content of the cellulose derivative in the support is from 50 to 90% by mass, more preferably from 50 to 70% by mass.
  • the content of the second polymer component in the support is preferably 5% by mass or more based on the cellulose derivative. Preferably, it is within the range of 10 to 50% by mass.
  • the interaction of the polymer components can be preferably exerted.
  • the thickness of the support is preferably in the range of 20 to 200 ⁇ m, more preferably in the range of 25 to 100 ⁇ m, and still more preferably in the range of 35 to 70 ⁇ m. If the thickness is 20 ⁇ m or more, wrinkles and the like are less likely to occur during handling, and there is sufficient strength against squeeze when water is applied, and there is no occurrence of unevenness after water application. Moreover, if thickness is 200 micrometers or less, it is excellent in transparency and curl recovery property, and water sticking workability
  • additional supports can be provided as shown in FIGS. 1B, 1D, 1E and 1G.
  • the additional support is not particularly limited as long as the effects of the present invention are not impaired.
  • the thickness of the additional support is preferably in the range of 5 to 200.
  • a composite support with reduced curling of the PET film can be obtained.
  • the curl recovery rate is a scale indicating the curl recovery property of an optical film wound in a roll and having a curl, and can be determined as follows.
  • the support was cut into a strip having a width of 35 mm (direction perpendicular to the transport direction during manufacture: TD direction) and a length of 120 mm (transport direction during manufacture: MD direction), and the temperature was 23 ° C. and the relative humidity was 55%. After being left for 1 day, it is wound around a core having a diameter of 50 mm.
  • the curl degree is represented by 1 / r, r represents the radius of curvature of the curled support, and the unit is m.
  • Curb recovery rate (curl degree before spraying-curl degree after spraying) / curl degree before spraying x 100 (%)
  • the curl recovery rate of the support according to the present invention is 20% or more, more preferably 50% or more.
  • the tear strength defined in the present invention can be determined by the following method.
  • the support according to the present invention is manufactured by Toyo Seiki Seisakusho Co., Ltd. It is calculated
  • 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. Say it.
  • the tear strength of the support according to the present invention is 150 mN or more, more preferably 190 mN or more, and most preferably 230 mN or more.
  • the upper limit of the tear strength is not particularly limited. However, if the strength is too strong, the cutting property of the support is deteriorated, and therefore it is preferably 3000 mN or less.
  • the optical film of the present invention is an optical film having at least an optical functional layer and an adhesive layer on a film-like support, and the support contains 30% by mass or more of a cellulose derivative.
  • Examples of the cellulose derivative according to the present invention include cellulose ester and cellulose ether.
  • the cellulose derivative at least part of the hydrogen atoms of the 2-position, 3-position, and 6-position hydroxy groups of the ⁇ -glucose ring contained in cellulose is substituted with at least one of an aliphatic acyl group and an alkyl group. Is.
  • the cellulose derivative is preferably a cellulose ester.
  • Specific examples of the cellulose ester include triacetyl cellulose, diacetyl cellulose, cellulose acetate propionate, cellulose acetate butyrate, and cellulose tripropionate.
  • the substituent that can be substituted for the first polymer component in the present invention is preferably a non-aromatic group from the viewpoint of durability when exposed to sunlight.
  • halogen atom fluorine atom, chlorine atom, bromine atom, iodine atom, etc.
  • alkyl group methyl group, ethyl group, n-propyl group, isopropyl group, tert-butyl group, n-octyl group, 2-ethylhexyl group)
  • Cycloalkyl group cyclohexyl group, cyclopentyl group, 4-n-dodecylcyclohexyl group, etc.
  • 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
  • the total acyl group substitution degree of the cellulose ester is preferably from 1.5 to 3.0, more preferably from 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.
  • acetyl group substitution degree X of cellulose ester and the total substitution degree Y of propionyl group and butyryl group satisfy the following formulas (I) and (II).
  • the cellulose ester contained in the optical film of the present invention may contain a plurality of cellulose esters having different degrees of substitution in order to obtain desired properties. For example, when two types of cellulose esters having different substitution degrees are included, the mixing ratio thereof can be 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.
  • the weight average molecular weight (Mw) and number average molecular weight (Mn) of the cellulose ester can be measured by gel permeation chromatography (GPC).
  • GPC gel permeation chromatography
  • the second polymer component in the present invention is compatible by a plurality of interactions with the first polymer component, preferably has a weight average molecular weight of 4000 to 500,000 and has a soft segment.
  • the term “compatible” refers to being mixed and transparent at the molecular level.
  • the interaction in the present invention include a hydrogen bond, a dipole-dipole interaction, an intermolecular force, and a CH- ⁇ interaction.
  • 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 second polymer component having a high molecular weight has many interaction points per main chain, and a plurality of interactions with the first polymer component.
  • the number of possible states increases exponentially and entropy increases, so the free energy of the cast increases negatively, so the first polymer component and the second polymer component interact.
  • a high degree of compatibility is possible.
  • Whether 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 simply mixed, there are two or more glass transition temperatures of the mixture because there is a glass transition temperature for 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 differential scanning calorimeter (for example, DSC-7 manufactured by Perkin Elmer, differential scanning calorimeter DSC220 manufactured by Seiko Instruments Inc.), and the rate of temperature increase is 20 It is measured at ° C./min and is defined as the midpoint glass transition temperature (Tmg) obtained according to JIS K7121 (1987).
  • DSC-7 differential scanning calorimeter
  • DSC220 differential scanning calorimeter 220 manufactured by Seiko Instruments Inc.
  • 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— , A moiety containing a bond such as —COO—, OCOO—, and —S—.
  • 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.
  • 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.
  • polyalkylene oxide and polyester are preferable, aliphatic polyester and polyalkylene oxide are more preferable, and aliphatic polyester is particularly preferable.
  • 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 include glycidyl ether, phenyl glycidyl ether, glycidol, glycidyl acrylate, butadiene monooxide, and butadiene dioxide. Of these, polyethylene oxide and polypropylene oxide are preferable, and polyethylene oxide is more preferable.
  • 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 preferably an aliphatic polyester having a weight average molecular weight of 4000 or more.
  • the aliphatic polyester in the present invention is preferably a polyester obtained by a condensation reaction of an aliphatic polyhydric alcohol and an aliphatic polybasic acid, or an aliphatic polyester obtained by ring-opening polymerization of a cyclic ester.
  • R 1 to R 6 each represent a hydrogen atom or a substituent, and the substituent is a substituent that may be substituted on the second polymer component described later. Since the general formula (1) in the present invention contains a large number of linking groups such as —CO— and —O— which are soft segments, the substituents of R 1 to R 6 do not impair the intended effect of the present invention. May introduce any substituent.
  • i represents an integer of 0 to 2
  • j represents an integer of 0 to 10
  • k represents an integer of 3 to 10.
  • i is preferably 0 to 1, and more preferably 1.
  • J in the general formula (1) is preferably 0 to 5, more preferably 1 to 4, and particularly preferably 3.
  • k is preferably 3 to 8, more preferably 3 to 5, and particularly preferably 3.
  • the group represented by R 1 to R 6 in the general formula (1) is preferably a hydrogen atom or an alkyl group, more preferably a hydrogen atom, a methyl group or an ethyl group, and particularly preferably a hydrogen atom.
  • A, b, and c represent constituent ratios (molar fractions), and the sum of a, b, and c is 1.
  • Particularly preferred is 45 to 0.55 / 0.15 to 0.25.
  • Examples of the aliphatic polyester 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, and polybutylene succinate adipate are preferable.
  • 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, pimelic acid, Examples include suberic acid, sebacic acid, azelaic acid, decanedicarboxylic acid, cyclohexanedicarboxylic acid, undecanedioic acid, dodecanedioic acid, and anhydrides thereof, 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, and 1,4-butanediol. 1,9-nonanediol, neopentyl glycol, 1,5-pentanediol, 1,6-hexanediol, decamethylene glycol, cyclohexanedimethanol, polytetramethylene glycol 1,4-cyclohexanedimethanol, and the like It is done.
  • polyoxyalkylene glycol as a part of the aliphatic polyhydric alcohol, and examples thereof include polyoxyethylene glycol, polyoxypropylene glycol, polyoxytetramethylene glycol, and copolymers thereof.
  • 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- At least one selected from 1,5-pentanediol, 1,6-hexanediol, 1,9-nonanediol, neopentyl glycol, polytetramethylene glycol 1,4-cyclohexanedimethanol, and the aliphatic polybase At least one fat selected from 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 Be a polybasic acid Preferred.
  • 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 More preferably, the aliphatic 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. preferable.
  • 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. No problem.
  • the polycondensation reaction can be carried out by a common transesterification method or esterification method, or a combination of both. If necessary, the degree of polymerization can be increased by increasing or decreasing the pressure in the reaction vessel.
  • 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 carried out by a method such as polymerization in a solvent or bulk polymerization using a known ring-opening polymerization catalyst.
  • a vertical reactor a batch reactor, a horizontal reactor, a twin screw extruder or the like is used, and the reaction is preferably carried out in bulk or in solution.
  • Metals such as antimony, cadmium, manganese, iron, zirconium, vanadium, iridium, lanthanum, selenium, and organic metal compounds thereof, salts of organic acids, metal alkoxides, metal oxides, etc. It can also be used in combination with a promoter such as an 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, still more preferably with respect to 100 mol of all dicarboxylic acids. Is 0.6 mol or less.
  • 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. Or you may combine 2 or more types.
  • the elastic modulus of the aliphatic polyester in the present invention is preferably 0.01 GPa or more and 1 GPa or less, and more preferably 0.1 GPa or more and 0.5 GPa or less.
  • the aliphatic polyester in the present invention preferably has a weight average molecular weight of 4000 or more.
  • 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 using a conversion molecular weight calibration curve obtained in advance from a standard monodisperse polystyrene constituent curve.
  • GPC gel permeation chromatography
  • HLC-8220 GPC manufactured by Tosoh Corporation
  • the weight average molecular weight of the aliphatic polyester is 4000 or more, there is no fear of bleeding out, and the aliphatic polyester does not act as a plasticizer for the resin to be mixed, and the rigidity and heat resistance of the resin are not significantly impaired.
  • 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), 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 component in the same manner as 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 UV resistance as a film, and the second component imparts flexibility and toughness, so the second polymer component is slightly destroyed by ultraviolet rays. This is because even if it is done, 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. Further, the first polymer components and the second polymer components may be cross-linked by a covalent bond, or may not be cross-linked. (Additive) In the optical film of the present invention, various additives can be added to the support so long as the intended function is not deteriorated.
  • sugar ester From the viewpoint of improving the plasticity of the highly transparent film having durability against sunlight in the present invention, a sugar ester can be further contained.
  • the sugar ester may be a compound having 1 to 12 furanose structures or pyranose structures, in which all or part of the hydroxy groups in the compound are esterified.
  • sugar esters include sucrose esters represented by the following general formula (FA).
  • R 1 to R 8 in formula (FA) each independently 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).
  • the substituted or unsubstituted arylcarbonyl group is preferably a substituted or unsubstituted arylcarbonyl group having 7 or more carbon atoms.
  • the arylcarbonyl group include a phenylcarbonyl group.
  • the substituent that the aryl group has include an alkyl group such as a methyl group, an alkoxyl group such as a methoxy group, and the like.
  • the average substitution degree of the acyl group of the sucrose ester is preferably in the range of 3.0 to 7.5. When the average substitution degree of the acyl group is within this range, sufficient compatibility is easily obtained. In particular, when cellulose ester is used as the first polymer component, the compatibility becomes high.
  • sucrose ester 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 compounds described in JP-A Nos. 62-42996 and 10-237084.
  • the content of the sugar ester is preferably 0.5 to 35.0% by mass, and preferably 5.0 to 30.0% by mass with respect to the total amount of the first polymer component and the second polymer component. Is more preferable.
  • plasticizers include polyester plasticizers, polyhydric alcohol ester plasticizers, polycarboxylic acid ester plasticizers (including phthalate ester plasticizers), glycolate plasticizers, ester plasticizers ( Citrate ester plasticizers, fatty acid ester plasticizers, phosphate ester plasticizers, trimellitic ester plasticizers, etc.). Of these, polyester plasticizers and phosphate ester plasticizers are preferred. These may be used alone or in combination of two or more.
  • the support according to the present invention may contain particles within a range not impairing transparency.
  • particles used in the present invention include inorganic particles such as calcium carbonate, calcium phosphate, silica, kaolin, talc, titanium dioxide, alumina, barium sulfate, calcium fluoride, lithium fluoride, zeolite, molybdenum sulfide, and crosslinked polymers. Examples thereof include organic particles such as particles and calcium oxalate.
  • the method of adding particles include a method of adding particles in a polyester as a raw material, a method of adding directly to an extruder, and the like. Well, you may use two methods together.
  • additives may be added in addition to the above particles as necessary.
  • additives include plasticizers other than sugar esters, stabilizers, lubricants, crosslinking agents, anti-blocking agents, antioxidants, dyes, pigments, ultraviolet absorbers, and the like.
  • ⁇ Method for producing support containing cellulose derivative ⁇ As a method for producing a support containing the cellulose derivative according to the present invention (hereinafter also simply referred to as a support), the usual inflation method, T-die method, calendar method, cutting method, casting method, emulsion method
  • the production method such as hot press method can be used, but from the viewpoint of suppression of coloring, suppression of foreign matter defects, suppression of optical defects such as die line, etc., the film forming methods are solution casting film forming method and melt casting film forming method.
  • the solution casting film forming method is preferable from the viewpoint of obtaining a uniform and smooth surface.
  • the production of the support according to the present invention includes a step of preparing a dope by dissolving at least a cellulose derivative, or a cellulose derivative and a second polymer component, and if necessary, an additive or the like in a solvent, and filtering the prepared dope.
  • the support according to the present invention preferably contains a cellulose derivative in the range of 60 to 95% by mass in the solid content.
  • Dissolution process In a dissolution vessel, dissolve the cellulose derivative, or the cellulose derivative and the second polymer component, and if necessary, the additives and the like in an organic solvent mainly composed of a good solvent for the cellulose derivative. This is a step of forming a dope, or a step of mixing the second polymer component and, if necessary, a compound solution such as an additive into the cellulose derivative solution to form a dope which is a main solution.
  • the organic solvent useful for forming the dope dissolves the cellulose derivative, or the cellulose derivative and the second polymer component, and other additives at the same time. Anything can be used without limitation.
  • methylene chloride as 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- 2-methyl-2-propanol, 1,1,1,3,3,3-hexafluoro-2-propanol, 2,2,3,3,3-pentafluoro-1-propanol, nitroethane, etc.
  • methylene chloride, methyl acetate, ethyl acetate, and acetone can be preferably used as the main solvent. Particularly preferably
  • the dope preferably 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.
  • the proportion of alcohol in the dope increases, the web gels and peeling from the metal support becomes easy.
  • the proportion of alcohol is small, dissolution of cellulose derivatives and other compounds in non-chlorine organic solvent systems
  • a method of forming a film using a dope having an alcohol concentration in the range of 0.5 to 15.0% by mass from the viewpoint of improving the flatness of the obtained support. Can be applied.
  • a dope composition in which a cellulose derivative and other compounds are dissolved in a total amount of 15 to 45% by mass in a solvent containing methylene chloride and a linear or branched aliphatic alcohol having 1 to 4 carbon atoms. It is preferable that it is a thing.
  • 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. Methanol and ethanol are preferred because of the stability, boiling point of these inner dopes, and good drying properties.
  • JP-A-9-95544 For dissolving the cellulose derivative, the second polymer component or other compound, a method carried out at normal pressure, a method carried out below the boiling point of the main solvent, a method carried out under pressure above the boiling point of the main solvent, JP-A-9-95544 Various dissolution methods such as a method of performing a cooling dissolution method as described in JP-A-9-95557 or JP-A-9-95538, a method of performing at a high pressure described in JP-A-11-21379 However, a method in which pressure is applied at a temperature equal to or higher than the boiling point of the main solvent is preferable.
  • the concentration of the cellulose derivative in the dope is preferably in the range of 10 to 40% by mass.
  • the metal support in the casting process is preferably a mirror-finished surface, and a stainless steel belt or a drum whose surface is plated with a casting is preferably used as the metal support.
  • the cast width can be in the range of 1 to 4 m, preferably in the range of 1.5 to 3 m, more preferably in the range of 2 to 2.8 m.
  • the surface temperature of the metal support in the casting step is set in the range of ⁇ 50 ° C. to below the temperature at which the solvent boils and does not foam, more preferably in the range of ⁇ 30 to 0 ° C. A higher temperature is preferred because the web can be dried faster, but if it is too high, the web may foam or the flatness may deteriorate.
  • a preferable support temperature is appropriately determined at 0 to 100 ° C., and more preferably within a range of 5 to 30 ° C.
  • the method for controlling the temperature of the metal support is not particularly limited, and there are a method of blowing warm 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.
  • ⁇ Pressure dies that can adjust the slit shape of the die base and make the film thickness uniform are preferred.
  • the pressure die include a coat hanger die and a T die, and any of them is preferably used.
  • the surface of the metal support is a mirror surface. In order to increase the film forming speed, two or more pressure dies may be provided on the metal support, and the dope amount may be divided and laminated.
  • the web on the support after casting is preferably dried on the support in an atmosphere of 40 to 100 ° C. In order to maintain the atmosphere at 40 to 100 ° C., it is preferable to apply hot air at this temperature to the upper surface of the web or heat by means such as infrared rays.
  • Peeling process It is the process of peeling the web which the solvent evaporated on the metal support body in a peeling position.
  • the peeled web is sent to the next step as a film-like support.
  • the temperature at the peeling position on the metal support is preferably in the range of 10 to 40 ° C, more preferably in the range of 11 to 30 ° C.
  • the amount of residual solvent at the time of peeling of the web on the metal support at the time of peeling is preferably 50 to 120% by mass depending on the strength of drying conditions, the length of the metal support, and the like.
  • the amount of solvent is determined.
  • the residual solvent amount of the web is defined by the following formula (Z).
  • Residual solvent amount (%) (mass before web heat treatment ⁇ mass after web heat treatment) / (mass after web heat treatment) ⁇ 100 Note that the heat treatment for measuring the residual solvent amount represents performing heat treatment at 115 ° C. for 1 hour.
  • the drying step can be divided into a preliminary drying step and a main drying step.
  • the web obtained by peeling from the metal support is dried.
  • the web may be dried while being conveyed by a large number of rollers arranged above and below, or may be dried while being conveyed while fixing both ends of the web with clips like a tenter dryer. .
  • the means for drying the web is not particularly limited, and can be generally performed with hot air, infrared rays, a heating roller, microwave, or the like, but it is preferably performed with hot air in terms of simplicity.
  • the drying temperature in the web drying process is preferably a glass transition point of the film of ⁇ 5 ° C. or less, and it is effective to perform a heat treatment at a temperature of 100 ° C. or more for 10 minutes or more and 60 minutes or less. Drying is performed at a drying temperature in the range of 100 to 200 ° C, more preferably in the range of 110 to 160 ° C.
  • the support according to the present invention can control the orientation of molecules in the film by stretching, and the planarity is improved.
  • the support according to the present invention is preferably stretched in at least one of the casting direction (MD direction) and the width direction (TD direction), and is manufactured by stretching in the width direction by at least a tenter stretching device. Is preferred.
  • the stretching operation may be performed in multiple stages.
  • simultaneous biaxial stretching may be performed or may be performed stepwise.
  • 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.
  • stretching steps are possible: -Stretch in the casting direction-> Stretch in the width direction-> Stretch in the casting direction-> Stretch in the casting direction-Stretch in the width direction-> Stretch in the width direction-> Stretch in the casting direction-> Stretch in the casting direction
  • Simultaneous biaxial stretching includes stretching in one direction and contracting the other while relaxing the tension.
  • the residual solvent amount at the start of stretching is preferably in the range of 2 to 10% by mass.
  • the amount of the residual solvent is 2% by mass or more, the film thickness deviation is small and is preferable from the viewpoint of flatness, and if it is within 10% by mass, the unevenness of the surface is reduced and the flatness is improved.
  • the support 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.
  • Tg glass transition temperature
  • 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 K 7121 (1987) using a commercially available differential scanning calorimeter with a temperature rising rate of 20 ° C./min. ).
  • Tmg midpoint glass transition temperature
  • a specific method for measuring the glass transition temperature Tg of the support can be measured using a differential scanning calorimeter DSC220 manufactured by Seiko Instruments Inc. according to JIS K 7121 (1987).
  • the support according to the present invention preferably stretches the web at least 1.1 times in the TD direction.
  • the range of stretching is preferably 1.1 to 1.5 times the original width, and more preferably 1.2 to 1.4 times. If it is in the said range, the movement of the molecule
  • the entire drying process or a part of the process as disclosed in Japanese Patent Application Laid-Open No. 62-46625 can be performed while holding the width ends of the web with clips or pins in the width direction.
  • a drying method (referred to as a tenter method), among them, a tenter method using clips and a pin tenter method using pins are preferably used.
  • Winding step This is a step of winding the support after the amount of residual solvent in the web is 2% by mass or less, and good dimensional stability is achieved by setting the amount of residual solvent to 0.4% by mass or less.
  • a support containing a cellulose derivative can be obtained.
  • a generally used method may be used, and there are a constant torque method, a constant tension method, a taper tension method, a program tension control method with a constant internal stress, and the like.
  • the support according to the present invention is preferably long and, specifically, preferably has a length of about 100 to 10,000 m, and is wound up in a roll shape.
  • the width of the support is preferably 1 m or more, more preferably 1.4 m or more, and particularly preferably 1.4 to 4 m.
  • the visible light transmittance measured by JIS R 3106 is preferably 60% or more, more preferably 70% or more, and further preferably 80%. That's it.
  • the haze is preferably less than 1%, and more preferably less than 0.5%. By setting the haze to less than 1%, there is an advantage that the transparency of the film becomes higher and it becomes easier to use as a film for optical applications.
  • the support according to the present invention preferably has an equilibrium water content of 4% or less at 25 ° C. and a relative humidity of 60%, more preferably 3% or less.
  • the equilibrium moisture content By setting the equilibrium moisture content to 4% or less, the dimensions are less likely to change even if the temperature and humidity change.
  • the optical functional layer according to the present invention is not particularly limited as long as it has a function of controlling optical characteristics.
  • a layer for controlling reflectance and transmittance, a microlens, a microprism, a scattering layer, and the like a layer that changes the direction of light or condenses light can be used.
  • a layer that selectively transmits or shields light having a specific wavelength can be preferably used.
  • 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, a low refractive index layer, and a high refractive index
  • the layer include layers that are alternately stacked and reflect only light having a wavelength corresponding to the film thickness (an optical reflection layer using a multilayer film).
  • 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 preferably applicable to a layer that selectively reflects light of a specific wavelength laminated on the substrate. In this method, the lower the interfacial mixing between the low refractive index layer and the high refractive index layer, the higher the interface reflection and the higher the reflectance. However, when a cellulose derivative is used as a support, the cellulose derivative is used as the solvent for coating.
  • the solvent can evaporate not only from the upper surface (air side) of the coating layer but also from the support side, the coating layer is quickly solidified, and there is less interfacial mixing between the low refractive index layer and the high refractive index layer. Therefore, it is preferable to apply the cellulose derivative to the support because high reflectance is obtained.
  • the support according to the present invention is used. It is highly preferred to apply.
  • the optical reflective layer by multilayer film expresses the 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 is measured, and the composition By this, it can be determined 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.
  • 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, It was confirmed that the mixed region was present by measuring the carbon concentration in the layer thickness direction, and further, its composition was measured by EDX (energy dispersive X-ray spectroscopy), and was etched by sputtering.
  • EDX energy dispersive X-ray spectroscopy
  • 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 can be used for the X-ray anode, and measurement can be 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 difference is preferably within the preferred range.
  • 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 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 reflection film by changing a specific wavelength region for increasing the reflectance. That is, if the specific wavelength region for increasing 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, it becomes a near infrared reflecting film.
  • a near infrared reflection film may be used.
  • 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 1.80 to 2.50, more preferably 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 referred to in the present invention can be measured by a known method, for example, static light scattering, gel permeation chromatography (GPC), time-of-flight mass spectrometry (TOF-MASS), etc. In the present invention, it is measured by a gel permeation chromatography method which is a generally known method.
  • GPC gel permeation chromatography
  • TOF-MASS time-of-flight mass spectrometry
  • 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 saponification degree 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 preferably 75 mol% or more from the viewpoint of solubility in 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 polyvinyl alcohol (A) and polyvinyl alcohol (B) is in the range of 2000 to 5000, it is preferable because cracks in 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 2000 to 5000, since the above effects can be exhibited more remarkably.
  • Polymerization degree P in the present specification refers to a viscosity average degree of polymerization, measured according to JIS K 6726 (1994), and measured in water at 30 ° C. after completely re-saponifying and purifying PVA. From the intrinsic viscosity [ ⁇ ] (dl / g) obtained, it is obtained by the following equation (1).
  • 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 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 0.1 to 10 mol%, preferably 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.).
  • Two or more kinds of modified polyvinyl alcohol can be used in combination, 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.
  • 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 in the range of 40% by mass to 100% by mass with respect to the total mass of all polyvinyl alcohols in the layer, more preferably 60% by mass to 95% by mass
  • the low refractive index layer The polyvinyl alcohol (B) is preferably contained in the range of 40% by mass to 100% by mass with respect to the total mass of all the polyvinyl alcohols in the low refractive index layer, and 60% by mass 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 in the range of 40% by mass to 100% by mass with respect to the total mass of all polyvinyl alcohols in the layer, more preferably 60% by mass to 95% by mass
  • the low refractive index layer The polyvinyl alcohol (B) is preferably contained in the range of 40% by mass to 100% by mass with respect to the total mass of all the polyvinyl alcohols in the low refractive index layer, and 60% by mass to 95% by mass. More preferred.
  • 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 when it is filtered through a G2 glass filter (maximum pores 40-50 ⁇ m) when dissolved in water at a concentration of 0.5% by mass at the temperature at which the water-soluble polymer is most soluble.
  • the mass of the insoluble matter separated by filtration is within 50% by mass of the added water-soluble polymer.
  • 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 of 2.0 or more and 3.0 or less. 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, second oxide oxide. Examples include 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, fine particles of titanium oxide or fine particles of zirconia oxide. It is preferable to contain at least one of them.
  • 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 difference from the low refractive index layer Is preferable from the viewpoint of imparting. 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 (2) 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 diameter of primary particles is the particle itself or the particles appearing on the cross section or surface of the refractive index layer is observed with an electron microscope, and the particle diameter of 1000 arbitrary particles is measured. It is obtained as its simple average value (number average).
  • the particle diameter 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 its salt or borax it is more preferable to use boric acid and its salt or borax in order to obtain the effects of the present invention.
  • boric acid and its salt, or borax 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.
  • a set coating process is used in which a multilayer coating of a high refractive index layer and a low refractive index layer is applied with a wet coater, the film surface temperature of the coating film is once cooled to about 15 ° C., and then the film surface is dried. In this case, the effect can be expressed more preferably.
  • the content of the curing agent in the high refractive index layer is preferably 1 to 10% by mass and more preferably 2 to 6% by mass with respect to 100% by mass of the solid content of the high refractive index layer.
  • the total amount of the curing agent used is preferably 1 to 600 mg per 1 g of polyvinyl alcohol, more preferably 100 to 600 mg per 1 g of polyvinyl alcohol.
  • 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 in the range of 20 to 99.9% by mass with respect to 100% by mass of the solid content of the low refractive index layer, and 25 to 80 More preferably, it is in the range of 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 0.1 to 70% by mass, and preferably 30 to 70% by mass with respect to 100% by mass of the solid content of the low refractive index layer. More preferably, it is more preferably 45 to 65% by 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.
  • the curing agent when polyvinyl alcohol is used as the second water-soluble binder resin applied to the low refractive index layer is preferably at least one of boric acid and a salt thereof, or borax. In addition to 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 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 becomes easier to control the viscosity, and as a result, the production stability when adding the optical film of the present invention to glass is further 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 amount of the lithium compound added is preferably in the range of 0.005 to 0.05 g, more preferably 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 for forming an optical reflective layer (also referred to as an optical reflective layer group) using a multilayer film used in the present invention is preferably formed by applying a wet coating method, and further, on the support according to the present invention, High refractive index layer coating solution containing first water-soluble binder resin and first metal oxide particles, and low refractive index layer coating solution containing second water soluble binder resin and second metal oxide particles And a production method including a step of wet coating.
  • 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 when performing simultaneous multilayer coating by the slide hopper coating method is preferably within the range of 5 to 150 mPa ⁇ s. -Within the range of s is more preferable.
  • 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 high refractive index layer coating solution and the low refractive index layer coating solution are heated to 30 ° C. or higher, and the high refractive index layer coating solution and the low refractive index are coated on the substrate.
  • the temperature of the formed coating film is preferably cooled (set) preferably to 1 to 15 ° C. and then dried at 10 ° C. or higher. More preferable drying conditions are a wet bulb temperature of 5 to 50 ° C. and a film surface temperature of 10 to 50 ° C.
  • 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 (setting time) from application of cold air to completion of setting is preferably within 5 minutes, preferably within 2 minutes. Further, the lower limit time is not particularly limited, but it is preferable to take 45 seconds or more. If the set time is too short, there are places where mixing of the components in the layer becomes insufficient. On the other hand, if the set time is too long, the interlayer diffusion of the metal oxide particles proceeds, and the difference in refractive index between the high refractive index layer and the low refractive index layer is insufficient. In addition, if the high elasticity of the heat ray blocking film unit between the high refractive index layer and the low refractive index layer occurs quickly, 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 0 to 25 ° C, more preferably 5 to 10 ° C. Further, the time during which the coating film is exposed to the cold air is preferably 10 to 120 seconds, although it depends on the transport speed of the coating film.
  • FIG. 2 is an example of an optical film of the present invention having an optical reflective layer of a multilayer film, and is a schematic cross-sectional view showing a configuration provided with a reflective layer unit having an optical reflective layer group on one surface side of a support. .
  • the optical film 10 of the present invention has a reflective layer unit U.
  • the reflective layer unit U includes, as an example, a high refractive index optical reflective layer containing a first water-soluble binder resin and first metal oxide particles, and a second water-soluble binder on the support 11.
  • the optical reflective layer group ML is formed by alternately laminating a resin and a low refractive index optical reflective layer containing second metal oxide particles.
  • the optical reflection layer group ML is composed of n layers of optical reflection layers T 1 to T n . For example, T 1 , T 3 , T 5 , (omitted), T n ⁇ 2 , and T n have a refractive index of 1.
  • T n-1 are in the range of refractive index of 1.80 to 2.50.
  • An example of a configuration having a high refractive index layer is given.
  • the refractive index as used in the field of this invention is the value measured in the environment of 25 degreeC.
  • a hard coat layer for improving scratch resistance on the outermost layer of the reflective layer unit, and a support is provided on the surface of the support on which the reflective layer unit is not provided. It is also preferable to provide an adhesive layer to be bonded to another substrate.
  • FIG. 3 is a schematic cross-sectional view showing another configuration of the optical film of the present invention having an optical reflective layer of a multilayer film, in which a reflective layer unit having an optical reflective layer group is provided on both sides of a support.
  • optical functional layer that absorbs a specific wavelength with a dye or pigment
  • An infrared absorbing layer will be described as an example of an optical functional layer that absorbs a specific wavelength with a dye or pigment.
  • the material contained in the infrared absorbing layer is not particularly limited, and examples thereof include an ultraviolet curable resin that is a binder component, a photopolymerization initiator, and an infrared absorber. 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.
  • UV curable resins are superior to other resins in hardness and smoothness, and are also advantageous from the viewpoint of dispersibility of ITO, ATO and heat conductive metal oxides.
  • the ultraviolet curable resin can be used without particular limitation as long as it forms a transparent layer by curing, and examples thereof include silicone resins, epoxy resins, vinyl ester resins, acrylic resins, and allyl ester resins. More preferred is an acrylic resin from the viewpoint of hardness, smoothness and transparency.
  • the acrylic resin is a reactive silica particle having a photosensitive group having photopolymerization reactivity introduced on its surface as described in International Publication No. 2008/035669 (In the following, it is preferable to simply include “reactive silica particles”.
  • the photopolymerizable photosensitive group include a polymerizable unsaturated group 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.
  • a polymerizable unsaturated group-modified hydrolyzable silane reacts with a silica particle that forms a silyloxy group and is chemically bonded to the silica particle by a hydrolysis reaction of the hydrolyzable silyl group.
  • the average particle diameter of the reactive silica particles is preferably 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 moieties or fully fluorinated alkyl ester derivatives (for example, biscoat 6FM (product) 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 moieties or fully fluorinated alkyl ester derivatives for example, biscoat 6FM (product) 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), and antimony from the viewpoints of visible light transmittance, infrared absorptivity, suitability for dispersion in resins, and the like.
  • ITO tin-doped indium oxide
  • ATO antimony-doped tin oxide
  • Zinc acid, 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 5 to 100 nm, more preferably 10 to 50 nm.
  • the thickness is less than 5 nm, the dispersibility in the resin and the infrared absorptivity are reduced. On the other hand, if it is larger than 100 nm, the visible light transmittance is lowered.
  • 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 absorbing layer is preferably 1 to 80% by mass, and more preferably 5 to 50% by mass with respect to the total mass of the infrared absorbing layer. 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, 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 optical reflective layer used in the present invention adopts a method of reflecting infrared light by providing a metal thin film.
  • the metal thin film is preferably composed of a metal layer or a metal layer and at least one of a metal oxide layer and a metal nitride layer.
  • the metal layer containing a metal exhibits an infrared reflecting function, and although not essential, the visible light transmittance can be increased by using at least one of a metal oxide layer and a metal nitride layer. .
  • the metal layer used in the present invention preferably contains silver having excellent infrared reflection performance as a main component, and contains at least either gold or palladium in a total amount of 2 to 5% by mass as 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. Further, 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 in the 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 optical reflective layer used in the present invention at least one of a metal oxide layer or a metal nitride layer is laminated on the above-described metal layer, or the metal layer is at least a metal oxide layer or a metal nitride layer.
  • the structure which sandwiched by either may be sufficient.
  • 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 10 to 100 nm, more preferably 30 to 60 nm. When the thickness is small, the visible light transmission performance is not significantly improved.
  • metal oxides can be formed together with the metal layer using a known technique such as a vacuum deposition method, a sputtering method, or an ion plating method.
  • the pressure-sensitive adhesive layer is a layer for allowing the optical film of the present invention to adhere to other substrates.
  • the optical film of this invention is a layer for making it adhere to a window glass.
  • the pressure-sensitive adhesive used for the pressure-sensitive adhesive layer is selected from rubber-based, acrylic-based, silicon-based, urethane-based pressure-sensitive adhesives. 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. If it is 5 ⁇ m or more, the adhesiveness is stable, and if it is 30 ⁇ m or less, the adhesive does not protrude from the side of the film and is easy to handle.
  • the type of separator (release sheet) to be attached 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 20 to 60 ⁇ m. A thickness of 10 ⁇ m or more is preferable because wrinkles in the film do not occur due to heat during coating and drying. Moreover, if it is 100 micrometers or less, it is preferable from a viewpoint of economical efficiency.
  • the adhesive layer is not particularly limited as long as it has a function of improving the adhesion between the layers. Adhesion or adhesion may be used. Preferably, it is a layer for bonding the acrylic layer and the resin coat layer.
  • the adhesive layer is required to have transparency, adhesion to adhere the layers to each other, moisture and heat resistance and light resistance that do not cause discoloration or peeling at temperature and humidity under the usage environment.
  • the adhesive layer may consist of only one layer or may consist of a plurality of layers.
  • the thickness of the adhesive layer is preferably 1 to 10 ⁇ m, more preferably 3 to 8 ⁇ m, from the viewpoints of adhesion, smoothness, reflectance of the reflecting material, and the like.
  • the resin is not particularly limited as long as it satisfies the above transparency, adhesion, heat-and-moisture resistance, and light resistance.
  • Polyester resin, urethane resin, acrylic resin, melamine resin Resin, epoxy resin, polyamide resin, vinyl chloride resin, vinyl chloride vinyl acetate copolymer resin, etc. can be used singly or as a mixed resin, polyester resin and melamine resin or polyester resin from the viewpoint of weather resistance
  • a mixed resin of a resin and a urethane-based resin is preferable, and a thermosetting resin in which a curing agent such as isocyanate is mixed such that an isocyanate is mixed with an acrylic resin is more preferable.
  • a method for forming the adhesive layer conventionally known coating methods such as a gravure coating method, a reverse coating method, and a die coating method can be used.
  • the adhesive layer is a metal oxide
  • it can be formed by various vacuum film forming methods such as silicon oxide, aluminum oxide, silicon nitride, aluminum nitride, lanthanum oxide, and lanthanum nitride.
  • various vacuum film forming methods such as silicon oxide, aluminum oxide, silicon nitride, aluminum nitride, lanthanum oxide, and lanthanum nitride.
  • HC layer As the hard coat material of the hard coat layer (also referred to as HC layer) according to the present invention, an inorganic material typified by polysiloxane, an active energy ray curable resin, or the like can be used. Inorganic materials require moisture curing (room temperature to warming), and it is preferable to use an active energy ray-curable resin in the present invention from the viewpoint of curing temperature, curing time, and cost.
  • the active energy ray resin refers to a resin that is cured through a crosslinking reaction or the like by irradiation with active rays such as ultraviolet rays or electron beams.
  • the active energy ray curable resin a component containing a monomer having an ethylenically unsaturated double bond is preferably used, and the active energy ray curable resin layer is cured by irradiation with an active ray such as an ultraviolet ray or an electron beam. It is formed.
  • an active energy ray curable resin include an ultraviolet curable resin and an electron beam curable resin, and a resin curable by ultraviolet irradiation is preferable.
  • an ultraviolet curable urethane acrylate resin for example, an ultraviolet curable urethane acrylate resin, an ultraviolet curable polyester acrylate resin, an ultraviolet curable epoxy acrylate resin, an ultraviolet curable polyol acrylate resin, or an ultraviolet curable epoxy resin is preferable. Used. Of these, ultraviolet curable acrylate resins are preferred.
  • UV curable acrylic urethane resins generally include 2-hydroxyethyl acrylate and 2-hydroxyethyl methacrylate (hereinafter referred to as acrylate) in products obtained by reacting a polyester polyol with an isocyanate monomer or a prepolymer. It is easily obtained by reacting an acrylate monomer having a hydroxyl group such as 2-hydroxypropyl acrylate.
  • a mixture of 100 parts Unidic 17-806 (Dainippon Ink Co., Ltd.) and 1 part Coronate L (Nihon Polyurethane Co., Ltd.) described in JP-A-59-151110 is preferably used.
  • An ultraviolet curable polyester acrylate resin can be easily obtained by reacting a monomer such as 2-hydroxyethyl acrylate, glycidyl acrylate, or acrylic acid with a hydroxyl group or carboxy group at the end of the polyester (see, for example, JP Sho 59-151112).
  • the ultraviolet curable epoxy acrylate resin is obtained by reacting a terminal hydroxyl group of an epoxy resin with a monomer such as acrylic acid, acrylic acid chloride, or glycidyl acrylate.
  • a monomer such as acrylic acid, acrylic acid chloride, or glycidyl acrylate.
  • ultraviolet curable polyol acrylate resins include ethylene glycol (meth) acrylate, polyethylene glycol di (meth) acrylate, glycerin tri (meth) acrylate, trimethylolpropane triacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, and dipenta. Examples include erythritol pentaacrylate, dipentaerythritol hexaacrylate, and alkyl-modified dipentaerythritol pentaacrylate.
  • the optical film of the present invention has a conductive layer, an antistatic layer, a gas barrier layer, an antifouling layer, a deodorizing layer, a droplet layer, a slippery layer, and abrasion resistance for the purpose of adding further functions on the support.
  • a layer, an electromagnetic wave shielding layer, an ultraviolet absorption layer, a printing layer, a fluorescent light emitting layer, a hologram layer, a release layer, and the like may be provided.
  • the optical film of the present invention is an optical film excellent in curl recovery and tear strength.
  • Conventional cellulose ester films are difficult to use because of insufficient strength, or PET films are strongly used. Is suitable for applications in which it is difficult to use, and can be suitably used for window films.
  • it can also be used suitably because the winding process can be easily removed by spraying, and the laminating process becomes easy.
  • PET Support Preparation of Support 1 (PET Support; Comparative Example)> Pellets of commercially available polyethylene terephthalate (PET, intrinsic viscosity 0.65) were vacuum-dried at 150 ° C. for 8 hours, melt-extruded in layers from a T die at 280 ° C. using an extruder, and electrostatically applied onto a cooling drum. The laminated unstretched sheet having a three-layer structure was obtained by closely adhering to the substrate while cooling and solidifying. This unstretched sheet was stretched 3.5 times in the longitudinal direction at 90 ° C. using a roll type longitudinal stretching machine.
  • PET polyethylene terephthalate
  • the obtained uniaxially stretched film was stretched by 50% of the total transverse stretching ratio in the first stretching zone 100 ° C. using a tenter-type transverse stretching machine, and further in the second stretching zone 120 ° C., the total transverse stretching ratio 3.6. It extended
  • heat treatment was performed at 100 ° C. for 2 seconds, and further heat setting was performed at the first heat setting zone 170 ° C. for 5 seconds, and heat setting was performed at the second heat setting zone 210 ° C. for 15 seconds.
  • the substrate 1 (biaxially stretched laminated polyester (PET: polyethylene terephthalate)) having a thickness of 50 ⁇ m was produced by gradually cooling to room temperature over 30 seconds while performing a 5% relaxation treatment in the lateral direction.
  • PET polyethylene terephthalate
  • polyester A and polyester B each was vacuum-dried at 150 ° C. for 8 hours, melt-extruded at 280 ° C. using three extruders, joined in layers in a T-die, and placed on a cooling drum It was made to adhere, applying static electricity, and solidified by cooling to obtain a laminated unstretched sheet having a three-layer structure.
  • polyester A was both outer layers and polyester B was an intermediate layer, and the extrusion amount of each extruder was adjusted so that the thickness ratio of each layer was 1: 2: 1.
  • This unstretched sheet was stretched 3.5 times in the longitudinal direction at 90 ° C. using a roll type longitudinal stretching machine.
  • the obtained uniaxially stretched film was stretched by 50% of the total transverse stretching ratio in the first stretching zone 100 ° C. using a tenter-type transverse stretching machine, and further in the second stretching zone 120 ° C., the total transverse stretching ratio 3.6. It extended
  • heat treatment was performed at 100 ° C. for 2 seconds, and further heat setting was performed at the first heat setting zone 170 ° C. for 5 seconds, and heat setting was performed at the second heat setting zone 210 ° C. for 15 seconds.
  • the substrate 2 (biaxially stretched laminated modified PET support) having a thickness of 120 ⁇ m (the thickness of each layer is 12.5 ⁇ m / 25 ⁇ m / 12.5 ⁇ m) is gradually cooled to room temperature over a period of 5% while being subjected to 5% relaxation treatment in the lateral direction.
  • Body (abbreviated as modified PET in Table 1)).
  • Fine particles (Aerosil R972V manufactured by Nippon Aerosil Co., Ltd.) 11 parts by mass Ethanol 89 parts by mass Among the components of the following fine particle addition liquid, methylene chloride was charged into the dissolution tank, and the prepared fine particle dispersion was slowly added in the following 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.
  • Fine particle additive Methylene chloride 99 parts by mass Fine particle dispersion 5 parts by mass Among the main dope components below, methylene chloride and ethanol were charged into a pressurized dissolution tank. Next, cellulose triacetate, tinuvin 928, and the prepared fine particle additive solution were added with stirring, and heated and stirred to completely dissolve. The obtained solution was used as Azumi filter paper No. manufactured by Azumi Filter Paper Co., Ltd. The main dope was prepared by filtration using 244.
  • the cellulose ester film web was evaporated at 35 ° C., slit to 1.65 m width, and stretched in the TD direction (film width direction) 1.15 times and MD direction (film length direction) with a tenter.
  • the residual solvent amount at the start of drying was 20%. Then, after drying for 15 minutes while transporting the inside of a drying device at 120 ° C.
  • the support according to the present invention was produced in the same manner as the production of the support 3 except that 30 parts by mass of polymethyl methacrylate (PMMA, Mw; 100,000) was added to the dope composition as the second polymer component. Body 4 was produced.
  • PMMA polymethyl methacrylate
  • the support 5 according to the present invention was prepared in the same manner as the production of the support 3, except that 30 parts by mass of polyethylene glycol (PEG, Mw; 3000) was added to the dope composition as the second polymer component. Was made.
  • PEG polyethylene glycol
  • the supports 6 to 39 were produced by changing the addition amount of the cellulose component (first polymer component) and the second polymer component as shown in Table 1.
  • DAC, CAP1, and CAP2 described in the first polymer component column in the table represent the following cellulose esters, respectively, and DAC, CAP1, and CAP2 are used instead of TAC when preparing the support. Each support was prepared.
  • CAP1 cellulose acetate having an acetyl group substitution degree of 1.68, a propionyl group substitution degree of 0.9, and a total acyl group substitution degree of 2.58 Propionate (weight average molecular weight 200000)
  • CAP2 cellulose acetate propionate (product name CAP482-20, manufactured by Eastman Chemical Co., Ltd., acetyl group substitution degree 0.2, propionyl group substitution degree 2.56, total acyl group substitution degree 2.76, Mn: 70000, Mw : 220,000)
  • PBS and PBSA in the table represent aliphatic polyesters synthesized as follows.
  • the support is cut into a strip of 35 mm (TD direction at the time of manufacture) ⁇ 120 mm (MD direction at the time of manufacture) and left to stand for 1 day at a temperature of 23 ° C. and a relative humidity of 55%. Wrap this.
  • the curl degree is represented by 1 / r, r represents the radius of curvature of the curled support, and the unit is m.
  • Curb recovery rate (curl degree before spraying-curl degree after spraying) / curl degree before spraying x 100 (%) (Tear strength)
  • JIS K 7128-2 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, and left for 1 day under conditions of a temperature of 23 ° C. and a relative humidity of 55%, and then measured under the same conditions.
  • the sample measures the tear load (mN) of a total of 10 sheets in the direction orthogonal to the transport direction (TD direction) and the transport direction (MD direction), and averages the values (converted as the same tear length and thickness). ) As the tear strength.
  • the supports 4 to 13, 15 to 22, 24 to 34, 36 to 39 according to the present invention the first polymer component
  • a differential scanning calorimeter DSC220 manufactured by Seiko Instruments Inc. was used as a differential scanning calorimeter, and the temperature was increased at a rate of 20 ° C./minute. According to JIS K7121 (1987). Accordingly, the midpoint glass transition temperature (Tmg) was determined.
  • ⁇ Undercoat coating solution 1 Copolymer latex liquid (solid content 30%) of butyl acrylate 30% by mass, t-butyl acrylate 20% by mass, styrene 25% by mass, 2-hydroxyethyl acrylate 25% by mass 50 g Compound (UL-1) 0.2g Hexamethylene-1,6-bis (ethyleneurea) 0.05g Finish with water 1000ml ⁇ Undercoat coating solution 2> 10g gelatin Compound (UL-1) 0.4g Silica particles (average particle size 3 ⁇ m) 0.1g Hardener (UL-2) 1g Finish with water 1000ml
  • subbing processes 2 were applied to the supports 3 to 39, respectively.
  • the undercoat layer coating solution 3 is applied with an extrusion coater to 15 ml / m 2 , passes through a 50 ° C. no-air zone (1 second), and then dried at 120 ° C. for 30 seconds. A support was obtained.
  • ⁇ Undercoat layer coating solution 3> 10g deionized gelatin 30 ml of pure water Acetic acid 20g The following crosslinking agent 0.2 mol / g gelatin The following nonionic fluorine-containing surfactant 0.2 g The undercoat layer coating solution 3 was made up to 1000 ml with an organic solvent of methanol / acetone 2/8.
  • surfactant The structure of the used crosslinking agent and nonionic fluorine-containing surfactant (abbreviated as surfactant) is shown below.
  • ⁇ Preparation of deionized gelatin> Ocein from which lime was removed by performing 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 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. After that, when the temperature of the mixed sol solution reaches 95 ° C., concentrated hydrochloric acid is added so that the hydrochloric acid concentration becomes 30 g / L. The mixture is stirred for 3 hours while maintaining the liquid temperature at 95 ° C. 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 +40 mV. Moreover, when the particle size was measured with a Zetasizer Nano manufactured by Malvern, the monodispersity was 16%.
  • 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 ⁇ Formation of hard coat layer (HC layer)> 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 above-prepared coating liquid A for hard coat layer is applied with a gravure coater under the condition that the dry layer thickness is 5 ⁇ m, and the drying section temperature is 90 ° C. After drying for 1 minute, the hard coat layer was cured by using an ultraviolet lamp to cure the hard coat layer with an illuminance of the irradiated part of 100 mW / cm 2 and an irradiation amount of 0.5 J / cm 2 .
  • the adhesive layer coating solution 1 prepared above was applied to a separator (NS-23MA: manufactured by Nakamoto Pax Co., Ltd.) so that the layer thickness after drying was 10 ⁇ m, and dried at 80 ° C. The infrared reflection layer surface and the adhesive layer surface were bonded together.
  • optical film 40 was prepared in the same manner as in the optical film 22 except that the infrared reflective layer was changed to the following silver (Ag) thin film infrared reflective layer.
  • Water sticking workability was evaluated using the following indices.
  • X The film peeled frequently and the workability was very bad.
  • ⁇ The edge part was lifted up by three or more during the first squeegee work, but the work could be performed without any problems.
  • ⁇ The edge part lifted up 1 or 2 during the first squeegee work, but the work could be done without any problems.
  • ⁇ Worked without problems with no lifting of edges (film unevenness) The squeegee unevenness was evaluated according to the following evaluation criteria.
  • ⁇ Clearly obvious squeegee unevenness is observed with 3 or more ⁇ ; Clearly obvious squeegee unevenness is seen with 1 or 2 ⁇ ⁇ : Squeegee unevenness is not known unless good ⁇ ; Squeegee unevenness is seen Cannot (film tears) ⁇ : Fatal film tear occurs when one or more sheets ⁇ ⁇ : Extremely weak tear occurs at 5 or more edges ⁇ : Extremely weak tear occurs at 2 to 4 edges ⁇ ⁇ : Edge Extremely weak tearing occurs on one sheet ⁇ : No film tearing Table 1 shows the outline of the above evaluation results and the sample configuration.
  • the optical films 4 to 13, 15 to 22, 24 to 34, and 36 to 40 of the present invention have excellent water workability and finished quality compared to the comparative optical films 1 to 3, 14, 23, and 35. It can be seen that (there is little film unevenness and film tearing).
  • the optical film of the present invention is an optical film excellent in curl recovery and tear strength.
  • Conventional cellulose ester films are difficult to use because of insufficient strength, or PET films are strongly used. Is suitable for applications in which it is difficult to use, and can be suitably used for window films.
  • it can also be used suitably because the winding process can be easily removed by spraying, and the laminating process becomes easy.
  • optical film 11 support ML, MLa, MLb optical reflecting layer group T 1 ⁇ T n, Ta 1 ⁇ Ta n , Tb 1 to Tb n Optical reflection layer U Reflection layer unit

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Physics & Mathematics (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Physics & Mathematics (AREA)
  • Optics & Photonics (AREA)
  • Toxicology (AREA)
  • Laminated Bodies (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Adhesive Tapes (AREA)
  • Adhesives Or Adhesive Processes (AREA)

Abstract

　La présente invention a pour but de fournir un film optique qui présente des caractéristiques exceptionnelles en termes de récupération lorsqu'il est enroulé et de résistance à la déchirure. L'invention a également pour but de fournir un film de fenêtre l'employant, qui présente une facilité exceptionnelle de collage à l'état humide, ainsi qu'une excellente qualité de fini. Pour atteindre ce but, l'invention porte sur un film optique qui possède au moins une couche optiquement fonctionnelle et une couche adhésive qui sont disposées sur un support en forme de film, ledit film optique étant caractérisé en ce que le support contient au moins 30 % en masse d'un dérivé de la cellulose, et est ajusté à un taux de récupération d'enroulement d'au moins 20 % et à une résistance à la déchirure d'au moins 150 mN.
PCT/JP2015/057703 2014-03-26 2015-03-16 Film optique et film de fenêtre l'employant Ceased WO2015146674A1 (fr)

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JP2014-063579 2014-03-26
JP2014063579A JP2017094488A (ja) 2014-03-26 2014-03-26 光学フィルム及びそれを用いたウインドウフィルム

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Cited By (1)

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CN106847086A (zh) * 2015-12-04 2017-06-13 三星显示有限公司 柔性显示装置

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JP6309422B2 (ja) * 2014-10-02 2018-04-11 日本カーバイド工業株式会社 粘着剤及び粘着シート
JP2020154003A (ja) * 2017-07-20 2020-09-24 コニカミノルタ株式会社 光反射成型体
EP3752558A1 (fr) * 2018-02-13 2020-12-23 Eastman Chemical Company Compositions et articles à base d'ester de cellulose et polyester aliphatique polymère
JP7099896B2 (ja) * 2018-07-20 2022-07-12 スリーエム イノベイティブ プロパティズ カンパニー ウィンドウフィルム
KR20230156111A (ko) * 2021-03-12 2023-11-13 주식회사 다이셀 열가소성 수지 조성물
JP2025001051A (ja) * 2021-09-27 2025-01-08 富士フイルム株式会社 セルロースアシレートフイルム、食品包装材、農業資材、偏光板用フイルム
EP4501575A4 (fr) * 2022-03-30 2025-07-16 Fujifilm Corp Procédé de production d'un film d'acylate de cellulose, et film d'acylate de cellulose

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WO2008015911A1 (fr) * 2006-07-31 2008-02-07 Konica Minolta Opto, Inc. Film de protection de plaque polarisante, plaque polarisante et écran à cristaux liquides
JP2012066513A (ja) * 2010-09-24 2012-04-05 Dainippon Printing Co Ltd 光学積層体、前面板及び画像表示装置に関する。
WO2013077252A1 (fr) * 2011-11-21 2013-05-30 コニカミノルタ株式会社 Film de protection contre les infrarouges et corps de protection contre les infrarouges

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WO2008015911A1 (fr) * 2006-07-31 2008-02-07 Konica Minolta Opto, Inc. Film de protection de plaque polarisante, plaque polarisante et écran à cristaux liquides
JP2012066513A (ja) * 2010-09-24 2012-04-05 Dainippon Printing Co Ltd 光学積層体、前面板及び画像表示装置に関する。
WO2013077252A1 (fr) * 2011-11-21 2013-05-30 コニカミノルタ株式会社 Film de protection contre les infrarouges et corps de protection contre les infrarouges

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106847086A (zh) * 2015-12-04 2017-06-13 三星显示有限公司 柔性显示装置
US10586942B2 (en) 2015-12-04 2020-03-10 Samsung Display Co., Ltd. Flexible display apparatus
CN106847086B (zh) * 2015-12-04 2020-09-04 三星显示有限公司 柔性显示装置
US11522154B2 (en) 2015-12-04 2022-12-06 Samsung Display Co., Ltd. Flexible display apparatus

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