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WO2018159811A1 - Film stratifié blanc et matériau d'enregistrement - Google Patents

Film stratifié blanc et matériau d'enregistrement Download PDF

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Publication number
WO2018159811A1
WO2018159811A1 PCT/JP2018/008008 JP2018008008W WO2018159811A1 WO 2018159811 A1 WO2018159811 A1 WO 2018159811A1 JP 2018008008 W JP2018008008 W JP 2018008008W WO 2018159811 A1 WO2018159811 A1 WO 2018159811A1
Authority
WO
WIPO (PCT)
Prior art keywords
film
weight
polyester
functional layer
layer
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/JP2018/008008
Other languages
English (en)
Japanese (ja)
Inventor
秀孝 木村
敬太 川浪
泰史 川崎
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Mitsubishi Chemical Corp
Original Assignee
Mitsubishi Chemical Corp
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Priority claimed from JP2017218863A external-priority patent/JP7052307B2/ja
Priority claimed from JP2017218862A external-priority patent/JP7052306B2/ja
Application filed by Mitsubishi Chemical Corp filed Critical Mitsubishi Chemical Corp
Priority to CN201880011701.1A priority Critical patent/CN110325363B/zh
Priority to EP18761242.9A priority patent/EP3590712B1/fr
Priority to CN202210350855.1A priority patent/CN114714731B/zh
Priority to KR1020197028778A priority patent/KR102601068B1/ko
Publication of WO2018159811A1 publication Critical patent/WO2018159811A1/fr
Priority to US16/553,802 priority patent/US11766853B2/en
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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Classifications

    • 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
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B27/08—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
    • 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
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/18—Layered products comprising a layer of synthetic resin characterised by the use of special additives
    • 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
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/32—Layered products comprising a layer of synthetic resin comprising polyolefins
    • 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
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/36—Layered products comprising a layer of synthetic resin comprising polyesters
    • 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
    • B32B33/00—Layered products characterised by particular properties or particular surface features, e.g. particular surface coatings; Layered products designed for particular purposes not covered by another single class
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03G—ELECTROGRAPHY; ELECTROPHOTOGRAPHY; MAGNETOGRAPHY
    • G03G7/00—Selection of materials for use in image-receiving members, i.e. for reversal by physical contact; Manufacture thereof
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2255/00—Coating on the layer surface
    • B32B2255/10—Coating on the layer surface on synthetic resin layer or on natural or synthetic rubber layer
    • 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
    • B32B2255/00—Coating on the layer surface
    • B32B2255/26—Polymeric coating
    • 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
    • B32B2307/20—Properties of the layers or laminate having particular electrical or magnetic properties, e.g. piezoelectric
    • B32B2307/21—Anti-static
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
    • Y02W30/00—Technologies for solid waste management
    • Y02W30/50—Reuse, recycling or recovery technologies
    • Y02W30/64—Paper recycling

Definitions

  • the present invention relates to a laminated white film. More specifically, the present invention relates to a plastic sheet suitable as a recording material that is an information printing medium that replaces paper such as copy paper.
  • Mass consumption of paper is not desirable from the standpoint of reducing deforestation, and recycled paper that has been collected from used paper and recycled into recycled pulp at paper mills has been used.
  • Recycled paper is used paper collected from its main raw materials, but to make recycled paper from the collected used paper, a certain amount of new wood resources are also required. Even if the utilization rate increases, wood resources are still consumed, and the use of recycled paper is not a fundamental solution to protect the forest environment.
  • energy is also required for the recycling process, there is a problem from the viewpoint of energy saving.
  • recycled paper is still inferior in quality to high-quality paper, and when copying paper made of recycled paper is used, the whiteness of the paper decreases and the color becomes gray.
  • paper that can be reused once it has been proposed by peeling and removing an image formed on the surface of the paper by an electrophotographic system such as a copying machine has been proposed.
  • a layer containing a polymer selected from polyvinyl alcohol, starch, carboxymethyl cellulose, polyvinyl acetate, and acrylic resin is provided on the surface on which the image of the base is recorded.
  • a reusable recording material is disclosed in which a compound having a linear or branched alkyl group or alkenyl group is provided on a layer to be contained, and a layer having toner repellency is provided (see, for example, Patent Document 1). .
  • such a recording material has a structure in which the thickness of the polymer layer is reduced in order to reduce the cost of the polymer layer, and because the base requires paper, the wood environment is not completely used. It is not a solution to protect.
  • the recorded image is impregnated into the fiber of the paper, so that the peeling and removal performance is insufficient.
  • plastic synthetic paper is also being examined.
  • synthetic paper made of polypropylene is used for daily necessities. (For example, see Patent Document 2)
  • JP 2005-234162 A Japanese Patent Laid-Open No. 10-204196
  • Patent Document 2 is vulnerable to heat, and when used in a copying machine or printer that fixes toner at a relatively high temperature, the synthetic paper melts in the copying machine, causing wrinkles and causing paper jams. could occur.
  • the present invention has been made in view of the above circumstances, and the problem to be solved is a laminated white that can be used as a recording material that is an information printing medium that replaces paper such as copy paper, and is extremely excellent in cost. To provide a film. It is also an object of the present invention to reduce film clogging in a conveying process in a copying machine as a recording material for copying paper and printer paper.
  • the gist of the present invention is that a polyester film having an apparent density of 0.7 to 1.3 g / cm 3 and a thickness of 10 to 1000 ⁇ m has a functional layer containing an antistatic agent on at least one side, and
  • the polyester film is a laminated white film characterized by containing a polymer incompatible with polyester.
  • the laminated white film of the present invention is used as a recording material, which is an information printing medium that replaces paper such as copy paper, because the polyester film as a base material contains a polymer incompatible with the polyester in addition to the polyester. In addition, it is a plastic film that is extremely cost effective. Furthermore, the laminated white film of the present invention can transfer a toner image suitably. That is, the toner image can be suitably transferred by an electrophotographic method or a thermal transfer method that transfers the toner image to the recording material. Further, after being used as a recording material, it is possible to easily peel off and remove characters and images from an image forming substance or the like formed on the surface. In addition, since the polyester film has a functional layer containing an antistatic agent on at least one surface, it is possible to reduce clogging of the film in a transport process in a copying machine as a recording material for copying paper or printer paper.
  • a release agent in the functional layer, after using it as a recording material as described above, it is possible to easily peel off characters and images from an image-forming substance containing a thermoplastic resin formed on the surface. Since it can be removed, it can be recycled. Therefore, a film having both the characteristics of toner image transfer, that is, the characteristic of fixing the image forming substance to the film base material, and the opposite of the characteristic of peeling the image forming substance from the film base material, can do.
  • a laminated white film 1 having a functional layer containing an antistatic agent on at least one side of a polyester film as a substrate (“the present laminated white film 1” and Will be described.
  • the polyester film used as the base material of the laminated white film 1 includes a polyester resin layer containing at least a polyester as a main component resin and a polymer incompatible with the polyester.
  • the “main component resin” means a resin having the highest content ratio among the resin components constituting the polyester resin layer. It can be assumed that the main component resin occupies 30% by mass or more, particularly 50% by mass or more, of which 80% by mass (including 100% by mass) among the resin components constituting the polyester resin layer.
  • the polyester film may be a single layer composed of the above polyester resin layer, or may be a two-layer, three-layer, four-layer or more multilayer having a polyester resin layer, and is particularly limited. is not. That is, when the polyester film is a single layer, the polyester film means the polyester resin layer itself. Moreover, when the said polyester film is two or more layers, all the layers may be a polyester resin layer, and one or more layers may be resin layers other than polyester. In particular, it is preferable that all the layers are polyester resin layers. Especially, it is preferable that the polyester film is laminated
  • a laminated structure is two layers means that it is comprised by two surface layers, and specifically, 2 of the composition from which mixing
  • the case where it forms with a layer is mentioned.
  • the polyester film as the substrate may be obtained by polycondensation of aromatic dicarboxylic acid and aliphatic glycol.
  • aromatic dicarboxylic acid include terephthalic acid, isophthalic acid, and 2,6-naphthalenedicarboxylic acid.
  • aliphatic glycol include ethylene glycol, diethylene glycol, trimethylene glycol, tetramethylene glycol, neopentyl glycol, 1 , 4-cyclohexanedimethanol and the like.
  • polyesters include polyethylene terephthalate (PET), polyethylene-2,6-naphthalenedicarboxylate (PEN), polybutylene terephthalate, and the like.
  • PET polyethylene terephthalate
  • PEN polyethylene-2,6-naphthalenedicarboxylate
  • Such a polyester may be a homopolymer that is not copolymerized, 20 mol% or less of the dicarboxylic acid component is a dicarboxylic acid component other than the main component, and / or 20 mol% or less of the diol component is other than the main component. It may be a copolyester that is a diol component. Moreover, those mixtures may be sufficient.
  • Polyester is a conventionally known method, for example, a method of directly obtaining a polyester by reaction of a dicarboxylic acid and a diol, or a reaction of a lower alkyl ester of a dicarboxylic acid and a diol with a conventionally known transesterification catalyst, and the presence of a polymerization catalyst. It can obtain by the method of performing a polymerization reaction under.
  • the polymerization catalyst known catalysts such as an antimony compound, a germanium compound, a titanium compound, and an aluminum compound can be used.
  • the intrinsic viscosity of the polyester is preferably 0.55 to 0.75 dl / g as measured by the method described in the Examples section below, and more preferably 0.60 dl / g or more or 0.70 dl. / G or less is more preferable.
  • the polyester film stretched at least in the uniaxial direction can contain innumerable fine cavities. Due to the fine cavities, the polyester film can not only scatter light and cause white opacity, but also reduce the apparent density of the polyester film.
  • an image forming substance containing a thermoplastic resin such as toner printed on the surface of the polyester film can be easily fixed and easily peeled and removed.
  • a polymer incompatible with polyester on the surface of the polyester film it contains a thermoplastic resin such as toner printed on the surface of the laminated white polyester film when used as a recording material for copying paper or printer paper.
  • the image forming substance can be easily fixed and easily removed. That is, by having a fine cavity on the surface layer of the polyester film or roughening the surface, an anchor effect for satisfactorily fixing the image forming substance can be exhibited. Further, since the surface layer contains a polymer that is incompatible with polyester, the fixing power of the image forming substance can be adjusted, so that it can be easily peeled and removed. Surprisingly, such an effect can be expressed in the same manner or even more significantly even when a functional layer described later is provided on the surface of the polyester film. Moreover, in order to ensure sufficient concealability and weight reduction, a polymer incompatible with polyester may be included in the intermediate layer as necessary.
  • the polymer incompatible with polyester may be contained in all layers of the polyester film, or may be selectively contained in a specific layer. Specifically, the polymer incompatible with the polyester may be contained in at least one surface layer of the polyester film or may be contained in the intermediate layer.
  • polystyrene examples thereof include polyolefin, polystyrene, polyacryl, polycarbonate, etc. Among them, polyolefin and polystyrene are preferable, and polyolefin is more preferable. . Further, among polyolefins, polypropylene, polyethylene, poly-4-methylpentene-1, amorphous polyolefin, and the like can be mentioned. Among these, polypropylene is more preferable in view of the formation of cavities and the ease of film formation. In addition, polyester different from the main component resin which comprises a polyester film can also be used as a polymer incompatible with polyester.
  • the content of propylene units in the polypropylene is preferably 80 mol% or more, more preferably 90 mol% or more, and even more preferably 95 mol% or more.
  • the content of the polymer incompatible with the polyester is 1 to 70 parts by mass of the polymer incompatible with the polyester with respect to 100 parts by mass of the polyester.
  • it is more preferably 2 parts by mass or more and 50 parts by mass or less, more preferably 3 parts by mass or more or 40 parts by mass or less, and more preferably 5 parts by mass or more or 35 parts by mass or less. Particularly preferred.
  • the melt flow index of polypropylene under the conditions of a temperature of 230 ° C. and a load of 2.16 kg (21.2 N) is usually 0.5 ml / 10 min or more as a lower limit.
  • it is 1 ml / 10 minutes or more, More preferably, it is 3 ml / 10 minutes or more, More preferably, it is 5 ml / 10 minutes or more. In the case of the above range, it is possible to generate a sufficient cavity size and to easily avoid breakage during stretching.
  • the upper limit is usually 50 ml / 10 minutes or less, preferably 40 ml / 10 minutes or less, more preferably 30 ml / 10 minutes or less, and further preferably 25 ml / 10 minutes or less. In the case of the above range, it is possible to avoid clip detachment at the time of transverse stretching, and it is possible to maintain productivity.
  • the lower limit of the content of the “polyester incompatible polymer” in the polyester film is usually 1% by weight or more, preferably 2% by weight or more, more preferably 3% by weight or more, still more preferably 5% by weight or more, particularly preferably. Is 8% by weight or more.
  • the film surface characters and images due to printed image forming substances and the like are easily fixed and peeled and removed, and the film can be repeatedly used as a recording material for copying paper and printer paper.
  • the upper limit of the content of the “polyester incompatible polymer” in the polyester film is usually 70% by weight or less, preferably 50% by weight or less, more preferably 40% by weight or less, more preferably 35% by weight or less, Especially preferably, it is 30 weight% or less, Most preferably, it is 25 weight% or less.
  • said content when a polyester film is a laminated structure, said content may mean the average content rate in a polyester film whole layer, and may mean content in a specific layer. Specifically, the content in at least one surface layer of the polyester film may mean the content in the intermediate layer.
  • middle layer is a surplus part which generate
  • the inclusion of recycled products has the effect of reducing costs and reducing environmental impact.
  • the content of the recycled product in the intermediate layer is preferably 95% by weight or less, more preferably 85% by weight or less with respect to the intermediate layer from the viewpoint of film formation stability due to a decrease in intrinsic viscosity in addition to color tone regulation.
  • the lower limit of the content of the recycled product in the intermediate layer is not limited and may be 0% by weight. From the viewpoint of cost reduction, it is preferably 1% by weight or more, more preferably 3% by weight or more, and further preferably 5% by weight or more.
  • the polyester film it is also possible for the polyester film to contain metal compound particles for the purpose of further improving concealability and whiteness.
  • the said polyester film is two or more layers, it is preferable to also contain a metal compound particle in the said polyester resin layer.
  • the layer containing the metal compound particles may be a surface layer or an intermediate layer. In order to effectively improve the concealability and whiteness, it is preferably contained in the surface layer.
  • the metal compound particles tend to compensate for the white opacity due to the light scattering effect generated by the fine cavities formed by blending the above-mentioned “polyester incompatible polymer”, so that a higher hiding degree and There is a tendency to obtain whiteness.
  • the metal compound particles include titanium oxide, calcium carbonate, barium sulfate, magnesium carbonate, barium carbonate, calcium sulfate, calcium phosphate, magnesium phosphate, kaolin, aluminum oxide, zirconium oxide, and the like. From the viewpoint of improving whiteness, titanium oxide, calcium carbonate, barium sulfate and the like are preferable, and among these, titanium oxide is particularly suitable.
  • the lower limit of the average particle diameter of the metal compound particles is usually 0.05 ⁇ m or more, preferably 0.10 ⁇ m or more, more preferably 0.20 ⁇ m or more, further preferably 0.25 ⁇ m or more, and the upper limit is usually 0.50 ⁇ m or less. , Preferably 0.45 ⁇ m or less, more preferably 0.40 ⁇ m or less.
  • the shape of the compound particles is not particularly limited, and may be any of a spherical shape, a block shape, a rod shape, a flat shape, and the like. Moreover, there is no restriction
  • the lower limit of the content of the metal compound particles is preferably 1% by weight or more, more preferably 2% by weight or more, further preferably 3% by weight or more, and the upper limit is usually 30% by weight or less, preferably 20% by weight. Hereinafter, it is more preferably 15% by weight or less, further preferably 13% by weight or less, and particularly preferably 10% by weight or less.
  • said content when a polyester film is a laminated structure, said content may mean the average content rate in a polyester film whole layer, and may mean content in a specific layer. Specifically, the content in at least one surface layer of the polyester film may mean the content in the intermediate layer.
  • the polyester film may contain particles other than the metal compound particles exemplified above.
  • the particles other than the metal compound particles exemplified above include silica particles and organic particles.
  • the organic particles include acrylic resins, styrene resins, urea resins, phenol resins, epoxy resins, and benzoguanamine resins. Of these, silica particles are preferred because they are particularly effective in a small amount.
  • the average particle diameter of the particles (silica particles or organic particles) other than the metal compound particles exemplified above is preferably more than 0.50 ⁇ m, more preferably 1.0 ⁇ m or more, further preferably 1.5 ⁇ m or more, particularly preferably. 2.0 ⁇ m or more.
  • the upper limit of the average particle size of the particles is usually 15.0 ⁇ m or less, preferably 12.0 ⁇ m or less, more preferably 10.0 ⁇ m or less, and further preferably 8.0 ⁇ m or less.
  • the film surface does not become too rough, and it is easy to peel off and remove characters and images such as image forming substances printed on the film surface, and the film is repeatedly recorded on copying paper and printer paper. It tends to be usable as a material. Furthermore, it is not necessary to extremely increase the thickness of the surface layer from the aspect of particle dropout, and the optimum range of the thickness is wide, which is a preferable form.
  • the shape of the particles (silica particles or organic particles) other than the metal compound particles exemplified above is not particularly limited, and may be any shape such as a spherical shape, a block shape, a rod shape, and a flat shape. Moreover, there is no restriction
  • the content of particles (silica particles or organic particles) other than the metal compound particles exemplified above depends on the average particle size, it cannot be said unconditionally.
  • a polyester film containing silica particles or organic particles it is usually 5% by weight or less, preferably 3% by weight or less, more preferably 2% by weight or less, still more preferably 1% by weight or less, and a preferred range.
  • the lower limit is 0.005% by weight or more, more preferably 0.05% by weight or more, and still more preferably 0.1% by weight or more. If it is the said range, it will become possible to make the surface roughness of a film moderate, and it exists in the tendency which can achieve the target slipperiness provision.
  • said content may mean the average content rate in a polyester film whole layer, and may mean content in a specific layer. Specifically, the content in at least one surface layer of the polyester film may mean the content in the intermediate layer.
  • the polyester film as the base material of the present laminated white film 1 contains an incompatible polymer, so that a fine independent space (cavity) is formed inside the film. ) Can be obtained. Therefore, in order to further refine the cavity or increase the concealability and whiteness, for example, a surfactant, inert particles, fluorescent whitening agent, and the like may be blended.
  • the polyester film as the substrate of the present laminated white film 1 has a laminated structure of two or more layers, if it is two layers, any one of them, and if it is three or more layers, the surface layer thereof is the polyester resin layer. Is preferred.
  • the surface layer contains the above polyester and a polymer that is incompatible with the polyester, a fine cavity can be provided by stretching. Whitening can be achieved. Further, since the surface roughness can be adjusted, the writing property can be improved, the image by the image forming substance or the like can be easily fixed, and it can be peeled off after use. If the surface layer further contains metal compound particles, the concealability and whiteness can be further increased, and the slipperiness can be improved by containing particles other than the metal compound particles.
  • the intermediate layer other than the surface layer contains the polyester
  • the polymer, metal compound particles, and particles other than the metal compound particles that are incompatible with the polyester may be contained as necessary. It is preferable from the viewpoint of cost reduction and environmental load reduction that the content of the metal compound particles and particles other than the metal compound particles is made as small as possible, and the recycled polyester is used.
  • the thickness of the polyester film is preferably 10 ⁇ m to 1000 ⁇ m, more preferably 20 ⁇ m or more and 500 ⁇ m or less, more preferably 30 ⁇ m or more and 400 ⁇ m or less, and particularly preferably 38 ⁇ m or more or 350 ⁇ m or less.
  • the hardness (stiffness) and handleability of the film can be made sufficient, and clogging of the film in the transporting process in the copying machine can be reduced.
  • the thickness of each surface layer is preferably 1 ⁇ m to 50 ⁇ m, especially 2 ⁇ m or more and 40 ⁇ m or less, particularly 3 ⁇ m or more or 30 ⁇ m or less, and especially 4 ⁇ m. More preferably, it is 25 ⁇ m or less.
  • the lower limit of the apparent density of the polyester film is 0.7 g / cm 3 or more, preferably 0.75 g / cm 3 or more, more preferably 0.8 g / cm 3 or more.
  • the film strength can be maintained, and the film is clogged during the transport process in the copying machine when used as a recording material instead of copying paper or printer paper as an information printing medium. Can be reduced, and optimal printing can be performed.
  • the upper limit of the apparent density is 1.3 g / cm 3 or less, preferably 1.2 g / cm 3 or less, more preferably 1.1 g / cm 3 or less.
  • the apparent density of the polyester film can be adjusted to form fine independent cavities inside the film by blending an incompatible polymer with a specific gravity lighter than that of polyester, the main component resin, and stretching it at least in the uniaxial direction. it can. However, it is not limited to these methods.
  • the arithmetic average roughness (Ra) of the surface of the polyester film is based on JIS B0601 (2001).
  • the arithmetic average roughness (Ra) varies depending on the application to be used, but the upper limit is usually 950 nm or less, preferably 850 nm or less, more preferably 800 nm or less.
  • the lower limit of the arithmetic average roughness (Ra) is usually 100 nm or more, preferably 200 nm or more, more preferably 300 nm or more, and further preferably 350 nm or more.
  • the b value (reflection method) which is an index representing the yellowness of the polyester film, is usually 0 or less, preferably ⁇ 0.20 or less, more preferably ⁇ 0.40 or less, even more preferably ⁇ 0.50 or less, particularly preferably. Is ⁇ 0.60 or less, and the lower limit is not particularly limited, but is preferably ⁇ 5.0 or more. By using in the said range, yellowness can be suppressed and whiteness can be made favorable. Further, when used as a recording material for color printing, the obtained image quality tends to be excellent.
  • the polyester film has a heat shrinkage in the film longitudinal direction (MD) and film width direction (TD) at 150 ° C. for 30 minutes of usually 2.8% or less, preferably 2.3% or less, more preferably as an absolute value. 2.0% or less.
  • a heat shrinkage rate of the polyester film in the above range, it is possible to prevent the film from being damaged in the dimensional stability due to heat when printing on a recording material by a method such as an electrophotographic method or a thermal transfer method. it can.
  • the edge portion of the film (sheet) that is, the portion where wrinkles are likely to occur, the generation of wrinkles in the polyester film can be suppressed, and distortion and unevenness occur in characters and images, resulting in deterioration of image quality. It tends to be possible to suppress the phenomenon.
  • wrinkles once wrinkles are generated, they cannot be erased and cannot be repeatedly used as a recording material for copying paper or printer paper.
  • the concealability (OD) of the polyester film is usually 0.30 or more, preferably 0.35 or more, more preferably 0.40 or more, and further preferably 0.45 or more, when a single film is measured with a Macbeth densitometer. It is. By using within the above range, the show-through when the entire surface is printed on both sides of the film is reduced, and it tends to be possible to obtain characters and images of good quality.
  • the upper limit of the concealing property (OD) is not particularly limited, but is preferably 1 or less, more preferably 0.9 or less, considering the balance of other physical properties.
  • the whiteness of the polyester film is determined by measuring the Hunter whiteness (Wb) when the film is a single sheet with a colorimeter.
  • the lower limit is usually 80.0% or more, preferably 81.0% or more, more preferably 82. It is 0% or more, more preferably 83.0% or more, and particularly preferably 83.5% or more.
  • the functional layer which comprises this laminated white film 1 is demonstrated.
  • This functional layer can serve as a recording layer on which the image forming substance adheres directly to the layer surface, for example.
  • the recording layer in the present invention is a layer that not only fixes the attached image forming substance but also has a role of removing the image forming substance together with the resin layer when a resin layer described later is provided.
  • the functional layer in the laminated white film 1 preferably has antistatic performance and release performance.
  • the present laminated white film 1 has a reduced apparent density, can be whitened without cost, and can easily remove and remove characters and images such as image forming substances containing a printed thermoplastic resin.
  • the functional layer it has been found that it may be difficult to express the ability to easily peel off and remove characters and images such as image forming substances on the surface. It is preferable to provide performance.
  • this laminated white film 1 is used for the purpose of preventing double feeding in the paper transport of copiers and multifunction machines, and preventing sticking between papers when handling paper. It is preferable to have a functional layer containing an agent on at least one side. In addition, by containing an antistatic agent in the functional layer, there is no clogging of the film in the multi-function machine, there is no occurrence of double feeding of the printed film, and each sheet can be conveyed independently, and dust adheres to it. Therefore, it is possible to obtain a film having a high quality and a film printed matter having a good image quality.
  • the antistatic agent contained in the functional layer is not particularly limited, and a conventionally known antistatic agent can be used.
  • a polymer type antistatic agent because of its good heat resistance and moist heat resistance.
  • the polymer type antistatic agent include a compound having an ammonium group, a polyether compound, a compound having a sulfonic acid group, a betaine compound, and a conductive polymer.
  • a compound having an ammonium group or a compound having a sulfonic acid group is preferable.
  • a compound having an ammonium group is more preferable.
  • Conductive polymers are preferred because they have the best antistatic properties. However, there is a possibility that the use is limited in applications where the material is expensive and coloring is extremely disliked.
  • Examples of the compound having an ammonium group include aliphatic amines, alicyclic amines, and ammonium amines of aromatic amines.
  • the compound having an ammonium group is preferably a compound having a polymer type ammonium group, and the ammonium group has a structure incorporated in the main chain or side chain of the polymer, not as a counter ion. It is preferable.
  • a polymer obtained by polymerizing a monomer containing an addition-polymerizable ammonium group or a precursor of an ammonium group such as an amine is preferably used.
  • a monomer containing an addition polymerizable ammonium group or a precursor of an ammonium group such as an amine may be polymerized alone, or it may be a copolymer of a monomer containing these and another monomer. May be.
  • compounds having an ammonium group compounds having a pyrrolidinium ring are also preferred in that they are excellent in antistatic properties and heat stability.
  • the two substituents bonded to the nitrogen atom of the compound having a pyrrolidinium ring are each independently an alkyl group, a phenyl group, and the like. Even if these alkyl groups and phenyl groups are substituted with the groups shown below, Good. Substitutable groups are, for example, hydroxyl group, amide group, ester group, alkoxy group, phenoxy group, naphthoxy group, thioalkoxy, thiophenoxy group, cycloalkyl group, trialkylammonium alkyl group, cyano group, and halogen. Further, the two substituents bonded to the nitrogen atom may be chemically bonded.
  • — (CH 2 ) m — (m 2 to 5), —CH (CH 3 ) CH (CH 3 ) —, —CH ⁇ CH—CH ⁇ CH—, —CH ⁇ CH—CH ⁇ N—, —CH ⁇ CH—N ⁇ CH—, —CH 2 OCH 2 —, — (CH 2 ) 2 O (CH 2 ) 2 — and the like.
  • a polymer having a pyrrolidinium ring can be obtained by cyclopolymerizing a diallylamine derivative using a radical polymerization catalyst.
  • the polymerization is carried out by using a polymerization initiator such as hydrogen peroxide, benzoyl peroxide, tertiary butyl peroxide in a polar solvent such as water or methanol, ethanol, isopropanol, formamide, dimethylformamide, dioxane, acetonitrile as a solvent.
  • a polymerization initiator such as hydrogen peroxide, benzoyl peroxide, tertiary butyl peroxide in a polar solvent such as water or methanol, ethanol, isopropanol, formamide, dimethylformamide, dioxane, acetonitrile as a solvent.
  • a compound having a polymerizable carbon-carbon unsaturated bond with a diallylamine derivative may be used as a copoly
  • the antistatic agent is preferably a polymer having a structure represented by the following formula (1) from the viewpoint of excellent antistatic properties and wet heat stability.
  • a single polymer or copolymer having the structure of the following formula (1) may be copolymerized, and further a plurality of other components may be copolymerized.
  • the substituent R 1 is a hydrogen atom or a hydrocarbon group such as an alkyl group having 1 to 20 carbon atoms or a phenyl group
  • R 2 is —O—, —NH— or —S—
  • R 3 is An alkylene group having 1 to 20 carbon atoms or another structure capable of forming the structure of Formula 1
  • R 4 , R 5 and R 6 are each independently a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, or a phenyl group.
  • X ⁇ is various counter ions.
  • the substituent R 1 is preferably a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.
  • 3 is preferably an alkyl group having 1 to 6 carbon atoms
  • R 4 , R 5 and R 6 are preferably each independently a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, more preferably , R 4 , R 5 , or R 6 is a hydrogen atom, and the other substituent is an alkyl group having 1 to 4 carbon atoms.
  • Examples of the anion that becomes a counter ion (counter ion) of the ammonium group of the compound having an ammonium group described above include ions such as halogen ions, sulfonates, sulfates, phosphates, nitrates, and carboxylates.
  • the number average molecular weight of the compound having an ammonium group is usually 1,000 to 500,000, preferably 2,000 to 350,000, more preferably 5,000 to 200,000.
  • the molecular weight is less than 1000, the strength of the functional layer may be weakened or the heat resistance stability may be poor.
  • the molecular weight exceeds 500,000, the viscosity of the coating solution increases, and the handleability and applicability may deteriorate.
  • polyether compounds include polyethylene oxide, polyether ester amide, acrylic resin having polyethylene glycol in the side chain, and the like.
  • the compound having a sulfonic acid group is a compound containing sulfonic acid or a sulfonate in the molecule.
  • a compound containing a large amount of sulfonic acid or a sulfonate such as polystyrene sulfonic acid is preferably used. .
  • the conductive polymer examples include polythiophene-based, polyaniline-based, polypyrrole-based, and polyacetylene-based polymers.
  • polythiophene-based polymers that use poly (3,4-ethylenedioxythiophene) in combination with polystyrene sulfonic acid.
  • the conductive polymer is preferable to the other antistatic agents described above in that the resistance value is low.
  • it is necessary to devise measures such as reducing the amount used in applications where coloring and cost are a concern.
  • the lower limit of the content of the antistatic agent in the functional layer is usually 1% by weight or more, preferably 3% by weight or more, more preferably 5% by weight or more, further preferably 10% by weight or more, and particularly preferably 20% by weight or more. is there.
  • the upper limit is usually 80% by weight or less, preferably 70% by weight or less, more preferably 60% by weight or less, still more preferably 55% by weight or less, and particularly preferably 50% by weight or less.
  • the functional layer with a release performance so that an image forming substance containing a thermoplastic resin formed on the film surface can be suitably peeled off after printing.
  • the functional layer having mold release performance may be the same as or different from the functional layer containing the antistatic agent.
  • the functional layer containing the antistatic agent has a releasing property for the reason described later.
  • the functional layer which has mold release performance and the functional layer containing an antistatic agent are different layers, it is preferable to make the functional layer which has mold release performance into an outer layer. It has been found that the function of separating and removing image forming substances and the like can be performed more appropriately by imparting release properties to the functional layer.
  • the functional layer preferably contains a release agent in order to impart release performance to the image forming substance or the like.
  • the release agent is not particularly limited, and a conventionally known release agent can be used.
  • a conventionally known release agent can be used.
  • examples thereof include a long-chain alkyl group-containing compound, a fluorine compound, a silicone compound, and wax.
  • a long-chain alkyl compound and a fluorine compound are preferable, and a long-chain alkyl compound is more preferable from the viewpoint of low contamination and excellent peeling and removal of the image forming substance.
  • a silicone compound is preferable when it is particularly important to remove and remove the image forming substance.
  • wax is effective when it is desired to emphasize the printability of the image forming material on the surface.
  • a long-chain alkyl group-containing compound is preferable among the above releasing agents from the viewpoint of wettability to the polyester film.
  • the long-chain alkyl group-containing compound is a compound having a linear or branched alkyl group having usually 6 or more, preferably 8 or more, and more preferably 12 or more carbon atoms.
  • the alkyl group include hexyl group, octyl group, decyl group, lauryl group, octadecyl group, and behenyl group.
  • the compound having an alkyl group include various long-chain alkyl group-containing polymer compounds, long-chain alkyl group-containing amine compounds, long-chain alkyl group-containing ether compounds, and long-chain alkyl group-containing quaternary ammonium salts. .
  • a polymer compound is preferable. Further, from the viewpoint of effectively obtaining releasability, a polymer compound having a long-chain alkyl group in the side chain is more preferable.
  • a polymer compound having a long-chain alkyl group in the side chain can be obtained by reacting a polymer having a reactive group with a compound having an alkyl group capable of reacting with the reactive group.
  • the reactive group include a hydroxyl group, an amino group, a carboxyl group, and an acid anhydride.
  • the compound having such a reactive group include polyvinyl alcohol, polyethyleneimine, polyethyleneamine, a reactive group-containing polyester resin, and a reactive group-containing poly (meth) acrylic resin.
  • polyvinyl alcohol is preferable in view of releasability and ease of handling.
  • Examples of the compound having an alkyl group capable of reacting with the reactive group include, for example, long-chain alkyl group-containing isocyanates such as hexyl isocyanate, octyl isocyanate, decyl isocyanate, lauryl isocyanate, octadecyl isocyanate, and behenyl isocyanate; hexyl chloride, octyl chloride Long chain alkyl group-containing acid chlorides such as decyl chloride, lauryl chloride, octadecyl chloride, and behenyl chloride; long chain alkyl group-containing amines; long chain alkyl group-containing alcohols.
  • long chain alkyl group-containing isocyanates are preferable, and octadecyl isocyanate is particularly preferable in consideration of releasability and ease of handling.
  • a polymer compound having a long-chain alkyl group in the side chain can also be obtained by copolymerization of a long-chain alkyl (meth) acrylate polymer or a long-chain alkyl (meth) acrylate and another vinyl group-containing monomer.
  • the long chain alkyl (meth) acrylate include hexyl (meth) acrylate, octyl (meth) acrylate, decyl (meth) acrylate, lauryl (meth) acrylate, octadecyl (meth) acrylate, and behenyl (meth) acrylate. It is done.
  • a fluorine compound is a compound containing a fluorine atom in the compound.
  • a polymer (polymer) containing a fluorine atom is preferable.
  • Organic fluorine compounds are preferably used from the viewpoint of coating appearance by in-line coating.
  • fluoroalkyl group-containing compounds such as perfluoroalkyl group-containing compounds, polymers of olefin compounds containing fluorine atoms, and aromatics such as fluorobenzene.
  • Group fluorine compounds and the like From the viewpoint of releasability, a fluoroalkyl group-containing compound is preferable, and among them, a perfluoroalkyl group-containing compound is preferable.
  • the compound containing the long-chain alkyl compound which is mentioned later can also be used for a fluorine compound.
  • perfluoroalkyl group-containing compound examples include perfluoroalkyl (meth) acrylate, perfluoroalkylmethyl (meth) acrylate, 2-perfluoroalkylethyl (meth) acrylate, 3-perfluoroalkylpropyl (meth) acrylate, Perfluoroalkyl group-containing (meth) acrylates such as 3-perfluoroalkyl-1-methylpropyl (meth) acrylate and 3-perfluoroalkyl-2-propenyl (meth) acrylate, and polymers thereof; perfluoroalkylmethyl vinyl ether, 2-perfluoroalkyl ethyl vinyl ether, 3-perfluoropropyl vinyl ether, 3-perfluoroalkyl-1-methylpropyl vinyl ether, 3-perfluoroalkyl-2-propenyl Perfluoroalkyl group-containing vinyl ether and polymers thereof such as vinyl ether and the like.
  • the perfluoroalkyl group preferably has 3 to 11 carbon atoms. Further, it may be a polymer with a compound containing a long-chain alkyl compound as described later. Moreover, it is also preferable that it is a polymer with vinyl chloride from a viewpoint of adhesiveness with a base material.
  • silicone compound examples include alkyl silicones such as dimethyl silicone and diethyl silicone, phenyl silicone having a phenyl group, and methyl phenyl silicone.
  • Silicone having various functional groups can be used, and examples thereof include ether groups, hydroxyl groups, amino groups, epoxy groups, carboxylic acid groups, halogen groups such as fluorine, and perfluoroalkyl groups.
  • silicones having vinyl groups and hydrogen silicones in which hydrogen atoms are directly bonded to silicon atoms are also common, and both are used in combination to form silicones (addition reaction between vinyl groups and hydrogen silane). It can also be used.
  • modified silicones such as acrylic graft silicone, silicone graft acrylic, amino-modified silicone, perfluoroalkyl-modified silicone as the silicone compound.
  • a curable silicone resin As the type of curable type, any of the curing reaction types such as a condensation type, an addition type, and an active energy ray curable type can be used.
  • the wax is a wax selected from natural waxes, synthetic waxes, and blended waxes.
  • Natural waxes are plant waxes, animal waxes, mineral waxes and petroleum waxes.
  • plant waxes include candelilla wax, carnauba wax, rice wax, wood wax, jojoba oil and the like.
  • Animal waxes include beeswax, lanolin, whale wax and the like.
  • mineral wax include montan wax, ozokerite, and ceresin.
  • petroleum wax include paraffin wax, microcrystalline wax, and petrolatum.
  • Synthetic waxes include synthetic hydrocarbons, modified waxes, hydrogenated waxes, higher fatty acid esters, fatty acid amides, amines, imides, ester waxes, ketones, and the like.
  • Specific examples of synthetic hydrocarbons include Fischer-Tropsch wax (also known as sazol wax) and polyethylene wax, as well as low molecular weight polymers (specifically, polymers having a number average molecular weight of 500 to 20000). And the following polymers, namely, polypropylene, ethylene / acrylic acid copolymer, polyethylene glycol, polypropylene glycol, polyethylene glycol and polypropylene glycol block or graft conjugate, and the like.
  • modified wax examples include montan wax derivatives, paraffin wax derivatives, and microcrystalline wax derivatives.
  • the derivative herein is a compound obtained by any of purification, oxidation, esterification, saponification treatment, or a combination thereof.
  • hydrogenated wax examples include hardened castor oil and hardened castor oil derivatives.
  • a synthetic wax is preferable as the release agent in the functional layer, among which polyethylene wax is more preferable, and oxidized polyethylene wax is more preferable.
  • the number average molecular weight of the synthetic wax is usually 500 to 30000, preferably 1000 to 15000, and more preferably 2000 to 8000, from the viewpoints of stability of properties such as blocking and handling properties.
  • the lower limit of the content of the release agent in the functional layer is usually 0% by weight or more, preferably 3% by weight or more, more preferably 5% by weight or more, still more preferably 8% by weight or more, and particularly preferably 10% by weight or more. is there.
  • the upper limit is usually 80% by weight or less, preferably 70% by weight or less, more preferably 60% by weight or less, still more preferably 50% by weight or less, and particularly preferably 40% by weight or less.
  • the functional layer includes a polymer. It is preferable to contain (an antistatic agent, a release agent, or a polymer other than the crosslinking agent described later).
  • polymers can be used as the polymer used for the functional layer.
  • the polymer include acrylic resin, urethane resin, polyester resin, polyvinyl (polyvinyl alcohol, vinyl chloride vinyl acetate copolymer, etc.), polyalkylene glycol, polyalkyleneimine, methylcellulose, hydroxycellulose, starches and the like.
  • acrylic resin, urethane resin, polyester resin, and polyvinyl alcohol are preferable from the viewpoint of improving appearance, adhesion to the film of the base material, antistatic performance and stabilization of mold release performance, acrylic resin, urethane resin, Polyester resin is more preferable, and acrylic resin and urethane resin are still more preferable.
  • acrylic resin and polyvinyl alcohol are preferable from the viewpoint of stabilization of antistatic performance and release performance, or stability in the state of a coating solution when a functional layer is formed by coating.
  • an acrylic resin or a urethane resin is preferable, and an acrylic resin is particularly preferable.
  • the acrylic resin as the polymer to be contained in the functional layer is a polymer composed of polymerizable monomers including acrylic and methacrylic monomers. These may be either homopolymers or copolymers, and copolymers with polymerizable monomers other than acrylic and methacrylic monomers. Moreover, the copolymer of these polymers and other polymers (for example, polyester, polyurethane, etc.) is also included. For example, a block copolymer or a graft copolymer. Alternatively, a polymer (possibly a mixture of polymers) obtained by polymerizing a polymerizable monomer in a polyester solution or a polyester dispersion is also included.
  • a polymer obtained by polymerizing a polymerizable monomer in a polyurethane solution or a polyurethane dispersion (sometimes a mixture of polymers) is also included.
  • a polymer (in some cases, a polymer mixture) obtained by polymerizing a polymerizable monomer in another polymer solution or dispersion is also included.
  • the polymerizable monomer is not particularly limited, and examples thereof include various carboxyl group-containing monomers such as acrylic acid, methacrylic acid, crotonic acid, itaconic acid, fumaric acid, maleic acid, citraconic acid, and salts thereof; Various hydroxyl group-containing monomers such as 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, monobutylhydroxyfumarate, monobutylhydroxyitaconate; methyl Various (meth) acrylates such as (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, lauryl (meth) acrylate; (meth) acrylamide, diacetone acrylamide, Various nitrogen-containing compounds such as methylolacrylamide or (meth) acrylonitrile; various styrene derivative
  • the urethane resin as the polymer to be contained in the functional layer is a polymer compound having a urethane bond in the molecule, and is usually prepared by a reaction between a polyol and an isocyanate.
  • the polyol include polyester polyols, polycarbonate polyols, polyether polyols, polyolefin polyols, and acrylic polyols. These compounds may be used alone or in combination.
  • polyester polyols examples include polycarboxylic acids (malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, sebacic acid, fumaric acid, maleic acid, terephthalic acid, isophthalic acid, etc.) Acid anhydrides and polyhydric alcohols (ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, dipropylene glycol, tripropylene glycol, butanediol, 1,3-butanediol, 1,4-butanediol, 2,3-butane Diol, 2-methyl-1,3-propanediol, 1,5-pentanediol, neopentyl glycol, 1,6-hexanediol, 3-methyl-1,5-pentanediol, 2-methyl-2,4- Pentanediol, 2-methyl-2-pro 1,3-propanediol, 1,
  • polycarbonate polyols are obtained from a polyhydric alcohol and a carbonate compound by a dealcoholization reaction.
  • Polyhydric alcohols include ethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, 1,5-pentane Diol, 1,6-hexanediol, 1,4-cyclohexanediol, 1,4-cyclohexanedimethanol, 1,7-heptanediol, 1,8-octanediol, 1,9-nonanediol, 1,10-decane Examples thereof include diol, neopentyl glycol, 3-methyl-1,5-pentanediol, and 3,3-dimethylol heptane.
  • Examples of the carbonate compound include dimethyl carbonate, diethyl carbonate, diphenyl carbonate, and ethylene carbonate.
  • Examples of the polycarbonate-based polyols obtained from these reactions include poly (1,6-hexylene) carbonate, poly (3- And methyl-1,5-pentylene) carbonate.
  • polyether polyols examples include polyethylene glycol, polypropylene glycol, polyethylene propylene glycol, polytetramethylene ether glycol, polyhexamethylene ether glycol and the like.
  • polyester polyols and polycarbonate polyols are more preferable among the above polyols.
  • polyisocyanate compound used for obtaining the urethane resin examples include aromatic diisocyanates such as tolylene diisocyanate, xylylene diisocyanate, methylene diphenyl diisocyanate, phenylene diisocyanate, naphthalene diisocyanate, and tolidine diisocyanate, ⁇ , ⁇ , ⁇ ′, Aliphatic diisocyanates having an aromatic ring such as ⁇ '-tetramethylxylylene diisocyanate, methylene diisocyanate, propylene diisocyanate, lysine diisocyanate, trimethylhexamethylene diisocyanate, hexamethylene diisocyanate and other aliphatic diisocyanates, cyclohexane diisocyanate, methylcyclohexane diisocyanate, isophorone diisocyanate , Dicyclohexylme Down diisocyanate, alicyclo
  • a chain extender may be used when synthesizing the urethane resin, and the chain extender is not particularly limited as long as it has two or more active groups that react with an isocyanate group. Alternatively, a chain extender having two amino groups can be mainly used.
  • chain extender having two hydroxyl groups examples include aliphatic glycols such as ethylene glycol, propylene glycol and butanediol, aromatic glycols such as xylylene glycol and bishydroxyethoxybenzene, neopentyl glycol hydroxypivalate, and the like. And glycols such as ester glycols.
  • chain extender having two amino groups examples include aromatic diamines such as tolylenediamine, xylylenediamine, diphenylmethanediamine, ethylenediamine, propylenediamine, hexanediamine, 2,2-dimethyl-1,3- Propanediamine, 2-methyl-1,5-pentanediamine, trimethylhexanediamine, 2-butyl-2-ethyl-1,5-pentanediamine, 1,8-octanediamine, 1,9-nonanediamine, 1,10- Aliphatic diamines such as decane diamine, 1-amino-3-aminomethyl-3,5,5-trimethylcyclohexane, dicyclohexylmethanediamine, isopropylidine cyclohexyl-4,4′-diamine, 1,4-diaminocyclohexane, 1 , 3-Bisaminomethylcyclohexane Alicyclic diamines, and the like of.
  • the urethane resin may use a solvent as a medium.
  • water is used as a medium.
  • a forced emulsification type using an emulsifier there are a forced emulsification type using an emulsifier, a self-emulsification type in which a hydrophilic group is introduced into the urethane resin, and a water-soluble type.
  • the self-emulsification type in which an ionic group is introduced into the structure of the urethane resin to form an ionomer is preferable because of excellent storage stability of the liquid and water resistance and transparency of the obtained functional layer.
  • examples of the ionic group to be introduced include various groups such as a carboxyl group, sulfonic acid, phosphoric acid, phosphonic acid, and quaternary ammonium salt.
  • a method for introducing a carboxyl group into a urethane resin various methods can be taken in each stage of the polymerization reaction. For example, there are a method of using a carboxyl group-containing resin as a copolymer component during prepolymer synthesis, and a method of using a component having a carboxyl group as one component such as polyol, polyisocyanate, and chain extender.
  • a method in which a desired amount of carboxyl groups is introduced using a carboxyl group-containing diol depending on the amount of this component charged is preferred.
  • dimethylolpropionic acid, dimethylolbutanoic acid, bis- (2-hydroxyethyl) propionic acid, bis- (2-hydroxyethyl) butanoic acid, and the like are copolymerized with a diol used for polymerization of a urethane resin.
  • the carboxyl group is preferably in the form of a salt neutralized with ammonia, amine, alkali metal, inorganic alkali or the like. Particularly preferred are ammonia, trimethylamine and triethylamine.
  • the carboxyl group from which the neutralizing agent has been removed in the drying step after coating can be used as a crosslinking reaction point by another crosslinking agent. Thereby, it is possible to further improve the durability, solvent resistance, water resistance, blocking resistance, and the like of the functional layer obtained in addition to excellent stability in the liquid state before coating.
  • the polyester resin as the polymer to be contained in the functional layer includes, for example, those composed of the following polyvalent carboxylic acid and polyvalent hydroxy compound as main constituent components. That is, as the polyvalent carboxylic acid, terephthalic acid, isophthalic acid, orthophthalic acid, phthalic acid, 4,4′-diphenyldicarboxylic acid, 2,5-naphthalenedicarboxylic acid, 1,5-naphthalenedicarboxylic acid, and 2,6 -Naphthalenedicarboxylic acid, 2,7-naphthalenedicarboxylic acid, 1,4-cyclohexanedicarboxylic acid, 2-potassium sulfoterephthalic acid, 5-sodium sulfoisophthalic acid, adipic acid, azelaic acid, sebacic acid, dodecanedicarboxylic acid, glutar Acid, succinic acid, trimellitic acid, trimesic acid, pyromellitic acid, trimellitic
  • ethylene As the polyvalent hydroxy compound, ethylene Recall, 1,2-propylene glycol, 1,3-propylene glycol, 1,3-propanediol, 1,4-butanediol, 1,6-hexanediol, 2-methyl-1,5-pentanediol , Neopentyl glycol, 1,4-cyclohexanedimethanol, p-xylylene glycol, bisphenol A-ethylene glycol adduct, diethylene glycol, triethylene glycol, polyethylene glycol, polypropylene glycol, Polytetramethylene glycol, polytetramethylene oxide glycol, dimethylolpropionic acid, glycerin, trimethylolpropane, sodium dimethylolethylsulfonate, potassium dimethylolpropionate, and the like can be used. One or more compounds may be appropriately selected from these compounds, and a polyester resin may be synthesized by a conventional polycondensation reaction.
  • the polyvinyl alcohol as the polymer to be contained in the functional layer has a polyvinyl alcohol moiety.
  • polyvinyl alcohol including modified compounds partially acetalized or butyralized with respect to polyvinyl alcohol is known.
  • Alcohol can be used.
  • the degree of polymerization of polyvinyl alcohol is not particularly limited, but is usually 100 or more, preferably 300 to 40,000. When the degree of polymerization is less than 100, the water resistance of the functional layer may decrease.
  • the degree of saponification of polyvinyl alcohol is not particularly limited, but is preferably 50 mol% or more, more preferably 70 to 99 mol%, still more preferably 80 to 98 mol%, and particularly preferably 86 to 97 mol%. It is a polyvinyl acetate saponified product.
  • the lower limit of the polymer content in the functional layer is usually 0% by weight or more, preferably 3% by weight or more, more preferably 5% by weight or more, still more preferably 10% by weight or more, and particularly preferably 15% by weight or more.
  • the upper limit is usually 80% by weight or less, preferably 70% by weight or less, more preferably 60% by weight or less, still more preferably 55% by weight or less, and particularly preferably 50% by weight or less.
  • the functional layer after crosslinking contains a crosslinked structure derived from the crosslinking agent. That is, the functional layer containing a crosslinking agent means a functional layer formed by curing a coating solution containing a crosslinking agent. Moreover, it exists in the tendency which can give the property of the wettability improvement to a base film by containing a crosslinking agent in a functional layer.
  • crosslinking agent conventionally known materials can be used, and examples thereof include oxazoline compounds, isocyanate compounds, epoxy compounds, melamine compounds, carbodiimide compounds, silane coupling compounds, hydrazide compounds, and aziridine compounds.
  • oxazoline compounds, isocyanate compounds, epoxy compounds, melamine compounds, carbodiimide compounds, and silane coupling compounds are preferable.
  • a melamine compound or an oxazoline compound is preferable, and in order to improve adhesion to the base film, an oxazoline compound, an isocyanate compound, an epoxy compound, or a carbodiimide compound is preferable.
  • oxazoline compounds and isocyanate compounds are preferred.
  • the above-mentioned materials can be used.
  • oxazoline compounds, isocyanate compounds, epoxy compounds, and silane coupling compounds are preferable for improving wettability, and among them, oxazoline compounds and isocyanate compounds are more preferable.
  • the most preferable material for the crosslinking agent is an oxazoline compound or an isocyanate compound.
  • These crosslinking agents may be used alone or in combination of two or more.
  • the oxazoline compound used as the crosslinking agent is particularly preferably a polymer containing an oxazoline group, and can be prepared by polymerization of an addition polymerizable oxazoline group-containing monomer alone or with another monomer.
  • Addition-polymerizable oxazoline group-containing monomers include 2-vinyl-2-oxazoline, 2-vinyl-4-methyl-2-oxazoline, 2-vinyl-5-methyl-2-oxazoline, 2-isopropenyl-2-oxazoline, Examples thereof include 2-isopropenyl-4-methyl-2-oxazoline, 2-isopropenyl-5-ethyl-2-oxazoline, and the like, and one or a mixture of two or more thereof can be used.
  • 2-isopropenyl-2-oxazoline is preferred because it is easily available industrially.
  • the other monomer is not limited as long as it is a monomer copolymerizable with an addition polymerizable oxazoline group-containing monomer.
  • (meth) acrylic acid esters such as alkyl (meth) acrylate; acrylic acid, methacrylic acid, itaconic acid, malein Unsaturated carboxylic acids such as acid, fumaric acid, crotonic acid, styrenesulfonic acid and salts thereof (sodium salt, potassium salt, ammonium salt, tertiary amine salt, etc.); unsaturated nitriles such as acrylonitrile, methacrylonitrile; Unsaturated amides such as (meth) acrylamide, N-alkyl (meth) acrylamide, N, N-dialkyl (meth) acrylamide; Vinyl esters such as vinyl acetate and vinyl propionate; Vinyl ethers such as methyl vinyl ether and ethyl vinyl ether ; Ethylene, propylene, etc.
  • Unsaturated carboxylic acids such as acid, fumaric acid, crotonic acid, styrenesulfonic acid and salt
  • alkyl examples include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a t-butyl group, a 2-ethylhexyl group, and a cyclohexyl group.
  • the isocyanate compound used as the crosslinking agent is a compound having an isocyanate derivative structure represented by isocyanate or blocked isocyanate.
  • the isocyanate include aromatic isocyanates such as tolylene diisocyanate, xylylene diisocyanate, methylene diphenyl diisocyanate, phenylene diisocyanate, naphthalene diisocyanate; and aromatic rings such as ⁇ , ⁇ , ⁇ ′, ⁇ ′-tetramethylxylylene diisocyanate.
  • Aliphatic isocyanates such as methylene diisocyanate, propylene diisocyanate, lysine diisocyanate, trimethylhexamethylene diisocyanate, hexamethylene diisocyanate; cyclohexane diisocyanate, methylcyclohexane diisocyanate, isophorone diisocyanate, methylene bis (4-cyclohexyl isocyanate), isopropylidene dicyclohexyl diisocyanate Ne Alicyclic isocyanates such as bets are exemplified.
  • polymers and derivatives such as burettes, isocyanurates, uretdiones, and carbodiimide modified products of these isocyanates are also included. These may be used alone or in combination.
  • isocyanates aliphatic or alicyclic isocyanates are more preferable than aromatic isocyanates in order to avoid yellowing due to ultraviolet rays.
  • the blocking agent When used in the state of blocked isocyanate, the blocking agent includes, for example, bisulfites, phenolic compounds such as phenol, cresol, and ethylphenol, and alcohols such as propylene glycol monomethyl ether, ethylene glycol, benzyl alcohol, methanol, and ethanol.
  • Compounds, active methylene compounds such as dimethyl malonate, diethyl malonate, methyl isobutanoyl acetate, methyl acetoacetate, ethyl acetoacetate, acetylacetone, mercaptan compounds such as butyl mercaptan, dodecyl mercaptan, ⁇ -caprolactam, ⁇ -valerolactam, etc.
  • Lactam compounds amine compounds such as diphenylaniline, aniline, ethyleneimine, acetanilide, acetic acid amide acid amide compounds, Examples include oxime compounds such as rumaldehyde, acetoaldoxime, acetone oxime, methyl ethyl ketone oxime, and cyclohexanone oxime, and these may be used alone or in combination of two or more.
  • an isocyanate compound blocked with an active methylene compound is particularly preferred from the viewpoint of adhesion to a substrate film and wettability to the substrate film.
  • the above isocyanate-based compounds may be used alone or as a mixture or combination with various polymers. In the sense of improving the dispersibility and crosslinkability of the isocyanate compound, it is also preferable to use a mixture or a bond with a polyester resin or a urethane resin.
  • epoxy compound used as the cross-linking agent examples include condensates of epichlorohydrin with ethylene glycol, polyethylene glycol, glycerin, polyglycerin, bisphenol A and other hydroxyl groups and amino groups, such as polyepoxy compounds and diepoxy compounds. Monoepoxy compounds, glycidylamine compounds, and the like.
  • polyepoxy compound examples include sorbitol polyglycidyl ether, polyglycerol polyglycidyl ether, pentaerythritol polyglycidyl ether, diglycerol polyglycidyl ether, triglycidyl tris (2-hydroxyethyl) isocyanate, glycerol polyglycidyl ether, trimethylolpropane.
  • Polyglycidyl ether As the diepoxy compound, for example, neopentyl glycol diglycidyl ether, 1,6-hexanediol diglycidyl ether, resorcin diglycidyl ether, ethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, propylene glycol diglycidyl ether , Polypropylene glycol diglycidyl ether, poly Tetramethylene glycol diglycidyl ether; monoepoxy compounds such as allyl glycidyl ether, 2-ethylhexyl glycidyl ether, phenyl glycidyl ether, and glycidyl amine compounds such as N, N, N ′, N′-tetraglycidyl-m-xyl Examples include range amine and 1,3-bis (N, N-diglycidylamino) cyclohexane.
  • the melamine compound used as the cross-linking agent is a compound having a melamine skeleton in the compound.
  • an alkylolized melamine derivative or an alkylolated melamine derivative is partially or completely etherified by reacting alcohol.
  • Compounds, and mixtures thereof can be used.
  • alcohol used for etherification methyl alcohol, ethyl alcohol, isopropyl alcohol, n-butanol, isobutanol and the like are preferably used.
  • a melamine compound either a monomer or a multimer more than a dimer may be sufficient, or a mixture thereof may be used.
  • the melamine compound contains a hydroxyl group. Further, a product obtained by co-condensing urea or the like with a part of melamine can be used, and a catalyst can be used to increase the reactivity of the melamine compound.
  • the carbodiimide-based compound used as the crosslinking agent is a compound having one or more carbodiimide or carbodiimide derivative structures in the molecule.
  • a polycarbodiimide compound having two or more carbodiimide structures in the molecule is preferred for better strength of the functional layer and the like.
  • the carbodiimide compound used as the crosslinking agent can be synthesized by a conventionally known technique, and generally a condensation reaction of a diisocyanate compound is used.
  • the diisocyanate compound is not particularly limited, and any of aromatic and aliphatic compounds can be used.
  • tolylene diisocyanate, xylene diisocyanate, diphenylmethane diisocyanate, phenylene diisocyanate, naphthalene diisocyanate, hexa examples include methylene diisocyanate, trimethylhexamethylene diisocyanate, cyclohexane diisocyanate, methylcyclohexane diisocyanate, isophorone diisocyanate, dicyclohexyl diisocyanate, and dicyclohexylmethane diisocyanate.
  • a surfactant may be added, or a polyalkylene oxide or a quaternary ammonium salt of a dialkylamino alcohol.
  • Hydrophilic monomers such as hydroxyalkyl sulfonates may be added and used.
  • the silane coupling compound used as the crosslinking agent is an organosilicon compound having a hydrolyzable group such as an organic functional group and an alkoxy group in one molecule.
  • a hydrolyzable group such as an organic functional group and an alkoxy group in one molecule.
  • (Meth) acrylic group-containing compound 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, N-2- (aminoethyl) -3-aminopropyltrimethoxysilane, N-2- (aminoethyl)- 3-aminopropyltriethoxysilane, N-2- (aminoethyl) -3-aminopropylmethyldimethoxysilane, N-2- (aminoethyl) -3-aminopropylmethyldiethoxysilane, 3-triethoxysilyl-N -Amino group-containing compounds such as (1,3-dimethylbutylidene) propylamine, N-phenyl-3-aminopropyltrimethoxysilane, N-phenyl-3-aminopropyltriethoxysilane; Tris (trimethoxysilylpropyl) Isocyan
  • an epoxy group-containing silane coupling compound a double bond-containing silane coupling compound such as a vinyl group or a (meth) acryl group, an amino group More preferred are silane coupling compounds.
  • the crosslinking agent contained in the functional layer usually exists in a state of reacting with the polymer or the crosslinking agent itself in the drying process or the film forming process. Therefore, the functional layer in the present laminated white film 1 exists as an unreacted product of these crosslinking agents, a compound after reaction, or a mixture thereof (compound derived from the crosslinking agent).
  • the lower limit of the content of the crosslinking agent in the functional layer is usually 0% by weight or more, preferably 3% by weight or more, more preferably 5% by weight or more, further preferably 8% by weight or more, and particularly preferably 10% by weight or more.
  • the upper limit is usually 80% by weight or less, preferably 70% by weight or less, more preferably 60% by weight or less, still more preferably 50% by weight or less, and particularly preferably 40% by weight or less.
  • content of a crosslinking agent means the content rate in the non-volatile component in the raw material (coating liquid) before bridge
  • the functional layer may contain particles for improving blocking and slipperiness. Further, the functional layer may contain an antifoaming agent, a coating property improver, a thickener, an organic lubricant, an ultraviolet absorber, an antioxidant, a foaming agent, and the like.
  • the thickness of the functional layer is usually 0.001 to 3 ⁇ m, preferably 0.005 to 1 ⁇ m, more preferably 0.01 to 0.5 ⁇ m, still more preferably 0.02 to 0.3 ⁇ m, and most preferably 0.03. ⁇ 0.2 ⁇ m.
  • the functional layer can be provided on one side of the polyester film as the base material, or can be provided on both sides of the polyester film. When provided on both sides, the film can be used as a recording material on both sides, and there are advantages such as improved handling of the film. In addition, by providing the functional layer on both sides, the curling property due to environmental changes such as temperature and humidity tends to be improved.
  • the surface resistance value is usually 1 ⁇ 10 13 ⁇ or less, preferably 1 ⁇ 10 12 ⁇ or less, more preferably 5 ⁇ 10 11 ⁇ or less, more preferably 1 ⁇ 10 11 ⁇ or less. Particularly preferably, it is 5 ⁇ 10 10 ⁇ or less.
  • the film tends to be effective for preventing sticking between films and preventing adhesion of dust and the like.
  • the recording material for copying paper and printer paper that can transfer toner images suitably by methods such as electrophotography and thermal transfer, prevention of double feeding in paper transportation of copying machines and multifunction devices, It becomes possible to prevent sticking between sheets.
  • blended for each layer is supplied to each melt-extrusion apparatus, and it heat-melts and kneads to the temperature which is more than melting
  • the molten polymer of each layer is then directed and laminated to the die, usually through a multi-manifold or feed block.
  • the molten sheet extruded from the die is rapidly cooled and solidified on the rotary cooling drum so as to have a temperature equal to or lower than the glass transition temperature, thereby obtaining a substantially amorphous unoriented sheet.
  • it is preferable to improve the adhesion between the sheet and the rotary cooling drum and an electrostatic application adhesion method and / or a liquid application adhesion method are preferably employed.
  • the sheet obtained as described above is stretched to form a film. Fine independent cavities contained in the polyester film are generated by such stretching.
  • the stretching conditions will be specifically described.
  • the unstretched sheet is preferably stretched 2.5 to 5 times at 70 to 150 ° C. in the longitudinal direction (longitudinal direction) to form a longitudinally uniaxially stretched film.
  • a longitudinally uniaxially stretched film is stretched 3 to 5 times at 70 to 160 ° C. in the width direction (lateral direction), and is usually 200 to 250 ° C., preferably 210 to 240 ° C., more preferably 215 to 240 ° C.
  • the heat treatment is usually performed for 5 to 600 seconds, preferably 8 to 300 seconds. By adjusting the heat treatment temperature within such a temperature range, the melt viscosity of the polymer incompatible with the polyester can be adjusted, and the roughness of the film surface can be adjusted.
  • the various conditions of the heat treatment step affect not only the heat shrinkage rate of the film but also the arithmetic average roughness (Ra) of the film surface. That is, by setting the temperature within the above range, in the case of a surface or a laminated structure, fine cavities formed by a polymer incompatible with the polyester existing on the surface layer are dissolved. By appropriately reducing the surface roughness, it is possible to easily peel and remove characters and images formed on the film surface by printing. This makes it possible to repeatedly use the film as a recording material for copying paper and printer paper.
  • Ra arithmetic average roughness
  • a method of relaxing 2 to 20% in the longitudinal direction and / or the transverse direction in the maximum temperature zone of the heat treatment and / or the cooling zone at the heat treatment outlet is preferable. Further, it is possible to add re-longitudinal stretching and re-lateral stretching as necessary.
  • the polyester film obtained by the above-described production method has a functional layer laminated on at least one side.
  • the functional layer can be provided by various known methods such as a coating method, a coextrusion method, and a transfer method. Of these, coating is preferred from the viewpoint of efficient production and performance.
  • the coating method examples include gravure coating, reverse roll coating, die coating, air doctor coating, blade coating, rod coating, bar coating, curtain coating, knife coating, transfer roll coating, squeeze coating, impregnation coating, kiss coating, and spray coating.
  • Conventionally known coating methods such as calendar coating and extrusion coating can be used.
  • the functional layer may be provided by in-line coating, which treats the film surface during the process of forming the polyester film, or may employ offline coating that is applied outside the system on the once produced film. Among them, the functional layer is more preferably formed by in-line coating.
  • In-line coating is a method of coating within the process of manufacturing a polyester film, and specifically, a method of coating at any stage from melt extrusion of a polyester to heat setting after stretching and winding up. Usually, it is coated on any of an unstretched sheet obtained by melting and quenching, a stretched uniaxially stretched film, a biaxially stretched film before heat setting, and a film after heat setting and before winding.
  • an unstretched sheet obtained by melting and quenching, a stretched uniaxially stretched film, a biaxially stretched film before heat setting, and a film after heat setting and before winding.
  • a method of stretching in the width direction (lateral direction) after coating a uniaxially stretched film stretched in the longitudinal direction (longitudinal direction) is particularly excellent. According to this method, film formation and functional layer formation can be performed at the same time, so there is an advantage in manufacturing cost.
  • the thickness of the functional layer can be changed by the stretching ratio. Compared to offline coating, thin film coating can be performed more easily.
  • the functional layer can be stretched together with the base film, whereby the functional layer can be firmly adhered to the base film.
  • the film in the production of a biaxially stretched polyester film, the film can be restrained in the longitudinal and lateral directions by stretching while gripping the film end with a clip, etc. High temperature can be applied while maintaining the properties. Therefore, if in-line coating is performed, the heat treatment performed after application can be performed at a high temperature that cannot be achieved by other methods, so that the film-forming property of the functional layer is improved and the functional layer and the base film are made stronger.
  • the functional layer can be made strong, the functional layer can be prevented from falling off, and the antistatic performance and the release performance can be improved.
  • a crosslinking reaction can be performed by the high temperature at the time of heat setting.
  • the functional layer is formed by coating the polyester film with a solution prepared by using the above-described series of compounds as a solution or solvent dispersion and adjusting the solid content concentration to about 0.1 to 80% by weight. It is preferable to produce a laminated white film.
  • a solution prepared by using the above-described series of compounds as a solution or solvent dispersion It is preferable to produce a laminated white film.
  • an aqueous solution or a water dispersion is more preferable.
  • the coating solution may contain a small amount of an organic solvent. Moreover, only one type of organic solvent may be used, and two or more types may be used as appropriate.
  • the drying and curing conditions for forming the functional layer are not particularly limited, but in the case of the coating method, the drying temperature of a solvent such as water used in the coating solution is usually 70 to 150 ° C., preferably Is 80 to 130 ° C, more preferably 90 to 120 ° C.
  • the drying time is generally 3 to 200 seconds, preferably 5 to 120 seconds.
  • a heat treatment step in the range of usually 150 to 270 ° C., preferably 170 to 250 ° C., more preferably 180 to 240 ° C. is performed in the film manufacturing process.
  • the time for the heat treatment step is generally 5 to 600 seconds, preferably 8 to 300 seconds.
  • the polyester film constituting the laminated white film 1 may be subjected to surface treatment such as corona treatment or plasma treatment in advance.
  • the laminated white film 1 can be provided with characters and images containing a thermoplastic resin such as an image forming substance on the functional layer.
  • the character and the image can be provided by a conventionally known method, and can be obtained by printing with a copying machine or a printer.
  • conventionally known materials can also be used for thermoplastic resins used for image forming substances and the like.
  • the image forming substance generally includes all substances capable of forming an image on a recording material, and may have any property such as solid particles, suspension, solution, etc. Ink is also included.
  • the colorant is not limited, and any of pigments, dyes, colored compounds and the like can be used. Among these, a toner in which a pigment is dispersed in a thermoplastic resin to form a fine particle is preferable.
  • the laminated white film 1 can further be provided with a resin layer on the image forming substance or the like or on the functional layer.
  • the main purpose of the resin layer may be to remove characters and images from the film together with the resin layer in order to reuse the laminated white film.
  • the curable resin layer As this resin layer, conventionally known materials can be used, and a curable resin layer formed from a curable resin composition is preferable.
  • the curable resin layer include a thermosetting resin layer made of a resin composition that is cured by heating, an active energy ray curable resin layer made of a resin composition that is cured by irradiation with active energy rays, and the like. Can be mentioned. Among these, the active energy ray-curable resin layer is preferable from the viewpoint that it is easy to peel off and remove all characters and images.
  • the active energy ray curable resin layer examples include an ultraviolet curable resin layer, an electron beam curable resin layer, and a visible light curable resin layer. In view of ease of handling and curable performance, the ultraviolet curable resin layer is preferable.
  • An example of the active energy ray-curable resin layer is a hard coat layer.
  • the material used for the active energy ray-curable resin layer is not particularly limited.
  • examples thereof include cured products such as reactive silicon compounds such as monofunctional (meth) acrylates, polyfunctional (meth) acrylates, and tetraethoxysilane.
  • cured products such as reactive silicon compounds such as monofunctional (meth) acrylates, polyfunctional (meth) acrylates, and tetraethoxysilane.
  • a polymerization cured product of a composition containing an active energy ray-curable (meth) acrylate is particularly preferable.
  • stacking white film it exists in the tendency which can exhibit a favorable peeling removal characteristic by using said material.
  • the composition containing the active energy ray-curable (meth) acrylate is not particularly limited.
  • a known monofunctional (meth) acrylate, a bifunctional (meth) acrylate, a mixture of one or more polyfunctional (meth) acrylates, a commercially available resin material for an active energy ray-curable hard coat, or these In addition to this, what added the other component can be used in the range which does not impair the objective of this embodiment.
  • the active energy ray-curable monofunctional (meth) acrylate is not particularly limited.
  • alkyl (meth) acrylate such as methyl (meth) acrylate, n-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, lauryl (meth) acrylate, stearyl (meth) acrylate, cyclohexyl (meth) acrylate, isobornyl (meth) acrylate, etc.
  • Hydroxyalkyl (meth) acrylate such as meth) acrylate, hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, hydroxybutyl (meth) acrylate, methoxyethyl (meth) acrylate, ethoxyethyl (meth) acrylate, methoxypropyl (meth) ) Acrylate, alkoxyalkyl (meth) acrylate such as ethoxypropyl (meth) acrylate, benzyl (meth) acrylate, phenoxyethyl (meth) Aromatic (meth) acrylates such as acrylate, phenoxypropyl (meth) acrylate, amino group-containing (meth) acrylates such as diaminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate, methoxyethylene glycol (meth) acrylate, phenoxy
  • the active energy ray-curable bifunctional (meth) acrylate is not particularly limited.
  • the active energy ray-curable polyfunctional (meth) acrylate is not particularly limited, and examples thereof include dipentaerythritol hexa (meth) acrylate, pentaerythritol tetra (meth) acrylate, and ditrimethylolpropane tetra (meth) acrylate.
  • Isocyanuric acid modified tri (meth) such as pentaerythritol tri (meth) acrylate, trimethylolpropane tri (meth) acrylate, isocyanuric acid ethylene oxide modified tri (meth) acrylate, ⁇ -caprolactone modified tris (acryloxyethyl) isocyanurate
  • pentaerythritol triacrylate hexamethylene diisocyanate urethane prepolymer pentaerythritol triacrylate toluene diisocyanate Tan prepolymers
  • urethane acrylates such as dipentaerythritol pentaacrylate hexamethylene diisocyanate urethane prepolymer, and the like.
  • composition containing the active energy ray-curable (meth) acrylate are not particularly limited. Examples thereof include inorganic or organic fine particles, polymerization initiators, polymerization inhibitors, antioxidants, antistatic agents, dispersants, surfactants, light stabilizers, and leveling agents.
  • inorganic or organic fine particles include inorganic or organic fine particles, polymerization initiators, polymerization inhibitors, antioxidants, antistatic agents, dispersants, surfactants, light stabilizers, and leveling agents.
  • solvent when the film is dried after film formation in the wet coating method, an arbitrary amount of solvent can be added.
  • the peeling and removing process is usually performed in an office or the like, not in a factory that manufactures the film. For this reason, it is preferable not to contain a solvent for indoor use such as in an office.
  • the resin (resin liquid) for forming the resin layer the content of the solvent is preferably 10% by weight or less, more preferably 5% by weight or less, further preferably 3% by weight or less, and particularly preferably 1% by weight or less. Most preferably, it does not contain a solvent (does not intentionally contain it).
  • Examples of the method for forming the resin layer include a general wet coating method such as a roll coating method and a die coating method, and an extrusion method.
  • the formed resin layer can be subjected to a curing reaction by heating, irradiation with active energy rays such as ultraviolet rays and electron beams as necessary.
  • Second Embodiment As an example of a second embodiment for carrying out the present invention, a laminated white polyester film (also referred to as “laminated white film”) 10 will be described.
  • a laminated white polyester film 10 (referred to as “the present laminated white polyester film 10”) as an example for carrying out the present invention is a laminated film having at least two layers containing polyester as a main component resin. At least the surface layer is characterized by containing polyester and a polymer incompatible with the polyester.
  • the laminated structure of the laminated white polyester film 10 may be a multilayer of two layers, three layers, four layers or more as long as it does not exceed the gist of the present invention, and is not particularly limited. Among these, a three-layer structure (surface layer / intermediate layer / surface layer) composed of both surface layers and an intermediate layer is preferable.
  • a laminated structure is two layers means that it is comprised by two surface layers, and specifically, 2 of the composition from which mixing
  • the surface layer of the laminated white polyester film 10 preferably contains at least a polyester as a main component resin and a polymer incompatible with the polyester.
  • the “main component resin” means a resin having the largest content ratio among the resin components constituting the surface layer. It can be assumed that the main component resin occupies 30% by mass or more, particularly 50% by mass or more, particularly 80% by mass or more (including 100% by mass) of the resin components constituting the surface layer.
  • polyester The polyester constituting the laminated white polyester film 10 is the same as the polyester as the base material in the laminated white film 1 or the polyester as the main component resin of the polyester resin layer.
  • the polyester film stretched at least in a uniaxial direction can contain innumerable fine cavities. Due to the fine cavities, the laminated white polyester film 10 not only scatters light and causes white opacity, but also reduces the apparent density of the laminated white polyester film 10.
  • the surface layer of the laminated white polyester film 10 contains a polymer that is incompatible with polyester, so that the toner printed on the surface of the laminated white polyester film 10 when used as a recording material for copying paper or printer paper, etc.
  • the image forming substance containing the thermoplastic resin can be easily peeled and removed.
  • a polymer incompatible with the polyester may be contained in the intermediate layer as necessary.
  • the polymer incompatible with the polyester is the same as the “polymer incompatible with the polyester” described in the laminated white film 1 described above.
  • the lower limit of the content of the “polyester incompatible polymer” in the surface layer of the laminated white polyester film 10 is usually 1% by weight or more, preferably 2% by weight or more, more preferably 3% by weight or more, and further preferably 5%. % By weight or more, particularly preferably 8% by weight or more.
  • the film surface it becomes easy to peel off and remove characters and images from printed image forming substances and the like, and there is a tendency that the film can be repeatedly used as a recording material for copying paper or printer paper.
  • the upper limit of the content of the polymer incompatible with the polyester in the surface layer is usually 70% by weight or less, preferably 50% by weight or less, more preferably 40% by weight or less, still more preferably 35% by weight or less, particularly preferably. 30% by weight or less, most preferably 25% by weight or less. By using in this range, the amount of cavities to be generated is not too large, and there is a tendency to easily suppress breakage during stretching.
  • the lower limit of the content of the “polyester incompatible with polyester” in each layer of the laminated white polyester film 10 is usually 1% by weight or more, preferably 2% by weight or more, more preferably 3% by weight or more, and further preferably. Is 5% by weight or more, particularly preferably 8% by weight or more. By using it in the above range, it has sufficient concealing property, and the effect of reducing the apparent density, that is, the weight reduction can be sufficient.
  • the upper limit of the content of the polymer incompatible with the polyester in each layer of the laminated white polyester film 10 is usually 70% by weight or less, preferably 50% by weight or less, more preferably 40% by weight or less, and further preferably 35% by weight. % Or less, particularly preferably 30% by weight or less, and most preferably 25% by weight or less. By using in this range, the amount of cavities to be generated is not too large, and there is a tendency to easily suppress breakage during stretching.
  • the intermediate layer is a range that does not impair the gist of the present invention, such as an ear part, a master roll ear part, and a master roll lower winding part generated during film production. You may mix with.
  • the inclusion of recycled products has the effect of reducing costs and reducing environmental impact.
  • the content of the recycled product in the intermediate layer is preferably 95% by weight or less, more preferably 85% by weight or less with respect to the intermediate layer from the viewpoint of film formation stability due to a decrease in intrinsic viscosity in addition to color tone regulation. More preferably, it is 70% by weight or less, particularly preferably 60% by weight or less, most preferably 40% by weight or less.
  • the laminated white polyester film 10 may contain metal compound particles for the purpose of further improving the concealability and whiteness.
  • the layer containing the metal compound particles may be a surface layer or an intermediate layer. In order to effectively improve the concealability and whiteness, it is preferably contained in the surface layer.
  • the metal compound particles used in the laminated white polyester film 10 tend to compensate for the white opacity due to the light scattering effect generated by fine cavities by blending incompatible polymers. It tends to get a degree.
  • the metal compound particles are the same as the metal compound particles described in the laminated white film 1.
  • the lower limit of the content of the metal compound particles is preferably 1% by weight or more, more preferably 2% by weight or more, and further preferably 3% by weight with respect to the entire surface layer of the laminated white polyester film 10 containing the metal compound particles.
  • the upper limit is usually 30% by weight or less, preferably 20% by weight or less, more preferably 15% by weight or less, still more preferably 13% by weight or less, and particularly preferably 10% by weight or less.
  • the surface layer of the present laminate white polyester film 10 includes particles other than the metal compound particles exemplified above for imparting slipperiness. It may be.
  • the particles other than the metal compound particles are the same as the “particles other than the metal compound particles” described in the laminated white film 1.
  • antioxidants in addition to the above-described particles and polymers incompatible with polyester, conventionally known antioxidants, heat stabilizers, lubricants, antistatic agents, fluorescent whitening agents, Dyes, pigments and the like can be added. Further, depending on the use, an ultraviolet absorber, particularly a benzoxazinone-based ultraviolet absorber may be contained.
  • the laminated white polyester film 10 is a laminated film having at least two layers containing polyester as a main component resin, and at least a surface layer of the laminated white polyester film 10 contains a polyester and a polymer incompatible with the polyester.
  • the arithmetic average roughness (Ra) of the surface layer is preferably 950 nm or less. If the surface layer contains polyester and a polymer that is incompatible with the polyester as described above, a fine cavity can be provided by stretching, so that weight reduction, concealability, and whitening can be realized. Since the surface roughness can be further adjusted, the writing property can be improved.
  • the surface layer further contains metal compound particles, the hiding property and whiteness can be further increased, and the slipperiness can be improved by containing particles other than the metal compound particles.
  • the intermediate layer other than the surface layer contains the polyester, a polymer incompatible with the polyester, metal compound particles, and particles other than the metal compound particles may be contained as necessary. It is preferable from the viewpoint of cost reduction and environmental load reduction that the content of the metal compound particles and particles other than the metal compound particles is made as small as possible, and the recycled polyester is used.
  • the thickness of the laminated white polyester film 10 is not particularly limited as long as it can be formed as a film.
  • the thickness is preferably 10 to 1000 ⁇ m, more preferably 20 to 500 ⁇ m, even more preferably 30 to 400 ⁇ m, and particularly preferably 38 to 350 ⁇ m. By using in the said range, it becomes possible to make the firmness and handleability of a film sufficient.
  • the metal compound particles and particles other than the metal compound particles are preferably contained in the surface layer.
  • the thickness of each surface layer is preferably 1 ⁇ m to 50 ⁇ m, especially 2 ⁇ m or more or 40 ⁇ m or less, especially 3 ⁇ m or more or 30 ⁇ m.
  • the thickness is more preferably 4 ⁇ m or more or 25 ⁇ m or less.
  • the lower limit of the apparent density of the laminated white polyester film 10 is usually 0.7 g / cm 3 or more, preferably 0.75 g / cm 3 or more, more preferably 0.8 g / cm 3 or more.
  • the strength of the film can be maintained, and clogging of the film in the transport process in the copying machine when used as a recording material in place of copying paper or printer paper as an information printing medium can be reduced. This makes it possible to perform optimal printing.
  • the upper limit is usually 1.3 g / cm 3 or less, preferably 1.2 g / cm 3 or less, more preferably 1.1 g / cm 3 or less.
  • the apparent density of the polyester film can be adjusted by blending an incompatible polymer having a specific gravity lighter than that of the polyester as the main component resin and stretching in at least a uniaxial direction. However, it is not limited to these methods.
  • the arithmetic average roughness (Ra) of the surface that is, the surface layer of the laminated white polyester film 10 is preferably 950 nm or less, more preferably 850 nm or less, and particularly preferably 800 nm or less.
  • the arithmetic average roughness (Ra) within the above range, characters and images such as image forming substances containing thermoplastic resin formed on the film surface by printing can be easily peeled and removed. Tends to be repeatedly used as a recording material for copying paper and printer paper.
  • the lower limit of the arithmetic average roughness (Ra) is preferably 100 nm or more, more preferably 200 nm or more, more preferably 300 nm or more, and particularly preferably 350 nm or more.
  • the arithmetic mean roughness (Ra) in this invention shall be based on the measuring method used in the Example mentioned later.
  • the b value (reflection method) which is an index representing the yellowness of the laminated white polyester film 10 is usually 0.00 or less, preferably ⁇ 0.20 or less, more preferably ⁇ 0.40 or less, and further preferably ⁇ 0. .50 or less, particularly preferably ⁇ 0.60 or less, and the lower limit is not particularly limited, but is preferably ⁇ 5.0 or more. By using in the said range, yellowness can be suppressed and whiteness can be made favorable. Further, when used as a recording material for color printing, the obtained image quality tends to be excellent.
  • the heat shrinkage in the film longitudinal direction (MD) and the film width direction (TD) at 150 ° C. for 30 minutes is usually 2.8% or less, preferably 2.3% or less as an absolute value. More preferably, it is 2.0% or less. If the heat shrinkage is in the above range, it is possible to prevent the dimensional stability of the film from being impaired due to the influence of heat when printing on a recording material by a method such as an electrophotographic method or a thermal transfer method. Even at the edge of the (sheet), that is, the portion where wrinkles are likely to occur, the generation of wrinkles can be suppressed, and the phenomenon of distortion and unevenness in characters and images can be suppressed and image quality can be reduced. It becomes possible. In addition, since wrinkles cannot be erased once they occur, they cannot be repeatedly used as a recording material for copying paper or printer paper, and therefore it is preferable that wrinkles are not generated as much as possible.
  • the concealability (OD) of the present laminated white polyester film 10 is usually 0.30 or more, preferably 0.35 or more, more preferably 0.40 or more, even more preferably, when a single film is measured with a Macbeth densitometer. 0.45 or more. By using it in the above range, the show-through when the entire surface is printed on both sides of the film is reduced, and high quality characters and images can be obtained.
  • the upper limit of the concealability (OD) is not particularly limited, but considering the balance of other physical properties, 1.0 or less is preferable, and 0.9 or less is more preferable.
  • the whiteness of the laminated white polyester film 10 is determined by measuring the Hunter whiteness (Wb) when the film is a single sheet with a colorimeter, and the lower limit is usually 80.0% or more, preferably 81.0% or more. Preferably it is 82.0% or more, More preferably, it is 83.0% or more, Most preferably, it is 83.5% or more.
  • Wb Hunter whiteness
  • the upper limit is not particularly limited.
  • the upper limit of the preferred range is 95.0% or less.
  • a functional layer may be provided on at least one side of the laminated white polyester film 10.
  • This functional layer can serve as a recording layer on which the image forming substance adheres directly to the layer surface, for example.
  • the recording layer in the present invention is a layer that not only fixes the attached image forming substance but also has a role of removing the image forming substance together with the resin layer when a resin layer described later is provided.
  • the functional layer preferably has antistatic performance and release performance.
  • the laminated white polyester film 10 has a reduced apparent density, can be whitened without cost, and can easily peel and remove characters and images such as image forming substances containing a printed thermoplastic resin. It is preferable to provide a polyester resin layer containing polyester and a polymer incompatible with polyester, and it is more preferable that the polyester resin layer has a surface layer. However, when a functional layer is provided, it has been found that it tends to be difficult to express the ability to easily peel and remove characters and images such as image forming substances on the surface layer. It is preferable that performance is also provided. That is, the functional layer is provided in order to provide a release performance so that characters and image forming substances such as toner containing a thermoplastic resin formed on the film surface can be suitably peeled and removed after printing. Preferably contains a release agent.
  • This laminated white polyester film 10 is used as a recording material for copying paper and printer paper that can transfer a toner image suitably by a system such as an electrophotographic system or a thermal transfer system, and prevents double feeding in the paper transport of a copier / multifunction machine.
  • the purpose is to prevent sticking between sheets when handling the sheets.
  • the functional layer has an antistatic performance in order to prevent the adhesion of dust and to obtain a high-quality film or a high-quality film print. From this viewpoint, it is preferable to have a functional layer containing an antistatic agent on at least one side.
  • the functional layer is a polymer (antistatic agent described above). It is further preferable to contain a polymer other than the release agent.
  • the antistatic agent, release agent and polymer used in the laminated white polyester film 10 are the same as the antistatic agent, release agent and polymer used in the laminated white film 1.
  • this laminated polyester film has the said functional layer, about the preferable value range of b value of this laminated polyester film, heat shrinkage rate, concealability (OD), and whiteness, it is the same as the above-mentioned numerical range. .
  • raw materials blended for each layer which are dried or not dried by a known method are supplied to each melt-extrusion apparatus, heated to a temperature equal to or higher than the melting point of each polymer, and melt-kneaded.
  • the molten polymer of each layer is then directed and laminated to the die, usually through a multi-manifold or feed block.
  • the molten sheet extruded from the die is rapidly cooled and solidified on the rotary cooling drum so as to have a temperature equal to or lower than the glass transition temperature, thereby obtaining a substantially amorphous unoriented sheet.
  • an electrostatic application adhesion method and / or a liquid application adhesion method are preferably employed.
  • the sheet obtained as described above is stretched to form a film. Fine independent cavities contained in the polyester film are generated by such stretching.
  • the unstretched sheet is preferably stretched 2.5 to 5 times at 70 to 150 ° C. in the longitudinal direction (longitudinal direction) to form a longitudinally uniaxially stretched film, and then the width direction ( The film is stretched 3 to 5 times in the transverse direction at 70 to 160 ° C., usually in the range of 200 to 250 ° C., preferably 210 to 240 ° C., more preferably 215 to 240 ° C., usually 5 to 600 seconds, preferably 8 It is preferable to perform a heat treatment for up to 300 seconds.
  • the conditions of the heat treatment step affect not only the heat shrinkage rate of the film but also the arithmetic average roughness (Ra) of the surface layer of the film. That is, by setting the temperature within the above range, fine cavities formed by a polymer incompatible with the polyester present on the surface of the surface layer are dissolved. By appropriately reducing the surface roughness, it is possible to easily peel and remove characters and images such as an image forming substance containing a thermoplastic resin formed on the film surface by printing. This makes it possible to repeatedly use the film as a recording material for copying paper and printer paper.
  • Ra arithmetic average roughness
  • a method of relaxing 2 to 20% in the longitudinal direction and / or the transverse direction in the maximum temperature zone of the heat treatment and / or the cooling zone at the heat treatment outlet is preferable. Further, it is possible to add re-longitudinal stretching and re-lateral stretching as necessary.
  • the functional layer can be provided by various known methods such as a coating method, a coextrusion method, and a transfer method. Among them, the coating method is preferable from the viewpoint of efficient production and imparting performance.
  • the film surface may be provided by in-line coating, which is processed during the process of forming the polyester film, or off-line coating may be employed that is applied outside the system on the manufactured film. . More preferably, it is formed by in-line coating.
  • In-line coating is a method of coating in the process of manufacturing a polyester film, and specifically, a method of coating at an arbitrary stage from melt-extrusion of polyester to heat-fixing and winding after stretching. Usually, it is coated on any of an unstretched sheet obtained by melting and quenching, a stretched uniaxially stretched film, a biaxially stretched film before heat setting, and a film after heat setting and before winding.
  • an unstretched sheet obtained by melting and quenching, a stretched uniaxially stretched film, a biaxially stretched film before heat setting, and a film after heat setting and before winding.
  • a method of stretching in the transverse direction after coating a uniaxially stretched film stretched in the longitudinal direction (longitudinal direction) is particularly excellent. According to this method, film formation and functional layer formation can be performed at the same time, so there is an advantage in manufacturing cost.
  • the thickness of the functional layer can be changed by the stretching ratio. Compared to offline coating, thin film coating can be performed more easily.
  • the functional layer can be stretched together with the base film, whereby the functional layer can be firmly adhered to the base film.
  • the film can be restrained in the longitudinal and lateral directions by stretching while gripping the film end with a clip, etc. High temperature can be applied while maintaining the properties. Therefore, since the heat treatment performed after coating can be performed at a high temperature that cannot be achieved by other methods, the film forming property of the functional layer can be improved, and the functional layer and the base film can be more firmly adhered to each other.
  • the functional layer can be made strong, preventing the functional layer from falling off, and improving the antistatic performance and the release performance.
  • Characters and images containing a thermoplastic resin such as an image-forming substance can be provided on the surface of the laminated white polyester film 10 where the functional layer is not provided or on the surface provided with the functional layer. It is. Characters and images can be provided by a conventionally known method, and can be obtained by printing with a copying machine or a printer. Moreover, conventionally well-known materials can be used also about thermoplastic resins, such as an image forming substance.
  • the laminated white polyester film 10 can further be provided with a resin layer on characters and images containing a thermoplastic resin such as an image forming substance.
  • the main purpose of the resin layer may be to remove characters and images from the film together with the resin layer in order to reuse the laminated white polyester film.
  • a conventionally well-known material can be used as a resin layer, and it is preferable that it is a curable resin layer.
  • the curable resin layer include a thermosetting resin layer and an active energy ray curable resin layer.
  • An active energy ray-curable resin layer is preferable from the viewpoint of easy separation and removal without leaving characters and images.
  • the active energy ray curable resin layer examples include an ultraviolet curable resin layer, an electron beam curable resin layer, and a visible light curable resin layer. In view of ease of handling and curable performance, the ultraviolet curable resin layer is preferable.
  • An example of the active energy ray-curable resin layer is a hard coat layer.
  • a material used for an active energy ray curable resin layer For example, hardened
  • reactive silicon compounds such as monofunctional (meth) acrylate, polyfunctional (meth) acrylate, and tetraethoxysilanecan be mentioned.
  • a polymerization cured product of a composition containing an active energy ray-curable (meth) acrylate is particularly preferable.
  • the composition containing the active energy ray-curable (meth) acrylate is not particularly limited.
  • a mixture of one or more known active energy ray-curable monofunctional (meth) acrylates, bifunctional (meth) acrylates, polyfunctional (meth) acrylates, and commercially available as an active energy ray-curable hard coat resin material In addition, those other than these may be used as long as the object of the present embodiment is not impaired.
  • the active energy ray-curable monofunctional (meth) acrylate is not particularly limited.
  • alkyl such as methyl (meth) acrylate, n-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, lauryl (meth) acrylate, stearyl (meth) acrylate, cyclohexyl (meth) acrylate, isobornyl (meth) acrylate, etc.
  • Hydroxyalkyl (meth) acrylate such as (meth) acrylate, hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, hydroxybutyl (meth) acrylate, methoxyethyl (meth) acrylate, ethoxyethyl (meth) acrylate, methoxypropyl ( Alkoxyalkyl (meth) acrylates such as meth) acrylate and ethoxypropyl (meth) acrylate, benzyl (meth) acrylate, phenoxyethyl (meth) ) Aromatic (meth) acrylates such as acrylate, phenoxypropyl (meth) acrylate, amino group-containing (meth) acrylates such as diaminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate, methoxyethylene glycol (meth) acrylate, phen
  • the active energy ray-curable bifunctional (meth) acrylate is not particularly limited.
  • the active energy ray-curable polyfunctional (meth) acrylate is not particularly limited.
  • composition containing the active energy ray-curable (meth) acrylate are not particularly limited. Examples thereof include inorganic or organic fine particles, polymerization initiators, polymerization inhibitors, antioxidants, antistatic agents, dispersants, surfactants, light stabilizers, and leveling agents.
  • inorganic or organic fine particles include inorganic or organic fine particles, polymerization initiators, polymerization inhibitors, antioxidants, antistatic agents, dispersants, surfactants, light stabilizers, and leveling agents.
  • solvent when the film is dried after film formation in the wet coating method, an arbitrary amount of solvent can be added.
  • the content of the solvent is preferably 10% by weight or less, more preferably 5% by weight or less, further preferably 3% by weight or less, and particularly preferably 1% by weight or less. Most preferably, the solvent is not contained (not intentionally contained).
  • Examples of the method for forming the resin layer include a general wet coating method such as a roll coating method and a die coating method, and an extrusion method.
  • the formed resin layer can be subjected to a curing reaction by heating, irradiation with active energy rays such as ultraviolet rays and electron beams as necessary.
  • the present invention is not limited to the following examples unless it exceeds the gist.
  • the measuring method used in the present invention is as follows.
  • the various physical property in this invention, its measuring method, and a definition are as follows.
  • MFI Melt flow index
  • the particle size was measured by a sedimentation method based on Stokes' resistance law using a centrifugal sedimentation type particle size distribution analyzer SA-CP3 manufactured by Shimadzu Corporation.
  • the average particle diameter was determined by using a value of 50% of integration (volume basis) in the equivalent spherical distribution of particles obtained by measurement.
  • Heat shrinkage rate (%) ⁇ (L0 ⁇ L1) / L0 ⁇ ⁇ 100 (In the above formula, L0 is the sample length before the heat treatment, L1 is the sample length after the heat treatment) Five points were measured in the film longitudinal direction (MD) and the width direction (TD), and the average value in each direction was determined.
  • MFP A full-color test image on which an A4 size cut film (sheet) is fed to imagino MPC5001it and image forming substances are placed by photographic printing. Obtained. Image quality was evaluated as follows.
  • MFP A film of the MFP when 100 sheets of A4 size cut film (sheet) are fed to imgioMPC5001it and 100 sheets are continuously printed by photographic printing. (Sheet) The transportability was evaluated as follows.
  • Example 1 group As examples of the first embodiment, examples 1-1 to 1-69 and comparative examples 1-1 to 1-2 will be described.
  • Antistatic agent (compound having ammonium group): (IB) A polymer compound having a number average molecular weight of 50000, wherein the counter ion is a methanesulfonic acid ion, comprising a structural unit of the following formula (2).
  • Releasing agent long chain alkyl group-containing compound: (IIA) 200 parts by weight of xylene and 600 parts by weight of octadecyl isocyanate were added to a four-necked flask and heated with stirring. From the time when xylene began to reflux, 100 parts by weight of polyvinyl alcohol having an average polymerization degree of 500 and a saponification degree of 88 mol% was added in small portions over a period of about 2 hours. After the addition of polyvinyl alcohol, the reaction was completed by further refluxing for 2 hours. When the reaction mixture was cooled to about 80 ° C. and added to methanol, the reaction product was precipitated as a white precipitate.
  • This precipitate was filtered off, and 140 parts by weight of xylene was added and heated to dissolve completely. Then, the operation of adding methanol again to cause precipitation was repeated several times, and then the precipitate was washed with methanol and dried and ground.
  • ⁇ Release agent (wax) (IIC) An emulsification facility with an internal capacity of 1.5 L equipped with a stirrer, thermometer, temperature controller, melting point 105 ° C., acid value 16 mgKOH / g, density 0.93 g / mL, number average molecular weight 5000 polyethylene oxide wax 300 g, ion-exchanged water 650 g 50 g of decaglycerin monooleate surfactant and 10 g of 48 wt% potassium hydroxide aqueous solution were added and replaced with nitrogen, sealed, stirred at 150 ° C. for 1 hour at high speed, cooled to 130 ° C., and the high-pressure homogenizer at 400 atm. A wax emulsion that has been passed through and cooled to 40 ° C.
  • Block polyisocyanate with active methylene obtained by adding 58.9 parts by weight of n-butanol and maintaining the reaction solution temperature at 80 ° C. for 2 hours and then adding 0.86 parts by weight of 2-ethylhexyl acid phosphate.
  • Example 1-1 Main vented biaxial with 80 parts by weight of a polyethylene terephthalate chip having an intrinsic viscosity of 0.67 dl / g and 20 parts by weight of a crystalline polypropylene homopolymer chip having a melt flow index of 10 ml / 10 min. Crystal in an extruder containing 15 parts by weight of a polyethylene terephthalate chip having an intrinsic viscosity of 0.66 dl / g and containing 50% by weight of titanium oxide particles having an average particle diameter of 0.32 ⁇ m for the surface layer, and a melt flow index of 8 ml / 10 min.
  • the two layers and three layers are co-extruded from the die. Extrusion and rapid solidification on a cooling roll having a surface temperature set at 30 ° C. using an electrostatic application adhesion method, yielding a substantially amorphous sheet having a thickness of 887 ⁇ m.
  • the obtained amorphous sheet was stretched 3.1 times in the longitudinal direction at 92 ° C., and then the aqueous coating solution 1 shown in Table 7 below was applied to both sides of the longitudinally stretched film with the thickness of the functional layer (after drying).
  • a laminated white film having a thickness of 74 ⁇ m was obtained with a thickness of (surface layer) / 62 ⁇ m (intermediate layer) / 6 ⁇ m (surface layer).
  • the image quality suitability, the characters, the image peeling / removal suitability, the print transportability, the writing property, and the functional layer appearance were all good.
  • the characteristics of this film are shown in Tables 4 and 8 below.
  • Examples 1-2 to 1-4 A laminated white film was obtained in the same manner as in Example 1-1 except that the thickness of the functional layer (after drying) was changed as shown in Table 1. As shown in Tables 4 and 8 below, the obtained laminated white film had good image quality and good writing properties.
  • Examples 1-5 to 1-14 A laminated white film was obtained in the same manner as in Example 1-1 except that the composition of the functional layer was changed.
  • the production conditions in each example are shown in Table 1 below, and the coating solution composition of the functional layer is shown in Table 7 below.
  • Tables 4 and 8 below the obtained polyester film had good image quality and good writing properties.
  • Example 1-15 40 parts by weight of a polyethylene terephthalate chip having an intrinsic viscosity of 0.63 dl / g, 15 parts by weight of a crystalline polypropylene homopolymer chip having a melt flow index of 7 ml / 10 minutes, and ears and masters produced during the production of the polyester of Example 1-1
  • a laminated white film having a thickness of 75 ⁇ m was obtained in the same manner as in Example 1-1, except that the mixed raw material obtained by mixing the recycled product from the roll ear portion at a ratio of 45% by weight was used as the intermediate layer.
  • the thickness of each layer of the obtained film was 6 ⁇ m / 63 ⁇ m / 6 ⁇ m.
  • the total amount of polypropylene derived from the crystalline polypropylene homopolymer chip and the recycled product in the intermediate layer is 24% by weight.
  • Examples 1-16 to 1-18 A laminated white film was obtained in the same manner as in Example 1-15 except that the functional layer thickness (after drying) was changed as shown in Table 1. As shown in Tables 4 and 8 below, the obtained laminated white film had good image quality and good writing properties.
  • Examples 1-19 to 1-27 A laminated white film was obtained in the same manner as in Example 1-15 except that the composition of the functional layer was changed.
  • the production conditions in each example are shown in Table 1 below, and the coating solution composition of the functional layer is shown in Table 7 below.
  • Tables 4 and 8 below the obtained polyester film was good in image quality suitability, character, image peeling / removal suitability, print transportability, and writing property.
  • Example 1-28 3 parts by weight of a polyethylene terephthalate chip having an intrinsic viscosity of 0.66 dl / g, 10 parts by weight of a crystalline polypropylene homopolymer chip having a melt flow index of 10 ml / 10 minutes, and ears and masters produced during the production of the polyester of Example 1-1
  • a laminated white film having a thickness of 75 ⁇ m was obtained in the same manner as in Example 1-1 except that the mixed material obtained by mixing the recycled product from the roll ear part at a ratio of 87% by weight was used as the intermediate layer.
  • the thickness of each layer of the obtained film was 6 ⁇ m / 63 ⁇ m / 6 ⁇ m.
  • Examples 1-29 to 1-31 A laminated white film was obtained in the same manner as in Example 1-28 except that the functional layer thickness (after drying) was changed as shown in Table 1. As shown in Tables 4 and 8 below, the obtained laminated white film had good image quality and good writing properties.
  • Examples 1-32 to 1-40 A laminated white film was obtained in the same manner as in Example 1-28, except that the composition of the functional layer was changed.
  • the production conditions in each example are shown in Table 1 below, and the coating solution composition of the functional layer is shown in Table 7 below.
  • Tables 4 and 8 below the obtained polyester film had good characters, proper image peeling and removal, printing transportability, and writing properties.
  • Example 1-41 A crystalline polypropylene homopolymer chip containing 15% by weight of a polyethylene terephthalate chip containing 50% by weight of titanium oxide particles having an average particle diameter of 0.32 ⁇ m and an intrinsic viscosity of 0.65 dl / g, and a melt flow index of 8 ml / 10 min.
  • a laminated white film having a thickness of 75 ⁇ m was obtained in the same manner as in Example 1-15 except that 82.1 parts by weight of the terephthalate chip was used as the surface layer.
  • the thickness of each layer of the obtained film was 6 ⁇ m / 63 ⁇ m / 6 ⁇ m.
  • Examples 1-42 to 1-44 A laminated white film was obtained in the same manner as in Example 1-41 except that the thickness of the functional layer (after drying) was changed as shown in Table 2. The obtained laminated white film had good image quality and good writing properties as shown in Tables 5 and 9 below.
  • Examples 1-45 to 1-53 A laminated white film was obtained in the same manner as in Example 1-41 except that the composition of the functional layer was changed.
  • the production conditions in each Example are shown in Table 2 below, and the coating solution composition of the functional layer is shown in Table 7 below.
  • Tables 5 and 9 below the obtained polyester film had good image quality, characters, image peeling / removal suitability, and print transportability.
  • Example 1-54 A crystalline polypropylene homopolymer chip containing 15% by weight of a polyethylene terephthalate chip containing 50% by weight of titanium oxide particles having an average particle size of 0.32 ⁇ m and an intrinsic viscosity of 0.65 dl / g, and a melt flow index of 8 ml / 10 min.
  • a laminated white film having a thickness of 75 ⁇ m was obtained in the same manner as in Example 1-15 except that 74.5 parts by weight was used as the surface layer and the coating solution was applied only on one side in the coating process after longitudinal stretching.
  • the thickness of each layer of the obtained film was 6 ⁇ m / 63 ⁇ m / 6 ⁇ m.
  • Example 1-55 15 parts by weight of a polyethylene terephthalate chip having an intrinsic viscosity of 0.66 dl / g containing 50% by weight of titanium oxide particles having an average particle diameter of 0.12 ⁇ m, and 15 parts by weight of a crystalline polypropylene homopolymer chip having a melt flow index of 8 ml / 10 minutes 10 parts by weight of polyethylene terephthalate chip having an intrinsic viscosity of 0.66 dl / g containing 3.5% by weight of silica particles having an average particle diameter of 4.1 ⁇ m and 60 weight of polyethylene terephthalate chip having an intrinsic viscosity of 0.69 dl / g
  • a laminated white film having a thickness of 75 ⁇ m was obtained in the same manner as in Example 1-15 except that the content of The thickness of each layer of the obtained film was 6 ⁇ m / 63 ⁇ m / 6 ⁇ m. When the obtained laminated white film was evaluated, characters and image peeling and removal were appropriate, and print
  • Examples 1-56 to 1-58 A laminated white film was obtained in the same manner as in Example 1-55 except that the functional layer thickness (after drying) was changed as shown in Table 2. The obtained laminated white film had good image quality and good writing properties as shown in Tables 5 and 9 below.
  • Examples 1-59 to 1-67 A laminated white film was obtained in the same manner as in Example 1-55 except that the composition of the functional layer was changed.
  • the production conditions in each Example are shown in Table 2 below, and the coating solution composition of the functional layer is shown in Table 7 below.
  • Tables 5 and 9 below the obtained polyester film was suitable for character and image peeling removal, and had good print transportability and writing property.
  • Example 1-68 15 parts by weight of a polyethylene terephthalate chip having an intrinsic viscosity of 0.66 dl / g, containing 50% by weight of titanium oxide particles having an average particle size of 0.32 ⁇ m, and 15 parts by weight of a crystalline polypropylene homopolymer chip having a melt flow index of 8 ml / 10 minutes
  • Example 1-15 except that 70 parts by weight of a polyethylene terephthalate chip having an intrinsic viscosity of 0.66 dl / g containing 5.0% by weight of silica particles having an average particle diameter of 11.1 ⁇ m was used as the surface layer.
  • a laminated white film having a thickness of 75 ⁇ m was obtained.
  • each layer of the obtained film was 6 ⁇ m / 63 ⁇ m / 6 ⁇ m.
  • the image quality suitability, print transportability, writing property and functional layer appearance were all good.
  • the characteristics of this film are shown in Tables 5 and 9 below.
  • Example 1-69 A laminated white film having a thickness of 75 ⁇ m and a thickness of each layer of 6 ⁇ m / 63 ⁇ m / 6 ⁇ m in the same manner as in Example 1-15, except that the heat treatment temperature in the film forming step was 201 ° C. for 10 seconds. Got. When the obtained laminated white film was evaluated, the print transportability, writing property, and functional layer appearance were all good. The characteristics of this film are shown in Tables 5 and 9 below.
  • Example 1-1 A polyester film was obtained in the same manner as in Example 1-1 except that in Example 1-1, a polyethylene terephthalate chip was used instead of the crystalline polypropylene homopolymer chip and no functional layer was provided. As shown in Tables 6 and 10, the obtained polyester film had poor image quality, character, image peeling / removal suitability, print transportability, and writing property.
  • Comparative Example 1-2 A laminated white film was obtained in the same manner as in Example 1-1 except that the composition of the functional layer was changed.
  • the production conditions of Comparative Example 1-2 are shown in Table 3 below, and the coating solution composition of the functional layer is shown in Table 7 below.
  • Tables 6 and 10 below the obtained polyester film was poor in image quality suitability and print transportability.
  • Example 2 group As examples of the second embodiment, examples 2-1 to 2-6 and comparative examples 2-1 to 2-2 will be described.
  • Example 2-1 As an intermediate layer, a mixed raw material obtained by mixing 80 parts by weight of a polyethylene terephthalate chip having an intrinsic viscosity of 0.67 dl / g and 20 parts by weight of a crystalline polypropylene homopolymer chip having a melt flow index of 10 ml / 10 minutes is 280 ° C. Was sent to the main vented twin screw extruder.
  • the two layers and three layers are co-extruded from the die.
  • the obtained unstretched sheet was stretched 3.1 times at 92 ° C. in the machine direction, guided to a tenter, and then stretched 3.8 times at 120 ° C. in the transverse direction, and then heat treated at 235 ° C. for 10 seconds.
  • a biaxially oriented laminated white polyester film having a thickness of 6 ⁇ m (surface layer) / 62 ⁇ m (intermediate layer) / 6 ⁇ m (surface layer) and a total thickness of 74 ⁇ m was obtained by relaxing 10% in the lateral direction.
  • the image quality suitability, characters, image peeling removal suitability, and writing property were all good.
  • the characteristics of this film are shown in Tables 12 and 13 below.
  • Example 2-2 As an intermediate layer, 40 parts by weight of a polyethylene terephthalate chip having an intrinsic viscosity of 0.63 dl / g, 15 parts by weight of a crystalline polypropylene homopolymer chip having a melt flow index of 7 ml / 10 min, and the polyester of Example 2-1 were produced.
  • the thickness of each layer of the obtained film was 6 ⁇ m / 63 ⁇ m / 6 ⁇ m.
  • the total amount of the polypropylene derived from the crystalline polypropylene homopolymer chip and the recycled product in the intermediate layer was 24% by weight.
  • the image quality suitability, characters, image peeling removal suitability, and writing property were all good.
  • the characteristics of this film are shown in Tables 12 and 13 below.
  • Example 2-3 As an intermediate layer, 3 parts by weight of a polyethylene terephthalate chip having an intrinsic viscosity of 0.66 dl / g, 10 parts by weight of a crystalline polypropylene homopolymer chip having a melt flow index of 10 ml / 10 min, and when producing the polyester of Example 2-1.
  • the thickness of each layer of the obtained film was 6 ⁇ m / 63 ⁇ m / 6 ⁇ m.
  • Example 2-4 As a surface layer, a crystalline polypropylene homopolymer having 15 parts by weight of a polyethylene terephthalate chip having an intrinsic viscosity of 0.66 dl / g and containing 50% by weight of titanium oxide particles having an average particle diameter of 0.12 ⁇ m and a melt flow index of 8 ml / 10 min.
  • a biaxially oriented laminated white polyester film having a thickness of 75 ⁇ m was obtained in the same manner as in Example 2-1, except that a mixed raw material mixed at a ratio of 60 parts by weight of the chip was used.
  • the thickness of each layer of the obtained film was 6 ⁇ m / 63 ⁇ m / 6 ⁇ m.
  • Example 2-5 As a surface layer, a crystalline polypropylene homopolymer containing 15 parts by weight of a polyethylene terephthalate chip having an average viscosity of 0.66 dl / g containing 50% by weight of titanium oxide particles having an average particle diameter of 0.32 ⁇ m and a melt flow index of 8 ml / 10 min.
  • a biaxially oriented laminated white polyester film having a thickness of 74 ⁇ m was obtained in the same manner as in Example 2-2 except that a mixed raw material in which polyethylene terephthalate chips of .69 dl / g were mixed at a ratio of 82.1 parts by weight was used. .
  • the thickness of each layer of the obtained film was 6 ⁇ m / 62 ⁇ m / 6 ⁇ m.
  • Example 2-6 As a surface layer, a crystalline polypropylene homopolymer containing 15 parts by weight of a polyethylene terephthalate chip having an average viscosity of 0.62 dl / g containing 50% by weight of titanium oxide particles having an average particle diameter of 0.32 ⁇ m and a melt flow index of 8 ml / 10 min.
  • a biaxially oriented laminated white polyester film having a thickness of 75 ⁇ m was obtained in the same manner as in Example 2-2, except that a mixed raw material in which 74.5 parts by weight of a polyethylene terephthalate chip / g was mixed was used.
  • the thickness of each layer of the obtained film was 6 ⁇ m / 63 ⁇ m / 6 ⁇ m.
  • a crystalline polypropylene homopolymer having 15 parts by weight of a polyethylene terephthalate chip having an intrinsic viscosity of 0.66 dl / g and containing 50% by weight of titanium oxide particles having an average particle diameter of 0.32 ⁇ m and a melt flow index of 8 ml / 10 min.
  • Example 2-2 a biaxially oriented laminated white polyester film having a thickness of 75 ⁇ m was obtained.
  • the thickness of each layer of the obtained film was 6 ⁇ m / 63 ⁇ m / 6 ⁇ m.
  • Tables 12 and 13 the obtained laminated white polyester film was poor in character and image peeling / removal suitability.
  • Example 2-2 Biaxial orientation with a thickness of 75 ⁇ m and a thickness of each layer of 6 ⁇ m / 63 ⁇ m / 6 ⁇ m in the same manner as in Example 2-2, except that the heat treatment temperature in the film forming step was 201 ° C. for 10 seconds.
  • a laminated white polyester film was obtained. As shown in Tables 12 and 13 below, the obtained laminated white polyester film was poor in image quality suitability and character and image peeling removal suitability.

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Abstract

Afin de produire un film stratifié blanc destiné à être utilisé comme matériau d'enregistrement, qui est un support d'impression d'informations servant à prendre la place d'un papier tel qu'un papier de copie, et qui est très économique, la présente invention porte sur un film blanc stratifié caractérisé en ce qu'au moins une surface d'un film de polyester de densité apparente de 0,7 à 1,3 g/cm3 et d'épaisseur de 10 à 1000 µm possède une couche fonctionnelle contenant un agent antistatique, et ledit film de polyester comprend un polymère qui est incompatible avec le polyester.
PCT/JP2018/008008 2017-03-02 2018-03-02 Film stratifié blanc et matériau d'enregistrement Ceased WO2018159811A1 (fr)

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CN201880011701.1A CN110325363B (zh) 2017-03-02 2018-03-02 层叠白色薄膜和被记录材料
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CN202210350855.1A CN114714731B (zh) 2017-03-02 2018-03-02 层叠白色薄膜和被记录材料
KR1020197028778A KR102601068B1 (ko) 2017-03-02 2018-03-02 적층 백색 필름 및 피기록재
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JP2017218863A JP7052307B2 (ja) 2017-03-02 2017-11-14 積層白色ポリエステルフィルムおよび被記録材
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WO2022176744A1 (fr) * 2021-02-17 2022-08-25 東洋紡株式会社 Film à base de polyester contenant des vides

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JPH11116716A (ja) * 1997-10-21 1999-04-27 Toray Ind Inc 白色ポリエステルフイルム
JP2001026089A (ja) * 1999-05-12 2001-01-30 Mitsubishi Polyester Film Copp 微細気泡含有ポリエステルフィルム
JP2005234162A (ja) 2004-02-19 2005-09-02 Ricoh Co Ltd 電子写真用紙、その製造方法、電子写真画像形成方法

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WO2022059580A1 (fr) * 2020-09-15 2022-03-24 東洋紡株式会社 Film de polyester contenant une cavité
WO2022176744A1 (fr) * 2021-02-17 2022-08-25 東洋紡株式会社 Film à base de polyester contenant des vides

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