JP2019064222A - Film - Google Patents

Abstract

To provide a film as a free-standing film which can be inexpensively manufactured, is excellent in strength, antistatic properties, transparency, heat resistance, flexibility and abrasion resistance, for overcoming such a problem that a method for providing a hard coat layer obtained by curing an acrylic material for imparting surface hardness to a film and forming a reflection preventing layer thereon is generally used, however the hard coat layer obtained by curing the acrylic material has high insulation property, and therefore is liable to be charged and to cause separating charge.SOLUTION: The film is provided that includes a hard coat layer including an antistatic agent on a substrate including an alicyclic epoxy compound and a glass filter, with a content of the antistatic agent of 2.0 pts.wt. to 4.0 pts.wt.SELECTED DRAWING: Figure 1

Description

  The present invention relates to a transparent film excellent in scratch resistance, antistatic property and strength.

  BACKGROUND OF THE INVENTION Flat panel displays such as liquid crystal displays, plasma displays, and electroluminescent (EL) displays have been reduced in thickness and weight. As a means of further reducing the thickness and weight, replacement of a glass substrate with a plastic film has been considered. By replacing the glass substrate with a plastic film, the flat panel display can be made thinner and lighter, and the flat panel display can be provided with properties such as cracking resistance and flexibility.

  Recently, a transparent film obtained by impregnating a glass fiber cloth with a transparent resin composition and curing the resin composition has been proposed (see Patent Documents 1 and 2). When manufacturing such a transparent film, the refractive index of the cured product of the transparent resin is a high refractive index resin having a refractive index larger than that of glass fiber and a low refractive index resin having a refractive index smaller than that of glass fiber. It mixes so that the refractive index of glass fiber may be approximated, and a resin composition is obtained. Then, a glass fiber cloth is impregnated with the resin composition, which is dried to semi-cure the resin composition to obtain a prepreg. Furthermore, a transparent film is obtained by pressure molding while heating this prepreg. As the high refractive index resin and the low refractive index resin, epoxy resin or the like is used. Moreover, in order to improve heat resistance, the imide resin is mixed with the resin composition.

  Thus, refraction of light in the transparent film can be suppressed by substantially matching the refractive index of the glass fiber with the refractive index of the cured product of the resin composition. Such transparent films are suitable for use in displays where excellent visibility is required in terms of optical properties. In addition to general physical properties such as transparency and dimensional stability required for liquid crystal displays etc., this transparent film has adhesion to a conductive film such as an indium tin oxide (ITO) film, surface smoothness, and gas barrier. It is noted as a material that can also impart performance such as gender.

Unexamined-Japanese-Patent No. 2004-307851 JP, 2009-066931, A

  In these transparent films, since the surface is relatively soft and easily scratched, a hard coat layer generally obtained by curing an acrylic material is provided to impart surface hardness, and anti-reflection is provided thereon. The technique of forming a layer is used. The hard coat layer is made of an acrylic material and has high surface hardness, high gloss, transparency and scratch resistance.

  However, a hard coat layer formed by curing an acrylic material has a problem that it is easy to be charged due to its high insulating property, and it is easy for peeling charge to occur. Peeling charge should be avoided as much as possible, as it causes defects in the fabrication of the display.

  Therefore, it is an object of the present invention to provide a film as a free standing film which can be manufactured inexpensively, is excellent in strength, is excellent in antistatic property, transparency, heat resistance, flexibility and scratch resistance. Do.

  According to one aspect of the present invention, a hard coat layer generally obtained by curing an acrylic material to impart surface hardness on a substrate containing an alicyclic epoxy compound (A) and a glass filler (B) And an anti-reflection layer is formed thereon. The hard coat layer is made of an acrylic material and has high surface hardness, high gloss, transparency and scratch resistance. The present invention provides a film having a hard coat layer containing an antistatic agent, wherein the content of the antistatic agent is in the range of 2.0 parts by weight to 4.0 parts by weight.

  According to the present invention, it is possible to provide a film as a free standing film excellent in scratch resistance, antistatic property and strength.

It is a sectional view showing roughly the film concerning one embodiment of the present invention. It is a figure showing roughly an example of a film manufacture device.

  Hereinafter, embodiments of the present invention will be described in detail. However, the present invention is not limited to the following embodiments.

<Film>
FIG. 1 is a cross-sectional view schematically showing a film according to an embodiment of the present invention.
This film 10 is a transparent free standing film having a two-layer structure. The term "self-supporting membrane" as used herein means a film that can be handled alone without being supported by a support such as a substrate. Also, as used herein, the term "film" means an article having a laminar shape and flexibility, and does not include the concept of thickness.

  The film 10 is composed of a resin composition and a glass filler described later.

[Alicyclic epoxy compound (A)]
The alicyclic epoxy compound (A) is a compound containing an alicyclic (aliphatic ring) structure and an epoxy group in one molecule. The epoxy group may be composed of two carbon atoms adjacent to each other in an alicyclic ring and an oxygen atom (hereinafter, such an epoxy group is referred to as “alicyclic epoxy group”), and a single bond to an alicyclic ring It may be directly linked with

  The number of alicyclic structures contained in one molecule of the alicyclic epoxy compound (A) may be one, or two or more. The number of epoxy groups contained in one molecule of the alicyclic epoxy compound (A) may be one or two or more. According to an example, the alicyclic epoxy compound (A) contains two alicyclic structures and two epoxy groups in one molecule, and the epoxy groups contain carbon atoms of different alicyclic structures. It is an alicyclic epoxy group.

  As a compound which has an alicyclic epoxy group, it can be used selecting arbitrarily from well-known thru | or a usual thing. The compound having an alicyclic epoxy group is preferably a compound having an epoxy group composed of two carbon atoms adjacent to each other in a cyclohexane ring and an oxygen atom, that is, a compound having a cyclohexene oxide group.

  As the compound having an alicyclic epoxy group, an alicyclic epoxy compound (alicyclic epoxy resin) represented by the following general formula (I) is particularly preferable in terms of heat resistance, light resistance and transparency. . In general, epoxy compounds are excellent in heat resistance. However, since an epoxy compound having a benzene ring such as a bisphenol A type epoxy compound has a conjugated double bond, it is inferior in transparency as compared with an epoxy compound having no conjugated double bond. Particularly high transparency can be achieved when using a cycloaliphatic epoxy compound represented by the following general formula (I).

  In the above general formula (I), R1 to R18 each independently represent a group selected from the group consisting of a hydrogen atom, a halogen atom, and an organic group.

  The organic group may be, for example, a hydrocarbon group or a group consisting of a carbon atom and a halogen atom, and together with the carbon atom and the hydrogen atom, a halogen atom, an oxygen atom, a sulfur atom, a nitrogen atom, and silicon It may be a group that contains a heteroatom such as an atom. As an example of a halogen atom, a chlorine atom, a bromine atom, and an iodine atom, and a fluorine atom etc. are mentioned.

  As an organic group, a group consisting of a hydrocarbon group, a carbon atom, a hydrogen atom and an oxygen atom, a halogenated hydrocarbon group, a group consisting of a carbon atom, an oxygen atom and a halogen atom, a carbon atom and a hydrogen atom And the group which consists of an oxygen atom and a halogen atom is preferable. When the organic group is a hydrocarbon group, the hydrocarbon group may be an aromatic hydrocarbon group, an aliphatic hydrocarbon group, or a group containing an aromatic skeleton and an aliphatic skeleton.

  Specific examples of the hydrocarbon group include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group, n-pentyl group and n-hexyl group , N-heptyl group, n-octyl group, 2-ethylhexyl group, n-nonyl group, n-decyl group, n-undecyl group, n-tridecyl group, n-tetradecyl group, n-pentadecyl group, n-hexadecyl group And linear alkyl groups such as n-heptadecyl, n-octadecyl, n-nonadecyl and n-icosyl; vinyl, 1-propenyl, 2-n-propenyl (allyl), 1-n -Chain-like alkenyl groups such as butenyl group, 2-n-butenyl group and 3-n-butenyl group; cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group And cycloalkyl groups such as cycloheptyl group; phenyl group, o-tolyl group, m-tolyl group, p-tolyl group, α-naphthyl group, β-naphthyl group, β-naphthyl group, biphenyl-4-yl group, biphenyl-3-yl group And aryl groups such as biphenyl-2-yl, anthryl and phenanthryl; and benzyl, phenethyl, α-naphthylmethyl, β-naphthylmethyl, α-naphthylethyl and β-naphthyl Aralkyl groups such as ethyl group can be mentioned.

  Specific examples of the halogenated hydrocarbon group include chloromethyl group, dichloromethyl group, trichloromethyl group, bromomethyl group, dibromomethyl group, tribromomethyl group, fluoromethyl group, difluoromethyl group, trifluoromethyl group, 2, 2,2-trifluoroethyl group, pentafluoroethyl group, heptafluoropropyl group, perfluorobutyl group, perfluoropentyl group, perfluorohexyl group, perfluoroheptyl group, perfluorooctyl group, perfluorononyl group, And halogenated linear alkyl groups such as perfluorodecyl group; 2-chlorocyclohexyl group, 3-chlorocyclohexyl group, 4-chlorocyclohexyl group, 2,4-dichlorocyclohexyl group, 2-bromocyclohexyl group, 3-bromocyclohexyl Groups and Halogenated cycloalkyl groups such as -bromocyclohexyl group; 2-chlorophenyl group, 3-chlorophenyl group, 4-chlorophenyl group, 2,3-dichlorophenyl group, 2,4-dichlorophenyl group, 2,5-dichlorophenyl group, 2, 6-dichlorophenyl group, 3,4-dichlorophenyl group, 3,5-dichlorophenyl group, 2-bromophenyl group, 3-bromophenyl group, 4-bromophenyl group, 2-fluorophenyl group, 3-fluorophenyl group, and Halogenated aryl groups such as 4-fluorophenyl group; and 2-chlorophenylmethyl group, 3-chlorophenylmethyl group, 4-chlorophenylmethyl group, 2-bromophenylmethyl group, 3-bromophenylmethyl group, 4-bromophenyl group Methyl group, 2-fluorophenylmethyl group, 3 Fluorophenyl methyl group, and halogenated aralkyl groups such as 4-fluorophenyl methyl groups.

  Specific examples of the group consisting of carbon atom, hydrogen atom and oxygen atom include hydroxy chains such as hydroxymethyl group, 2-hydroxyethyl group, 3-hydroxy-n-propyl group and 4-hydroxy-n-butyl group Alkyl groups; halogenated cycloalkyl groups such as 2-hydroxycyclohexyl, 3-hydroxycyclohexyl and 4-hydroxycyclohexyl; 2-hydroxyphenyl, 3-hydroxyphenyl, 4-hydroxyphenyl, 2, Hydroxyaryl such as 3-dihydroxyphenyl group, 2,4-dihydroxyphenyl group, 2,5-dihydroxyphenyl group, 2,6-dihydroxyphenyl group, 3,4-dihydroxyphenyl group, and 3,5-dihydroxyphenyl group Group; 2-hydroxyphenylmethyl group, 3-hydric group Hydroxyaralkyl groups such as xyphenyl methyl group and 4-hydroxyphenyl methyl group; methoxy group, ethoxy group, n-propyloxy group, isopropyloxy group, n-butyloxy group, isobutyloxy group, sec-butyloxy group, tert- Butyloxy group, n-pentyloxy group, n-hexyloxy group, n-heptyloxy group, n-octyloxy group, 2-ethylhexyloxy group, n-nonyloxy group, n-decyloxy group, n-undecyloxy group, n-tridecyloxy group, n-tetradecyloxy group, n-pentadecyloxy group, n-hexadecyloxy group, n-heptadecyloxy group, n-octadecyloxy group, n-nonadecyloxy group, and n-icosyloxy A linear alkoxy group such as a group; vinyloxy group, 1 A chain alkenyloxy group such as propenyloxy group, 2-n-propenyloxy group (allyloxy group), 1-n-butenyloxy group, 2-n-butenyloxy group, and 3-n-butenyloxy group; phenoxy group, o- Tolyloxy group, m-tolyloxy group, p-tolyloxy group, α-naphthyloxy group, β-naphthyloxy group, biphenyl-4-yloxy group, biphenyl-3-yloxy group, biphenyl-2-yloxy group, anthryloxy group And aryloxy groups such as phenanthryloxy group; benzyloxy group, phenethyloxy group, α-naphthylmethyloxy group, β-naphthylmethyloxy group, α-naphthylethyloxy group, β-naphthylethyloxy group and the like Aralkyloxy group; methoxymethyl group, ethoxymethyl group, n-pro Pyryloxymethyl group, 2-methoxyethyl group, 2-ethoxyethyl group, 2-n-propyloxyethyl group, 3-methoxy-n-propyl group, 3-ethoxy-n-propyl group, 3-n-propyloxy Alkoxyalkyl groups such as -n-propyl group, 4-methoxy-n-butyl group, 4-ethoxy-n-butyl group, and 4-n-propyloxy-n-butyl group; methoxymethoxy group, ethoxymethoxy group, n-Propyloxymethoxy group, 2-methoxyethoxy group, 2-ethoxyethoxy group, 2-n-propyloxyethoxy group, 3-methoxy-n-propyloxy group, 3-ethoxy-n-propyloxy group, 3- n-propyloxy-n-propyloxy group, 4-methoxy-n-butyloxy group, 4-ethoxy-n-butyloxy group, and 4-n Alkoxyalkoxy groups such as propyloxy-n-butyloxy group; alkoxyaryl groups such as 2-methoxyphenyl group, 3-methoxyphenyl group, and 4-methoxyphenyl group; 2-methoxyphenoxy group, 3-methoxyphenoxy group, and Alkoxy aryloxy groups such as 4-methoxyphenoxy group; formyl groups, acetyl groups, propionyl groups, butanoyl groups, pentanoyl groups, hexanoyl groups, heptanoyl groups, octanoyl groups, nonanoyl groups, aliphatic acyl groups such as decanoyl groups; benzoyl Aromatic acyl group such as α-naphthoyl group and β-naphthoyl group; methoxycarbonyl group, ethoxycarbonyl group, n-propyloxycarbonyl group, n-butyloxycarbonyl group, n-pentyloxycarbonyl group, n- Hillika Linear alkyloxycarbonyl groups such as bonyl group, n-heptyloxycarbonyl group, n-octyloxycarbonyl group, n-nonyloxycarbonyl group, and n-decyloxycarbonyl group; phenoxycarbonyl group, α-naphthoxy carbonyl group And aryloxycarbonyl groups such as β-naphthoxycarbonyl group; formyloxy group, acetyloxy group, propionyloxy group, butanoyloxy group, pentanoyloxy group, hexanoyloxy group, heptanoyloxy group, octanoyloxy group Aliphatic acyloxy groups such as groups, nonanoyloxy groups, and decanoyloxy groups; and aromatic acyloxy groups such as benzoyloxy groups, α-naphthoyloxy groups, and β-naphthoyloxy groups.

It is more preferable that all of R _{1 to} R ₁₈ be hydrogen atoms, particularly in view of the hardness of the cured product obtained using the curable composition.

  In the above general formula (I), X is a single bond or a linking group (a divalent group having one or more atoms).

  Examples of the linking group include divalent hydrocarbon groups, carbonyl groups, ether groups (ether bonds), thioether groups (thioether bonds), ester groups (ester bonds), carbonate groups (carbonate bonds), amide groups (amides (amides) A bond, and a group in which a plurality of these are linked, and the like.

  As said bivalent hydrocarbon group, a C1-C18 linear or branched alkylene group, bivalent alicyclic hydrocarbon group etc. are mentioned, for example. Examples of the linear or branched alkylene group having 1 to 18 carbon atoms include a methylene group, a methylmethylene group, a dimethylmethylene group, an ethylene group, a propylene group, and a trimethylene group. Examples of the divalent alicyclic hydrocarbon group include a 1,2-cyclopentylene group, a 1,3-cyclopentylene group, a cyclopentylidene group, a 1,2-cyclohexylene group, and a 1,3-cyclohexene group. And bivalent cycloalkylene groups (including cycloalkylidene groups) such as silene group, 1,4-cyclohexylene group, and cyclohexylidene group.

  The linking group X is preferably a linking group containing an oxygen atom. As such a linking group X, for example, -CO- (carbonyl group), -O-CO-O- (carbonate group), -COO- (ester group), -O- (ether group), -CONH- (Amide group), a group in which a plurality of these groups are connected, and a group in which one or more of these groups are connected to one or more of divalent hydrocarbon groups. As a bivalent hydrocarbon group, what was illustrated above is mentioned, for example.

  As the alicyclic epoxy compound represented by the above general formula (I), for example, commercially available products such as trade names “Ceroxide 2021 P” and “Ceroxide 2081” (all manufactured by Daicel Co., Ltd.) can be used. . In addition, as the alicyclic epoxy compound represented by the general formula (I), for example, a commercially available product such as a trade name “Ceroxide 8000” (manufactured by Daicel Co., Ltd.) may be used as a compound in which X is a single bond. it can.

  The alicyclic epoxy compounds (A) can be used alone or in combination of two or more. Among the above, as the alicyclic epoxy compound (A), 3 ′, 4′-epoxycyclohexylmethyl 3,4-epoxycyclohexane carboxylate (trade name “Ceroxide 2021 P”) and ε-caprolactone modified 3 ′, 4 ′ Particular preference is given to using at least one of: epoxycyclohexylmethyl 3,4-epoxycyclohexanecarboxylate.

<Glass filler>
Glass filler (B) is a general-purpose alkali-free glass (E glass), acid-resistant alkali-containing glass (C glass), glass with high strength and high modulus (S glass, T glass) as a glass for forming a substrate. Etc.), alkali resistant glass (AR glass), etc. can be used, and it is not particularly limited, but particularly, highly versatile non-alkali glass is preferably used.

  The amount of the glass filler (B) is preferably 1 to 90 parts by weight, more preferably 10 to 80% by weight, and still more preferably 30 to 70 parts by weight. If the compounding quantity of a glass filler is this range, shaping | molding is easy and the effect of the improvement of the intensity | strength by compounding and the fall of linear expansion are recognized.

  When glass fiber is used as the glass filler, the filament diameter is preferably in the range of 1 μm to 10 μm, and particularly preferably in the range of 3 μm to 7 μm, but is not particularly limited. .

<Hard coat material>
Among acrylic materials, polyfunctional urethane acrylates can be suitably used because the desired molecular weight and molecular structure can be designed, and the physical properties of the hard coat layer to be formed can be easily balanced. . The urethane acrylate is obtained by reacting a polyhydric alcohol, a polyvalent isocyanate and a hydroxyl group-containing acrylate. Specifically, manufactured by Kyoeisha Chemical Co., Ltd., UA-306H, UA-306T, UA-306I, etc., Nippon Synthetic Chemical Co., Ltd., UV-1700B, UV-6300B, UV-7600B, UV-7605B, UV-7640B, UV U-7HA, U-6HA, UA-100H, U-6LPA, U-15HA, UA-32P, U-324A, etc., manufactured by Daicel UBC, Ebecryl-1290, Ebecryl. -1290 K, Ebecryl-5129 etc., Negami-Kogyo Co., Ltd. make, UN-3220HA, UN-3220HB, UN-3220HC, UN-3220HS etc. can be mentioned although it is not this limitation.

In addition to these, polyether resins having an acrylate functional group, polyester resins, epoxy resins, alkyd resins, spiroacetal resins, polybutadiene resins, polythiol polyene resins, etc. may be used as ionizing radiation-curable materials. it can.
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[Antistatic agent]
The antistatic agent has the function of reducing the surface resistance of the film 10. As the antistatic agent, for example, one or more of a surfactant, an inorganic oxide filler, and a π-conjugated conductive polymer can be used. The addition amount of the antistatic agent is appropriately adjusted so that the surface resistance of the film is 1.0 × 10 ⁶ Ω / □ or more and 1.0 × 10 ¹¹ Ω / □ or less. When the addition amount of the antistatic agent is too small, a sufficient antistatic function can not be obtained. The addition of a large amount of antistatic agent lowers the surface resistance, which is advantageous as an antistatic function. However, excessive addition is disadvantageous in cost and transparency. Therefore, the addition amount adjusted so that surface resistance may be 1.0 * 10 < ⁶ > ohm / square or more and 1.0 * 10 < ¹¹ > ohm / square or less is preferable.

  In the case where the hard coat layer forming coating solution containing the antistatic agent is cured by ultraviolet light, a photopolymerization initiator is added to the hard coat layer forming coating solution containing the antistatic agent. Any photopolymerization initiator may be used as long as it generates a radical when irradiated with ultraviolet light. For example, acetophenones, benzoins, benzophenones, phosphine oxides, ketals, anthraquinones, thioxanthones Can. Further, the addition amount of the photopolymerization initiator is preferably in the range of 0.1 parts by weight or more and 10 parts by weight or less with respect to 100 parts by weight of the ionizing radiation curable material, and further 1 part by weight or more It is preferable that it is the following.

<Resin composition>
As a resin composition, in addition to an alicyclic epoxy compound (A), an acrylic resin to be a hard coat layer, and an antistatic agent, a polyol compound (C) and an acid generator (D) may be blended. Below, each component is demonstrated.

[Polyol compound (C)]
By including the polyol compound (C) in the resin composition, a cured product having high flexibility can be formed, and it is possible to produce a sheet that can be self-supported only by the cured product of the resin composition.

  The polyol compound (C) is a polymer (oligomer or polymer) having two or more hydroxyl groups in one molecule and having a number average molecular weight of, for example, 200 or more. The polyol compound (C) includes, for example, polyether polyols, polyester polyols, and polycarbonate polyols. In addition, a polyol compound can be used individually or in combination of 2 or more types.

  The hydroxyl group (two or more hydroxyl groups) of the polyol compound (C) may be an alcoholic hydroxyl group or a phenolic hydroxyl group. Moreover, the number of hydroxyl groups that the polyol compound (C) has in one molecule may be two or more, and is not particularly limited.

  The position of the hydroxyl group (two or more hydroxyl groups) in the polyol compound (C) is not particularly limited, but from the viewpoint of reactivity with the curing agent, it exists at at least one end of the polyol molecule (end of polymer main chain) It is preferred to be present, and it is particularly preferred to be present at at least both ends of the polyol molecule.

  The polyol compound (C) only needs to be capable of forming a liquid resin composition after being blended with other components, and may itself be a solid or a liquid.

  The ratio of the amount of the alicyclic epoxy compound (A) to the total amount of the alicyclic epoxy compound (A) and the polyol compound (C) is preferably 50 parts by weight or more and 80 parts by weight or less, and 70 parts by weight More preferably, it is not less than 75 parts by weight. If this proportion is too small, the crosslink density may be low in the cured product of the resin composition, and high heat resistance may not be obtained. If this ratio is too large, the cured product of the resin composition may be hard and brittle, and high flexibility may not be obtained.

  The number average molecular weight of the polyol compound (C) is not particularly limited, but is, for example, 200 or more, preferably 200 or more and 100000 or less, and more preferably 300 or more and 1000 or less. When a number average molecular weight is too small, when peeling the film which is a hardened | cured material of a resin composition from the base material which coats a resin composition, a fracture | rupture and a crack may generate | occur | produce in a film. On the other hand, when the number average molecular weight is too large, the polyol compound may be precipitated in the liquid resin composition, or the polyol compound may not be dissolved in other components. In addition, the number average molecular weight of a polyol compound (C) means the number average molecular weight of standard polystyrene conversion measured by gel permeation chromatography (GPC).

  The polyol compound (C) preferably has a hydroxyl value of 190 or more and 550 KOHmg / g or less. If the hydroxyl value is too small, the crosslink density in the cured product of the resin composition may be low, and high heat resistance may not be obtained. When the hydroxyl value is too large, the amount of hydroxyl groups is excessive with respect to the amount of epoxy groups, and it is possible that floating monomers which do not contribute to the reaction may be generated in the cured product. As a result, the thermal weight change may be large, resulting in a decrease in heat resistance and an increase in hygroscopicity.

  As the polyol compound (C), for example, a polyester polyol (including a polyester polyol oligomer) having an ester skeleton (polyester skeleton) in the molecule, and a polyether polyol (polyether polyol) having an ether skeleton (polyether skeleton) in the molecule And a polycarbonate polyol (including a polycarbonate polyol oligomer) having a carbonate skeleton (polycarbonate skeleton) in the molecule. As the polyol compound (C), other compounds such as phenoxy resin, epoxy equivalent is 1000 g / eq. Also included are bisphenol type high molecular weight epoxy resins, polybutadienes having hydroxyl groups, and acrylic polyols.

  Examples of the polyester polyol include polyester polyols obtained by condensation polymerization (for example, transesterification) of a polyol and a polycarboxylic acid (polybasic acid) or of a hydroxycarboxylic acid, and ring opening polymerization of lactones. Polyester polyol etc. are mentioned.

  Examples of the polyol used for condensation polymerization to obtain the above polyester polyol include ethylene glycol, diethylene glycol, 1,2-propanediol, 2-methyl-1,3-propanediol, 1,3-propanediol, 4-butanediol, 1,3-butanediol, 2,3-butanediol, 1,5-pentanediol, 2-methyl-1,5-pentanediol, 3-methyl-1,5-pentanediol, 2, 3,5-trimethyl-1,5-pentanediol, 1,6-hexanediol, 2-ethyl-1,6-hexanediol, 2,2,4-trimethyl-1,6-hexanediol, 2,6- Hexanediol, 1,8-octanediol, 1,4-cyclohexanedimethanol, 1,2-dimethylol Hexane, 1,3-dimethylolcyclohexane, 1,4-dimethylolcyclohexane, 1,12-dodecanediol, polybutadienediol, neopentyl glycol, tetramethylene glycol, propylene glycol, dipropylene glycol, glycerin, trimethylolpropane, 1 And 3-dihydroxyacetone, hexylene glycol, 1,2,6-hexanetriol, ditrimethylolpropane, mannitol, sorbitol, and pentaerythritol.

  Examples of polycarboxylic acids used for condensation polymerization to obtain the above polyester polyols include oxalic acid, adipic acid, sebacic acid, fumaric acid, malonic acid, succinic acid, glutaric acid, azelaic acid, citric acid, 2, 6 Naphthalene dicarboxylic acid, phthalic acid, isophthalic acid, terephthalic acid, citraconic acid, 1,10-decanedicarboxylic acid, methylhexahydrophthalic anhydride, hexahydrophthalic anhydride, methyltetrahydrophthalic anhydride, tetrahydrophthalic anhydride, An example is pyromellitic anhydride and trimellitic anhydride.

  As a hydroxycarboxylic acid used for condensation polymerization for obtaining the above-mentioned polyester polyol, lactic acid, malic acid, glycolic acid, dimethylol propionic acid, and dimethylol butanoic acid are mentioned, for example.

  As lactones used for the ring-opening polymerization for obtaining the said polyester polyol, (epsilon) -caprolactone, (delta) -valerolactone, and (gamma) -butyrolactone are mentioned, for example.

  Examples of the polyester polyol include “Placcel 205”, “Placcel 205H”, “Placcel 205U”, “Placcel 205BA”, “Placcel 208”, “Placcel 210”, “Placcel 210CP”, and “Placcel 210BA”, for example. “Placcel 212”, “Placcel 212 CP”, “Placcel 220”, “Placcel 220 CPB”, “Placcel 220 NP1”, “Placcel 220 BA”, “Placcel 220 ED”, “Placcel 220 EB”, “Placcel 220 EC”, “Placcel 230”, “Placcel 230CP”, “Placcel 240”, “Placcel 240CP”, “Placcel 210N”, “Placcel 220N”, “Placcel L205AL”, “Placcel L208A , "Placcel L212AL", "Placcel L220AL", "Placcel L230AL", "Placcel 305", "Placcel 308", "Placcel 312", "Placcel L312AL", "Placcel 320", "Placcel L320AL", "Placcel L330AL" Commercial products such as “Placcel 410”, “Placcel 410D”, “Placcel 610”, “Placcel P 3403”, and “Placcel CDE 9 P” (all manufactured by Daicel Co., Ltd.) can be used.

  As said polyether polyol, the polyether polyol obtained by the addition reaction of the cyclic ether compound to polyols, and the polyether polyol obtained by the ring-opening polymerization of an alkylene oxide are mentioned, for example.

  More specifically, examples of the polyether polyol include ethylene glycol, diethylene glycol, 1,2-propanediol (propylene glycol), 2-methyl-1,3-propanediol, 1,3-propanediol, and the like. 2,4-butanediol (tetramethylene glycol), 1,3-butanediol, 2,3-butanediol, 1,5-pentanediol, 2-methyl-1,5-pentanediol, 3-methyl-1,5 -Pentanediol, 2,3,5-trimethyl-1,5-pentanediol, 1,6-hexanediol, 2-ethyl-1,6-hexanediol, 2,2,4-trimethyl-1,6-hexane Diol, 2,6-hexanediol, 1,8-octanediol, 1,4-cyclohexanedimethanol 1,2-dimethylol cyclohexane, 1,3-dimethylol cyclohexane, 1,4-dimethylol cyclohexane, 1,12-dodecanediol, polybutadiene diol, neopentyl glycol, dipropylene glycol, glycerin, trimethylol propane, 1 1, 3-dihydroxyacetone, hexylene glycol, 1,2,6-hexanetriol, ditrimethylolpropane, mannitol, sorbitol, and a polymer of polyols such as pentaerythritol; the above polyols, ethylene oxide, propylene oxide, 1 Adducts with alkylene oxides such as 2-butylene oxide, 1,3-butylene oxide, 2,3-butylene oxide, tetrahydrofuran, and epichlorohydrin; Ring-opened polymer of a cyclic ether such as tetrahydrofuran (for example, poly tetramethylene glycol) and the like.

  As said polyether polyol, for example, trade name "PEP-101" (made by Freund Sangyo Co., Ltd.), trade name "Adecaplulonic L", "Adecaplulonic P", "Adecaplulonic F", "Adecaplulonic R" “Adecaplulonic TR” and “Adeca PEG” (all from Adeka Co., Ltd.); trade names “PEG # 1000”, “PEG # 1500”, and “PEG # 11000” (all from NOF Corporation) Trade names "New pole PE-34", "New pole PE-61", "New pole PE-78", "New pole PE-108", "PEG-200", "PEG-600", " PEG-2000 "," PEG-6000 "," PEG-10000 ", and" PEG-20000 "(all from Sanyo Chemical Industries, Ltd.); Name "PTMG1000", "PTMG1800", and "PTMG2000" (both manufactured by Mitsubishi Chemical Corp.); can be used as well as "PTMG prepolymer" (manufactured by Mitsubishi Plastics Inc.), and commercial products.

  The polycarbonate polyol is a polycarbonate having two or more hydroxyl groups in the molecule. Among them, as the polycarbonate polyol, polycarbonate diol having two terminal hydroxyl groups in the molecule is preferable.

  The polycarbonate polyol is a phosphation method, or a carbonate exchange reaction using a dialkyl carbonate such as dimethyl carbonate and diethyl carbonate or diphenyl carbonate as in the method of producing a conventional polycarbonate polyol (JP-A-62-187725, particularly JP-A-2-175721, JP-A-2-49025, JP-A-3-220233, JP-A-3-252420 and the like) and the like. Since the carbonate bond in the polycarbonate polyol is less susceptible to thermal decomposition, the cured product of the resin composition containing the polycarbonate polyol exhibits excellent stability even under high temperature and high humidity.

  Examples of the polyol used in the carbonate exchange reaction with the above dialkyl carbonate or diphenyl carbonate include, for example, 1,6-hexanediol, ethylene glycol, diethylene glycol, 1,3-propanediol, 1,4-butanediol, and 1,3-butanediol. Diol, 2,3-butanediol, 1,5-pentanediol, 3-methyl-1,5-pentanediol, 1,4-cyclohexanedimethanol, 1,8-octanediol, 1,9-nonanediol, 1 12-dodecanediol, butadiene diol, neopentyl glycol, tetramethylene glycol, propylene glycol, and propylene glycol.

  Examples of the polycarbonate polyols include, for example, trade names “PLAC CELL CD 205 PL”, “PLAC CELL CD 205 HL”, “PLAC CELL CD 210 PL”, “PLAC CELL CD 210 HL”, “PLAC CELL CD 220 PL”, and “PLAC CELL CD 220 HL” (all manufactured by Daicel Corporation); Trade names "UH-CARB50", "UH-CARB100", "UH-CARB300", "UH-CARB90 (1/3)", "UH-CARB90 (1/1)", and "UC-CARB100" (any one Ube Industries, Ltd .; and “PCDL T4671”, “PCDL T4672”, “PCDL T5650J”, “PCDL T5651”, and “PCDL T5652” (all are manufactured by Asahi Kasei Chemicals Corporation) Use a commercial product Can be

  As polyols other than the said polyether polyol, polyester polyol, and a polycarbonate polyol, the brand names "YP-50", "YP-50S", "YP-55U", "YP-70", "ZX-1356-" are mentioned, for example. 2 "," YPB-43C "," YPB-43M "," FX-316 "," FX-310T40 "," FX-280S "," FX-293 "," YPS-007A30 ", and" TX-1016 Phenoxy resins such as “JER1256”, “jER4250”, and “jER4275” (all from Mitsubishi Chemical Co., Ltd.); and “Epototh YD-”. 014 "," Epotote YD-017 "," Epotote YD-019 "," Epotote YD-020G "," Epotote YD 904 "," Epotote YD-907 ", and" Epotote YD-6020 "(all are manufactured by Nippon Steel Chemical Co., Ltd.), and trade names" jER1007 "," jER1009 "," jER1010 "," jER1005F "," The epoxy equivalents of jER1009F, jER1006FS, and jER1007FS (all manufactured by Mitsubishi Chemical Corporation) are 1,000 g / eq. Bisphenol-type polymer epoxy resin that exceeds the brand name; “Poly bd R-45 HT”, “Poly bd R-15 HT”, “Poly ip”, and “KRASOL” (all from Idemitsu Kosan Co., Ltd.), and trade names Polybutadienes having a hydroxyl group such as "α-ω polybutadiene glycol G-1000", "α-ω polybutadiene glycol G-2000", and "α-ω polybutadiene glycol G-3000" (all from Nippon Soda Co., Ltd.) Brand names "Hitaloid 3903", "Hitaloid 3904", "Hitaloid 3905", "Hitaloid 6500", "Hitaloid 6500B", and "Hitaloid 3018X" (all manufactured by Hitachi Chemical Co., Ltd.), and trade names "Acrydic DL-1537", "Acrydic BL-616" "," Acrydic AL-1157 "," Acrydic A-322 "," Acrydic A-817 "," Acrydic A-870 "," Acrydic A-859-B "," Acrydic A-829 " "," Aklydic A-49-394-IM "(all from DIC Corporation), trade names" Dianal SR-1346 "," Dianal SR-1237 ", and" Dianal AS-1139 " Commercially available products such as acrylic polyols such as (all manufactured by Mitsubishi Rayon Co., Ltd.) can be used.

  In addition, the said polyol compound can be used individually or in combination of 2 or more types. The polyol compound (C) is a polyester polyol, for example, a polycaprolactone triol such as "Placcel 305" and "Placcel 308" (both manufactured by Daicel Co., Ltd.), and a trade name "Placcel CD 205 PL" (Daicel Co., Ltd. Particularly preferred is at least one of carbonate diols such as

  The proportion of the amount of the polyol compound (C) in the total amount of the alicyclic epoxy compound (A) and the polyol compound (C) is preferably in the range of 20 parts by weight to 50 parts by weight, 25 parts by weight More preferably, it is in the range of not less than 30 parts by weight. If this ratio is too small, the cured product of the resin composition may be hard and brittle, and high flexibility may not be obtained. If this proportion is too large, the crosslink density in the cured product of the resin composition will be low, the amount of hydroxyl groups will be excessive relative to the amount of epoxy groups, and the resin composition may not be sufficiently cured.

[Acid Generator (D)]
The acid generator (D) has the function of initiating the polymerization of the compound having an epoxy group in the resin composition. The acid generator (D) is preferably a cationic polymerization initiator which generates cationic species by irradiation with ionizing radiation such as ultraviolet irradiation or heat treatment to initiate polymerization of the alicyclic epoxy compound (A). The acid generator (D) can be used alone or in combination of two or more.

  Examples of cationic polymerization initiators that generate cationic species by ionizing radiation include hexafluoroantimonate salts, pentafluorohydroxyantimonate salts, hexafluorophosphate salts, hexafluoroarsenate salts, triallylsulfonium salts and derivatives thereof, And diallyl iodonium salts and derivatives thereof.

Examples of triallylsulfonium salts and their derivatives include triallylsulfonium hexafluorophosphate salts and their derivatives, and triallylsulfonium hexafluoroantimonate salts and their derivatives.
Examples of diallyiodonium salts and derivatives thereof include diallyiodonium hexafluorophosphate salts and derivatives thereof, and diallyiodonium tetrafluoroborate salts and derivatives thereof.
These cationic polymerization initiators (cationic catalysts) can be used alone or in combination of two or more.

  As such a cationic polymerization initiator, for example, trade name "UVACURE 1590" (made by Daicel Cytech Co., Ltd.); trade names "CD-1010", "CD-1011", and "CD-1012" (all of them) Product name “IRGACURE 264” and “IRGACURE 250” (both from Ciba Japan Ltd.); trade name “CIT-1682” (Nippon Soda Co., Ltd.); trade name “CPI— 101A "," CPI-100P "," CPI-210S ", and" CPI-110A "(all from San-Apro Co., Ltd.); trade name" Adeka Optomer SP-170 "," Adeka Optomer SP-172 " And “Adeka Optomer SP-150” (all manufactured by ADEKA Co., Ltd.); and trade name “Sirikolise UV CATA 211” (rough Commercial products such as Kawa Chemical Industry Co., Ltd. can be used. Preferably, trade names "SP-170" and "SP-172" (all are manufactured by ADEKA Co., Ltd.), and trade names "CPI-210S", "CPI-101A" and "CPI-110A" (any one) One or more of San-Apro Co., Ltd.).

  As a cationic polymerization initiator which generate | occur | produces cationic species by heat-processing, an aryldiazonium salt, an aryl iodonium salt, an aryl sulfonium salt, and an allene-ion complex are mentioned, for example.

  As such a cationic polymerization initiator, for example, trade names "PP-33", "CP-66", and "CP-77" (all of which are manufactured by ADEKA Co., Ltd.); trade name "FC-509" (trade name) 3 M (trade name) product; trade name "UVE 1014" (G.E. stock product); trade name "San Aid SI-60L", "San Aid SI-80 L", "San Aid SI-100 L", "San Aid SI-" Commercial products such as 110L and San-Aid SI-150L (all manufactured by Sanshin Chemical Industry Co., Ltd.); and trade name "CG-24-61" (manufactured by Ciba Japan Co., Ltd.) can be used. .

  Furthermore, a compound of a chelate compound of metal such as aluminum or titanium with acetoacetic acid or diketones and silanol such as triphenylsilanol, or a chelate compound of metal such as aluminum or titanium with acetoacetic acid or diketones and bisphenol S Compounds with phenols such as can also be used as the cationic polymerization initiator.

  The amount of the acid generator (D) is preferably 0.05 or more and 0.5 or less parts by weight with respect to 100 parts by weight in total of the alicyclic epoxy compound (A) and the polyol compound (C). And more preferably 0.05 or more and 0.1 or less parts by weight. If the amount of the acid generator (D) is too small, the crosslink density may be low in the cured product of the resin composition, and high heat resistance may not be obtained. When the amount of the acid generator (D) is too large, a cured product having high transparency may not be obtained.

<Production of film>
In the film 10 shown in FIG. 1, for example, a coating film made of the above resin composition is formed on a support, the coating film is irradiated with ionizing radiation, and the coating film is subjected to post-baking to obtain a coating film. Are obtained by subsequently curing the cured film from the support. For the production of the film 10, for example, an apparatus shown in FIG. 2 can be used.

FIG. 2 is a view schematically showing an example of a film manufacturing apparatus.
The film manufacturing apparatus 100 is a roll-to-roll die coater. This film manufacturing apparatus includes a winding roll 110, a carrier film 120, guide rolls 130a to 130e, a backup roll 140, a die head 150, an ionizing radiation irradiator 160, a heater 170, a peeling roll 180, and Take rolls 190a and 190b are included.

  The carrier film 120 is wound around the unwinding roll 110. The unwinding roll 110 unwinds the carrier film 120.

  The carrier film 120 has a belt shape. The resin composition described above is applied onto the carrier film 120, and the coating film made of the resin composition is cured on the carrier film 120.

  The carrier film 120 can releasably support the cured product of the resin composition. As the carrier film 120, for example, polyester film, polyethylene film, polypropylene film, cellophane, cellulose diacetate film, cellulose acetate butyrate film, cellulose acetate phthalate film, cellulose acetate propionate film (CAP film), cellulose triacetate and cellulose Films comprising cellulose esters such as nitrates or derivatives thereof, polyvinylidene chloride films, polyvinyl alcohol films, ethylene vinyl alcohol films, syndiotactic polystyrene films, polycarbonate films, norbornene resin films, polymethylpentene films, poly Ether ketone film, polyether Sul Down film, polysulfone film, polyether ketone imide film, a polyamide film, a fluororesin film, a nylon film, polymethyl methacrylate film, acrylic film, and polyarylate films.

  The thickness of the carrier film 120 is not limited, but is preferably 6 μm to 700 μm, more preferably 40 μm to 250 μm, and still more preferably 50 μm to 150 μm.

  The guide rolls 130a to 130e are configured to convey the carrier film 120 unwound from the unwinding roll 110 to the area between the die head 150 and the backup roll 140, the area in front of the ionizing radiation irradiator 160, the heater 170, and the winding roll. Guide to 190 a sequentially.

  The backup roll 140 is installed to face the die head 150. The backup roll 140 rolls on the back surface of the carrier film 120 passing between the die head 150 and the backup roll 140 and plays a role of keeping the distance between the carrier film 120 and the die head 150 constant.

  The die head 150 supplies the resin composition on the surface of the carrier film 120 passing between the die head 150 and the backup roll 140. Thereby, a coating film made of a resin composition is formed on the surface of the carrier film 120.

  Here, although the die-coating method which utilizes the die head 150 for coating of a resin composition is demonstrated, you may utilize another method for coating of a resin composition. For coating the resin composition, for example, dipping method, method using a wire bar, roll coating method, gravure coating method, reverse coating method, air knife coating method, comma coating method, curtain method, screen printing method, spray coating A known method such as a method and a gravure offset method can be used.

  The hard coat layer 1 may be sequentially laminated after the application of the epoxy resin composition 2, or two layers of the hard coat layer 1 and the epoxy resin composition 2 may be simultaneously laminated.

  The thickness after curing of the coating film made of the resin composition, that is, the thickness of the film 10 is preferably 1 μm or more and 250 μm or less. If it is too thin, the strength of the film 10 is low, and there is a high possibility that the film 1 will break when it is peeled off from the carrier film 120. If it is too thick, the storage elastic modulus of the cured product becomes very high due to high reaction heat, and as a result, the film 1 may become hard and brittle, and flexibility may be insufficient.

  The ionizing radiation irradiator 160 is installed to face the surface of the carrier film 120. The coating film on the carrier film 120 is irradiated with ionizing radiation. When the carrier film 120 transmits ionizing radiation, the ionizing radiation irradiator 160 may be disposed to face the back surface of the carrier film 120.

  Here, the term "ionizing radiation" refers to high energy radiation which can generate an acid in the resin composition by decomposing (ionizing) components contained in the resin composition, specifically, an acid generator, for example, X Means radiation or ultraviolet light. Ultraviolet light is typically used as ionizing radiation.

  The ionizing radiation irradiator 160 activates the acid generator contained in the resin composition by irradiating the coating film with ionizing radiation. That is, the acid generator is decomposed (ionized) to generate an acid in the resin composition. The acid plays a role as a catalyst that promotes polymerization and crosslinking in the resin composition. Therefore, polymerization and crosslinking proceed in the resin composition by ionizing radiation to the coating film, and as a result, the coating film is cured.

  As a light source of the ionizing radiation irradiator 160, one that emits light of a wavelength suitable for the decomposition of the (C) acid generator is appropriately selected. As this light source, a lamp emitting a wavelength of 400 nm or less is preferable. Such lamps include, for example, chemical lamps, low pressure mercury lamps, high pressure mercury lamps, metal halide lamps, and visible light halogen lamps.

  The ionizing radiation may be performed in air or in an inert gas such as nitrogen and argon.

Integrated light quantity of ionizing radiation is preferably to 10 mJ / cm ² or more 3000 mJ / cm ² or less, more preferably, to 100 mJ / cm ² or more 1000 mJ / cm ² or less, 200 mJ / cm ² or more 500 mJ / cm ² or less It is further preferable to

  The heater 170 post-bakes the coating film irradiated with the ionizing radiation. Post-baking completes the reaction in the resin composition. When post-baking is performed, the crosslink density in the film 1 can be increased, and the heat resistance is enhanced.

  For heating by the heater 170, for example, heating methods such as hot air drying, hot roll drying, high frequency irradiation, and infrared irradiation can be used alone or in combination of two or more kinds. The heating temperature is preferably in the range of 80 to 160 ° C. The heating time is preferably 30 seconds to 600 seconds.

  The peeling roll 180 is set to roll on the film 10 supported by the carrier film 120. The peeling roll 180 sharply and largely changes the moving direction of the film 10 with respect to the moving direction of the carrier film 120, thereby peeling the film 10 from the carrier film 120.

  The winding roll 190a winds up the carrier film 120 from which the film 10 has been peeled off. Further, the winding roll 190 b winds up the film 10 peeled off from the carrier film 120.

  The winding roll 190 a applies tension to the carrier film 120. The tension applied to the carrier film 120 by the winding roll 190a varies depending on the thickness and the material of the carrier film 120, but is preferably 10 N / m to 500 N / m.

  Below, the Example of this invention is described.

Example 1
The film 10 shown in FIG. 1 was produced by the following procedure.

<Formation of alicyclic epoxy resin layer>
First, 80 parts by weight of a cycloaliphatic epoxy compound (A), 20 parts by weight of a polyol compound (C), and 0.05 parts by weight of an acid generator (D) were added to a planetary stirring and defoaming machine (Mazelle Star KK 5000, The coating solution was prepared by stirring for 15 minutes using KURABO product).

  As the alicyclic epoxy compound (A), Celoxide 2021P (manufactured by Daicel Co., Ltd.) was used. As the polyol compound (C), Plaxel 305 (manufactured by Daicel Co., Ltd.) was used. And, as an acid generator (D), Adeka Optomer SP-170 (trade name ADEKA) was used.

<Formation of alicyclic epoxy resin layer>
Next, on the other hand, a plain weave glass fiber fabric (B) having a basis weight of 47 g / m 2 surface-treated with a cationic silane coupling agent having a quaternary ammonium salt structure is prepared. And coated with ultraviolet rays to produce a film 1 having a thickness of 100 μm. Here, as the carrier film 120, a polyethylene terephthalate (PET) sheet (Mellenex S, manufactured by Teijin Ltd.) having a thickness of 250 μm was used. As a light source of the ionizing radiation irradiator 160, a high pressure mercury lamp (manufactured by Eye Graphics Co., Ltd.) was used. The exposure was performed so that the integrated light amount was 500 mJ / cm 2. Post-baking was performed at 150 ° C. for 180 seconds. The carrier film 120 was wound at a tension of 50 N / m.

<Formation of hard coat layer>
Prepare 4.0 parts by weight of antimony doped tin oxide particle dispersion liquid (ATO / average particle diameter 8 nm / solid content ratio 30 wt% / dispersion medium isopropyl alcohol) as conductive particles, and dipentaerythritol hexaacrylate as an ionizing radiation curable material 7.8 parts by weight of (DPHA), 7.8 parts by weight of pentaerythritol tetraacrylate (PETA), and 23.3 parts by weight of urethane acrylate UA-306T (manufactured by Kyoeisha Chemical Co., Ltd.) were prepared as Irgacure 184 (photopolymerization initiator) Prepare 57.2 parts by weight of a mixed solvent prepared by mixing 2.0 parts by weight of Ciba Japan Co., Ltd., and mixing methyl ethyl ketone, dimethyl carbonate and diacetone alcohol in a weight ratio of 4: 4: 2 as solvents. Hard coat layer type with solid content of 40 wt% containing antistatic agent by mixing To obtain a use coating liquid.

  The obtained coating liquid was coated on a transparent resin film by a wire bar coater to form a coating, and room temperature drying was performed at 25 ° C. for 30 seconds in a semi-sealed space under a solvent atmosphere of 2 to 5 vol% (Primary Drying process). The time for the solvent contained in the coating on the transparent substrate in the room temperature drying step to be 10 wt% or less was 4 seconds. After drying at room temperature, it is dried at 80 ° C. for 1 minute in an oven (secondary drying step), and after drying, it is irradiated with ultraviolet light at an exposure amount of 400 mJ / cm 2 with a conveyor type ultraviolet curing device. A hard coat layer with a thickness of 5 μm was formed.

Example 2
The conditions are the same as in Example 1 except that the addition amount of ATO is 2.0 parts by weight, and a hard coat layer containing an antistatic agent with a thickness of 5 μm is formed on the transparent epoxy resin film.

Comparative Example 1
The conditions are the same as in Example 1 except that the addition amount of ATO is 1.0 part by weight, and a hard coat layer containing an antistatic agent having a thickness of 5 μm is formed on the transparent epoxy resin film.

Comparative Example 2
The conditions were the same as in Example 1 except that the glass filler was not added to the ultraviolet ray curable resin composition.

<Evaluation>
[Surface resistance]
The surface resistances of the films obtained in Examples and Comparative Examples were measured with a high resistance resistivity meter (Hirester MCP-HT260, manufactured by Dia Instruments Co., Ltd.) according to JIS K6911. In addition, the surface resistance of the side containing an antistatic agent is measured.

[Tensile strength]
The stress value at the time of 10% extending | stretching of the tension test by the tension roller of the film in a present Example was measured on the conditions of 300 mm / min of tensile strength based on JISK7127.

Based on the results in Table 1, it is inferred that Comparative Example 1, which does not contain a glass filler, has a large surface resistance and is easily charged. On the other hand, in Examples 1 and 2, the surface resistance is small, and the antistatic function can be sufficiently ensured.
Moreover, in the comparative example 2 which has not added the glass filler, it became a result inferior to tensile strength.

In the present invention, it is possible to provide a film which can be manufactured inexpensively and which can suppress the risk of charging in a self-standing film excellent in transparency, heat resistance, flexibility and scratch resistance.

DESCRIPTION OF SYMBOLS 1 hard coat layer containing antistatic agent 2 alicyclic epoxy resin layer 10 laminated film 100 film manufacturing apparatus 110 unwinding roll 120 carrier film 130a to 130e guide roll 140: Backup roll, 150: Die head, 160: Ionizing radiation irradiator, 170: Heater, 180: Peeling roll, 190a and 190b: Winding roll

Claims (7)

A substrate comprising an alicyclic epoxy compound (A) and a glass filler (B),
A hard coat layer containing an antistatic agent formed on at least one surface of the substrate;
A film characterized in that the content of the antistatic agent is 2.0 parts by weight or more and 4.0 parts by weight or less.   The substrate is a cured product of a resin composition further containing a polyol compound (C) and an acid generator (D), and the total of the alicyclic epoxy compound (A) and the polyol compound (C) The ratio of the amount of the alicyclic epoxy compound (A) to the amount is 50 parts by weight or more and 80 parts by weight or less, and the amount of the acid generator (D) is the same as the amount of the alicyclic epoxy compound (A) 2. The film according to claim 1, wherein the amount is 0.05 parts by weight or more and 0.5 parts by weight or less based on 100 parts by weight of the total amount with the polyol compound (C).   The film according to any one of claims 1 to 3, wherein the antistatic agent is one or more selected from the group consisting of a surfactant, an inorganic oxide filler, and a π-conjugated conductive polymer.   The alicyclic epoxy compound (A) is 3 ', 4'-epoxycyclohexylmethyl 3,4-epoxycyclohexane carboxylate and &agr; -caprolactone modified 3', 4'-epoxycyclohexylmethyl 3,4-epoxycyclohexane carboxylate The film according to any one of claims 1 to 4, which is one or more selected from the group consisting of   The film according to any one of claims 1 to 5, wherein the glass filler (B) is a glass fiber cloth.   The film according to any one of claims 2 to 6, wherein the polyol compound (C) is at least one of polycaprolactone triol and polycarbonate diol.   The film according to any one of claims 2 to 7, wherein the acid generator (D) contains a sulfonium salt.

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