JP6953749B2 - Film and image display device - Google Patents

Description

The present invention relates to a film and an image display device using the film.

Conventionally, flat panel displays such as liquid crystal displays, plasma displays, and electroluminescence (EL) displays have been made thinner and lighter. As a means for further promoting the thinness and weight reduction, replacement of the glass substrate with a plastic film is being 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 crack 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 to 3). When producing such a transparent film, a high refractive index resin having a higher refractive index than glass fiber and a low refractive index resin having a lower refractive index than glass fiber are used to obtain a cured product of the transparent resin. A resin composition is obtained by mixing so as to be close to the refractive index of glass fibers. Then, the glass fiber cloth is impregnated with the resin composition, dried, and the resin composition is semi-cured to obtain a prepreg. Further, a transparent film is obtained by pressure molding while heating the prepreg. Epoxy resins and the like are used as the high refractive index resin and the low refractive index resin. Further, in order to improve the heat resistance, an imide resin is mixed in the resin composition.

In this way, by making the refractive index of the glass fiber substantially the same as the refractive index of the cured product of the resin composition, it is possible to suppress the refraction of light in the transparent film. Such a transparent film is suitable for use in a display that requires excellent visibility in terms of optical characteristics. In addition to general physical properties such as transparency and dimensional stability required for liquid crystal displays, this transparent film has adhesion to a conductive film such as an indium tin oxide (ITO) film, surface smoothness, and a gas barrier. It is attracting attention as a material that can also impart performance such as sexual characteristics.

Further, in order to obtain a transparent film having excellent hardness and transparency, it has been proposed to set the temperature before the step of curing the resin composition containing the epoxy compound to a specific temperature or lower (Patent Document 4). ..

Japanese Unexamined Patent Publication No. 2004-307851 Japanese Unexamined Patent Publication No. 2009-066931 Japanese Unexamined Patent Publication No. 2011-93966 JP-A-2015-30839

However, all of the above-mentioned techniques require a base material such as a glass fiber cloth, or there is room for improvement in terms of flexibility and the like. The use of substrates such as fiberglass cloth is disadvantageous in terms of transparency and cost. Insufficient flexibility also limits the application of transparent films. Further, in order to enable a wide range of applications of the transparent film, the transparent film is also required to have sufficient heat resistance.
Therefore, an object of the present invention is to provide a film as a self-supporting film which can be produced at low cost and has excellent transparency, heat resistance and flexibility.

According to the first aspect of the present invention, it is a film as a self-supporting film having a single-layer structure, which is an alicyclic epoxy compound (A), a polyol compound (B), an acid generator (C), and benzoxazine. The amount of the alicyclic epoxy compound (A) in the total amount of the alicyclic epoxy compound (A) and the polyol compound (B), which comprises a cured product of the resin composition containing the monomer (D). The ratio of the acid generator (C) is in the range of 50 to 80% by mass, and the amount of the acid generator (C) is 100 parts by mass of the total amount of the alicyclic epoxy compound (A) and the polyol compound (B). The amount of the benzoxazine monomer (D) is 100 parts by mass, which is the total amount of the alicyclic epoxy compound (A) and the polyol compound (B). in the range of 10 to 60 parts by mass with respect to a thickness of Ri near the range of 1 to 250 [mu] m, the polyol compound (B) is at least one of a polycaprolactone triol and polycarbonate diol, number average molecular weight is in the range of 200 to 100000 g / mol, hydroxyl value Ru near the range of 190 to 550KOHmg / g film is provided.

According to the second aspect of the present invention, there is provided a multilayer film comprising two or more layers constituting a multilayer structure, and at least one of these layers is a film according to the first aspect.

According to the third aspect of the present invention, the film according to the first aspect and one or more layers selected from the group consisting of a low reflection layer, an antiglare layer, and a hard coat layer and provided on the film are provided. Optical film is provided.

According to the fourth aspect of the present invention, an image display device including the film according to the first side surface, the multilayer film according to the second side surface, or the optical film according to the third side surface is provided.

A cross-sectional view schematically showing a film according to an embodiment of the present invention. The figure which shows an example of the film manufacturing apparatus schematicly. FIG. 5 is a cross-sectional view schematically showing an application example of the film shown in FIG.

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 1 is a transparent self-supporting film having a single-layer structure. The term "self-supporting film" used here means a film that can be handled by itself without being supported by a support such as a substrate. Further, the term "film" used here means an article having a thin layer shape and flexibility, and does not include the concept of thickness.

The film 1 is made of a cured product of a resin composition described later. That is, the film 1 does not include a woven fabric or non-woven fabric made of various materials such as glass, metal, carbon, protein, cellulose, and synthetic resin, and a porous layer made of such materials.

<Resin composition>
The resin composition contains an alicyclic epoxy compound (A), a polyol compound (B), an acid generator (C), and a benzoxazine monomer (D). Each component will be described below.

[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 and oxygen atoms adjacent to each other in the alicyclic (hereinafter, such an epoxy group is referred to as an "alicyclic epoxy group") and is single bonded to the alicyclic. It may be directly connected with.

The number of alicyclic structures contained in one molecule of the alicyclic epoxy compound (A) may be one or two or more. Further, the number of epoxy groups contained in one molecule of the alicyclic epoxy compound (A) may be 1, or may be 2 or more. According to one example, the alicyclic epoxy compound (A) contains two alicyclic structures and two epoxy groups in one molecule, and these epoxy groups contain carbon atoms having separate alicyclic structures. It is an alicyclic epoxy group.

As the compound having an alicyclic epoxy group, a compound can be arbitrarily selected and used from known and commonly used compounds. The compound having an alicyclic epoxy group preferably has an epoxy group composed of two carbon atoms and oxygen atoms adjacent to each other in the cyclohexane ring, 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 have excellent heat resistance. However, an epoxy compound having a benzene ring, such as a bisphenol A type epoxy compound, has a conjugated double bond and is therefore inferior in transparency to an epoxy compound having no conjugated double bond. When the alicyclic epoxy compound represented by the following general formula (I) is used, particularly high transparency can be achieved.

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

Examples of the organic group include a hydrocarbon group and a group consisting of a carbon atom and a halogen atom, as well as a halogen atom, an oxygen atom, a sulfur atom, a nitrogen atom, and silicon, together with a carbon atom and a hydrogen atom. It may be a group containing a hetero atom such as an atom. Examples of halogen atoms include chlorine atom, bromine atom, iodine atom, fluorine atom and the like.

The organic group includes a hydrocarbon group, a group consisting of 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, and a carbon atom and a hydrogen atom. , An oxygen atom, and a group consisting of a halogen atom are 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 , N-Heptadecyl group, n-octadecyl group, n-nonadecil group, n-icosyl group and other chain alkyl groups; vinyl group, 1-propenyl group, 2-n-propenyl group (allyl group), 1-n Chain alkenyl groups such as -butenyl group, 2-n-butenyl group, and 3-n-butenyl group; cycloalkyl groups such as cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, and cycloheptyl group; phenyl group , O-tolyl group, m-tolyl group, p-tolyl group, α-naphthyl group, β-naphthyl group, biphenyl-4-yl group, biphenyl-3-yl group, biphenyl-2-yl group, anthryl group, And aryl groups such as phenanthryl groups; and aralkyl groups such as benzyl group, phenethyl group, α-naphthylmethyl group, β-naphthylmethyl group, α-naphthylethyl group and β-naphthylethyl group.

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, and perfluoropentyl group, perfluorohexyl group, perfluoroheptyl group, perfluorooctyl group, perfluorononyl group, And halogenated chain alkyl groups such as perfluorodecyl groups; 2-chlorocyclohexyl group, 3-chlorocyclohexyl group, 4-chlorocyclohexyl group, 2,4-dichlorocyclohexyl group, 2-bromocyclohexyl group, 3-bromocyclohexyl Group and cycloalkyl halide group such as 4-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-fluoro Aryl halide groups such as phenyl group and 4-fluorophenyl group; and 2-chlorophenylmethyl group, 3-chlorophenylmethyl group, 4-chlorophenylmethyl group, 2-bromophenylmethyl group, 3-bromophenylmethyl group, Examples thereof include halogenated aralkyl groups such as 4-bromophenylmethyl group, 2-fluorophenylmethyl group, 3-fluorophenylmethyl group, and 4-fluorophenylmethyl group.

Specific examples of the group consisting of a carbon atom, a hydrogen atom, and an oxygen atom include a hydroxy chain such as a hydroxymethyl group, a 2-hydroxyethyl group, a 3-hydroxy-n-propyl group, and a 4-hydroxy-n-butyl group. State Alkyl group; Cycloalkyl halide group such as 2-hydroxycyclohexyl group, 3-hydroxycyclohexyl group, and 4-hydroxycyclohexyl group; 2-hydroxyphenyl group, 3-hydroxyphenyl group, 4-hydroxyphenyl group, 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; hydroxyaralkyl group such as 2-hydroxyphenylmethyl group, 3-hydroxyphenylmethyl group, and 4-hydroxyphenylmethyl 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 -Desyloxy group, n-undecyloxy group, n-tridecyloxy group, n-tetradecyloxy group, n-pentadecyloxy group, n-hexadecyloxy group, n-heptadecyloxy group, n-octadecyloxy group Chain alkoxy groups such as groups, n-nonadesyloxy groups, and n-icosyloxy groups; vinyloxy groups, 1-propenyloxy groups, 2-n-propenyloxy groups (allyloxy groups), 1-n-butenyloxy groups, 2-n. Chain alkenyloxy groups such as -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 Aryloxy groups such as -4-yloxy group, biphenyl-3-yloxy group, biphenyl-2-yloxy group, anthryloxy group, and phenanthryloxy group; benzyloxy group, phenethyloxy group, α-naphthylmethyloxy Aralkyloxy groups such as groups, β-naphthylmethyloxy groups, α-naphthylethyloxy groups, and β-naphthylethyloxy groups; methoxymethyl groups, ethoxymethyl groups, n- Propyloxymethyl 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-ptyl 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- alkoxyalkoxy groups such as n-propyloxy-n-propyloxy group, 4-methoxy-n-butyloxy group, 4-ethoxy-n-butyloxy group, and 4-n-propyloxy-n-butyloxy group; 2-methoxy An alkoxyaryl group such as a phenyl group, a 3-methoxyphenyl group, and a 4-methoxyphenyl group; an alkoxyaryloxy group such as a 2-methoxyphenoxy group, a 3-methoxyphenoxy group, and a 4-methoxyphenoxy group; a formyl group, an acetyl group. Aliphatic acyl groups such as groups, propionyl groups, butanoyl groups, pentanoyl groups, hexanoyl groups, heptanoyl groups, octanoyl groups, nonanoyl groups, and decanoyle groups; aromatic groups such as benzoyl groups, α-naphthoyl groups, and β-naphthoyl groups. Acyl group; methoxycarbonyl group, ethoxycarbonyl group, n-propyloxycarbonyl group, n-butyloxycarbonyl group, n-pentyloxycarbonyl group, n-hexylcarbonyl group, n-heptyloxycarbonyl group, n-octyloxycarbonyl group Chain alkyloxycarbonyl groups such as groups, n-nonyloxycarbonyl groups, and n-decyloxycarbonyl groups; aryloxycarbonyl groups such as phenoxycarbonyl groups, α-naphthoxycarbonyl groups, and β-naphthoxycarbonyl groups; Aliphatic acyloxys such as formyloxy group, acetyloxy group, propionyloxy group, butanoyloxy group, pentanoyloxy group, hexanoyloxy group, heptanoyloxy group, octanoyloxy group, nonanoyloxy group, and decanoyyloxy group. Groups; and aromatic acyloxy groups such as benzoyloxy group, α-naphthyloxy group, and β-naphthyloxy group.

It is more preferable that all of R1 to R18 are hydrogen atoms, particularly from the viewpoint of the hardness of the cured product obtained by using the curable composition.

Further, 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 a divalent hydrocarbon group, a carbonyl group, an ether group (ether bond), a thioether group (thioether bond), an ester group (ester bond), a carbonate group (carbonate bond), and an amide group (amide). Bonding), and groups in which a plurality of these are linked are mentioned.

Examples of the divalent hydrocarbon group include a linear or branched alkylene group having 1 to 18 carbon atoms, a divalent alicyclic hydrocarbon group and the like. 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-cyclohexyl group. Examples thereof include a divalent cycloalkylene group (including a cycloalkylidene group) such as a silene group, a 1,4-cyclohexylene group and a cyclohexylidene group.

As the linking group X, a linking group containing an oxygen atom is preferable. Examples of such linking group X include -CO- (carbonyl group), -O-CO-O- (carbonate group), -COO- (ester group), -O- (ether group), and -CONH-. Examples thereof include (amide group), a group in which a plurality of these groups are linked, and a group in which one or two or more of these groups and one or two or more of divalent hydrocarbon groups are linked. Examples of the divalent hydrocarbon group include those exemplified above.

As the alicyclic epoxy compound represented by the general formula (I), for example, commercially available products such as the trade names "Selokiside 2021P" and "Selokiside 2081" (both manufactured by Daicel Corporation) can be used. .. Further, as the alicyclic epoxy compound represented by the general formula (I) in which X is a single bond, for example, a commercially available product such as the trade name "Selokiside 8000" (manufactured by Daicel Corporation) may be used. can.

The alicyclic epoxy compound (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-epoxycyclohexanecarboxylate (trade name "celloxide 2021P") and ε-caprolactone-modified 3', 4' It is particularly preferred to use at least one of the −epoxycyclohexylmethyl 3,4-epoxycyclohexanecarboxylate.

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 (B) is preferably in the range of 50 to 80% by mass, and is preferably 70 to 80%. It is more preferably in the range of 75% by mass. If this ratio is too small, the crosslink density of the cured product of the resin composition becomes low, and high heat resistance may not be obtained. If this ratio is too large, the cured product of the resin composition becomes hard and brittle, and high flexibility may not be obtained.

[Polyform compound (B)]
By including the polyol compound (B) in the resin composition, it is possible to form a cured product having high flexibility, and it is possible to produce a sheet that can stand on its own only with the cured product of the resin composition. Become.

The polyol compound (B) 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 (B) includes, for example, a polyether polyol, a polyester polyol, and a polycarbonate polyol. The polyol compound can be used alone or in combination of two or more.

The hydroxyl group (two or more hydroxyl groups) contained in the polyol compound (B) may be an alcoholic hydroxyl group or a phenolic hydroxyl group. Further, the number of hydroxyl groups contained in one molecule of the polyol compound (B) may be 2 or more, and is not particularly limited.

The positions of the hydroxyl groups (two or more hydroxyl groups) in the polyol compound (B) are not particularly limited, but are present at at least one end of the polyol molecule (the end of the polymer main chain) from the viewpoint of reactivity with the curing agent. It is particularly preferable that it is present at at least both ends of the polyol molecule.

The polyol compound (B) may be a solid or a liquid as long as it can form a liquid resin composition after being blended with other components.

The number average molecular weight of the polyol compound (B) is not particularly limited, but is, for example, 200 or more, preferably in the range of 200 to 100,000, and more preferably in the range of 300 to 1000. If the number average molecular weight is too small, the film may be broken or cracked when the film, which is a cured product of the resin composition, is peeled off from the base material on which the resin composition is applied. On the other hand, if the number average molecular weight is too large, the polyol compound may precipitate in the liquid resin composition, or the polyol compound may not be dissolved in other components. The number average molecular weight of the polyol compound (B) means a standard polystyrene-equivalent number average molecular weight measured by gel permeation chromatography (GPC).

The polyol compound (B) preferably has a hydroxyl value in the range of 190 to 550 KOH mg / g. If the hydroxyl value is too small, the crosslink density of the cured product of the resin composition becomes low, and high heat resistance may not be obtained. If the hydroxyl value is too large, the amount of hydroxyl groups becomes excessive with respect to the amount of epoxy groups, and suspended monomers that do not contribute to the reaction may be generated in the cured product. As a result, the change in thermogravimetric analysis becomes large, which may cause a decrease in heat resistance and an increase in hygroscopicity.

Examples of the polyol compound (B) include 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. (Including an oligomer), a polycarbonate polyol having a carbonate skeleton (polycarbonate skeleton) in the molecule (including a polycarbonate polyol oligomer), and the like. The polyol compound (B) includes other compounds such as phenoxy resin and epoxy equivalent of 1000 g / eq. Also included are bisphenol-type high molecular weight epoxy resins exceeding the above, polybutadienes having hydroxyl groups, and acrylic polyols.

The polyester polyol is, for example, a polyester polyol obtained by condensation polymerization of a polyol and a polycarboxylic acid (polybasic acid) or a hydroxycarboxylic acid (for example, a transesterification reaction), or a polyester polyol obtained by ring-opening polymerization of lactones. Examples include polyester polyol.

Examples of the polyol used for the condensation polymerization for obtaining the polyester polyol include ethylene glycol, diethylene glycol, 1,2-propanediol, 2-methyl-1,3-propanediol, 1,3-propanediol, and 1, 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-dimethylolcyclohexane, 1,3-dimethylolcyclohexane, 1,4-dimethylolcyclohexane, 1,12-dodecanediol, polybutadiene Diol, neopentyl glycol, tetramethylene glycol, propylene glycol, dipropylene glycol, glycerin, trimethylolpropane, 1,3-dihydroxyacetone, hexyleneglycol, 1,2,6-hexanetriol, ditrimethylolpropane, mannitol, sorbitol , And pentaerythritol.

Examples of the polycarboxylic acid used for the condensation polymerization for obtaining the polyester polyol include oxalic acid, adipic acid, sebacic acid, fumaric acid, malonic acid, succinic acid, glutaric acid, azelaic acid, citric acid, 2,6. -Naphthalenedicarboxylic acid, phthalic acid, isophthalic acid, terephthalic acid, citraconic acid, 1,10-decandicarboxylic acid, methylhexahydrohydride phthalic acid, hexahydrohydride phthalic acid, methyltetrahydrophthalic acid anhydride, tetrahydrophthalic acid anhydride, Examples thereof include pyromellitic anhydride and trimellitic anhydride.

Examples of the hydroxycarboxylic acid used for the condensation polymerization for obtaining the polyester polyol include lactic acid, apple acid, glycolic acid, dimethylolpropionic acid, and dimethylolbutanoic acid.

Examples of the lactones used for ring-opening polymerization for obtaining the polyester polyol include ε-caprolactone, δ-valerolactone, and γ-butyrolactone.

Examples of the polyester polyol include the trade names "Plaxel 205", "Plaxel 205H", "Plaxel 205U", "Plaxel 205BA", "Plaxel 208", "Plaxel 210", "Plaxel 210CP", "Plaxel 210BA", "Plaxel 212", "Plaxel 212CP", "Plaxel 220", "Plaxel 220CPB", "Plaxel 220NP1", "Plaxel 220BA", "Plaxel 220ED", "Plaxel 220EB", "Plaxel 220EC", "Plaxel 230", "Plaxel 230CP", "Plaxel 240", "Plaxel 240CP", "Plaxel 210N", "Plaxel 220N", "Plaxel L205AL", "Plaxel L208AL", "Plaxel L212AL", "Plaxel L220AL", "Plaxel L230AL", "Plaxel 305", "Plaxel 308", "Plaxel 312", "Plaxel L312AL", "Plaxel 320", "Plaxel L320AL", "Plaxel L330AL", "Plaxel 410", "Plaxel 410D", "Plaxel 610", Commercially available products such as "Plaxel P3403" and "Plaxel CDE9P" (both manufactured by Daicel Corporation) can be used.

Examples of the above-mentioned polyether polyol include a polyether polyol obtained by adding a cyclic ether compound to polyols and a polyether polyol obtained by ring-opening polymerization of an alkylene oxide.

More specifically, the polyether polyol includes, for example, ethylene glycol, diethylene glycol, 1,2-propanediol (propylene glycol), 2-methyl-1,3-propanediol, 1,3-propanediol, 1 , 4-Butandiol (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-dimethylolcyclohexane, 1,3-dimethylolcyclohexane, 1,4-dimethylolcyclohexane, 1, 12-Dodecanediol, polybutadienediol, neopentyl glycol, dipropylene glycol, glycerin, trimethylolpropane, 1,3-dihydroxyacetone, hexyleneglycol, 1,2,6-hexanetriol, ditrimethylolpropane, mannitol, sorbitol, And multimers of polyols such as pentaerythritol; the above polyols and ethylene oxide, propylene oxide, 1,2-butylene oxide, 1,3-butylene oxide, 2,3-butylene oxide, tetrahydrofuran, and epichlorohydrin. Additions with alkylene oxides such as; and ring-opening polymers of cyclic ethers such as tetrahydrofuran (eg, polytetramethylene glycol).

Examples of the above-mentioned polyether polyol include the trade name "PEP-101" (manufactured by Freund Sangyo Co., Ltd.), the trade names "Adecapluronic L", "Adecapluronic P", "Adecapluronic F", and "Adecapluronic R". , "Adeca Pluronic TR", and "Adeca PEG" (both manufactured by Adeca Co., Ltd.); trade names "PEG # 1000", "PEG # 1500", and "PEG # 11000" (both manufactured by Nichiyu Co., Ltd.) Made by); Product 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-10000" (all manufactured by Sanyo Kasei Kogyo Co., Ltd.); trade names "PTMG1000", "PTMG1800", and "PTMG2000" ( In each case, commercially available products such as "PTMG prepolymer" (manufactured by Mitsubishi Resin Co., Ltd.) can be used.

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

The above-mentioned polycarbonate polyol can be used by the phosgene method or a carbonate exchange reaction using a dialkyl carbonate or a diphenyl carbonate such as dimethyl carbonate and diethyl carbonate (Japanese Patent Laid-Open No. 62-187725), in the same manner as a method for producing a normal polycarbonate polyol. It is synthesized according to Kaihei 2-175721, Japanese Patent Application Laid-Open No. 2-49025, Japanese Patent Application Laid-Open No. 3-220233, Japanese Patent Application Laid-Open No. 3-252420, etc.). Since the carbonate bond in the polycarbonate polyol is not easily decomposed by heat, 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 together with the above dialkyl carbonate or diphenyl carbonate include 1,6-hexanediol, ethylene glycol, diethylene glycol, 1,3-propanediol, 1,4-butanediol, and 1,3-butane. Glycol, 2,3-butanediol, 1,5-pentanediol, 3-methyl-1,5-pentanediol, 1,4-cyclohexanedimethanol, 1,8-octanediol, 1,9-nonanediol, 1 , 12-Dodecanediol, butadienediol, neopentyl glycol, tetramethylene glycol, propylene glycol, and propylene glycol.

Examples of the polycarbonate polyol include the trade names "Plaxel CD205PL", "Plaxel CD205HL", "Plaxel CD210PL", "Plaxel CD210HL", "Plaxel CD220PL", and "Plaxel CD220HL" (all manufactured by Daicel Corporation). Product names "UH-CARB50", "UH-CARB100", "UH-CARB300", "UH-CARB90 (1/3)", "UH-CARB90 (1/1)", and "UC-CARB100" (any of them) Also manufactured by Ube Industries, Ltd.; and trade names such as "PCDL T4671", "PCDL T4672", "PCDL T5650J", "PCDL T5651", and "PCDL T5652" (all manufactured by Asahi Kasei Chemicals Co., Ltd.) Commercially available products can be used.

Examples of the polyols other than the above-mentioned polyether polyol, polyester polyol, and polycarbonate polyol include trade names "YP-50", "YP-50S", "YP-55U", "YP-70", and "ZX-1356-". 2 ”,“ YPB-43C ”,“ YPB-43M ”,“ FX-316 ”,“ FX-310T40 ”,“ FX-280S ”,“ FX-293 ”,“ YPS-007A30 ”, and“ TX-1016 ” (All manufactured by Nippon Steel Chemical Co., Ltd.) and phenoxy resins such as the product names "jER1256", "jER4250", and "jER4275" (both manufactured by Mitsubishi Chemical Co., Ltd.); 014 ”,“ Epototo YD-017 ”,“ Epototo YD-019 ”,“ Epototo YD-020G ”,“ Epototo YD-904 ”,“ Epototo YD-907 ”, and“ Epototo YD-6020 ”(all new days Tetsugaku Co., Ltd.), product names "jER1007", "jER1009", "jER1010", "jER1005F", "jER1009F", "jER1006FS", and "jER1007FS" (all manufactured by Mitsubishi Chemical Co., Ltd.), etc. The epoxy equivalent of 1000 g / eq. Bisphenol type high molecular weight epoxy resin exceeding the above; trade names "Poly bd R-45HT", "Poly bd R-15HT", "Poly ip", and "KRASOL" (all manufactured by Idemitsu Kosan Co., Ltd.) and trade names. Polybutadienes having hydroxyl groups such as "α-ω polybutadiene glycol G-1000", "α-ω polybutadiene glycol G-2000", and "α-ω polybutadiene glycol G-3000" (all manufactured by Nippon Soda Co., Ltd.) In addition, the product names "Hitaroid 3903", "Hitaroid 3904", "Hitaroid 3905", "Hitaroid 6500", "Hitaroid 6500B", and "Hitaroid 3018X" (all manufactured by Hitachi Kasei Kogyo Co., Ltd.) and product names. "Acrydic DL-1537", "Acrydic BL-616", "Acrydic AL-1157", "Acrydic A-322", "Acrydic A-817", "Acrydic A-870", "Acrylic" "Dick A-859-B", "Acrydic A-829", and "Acrydic A-49-394-IM" (all manufactured by DIC Co., Ltd.), trade names "Dianar SR-1346", "Diamond" Commercially available products such as acrylic polyols such as "Nar SR-1237" and "Dianar AS-1139" (both manufactured by Mitsubishi Rayon Co., Ltd.) can be used.

The above polyol compound can be used alone or in combination of two or more. The polyol compound (B) is a polyester polyol, for example, polycaprolactone triol such as the trade names "Plaxel 305" and "Plaxel 308" (both manufactured by Daicel Corporation), and the trade name "Plaxel CD205PL" (Daicel Co., Ltd.). It is particularly preferable that it is at least one of the carbonate diols such as (manufactured by).

The ratio of the amount of the polyol compound (B) to the total amount of the alicyclic epoxy compound (A) and the polyol compound (B) is preferably in the range of 20 to 50% by mass, preferably 25 to 30% by mass. It is more preferable that it is within the range of. If this ratio is too small, the cured product of the resin composition will have a hard and brittle property, and high flexibility may not be obtained. If this ratio is too large, the crosslink density in the cured product of the resin composition becomes low, the amount of hydroxyl groups becomes excessive with respect to the amount of epoxy groups, and the resin composition may not be sufficiently cured.

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

Examples of the cationic polymerization initiator that generates a cationic species by ionization irradiation include hexafluoroantimonate salt, pentafluorohydroxyantimonate salt, hexafluorophosphate salt, hexafluoroarsenate salt, triallylsulfonium salt and derivatives thereof. In addition, diallyl iodonium salt and its derivatives can be mentioned.

Examples of the triallyl sulfonium salt and its derivative include a triallyl sulfonium hexafluorophosphate salt and its derivative, and a triallyl sulfonium hexafluoroantimonate salt and its derivative.
Examples of the diallyl iodonium salt and its derivative include a diallyl iodonium hexafluoroborate salt and its derivative, and a diallyl iodonium tetrafluoroborate salt and its derivative.
These cationic polymerization initiators (cationic catalysts) can be used alone or in combination of two or more.

Examples of such a cationic polymerization initiator include trade names "UVACURE1590" (manufactured by Daicel Cytec Co., Ltd.); trade names "CD-1010", "CD-1011", and "CD-1012" (all of which are used. (Made by Sartmer, USA); Product names "Irgacure 264" and "Irgacure 250" (both manufactured by Ciba Japan Co., Ltd.); Product name "CIT-1682" (manufactured by Nippon Soda Co., Ltd.); Product name "CPI-" 101A ”,“ CPI-100P ”,“ CPI-210S ”, and“ CPI-110A ”(all manufactured by Sun Appro Co., Ltd.); , And "ADEKA PUTMER SP-150" (both manufactured by ADEKA Corporation); and commercially available products such as the trade name "Cyricollies UV CATA211" (manufactured by Arakawa Chemical Industry Co., Ltd.) can be used. Preferably, the product names "SP-170" and "SP-172" (both manufactured by ADEKA Corporation), and the product names "CPI-210S", "CPI-101A" and "CPI-110A" (all are manufactured by ADEKA Corporation). It is one or more of Sun Appro Co., Ltd.

Examples of the cationic polymerization initiator that generates a cationic species by heat treatment include an aryldiazonium salt, an aryliodonium salt, an arylsulfonium salt, and an allene-ion complex.

Examples of such a cationic polymerization initiator include trade names "PP-33", "CP-66", and "CP-77" (all manufactured by ADEKA Corporation); trade name "FC-509" ( 3M Co., Ltd.); Product name "UVE1014" (GE Co., Ltd.); Product names "Sun Aid SI-60L", "Sun Aid SI-80L", "Sun Aid SI-100L", "Sun Aid SI-" "110L" and "Sun Aid SI-150L" (both manufactured by Sanshin Chemical Industry Co., Ltd.); and commercially available products such as the trade name "CG-24-61" (manufactured by Ciba Japan Co., Ltd.) can be used. ..

Further, a compound of a metal such as aluminum or titanium and a chelate compound of acetacetic acid or diketone and silanol such as triphenylsilanol, or a chelate compound of a metal such as aluminum or titanium and acetacetic acid or diketone and bisphenol S. Compounds with phenols such as the above can also be used as the above-mentioned cationic polymerization initiator.

The amount of the acid generator (C) shall be in the range of 0.05 to 0.5 parts by mass with respect to 100 parts by mass of the total amount of the alicyclic epoxy compound (A) and the polyol compound (B). Is preferable, and more preferably it is in the range of 0.05 to 0.1 parts by mass. If the amount of the acid generator (C) is too small, the crosslink density of the cured product of the resin composition becomes small, and high heat resistance may not be obtained. If the amount of the acid generator (C) is too large, it may not be possible to obtain a cured product having high transparency.

[Benzoxazine Monomer (D)]
The benzoxazine monomer (D) refers to a monomer having one or more benzoxazine groups per molecule. The benzoxazine monomer (D) has the effect of increasing the glass transition point Tg of the resin composition.

The benzoxazine monomer (D) is, for example, a monomer having one benzoxazine group per molecule, that is, a monobenzoxazine monomer. The monobenzoxazine monomer preferably has a structure represented by the following general formula (II).

In the general formula (II), R is an allyl group, a phenyl group, an alkyl group having 1 to 8 carbon atoms, or a cycloalkyl group having 3 to 8 carbon atoms. The hydrogen atoms of the phenyl group, the alkyl group, and the cycloalkyl group may be substituted with a substituent. Examples of the substituent include an amino group, an alkyl group having 1 to 4 carbon atoms, and an allyl group. A phenyl group, an alkyl group, or a cycloalkyl group can have, for example, 1 to 4 hydrogen atoms substituted with a substituent. Preferably, R is a phenyl group.

The benzoxazine monomer (D) may be a monomer having two or more benzoxazine groups per molecule. The use of such benzoxazine monomers is advantageous, for example, in increasing the crosslink density. As the monomer having two or more benzoxazine groups per molecule, for example, it has a plurality of benzoxazine groups contained in the compound represented by the general formula (II), and their nitrogen atoms are attached to each other via a bonding group. Combined ones can be used. As such a benzoxazine monomer, for example, 3,3'(-methylene-1,4-diphenylene) bis (3,4-dihydro-2H-1,3-benzoxazine) can be used. This benzoxazine monomer is commercially available from Shikoku Chemicals Corporation under the trade name of "Pd type", for example.

The benzoxazine monomer (D) may be a plurality of types of monomers. For example, the benzoxazine monomer (D) may be a plurality of types of monomers having different numbers of benzoxazine groups per molecule.
[Other ingredients (E)]
The resin composition can further contain another component (E), if necessary.
For example, the resin composition may further contain a cationically reactive compound such as a vinyl ether compound for curability adjustment. Further, the resin composition may further contain an oxetane compound in order to reduce the viscosity and adjust the reaction rate. Further, the resin composition may further contain a radical reactive compound for adjusting the adhesion between the base material and the layer obtained by curing the resin composition.

The resin composition contains other components such as antioxidants, ultraviolet absorbers, light stabilizers (HALS, etc.), matting agents (silica, glass powder, metal oxides, etc.), colorants (dye, pigment, etc.), Light diffusing agents, low shrinkage agents, anti-settling agents, antifoaming agents, antistatic agents, antifogging agents, dispersants, thickeners, anti-sagging agents, desiccants, leveling agents, coupling agents, adhesion promoters, anti-corrosion agents Rust pigments, heat stabilizers, film initiators, slip agents, scratch agents, plasticizers, antibacterial agents, antifungal agents, antifouling agents, flame retardants, polymerization inhibitors, photopolymerization accelerators, sensitizers, It may further contain one or more of an additive such as a thermal initiator (thermal cationic polymerization initiator, thermal radical polymerization initiator) and a mold release agent.

The amount of the component (E) is preferably 10 parts by mass or less with respect to 100 parts by mass of the total amount of the alicyclic epoxy compound (A), the polyol compound (B) and the benzoxazine monomer (D). It is more preferably 1 part by mass or less.

<Preparation of resin composition>
The above resin composition is obtained by uniformly mixing the above-mentioned components. For this mixing, for example, a stirrer such as a dispermixer, an ultramixer, a homogenizer, and a planetary stirrer / defoamer can be used without particular limitation. This mixing is preferably performed in an environment not irradiated with ionizing radiation in order to prevent activation of the acid generator.

<Manufacturing of film>
In the film 1 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 further subjected to prebaking to form a coating film. It is obtained by curing and then peeling the cured film from the support. For the production of the film 1, for example, the apparatus shown in FIG. 2 can be used.

FIG. 2 is a diagram schematically showing an example of a film manufacturing apparatus.
The film manufacturing apparatus 100 is a roll-to-roll type die coater. This film manufacturing apparatus winds the unwinding roll 110, the carrier film 120, the guide rolls 130a to 130e, the backup roll 140, the die head 150, the ionizing radiation irradiator 160, the heater 170, and the peeling roll 180. Includes take rolls 190a and 190b.

A 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 above-mentioned resin composition 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 support the cured product of the resin composition in a peelable manner. Examples of the carrier film 120 include 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 made of cellulose esters such as nitrates or derivatives thereof, polyvinylidene chloride film, polyvinyl alcohol film, ethylene vinyl alcohol film, syndiotactic polystyrene film, polycarbonate film, norbornene resin film, polymethylpentene film, poly Examples thereof include ether ketone film, polyether sulfone film, polysulfone film, polyether ketoneimide film, polyamide film, fluororesin film, nylon film, polymethylmethacrylate film, acrylic film, and polyarylate film.

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

The guide rolls 130a to 130e are formed by rolling the carrier film 120 unwound from the unwinding roll 110 into a region between the die head 150 and the backup roll 140, a region in front of the ionizing radiation irradiator 160, a heater 170, and a winding roll. We will guide you to 190a in sequence.

The backup roll 140 is installed so as 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 onto the surface of the carrier film 120 that passes between the die head 150 and the backup roll 140. As a result, a coating film made of the resin composition is formed on the surface of the carrier film 120.

Here, the die coating method using the die head 150 for coating the resin composition is described, but other methods may be used for coating the resin composition. For coating the resin composition, for example, dipping method, wire bar method, roll coating method, gravure coating method, reverse coating method, air knife coating method, comma coating method, curtain method, screen printing method, spray coating method. A well-known method such as a method and a gravure offset method can be used.

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

The ionizing radiation irradiator 160 is installed so as 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 installed so as to face the back surface of the carrier film 120.

Here, the term "ionizing radiation" refers to high-energy radiation capable of decomposing (ionizing) a component contained in a resin composition, specifically an acid generator, to generate an acid in the resin composition, for example, X. It means a line or an ultraviolet ray. Ultraviolet rays are typically used as the 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 serves as a catalyst to promote polymerization and cross-linking in the resin composition. Therefore, by irradiating the coating film with ionizing radiation, polymerization and cross-linking proceed in the resin composition, and as a result, the coating film is cured.

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

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

Integrated light quantity of ionizing radiation, preferably in the range of 10 to 3000 mJ / cm ^2, more preferably in a range of 100 to 1000 mJ / cm ^2, be in the range of 200 to 500 mJ / cm ² Is more preferable.

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

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. The heating temperature is preferably in the range of 80 to 160 ° C. The heating time is preferably in the range of 30 to 600 seconds.

The release roll 180 is installed so as to roll on the film 1 supported by the carrier film 120. The peeling roll 180 sharply and greatly changes the moving direction of the film 1 with respect to the moving direction of the carrier film 120, whereby the film 1 is peeled from the carrier film 120.

The take-up roll 190a winds up the carrier film 120 from which the film 1 has been peeled off. Further, the take-up roll 190b winds up the film 1 peeled off from the carrier film 120.

The take-up roll 190a applies tension to the carrier film 120. The tension applied to the carrier film 120 by the take-up roll 190a varies depending on the thickness and material of the carrier film 120, but is preferably in the range of 10 to 500 N / m.
The film 1 is manufactured, for example, as described above.

As described above, this film 1 does not contain a base material such as a glass fiber cloth. Therefore, this film 1 is advantageous in terms of transparency and cost as compared with a film containing a base material such as a glass fiber cloth. Further, this film 1 is obtained from the above-mentioned resin composition. Such a film 1 is excellent in transparency, heat resistance and flexibility. That is, this film 1 is a film as a self-supporting film that can be manufactured at low cost and has excellent transparency, heat resistance, and flexibility.

<Application example of film>
FIG. 3 is a cross-sectional view schematically showing an application example of the film shown in FIG.
FIG. 3 depicts a multilayer film 10 including the film 1 shown in FIG. The multilayer film 10 is, for example, an optical film.

The multilayer film 10 includes a second layer 2 in addition to the film 1 as the first layer. The film 1 and the second layer 2 form a multilayer structure. Although only the second layer 2 is drawn as a layer other than the film 1 in FIG. 3, the multilayer film 10 may include two or more layers other than the film 1.

The second layer 2 may be a self-supporting film or a film that cannot be handled by itself. In the latter case, the film 1 serves as a base material for the second layer 2.

The second layer 2 is, for example, a low reflection layer, an antiglare layer, or a hard coat layer. When the multilayer film 10 contains two or more layers other than the film 1, the two or more layers other than the film 1 include two or more selected from the group consisting of a low reflection layer, an antiglare layer, and a hard coat layer. You may.

As described above, the film 1 can be manufactured at low cost and is excellent in transparency, heat resistance and flexibility. Therefore, the multilayer film 10 obtained by using this film 1 can also be manufactured at low cost, and can have excellent transparency, heat resistance, and flexibility.

The film 1 and the multilayer film 10 described above can be used in an image display device such as a flat panel display, for example. Examples of the flat panel display include a liquid crystal display, a plasma display, and an EL display. The film 1 and the multilayer film 10 can be used as a protective film, a TFT (Thin Film Transistor) substrate, a color filter substrate, a sealing substrate, and the like in an image display device.

Examples of the present invention will be described below. However, the present invention is not limited to the matters described below.

<Example 1>
The film 1 shown in FIG. 1 was produced by the following procedure.
First, 70 parts by mass of the alicyclic epoxy compound (A), 30 parts by mass of the polyol compound (B), 0.05 parts by mass of the acid generator (C), and 10 parts by mass of the benzoxazine monomer (D). ) Was stirred for 15 minutes using a planetary stirring defoaming machine (Massel Star KK5000, manufactured by KURABO) to prepare a coating solution. Here, as the alicyclic epoxy compound (A), celloxide 2021P (manufactured by Daicel Corporation) was used. Further, as the polyol compound (B), Praxel 308 (manufactured by Daicel Corporation) was used. Further, as the acid generator (C), CPI-110A (manufactured by Sun Appro Co., Ltd.) was used. Then, as the benzoxazine monomer, Pd type (manufactured by Shikoku Chemicals Corporation) was used.

Next, using this coating liquid, a film 1 having a thickness of 50 μm was produced by the method described with reference to FIG. Here, as the carrier film 120, a polyethylene terephthalate (PET) sheet (Melinex S, manufactured by Teijin Limited) having a thickness of 250 μm was used. A high-pressure mercury lamp (manufactured by Eye Graphics Co., Ltd.) was used as the light source of the ionizing radiation irradiator 160. The exposure was performed so that the integrated light intensity was 500 mJ / cm ^2. Post-baking was performed at 160 ° C. for 180 seconds. The carrier film 120 was wound with a tension of 50 N / m.

<Examples 2 to 5 and Comparative Examples 1 to 5>
A film was prepared in the same manner as in Example 1 except that the composition of the resin composition was changed as shown in Table 1 below.

<Comparative Example 6>
A film was produced by the same method as in Example 1 except that BS575CB (manufactured by Arakawa Chemical Industry Co., Ltd.), which is a radical curable composition, was used as the resin composition.

<Comparative Example 7>
A commercially available film, Lumirror T60 # 75 (manufactured by Toray Industries, Inc.) was prepared.

<Evaluation method>
(transparency)
The transmittance of the film was measured at a measurement wavelength of 400 nm using a transmissometer (UV-VISLIBLE SPECTROPHOTOMETER UV2450, manufactured by SHIMADZU). Further, after the film was left in an environment of 200 ° C. for 60 minutes, the transmittance was measured by the same method.

Then, the transparency of the film was judged according to the following criteria. That is, the case where the initial transmittance is 90% or more and the rate of decrease of the transmittance with respect to the initial transmittance after 60 minutes at 200 ° C. is 1% or less is determined as “◯”. Then, when the initial transmittance is less than 90%, or when the reduction rate of the transmittance with respect to the initial transmittance after 60 minutes at 200 ° C. exceeds 1%, it is determined as "x".

(Heat-resistant)
The thermogravimetric change of the film was measured using a dynamic viscoelasticity measuring device (DMS6100, manufactured by Hitachi High-Tech Science Co., Ltd.). Here, the sample size was 10 mm × 50 mm, the measurement cycle was 10 Hz, the measurement temperature was 25 to 300 ° C., the temperature rising rate was 2 ° C./min, the sampling pitch was 3 seconds, and the measurement atmosphere was N ₂ purged.

Then, the heat resistance of the film was judged according to the following criteria. That is, those having a glass transition temperature Tg (= loss elastic modulus E ″ / storage elastic modulus E ″) of 150 ° C. or higher were designated as “◯”, and those having a glass transition temperature of less than 150 ° C. were designated as “x”.

(Flexible)
Using a mandrel tester, it was wound around a cylinder having a diameter of 0.4 mm. Then, the one in which the crack occurred was determined as "◯", and the one in which the crack did not occur was determined as "x".
The evaluation results are summarized in Table 1 below.

As shown in Table 1, the films according to Examples 1 to 5 showed excellent performance in all of transparency, heat resistance, and flexibility. On the other hand, the films according to Comparative Examples 1 to 7 were insufficient in at least one performance of transparency, heat resistance, and flexibility.
The inventions described in the original claims are added below.
[1]
A film as a self-supporting film having a single-layer structure, which contains an alicyclic epoxy compound (A), a polyol compound (B), an acid generator (C), and a benzoxazine monomer (D). It is composed of a cured product of the composition, and 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 (B) is 50 to 80% by mass. Within the range, the amount of the acid generator (C) is 0.05 to 0.5 mass with respect to 100 parts by mass of the total amount of the alicyclic epoxy compound (A) and the polyol compound (B). The amount of the benzoxazine monomer (D) is 10 to 60 parts by mass with respect to 100 parts by mass of the total amount of the alicyclic epoxy compound (A) and the polyol compound (B). A film that is in range.
[2]
The alicyclic epoxy compound (A) contains 3', 4'-epoxycyclohexylmethyl 3,4-epoxycyclohexanecarboxylate and ε-caprolactone-modified 3', 4'-epoxycyclohexylmethyl 3,4-epoxycyclohexanecarboxylate. Item 2. The film according to Item 1, which is at least one of the above.
[3]
Item 2. The film according to Item 1 or 2, wherein the polyol compound (B) is at least one of polycaprolactone triol and polycarbonate diol.
[4]
Item 6. The film according to any one of Items 1 to 3, wherein the acid generator (C) contains a sulfonium salt.
[5]
Item 6. The film according to any one of Items 1 to 4, wherein the benzoxazine monomer (D) has two or more benzoxazine groups per molecule.
[6]
Item 6. The film according to any one of Items 1 to 5, wherein the polyol compound (B) has a number average molecular weight in the range of 200 to 100,000 g / mol and a hydroxyl value in the range of 190 to 550 KOH mg / g.
[7]
Item 6. The film according to any one of Items 1 to 6, which has a film thickness in the range of 1 to 250 μm.
[8]
A multilayer film comprising two or more layers constituting a multilayer structure, wherein at least one of the layers is the film according to any one of Items 1 to 7.
[9]
An optics comprising the film according to any one of Items 1 to 7 and one or more layers selected from the group consisting of a low reflection layer, an antiglare layer, and a hard coat layer and provided on the film. the film.
[10]
An image display device comprising the film according to any one of Items 1 to 7, the multilayer film according to Item 8, or the optical film according to Item 9.

1 ... film (first layer), 2 ... second layer 2, 10 ... multilayer 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 film as a self-supporting film having a single-layer structure, which contains an alicyclic epoxy compound (A), a polyol compound (B), an acid generator (C), and a benzoxazine monomer (D). It is composed of a cured product of the composition, and 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 (B) is 50 to 80% by mass. Within the range, the amount of the acid generator (C) is 0.05 to 0.5 mass with respect to 100 parts by mass of the total amount of the alicyclic epoxy compound (A) and the polyol compound (B). The amount of the benzoxazine monomer (D) is 10 to 60 parts by mass with respect to 100 parts by mass of the total amount of the alicyclic epoxy compound (A) and the polyol compound (B). in the range, thickness Ri near the range of 1 to 250 [mu] m, the polyol compound (B) is at least one of a polycaprolactone triol and polycarbonate diol, number average molecular weight of 200 to 100000 g / mol located among a hydroxyl value of Ru near the range of 190 to 550KOHmg / g film. The alicyclic epoxy compound (A) contains 3', 4'-epoxycyclohexylmethyl 3,4-epoxycyclohexanecarboxylate and ε-caprolactone-modified 3', 4'-epoxycyclohexylmethyl 3,4-epoxycyclohexanecarboxylate. The film according to claim 1, which is at least one of the above. The film according to claim 1 or 2 , wherein the acid generator (C) contains a sulfonium salt. The film according to any one of claims 1 to 3 , wherein the benzoxazine monomer (D) has two or more benzoxazine groups per molecule. A multilayer film comprising two or more layers constituting a multilayer structure, wherein at least one of the layers is the film according to any one of claims 1 to 4. The film according to any one of claims 1 to 4 is provided with one or more layers selected from the group consisting of a low reflection layer, an antiglare layer, and a hard coat layer and provided on the film. Optical film. An image display device comprising the film according to any one of claims 1 to 4 , the multilayer film according to claim 5 , or the optical film according to claim 6.

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