JP6938951B2 - Multilayer film - Google Patents

Description

The present invention relates to a multilayer film used for a flexible substrate, a protective film, a sheet lens, an optical member such as an optical waveguide, etc. in an electronic device.

Various resin materials are used as materials for constituting optical members such as flexible substrates and protective films in electronic devices such as displays (organic EL devices, liquid crystal display devices, touch panels, etc.), sheet lenses, optical waveguides, etc. There is. Among them, epoxy resins have excellent thermal properties, mechanical properties, and electrical properties, and are therefore used in various industrial materials such as adhesives, paints, electrical and electronic materials, and structural materials. The properties required for such epoxy resins are increasing year by year, and in recent years, materials having high transparency, heat resistance, and flexibility have been particularly demanded.

Among the epoxy resins, the alicyclic epoxy resin is known as a material having excellent transparency and heat resistance. However, since the alicyclic epoxy resin is brittle, it is necessary to modify the mechanical properties by blending additives or the like when it is used in an application requiring flexibility. Patent Document 1 describes a means for reducing the crosslink density of a cured product by blending a polyol such as a polyester polyol as a modifier (diluent) with an alicyclic epoxy resin. It was difficult to achieve both heat resistance.

In order to solve the above problems, Patent Document 2 describes a curable resin composition containing a radically polymerizable compound, an alicyclic epoxy compound, and an acid anhydride or a cationic curing agent. However, the inherent transparency of the alicyclic epoxy resin is impaired, and the flexibility to withstand continuous production processes such as roll-to-roll is insufficient, and sufficient physical properties can be obtained for industrial base material applications. I wasn't.

JP-A-2007-308683 International Publication No. 2014/061648

The present invention has been made in view of the above-mentioned problems, and has heat resistance, flexibility, and transparency that can be used for a flexible substrate, a protective film, a sheet lens, an optical member such as an optical waveguide, etc. in an electronic device. The purpose is to provide an excellent film.

In order to solve the above-mentioned problems, the invention according to claim 1 is a multilayer film having a three-layer structure in which layers (L1) / layers (L2) / layers (L3) are laminated in this order. It has the independence that it can be handled independently without the need for a support,
Both L1 and L3 are composed of a resin composition containing an alicyclic epoxy compound (A) and an acid generator (C), or a resin composition further containing a polyol compound (B), and the L2 Is composed of a resin composition containing the alicyclic epoxy compound (A), the acid generator (C), and the polyol compound (B).
The alicyclic epoxy compound (A) includes 3', 4'-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate and ε-caprolactone-modified 3', 4'-epoxycyclohexylmethyl-3,4-epoxy. At least one with cyclohexane carboxylate,
The polyol compound (B) is at least one of polycaprolactone triol and polycarbonate diol.
The acid generator (C) contains a triallyl sulfonium salt and contains.
Moreover, the L2 is a multilayer film characterized by having a composition different from that of L1 and L3.

In the invention according to claim 2 , the polyol compound (B) has a number average molecular weight in the range of 200 to 100,000 g / mol.
The multilayer film according to claim 1 , wherein the hydroxyl value is in the range of 190 to 550 mgKOH / g.

The invention according to claim 3 is the L1 and the L3 is
The amount of the alicyclic epoxy compound (A) with respect to the total amount of the alicyclic epoxy compound (A) and the polyol compound (B) is in the range of 80 to 100% by mass.
Moreover, the amount of the acid generator (C) with respect to 100 parts by mass of the total amount of the alicyclic epoxy compound (A) and the polyol compound (B) is in the range of 0.05 to 0.5 parts by mass. The multilayer film according to any one of claims 1 and 2, characterized by the above.

In the invention according to claim 4 , the above L2 is
The amount of the alicyclic epoxy compound (A) with respect to the total amount of the alicyclic epoxy compound (A) and the polyol compound (B) is in the range of 50 to 80% by mass.
Moreover, the amount of the acid generator (C) with respect to 100 parts by mass of the total amount of the alicyclic epoxy compound (A) and the polyol compound (B) is in the range of 0.05 to 0.5 parts by mass. The multilayer film according to any one of claims 1 to 3 , wherein the multilayer film is characterized by the above.

The invention according to claim 5 is an optical member comprising the multilayer film according to any one of claims 1 to 4.

The invention according to claim 6 is an electronic device comprising the multilayer film according to any one of claims 1 to 4.

The multilayer film according to the present invention is a film having excellent heat resistance, flexibility, and transparency, and is a flexible substrate, a protective film, etc. in electronic devices such as displays (organic EL devices, liquid crystal display devices, touch panels, etc.) and solar cells. , Sheet lenses, optical waveguides, and other optical members.

It is a schematic cross-sectional view of the multilayer film which concerns on embodiment of this invention. It is a block diagram which shows an example of the manufacturing apparatus of the multilayer film of this invention.

Hereinafter, the multilayer film according to the embodiment of the present invention will be described in detail. The same components are designated by the same reference numerals unless there is a reason for convenience, and duplicate description will be omitted. Further, in the drawings used in the following description, in order to make the features easy to understand, the featured portions may be enlarged and shown, and the dimensional ratio of each component is not the same as the actual one.

<Multilayer film>
FIG. 1 is a schematic cross-sectional view of a multilayer film according to an embodiment of the present invention. The multilayer film 1 is a multilayer film having a three-layer structure in which layers (L1: upper layer) / layer (L2: intermediate layer) / layer (L3: lower layer) are laminated in this order, and can be handled independently without the need for a support. It is a self-supporting film that can be self-supporting. Here, the "self-supporting film" 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 a flexible sheet shape, and does not include the concept of thickness.

The multilayer film 1 is composed of a cured product of a resin composition described later, and is a woven fabric or non-woven fabric made of various materials such as glass, metal, carbon, protein, cellulose, and synthetic resin, and a porous material made of such a material. Does not contain layers.

Both L1 and L3 are composed of a resin composition containing an alicyclic epoxy compound (A) and an acid generator (C), or a resin composition further containing a polyol compound (B), and the L2 is It is composed of a resin composition containing the alicyclic epoxy compound (A), the acid generator (C) and the polyol compound (B).

<Resin composition>
[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 different alicyclic structures. It is a cyclic epoxy group.

As the compound having an alicyclic epoxy group, any known compound can be selected and used. 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 made of an alicyclic epoxy resin represented by the following chemical structural formula 1 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 chemical structural formula 1 is used, particularly high transparency can be achieved.

In the above chemical structural formula 1, R _{1 to} R ₁₈ are groups independently selected from the group consisting of a hydrogen atom, a halogen atom, and an organic group.

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

Organic groups include a hydrocarbon group and a carbon atom, a hydrogen atom and an oxygen atom, a halogenated hydrocarbon group and a carbon atom, an oxygen atom and a halogen atom, and a carbon atom, a hydrogen atom and an oxygen atom. And a group consisting of 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 , 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 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 group, propionyl group, butanoyl group, pentanoyl group, hexanoyl group, heptanoyl group, octanoyl group, nonanoyl group, and decanoyyl group; aromatic groups such as benzoyl group, α-naphthoyl group, and β-naphthoyl group. 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.

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.

It is more preferable that all of R _{1 to} R ₁₈ are hydrogen atoms, particularly from the viewpoint of the hardness of the cured product obtained by using the curable composition.

In the above chemical structural formula 1, 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 chemical structural formula 1, for example, commercially available products such as the trade names "Ceroxide 2021P" and "Ceroxide 2081" (both manufactured by Daicel Corporation) can be used. Further, as the alicyclic epoxy compound represented by the chemical structural formula 1 in which X is a single bond, for example, a commercially available product such as the trade name “Selokiside 8000” (manufactured by Daicel Corporation) can be used. ..

The alicyclic epoxy compound (A) can be used alone or in combination of two or more. Among the above, 3', 4'-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate (trade name "celloxide 2021P") and ε-caprolactone-modified 3', 4'-epoxycyclohexylmethyl-3,4- It is particularly preferred to use at least one with epoxycyclohexanecarboxylate.

[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-like film that can stand on its own only with the cured product of the resin composition. ..

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, polyester polyols, polyether polyols, and polycarbonate polyols. 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. In addition, the polyol compound (B)
The number of hydroxyl groups contained in one molecule 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 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 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 mgKOH / 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 (polyester polyol) having an ether skeleton (polyester skeleton) in the molecule. Examples thereof include a polycarbonate polyol (including a polycarbonate polyol oligomer) having a carbonate skeleton (polycarbonate skeleton) in the molecule (including an oligomer). The polyol compound (B) includes other compounds such as a phenoxy resin and an 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, an ester exchange reaction), or a polyester polyol obtained by ring-opening polymerization of lactones. Examples include polyester polyols.

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, examples of the polyether polyol include ethylene glycol, diethylene glycol, 1,2-propanediol (propylene glycol), 2-methyl-1,3-propanediol, 1,3-propanediol, and 1,3-propanediol. , 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 Didiol, 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,
Multimers of polyols such as glycerin, trimethylolpropane, 1,3-dihydroxyacetone, hexylene glycol, 1,2,6-hexanetriol, ditrimethylolpropane, mannitol, sorbitol, and pentaerythritol; Additives with alkylene oxides such as ethylene oxide, propylene oxide, 1,2-butylene oxide, 1,3-butylene oxide, 2,3-butylene oxide, tetrahydrofuran, and epichlorohydrin; and cyclic ethers such as tetrahydrofurans. Ring-opening polymer (for example, polytetramethylene glycol) can be mentioned.

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". , "Adecapurronic 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 polyester polyol, the polyether polyol, and the 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 trade names "Plaxel 305" and "Plaxel 308" (both manufactured by Daicel Co., Ltd.) and trade name "Plaxel CD205PL" (manufactured by Daicel Co., Ltd.). ) And at least one of them is particularly preferable.

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) in the layer (L1) and the layer (L3) constituting the multilayer film 1 is 80. It is preferably in the range of ~ 100% by mass, and more preferably in the range of 90 to 100% by mass. If this ratio is too small, the heat resistance may decrease.

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) in the layer (L2) constituting the multilayer film 1 is 50 to 80% by mass. It is preferably in the range, more preferably in the range of 60 to 70% by mass. If this ratio is too large, the cured product of the resin composition becomes hard and brittle, and high flexibility may not be obtained. If this ratio is too small, 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 cannot be sufficiently cured, or the heat resistance becomes poor. May decrease.

[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.

Here, the ionizing radiation is a high-energy radiation capable of decomposing (ionizing) a component contained in the resin composition, specifically an acid generating agent, to generate an acid in the resin composition, for example, X-rays or ultraviolet rays. Means. Ultraviolet rays are typically used as the ionizing radiation.

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). One or more of Sun Appro Co., Ltd. can be used.

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 the cationic polymerization initiator as described above include trade names "PP-33", "CP-66", and "CP-77" (all manufactured by ADEKA Corporation); trade name "FC-509". (Manufactured by 3M Co., Ltd.); Product name "UVE1014" (manufactured by 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.) are used. can.

Further, a compound of a metal such as aluminum or titanium and a chelate compound of acetacetic acid or diketones and silanol such as triphenylsilanol, or a chelate compound of a metal such as aluminum or titanium and acetacetic acid or diketones 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) in the layer (L1), the layer (L2), and the layer (L3) constituting the multilayer film 1 is 100, which is the total amount of the alicyclic epoxy compound (A) and the polyol compound (B). It is preferably in the range of 0.05 to 0.5 parts by mass, and more preferably in the range of 0.05 to 0.1 parts by mass with respect to 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.

As described above, in L1 and L3, the amount of the alicyclic epoxy compound (A) is in the range of 80 to 100% by mass with respect to the total amount of the alicyclic epoxy compound (A) and the polyol compound (B). In L2, the amount of the alicyclic epoxy compound (A) is also in the range of 50 to 80% by mass, and in L1, L2, and L3, the sum of the alicyclic epoxy compound (A) and the polyol compound (B). The amount of the acid generator (C) with respect to 100 parts by mass is excellent in flexibility in the low temperature to normal temperature range by forming a multilayer film having a three-layer structure in the range of 0.05 to 0.5 parts by mass. The layer (L2) supports the layer (L1) and the layer (L3), and the layer (L1) and the layer (L3) having excellent heat resistance in the normal temperature to high temperature region support the layer (L2), so that the heat resistance is high. It is a film with excellent flexibility.

[Other components (D)]
The resin composition can further contain the other component (D), if necessary. For example, a cationically reactive compound such as a vinyl ether compound may be further contained for adjusting the curability. Further, an oxetane compound may be further contained in order to reduce the viscosity and adjust the reaction rate. Further, a radical reactive compound may be further contained in order to adjust the adhesion between the base material and the layer obtained by curing the resin composition.

The resin composition also 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 agent, low shrinkage agent, anti-settling agent, defoaming agent, anti-static agent, anti-fog agent, dispersant, thickener, anti-sagging agent, desiccant, leveling agent, coupling agent, adhesion promoter, Anti-rust pigments, heat stabilizers, film-material modifiers, slip agents, scratch agents, plastic agents, antibacterial agents, antifungal agents, antifouling agents, flame retardants, polymerization inhibitors, photopolymerization accelerators, sensitizers , A thermal initiator (thermal cationic polymerization initiator, thermal radical polymerization initiator), and one or more of additives such as a mold release agent may be further contained.

The amount of the component (D) is preferably 10 parts by mass or less, preferably 1 part by mass or less, based on 100 parts by mass of the total amount of the alicyclic epoxy compound (A) and the polyol compound (B). Is more preferable.

As another embodiment of the present invention, by using the multilayer film of the present invention, an optical member such as a sheet lens or an optical waveguide having excellent heat resistance, flexibility and transparency can be obtained, and a display (organic) can be obtained. An electronic device having excellent heat resistance, flexibility, and transparency can be obtained by using it for a flexible substrate such as an EL device, a liquid crystal display device, a touch panel, etc., a solar cell, or a protective film.

<Preparation of resin composition>
The above resin composition is obtained by uniformly mixing the above-mentioned components. The mixing is not particularly limited, but a stirrer such as a dispermixer, an ultramixer, a homogenizer, and a planetary stirrer / defoamer can be used. This mixing is preferably carried out in an environment not irradiated with ionizing radiation in order to prevent activation of the acid generator.

<Manufacturing of multilayer film>
In the multilayer 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 cure the coating film. It is obtained by allowing the film to be allowed to grow and then peeling the cured film from the support. For lamination, one layer may be applied and cured, and the layers may be sequentially laminated, but three layers may be applied on the support in an uncured state using a multi-layer die capable of simultaneously applying the three layers. It is also possible to cure the three layers at the same time. From the viewpoint of adhesion between layers, a method using a multilayer die is more preferable. For the production of the multilayer film 1, for example, the apparatus shown in FIG. 2 can be used.

FIG. 2 is a configuration diagram showing an example of the multilayer film manufacturing apparatus of the present invention. The multilayer film manufacturing apparatus 100 is a roll-to-roll type die coater, which includes an unwinding roll 110, a carrier film 120, guide rolls 130a to 130e, a backup roll 140, a die head 150, and an ionizing radiation irradiator 160. A heater 170, a peeling roll 180, and winding rolls 190a and 190b are provided.

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 particularly limited, but is preferably in the range of 6 to 700 μm, more preferably in the range of 40 to 250 μm, and further preferably in the range of 50 to 150 μm. 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, 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, And well-known methods such as the 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 multilayer film 1 is preferably in the range of 1 to 250 μm. If it is too thin, the strength of the multilayer film 1 is low, and there is a high possibility that the multilayer film 1 will break when peeled from the carrier film 120. If it is too thick, the heat of reaction becomes high and the storage elastic modulus of the cured product becomes very high, and as a result, the multilayer film 1 becomes hard and brittle, 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.

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 is preferably in the range of 10~3000mJ / cm ^2, more preferably in the range of 100~1000mJ / cm ^2, be in the range of 200~500mJ / 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 multilayer 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 multilayer film 1 supported by the carrier film 120. The release roll 180 abruptly and greatly changes the moving direction of the multilayer film 1 with respect to the moving direction of the carrier film 120, thereby peeling the multilayer film 1 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 multilayer 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.

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

<Example 1>
The multilayer film 1 shown in FIG. 1 was produced by the following procedure.
As the alicyclic epoxy compound (A), celloxide 2021P (manufactured by Daicel Corporation) was used. As the polyol compound (B), Praxel 305 (manufactured by Daicel Corporation) having a molecular weight of 550 g / mol and a hydroxyl value of 305 mgKOH / g was used. Further, as the acid generator (C), ADEKA PUTMER SP-170 (manufactured by ADEKA Corporation) was used. In the layer (L1) and the layer (L3), 100 parts by mass of the alicyclic epoxy compound (A) and 0.05 parts by mass of the acid generator (C) are mixed with a planetary stirring defoamer (Mazelstar KK5000, manufactured by KURABO). ) Was stirred for 15 minutes to prepare a coating solution. In the layer (L2), 60 parts by mass of an alicyclic epoxy compound (A), 40 parts by mass of a polyol compound (B), and 0.05 parts by mass of an acid generator (C) are mixed with a planetary stirring defoamer. A coating solution prepared by stirring for 15 minutes using (Mazelstar KK5000, manufactured by KURABO) was used.

Next, using the above-mentioned coating liquid, the total thickness of the layer (L1) and the layer (L3) is 15 μm, and the thickness of the layer (L2) is 50 μm by the method described with reference to FIG. Three layers of 80 μm multilayer film 1 were produced at the same time. 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 150 ° C. for 180 seconds. The carrier film 120 was wound by a take-up roll 190a with a tension of 50 N / m to obtain a peeled roll of the multilayer film 1.

<Comparative example 1>
It is composed of only the layer (L2) without providing the layer (L1) and the layer (L3), and the layer (L2) contains 100 parts by mass of the alicyclic epoxy compound (A) and 0.05 parts by mass of the acid generator. A single-layer film having a thickness of 80 μm was prepared by the same method as in Example 1 except that a coating solution prepared by stirring (C) with a planetary stirring defoamer (Mazelstar KK5000, manufactured by KURABO) for 15 minutes was used. Made.

<Comparative example 2>
It is composed of only the layer (L2) without providing the layer (L1) and the layer (L3), and the layer (L2) contains 80 parts by mass of the alicyclic epoxy compound (A) and 20 parts by mass of the polyol compound (B). And 0.05 parts by mass of the acid generator (C) are the same as in Example 1 except that a coating solution prepared by stirring with a planetary stirring defoamer (Mazelstar KK5000, manufactured by KURABO) for 15 minutes was used. Depending on the method
A single-layer film having a film thickness of 80 μm was produced.

<Comparative example 3>
The layer (L1) and the layer (L3) are not provided, and only the layer (L2) is formed. In the layer (L2), 60 parts by mass of the alicyclic epoxy compound (A) and 40 parts by mass of the polyol compound (B) And 0.05 parts by mass of the acid generator (C) are the same as in Example 1 except that a coating solution prepared by stirring with a planetary stirring defoamer (Mazelstar KK5000, manufactured by KURABO) for 15 minutes was used. By the method, a single-layer film having a thickness of 80 μm was produced.

<Comparative example 4>
As the layer (L2), a commercially available PET film, Lumirer T60 # 50 (manufactured by Toray Industries, Inc.) is used, and the layer (L1) and the layer (L3) are shown as the same resin composition coating liquid and film thickness as in Example 1. A multilayer film was produced by forming a film on each side with the device of No. 2.

<Evaluation method>
(Heat-resistant)
A sample having a size of 40 mm × 10 mm was cut out from the films obtained in Example 1 and Comparative Examples 1 to 4, and the glass transition temperature (Tg) thereof was measured using a dynamic viscoelasticity measuring device DMS6100 (manufactured by Hitachi High-Tech Science Co., Ltd.). The measurement was performed under the conditions shown in Table 1.

(Flexible)
The films obtained in Example 1 and Comparative Examples 1 to 4 were wound around a cylinder having a diameter of 0.4 mm using a mandrel tester, and those with cracks were judged as "○" and no cracks were generated. It was judged as "x".

(transparency)
The total light transmittance of the films obtained in Example 1 and Comparative Examples 1 to 4 was measured using a Haze meter (NDH7000SP manufactured by Nippon Denshoku Kogyo Co., Ltd.) in accordance with JIS K7361-1.

<Evaluation result>
The evaluation results are summarized in Table 2 below.

From the results in Table 2, when Example 1 and Comparative Example 4 are compared, the transparency of Example 1 using the resin composition specified in the present invention is improved as compared with Comparative Example 4 using a general PET film. bottom. Further, when Example 1 and Comparative Examples 1 to 3 are compared, in Example 1 in which the resin composition specified in the present invention is used and a three-layer structure is formed, a multilayer film having both heat resistance and flexibility is obtained. rice field.

On the other hand, in Comparative Example 1, L2 did not contain the polyol compound (B), and in Comparative Example 2, the amount of the alicyclic epoxy compound (A) in L2 was high, and both Comparative Examples 1 and 2 had a three-layer structure. The lack of flexibility reduced flexibility. Further, in Comparative Example 3, since the amount of the alicyclic epoxy compound (A) in L2 was low and the structure was not three-layered, the Tg was low and the heat resistance was lowered.

The multilayer film of the present invention includes various electronic papers such as liquid crystal displays, organic EL displays, field emission displays, electrophoresis type, twist ball type, electron powder fluid type, and magnetic migration type, which are used in the fields of electric and electronic parts. It can be used in the field of display devices as a substitute for a flexible display substrate, a protective film for a color filter, or a glass substrate such as a transparent conductive film substrate or a TFT substrate. It can also be used in the field of optical communication such as optical fibers and optical wave guides.

1 ... Multilayer film, L1 ... Upper layer, L2 ... Intermediate layer, L3 ... Lower layer, 100 ... Film manufacturing equipment, 110 ... Unwinding roll, 120 ... Carrier film, 130a-130e ... Guide roll, 140 ... Backup roll, 150 ... Die head , 160 ... Ionizing radiation irradiator, 170 ... Heater, 180 ... Peeling roll, 190a and 190b ... Winding roll

Claims (6)

It is a multilayer film having a three-layer structure in which layers (L1) / layers (L2) / layers (L3) are laminated in this order, and the multilayer film has a self-supporting property that can be handled independently without the need for a support. ,
Moreover, each of the above L1 and L3 is composed of a resin composition containing an alicyclic epoxy compound (A) and an acid generator (C), or a resin composition further containing a polyol compound (B).
Further, the L2 is composed of a resin composition containing the alicyclic epoxy compound (A), the acid generator (C) and the polyol compound (B).
The alicyclic epoxy compound (A) includes 3', 4'-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate and ε-caprolactone-modified 3', 4'-epoxycyclohexylmethyl-3,4-epoxy. At least one with cyclohexane carboxylate,
The polyol compound (B) is at least one of polycaprolactone triol and polycarbonate diol.
The acid generator (C) contains a triallyl sulfonium salt and contains.
Further, the L2 is a multilayer film having a composition different from that of L1 and L3.
The multilayer film according to claim 1 , 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 mgKOH / g. In L1 and L3, the amount of the alicyclic epoxy compound (A) with respect to the total amount of the alicyclic epoxy compound (A) and the polyol compound (B) is in the range of 80 to 100% by mass. Moreover, the amount of the acid generator (C) with respect to 100 parts by mass of the total amount of the alicyclic epoxy compound (A) and the polyol compound (B) is in the range of 0.05 to 0.5 parts by mass. The multilayer film according to any one of claims 1 and 2. In L2, the amount of the alicyclic epoxy compound (A) with respect to the total amount of the alicyclic epoxy compound (A) and the polyol compound (B) is in the range of 50 to 80% by mass, and the fat. The amount of the acid generator (C) with respect to 100 parts by mass of the total amount of the cyclic epoxy compound (A) and the polyol compound (B) is in the range of 0.05 to 0.5 parts by mass. The multilayer film according to any one of claims 1 to 3. An optical member comprising the multilayer film according to any one of claims 1 to 4. An electronic device comprising the multilayer film according to any one of claims 1 to 4.

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