TWI512030B - Cation polymerized resin composition, optical material and lamination obtained by using the same - Google Patents

Description

Cationic polymerizable resin composition, optical material obtained using the same, laminated body

The present invention relates to a cationically polymerizable resin composition which is provided with a cured product excellent in curability, transparency, and flexibility.

The cationically polymerizable resin composition is characterized in that it is less likely to cause hardening of oxygen in the atmosphere, and the curing reaction can be performed after the supply of energy such as ultraviolet rays is stopped, and various types of fields are available. The research is in progress.

Among them, in recent years, in order to utilize the above-described characteristics of the cationically polymerizable resin composition, attention has been paid to applications for optical applications, and in particular, the use of materials for liquid crystal modules has been actively progressing.

The main properties required for the material for the liquid crystal module include curability and transparency of the resin composition.

In the cationically polymerizable resin composition having the above-mentioned curable property and transparency, there is disclosed a photocurable resin composition for an optical member (see Patent Document 1), which comprises a flexible cationically polymerizable compound and a naphthene. The epoxy resin, the oxetane compound, and the cationic polymerization initiator of the skeleton, the flexible cationically polymerizable compound is a modified polyphenol obtained by acetalizing a polyhydric phenol or a polyvalent vinyl ether. It is obtained by performing epoxy propyl etherification.

However, recently, in the case where a liquid crystal TV, a personal computer, a mobile phone, and the like using a finger touch operation screen are gradually becoming mainstream, a material having flexibility is required in order to alleviate the pressing force on a screen such as a finger. However, it is difficult to exhibit sufficient flexibility in a cationically polymerizable resin composition such as an epoxy resin or an oxetane compound.

In view of the above, as a method for improving the flexibility, there is disclosed a curable resin composition (see, in particular, an example of Patent Document 2) which contains an acryl-based two-end polymer, an epoxy compound, and/or oxygen. A heterocyclic butane compound obtained by reacting n-butyl acrylate/ethyl acrylate/2-methoxyethyl acrylate with potassium acrylate.

However, according to the above invention, when the use ratio of the monoalkyleneoxy group-containing acrylic monomer used in the acrylic polymer is low, the curability of the resin composition is poor, and as a result, the transparency is also poor.

As mentioned above, although the industry requires materials that are hardenable, transparent, and flexible, it has not yet been found.

[Previous Technical Literature] [Patent Literature]

[Patent Document 1] JP-A-2010-248387

[Patent Document 2] JP-A-2006-265483

An object of the present invention is to provide a cationically polymerizable resin composition which is provided with a cured product having excellent curability, transparency, and flexibility.

In order to solve the above problems, the inventors of the present invention have focused on the use of an epoxy compound and a vinyl polymer as a softening component in combination.

However, when the ethylene-based polymer and the epoxy compound are used in combination, there is a problem that the two cannot be dissolved and become cloudy.

Therefore, the inventors of the present invention have conducted research on an ethylene-based polymer which enhances the compatibility with an epoxy compound.

As a result, when a (meth)acrylic monomer containing 1 mol of an alkoxy group is used in a specific mass ratio, it is found that a cationically polymerizable resin having a cured product excellent in curability, transparency, and flexibility can be obtained. The present invention has been completed.

In other words, the present invention provides a cationically polymerizable resin composition comprising a vinyl polymer (A) obtained by polymerizing a vinyl monomer (a), an epoxy compound (B), and cationic polymerization. The cationically polymerizable resin composition of the starting agent (C), wherein the ethylene-based polymer (A) is used in an amount of from 1 to 35 % by mass based on the total amount of the vinyl-based monomer (a). The alkoxy group (meth)acrylic monomer (a1) is obtained by polymerization.

Moreover, the present invention provides an optical material obtained by using the above cationically polymerizable resin composition.

Furthermore, the present invention provides a laminate which is formed on the surface of the image display portion of the liquid crystal panel, and which is formed by using the cationically polymerizable resin composition in order, and (ii) comprising the protective substrate. Laminated.

The cationically polymerizable resin composition of the present invention contains a vinyl polymer (A), an epoxy compound (B), and a cationic polymerizable initiator (C) obtained by polymerizing a vinyl monomer (a). Cationic polymer resin group Adult.

Since the ethylene-based polymer (A) is used in an amount of 35 to 100% by mass based on the total amount of the vinyl monomer (a), a (meth)acrylic monomer having 1 mol of an alkoxy group (a1) is used. Further, those obtained by polymerization can obtain a cured product excellent in curability, transparency, and flexibility, and therefore can be suitably used for optical applications. In particular, it is suitable for use as an adhesive for liquid crystal modules and other materials for liquid crystal modules. In particular, in the liquid crystal module, it is particularly suitable to use a material for use as a space provided between a protective substrate including glass and plastic and a liquid crystal panel, and the void is referred to as an air gap.

[Formation for implementing the invention]

First, the ethylene-based polymer (A) used in the present invention will be described.

The vinyl polymer (A) is obtained by polymerizing a vinyl monomer (a) containing, as an essential component, a (meth)acrylic monomer (a1) containing 1 mol of an alkyleneoxy group.

The (meth)acrylic monomer (a1) containing 1 mol of the alkyleneoxy group is not particularly limited as long as it is a monoalkyloxy(meth)acrylic acid monomer, and methoxy (meth)acrylate is exemplified. Methyl ester, ethoxymethyl (meth)acrylate, ethyl (meth) 2-ethoxyacrylate, 2-propoxyethyl (meth)acrylate, 2-butoxy (meth)acrylate Ethyl ethyl ester, (meth) 2-methoxyethyl acrylate, 3-methoxypropyl (meth)acrylate, 2-ethoxypropyl (meth)acrylate, 3-(meth)acrylate Ethoxypropyl ester, 2-methoxybutyl (meth)acrylate, 3-methoxybutyl (meth)acrylate, 4-methoxybutyl (meth)acrylate, (meth)acrylic acid 2-ethoxybutyl ester, (methyl) 3-ethoxybutyl acrylate, 4-ethoxybutyl (meth)acrylate, γ-(methacryloxypropyl)trimethoxydecane, ethoxylated o-phenylphenol (methyl Acrylate or the like, these may be used alone or in combination of two or more. Among these, in view of easiness of obtaining raw materials and control of molecular weight in synthesis, it is preferred to use an acrylic monomer containing a monoalkyloxy group to use 2-methoxyethyl acrylate, 2- Ethyl ethoxyacrylate is particularly preferred.

Examples of the vinyl monomer (a) which can be used in combination with the (meth)acrylic monomer (a1) containing 1 mol of an alkyleneoxy group include (meth)acrylic acid and methyl (meth)acrylate. Ethyl (meth)acrylate, n-propyl (meth)acrylate, isopropyl (meth)acrylate, n-butyl (meth)acrylate, isobutyl (meth)acrylate, (meth)acrylic acid Tributyl ester, n-amyl (meth)acrylate, n-hexyl (meth)acrylate, cyclohexyl (meth)acrylate, n-heptyl (meth)acrylate, n-octyl (meth)acrylate, (a) Isooctyl acrylate, 2-ethylhexyl (meth)acrylate, decyl (meth)acrylate, decyl (meth)acrylate, dodecyl (meth)acrylate, benzene (meth)acrylate Ester, methyl (meth) acrylate, benzyl (meth) acrylate, trifluoromethyl methyl (meth) acrylate, 2-trifluoromethyl ethyl (meth) acrylate, (meth) acrylate 2-perfluoroethyl ethyl ester, 2-perfluoroethyl-2-perfluorobutyl (meth)acrylate, 2-perfluoroethyl (meth)acrylate, 2-(meth)acrylate Fluoromethyl ester, diperfluoromethyl methyl (meth)acrylate, (A) 2-Perfluoromethyl-2-perfluoroethylethyl acrylate, 2-perfluorohexylethyl (meth)acrylate, 2-perfluorodecylethyl (meth)acrylate, (methyl) (meth)acrylic acid monomer such as 2-perfluorohexadecyl acrylate, 2-hydroxyethyl (meth)acrylate, 3-hydroxypropyl (meth)acrylate, (meth) propyl Hydroxy-containing (meth)acrylic monomers such as 3-hydroxybutyl acrylate, 4-hydroxybutyl (meth) acrylate, neopentyl alcohol tri(meth) acrylate, styrene, p-methyl styrene Ethylene such as ethyl styrene, propyl styrene, isopropyl styrene, styrene monomer such as p-tert-butyl styrene, vinyl acetate, vinyl propionate or trimethyl vinyl acetate The monomer or the like may be used singly or in combination of two or more kinds, and can be appropriately determined depending on the use to be used.

Among these, it is preferable to obtain a (meth)acrylic polymer using a (meth)acrylic monomer from the viewpoint of good workability by flexibility and viscosity, and to use an alkane having 1 to 6 carbon atoms. The acrylic monomer is particularly preferred.

By using the (meth)acrylic monomer (a1) containing 1 mol of the alkylene group as the total amount of the vinyl monomer (a), it is 35 to 100% by mass, and the supply can be provided with curability and transparency. A cationically polymerizable resin composition of a cured product having properties and flexibility. Among them, from the viewpoint of further reducing the haze value, it is preferred to use 42 to 100% by mass. When the use ratio of the (meth)acrylic monomer (a1) containing 1 mol of the alkyleneoxy group is less than 35% by mass, the curability is particularly deteriorated, and as a result, the transparency is also poor.

As a method for producing the ethylene-based polymer (A), a vinyl monomer (a1) containing 1 mol of an alkoxy group-containing (meth)acrylic monomer (a1) can be used by a conventionally known method. And preferably a radical polymerization initiator, wherein the epoxy compound (B) is preferably mixed and stirred at a temperature of 40 to 150 ° C for radical polymerization to form the above-mentioned ethylene-based polymer. The method of producing the mixture (A) and the epoxy compound (B) is preferable from the viewpoint of suppressing an increase in viscosity in the reaction system and improving production stability. At this time, the epoxy compound (B) does not polymerize with each other and functions as a diluent.

Further, in the above method, it is preferred to drip the mixed vinyl monomer (a) from the viewpoint of suppressing the reaction heat from causing the reaction to be out of control.

Examples of the radical polymerization initiator include, for example, benzammonium peroxide, ruthenium peroxide, ruthenium peroxide, etc., dibutyl cumene peroxide, and hydrogen peroxide. a peroxy ester such as a dialkyl peroxide such as propylbenzene, a third butyl laurate or a third butyl peroxybenzoate; or a cumene hydroperoxide; Hydrogen peroxide such as hydrogen peroxide or peroxybutyl peroxide. The amount of the radical polymerization initiator to be used is preferably 0.1 to 10 parts by mass based on 100 parts by mass of the total amount of the vinyl monomer (a).

In addition, the weight average molecular weight of the ethylene-based polymer (A) obtained by the above method is preferably from 5,000 to 100,000, more preferably from 10,000 to 30,000, from the viewpoint of good coating workability. Further, the weight average molecular weight of the ethylene-based polymer (A) is a value obtained by using gel permeation chromatography (GPC) and using tetrahydrofuran as an eluent, and converting the polystyrene.

Further, the ethylene-based polymer (A) obtained by the above method preferably has no vinyl group at its end. When a vinyl group is present at the terminal of the above (A), in the cationically polymerizable resin composition of the present invention, polymerization of the vinyl group at the terminal causes a higher molecular weight of the vinyl polymer and impairs flexibility.

Next, the epoxy compound (B) used in the present invention will be described.

The epoxy compound (B) is not particularly limited as long as it has an epoxy group, and for example, bisphenol A type epoxy propyl ether, bisphenol F type epoxidized propyl ether, and bisphenol S type ring can be used. An aromatic epoxy compound such as oxypropyl ether and bisphenol AD type epoxy propyl ether; trimethylolpropane diepoxypropyl ether, 1,6-hexanediol diepoxypropyl ether, 1, 4-butanediol diepoxypropyl ether, cyclohexane dimethanol diepoxypropyl ether, propylene glycol diepoxypropyl ether, neopentyl glycol diepoxypropyl ether, etc. Ether-based aliphatic epoxy compound; trimethylolpropane triepoxypropyl ether, glycerol triepoxypropyl ether, polyglycerol triepoxypropyl ether, diglycerin triepoxypropyl ether, etc. An epoxy compound having an alkoxy group such as an aliphatic epoxy compound of a glycidyl ether, diethylene glycol diepoxypropyl ether or polyethylene glycol diepoxypropyl ether; 1) 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate (wherein a compound of a is 0), and a caprolactone modification thereof (in the formula, a Compound of 1), its trimethyl caprolactone modification And a pentanolactone modification or the like, wherein two carbon atoms (usually adjacent to each other) of the carbon atoms forming the alicyclic structure of the alicyclic compound have a common oxygen atom bonded thereto. Epoxy-based alicyclic epoxy compounds, etc., which may be used singly or in combination. (In the above formula (1), a represents 0 or 1).

As the 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate represented by the above formula (1) and its caprolactone modified product, for example, CELLOXIDE 2021, CELLOXIDE 2021A, CELLOXIDE 2021P, Commercial products such as CELLOXIDE 2080, CELLOXIDE 2081, CELLOXIDE 2083, CELLOXIDE 2085 (above, manufactured by DAICEL Chemical Industry Co., Ltd.), Cyracure UVR-6105, Cyracure UVR-6107, and Cyracure UVR-6110 (above, manufactured by Dow Chemical Co., Ltd.).

In the above-mentioned, the cationically polymerizable resin composition of the present invention is used as a material for use in a space referred to as an air gap, and can further improve transparency in a low-wavelength region and has retardation hardening and dark-hardening. From the viewpoint of the use, it is more preferable to use an epoxy compound having no alicyclic epoxy group. In addition, the term "delay hardening property" refers to a property of irradiating an ultraviolet ray having a predetermined amount of light by a reaction for controlling anionic polymerization, and then having a characteristic of not being cured immediately but being cured after a certain period of time, and curing is completed. After the ultraviolet ray is irradiated, the curing proceeds even if the ultraviolet ray is not irradiated.

Among the above epoxy compounds having no alicyclic epoxy group, from the viewpoint of particularly good transparency, 1,6-hexanediol diepoxypropyl ether and 1,4-butanediol diepoxide are used. Propyl ether, cyclohexane dimethanol diepoxypropyl ether, neopentyl glycol diepoxypropyl ether, trimethylolpropane diepoxypropyl ether, trimethylolpropane triepoxypropyl ether It is especially good.

The mass ratio of the ethylene-based polymer (A) to the epoxy compound (B) is (A)/(B)=50/50-80 from the viewpoint of further improving the curability of the cationically polymerizable resin composition. /20 is better, with (A) / (B) = 60 / 40 ~ 70 / 30 is particularly good. Moreover, the mass of the said vinyl type polymer (A) shows the total mass of the said vinyl type monomer (a).

Further, the cationically polymerizable resin composition of the present invention may be used in combination with the epoxy compound (B) in combination with other cationically polymerizable compounds as long as the effects of the present invention are not impaired.

The other cation-polymerizable compound may, for example, be an oxetane compound having 1 to 4 oxetanyl groups, and these may be used alone or in combination of two or more.

The oxetane compound having one oxetanyl group, for example, an oxetane compound represented by the following formula (2),

(R ₁ in the general formula (2) represents a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, an alkoxyalkyl group having 1 to 5 carbon atoms, or a hydroxyalkyl group having 1 to 6 carbon atoms. R ₂ represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms which may be branched, an aliphatic cyclic structure, or an aromatic structure).

Examples of the alkyl group having 1 to 8 carbon atoms which can constitute R _{1 in} the above formula (2) include a methyl group, an ethyl group, a n-propyl group, an isopropyl group and a 2-ethylhexyl group.

Examples of the alkoxyalkyl group having 1 to 5 carbon atoms which can form R _{1 in} the above formula (2) include a methoxymethyl group, an ethoxymethyl group, and a methoxyethyl group. Ethoxyethyl, propoxyethyl and the like.

In addition, examples of the hydroxyalkyl group having 1 to 6 carbon atoms which can form R _{1 in} the above formula (2) include a methylol group, a hydroxyethyl group, a hydroxypropyl group and the like.

The alkyl group having 1 to 10 carbon atoms which may be branched by R _{2 in} the above formula (2) may, for example, be a linear alkyl group such as a methyl group or an ethyl group or a propyl group, and A branched alkyl group of 2-ethylhexyl or the like.

The aliphatic cyclic structure which can constitute R _{2 in} the above formula (2) is, for example, a cyclohexyl group. The cyclohexyl group or the like may have an alkyl group or the like which substitutes a hydrogen atom.

In addition, examples of the aromatic structure which can constitute R _{2 in} the above formula (2) include a phenyl group and the like. The phenyl group or the like may have an alkyl group or the like which substitutes a hydrogen atom.

Examples of the oxetane compound having 2 to 4 oxetanyl groups include oxetane compounds represented by the following formulas (3) and (4).

R ₁ in the above formulas (3) and (4) each independently represent a hydrogen atom, a linear, branched or cyclic alkyl group having 1 to 6 carbon atoms, an allyl group, an aryl group, or the like. The aralkyl group, the furyl group or the thienyl group, and the R ₂ groups each independently represent a divalent organic residue, and the Z series each independently represents an oxygen atom or a sulfur atom.

The linear, branched or cyclic alkyl group having 1 to 6 carbon atoms represented by R ₁ in the above general formulae (3) and (4) may, for example, be a methyl group, an ethyl group or a positive or Isopropyl, n-, iso- or tert-butyl, pentyl, hexyl, cyclohexyl, etc., and, as the aryl group, for example, a phenyl group, a naphthyl group, a tolyl group, a xylyl group, etc., and an aralkyl group For example, there are a benzyl group, a phenethyl group and the like.

In addition, as the divalent organic residue represented by R ₂ in the above formula (3), for example, a linear, branched or cyclic alkyl group having 4 to 30 carbon atoms is used. a poly(oxyalkylene) group, a phenylene group, a benzene dimethyl group, a structure represented by the following formulas (5) and (6),

R ₃ in the above formula (5) represents an oxygen atom, a sulfur atom, CH ₂ , NH, SO, SO ₂ , C(CF ₃ ) ₂ or C(CH ₃ ) ₂ .

R ₄ in the above formula (6) represents an alkylene group having 1 to 6 carbon atoms, an arylene group, and a functional group represented by the following formula (7).

In the above formula (7), a represents an integer of 1 to 6, and b represents an integer of 1 to 15.

As the above formula (7), b is preferably an integer of 1 to 3.

The oxetane compound having 2 to 4 oxetane ring structures is, for example, commercially available ARON OXETANE OXT-221, OXETANE OXT-121, OXETANE OXT-223 (above, East Asia Synthesis) )), ETERNACOLL OXBP (above, Ube Industries Co., Ltd.).

Next, the cationically polymerizable initiator (C) used in the present invention will be described.

The cationically polymerizable initiator (C) is a photocationic polymerization initiator which generates an acid capable of starting cationic polymerization by irradiation with an energy ray such as ultraviolet rays, and a thermal cationic polymerization property which generates an acid by heating or the like. In the case of using a material for a liquid crystal module, the present invention is preferably a photocationic polymerization initiator, in view of preventing heat from causing discoloration or the like.

The photocationic polymerization initiator can be, for example, an aromatic moiety, an aromatic iodonium, an aromatic diazonium, an aromatic ammonium, a thianthrenium, or a thioxantonium. , (2,4-cyclopentadien-1-yl)[(1-methylethyl)benzene]-Fe cation, the anion moiety is from BF ₄ ^- , PF ₆ ^- , SbF ₆ ^- , [BX ₄ ] ^- consisting of onium salts (wherein, X is substituted with the based at least two fluorine or trifluoromethyl phenyl), used alone or in combination of two or more.

As the aromatic sulfonium salt, for example, bis[4-(diphenylfluorenyl)phenyl]thioether bishexafluorophosphate and bis[4-(diphenylfluorenyl)phenyl]thioether bis(6) can be used. Fluorononanoate, bis[4-(diphenylfluorenyl)phenyl]thioether bistetrafluoroborate, bis[4-(diphenylfluorenyl)phenyl]thioether quinone (pentafluorophenyl) Borate, diphenyl-4-(phenylthio)phenylphosphonium hexafluorophosphate, diphenyl-4-(phenylthio)phenylphosphonium hexafluoroantimonate, diphenyl-4- (phenylthio)phenylphosphonium tetrafluoroborate, diphenyl-4-(phenylthio)phenylphosphonium (pentafluorophenyl)borate, triphenylsulfonium hexafluorophosphate, triphenyl Hexafluorodecanoate, triphenylsulfonium tetrafluoroborate, triphenylsulfonium (pentafluorophenyl) borate, bis[4-(bis(4-(2-hydroxyethoxy)) Phenylfluorenyl)phenyl]thioether bishexafluorophosphate, bis[4-(bis(4-(2-hydroxyethoxy))phenyl) phenyl) thioether bis(hexafluoroantimonic acid) Ester, bis[4-(bis(4-(2-hydroxyethoxy)phenyl) phenyl) thioether bistetrafluoroborate, bis[4-(di(4-(2-hydroxy)) Oxyphenyl)phenylmercapto)phenyl)thioether quinone (pentafluorophenyl) borate.

Further, as the aromatic iodonium, for example, diphenyliodonium hexafluorophosphate, diphenyliodonium hexafluoroantimonate, diphenyliodonium tetrafluoroborate, diphenyliodonium can be used. (pentafluorophenyl)borate, bis(dodecylphenyl)iodonium hexafluorophosphate, bis(dodecylphenyl)iodonium hexafluoroantimonate, bis(dodecylphenyl)iodine Tetrafluoroborate, bis(dodecylphenyl)iodonium (pentafluorophenyl)borate, tetrakis-methylphenyl-4-(1-methylethyl)phenyliodonium Fluorophosphate, 4-methylphenyl-4-(1-methylethyl)phenyliodonium hexafluoroantimonate, 4-methylphenyl-4-(1-methylethyl)phenyl Iodine tetrafluoroborate, 4-methylphenyl-4-(1-methylethyl)phenyliodonium (pentafluorophenyl) borate, and the like.

As the aromatic diazonium salt, for example, phenyldiazonium hexafluorophosphate, phenyldiazonium hexafluoroantimonate, phenyldiazonium tetrafluoroborate, or phenyldiazonium can be used. (pentafluorophenyl) borate and the like.

Further, as the aromatic ammonium salt, 1-benzyl-2-cyanopyridinium hexafluorophosphate, 1-benzyl-2-cyanopyridinium hexafluoroantimonate, 1-benzyl-2 can be used. -cyanopyridinium tetrafluoroborate, 1-benzyl-2-cyanopyridinium (pentafluorophenyl) borate, 1-(naphthylmethyl)-2-cyanopyridinium hexafluorophosphate Ester, 1-(naphthylmethyl)-2-cyanopyridinium hexafluoroantimonate, 1-(naphthylmethyl)-2-cyanopyridinium tetrafluoroborate, 1-(naphthylmethyl)- 2-cyanopyridinium (pentafluorophenyl) borate or the like.

Further, as the thioxanthene salt, S-biphenyl 2-isopropylthioxanthene hexafluorophosphate or the like can be used.

Further, as the (2,4-cyclopentadien-1-yl)[(1-methylethyl)benzene]-Fe salt, (2,4-cyclopentadien-1-yl) can be used. (1-methylethyl)benzene]-Fe(II) hexafluorophosphate, (2,4-cyclopentadien-1-yl)[(1-methylethyl)benzene]-Fe(II) Hexafluorodecanoate, (2,4-cyclopentadien-1-yl)[(1-methylethyl)benzene]-Fe(II) tetrafluoroborate, (2,4-cyclopentane Alken-1-yl)[(1-methylethyl)benzene]-Fe(II) quinone (pentafluorophenyl) borate or the like.

The photocationic polymerization initiator is, for example, commercially available CPI-100P, CPI-110P, CPI-101A, CPI-200K, CPI-210S (above, manufactured by SAN-APRO), and Cyracure photohardening. Starting agent UVI-6990, Cyracure photohardening initiator UVI-6992, Cyracure photohardening initiator UVI-6976 (above, Dow‧Chemical Japan), ADEKA OPTOMER-SP-150, ADEKA OPTOMER-SP -152, ADEKA OPTOMER-SP-170, ADEKA OPTOMER-SP-172, ADEKA OPTOMER-SP-300 (above, ADEKA (share) system), CI-5102, CI-2855 (above, Japan Soda (share) system) , SANEIDO SI-60L, SANEIDO SI-80L, SANEIDO SI-100L, SANEIDO SI-110L, SANEIDO SI-180L, SANEIDO SI-110, SANEIDO SI-180 (above, Sanxin Chemical Industry Co., Ltd.), ESACURE 1064, ESACURE 1187 (manufactured by Lamberti Co., Ltd.), OMNICAT 550 (manufactured by IGM Resins Co., Ltd.), IRGACURE 250 (manufactured by CIBA ‧ SPECIA LTY CHEMICALS), RHODORSILPHOTOINITIA TOR 2074 (manufactured by Rhodia ‧ Japan Co., Ltd.), and the like.

Further, as the thermal cationically polymerizable initiator, for example, a benzyl sulfonium salt, a thiophene hydrazine, a tetrahydrothiophene sulfonium salt, a benzylammonium salt, a pyridinium salt, a phosphonium salt, a carboxylic acid ester, a sulfonate, or an amine can be used.醯imine and so on.

As the thermal cationic polymerization initiator, "ADEKAOPTON CP77", "ADEKAOPTON CP66" (above, ADEKA), "CI-2639", "CI-2624" (above, Japan Soda (share)) can also be used. Commercial products such as "SANEIDO SI-60L", "SANEIDO SI-80L", and "SANEIDO SI-100L" (above, Sanshin Chemical Industry Co., Ltd.).

The amount of use of the cationically polymerizable initiator (C) is not particularly limited, and is preferably 0.01 to 5 parts by mass based on 100 parts by mass of the total mass of the component (A) and the component (B).

Next, a method for producing the cationically polymerizable resin composition of the present invention will be described.

The cationically polymerizable resin composition of the present invention is a mixture of the ethylene-based polymer (A) and the epoxy compound (B), for example, using a homomixer, an ultra-speed stirrer, a dispersing mixer, a paddle mixer or the like. X), the cationically polymerizable initiator (C), and a cationically polymerizable compound other than the above, and other additives are mixed and stirred to produce.

From the viewpoint of coating workability, the cationically polymerizable resin composition obtained by the above method is preferably 100 to 100,000 mPa·s, preferably 500 to 20,000 mPa·s. Further, the viscosity is a value measured at 25 ° C using a B-type viscometer.

The cationically polymerizable resin composition of the present invention may be added with various additives as necessary insofar as the effects of the present invention are not impaired.

As the various additives described above, for example, a thixotropic imparting agent, a sensitizer, a leveling agent, an antioxidant, an adhesion-imparting agent, a wax, a heat stabilizer, a light stabilizer, a fluorescent whitening agent, a foaming agent, and a thermoplastic resin can be used. , thermosetting resin, organic solvent, conductivity imparting agent, antistatic agent, moisture permeability improving agent, water repellent, hollow foam, compound containing crystal water, flame retardant, water absorbing agent, moisture absorbent, Deodorant, foam stabilizer, antifoaming agent, antifungal agent, preservative, algicide, anti-adhesive agent, water repellent, organic and inorganic water-soluble compound, etc.

As the thixotropy-imparting agent, for example, surface-treated calcium carbonate, finely divided cerium oxide, bentonite, zeolite, or the like can be used.

The cationically polymerizable resin composition of the present invention can be cured by irradiation with an energy ray such as ultraviolet rays.

The energy ray for irradiating the ultraviolet rays or the like is preferably 50 to 5000 mJ/cm ^{2 , more} preferably 100 to 3000 mJ/cm ² , and particularly preferably 300 to 1500 mJ/cm ² .

As a source of ultraviolet rays, for example, a well-known lamp such as a xenon lamp, a neon-mercury lamp, a halogenated metal lamp, a high pressure mercury lamp, or a low pressure mercury lamp can be used. In addition, the ultraviolet irradiation amount is based on a value measured by a wavelength of 300 to 390 nm using UV CHECKER-UVR-N1 (manufactured by GS YUASA Co., Ltd.).

Further, it is also possible to further promote hardening by heating at about 40 to 80 ° C after the irradiation of the energy ray as necessary.

The cationically polymerizable resin composition of the present invention contains a vinyl polymer (A), an epoxy compound (B), and a cationic polymerizable initiator (C) obtained by polymerizing a vinyl monomer (a). In the cationically polymerizable resin composition, the ethylene-based polymer (A) is used in an amount of from 35 to 100% by mass based on the total amount of the vinyl monomer (a), and contains 1 mol of an alkoxy group ( When the methyl group-acrylic monomer (a1) is obtained by polymerization, a cured product excellent in curability, transparency, and flexibility can be obtained, and thus it can be suitably used for optical applications. In particular, it is suitable for use as an adhesive for liquid crystal modules and other materials for liquid crystal modules. In particular, in the liquid crystal module, it is particularly suitable to use a material for use as a space provided between a protective substrate including glass and plastic and a liquid crystal panel, and the void is referred to as an air gap.

The air gap is used to ensure that the external impact is directly transmitted to the liquid crystal panel to cause damage to the liquid crystal panel.

When the cationically polymerizable resin composition of the present invention is used as a material for use in the space of the air gap, at least the cationically polymerizable resin composition of the present invention is used on the surface of the image display portion of the liquid crystal panel. The formed layer (i) and the protective layer (ii) including the protective substrate are laminated.

Here, the layer (i) can be formed by using the cationically polymerizable resin composition, and the thickness thereof varies depending on the field of use of the liquid crystal display, etc., but is caused by a thinning of the liquid crystal display, which is approximately 10~. A thickness of 500 μm is preferred, and a thickness of 50 to 500 μm is more preferable.

Further, the protective layer (ii) is provided for the purpose of preventing the image display portion of the liquid crystal panel constituting the liquid crystal display from being damaged by an external impact. As the protective layer (ii), a transparent plastic substrate, a glass substrate, or the like which can visualize the image displayed on the liquid crystal panel or the like is preferably used. Further, the surface of the substrate may be colored.

As the plastic substrate, a substrate containing an acrylic resin or the like which is generally used, including PC (polycarbonate), PBT (polybutylene terephthalate), and PPS (polyphenylene sulfide) can be used. A substrate such as PPE (polyphenylene ether), PET (polyethylene terephthalate), COP (cycloolefin polymer) or the like.

Further, the liquid crystal panel is not particularly limited as long as it can display a desired image, and can be used by a user.

As the liquid crystal panel, one or both sides of the liquid crystal material may be sealed between a transparent substrate including glass and plastic, and the polarizing plate, the polarizing filter, the electrode, and the required viewing angle compensation film may be used. The various functionalities give the substrate a laminate.

It is preferable that the layer (i) and the protective layer (ii) are directly laminated on the surface of the image display portion of the liquid crystal panel, specifically, the surface of the polarizing plate and the polarizing filter that constitute the outermost portion of the liquid crystal panel. Preferably, the surface area layer of the polarizing plate is preferably in order.

As the polarizing plate, a plastic substrate containing a hydrophilic polymer compound such as polyvinyl alcohol, partially methylalized polyvinyl alcohol, or an ethylene-vinyl acetate copolymer-based partial saponified product can be used, and iodine and two colors are adsorbed. A dichroic material such as a dye is uniaxially stretched; and a polyene-based alignment film such as a dehydrated material of polyvinyl alcohol or a dehydrochlorinated product of polyvinyl chloride.

Further, a protective film containing a cellulose acetate resin and a resin called a cycloolefin resin may be attached to the surface of the polarizing plate as needed.

The thickness of the liquid crystal panel described above may be in accordance with the field and use of the liquid crystal display of the present invention, the required function, and the like.

Next, a method of producing a liquid crystal display using the cationically polymerizable resin composition of the present invention will be described.

The method for producing a liquid crystal display using the cationically polymerizable resin composition of the present invention is, for example, a liquid crystal panel and a protective layer (ii) integrated in advance and between the liquid crystal panel and the protective layer (ii). A liquid crystal display having a gap which is generally called an air gap, after the gap flows into the cationically polymerizable resin composition, the inflow port is closed, and then ultraviolet rays are irradiated from the protective layer (ii), and further, at 40 to 80 ° C. A method of heating the above-mentioned cationically polymerizable resin composition by heating at a temperature. In addition, from the viewpoint of uniform curing, the cationically polymerizable resin composition which has been irradiated with ultraviolet rays in advance may be rapidly flowed into the voids after the irradiation and the inlet is closed, and then by 40 to 80 ° C. The cationically polymerizable resin composition is cured by heating at a temperature.

Further, as a method of producing a liquid crystal display using the cationically polymerizable resin composition of the present invention, in addition to the above methods, the following method can also be employed.

Applying the cationically polymerizable resin composition to the surface of the image display portion of the liquid crystal panel, and irradiating the coated surface with ultraviolet rays, placing the protective substrate on which the protective layer (ii) is formed on the coated surface, bonding them, and bonding them a method of curing the cationically polymerizable resin composition; and applying the cationically polymerizable resin composition to the protective substrate of the protective layer (ii), and irradiating the coated surface with ultraviolet rays, and then placing the coated surface on the coated surface A method of curing the surface of the image display portion of the liquid crystal panel and bonding the cationically polymerizable resin composition.

The cationically polymerizable resin composition may be further heated at a temperature of approximately 40 to 80 ° C after being irradiated with ultraviolet rays.

The thickness of the liquid crystal panel described above may be in accordance with the field and use of the liquid crystal display of the present invention, the required function, and the like.

[Examples]

Hereinafter, the present invention will be more specifically described by the examples, but the scope of the invention is not limited by the examples.

Further, the present invention is not limited to the prior art, and "parts" are "parts by mass" and "%" is "mass%".

[Synthesis Example 1]

<Synthesis of a mixture of a vinyl monomer and an epoxy compound (X-1)>

In a reaction vessel equipped with a stirrer, a reflux condenser, a thermometer, a dropping funnel, and a nitrogen inlet, 18 parts of cyclohexane dimethanol digoxypropyloxy ether was added and replaced with nitrogen, and then dissolved at 80 ° C for 5 hours. 5 parts of cyclohexanedimethanol diglycidoxy ether, 5 parts of 1,2-,3,3-tetramethylbutyl peroxy-2-ethylhexanoate, and 60 parts of 2-methoxy After ethyl acrylate, one part of 1,1,3,3-tetramethyl peroxy-2-ethylhexanoate dissolved in 2 parts of cyclohexane dimethanol digoxypropyl ether was added dropwise. After the butyl ester, the mixture was reacted at 80 ° C for 3 hours and 30 minutes to obtain a mixture (X-1) of a vinyl monomer having a weight average molecular weight of 58453 and an epoxy compound.

[Synthesis Example 2]

<Synthesis of a mixture of a vinyl monomer and an epoxy compound (X-2)>

In a reaction vessel equipped with a stirrer, a reflux condenser, a thermometer, a dropping funnel, and a nitrogen inlet, 13 parts of cyclohexane dimethanol digoxypropyloxy ether was added and replaced with nitrogen, and then dissolved at 80 ° C for 5 hours. 5 parts of cyclohexanedimethanol diepoxypropoxy ether, 5 parts of 1,2-,3,3-tetramethylbutyl peroxy-2-ethylhexanoate, and 70 parts of 2-methoxy After ethyl acrylate, one part of 1,1,3,3-tetramethyl peroxy-2-ethylhexanoate dissolved in 2 parts of cyclohexane dimethanol digoxypropyl ether was added dropwise. After the butyl ester, the mixture was reacted at 88 ° C for 5 hours to obtain a mixture (X-2) of a vinyl monomer having a weight average molecular weight of 44,858 and an epoxy compound.

[Synthesis Example 3]

<Synthesis of a mixture of a vinyl monomer and an epoxy compound (X-3)>

In a reaction vessel equipped with a stirrer, a reflux condenser, a thermometer, a dropping funnel, and a nitrogen inlet, 13 parts of cyclohexane dimethanol digoxypropyloxy ether was added and replaced with nitrogen, and then dissolved at 80 ° C for 5 hours. 5 parts of cyclohexanedimethanol diepoxypropoxy ether 5 parts of 1,2-,3,3-tetramethylbutyl peroxy-2-ethylhexanoate, 56 parts of 2-methoxy Ethyl acrylate and 14 parts of n-butyl acrylate, and then 1 part of peroxy-2-ethylhexanoic acid 1,1,3 dissolved in 2 parts of cyclohexane dimethanol digoxyloxy ether After 3-methylbutyl butyl ester, it was reacted at 88 ° C for 5 hours to obtain a mixture (X-3) of a vinyl monomer having a weight average molecular weight of 23414 and an epoxy compound.

[Synthesis Example 4]

<Synthesis of a mixture of a vinyl monomer and an epoxy compound (X-4)>

In a reaction vessel equipped with a stirrer, a reflux condenser, a thermometer, a dropping funnel, and a nitrogen inlet, 13 parts of cyclohexane dimethanol digoxypropyloxy ether was added and replaced with nitrogen, and then dissolved at 80 ° C for 5 hours. 5 parts of cyclohexanedimethanol diepoxypropoxy ether, 5 parts of 1,2-,3,3-tetramethylbutyl peroxy-2-ethylhexanoate, 42 parts of 2-methoxyl Ethyl acrylate and 28 parts of n-butyl acrylate, and then 1 part of peroxy-2-ethylhexanoic acid 1,1,3 dissolved in 2 parts of cyclohexane dimethanol diepoxypropoxy ether After the 3-tetramethylbutyl ester was reacted at 88 ° C for 5 hours, a mixture (X-4) of a vinyl monomer having a weight average molecular weight of 16382 and an epoxy compound was obtained.

[Synthesis Example 5]

<Synthesis of a mixture of a vinyl monomer and an epoxy compound (X-5)>

In a reaction vessel equipped with a stirrer, a reflux condenser, a thermometer, a dropping funnel, and a nitrogen inlet, 13 parts of cyclohexane dimethanol digoxypropyloxy ether was added and replaced with nitrogen, and then dissolved at 80 ° C for 5 hours. 5 parts of cyclohexanedimethanol diepoxypropoxy ether, 5 parts of 1,2-,3,3-tetramethylbutyl peroxy-2-ethylhexanoate, 35 parts of 2-methoxy Ethyl acrylate and 35 parts of n-butyl acrylate, and then 1 part of peroxy-2-ethylhexanoic acid 1,1,3 dissolved in 2 parts of cyclohexane dimethanol digoxyloxy ether After 3-methylbutyl butyl ester, it was reacted at 88 ° C for 5 hours to obtain a mixture (X-5) of a vinyl monomer having a weight average molecular weight of 25,114 and an epoxy compound.

[Synthesis Example 6]

<Synthesis of a mixture of a vinyl monomer and an epoxy compound (X-6)>

In a reaction vessel equipped with a stirrer, a reflux condenser, a thermometer, a dropping funnel, and a nitrogen inlet, 13 parts of cyclohexane dimethanol digoxypropyloxy ether was added and replaced with nitrogen, and then dissolved at 80 ° C for 5 hours. 5 parts of cyclohexanedimethanol diepoxypropoxy ether, 5 parts of 1,2-,3,3-tetramethylbutyl peroxy-2-ethylhexanoate, 29.4 parts of 2-methoxy Ethyl acrylate and 40.6 parts of n-butyl acrylate, followed by dropwise addition of 1 part of peroxy-2-ethylhexanoic acid 1,1,3 dissolved in 2 parts of cyclohexane dimethanol diepoxypropoxy ether After the 3-tetramethylbutyl ester was reacted at 88 ° C for 5 hours to obtain a mixture (X-6) of a vinyl monomer having a weight average molecular weight of 14,066 and an epoxy compound.

[Synthesis Example 7]

<Synthesis of a mixture of a vinyl monomer and an epoxy compound (X-7)>

In a reaction vessel equipped with a stirrer, a reflux condenser, a thermometer, a dropping funnel, and a nitrogen inlet, 13 parts of cyclohexane dimethanol digoxypropyloxy ether was added and replaced with nitrogen, and then dissolved at 80 ° C for 5 hours. 5 parts of cyclohexanedimethanol diepoxypropoxy ether, 5 parts of 1,2-,3,3-tetramethylbutyl peroxy-2-ethylhexanoate, 28 parts of 2-methoxyl Ethyl acrylate and 42 parts of n-butyl acrylate, and then 1 part of peroxy-2-ethylhexanoic acid 1,1,3 dissolved in 2 parts of cyclohexane dimethanol digoxyloxy ether After 3-methylbutyl butyl ester, it was reacted at 88 ° C for 5 hours to obtain a mixture (X-7) of a vinyl monomer having a weight average molecular weight of 14,485 and an epoxy compound.

[Synthesis Example 8]

<Synthesis of a mixture of a vinyl monomer and an epoxy compound (X-8)>

In a reaction vessel equipped with a stirrer, a reflux condenser, a thermometer, a dropping funnel and a nitrogen inlet, 13 parts of 3,4-epoxycyclohexenylmethyl-3',4'-epoxycyclohexenecarboxylic acid was added. After the ester was replaced with nitrogen, 5 parts of 3,4-epoxycyclohexenylmethyl-3',4'-epoxycyclohexene carboxylate was added dropwise at 80 ° C for 5 hours. 1,1,3,3-tetramethylbutyl peroxy-2-ethylhexanoate, 70 parts of ethyl 2-methoxyacrylate, and then dissolved in 2 parts of 3,4-epoxycyclohexane Alkenylmethyl-3',4'-epoxycyclohexenecarboxylate 1 part of 1,1,3,3-tetramethylbutyl peroxy-2-ethylhexanoate, after 88 The mixture was reacted at ° C for 5 hours to obtain a mixture (X-8) of a vinyl monomer having a weight average molecular weight of 54134 and an epoxy compound.

[Synthesis Example 9]

<Synthesis of a mixture of a vinyl monomer and an epoxy compound (X-9)>

In a reaction vessel equipped with a stirrer, a reflux condenser, a thermometer, a dropping funnel, and a nitrogen inlet, 13 parts of cyclohexane dimethanol digoxypropyloxy ether was added and replaced with nitrogen, and then dissolved at 80 ° C for 5 hours. 5 parts of cyclohexanedimethanol diepoxypropoxy ether, 5 parts of 1,2-,3,3-tetramethylbutyl peroxy-2-ethylhexanoate, 24.5 parts of 2-methoxyl Ethyl acrylate and 45.5 parts of n-butyl acrylate, followed by dropwise addition of 1 part of peroxy-2-ethylhexanoic acid 1,1,3 dissolved in 2 parts of cyclohexane dimethanol diepoxypropoxy ether After 3-methylbutyl butyl ester, it was reacted at 88 ° C for 5 hours to obtain a mixture (X-9) of a vinyl monomer having a weight average molecular weight of 19,248 and an epoxy compound.

[Comparative Synthesis Example 1]

<Synthesis of a mixture of a vinyl monomer and an epoxy compound (X-10)>

In a reaction vessel equipped with a stirrer, a reflux condenser, a thermometer, a dropping funnel, and a nitrogen inlet, 13 parts of cyclohexane dimethanol digoxypropyloxy ether was added and replaced with nitrogen, and then dissolved at 80 ° C for 5 hours. 5 parts of cyclohexanedimethanol diepoxypropoxy ether, 5 parts of 1,2-,3,3-tetramethylbutyl peroxy-2-ethylhexanoate, 21 parts of 2-methoxyl Ethyl acrylate and 49 parts of n-butyl acrylate, and then 1 part of peroxy-2-ethylhexanoic acid 1,1,3 dissolved in 2 parts of cyclohexane dimethanol digoxypropyl ether After the 3-tetramethylbutyl ester was reacted at 88 ° C for 5 hours to obtain a mixture (X-10) of a vinyl monomer having a weight average molecular weight of 16625 and an epoxy compound.

[Comparative Synthesis Example 2]

<Synthesis of a mixture of a vinyl monomer and an epoxy compound (X-11)>

In a reaction vessel equipped with a stirrer, a reflux condenser, a thermometer, a dropping funnel, and a nitrogen inlet, 13 parts of cyclohexane dimethanol digoxypropyloxy ether was added and replaced with nitrogen, and then dissolved at 80 ° C for 5 hours. 5 parts of cyclohexanedimethanol diepoxypropoxy ether, 5 parts of 1,2-,3,3-tetramethylbutyl peroxy-2-ethylhexanoate, 7 parts of 2-methoxyl Ethyl acrylate and 63 parts of n-butyl acrylate, and then 1 part of peroxy-2-ethylhexanoic acid 1,1,3 dissolved in 2 parts of cyclohexane dimethanol digoxyloxy ether After the 3-tetramethylbutyl ester was reacted at 88 ° C for 5 hours to obtain a mixture (X-11) of a vinyl monomer having a weight average molecular weight of 13,659 and an epoxy compound.

[Comparative Synthesis Example 3]

<Synthesis of a mixture of a vinyl monomer and an epoxy compound (X-12)>

In a reaction vessel equipped with a stirrer, a reflux condenser, a thermometer, a dropping funnel, and a nitrogen inlet, 13 parts of cyclohexane dimethanol digoxypropyloxy ether was added and replaced with nitrogen, and then dissolved at 80 ° C for 5 hours. 5 parts of cyclohexanedimethanol diepoxypropoxy ether, 5 parts of 1,2-,3,3-tetramethylbutyl peroxy-2-ethylhexanoate, and 70 parts of n-butyl acrylate Thereafter, 1 part of 1,1,3,3-tetramethylbutyl peroxy-2-ethylhexanoate dissolved in 2 parts of cyclohexane dimethanol digoxyloxy ether was added dropwise. The mixture was reacted at 88 ° C for 5 hours to obtain a mixture (X-12) of a vinyl monomer having a weight average molecular weight of 13050 and an epoxy compound.

[Example 1]

100 parts of the mixture (X-1) of the ethylene-based polymer obtained in Synthesis Example 1 and the epoxy compound and 0.6 parts of CPI-100P as a photocationic polymerization initiator were placed in a dispersing mixer. A 50% solution of propylene carbonate of diphenyl-4-(phenylthio)phenylphosphonium hexafluorophosphate) was mixed and stirred to prepare a cationically polymerizable resin composition having a viscosity of 26,000 mPa·s (25 ° C).

[Examples 2 to 9 and Comparative Examples 1 to 3]

A cationically polymerizable resin composition was obtained in the same manner as in Example 1 except that the types of the mixture of the ethylene-based polymer and the epoxy compound to be used were changed as shown in Tables 1 to 3.

[Method for Measuring Weight Average Molecular Weight of Ethylene Polymer]

The weight average molecular weight of the ethylene-based polymer used in the examples and the comparative examples was measured as follows.

(measurement device ‧ conditions)

TOSOH (share) system, integral GPC device

Device: HLC-8220GPC

Detector: RI (differential refractometer)

Column: TSK-gel G5000HxL (7.8×300mm)×1G4000HxL (7.8×300mm)×1G3000HxL (7.8×300mm)×1G2000HxL (7.8×300mm)×1

Mobile phase: THF

Flow rate: 1.0mL/min

Set temperature: 40 ° C

Injection amount: 100 μl (sample concentration: 0.4%)

The weight average molecular weight changed from polystyrene (*) was measured.

※Polystyrene: TOSOH (stock) TSK standard styrene

[Evaluation method of sclerosing property]

The cationically polymerizable resin composition obtained in the examples and the comparative examples was applied onto a release-treated polyethylene terephthalate film (release PET) at a film thickness of about 100 μm using a coater.

Next, a conveyor belt type ultraviolet irradiation apparatus CSOT-40 (manufactured by GS YUASA, using a high-pressure mercury lamp, having a strength of 120 W/cm, which is set to have an ultraviolet irradiation amount of 200 mJ/cm ² per pass through the apparatus, is used. The speed of the conveyor belt was 10 m/min, and the coated product was passed through the apparatus 5 times and the coated surface was irradiated with ultraviolet rays, and then heated at a temperature of 40 to 80 ° C for about 5 minutes to obtain a release PET and a cationically polymerizable resin. A laminate of films.

The film-based curing of the laminate immediately after the ultraviolet irradiation and the heat curing was evaluated as "○", and the "X" was evaluated when the film was not cured.

[Evaluation method of transparency]

The cationically polymerizable resin film was peeled off from the laminate, and an ultraviolet-visible spectrophotometer V-570 (manufactured by JASCO Corporation) and a haze meter NDH5000 (manufactured by Nippon Denshoku Co., Ltd.) were used, in accordance with JIS K 7105. The total light transmittance and haze of the cationically polymerizable resin film were measured. In addition, when the evaluation of the curability is "x" and the cationically polymerizable resin film cannot be peeled off from the laminate, the transparency of the cationically polymerizable resin film cannot be evaluated, and it is evaluated as "-".

(total light transmittance)

When the total light transmittance at 380 nm, 500 nm, and 780 nm is 90% or more, it is evaluated as "○", 80% or more to less than 90% is "△", and less than 80% is "X".

(haze)

When the haze value is less than 0.5, it is evaluated as "○", 0.5 or more and less than 1.0 is "△", and 1.0 or more is "x".

In addition, the evaluation of the total light transmittance and the evaluation of the haze is "△", and the transparency of the usable level is used, and the "○" is a person having good transparency.

In addition, the evaluation of the haze is "△" or "X", and the curability of the cationically polymerizable resin composition is poor, and the compatibility between the ethylene-based polymer and the epoxy compound is poor.

[Evaluation method of softness]

The storage of the elastic modulus of the cationically polymerizable resin film having a thickness of 1 mm was measured at a temperature increase rate of 2 ° C/min, a frequency of 1 Hz, and a measurement temperature of -50 to 200 ° C using an ARES viscoelasticity measuring apparatus manufactured by TA Instruments. (hereinafter, E'). When E' of 25 ° C is less than 5.0 × 10 ⁵ , it is evaluated as "○", and when it is 5.0 × 10 ⁵ or more, it is evaluated as "X". In addition, when the evaluation of the curability is "x" and the cationically polymerizable resin film cannot be peeled off from the laminate, the flexibility of the cationically polymerizable resin film cannot be evaluated, and it is evaluated as "-".

Further, the omitted terms in Tables 1 to 3 will be described.

"nBA": n-butyl acrylate

"2-MTA": 2-methoxyethyl acrylate

[Embodiment 10]

(Manufacture of liquid crystal display)

The cationically polymerized resin composition obtained in Example 1 was coated on the entire surface of the glass substrate of the protective substrate by using a coater at a thickness of about 100 μm.

Next, a conveyor belt type ultraviolet irradiation apparatus CSOT-40 (manufactured by GS YUASA, using a high-pressure mercury lamp, and having a strength of 120 W/cm) was used to irradiate each coated surface with ultraviolet rays having an irradiation amount of about 1000 mJ/cm ² . .

Thereafter, a liquid crystal display manufactured by bonding the surface of the liquid crystal panel including the polarizing plate to the ultraviolet irradiation surface and curing it at 50 ° C for 1 minute was used. Further, as the liquid crystal panel, a liquid crystal panel having a longitudinal direction of 100 mm × a lateral direction of 100 mm × a thickness of 0.2 mm, which is a commercially available polarizing plate, is used, and the commercially available polarizing plate is on both sides of a polarizer including polyvinyl alcohol. There is a protective layer comprising cellulose triacetate.

Claims (8)

A cationically polymerizable resin composition comprising a cationic polymerization of a vinyl polymer (A), an epoxy compound (B), and a cationic polymerizable initiator (C) obtained by polymerizing a vinyl monomer (a) The vinyl resin (A) is used in an amount of 35 to 100% by mass based on the total amount of the vinyl monomer (a), and contains 1 mol of an alkylene group (methyl group). The acrylic monomer (a1) is obtained by polymerization. The cationically polymerizable resin composition according to claim 1, wherein the mass ratio of the ethylene-based polymer (A) to the epoxy compound (B) is (A)/(B)=50/50 to 80/ 20. The cationically polymerizable resin composition according to claim 1 or 2, wherein the (meth)acrylic monomer (a1) containing 1 mol of an alkoxy group is a mono-ethoxylated acrylic monomer. The cationically polymerizable resin composition of claim 3, wherein the mono-ethoxylated acrylic acid single system is selected from the group consisting of ethyl 2-methoxyacrylate and ethyl 2-ethoxyacrylate. One or more of the groups. The cationically polymerizable resin composition according to claim 1 or 2, wherein the epoxy compound (B) is not an alicyclic epoxy group. The cationically polymerizable resin composition according to claim 5, wherein the epoxy compound having no alicyclic epoxy group is selected from the group consisting of 1,6-hexanediol diepoxypropyl ether, 1, 4 - Butanediol diepoxypropyl ether, cyclohexane dimethanol diepoxypropyl ether, neopentyl glycol diepoxypropyl ether, trimethylolpropane diepoxypropyl ether and trimethylol Propane triepoxy One or more of the group of propyl ethers. An optical material obtained by using the cationically polymerizable resin composition according to any one of claims 1 to 6. A layered body (i) and a layer formed by using the cationically polymerizable resin composition according to any one of claims 1 to 6 in the order of the image display portion of the liquid crystal panel, and including The protective layer (ii) of the protective substrate is laminated.