JPH1077321A - Resin composition and member obtained by curing the same by active energy ray - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a resin composition comprising an amorphous thermoplastic resin and a specific bis(meth)acrylate, excellent in chemical and thermal resistances and suitable as an optical lens, etc., instead of a glass base. SOLUTION: This resin composition comprises (A) 99-1wt.% amorphous thermoplastic resin and (B) 1-99wt.% bis(meth)acrylate curable by active energy rays. Preferably, the component A is an amorphous polyolefin, especially a ring-opening polymer or its hydrogenated polymer of tetra-3-dodecen having a polar group or its derivative, and the component B contains at least one kind of bis(meth)acrylate selected from compounds of formula I [R<1> and R<2> are each H or methyl; R<3> and R<4> are each a 1-6c hydrocarbon; X is a halogen, a 1-6C alkyl, etc.; (a) is 0-4] and II [R<5> and R<6> are each H or methyl; (b) is 1 or 2; (c) is 0 or 1].

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a resin composition for glass replacement having good chemical resistance and heat resistance, and a member obtained by curing the resin composition with active energy rays. It can be suitably used for lenses, optical disk substrates, plastic liquid crystal substrates, plastic color filters, plastic solar cell substrates, touch panels, optical elements and the like.

[0002]

2. Description of the Related Art Conventionally, an amorphous thermoplastic resin has been used as a substitute for glass in terms of transparency. However, there is a problem in that the amorphous thermoplastic resin is inferior in chemical resistance, and also has a problem in that the range of usable heat resistance is limited because it flows above the glass transition temperature. For this reason, JP-A-6-116406 proposes an amorphous thermoplastic resin layer provided with a photocurable resin layer on the surface thereof for the purpose of improving chemical resistance. If the layer is damaged by external force,
There is a disadvantage that it is easily swollen and dissolved by a solvent or the like.

[0003] On the other hand, a method of crosslinking a thermoplastic resin by adding a peroxide to the thermoplastic resin for the purpose of improving heat resistance has been generally proposed. Is limited, and is currently used only for polyethylene resins, and it is difficult to improve heat resistance by crosslinking an amorphous thermoplastic resin. On the other hand, the photocured resin itself is excellent in chemical resistance, but has a drawback that when the molded product is thin, it is easily broken due to poor impact resistance.

[0004]

In view of the above circumstances, the present invention is directed to a transparent plate, an optical lens, an optical disk substrate, a plastic liquid crystal substrate, a plastic color filter, a plastic solar cell substrate, a touch panel, instead of a glass substrate.
An object of the present invention is to provide a resin composition and a member that can be suitably used for an optical element and the like.

[0005]

In order to solve the above-mentioned problems, the present invention relates to an amorphous thermoplastic resin of 99 to 1% by weight and an active energy ray-curable bis (meth) acrylate of 1 to 99% by weight. The invention according to claim 6 of the present invention relates to a member obtained by curing the resin composition with an active energy ray. Hereinafter, the present invention will be described in detail.

The resin composition of the present invention comprises an amorphous thermoplastic resin and a bis (meth) acrylate which is cured by active energy rays. The amorphous thermoplastic resin of the present invention has a crystallinity of 5% or less by X-ray analysis, and specifically includes PS (polystyrene), SAN (styrene-acrylonitrile copolymer), PC ( Polycarbonate), PMMA (polymethyl methacrylate), PE
Examples include S (polyether sulfone), PAR (polyarylate), amorphous polyolefin, PPO (polyphenylene oxide), PVC (polyvinyl chloride), polycyclohexyl methacrylate, and fluorene copolymerized polyester. Of these, amorphous polyolefins are preferred because birefringence is unlikely to occur, and because of their low hygroscopicity, applicable applications are widened. The amorphous polyolefin is a polymer having a cyclic structure, and is a resin which can be said to be an amorphous polyolefin from the structure and properties thereof. Specific examples of the amorphous polyolefin include the following.

(A) A copolymer of an addition reaction product of cyclopentadiene or a derivative thereof with norbornadiene or a derivative thereof and a compound having a vinyl group, or a hydrogenated product of the copolymer. Here, the compound having a vinyl group refers to an α-olefin, a 1,3-conjugated diene,
It is an unsaturated monomer selected from styrene and styrene derivatives. Specific examples of α-olefins include ethylene,
Propylene, butylene, etc., as specific examples of 1,3-conjugated dienes, butadiene, isoprene, pentadiene, etc., and specific examples of styrene derivatives, o-methylstyrene, m-methylstyrene, p-methylstyrene, α-methylstyrene, o-chlorostyrene, m-styrene -Chlorostyrene, p-chlorostyrene, o-ethylstyrene, m-ethylstyrene, p-ethylstyrene, p-methoxystyrene, p-chloroethylstyrene, p-methyl-α-methylstyrene and the like. In addition, these can also be used as a mixture of two or more types.

(B) A copolymer of an addition reaction product of dicyclopentadiene or a derivative thereof with ethylene and the above-mentioned compound having a vinyl group, or a hydrogenated product of the copolymer. (C) Tetra-3-dodecene having a polar group or a derivative thereof, and / or bicyclohepto-2 having a polar group
A ring-opened polymer of -ene or a derivative thereof or a hydrogenated product of these ring-opened polymers.

(D) A ring-opened polymer of tetra-3-dodecene having a polar group or a derivative thereof and / or bicyclohept-2-ene or a derivative thereof having a polar group with another cyclic olefin, or a hydrogenated product of these ring-opened polymers . In the above, examples of the amorphous polyolefin of (A) and (B) include an amorphous resin represented by the following general formula (3).

[0010]

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[In the formula (3), d and e may be different from each other and each represent an integer of 1 or more. R ⁷ represents a hydrogen atom, a hydrocarbon group or a C ₆ H ₄ R ⁸ group, and R ⁸ represents a hydrogen atom, a hydrocarbon group, an alkoxy group, a halogenated hydrocarbon group or a halogen atom. Examples of the hydrocarbon group include a methyl group and an ethyl group. Y is cyclopentadiene,
Cyclopentadiene derivatives, norbornadiene, norbornadiene derivatives, dicyclopentadiene, dicyclopentadiene and hydrogenated products thereof are shown. Here, the hydrogenated product of the addition reaction product of cyclopentadiene or its derivative with norbornadiene or its derivative, or the addition reaction product of dicyclopentadiene or its derivative with ethylene is represented by the following general formula (4). Things.

[0012]

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[In the formula (4), f represents an integer of 0 or 1. g represents 0 or an integer. h represents 0 or 1, R ⁹
To R ²⁶ and Ra and Rb each independently represent an atom or a group selected from the group consisting of a hydrogen atom, a halogen atom and a hydrocarbon group, and R 15 to R 18 are bonded to each other to form a monocyclic or polycyclic ring; And the monocyclic or polycyclic ring may have a double bond, and R ²³ and R ^{23
And 24} or R ²⁵ and R ²⁶ may form an alkylidene group. ]

As a compound represented by the above formula (4)
Is bicyclo [2,2,1] hept-2-ene, tetra
Cyclo [4,4,0,1^2,5, 1^7,10] ー 3 de-decene,
Hexacyclo [6,6,1,1^3,6, 1^10,13, 0^2,7, 0
^9,14] -4-heptadecene, octacyclo [8,8,
0,1^2,9, 1^4,7, 1^11,18, 1^13,16, 0^3,8, 0^12,17] -5
Dococene, pentacyclo [6,6,1,1^3,6, 0^2,7,
0^9,14] -4-Hexadecene, heptacyclo [8,8,
0,1^2,9, 1^4,7, 1^11,18, 0^3,8, 0^12,17] -5-eiko
Sen, pentacyclo [6,5,1,1^3,6, 0^2,7,
0^9,13] -4-pentadecene, pentacyclo [6,5
1,1^3,6, 0^2,7] -4,10-pentadecadiene, bird
Cyclo [4,3,0,1^2,5] -3-Decene, tricyclo
[4,4,0,12,5] -3-undecene, pentane
Black [7,4,0,1^2,5, 1^9,12, 0^8,13] -3-Penta
Decene, heptacyclo [8,7,0,1^3,6, 1^10,17, 1
^12,15, 0^2,7, 0 ^11,16] -4-Eicosene, Pentasik
B [8, 4, 0, 1^2,5, 1^9,12, 0^8,13] -3-Hexade
Sen, heptacyclo [8,8,0,1^4,7, 1^11,18, 1
^13,16, 0^{3, 8}, 0^12,17] -5-Hen Eikosen, Inashiku
B [10, 9, 1, 1]^4,7, 1^13,20, 1^15,18, 0^2,10, 0
^3,8, 0^12,21, 0^14,19] -5-pentacocene, nonacyclo
[10,10,1,1^5,8, 1^14,21, 1^16,19, 0^2,11, 0
^4,9, 0^13,22, 0^15,20] -5-hexacocene and the like
Derivatives having the following substituents on their skeleton include
You. As substituents, chlorine, bromine, fluorine, methyl
Group, ethyl group, propyl group, phenyl group, naphthyl group,
Butyl, cyclohexyl, ethylidene, propyl
Examples include a den group and a benzyl group.

Next, examples of the amorphous polyolefin (C) include an amorphous polymer represented by the following general formula (5).

Embedded image

[In the formula (5), j and k may be different from each other and represent 0 or a positive integer of 1 or more. Further, the annular 5-membered ring units, tetracyclo [4,4,0,1 ^2,5 having a halogen atom or a hydrocarbon group substituents may have a 'polar group such as 1
^{The [7,10} ] -3-dodecene or derivative and the bicyclo [2,2,1] hept-2-ene or derivative having a polar group are represented by the following general formula (6).

[0017]

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[In the formula (6), m represents 0 or 1. R ²⁷
To R ³⁰ may be different from each other and represent a substituent selected from a carboxyl group, an acetoxy group, a cyano group, a halogen atom, a hydrogen atom, and a hydrocarbon group. R ^{C1 to} R ^C8 may be different from each other and are selected from the group consisting of a hydrogen atom, a halogen atom, and a hydrocarbon group. Examples of the hydrocarbon group include a methyl group, an ethyl group, a propyl group, a phenyl group, a naphthyl group, a butyl group, a cyclohexyl group, an ethylidene group, a propylidene group, and a benzyl group. ]

The amorphous polyolefin (D) is a ring-opened polymer of the above formula (6) and another cyclic olefin or a hydrogenated product thereof. Here, specific examples of other cyclic olefins include cyclopentene, cyclooctene,
Cycloolefins such as 1,5-cyclooctentadiene and 1,5,9-cycldedecatriene, bicyclohept-2-ene, tricyclo-3-decene, and tricyclo-9
And polycycloalkenes such as -undecene, tetracyclo-3-dodecene, pentacyclo-4-pentadecene, and pentacyclo-4-hexadecene. As the amorphous polyolefin in the present invention, one kind or a mixture of two or more kinds may be used.

Further, among the amorphous polyolefins,
(C) Tetra-3-dodecene having a polar group or a derivative thereof, and / or bicyclohepto-2 having a polar group
And (D) tetra-3-dodecene having a polar group or a derivative thereof and / or bicyclohept-2-ene or a derivative thereof having a polar group, When a ring-opening polymer with a cyclic olefin or a hydrogenated product of these ring-opening polymers is used as a member of an optical disk substrate, a plastic liquid crystal substrate, a plastic color film, a plastic solar cell substrate, a touch panel, etc., an organic or inorganic substance The adhesiveness during processing such as vapor deposition and coating is excellent, and is particularly preferable.

In this case, specific deposition means SiO, I
This is the formation of a thin film of TO, SiO ₂ , Al, or the like. The coating process includes, for example, coating of a barrier resin such as EVOH or PVDC or coating of a color dye.
Another component of the resin composition of the present invention is bis (meth) acrylate which is cured by active energy rays. Bis (meth) acrylate that is cured by an active energy ray is represented by the following general formula (7), and is cured by an active energy ray to become a resin.

[0022]

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[In the formula (7), R ³¹ and R ³² may be different from each other and represent hydrogen or a methyl group. R ³³ has 5 carbon atoms
An element selected from S, N, O, Si, P, and F may be contained in the aliphatic group, alicyclic group, and aromatic group having 0 or less. Among them, at least one kind of bis (meth) acrylate selected from sulfur-containing bis (meth) acrylate represented by the following general formula (1) and alicyclic skeleton bis (meth) acrylate represented by the following general formula (2) Is preferred in terms of chemical resistance, rigidity and the like. In addition, "(meth) acrylate" is a general term for acrylate or methacrylate.

[0024]

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[In the formula (1), R ¹ and R ² may be different from each other and represent a hydrogen atom or a methyl group. R ³ and R ⁴
May be different from each other, and an oxygen atom and / or
Or a hydrocarbon group having 1 to 6 carbon atoms which may have a sulfur atom. X represents a substituent selected from a halogen atom or an alkyl group having 1 to 6 carbon atoms and an alkoxy group having 1 to 6 carbon atoms, and a represents an integer of 0 to 4. However, when a is an integer of 2 or more, a plurality of Xs may be different from each other. ]

[0026]

Embedded image [In the formula (2), R ⁵ and R ⁶ may be different from each other;
It represents a hydrogen atom or a methyl group. b represents 1 or 2, c
Represents 0 or 1. ]

Specific examples of the sulfur-containing (meth) acrylate compound represented by the general formula (1) include, for example, p-bis (β-methacryloyloxyethylthio)
Xylylene (R ¹ : methyl, R ² : methyl, R ³ : ethylene, R ⁴ : methylene, 1: 0), p-bis (β-acryloyloxyethylthio) xylylene, m-bis (β-
Methacryloyloxyethylthio) xylylene, m-bis (β-acryloyloxyethylthio) xylylene,
p-bis (β-methacryloyloxyethyloxyethylthio) xylylene, p-bis (β-methacryloyloxyethylthioethylthio) xylylene, p-bis (β
-Methacryloyloxyethylthio) tetrabromoxylylene, m-bis (β-methacryloyloxyethylthio) tetrachloroxylylene and the like. These compounds can be synthesized, for example, by the method described in JP-A-62-195357.

Specific examples of the alicyclic skeleton bis (meth) acrylate compound represented by the above general formula (2) include bis (oxymethyl) tricyclo [5.2.1.0 ^2,6 ] decane = diacrylate Bis (oxymethyl) tricyclo [5.2.1.0 ^2,6 ] decane dimethacrylate,
Bis (oxymethyl) tricyclo [5.2.1.
0 ^{2, 6]} decane = acrylate methacrylate and mixtures thereof, bis (oxymethyl) pentacyclo [6.
5.1.1 ^3,6 . 0 ^2,7 . 0 ^9,13 ] pentadecane diacrylate, bis (oxymethyl) pentacyclo [6.
5.1.1 ^3,6 . 0 ^2,7 . 0 ^9,13 ] pentadecane dimethacrylate, bis (oxymethyl) pentacyclo [6.5.1.1 ^3,6 . 0 ^2,7 . 0 ^9,13 ] pentadecane =
There are acrylate methacrylates and mixtures thereof. These tricyclodecane compounds and pentacyclopentadecane compounds may be used in combination of two or more in the group and / or between the groups.
It can be synthesized by the method described in Japanese Patent Application Laid-Open No. 225508/1990.

The bis (meth) acrylates represented by the general formulas (1) and (2) can be used alone or in combination of two or more. When the compound of the general formula (1) is used alone, the refractive index of the resin composition cured by the active energy ray is the sodium D line (589.3 nm).
At room temperature becomes 1.54 to 1.65 and has a high refractive index. When the compound of the general formula (2) is used alone, the refractive index is relatively low, from 1.47 to 1.51. Therefore, by using two or more compounds represented by the general formulas (1) and (2) in combination, a resin composition cured by an active energy ray having a desired refractive index between 1.47 to 1.65 can be obtained. Obtainable. In addition, the above general formula (1)
The bis (meth) acrylates represented by the formulas (2) and (2) can be used by polymerizing the bis (meth) acrylate alone. By blending at least one mercapto compound selected from mercapto compounds having a thiol group, birefringence can be reduced and moderate toughness can be imparted.

[0030]

Embedded image [In the formula (8), a plurality of R ³⁴ may be different from each other;
Each represents a methylene group or an ethylene group. R ³⁵ represents a hydrocarbon residue having 2 to 15 carbon atoms which may contain an oxygen atom and / or a sulfur atom in the carbon chain. n shows the integer of 2-6. ]

[0031]

Embedded image [In the formula (9), Z may be different from each other, and HS- (C
_{H 2) r - (CO)} (OCH 2 -CH 2) s - (CH 2)
_t- . Here, r is an integer of 1-4, s is an integer of 1-4, and t is an integer of 0-2. ]

[0032]

Embedded image [In the formula (10), R ³⁶ and R ³⁷ may be different from each other and represent a hydrocarbon group having 1 to 3 carbon atoms. o and p each represent 0 or 1. q represents 1 or 2. ]

The mercaptan compound represented by the general formula (8) is a di- to hexavalent thioglycolate or thiopropionate. Specific examples include, for example, pentaerythritol tetrakis (β-thiopropionate), pentaerythritol tetrakis (thioglycolate), trimethylolpropane tris (β-thiopropionate), trimethylolpropane tris (thioglycolate), Diethylene glycol bis (β
-Thiopropionate), diethylene glycol bis (thioglycolate), triethylene glycol bis (β-thiopropionate), triethylene glycol bis (thioglycolate), dipentaerythritol hexakis (β-thiopropionate) ), Dipentaerythritol hexakis (thioglycolate) and the like.

The compound represented by the above general formula (9) is
ω-SH group-containing triisocyanurate. Specific examples include, for example, tris [2- (β-thiopropionyloxy) ethyl] triisocyanurate, tris (2-
Thioglyconyloxyethyl) triisocyanurate,
Tris [2- (β-thiopropionyloxyethoxy)
Ethyl] triisocyanurate, tris (2-thioglyconyloxyethoxyethyl) triisocyanurate,
Tris [3- (β-thiopropionyloxy) propyl] triisocyanurate, tris (3-thioglyconyloxypropyl) triisocyanurate and the like can be mentioned. The compound represented by the general formula (10) is represented by α, ω
—SH group-containing compound. Specific examples include, for example, benzene dimercaptan, xylylene dimercaptan,
4,4'-dimercaptodiphenyl sulfide and the like can be mentioned.

Further, in addition to the above-mentioned mercapto compound, other monomers capable of radical polymerization are mixed with the bis (meth) acrylate in an amount of up to about 30 parts by weight based on 100 parts by weight of the bis (meth) acrylate. And then copolymerized. Other monomers used at this time include, for example, methyl (meth) acrylate, phenyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, methacryloyloxymethyltetracyclododecan, methacryloyloxymethyltetracyclododecene, Ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate,
1,6-hexanediol di (meth) acrylate,
2,2-bis [4- (β-methacryloyloxyethoxy) phenyl] propane, 2,2′-bis [4- (β-
(Meth) acrylate compounds such as methacryloyloxyethoxy) cyclohexyl] propane, 1,4-bis (methacryloyloxymethyl) cyclohexane, and trimethylolpropane tri (meth) acrylate; styrene, chlorostyrene, divinylbenzene, and α-methylstyrene; Core and / or side chain substituted and unsubstituted styrene and the like. Among these other monomers, methacryloyloxymethylcyclododecane, 2,2-bis [4- (β-methacryloyloxyethoxy) phenyl] propane, 2,2-bis [4- (β-methacryloyloxyethoxy) cyclohexyl ] Propane, 1,4
-Bis (methacryloyloxymethyl) cyclohexane, and mixtures thereof, are particularly preferred. Furthermore, these may contain small amounts of antioxidants, ultraviolet absorbers, dyes and pigments, fillers and the like.

The mixing ratio between the amorphous thermoplastic resin constituting the resin composition of the present invention and the bis (meth) acrylate which is cured by the active energy ray is 99 to ％ 1% by weight of the amorphous thermoplastic resin. It is 1 to 99% by weight of bis (meth) acrylate which is cured by energy rays. If the amount of bis (meth) acrylate cured by the active energy ray is less than 1% by weight, the effect of chemical resistance cannot be obtained, and
Exceeding the weight% is not preferred because the toughness is reduced.
Preferably, the bis (meth) acrylate which is cured by the active energy ray is 10 to 95% by weight. The difference between the refractive index of the amorphous thermoplastic resin and the refractive index of the resin obtained by curing bis (meth) acrylate with an active energy ray is preferably 0.05 or less, particularly preferably 0.03 or less. If the difference in the refractive index exceeds 0.05, the transparency is lowered, and therefore, there is a tendency that it cannot be used for such purposes. The measurement of the refractive index was performed at 25 ° C. and a wavelength of 589.
It is a measurement result under the condition of 3 nm (sodium D line).

The resin composition of the present invention is cured by an active energy ray to form a member. Active energy rays are
UV rays, electron beams, and the like. The method of molding the member can be selected according to the viscosity of the resin composition of the amorphous thermoplastic resin and the bis (meth) acrylate that is cured by the active energy ray. For example, by extruding a resin composition, molding by curing with an active energy ray, casting a resin composition dissolved in a solvent, evaporating the solvent, and then curing with an active energy ray. Molding, or if the mixture has high flowability, cast directly onto a roll or belt,
Or, at least one surface made of polished glass or the like is used for two opposing flat plates that can transmit active energy rays, and is injected into an injection mold in which a cavity is formed by a spacer or the like and a peripheral portion is sealed, and the active energy rays are used. It can be molded by curing.

When the member cured by the active energy ray has an Izod impact strength of 0.5 kgf · cm / cm or more, the toughness tends to be excellent because of its toughness. It tends to be excellent in transparency as a shape or a film-like member and is preferable. The irradiation amount of the active energy ray may be an amount that cures the resin composition. When the member is used in place of a glass plate such as a transparent plate, an optical lens, an optical disk substrate, a plastic liquid crystal substrate, a plastic color filter, a plastic solar cell substrate, a touch panel, and an optical element, a sheet or film is preferable. . In this case, the sheet shape or the film shape is not limited to a long shape, but also includes a short flat shape.

When the active energy ray is an ultraviolet ray, it is cured by, for example, a known radical polymerization in which a photopolymerization initiator for generating a radical is added. Examples of the photopolymerization initiator include benzophenone, benzoin methyl ether, benzoin isopropyl ether, diethoxyacetophenone, 1-hydroxycyclohexylphenyl ketone, 2,6-dimethylbenzoyldiphenylphosphine oxide, and 2,4,6-trimethylbenzoyldiphenylphosphine oxide. And the like. Preferred photoinitiators are 2,4,6-trimethylbenzoyldiphenylphosphine oxide and benzophenone. Two or more of these photopolymerization initiators may be used in combination.

The addition amount of the photopolymerization initiator is usually 0.01 to 1 part by weight, preferably 0.02 to 0.3 part by weight, per 100 parts by weight of bis (meth) acrylate. If the amount of the photopolymerization initiator is too large, the polymerization proceeds rapidly, causing not only an increase in birefringence but also a deterioration in hue. If the amount is too small, the composition cannot be cured sufficiently. The amount of the active energy rays to be irradiated is arbitrary as long as the photopolymerization initiator generates radicals.However, if the amount is extremely small, the heat resistance and mechanical properties of the cured product are sufficiently exhibited due to incomplete polymerization. Conversely, if it is extremely excessive, on the contrary, deterioration of the cured product due to light such as yellowing occurs, so that 200 to 200 to match the composition of the monomer and the type and amount of the photopolymerization initiator.
Irradiation with ultraviolet light of 400 nm is preferably performed in the range of 0.1 to 200 J. Specific examples of the lamp to be used include a metal halide lamp and a high-pressure mercury lamp.

For the purpose of promptly completing the curing, thermal polymerization may be used in combination. That is, the composition and the whole mold are usually heated in the range of 30 to 300 ° C. simultaneously with the light irradiation. In this case, a radical polymerization initiator may be added in order to complete the polymerization better, but excessive use causes an increase in birefringence and a deterioration in hue. Specific examples of the thermal polymerization initiator include benzoyl peroxide, diisopropyl peroxy carbonate, t-butyl peroxy (2-ethylhexanoate), and the amount used is 1 part by weight or less based on 100 parts by weight of the monomer. Is preferred. Further, in the present invention, the completion of the polymerization reaction and the internal strain generated during the polymerization can be reduced by heating the cured product after performing the radical polymerization by light irradiation. The heating temperature is appropriately selected according to the composition of the cured product and the glass transition temperature. However, since excessive heating results in deterioration of the hue of the cured product, a temperature around the glass transition temperature or lower is preferable.

[0042]

EXAMPLES Hereinafter, the contents and effects of the present invention will be described in more detail with reference to examples, but the present invention is not limited to the following examples unless it exceeds the gist of the present invention. The evaluation of the resin composition and the member was measured by the following method. <Parallel light transmittance> The members obtained by the examples and the comparative examples were measured in accordance with JIS-K7105 in a size of 5 cm × 5.
cm × 1 mm test piece, and manufactured by Suga Test Machine Co., Ltd.
The parallel light transmittance (%) was measured using GM-2DP.

<Chemical Resistance> The members obtained in Examples and Comparative Examples were made into test pieces of 1 cm × 1 cm × 1 mm, and the test pieces were put in xylene at 25 ° C. for 24 hours, and the appearance and corrosion were dissolved. Observation, no change in appearance:
、, swelling and whitening occurred: 樹脂, resin dissolved and the shape did not remain: x. <Izod impact strength (kgf · cm / cm)> The members obtained in Examples and Comparative Examples were subjected to JIS-K 6911.
63.4mm length x 12.7mm width x 2 thickness
A mechanically polished test piece having a size of 1 mm (thickness of 2 mm was used by laminating 1 mm) was prepared and measured with an Izod impact tester.

Production Example 1 An amorphous polyolefin having a polar group was produced by the following method. A flask equipped with a stirrer, a reflux condenser, and a three-way cock is replaced with nitrogen gas, and 8-methyl-8-carboxymethyltetracyclo- [4.4.0.1 ^{2,5 17, 10} ] -3d decene 10
0 parts by weight, 12.1 parts by weight of 1-hexene as a molecular weight modifier, 400 parts by weight of 1,2 dichloroethane as a solvent, and 1.7 parts by weight of an n-hexane solution containing 10% by weight of diethylaluminum chloride as a solvent. ,
1.8 parts by weight of a chlorobenzene solution containing 2% by weight of tungsten hexachloride and 0.1 parts by weight of 1,2 dichloroethane solution containing 10% by weight of paraaldehyde are added.
For 5 hours.

100 parts by weight of the above reaction product was dissolved in 2,000 parts by weight of tetrahydrofuran, and 10% by weight of palladium (5% concentration palladium) supported on activated carbon was added as a catalyst to adjust the charged hydrogen pressure to 150 kg / cm ² .
A hydrogenation reaction was performed at 150 ° C. for 4 hours. After cooling,
The pressure of the hydrogen gas in the vessel was released, the catalyst was filtered from the reaction solution, and then methanol was added to obtain a hydrogenated polymer, an amorphous polyolefin having a polar group. This polymer has a refractive index of 1.51 and a glass transition temperature Tg of 168.
° C, the intrinsic viscosity was 0.48 dl / g (at 30 ° C in chloroform) and the density was 1.06 g / cm ³ .

Example 1 100 g of an amorphous polyolefin having a polar group polymerized in Production Example 1 was dissolved in 200 g of methylene chloride, and bis (oxymethyl) tricyclo [5.2.1.0 was added thereto.
^2,6 ] decane = 100 g of dimethacrylate (refractive index after curing is 1.49) and 2,4,6-trimethylbenzoyldiphenylphosphine oxide (BAS) as a photoinitiator
After 0.05 g of “Lucillin TPO” manufactured by Company F) and 0.05 g of benzophenone were uniformly stirred and mixed, methylene chloride was removed to obtain a resin composition. This resin composition was poured into a mold of optically polished glass using a silicon plate having a thickness of 1 mm as a spacer, and an output of 80 W / cm on the glass surface was used.
Irradiation was performed for about 20 minutes using a metal halide lamp of No. 4 so that the energy became 40 J / cm ² . After the irradiation, the glass mold was released to obtain a cured product having a thickness of 1 mm. Table 1 shows the evaluation results of the obtained members.

Example 2 200 g of the amorphous polyolefin having a polar group polymerized in Production Example 1 was dissolved in 200 g of methylene chloride, and bis (oxymethyl) tricyclo [5.2.1.0 was added thereto.
^2,6 ] decane = dimethacrylate 800 g (refractive index after curing 1.49), and 2,4,6-trimethylbenzoyldiphenylphosphine oxide (BAS) as a photoinitiator
After uniformly mixing 0.4 g of “Lucillin TPO” manufactured by Company F and 0.4 g of benzophenone with stirring, the mixture was cast on a metal belt in a nitrogen atmosphere using a metal halide lamp having an output of 80 W / cm. 4 from the top
Irradiation was performed for about 5 minutes so that the energy became 0 J / cm ² . A cured sheet (member) having a thickness of 1 mm was obtained. Table 1 shows the evaluation results of the obtained members.

Example 3 In Example 1, the resin composition was used as an amorphous polyolefin as ZEONEX 450, manufactured by Zeon Corporation.
20 g having a refractive index of 1.53 was dissolved in 40 g of xylene, and bis (oxymethyl) tricyclo [5.
2.1.0 ^2,6 ] decane = dimethacrylate 980 g
(Refractive index after curing 1.49), 2,4,4 as photoinitiator
A member was obtained in the same manner as in Example 1 except that 0.5 g of 6-trimethylbenzoyldiphenylphosphine oxide (“Lucillin TPO” manufactured by BASF) and 0.5 g of benzophenone were used. Table 1 shows the evaluation results of the obtained members.

Example 4 Polyarylate resin (manufactured by Kanegafuchi Chemical Co., Ltd., Elimec)
100 g of methylene chloride was dissolved in 100 g of methylene chloride, and 900 g of p-bis (β-methacryloyloxyethylthio) xylylene was added thereto (refractive index of 1.60 after curing).
60), 0.5 g of 2,4,6-trimethylbenzoyldiphenylphosphine oxide (“Lucillin TPO” manufactured by BASF) as a photoinitiator, and 0.5 of benzophenone
g was uniformly stirred and mixed. The mixture was cast on a metal belt in a nitrogen atmosphere, placed in a sheet at 80 ° C. in a drying furnace to evaporate and dry the solvent, and then output 80 W / cm.
30 J / cm ² from the top using a metal halide lamp
Irradiation was performed for about 5 minutes to obtain energy. 1mm thick
A cured sheet (member) was obtained. Table 1 shows the evaluation results of the obtained members.

Example 5 In Example 1, the resin composition was changed to a polymethyl methacrylate resin (Acrypet V, manufactured by Mitsubishi Rayon Co., Ltd.).
50 g of a refractive index of 1.49) was dissolved in 50 g of methylene chloride, and bis (oxymethyl) tricyclo [5.
2.1.0 ^2,6 ] decane = dimethacrylate 950 g
(Refractive index after curing 1.49), 2,4,4 as photoinitiator
A member was obtained in the same manner as in Example 1 except that 0.5 g of 6-trimethylbenzoyldiphenylphosphine oxide (“Lucillin TPO” manufactured by BASF) and 0.5 g of benzophenone were used. Table 1 shows the evaluation results of the obtained members.

Example 6 In Example 1, the resin composition was dissolved in 100 g of methylene chloride by dissolving 50 g of polycarbonate (Iupilon H-4000, refractive index 1.58, manufactured by Mitsubishi Engineering-Plastics Corporation). Bis (oxymethyl) tricyclo [5.2.1.0 ^2,6 ] decane = 950 g (refractive index after curing 1.49), 2,4,6-trimethylbenzoyldiphenylphosphine oxide as a photoinitiator ("Lucirin TPO" manufactured by BASF)
A member was obtained in the same manner as in Example 1, except that 0.5 g of benzophenone and 0.5 g of benzophenone were used. Table 1 shows the evaluation results of the obtained members.

Comparative Example 1 The amorphous polyolefin having a polar group polymerized in Production Example 1 was extruded at 310 ° C. in a facility equipped with a T-die having a width of 400 mm in a 40 mm extruder and heated to 150 ° C.
The sheet was cast on a roll having a diameter of 00 mm to obtain a sheet having a thickness of 1 mm. Table 1 shows the evaluation results of the obtained members. Comparative Example 2 In Comparative Example 1, the raw material was polycarbonate (Iupilon H-400 manufactured by Mitsubishi Engineering-Plastics Corporation).
0, refractive index 1.58), extruded at 270 ° C, 12
A sheet having a thickness of 1000 μm was obtained in the same manner as in Example 1, except that the sheet was cast on a 400 mmφ roll heated to 0 ° C.
Table 1 shows the evaluation results of the obtained members.

Comparative Example 3 In Example 1, bis (oxymethyl) tricyclo [5.2.1.0 ^2,6 ] decane = dimethacrylate 1000 g (refractive index after curing 1.49) was used. As a photoinitiator, 2,4,6-trimethylbenzoyldiphenylphosphine oxide ("Lucillin T" manufactured by BASF)
PO ") A member was obtained in the same manner as in Example 1, except that the composition was prepared by uniformly mixing and stirring 0.5 g of benzophenone and 0.5 g of benzophenone. Table 1 shows the evaluation results of the obtained members.

[0054]

[Table 1]

In Table 1, A represents an amorphous thermoplastic resin, and B represents a bis (meth) acrylate curable by an active energy ray. As shown in Table 1, the resin composition of the present invention and the member made of the resin composition are excellent in chemical resistance. It can be seen that members made of the resin composition of the present invention have high Izod impact strength.

[0056]

Industrial Applicability The resin composition of the present invention is excellent in the chemical resistance required for use in a substrate such as a liquid crystal substrate, a solar cell substrate, a touch panel, an optical element, etc. instead of a glass substrate. When it is used, it is easy to mold into a member, and is superior in impact strength to a glass substrate. When the difference in the refractive index of the resin composition is 0.05 or less, not only the chemical resistance but also the transparency are good, and the resin composition is more preferable.

Claims (9)

[Claims] 1. A resin composition comprising 99 to 1% by weight of an amorphous thermoplastic resin and 1 to 99% by weight of a bis (meth) acrylate curable by active energy rays. 2. The resin composition according to claim 1, wherein the amorphous thermoplastic resin is an amorphous polyolefin. 3. The amorphous polyolefin is a ring-opened polymer of tetra-3-dodecene or a derivative thereof having a polar group or / and bicyclohept-2-ene or a derivative thereof having a polar group or a hydrogenated product of these ring-opened polymers. The resin composition according to claim 2. 4. A ring-opening polymer of tetra-3-dodecene or a derivative thereof having a polar group as an amorphous polyolefin and / or a bicyclohept-2-ene or a derivative thereof having a polar group with another cyclic olefin, or a ring-opening polymer thereof. The resin composition according to claim 2, which is a hydrogenated product of the above. 5. The bis (meth) acrylate curable by an active energy ray comprises at least one bis (meth) acrylate selected from the following formulas (1) and (2). Item 5. The resin composition according to any one of Items 1 to 4. Embedded image [In the formula (1), R ¹ and R ² may be different from each other;
It represents a hydrogen atom or a methyl group. R ³ and R ⁴ may be different from each other and represent a hydrocarbon group having 1 to 6 carbon atoms which may have an oxygen atom and / or a sulfur atom in a carbon chain. X represents a substituent selected from a halogen atom or an alkyl group having 1 to 6 carbon atoms and an alkoxy group having 1 to 6 carbon atoms, and a represents an integer of 0 to 4. However, when a is an integer of 2 or more, a plurality of Xs may be different from each other. ] [In the formula (2), R ⁵ and R ⁶ may be different from each other;
It represents a hydrogen atom or a methyl group. b represents 1 or 2, c
Represents 0 or 1. ] 6. The method according to claim 1, wherein the difference between the refractive index of the amorphous thermoplastic resin and the refractive index of the resin obtained by curing bis (meth) acrylate with active energy rays is 0.05 or less. 5. The resin composition according to any one of 5. 7. A member obtained by curing a resin composition comprising 99 to 1% by weight of an amorphous thermoplastic resin and 1 to 99% by weight of a bis (meth) acrylate curable by an active energy ray by an active energy ray. . 8. An Izod impact strength of 0.5 kgf · c
The member according to claim 7, wherein the member is not less than m / cm. 9. The member according to claim 7, wherein the member is formed into a sheet shape or a film shape, and the parallel light transmittance of the member is 80% or more.