JP2012046566A - Electron beam-curable composition, and resin film or sheet - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an electron beam-curable composition which can provide a low-water absorption rate cured material, is excellent in the balance between a yellowing degree and a water absorption rate after heat-resistant and light-resistant tests and enables a long-term use under high-temperature high-humidity environment, and to provide a resin sheet obtained from the composition.SOLUTION: The electron beam-curable composition includes the urethane (meth)acrylate (A) which is a reaction product of polycarbonate diol or polyester diol, organic diisocyanate and hydroxyl group-containing (meth)acrylate, and a compound (B) having an alicyclic skeleton and one (meth)acryloyl group. The water absorption rate of the cured material is 1.0% or less.

Description

The present invention relates to an electron beam curable composition used for production of a resin film or sheet, and a resin film or sheet obtained by applying the composition to a substrate, and belongs to these technical fields.
In the following, for the sake of convenience, unless otherwise specified, “resin film or sheet” is referred to as “resin sheet”. Further, acrylate or methacrylate is represented as (meth) acrylate.

  Conventionally, resin sheets obtained by crosslinking (meth) acrylic monomers and oligomers by irradiation with electron beams have been proposed.

For example, Patent Document 1 discloses a resin film obtained by crosslinking at least one acrylic monomer by electron beam irradiation and having a volume shrinkage of 1.0% or less.
However, when the epoxy acrylate specifically disclosed as the raw material acrylic monomer in Patent Document 1 is used, the degree of yellowing after the heat resistance test and the light resistance test is a serious problem.
On the other hand, in Patent Document 1, it is unclear what kind of compound urethane acrylate is (Patent Document 1: [0021]), but aliphatic diisocyanate and hydroxyl group specifically disclosed as urethane acrylate in Example 3 In the case of using an acrylate reaction product (so-called adduct body) having the above (Patent Document 1: [0038]), there is a disadvantage that the crosslinking density is too high and the film becomes brittle.

Patent Document 2 discloses a resin sheet obtained by curing a composition containing a urethane (meth) acrylate-based oligomer and a reactive dilution monomer with active energy rays. As an example, a resin sheet can be produced by electron beam curing. Specifically disclosed.
However, when acryloylmorpholine or N-vinylformaldehyde specifically disclosed as a reactive diluent monomer is used, there is a problem in use in a moisture-resistant environment, such as an increase in water absorption.

JP 2009-30041 A JP 2009-91586 A

  As described above, the resin sheet obtained by crosslinking and curing conventional (meth) acrylic monomers and oligomers by electron beam irradiation has a high yellowing degree after heat resistance test and light resistance test, and has a high water absorption rate. There was a problem that it could not be used for a long time under high temperature and high humidity conditions.

  The present invention has a cured product with a low water absorption rate, excellent balance between yellowing degree and water absorption rate after heat resistance test and light resistance test, and can be used for a long time in a high temperature and high humidity environment. It aims at providing the resin sheet obtained from the composition and the said composition.

  As a result of intensive studies to solve the above problems, the present inventors have developed urethane (meth) acrylate and alicyclic skeleton produced from polycarbonate diol or polyester diol, organic diisocyanate and hydroxyl group-containing (meth) acrylate. The present inventors have found that an electron beam curable composition containing (meth) acrylate having can solve the above-mentioned problems, and have completed the present invention.

According to the composition of the present invention, the water absorption of the obtained cured product is low, and the balance between the yellowing degree and the water absorption after the heat resistance test and the light resistance test is excellent.
Therefore, the electron beam curable resin sheet of the present invention includes an optical film, a light-resistant (weather-resistant) sheet for outdoor use such as a solar cell, a flame-retardant sheet, a heat-dissipating sheet, a diffusion sheet for LED lighting / organic EL lighting, and an adhesive property. Sheet, transparent heat-resistant sheet for flexible electronics, sheet for printable electronics, various functional films (for example, hard coat film and decorative film) and surface-shaped film (for example, moth-eye type antireflection film and texture structure for solar cell) The film can be suitably applied to uses such as a base film of the attached film.

The present invention relates to a urethane (meth) acrylate (A) (hereinafter simply referred to as “component (A)”) which is a reaction product of polycarbonate diol or polyester diol, organic diisocyanate and hydroxyl group-containing (meth) acrylate, and an alicyclic skeleton. And a compound (B) having one (meth) acryloyl group (hereinafter simply referred to as “component (B)”),
The present invention relates to an electron beam curable composition having a water absorption of 1.0% or less.
Hereinafter, the present invention will be described in detail. In the present specification, a crosslinked product and a cured product obtained by irradiating the composition with an electron beam are collectively referred to as a “cured product”.

1. Component (A) The component (A) used in the present invention is a urethane which is a reaction product of polycarbonate diol or polyester diol (hereinafter collectively referred to as “diol a”), organic diisocyanate, and hydroxyl group-containing (meth) acrylate. (Meth) acrylate.
The component (A) has a lower degree of yellowing after the heat resistance test and after the light resistance test by using diol a as a polyol as compared with other urethane (meth) acrylates.

As component (A), a diol a and an organic diisocyanate are reacted to produce an isocyanate group-containing compound, which is then reacted with a hydroxyl group-containing (meth) acrylate (hereinafter referred to as “compound A1”), and a diol. a, a compound obtained by simultaneously reacting an organic diisocyanate and a hydroxyl group-containing (meth) acrylate (hereinafter referred to as “compound A2”), and the like, and the compound A1 is preferable because the molecular weight is easily controlled.
As the component (A), both oligomers and polymers can be used, and those having a weight average molecular weight of 1,000 to 50,000 are preferable, and more preferably 5,000 to 30,000.
In the present invention, the weight average molecular weight is a value obtained by converting the molecular weight measured by gel permeation chromatography into polystyrene.

In the diol a, examples of the polycarbonate diol include a reaction product of a low molecular weight diol, a polyether diol, and / or a bisphenol such as bisphenol A and a dialkyl ester carbonate such as ethylene carbonate and dibutyl ester carbonate.
Here, examples of the low molecular weight diol include ethylene glycol, propylene glycol, cyclohexanedimethanol, 3-methyl-1,5-pentanediol, 1,5-pentanediol, 1,6-hexanediol, and the like.
Examples of polyether diols include polyalkylene glycols such as polyethylene glycol, polypropylene glycol and polytetramethylene glycol, and block or random polymer diols such as polyethylene polypropoxy block polymer diols.

  In the diol a, as the polyester diol, the low molecular weight diol or / and the polyether diol and a dibasic acid such as adipic acid, succinic acid, phthalic acid, tetrahydrphthalic acid, hexahydrophthalic acid and terephthalic acid, or The esterification reaction product with acid components, such as the anhydride, etc. are mentioned.

Examples of organic diisocyanates include hexamethylene diisocyanate, lysine methyl ester diisocyanate, 2,4,4-trimethylhexamethylene diisocyanate, dimer acid diisocyanate and other aliphatic diisocyanates, isophorone diisocyanate (hereinafter referred to as “IPDI”), 4,4′- Methylenebis (cyclohexyl isocyanate) (hereinafter referred to as “H12MDI”), alicyclic diisocyanates such as ω, ω′-diisocyanate dimethylcyclohexane, aliphatic diisocyanates having an aromatic ring such as xylylene diisocyanate, tetramethylxylylene diisocyanate, p- Phenylene diisocyanate, tolylene diisocyanate (hereinafter referred to as “TDI”), 4,4′-diphenylmethane diisocyanate (hereinafter referred to as “TDI”) , "MDI"), aromatic diisocyanates such as naphthalene-1,5-diisocyanate and tolidine diisocyanate, and mixtures of two or more thereof.
Among the compounds described above, IPDI and H12MDI are preferable when the cured product requires light resistance (weather resistance), and TDI and MDI are preferable when the cured product requires mechanical strength.

As the hydroxyl group-containing (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, hydroxybutyl (meth) acrylate, hydroxypentyl (meth) acrylate, hydroxyhexyl (meth) acrylate, hydroxy Examples include octyl (meth) acrylate, pentaerythritol tri, di or mono (meth) acrylate, and hydroxyalkyl (meth) acrylate such as trimethylolpropane di or mono (meth) acrylate.
Among the above-described compounds, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, and hydroxybutyl (meth) acrylate are preferable in terms of excellent sheet flexibility.

(A) A component may be manufactured according to the conventional method.
In the case of producing compound A1, in the presence of a urethanization catalyst such as dibutyltin dilaurate, the diol a and the organic diisocyanate to be used are heated and stirred to carry out an addition reaction, and further a hydroxyalkyl (meth) acrylate is added, and then heated and stirred to carry out an addition reaction. Examples of the method for producing compound A2 include a method in which diol a, organic diisocyanate and hydroxyalkyl (meth) acrylate are simultaneously added and heated and stirred in the presence of the same catalyst as described above.

  These compounds may be used alone or in combination of two or more.

2. Component (B) The component (B) is a compound having an alicyclic skeleton and one (meth) acryloyl group. In this invention, the hardened | cured material of a composition can make a thing with a low water absorption rate by including (B) component.

  As the component (B), isobornyl (meth) acrylate, dicyclopentenyl (meth) acrylate, dicyclopentanyl (meth) acrylate, cyclohexyl (meth) acrylate, cyclohexyl (meth) acrylate, trimethylcyclohexyl (meth) acrylate and 1 -Adamantyl (meth) acrylate etc. are mentioned.

  As the component (B), only one kind of the aforementioned compounds may be used, or two or more kinds may be used in combination.

  Component (B) is an isobornyl (meth) acrylate or dicyclopentenyl (meth) compound that is excellent in heat resistance and light resistance among the above-mentioned compounds and has a relatively high homopolymer glass transition temperature of 50 ° C. or higher. Acrylate and dicyclopentanyl (meth) acrylate are preferred.

3. Electron beam curable composition The present invention is an electron beam curable composition containing the component (A) and the component (B) as essential components.
As a manufacturing method of a composition, what is necessary is just to follow a conventional method, using (A) component and (B) component, using other components further as needed, and obtaining these by stirring and mixing. it can.

Further, the composition of the present invention needs to have a water absorption of 1.0% or less. Due to the low water absorption, dimensional changes of the cured product can be suppressed in use in a moisture-resistant environment.
In the present invention, the water absorption means a value measured according to the following method.
That is, a cured product of the composition is cut into 5 cm × 5 cm and used as a test piece. The test piece is heated in nitrogen at 210 ° C. for 1 hour to completely dry the cured product, and then allowed to cool in a desiccator, and the test piece is weighed (W1). Next, the test piece is immersed in distilled water at 80 ° C. for 20 hours, and after taking out, the water on the surface of the test piece is gently wiped and weighed (W2).
The water absorption means the result calculated according to the following formula (1) based on the obtained results of W1 and W2.
Water absorption (%) = (W2−W1) / W1 × 100 (1)

The proportion of the component (A) and the component (B) may be appropriately set according to the purpose, but the component (A) is 20 to 95% by weight based on the total amount of the component (A) and the component (B). And (B) component 5-80 weight% is preferable, More preferably, (A) component 30-90 weight% and (B) component 10-70 weight%.
(A) By making the ratio of a component into 20 weight% or more, the hardened | cured material obtained can be made excellent in a softness | flexibility, On the other hand, by making it 95 weight% or less, the viscosity of a composition is made low, It can be excellent in coatability.

  The composition of the present invention is an electron beam curable composition, and a conventionally known photopolymerization initiator can be blended if necessary, but preferably does not contain a photopolymerization initiator. By not containing a photopolymerization initiator, the obtained cured product can be excellent in heat resistance and weather resistance.

The composition of the present invention essentially comprises the component (A) and the component (B), but various components can be blended depending on the purpose.
Specifically, an ethylenically unsaturated compound other than the components (A) and (B) [hereinafter referred to as component (C)], an organic solvent [hereinafter referred to as component (D)], a polymerization inhibitor and / or an antioxidant. Agents, light resistance improvers, flame retardants, heat dissipation fillers, light diffusing agents, inorganic materials, and the like.
Hereinafter, these components will be described.

-Component (C) The component (C) is an ethylenically unsaturated compound other than the components (A) and (B).
(C) A component is a component mix | blended as needed for the purpose of reducing the viscosity of the whole composition, and the purpose of adjusting other physical properties.

  Specific examples of the component (C) include (meth) acrylates (hereinafter referred to as “other (meth) acrylates”) other than the components (A) and (B).

  Other (meth) acrylates include a compound having one (meth) acryloyl group (hereinafter referred to as “monofunctional (meth) acrylate”) and a compound having two or more (meth) acryloyl groups (hereinafter referred to as “multiple”). Functional (meth) acrylate ”and the like.

  Specific examples of the monofunctional (meth) acrylate include, for example, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, n-butyl (meth) acrylate, i-butyl (meth) acrylate, t- Butyl (meth) acrylate, hexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, lauryl (meth) acrylate, stearyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, glycidyl (meth) acrylate, dimethylaminoethyl ( (Meth) acrylate, diethylaminoethyl (meth) acrylate, benzyl (meth) acrylate, allyl (meth) acrylate, 2-ethoxyethyl (meth) acrylate, phenoxyethyl (meth) acrylate, о-fe Nylphenol EO modified (n = 1 to 4) (meth) acrylate, p-cumylphenol EO modified (n = 1 to 4) (meth) acrylate, phenyl (meth) acrylate, о-phenylphenyl (meth) acrylate, Examples thereof include p-cumylphenyl (meth) acrylate.

Specific examples of the polyfunctional (meth) acrylate include bisphenol A EO-modified (n = 1 to 2) di (meth) acrylate, bisphenol A di (meth) acrylate, ethylene glycol di (meth) acrylate, and diethylene glycol di (meth). Acrylate, triethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, polyethylene glycol (n = 5-14) di (meth) acrylate, propylene glycol di (meth) acrylate, dipropylene glycol di (meth) Acrylate, tripropylene glycol di (meth) acrylate, tetrapropylene glycol di (meth) acrylate, polypropylene glycol (n = 5-14) di (meth) acrylate, 1,3-butylene glycol Di (meth) acrylate, 1,4-butanediol di (meth) acrylate, polybutylene glycol (n = 3 to 16) di (meth) acrylate, poly (1-methylbutylene glycol) (n = 5 to 20) di (Meth) acrylate, 1,6-hexanediol di (meth) acrylate, 1,9-nonanediol di (meth) acrylate, neopentyl glycol di (meth) acrylate, hydroxypivalate neopentyl glycol di (meth) acrylate, Examples thereof include dicyclopentanediol di (meth) acrylate and bifunctional (meth) acrylate of tricyclodecane dimethylol di (meth) acrylate.
In the above, EO modification means ethylene oxide modification, and n means the number of repeating alkylene oxide units.

As the component (C), only one kind of the aforementioned compounds may be used, or two or more kinds may be used in combination.
As the component (C), a monofunctional (meth) acrylate is preferable among the above-described compounds in terms of excellent flexibility of the obtained cured product.

In this invention, what does not contain the ethylenically unsaturated compound which has a polar group as (C) component is preferable. Thereby, the water absorption rate of hardened | cured material can be made low.
Examples of the polar group include acidic groups such as carboxyl group, sulfone group, and phosphoric acid group, salts of acidic groups, morpholyl groups, amino groups, amide groups, and cyclic imide groups such as maleimide groups and hydroxyl groups. Examples of the ethylenically unsaturated compound having a polar group include (meth) acrylic acid, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, and (meth) acryloylmorpholine. N-vinylformamide, N- (meth) acryloyloxyethyl hexahydrophthalimide, and the like.

  The proportion of the component (C) may be appropriately set according to the purpose, and may be an amount that does not decrease the physical properties such as the water absorption rate and elongation rate of the obtained cured product, but is 100 parts by weight of the component (A). The content is preferably 1 to 100% by weight, more preferably 1 to 80% by weight.

-(D) component The composition of this invention contains the organic solvent of (D) component for the objective, such as improving the coating property to a base material.

Specific examples of the component (D) include hydrocarbon solvents such as n-hexane, benzene, toluene, xylene, ethylbenzene and cyclohexane;
Methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, isobutyl alcohol, 2-methoxyethanol, 2-ethoxyethanol, 2- (methoxymethoxy) ethanol, 2-isopropoxyethanol, 2-butoxy Ethanol, 2-isopentyloxyethanol, 2-hexyloxyethanol, 2-phenoxyethanol, 2-benzyloxyethanol, furfuryl alcohol, tetrahydrofurfuryl alcohol, diethylene glycol, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, 1 Alcohol-based solvents such as methoxy-2-propanol and 1-ethoxy-2-propanol;
Ether solvents such as tetrahydrofuran, dioxane, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, ethylene glycol dibutyl ether, bis (2-methoxyethyl) ether, bis (2-ethoxyethyl) ether and bis (2-butoxyethyl) ether;
Ketone solvents such as acetone, methyl ethyl ketone, methyl-n-propyl ketone, diethyl ketone, butyl methyl ketone, methyl isobutyl ketone, methyl pentyl ketone, di-n-propyl ketone, diisobutyl ketone, phorone, isophorone, cyclohexanone and methylcyclohexanone Can be mentioned.

  As the component (D), only one of the aforementioned compounds may be used, or two or more may be used in combination.

  The proportion of the component (D) may be set as appropriate, but is preferably 10 to 90% by weight, more preferably 40 to 80% by weight in the composition.

● Polymerization inhibitor or / and antioxidant It is preferable to add a polymerization inhibitor or / and an antioxidant to the composition of the present invention, which can improve the storage stability of the composition of the present invention. .
As the polymerization inhibitor, hydroquinone, hydroquinone monomethyl ether, 2,6-di-tert-butyl-4-methylphenol, and various phenolic antioxidants are preferable. A secondary antioxidant or the like can also be added.
The total blending ratio of these polymerization inhibitors and / or antioxidants is preferably 0.001 to 3% by weight, more preferably 0.01 to 0.00%, based on 100 parts by weight of the component (A). 5% by weight.

● Light resistance improver The composition of the present invention may contain an ultraviolet absorber or a light stabilizer depending on the application.
Examples of the ultraviolet absorber include 2- (2′-hydroxy-5-methylphenyl) benzotriazole, 2- (2′-hydroxy-3 ′, 5′-di-t-butylphenyl) benzotriazole, 2- (2 Benzotriazole compounds such as'-hydroxy-3'-t-butyl-5'-methylphenyl)benzotriazole;
Triazine compounds such as 2,4-bis (2,4-dimethylphenyl) -6- (2-hydroxy-4-iso-octyloxyphenyl) -s-triazine;
2,4-dihydroxy-benzophenone, 2-hydroxy-4-methoxy-benzophenone, 2-hydroxy-4-methoxy-4'-methylbenzophenone, 2,2'-dihydroxy-4-methoxybenzophenone, 2, 4, 4 ' -Trihydroxybenzophenone, 2,2 ', 4,4'-tetrahydroxybenzophenone, 2,3,4,4'-tetrahydroxybenzophenone, 2,3', 4,4'-tetrahydroxybenzophenone, or 2,2 A benzophenone compound such as'-dihydroxy-4,4'-dimethoxybenzophenone can also be added.
Examples of the light stabilizer include N, N′-bis (2,2,6,6-tetramethyl-4-piperidyl) -N, N′-diformylhexamethylenediamine, bis (1,2,6,6). -) Pentamethyl-4-piperidyl) -2- (3,5-ditertiarybutyl-4-hydroxybenzyl) -2-n-butylmalonate, bis (1,2,2,6,6-pentamethyl-4- Low molecular weight hindered amine compounds such as piperidinyl) sebacate; N, N′-bis (2,2,6,6-tetramethyl-4-piperidyl) -N, N′-diformylhexamethylenediamine, bis (1,2 Hindered amine light stabilizers such as high molecular weight hindered amine compounds such as 2,6,6-pentamethyl-4-piperidinyl) sebacate can also be added.
The blending ratio of the light resistance improver is preferably 0 to 5% by weight, more preferably 0 to 1% by weight, based on 100 parts by weight of the component (A).

-Flame retardant A flame retardant can be added to the composition of this invention according to a use.
Examples of flame retardants include halogen flame retardants such as polychloroparaffin, chlorinated polyethylene, tetrabromoethane, and tetrabromobisphenol;
Phosphoric esters such as tricresyl phosphate, triphenyl phosphate, trioctyl phosphate; phosphorus-based flame retardants such as bisphenol A diphosphate, resorcin diphosphate, tetraxylenyl resorcin diphosphate, etc. Flame retardant;
Aliphatic amine compounds, aromatic amine compounds, nitrogen-containing heterocyclic compounds, cyanide compounds, aliphatic amides and aromatic amides, phosphates such as urea, thiourea, ammonium polyphosphate and ammonium polyphosphate, melamine polyphosphate and phosphazene Nitrogen-based flame retardants of compounds;
Silicone resin such as phenylpropyl silicone resin; silicone powder; silicone flame retardant such as silicone oil;
Inorganic compounds such as antimony trioxide, aluminum hydroxide, magnesium hydroxide, zinc borate, and barium borate can also be added a flame retardant containing no halogen.
Among these, phosphorus flame retardants, nitrogen compound flame retardants, and silicone flame retardants are preferable.
The blending ratio of the flame retardant is preferably 0 to 100% by weight, more preferably 0 to 50% by weight, based on 100 parts by weight of the component (A).

● Heat radiating filler A heat radiating filler can be added to the composition of the present invention depending on the application.
As the heat dissipating filler, alumina, zinc oxide, silicon oxide, magnesium oxide, boron nitride, silicon carbide, silicon nitride, aluminum nitride, graphite, ferrite, carbon fiber (for example, Teijin's Lahima) may be added. it can.
It is preferable that the mixture rate of a thermal radiation filler is 0-100 weight% with respect to 100 weight part of (A) component, More preferably, it is 0-50 weight%.

Light diffusing agent A light diffusing agent can be added to the composition of the present invention depending on the application.
As the light diffusing agent, inorganic fillers such as silica, aluminum hydroxide, aluminum oxide, zinc oxide, barium sulfide, magnesium silicate;
An organic filler such as acrylic resin, acrylonitrile resin, polyurethane, polyvinyl chloride, polystyrene, polyacrylonitrile, polyamide, or the like can also be added.
The blending ratio of the light diffusing agent is preferably 0 to 100% by weight, more preferably 0 to 50% by weight with respect to 100 parts by weight of the component (A).

● Inorganic materials Inorganic materials can be blended for the purpose of improving strength and reducing the coefficient of linear expansion.
Examples of the inorganic material include glass fiber, colloidal silica, silica, alumina, talc, and clay.
The blending ratio of the inorganic material is preferably 0 to 100% by weight, more preferably 0 to 50% by weight, based on 100 parts by weight of the component (A).

4). Method of Use The composition of the present invention can employ various methods of use depending on the purpose. Specifically, the composition can be applied to a substrate and cured by irradiation with an electron beam, For example, a method of curing by irradiating with an electron beam after bonding to a base material may be used.

As a substrate, in addition to a release-treated sheet or film (hereinafter referred to as “release material”), a surface treatment (for example, hard coat treatment) or a material intended for adhesion (hereinafter referred to as “adhered body”). ).
Examples of the release material include a surface untreated OPP film (polypropylene) and a silicone-treated polyethylene terephthalate film.
Examples of the material of the adherend include metals such as polymers, glass, ceramics, steel plates and aluminum, vapor deposition films of metals and metal oxides, and silicon.
Polymers include cellophane, polyester such as polyethylene terephthalate and polyethylene naphthalate, polyamide, polyimide, polycarbonate, urea / melamine resin, epoxy resin, polyurethane, polylactic acid, polyethylene, polypropylene, cycloolefin polymer, acrylic resin, methacrylic resin, poly Examples include vinyl chloride, polystyrene, polyvinyl acetate, polyvinyl alcohol, triacetyl cellulose, hydroxypropyl cellulose, polyether sulfone, copolymers of the above polymers, liquid crystal polymers, and fluororesins, and films or sheets are preferred.

  As a coating method, it may be appropriately set depending on the purpose, and it is applied with a conventionally known bar coater, applicator, doctor blade, knife coater, comma coater, reverse roll coater, die coater, gravure coater, micro gravure coater, etc. The method of doing is mentioned.

  What is necessary is just to set suitably irradiation conditions, such as a dose in electron beam irradiation, according to the composition to be used, a base material, the objective, etc.

5. Resin Sheet The composition of the present invention can be preferably used for the production of a resin sheet.
As a form of the resin sheet, a cured product (hereinafter simply referred to as “cured product”) formed by electron beam irradiation of the composition is formed on a film or sheet-like substrate (hereinafter simply referred to as “substrate”). Can be mentioned.
Moreover, the substrate / cured product / substrate may be formed in this order. In this case, what is the base material by which any one or both of the base material was mold-released is also mentioned.
Hereinafter, the manufacturing method and application of the resin sheet will be described.

5-1. Production method of resin sheet The production method of the resin sheet may be in accordance with a conventional method. For example, the resin sheet can be produced by applying the composition to a substrate and then irradiating it with an electron beam.
Hereinafter, a part of the description will be given with reference to FIGS. 1 and 2.

FIG. 1 shows an example of a preferred method for producing a resin sheet composed of a substrate / cured product.
In FIG. 1, (1) means a substrate.
When the composition is a solventless type (FIG. 1: A1), the composition is applied to a substrate [FIG. 1: (1)]. When the composition contains an organic solvent or the like (FIG. 1: A2), the composition is applied to a substrate [FIG. 1: (1)] and then dried to evaporate the organic solvent (FIG. 1: 1). -1).
By irradiating an electron beam with respect to the sheet | seat in which a composition layer is formed in a base material, the resin sheet comprised from a base material / cured material is obtained. The electron beam is usually irradiated from the composition layer side, but when the substrate is transparent, it can also be irradiated from the substrate side.
In the above, if a release material is used as the substrate (1), a resin sheet composed of the release material / cured product can be produced.

  The coating amount of the composition of the present invention may be appropriately selected according to the application to be used, but it is preferable to apply the coating so that the film thickness after drying the organic solvent or the like is 5 to 500 μm. Preferably it is 10-500 micrometers.

When the composition contains an organic solvent or the like, it is dried after coating to evaporate the organic solvent or the like.
What is necessary is just to set drying conditions suitably according to the organic solvent etc. to be used, and the method etc. which heat to the temperature of 40-120 degreeC are mentioned.

  What is necessary is just to set suitably irradiation conditions, such as a dose in electron beam irradiation, according to the composition to be used, a base material, the objective, etc.

FIG. 2 shows an example of a preferable method for producing a resin sheet composed of a substrate / cured product / substrate.
In FIG. 2, (1), (3), and (4) mean a substrate.
When the composition is a solventless type (FIG. 2: A1), the composition is applied to a substrate [FIG. 2: (1)]. When the composition contains an organic solvent or the like (FIG. 2: A2), the composition is applied to a substrate [FIG. 2: (1)] and then dried to evaporate the organic solvent (FIG. 2: 2). -1). Resin in which the base material, cured product, and base material are formed in this order by laminating the base material (3) to the composition layer and then irradiating the electron beam or laminating the base material after the electron beam irradiation. A sheet is obtained.
In the above, if a release material is used as the base materials (1) and (4), a resin sheet composed of a release material / cured product / release material can be produced.
In the above, if a release material is used as the base materials (1) and (3), a resin sheet composed of a release material / cured product / release material can be produced.

5-2. Application of resin sheet Specific applications of the resin sheet of the present invention include optical films, outdoor light-resistant (weather-resistant) sheets such as solar cells, flame-retardant sheets, heat-dissipating sheets, diffusion for LED lighting and organic EL lighting Sheet, adhesive sheet, transparent heat-resistant sheet for flexible electronics, sheet for printable electronics, various functional films (for example, hard coat film and decorative film) and surface-shaped film (for example, moth-eye type anti-reflection film and solar And a base film of a textured film for batteries).

  Hereinafter, the present invention will be described more specifically with reference to examples and comparative examples. In the following, “parts” means parts by weight.

(1) Example (Production of composition)
The components shown in Table 1 below were charged in a stainless steel container at the ratio shown in Table 1, and stirred with a magnetic stirrer while heating to obtain a composition. The numbers in Table 1 mean the number of copies.

The abbreviations in Table 1 mean the following.
UCA002: Polycarbonate urethane acrylate, Art Resin UCA-002 manufactured by Negami Kogyo Co., Ltd. [weight average molecular weight (hereinafter abbreviated as “Mw”): 7,000]
UN9200: Polycarbonate urethane acrylate, Art Resin UN-9200A (Mw: 15,000) manufactured by Negami Kogyo Co., Ltd.
KY111: Polyester urethane acrylate, Art Resin KY-111 (Mw: 16,000) manufactured by Negami Kogyo Co., Ltd.
-IBXA: Isobornyl acrylate, IBXA manufactured by Osaka Organic Chemical Industry Co., Ltd.
FA511AS: dicyclopentenyl acrylate, manufactured by Hitachi Chemical Co., Ltd. FA-511AS
FA513AS: dicyclopentanyl acrylate, FA-513AS manufactured by Hitachi Chemical Co., Ltd.
M1600: Polyether urethane acrylate, Aronix M-1600 manufactured by Toagosei Co., Ltd.
LPVC3: Polyether urethane acrylate, Art Resin LPVC-3 (Mw: 16,000) manufactured by Negami Kogyo Co., Ltd.
SP1509: bisphenol A epoxy acrylate, Lipoxy SP-1509 manufactured by Showa Polymer Co., Ltd.
ACMO: acryloylmorpholine, ACMO manufactured by Kojin Co., Ltd.
M140: N-acryloyloxyethylhexahydrophthalimide, Aronix M-140 manufactured by Toagosei Co., Ltd.
Dc1173: 2-hydroxy-2-methyl-1-phenylpropan-1-one, DAROCUR-1173 manufactured by BASF Japan

(2) Examples 8 to 14 and Comparative Examples 9 to 15 (Production of resin sheet by electron beam curing)
Example 1-7 and a release film “CERAPEEL BX8” (silicone-treated polyethylene terephthalate film, thickness 38 μm, hereinafter simply referred to as “CERAPEEL BX8”) manufactured by Toray Film Processing Co., Ltd. having a width of 300 mm × a length of 300 mm. The compositions obtained in Comparative Examples 3 to 8 were heated and coated with an applicator so that the film thickness was 100 μm.
Thereafter, “Celape BKE” (silicone-treated polyethylene terephthalate film, thickness 38 μm; hereinafter simply referred to as “Celapele BKE”) having a width of 300 mm × a length of 300 mm was laminated on the composition layer, and then I Electron Co., Ltd. Using a beam electron beam irradiation apparatus, an electron beam was irradiated under the conditions of an acceleration voltage of 200 kV, a dose of 50 kGy (adjusted by a beam current and a conveyance speed), and an oxygen concentration of 300 ppm or less to obtain a resin sheet.
After curing, it was peeled off from the silicone-treated polyethylene terephthalate film and used for the heat resistance test, light resistance test and evaluation of water absorption rate described later.

(3) Comparative Examples 9 and 10 (Production of resin sheet by ultraviolet curing)
The UV-curable composition obtained in Comparative Examples 1 and 2 was heated on a 300 mm wide x 300 mm long therapy BX8 and coated with an applicator so that the film thickness was 100 μm.
Then, after laminating 300 mm width x 300 mm length therapy BKE on the composition layer, a conveyor type ultraviolet irradiation device (high pressure mercury lamp, lamp height 12 cm, 365 nm irradiation intensity 400 mW / cm, manufactured by Eye Graphics Co., Ltd.) ² (Measurement value of UV POWER PUCK manufactured by Fusion UV Systems Japan Co., Ltd.) was adjusted to carry out ultraviolet irradiation with an integrated light amount of 1,000 mJ / cm ² to obtain a resin sheet.
After curing, it was peeled off from the silicone-treated polyethylene terephthalate film and used for the heat resistance test, light resistance test and water absorption evaluation described below.

[Heat resistance test]
The resin sheets obtained in the examples and comparative examples were left in a constant temperature bath at 100 ° C. for 500 hours, and the change in yellow index (hereinafter referred to as YI) was measured to evaluate the heat resistance of the resin sheets. The results are shown in Table 2.
YI was measured by using a high-speed integrating sphere type spectral transmittance measuring device (SPECTROTOPOMETER DOT-3C manufactured by Murakami Color Research Laboratory Co., Ltd.).

(Light resistance test)
Resin sheets obtained in Examples and Comparative Examples were left in an ultraviolet fade meter (UV Long Life Fade Meter FAL-5H type, manufactured by Suga Test Co., Ltd.) for 500 hours, and the change in YI was measured. The light resistance of was evaluated. The results are shown in Table 2.
YI was measured using a high-speed integrating sphere type spectral transmittance measuring device.

[Water absorption rate]
The obtained resin sheet was cut out into 5 cm x 5 cm, and this was made into the test piece. The test piece was heated in nitrogen at 210 ° C. for 1 hour to completely dry the cured product, and then allowed to cool in a desiccator, and the test piece was weighed (W1). Subsequently, the test piece was immersed in distilled water at 80 ° C. for 20 hours, and after taking out, the water on the surface of the test piece was lightly wiped and weighed (W2), and the water absorption was calculated according to the following formula (1). The results are shown in Table 2.
Water absorption (%) = (W2−W1) / W1 × 100 (1)

Examples 8-14 are resin sheets obtained from Examples 1-7, which are the compositions of the present invention, and contain a component (A) that is a urethane acrylate produced from a polycarbonate diol or a polyester diol. Since the yellowing degree after a property test and a light resistance test is small and the component (B) which is a monofunctional (meth) acrylate having an alicyclic structure is included, the water absorption is small.
In contrast, although Comparative Examples 9 and 10 contain the components (A) and (B), the compositions of Comparative Examples 1 and 2 obtained by blending the photopolymerization initiator were not electron beams. It was a resin sheet produced by irradiating with ultraviolet rays, and the degree of yellowing after the heat resistance test and after the light resistance test was large.
Comparative Examples 11 to 13 are resin sheets produced from the compositions of Comparative Examples 3 to 5 containing urethane acrylate produced from epoxy acrylate or polyether polyol, and yellowing after the heat resistance test and after the light resistance test The degree was great.
Comparative Examples 14 and 15 are resin sheets produced from the compositions of Comparative Examples 6 and 7 that do not contain any component (B), and have a large water absorption rate, after the heat resistance test and after the light resistance test. The degree of yellowing was also large.

The electron beam curable composition of this invention can be used conveniently for manufacture of a resin sheet.
Furthermore, as described in detail above, the resin sheet of the present invention is a light-resistant (weather-resistant) sheet for outdoor use such as an optical film and a solar cell, a flame-retardant sheet, a heat-dissipating sheet, a diffusion for LED lighting and organic EL lighting. Sheets, adhesive sheets, transparent heat-resistant sheets for flexible electronics, sheets for printable electronics, various functional films, and base films of films with surface shapes are preferably used.

FIG. 1 shows an example of the production of a resin sheet using the composition of the present invention. FIG. 2 shows an example of production of a resin sheet using the composition of the present invention.

Claims (12)

Polyurethane (meth) acrylate (A) which is a reaction product of polycarbonate diol or polyester diol, organic diisocyanate and hydroxyl group-containing (meth) acrylate, and compound (B) having an alicyclic skeleton and one (meth) acryloyl group Including
An electron beam curable composition in which the water absorption of the cured product is 1.0% or less.   The electron beam curable composition according to claim 1, comprising 20 to 95% by weight of component (A) and 5 to 80% by weight of component (B) based on the total amount of component (A) and component (B).   The electron beam curable type according to claim 1 or 2, wherein the component (B) is at least one selected from isobornyl (meth) acrylate, dicyclopentenyl (meth) acrylate, and dicyclopentanyl (meth) acrylate. Composition.   Furthermore, the electron beam curable composition of any one of Claims 1-3 containing the ethylenically unsaturated group containing compound (C) other than (A) component and (B) component.   The electron beam curable composition according to claim 4, wherein the component (C) does not contain an ethylenically unsaturated compound having a polar group.   The electron beam curable composition according to any one of claims 1 to 5, wherein the composition does not contain a photopolymerization initiator.   The resin film or sheet | seat in which the electron beam irradiation hardened | cured material of the composition of any one of Claims 1-6 is formed in a film or a sheet-like base material.   The film or sheet-like substrate, the electron beam irradiation cured product of the composition according to any one of claims 1 to 6, and the film or sheet-like substrate are formed in this order. Resin film or sheet.   The resin film or sheet according to claim 7 or 9, wherein either one or both of the film and the sheet-like substrate is a release-treated substrate.   A resin film that irradiates an electron beam from the coated surface or the film or sheet-like substrate side after coating the composition according to any one of claims 1 to 6 on the film or sheet-like substrate. Sheet manufacturing method.   After coating the composition of any one of Claims 1-6 to a film or a sheet-like base material, another film or a sheet-like base material is bonded to the coating surface, and a film or sheet A method for producing a resin film or sheet in which an electron beam is irradiated from either side of a substrate.   The method for producing a resin film or sheet according to claim 10 or 11, wherein either one or both of the film and the sheet-like substrate is a release-treated substrate.

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