KR20080063138A - Photoradical curable resin composition and method for preparing the composition - Google Patents

Abstract

A radiation radical curing resin composition, and a method for preparing the composition are provided to obtain a cured product within a very short time irrespective of the absence/presence of oxygen and to improve surface curing property and thick film curing property. A radiation radical curing resin composition comprises a radiation radical initiator; a radical chain transfer agent; a radical polymerizable compound; and optionally a solvent. The composition is cured by the irradiation of a UV light emitting diode. Preferably the radiation radical initiator is at least one selected from a ketone compound, an acyl phosphine compound, a thioxanthone compound and a metallocene compound.

Description

Optical radical curable resin composition and the manufacturing method of the said composition {PHOTORADICAL CURABLE RESIN COMPOSITION AND METHOD FOR PREPARING THE COMPOSITION}

The present invention relates to an optical radical curable resin composition having an ultraviolet light emitting diode as a light source for curing, and a method for producing the optical radical curable resin composition.

As addition polymerization reaction which hardens | cures by ultraviolet light irradiation, it is classified roughly into two types, a thing with a radical and a cation with a polymerization active species. Among these, the radical photocurable resin is excellent in terms of environmental safety and productivity because of its properties such as solventlessness and immediate curing property, and has been used for coating materials and optical molding applications. Although mercury lamps have been used for a long time as the ultraviolet light source for curing, alternative light sources have been expected because of their short lifespan and high power consumption, and the use of environmental load materials.

Recently, ultraviolet light emitting diodes have been put into practical use as ultraviolet light sources with low environmental loads replacing mercury lamps, and are attracting attention as light sources for curing for photocurable resin materials. However, although ultraviolet light-emitting diodes save energy in comparison with mercury lamps, the irradiation light intensity is weak and is a quasi-monochrome light source. Therefore, it is difficult to generate sufficient polymerization active species to cure with existing photocurable resin compositions. Moreover, in the radical photocurable resin, although the surface hardening problem existed conventionally by the inhibition of the polymerization reaction which caused oxygen in air, since the irradiation light intensity is insufficient in the hardening reaction using an ultraviolet light-emitting diode light source, surface hardening failure is bad. This tended to become more pronounced. Therefore, these problems were solved and the radical photocurable resin composition which has favorable sclerosis | hardenability was needed even if an ultraviolet light-emitting diode light source was used.

Moreover, the following documents are mentioned as a prior art concerning this invention.

[Patent Document 1] Japanese Patent Application Laid-Open No. 2006-022228

[Patent Document 2] Japanese Unexamined Patent Publication No. 06-264033

The present invention is directed to the above-mentioned radical photocurable resin composition and a method for producing the composition, which are cured even in the presence of oxygen at low illumination by irradiation of an ultraviolet light-emitting diode light source and have good surface curability and deep curability (thick film curability). It aims to provide.

MEANS TO SOLVE THE PROBLEM The present inventors earnestly examined in order to achieve the said objective, and, as a result, in addition to a radical radical initiator, the radical compound, the radically polymerizable compound, especially the polymeric compound containing an acryl group and / or methacryl group (polymerizable monomer) By using the composition containing these, it discovered that the cured resin composition which satisfy | fills both surface curability and deep curability is also obtained by irradiation of an ultraviolet light-emitting diode light source, and came to complete this invention.

That is, this invention provides the following radical photocurable resin composition and its manufacturing method.

Claim 1:

 The radical photocurable resin composition which contains (A) radical photoinitiator, (B) radical chain transfer agent, (C) radically polymerizable compound, and optionally a solvent, and hardens | cures by irradiation of a ultraviolet light emitting diode.

Claim 2:

The method according to claim 1, wherein (A) the radical radical initiator

(A1) ketone compound,

(A2) acylphosphine compounds,

(A3) thioxanthone compound,

(A4) metallocene compound

1 type or 2 or more types of radicals curable resin composition chosen from.

Claim 3:

The radically polymerizable compound which is (C) component of Claim 1 or 2 contains an acrylic acid ester group and / or methacrylic acid ester group.

Claim 4:

Preparation of the radical photocurable resin composition of Claim 1 containing the process of mix | blending this to (C) radically polymerizable compound after dissolving and homogenizing only (A) radical photonic initiator and (B) radical chain transfer agent once. Way.

By using the radical photocurable resin composition of this invention, when hardening the said composition using an ultraviolet light-emitting diode, hardened | cured material can be obtained in a very short time irrespective of the presence or absence of oxygen which is a polymerization inhibitor, and high surface curability and thick film curability Can be compatible. From these characteristics, it became possible to use an ultraviolet light-emitting diode as a low dose photoradical curable resin composition which makes a light source for hardening.

Hereinafter, the present invention will be described in more detail.

The radical photocurable resin composition of the present invention

(A) Photo radical initiator which generate | occur | produces a polymerization active species by light irradiation with an ultraviolet light emitting diode,

(B) radical chain transfer agent to improve the reactivity of the polymerization active species,

(C) a radically polymerizable compound, especially a polymerizable compound containing at least one acrylic group and / or methacryl group in a molecule

Containing, if necessary

(D) solvent

It further contains.

(A) photo radical initiator

As the photoradical initiator, any compound which generates a polymerization active species by light irradiation with an ultraviolet light emitting diode can be used, but in particular

(A1) ketone compound,

(A2) acylphosphine compounds,

(A3) thioxanthone compound,

(A4) metallocene compound

1 type, or 2 or more types chosen from are used.

As a ketone compound (A1), what can be used as an optical radical initiator can be used without a restriction | limiting, Specifically, (alpha)-hydroxycyclohexyl phenyl ketone, 2-hydroxy-2- methyl-1- phenyl propanone, 2 -Hydroxy-2-methyl-1- (4-isopropylphenyl) propanone, 2-hydroxy-2-methyl-1- (4-dodecylphenyl) propanone and 2-hydroxy-2-methyl- 1-[(2-hydroxyethoxy) phenyl] propanone, benzophenone, 2-methylbenzophenone, 3-methylbenzophenone, 4-methylbenzophenone, 4-methoxybenzophenone, 2-chlorobenzophenone, 4-chlorobenzophenone, 4-bromobenzophenone, 2-carboxybenzophenone, 2-ethoxycarbonylbenzophenone, benzophenonetetracarboxylic acid or tetramethylester thereof, 4,4'-bis (dialkylamino ) Benzophenones (for example, 4,4'-bis (dimethylamino) benzophenone, 4,4'-bis (dicyclohexylamino) benzophenone, 4,4'-bis (diethylamino) benzophenone, 4,4'-bis (dihydroxyethyl Mino) benzophenone, 4-methoxy-4'-dimethylaminobenzophenone, 4,4'-dimethoxybenzophenone, 4-dimethylaminobenzophenone, 4-dimethylaminoacetophenone, benzyl, anthraquinone, 2-t -Butylanthraquinone, 2-methylanthraquinone, phenanthraquinone, fluorenone, 2-benzyl-dimethylamino-1- (4-morpholinophenyl) -1-butanone, 2-methyl-1- [4- (Methylthio) phenyl] -2-morpholino-1-propanone, 2-hydroxy-2-methyl- [4- (1-methylvinyl) phenyl] propanol oligomer, benzoin, benzoin ethers (example For example, benzoin methyl ether, benzoin ethyl ether, benzoin propyl ether, benzoin isopropyl ether, benzoin phenyl ether, benzyl dimethyl ketal), acridon, chloroacridone, N-methylacridone, N-butyl acridone, N-butyl-chloroacridone, etc. are mentioned.

As the acylphosphine compound (A2) used as the radical photoinitiator, those which can be used as the radical radical initiator can be used without limitation, specifically 2,4,6-trimethylbenzoyldiphenylphosphine oxide, 2,6- Dimethoxybenzoyldiphenylphosphine oxide, 2,6-dichlorobenzoyldiphenylphosphine oxide, 2,4,6-trimethylbenzoylmethoxyphenylphosphine oxide, 2,4,6-trimethylbenzoylethoxyphenylphosphine ox A seed, 2,3,5,6-tetramethylbenzoyldiphenylphosphine oxide, benzoyldi- (2,6-dimethylphenyl) phosphonate, and the like. As bisacyl phosphine oxide, bis- (2, 6- dichloro benzoyl) phenyl phosphine oxide, bis- (2, 6- dichloro benzoyl)-2, 5- dimethylphenyl phosphine oxide, bis- (2, 6- Dichlorobenzoyl) -4-propylphenylphosphineoxide, bis- (2,6-dichlorobenzoyl) -1-naphthylphosphineoxide, bis- (2,6-dimethoxybenzoyl) phenylphosphineoxide, bis- ( 2,6-dimethoxybenzoyl) -2,4,4-trimethylpentylphosphineoxide, bis- (2,6-dimethoxybenzoyl) -2,5-dimethylphenylphosphineoxide, bis- (2,4, 6-trimethylbenzoyl) phenylphosphine oxide and (2,5,6-trimethylbenzoyl) -2,4,4-trimethylpentylphosphine oxide.

As a thioxanthone compound, what can be used as an optical radical initiator can be used without a restriction | limiting, Specifically, 2-isopropyl thioxanthone, 4-isopropyl thioxanthone, 2, 4- diethyl thioxide Santone, 2, 4- dichloro thioxanthone, 1-chloro-4- propoxy thioxanthone, etc. are mentioned.

(A4) As a metallocene compound, it is a photoinitiator which generate | occur | produces a radical by light irradiation of wavelength 400-700 nm. As the metallocene compound (A4), a transition element whose central metal is represented by Fe, Ti, V, Cr, Mn, Co, Ni, Mo, Ru, Rh, Lu, Ta, W, Os, Ir, etc. can be used. Of these, however, titanocene compounds are preferred, and among the titanocene compounds, bis (η ⁵ -2,4-cyclopentadien-1-yl) -bis [2,6-difluoro-3- (pyrrole-1) Most preferred is -yl) phenyl] titanium.

When the mass fraction of the photopolymerization initiators (A1) to (A4) used in the photoradical curable resin composition of the present invention is 0.05 to 15 mass%, it is highly sensitive to the ultraviolet light emitting diode light source, and the thick film curability is improved. More preferably, thick-film sclerosis | hardenability further improves in the range whose (A1)-(A4) is 0.5-6 mass%. The photoinitiators of these (A1)-(A4) may be used independently, and may be used in combination of 2 or more type.

(B) radical chain transfer agent

As a radical chain transfer agent, the compound which has the function which reactivates the polymerization active species trapped by inert radical supplements, such as oxygen, and contributes to the improvement of surface hardenability can be used without limitation. As the compound to be a chain transfer agent, for example, N, N-dimethylaniline, N, N-dimethyl-p-toluidine, N, N-dimethyl-m-toluidine, N, N-diethyl-p-toluidine, N, N-dimethyl-3,5-dimethylaniline, N, N-dimethyl-3,4-dimethylaniline, N, N-dimethyl-4-ethylaniline, N, N-dimethyl-4-isopropylaniline, N, N -Dimethyl-4-t-butylaniline, N, N-dimethyl-3,5-di-t-butylaniline, N, N-bis (2-hydroxyethyl) -3,5-dimethylaniline, N, N -Di (2-hydroxyethyl) -p-toluidine, N, N-bis (2-hydroxyethyl) -3,4-dimethylaniline, N, N-bis (2-hydroxyethyl) -4-ethyl Aniline, N, N-bis (2-hydroxyethyl) -4-isopropylaniline, N, N-bis (2-hydroxyethyl) -4-t-butylaniline, N, N-bis (2-hydroxy Oxyethyl) -3,5-di-isopropylaniline, N, N-bis (2-hydroxyethyl) -3,5-di-t-butylaniline, 4-N, N-dimethylaminobenzoic acid ethyl ester, 4-N, N-dimethylaminobenzoic acid methyl ester, N, N-dimethylaminobenzoic acid n-butoxide Cyethyl ester, 4-N, N-dimethylaminobenzoic acid 2- (methacryloyloxy) ethyl ester, 4-N, N-dimethylaminobenzophenone, trimethylamine, triethylamine, N-methyldiethanolamine, N-ethyldiethanolamine, Nn-butyldiethanolamine, N-lauryldiethanolamine, triethanolamine, 2- (dimethylamino) ethyl methacrylate, N-methyldiethanolamine dimethacrylate, N-ethyl Diethanolamine dimethacrylate, triethanolamine monomethacrylate, triethanolamine dimethacrylate, triethanolamine trimethacrylate, and the like, and the like, but particularly preferred amines are 2-ethylhexyl-4-dimethylaminobenzoate. .

When the mass fraction of the radical chain transfer agent (B) used in the photoradical curable resin composition of the present invention is 0.01 to 10% by mass, it becomes highly sensitive to the ultraviolet light-emitting diode light source and improves surface curability in air. More preferably, in the range which (B) is 0.5-5 mass%, surface hardenability further improves. These radical chain transfer agents may be used alone or in combination of two or more thereof.

(C) radically polymerizable compound

As a radically polymerizable compound, Preferably, 1 type, or 2 or more types of radically polymerizable monomers chosen from a monofunctional, bifunctional, trifunctional or more than trifunctional (polyfunctional) acrylate ester monomer and / or methacrylic acid ester monomer are mentioned. The acrylic acid ester residue and / or the methacrylic acid ester residue derived from the compound and the acrylic acid ester monomer and / or the methacrylic acid ester monomer are, for example, linear such as organopolysiloxane (silicon), polyurethane, polyether or the like. The radically polymerizable high molecular compound which introduce | transduced 1 or more in the terminal or molecular chain of a polymer (polymer) chain, and was modified by the said (meth) acrylic acid ester residue is used preferably.

Specifically as a radically polymerizable (monomer) compound, the compound which has an unsaturated bond and has radical addition reactivity can be used without a restriction | limiting, A monofunctional, bifunctional, trifunctional or more thing can be mentioned, Monofunctional (meth) As an example of acrylic ester, methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) Acrylate, tert-butyl (meth) acrylate, n-hexyl (meth) acrylate, cyclohexyl (meth) acrylate, tert-butylcyclohexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, Acetoxyethyl (meth) acrylate, phenyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-methoxyethyl (meth) acrylate, 2-ethoxyethyl (meth) acrylate, 2 -(2-methoxyethoxy) ethyl (meth Acrylate, 3-phenoxy-2-hydroxypropyl (meth) acrylate, benzyl (meth) acrylate, diethylene glycol monomethyl ether (meth) acrylate, diethylene glycol monoethyl ether (meth) acrylate , Diethylene glycol monophenyl ether (meth) acrylate, triethylene glycol monomethyl ether (meth) acrylate, triethylene glycol monoethyl ether (meth) acrylate, polyethylene glycol monomethyl ether (meth) acrylate, polyethylene glycol Monoethyl ether (meth) acrylate, β-phenoxyethoxyethyl acrylate, nonylphenoxy polyethylene glycol (meth) acrylate, dicyclopentanyl (meth) acrylate, dicyclopentenyl (meth) acrylate, Dicyclopentenyloxyethyl (meth) acrylate, trifluoroethyl (meth) acrylate, octafluoropentyl (meth) arc Rate, and the like perfluorooctyl (meth) acrylate, tribromo phenyl (meth) acrylate, tribromo phenyl oxyethyl (meth) acrylate.

Examples of the difunctional (meth) acrylic acid esters include 1,6-hexanediol diacrylate, 1,6-hexanediol dimethacrylate, ethylene glycol diacrylate, ethylene glycol dimethacrylate and neopentyl glycol diacrylamide. Latene, neopentylglycol dimethacrylate, triethyleneglycol diacrylate, triethyleneglycol dimethacrylate, bis (acryloyloxyethyl) ether of bisphenol A, 3-methylpentanediol diacrylate, 3-methyl Pentanediol dimethacrylate etc. are mentioned.

Examples of trifunctional or higher (meth) acrylic acid esters include trimethylolpropane triacrylate, trimethylolpropane trimethacrylate, pentaerythritol triacrylate, pentaerythritol trimethacrylate, pentaerythritol tetraacrylate, and penta. Erythritol tetramethacrylate, dipentaerythritol pentaacrylate, dipentaerythritol pentamethacrylate, dipentaerythritol hexaacrylate, dipentaerythritol hexamethacrylate, and the like.

In addition, polymers (polymer materials) which are radically polymerized into polymer materials such as (meth) acrylic acid esters into polymer materials such as polysiloxanes, polyurethanes, and polyethers and modified with radical polymerizable monomers. ) May be used, or each material may be used in combination.

The said (meth) acrylic acid ester compounds can also be used individually or in combination of 2 types or more, respectively.

In the present invention, when the mass fraction of the (meth) acrylic acid esters (C) used in the photoradical curable resin composition is 30 to 99% by mass, it becomes highly sensitive to the ultraviolet light-emitting diode light source, and the curing rate and the thick film curability are improved. . More preferably, the curing rate and the thick film curability are further improved within the range of (C) of 70 to 98 mass%. These (meth) acrylic acid esters may be used independently and may be used in combination of 2 or more type.

Moreover, as a component used for the photoradical curable resin composition of this invention, the function of each component of above-mentioned (A), (B), (C) may be given to one or some compound, As an example of such a component, Silicone resins, urethane resins, ether resins and copolymers thereof modified with acrylic acid ester residues and / or methacrylic acid ester residues.

Moreover, in order to improve the adhesiveness after hardening of hardened | cured material, it is preferable to add an adhesion | attachment adjuvant to the radical photocurable resin composition of this invention. Specifically, the compound which has cyanoacrylate frame | skeleton, such as alkyl ester of cyanoacrylic acid, such as methylcyanoacrylate, ethylcyanoacrylate, propylcyanoacrylate, and butylcyanoacrylate, and (beta) -glycid Doxyethyltrimethoxysilane, α-glycidoxypropyltrimethoxysilane, β-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, α-glycidoxybutyltrimethoxysilane , β-glycidoxybutyl trimethoxy silane, γ-glycidoxy butyl trimethoxy silane, δ-glycidoxy butyl trimethoxy silane, (3,4-epoxycyclohexyl) methyltrimethoxysilane, β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, γ- (3,4-epoxycyclohexyl) propyltrimethoxysilane, δ- (3,4-epoxycyclohexyl) butyltrimethoxysilane Epoxy functional group containing alkoxysilane represented by these etc., and these parts There may be mentioned silane coupling agents such as hydrolysis and condensation, the skeleton of these adhesion aid component may be plural kinds of combinations by a chemical bond. Moreover, as a preferable compounding quantity, when it adds in the range of about 0.1-10 mass%, Preferably it is about 0.5-5 mass% of the whole composition, adhesiveness with respect to the to-be-adhered body of the said optical radical curable resin composition can be improved, for example. have.

Moreover, although a solvent can be mix | blended with the composition of this invention as needed, specifically, as a solvent, it is 5-15 carbon atoms, such as n-pentane, n-hexane, n-heptane, isooctane, cyclopentane, cyclohexane, etc. Non-polar hydrocarbon solvents can be used. Hetero containing solvents (ie, solvents containing hetero atoms other than carbon and hydrogen) may also be used, for example ethanol, propanol, butanol, cyclohexanol, diethyl ether, tetrahydrofuran, 1,4-dioxane Alcohols such as acetone, ethyl acetate, and butyl acetate, ether solvents, and ester solvents may also be used, and silane solvents such as hexamethyldisilane and hexamethyldisiloxane may also be used. In addition, fluorine-containing solvents such as fluoroalkane and fluoroalkyl ether can also be used. Moreover, as its preferable compounding quantity, for example, adding in the range of 0.1-50 mass% of the whole composition can improve the solubility of the said photo radical initiator.

Manufacturing method of optical radical curable resin composition

The compound which becomes an optical radical initiator often contains an aromatic compound and a polar group in a molecule | numerator in order to absorb light efficiently. Since these compound groups have high crystallinity, the solubility with respect to a base monomer may be low. In this case, in the present invention, it is preferable to dissolve and homogenize the photoradical initiator and the radical chain transfer agent (starting aid) at a high temperature of 50 to 150 ° C in advance to dissolve the obtained liquid in the radically polymerizable compound. In this case, this liquid is stable at room temperature, and for this reason, dissolution to a radically polymerizable compound can be performed at room temperature. In addition, in the photoradical curable resin composition obtained in this way, recrystallization of an optical radical initiator and a radical chain transfer agent is suppressed.

Curing of the Radical Radical Curable Resin Composition

Conventionally, when the ultraviolet light-emitting diode was irradiated with an ultraviolet light-radical curable resin composition as a light source instead of conventional light sources such as a high pressure mercury lamp and a xenon lamp to cure these resins, it was generally a case of poor curing. As a reason for this, while a high-pressure mercury lamp or a xenon lamp light source has an ultraviolet emission spectrum in a wide wavelength range and exhibits high resin curability, an ultraviolet light emitting diode has a quasi-monochrome color having an emission wavelength at any one of 220 to 370 nm. Since it is a light source, hardening reaction cannot fully be caused to an ultraviolet curable resin. Therefore, in the conventional radical photocurable resin composition, it becomes a hardening defect, and especially hardening defect of a core part arises. Moreover, when oxygen, such as air, exists, since it functions as a polymerization inhibitor, the surface also becomes hardening in many cases. On the other hand, the radical photocurable resin composition which concerns on this invention can harden | cure not only existing light sources, such as a high pressure mercury lamp and a xenon lamp, but also under the irradiation conditions of the ultraviolet light-emitting diode in which hardening defects were frequently mentioned above, and a high surface Curability and deep curability can be obtained. Suitably, high sclerosis | hardenability can be obtained by the ultraviolet light-emitting diode light source which has a light emission wavelength in 365 nm. In addition, irradiation of an ultraviolet light-emitting diode can be performed satisfactorily in any atmosphere, such as under atmospheric pressure, oxygen-containing atmosphere, such as inert gas, such as nitrogen and argon, and under reduced pressure, for example, Can be performed at room temperature (for example, 25 ° C).

<Example>

Hereinafter, although an Example and a comparative example demonstrate this invention further in detail, this invention is not limited to these Examples. In the following description, a part means a mass part.

Example 1

Preparation of Photoradical Curable Resin Compositions:

2-dimethylamino-2- (4-methylbenzyl) -1- (4-morpholin-4-yl-phenyl) -butan-1-one (Ciba Specialty Chemicals make, brand name Irgacure 379) 1.5 parts, 2-hydroxy-2-methyl-1-phenyl-propan-1-one (manufactured by Ciba Specialty Chemicals, trade name DAROCURE 1173) 1 part, 2-ethylhexyl-4-dimethylaminobenzoate (Shiba Specialty Chemicals, trade name Darocure EHA) 1 part, 2 parts of 2,4-diethyl thioxanthone (manufactured by Nippon Kayaku Co., Ltd., DETX-S) were mixed and then dissolved by heating at 100 ° C. for 15 minutes. I was. This liquid was cooled to room temperature and added to 100 parts of acrylic modified silicone (Formula 1) to obtain an optical radical curable resin composition by stirring and defoaming operation.

Example 2

In the composition in Example 1, 2-dimethylamino-2- (4-methylbenzyl) -1- (4-morpholin-4-yl-phenyl) -butan-1-one was changed to 0.6 parts, and 2- 0.6 parts of benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1 (Siba Specialty Chemicals make, brand name Irgacure 369) were mixed, and operation similar to Example 1 was added and the light was added. A radical curable resin composition was obtained.

Example 3

In the composition in Example 1, 2,4-diethyl thioxanthone (made by Nippon Kayaku Co., Ltd., product name DETX-S) was changed to 0.15 parts, and the same operation as in Example 1 was added to form an optical radical curable resin composition. Got it.

Example 4

In the composition of Example 1, 3 parts of 1-hydroxycyclohexyl-phenyl ketone (Ciba Specialty Chemicals, trade name Irgacure 184) was added, and the same operation as in Example 1 was added to the optical radical curable resin composition. Got.

Example 5

In the composition in Example 1, 2-dimethylamino-2- (4-methylbenzyl) -1- (4-morpholin-4-yl-phenyl) -butan-1-one was changed to 0.6 part, and 2 -Benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1 (available from Ciba Specialty Chemicals, trade name Irgacure 369) is added 0.6 parts of 1-hydroxycyclohexyl- Three parts of phenyl ketone (Ciba Specialty Chemicals make, brand name Irgacure 184) are added, and p-dimethylamino instead of 2-ethylhexyl-4-dimethylaminobenzoate (Ciba Specialty Chemicals make, brand name Tarocure EHA) 1 part of isobenzoic acid isoamyl ester (made by Nippon Kayaku Co., Ltd., brand name KAYACURE DMBI) was added, and operation similar to Example 1 was added and the optical radical curable resin composition was obtained.

Example 6

In the composition of Example 1, the acrylic modified silicone of the said Formula (1) was changed to acrylic modified urethane (NXBK Corporation, HX-620), and the operation similar to Example 1 was added, and the radical photocurable resin composition was obtained.

Moreover, about each resin, as for the following, evaluation was performed about the surface hardening property of the hardened | cured material and deep-hardening property when irradiated with an ultraviolet light-emitting diode light source in normal temperature (25 degreeC) in air | atmosphere. As an ultraviolet light-emitting diode irradiation apparatus, Matsushita Denki Sangyo make cure (spot type, ANUJ-5010) 2 lights etc. were connected and used at 10 mm intervals. These UV-LEDs were irradiated at a focal length of 10 mm and a scanning speed of 80 mm / s. The evaluation results are shown in Table 1.

Evaluation of Surface Hardness

An optical radical curable resin composition was made to flow in the mold frame of length 5cm, width 1mm, and thickness of 600 micrometers formed on the glass plate, and the linear cured sample was produced. Subsequently, hardening reaction is performed by light irradiation with an ultraviolet light-emitting diode on the said conditions, and after contacting the hardened | cured material surface immediately after irradiation with a rubber glove, a contact site is pressed against a black polypropylene board, and the transition to a board is pressed. It judged as follows.

X: There is adhesiveness on the hardened | cured material surface, and there exists a transition.

(Triangle | delta): There exists a little adhesiveness on the hardened | cured material surface, and there exists a transition of trace amount.

(Circle): There is no adhesiveness on the hardened | cured material surface, and there is no transition.

Deep sclerosis evaluation

The said photocured material was peeled off from a glass plate immediately after ultraviolet irradiation, and the deep part hardenability was determined as follows by the quantity of the liquid uncured thing which remained on the glass plate.

X: Uncured thing exists on the glass plate after hardened | cured material peeling.

(Triangle | delta): There exists some unhardened | cured material on the glass plate after hardened | cured material peeling.

(Circle): Unhardened | cured material does not exist on the glass plate after hardened | cured material peeling.

 Comparative Example 1

Preparation of Photoradical Curable Resin Compositions:

4-hydroxy-2-methyl-1-phenyl-propan-1-one (Ciba Specialty Chemicals, trade name Tarocure 1173) 4 parts, 2-methyl-1- [4- (methylthio) phenyl] -2 -1 part of morpholino propane-1-one (Ciba Specialty Chemicals make, brand name Irgacure 907) was mixed. This liquid was added to 100 parts of acrylic modified silicone (KJC-7807R, manufactured by Shin-Etsu Chemical Co., Ltd.), and the optical radical curable resin composition was obtained by performing the same operation as Example 1.

The result of having hardened the said comparative radical photocurable resin composition by UV-LED irradiation using the same method as an Example is shown in Table 2.

Next, each resin was evaluated regarding the storage stability of the resin at the time of storage. The photoradical curable resin composition of Examples 1-6 and Comparative Example 1 was sealed in 500 g of brown polyethylene bottles, and the presence or absence of precipitation of each compounding agent melt | dissolved on the conditions of -40 degreeC and 168 hours was determined. The results are shown in Table 3.

From the said result, the radical photocurable resin composition of the comparative example 1 was not able to satisfy surface curability and deep curability in the hardening reaction using an ultraviolet light-emitting diode light source. On the other hand, it was proved that the radical photocurable resin composition of this invention satisfy | fills both hardening characteristics, and expresses sufficient hardening performance even in low light quantity. In addition, the storage stability was found to be improved compared to the existing resin composition.

Claims (4)

The radical photocurable resin composition which contains (A) radical photoinitiator, (B) radical chain transfer agent, (C) radically polymerizable compound, and optionally a solvent, and hardens | cures by irradiation of a ultraviolet light emitting diode. The method according to claim 1, wherein (A) the radical radical initiator (A1) ketone compound, (A2) acylphosphine compounds, (A3) thioxanthone compound, (A4) metallocene compound 1 type or 2 or more types of radicals curable resin composition chosen from. The radically polymerizable compound which is (C) component of Claim 1 or 2 contains an acrylic acid ester group and / or methacrylic acid ester group. Preparation of the radical photocurable resin composition of Claim 1 containing the process of mix | blending this to (C) radically polymerizable compound after dissolving and homogenizing only (A) radical photonic initiator and (B) radical chain transfer agent once. Way.