KR101446804B1 - Photoradical curable resin composition and method for preparing the composition - Google Patents

Abstract

The present invention relates to a photo-radical curable resin composition comprising (A) a photo-radical initiator, (B) a radical chain transfer agent, (C) a radically polymerizable compound, and optionally a solvent, and curing by irradiation of an ultraviolet light- .

By using the photo-radical curable resin composition of the present invention, it is possible to obtain a cured product in a very short time regardless of the presence or absence of oxygen, which is a polymerization inhibitor, when the composition is cured using an ultraviolet light emitting diode, . From these properties, it has become possible to use the ultraviolet light-emitting diode as a low-dose photo-radical curable resin composition as a curing light source.

A radical photoinitiator, a photo radical initiator, a radical chain transfer agent, a radically polymerizable compound, an ultraviolet light emitting diode, a photo radical curable resin composition

Description

TECHNICAL FIELD [0001] The present invention relates to a photo-radical-curable resin composition and a method for producing the same. BACKGROUND ART < RTI ID = 0.0 > PHOTORADICAL CURABLE RESIN COMPOSITION AND METHOD FOR PREPARING THE COMPOSITION &

The present invention relates to a photo-radical curable resin composition which uses an ultraviolet light-emitting diode as a light source for curing, and a process for producing the photo-radical curable resin composition.

The addition polymerization reaction for curing by irradiation with ultraviolet light is roughly classified into two types, that is, a polymerization active radical and a cation. Among them, the photo-radical curable resin is superior in terms of environmental safety and productivity due to its solubility and immediate curability, and has been used for coating materials and stereolithography. Although mercury lamps have been used for a long time as these ultraviolet light sources for curing, they are expected to have a substitute light source because they have a short life span and high power consumption and use environmental load substances.

Recently, an ultraviolet light emitting diode has been put to practical use as an ultraviolet light source with a low environmental load to replace a mercury lamp, and has attracted attention as a curing light source for a photo-curable resin material. However, since ultraviolet light emitting diodes save energy compared to mercury lanterns, they have a weak irradiated light intensity and are quasi-monochromatic light sources, so that it is difficult to generate sufficient polymerization active species for curing with conventional photocurable resin compositions. Further, in the photo radical curable resin, there has been a problem of surface hardening defects due to inhibition of polymerization reaction caused by oxygen in the air in the past. However, in the curing reaction using the ultraviolet light emitting diode light source, And there was a tendency to become more prominent. Therefore, there is a need for a photo-radical curable resin composition having good curability even when an ultraviolet light-emitting diode light source is used.

As prior art related to the present invention, the following documents can be cited.

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

[Patent Document 2] JP-A-06-264033

The present invention relates to a photo-radical curable resin composition having good surface hardenability and deep curing property (thick film curability), which is cured even in the presence of oxygen under low illumination by irradiation with an ultraviolet light emitting diode light source, The purpose is to provide.

The present inventors have intensively studied in order to achieve the above object. As a result, they have found that addition of a radical chain transfer agent, a radical polymerizing compound, especially a polymerizable compound (polymerizable monomer) containing an acrylic group and / or a methacryl group, The present inventors have found that a cured resin composition satisfying both the surface hardening property and the deep curing property can be obtained even by irradiation of an ultraviolet light emitting diode light source, thereby completing the present invention.

That is, the present invention provides a photo-radical-curable resin composition and a process for producing the same.

Claim 1:

(A) a photo radical initiator,
(B) a radical chain transfer agent, and
(Polymer) chain comprising an organopolysiloxane (silicone), wherein the acrylic ester residue and / or the methacrylate ester residue derived from the bifunctional acrylic ester monomer and / or the methacrylate ester monomer (C) (Meth) acrylic acid ester residue introduced by introducing at least one compound into the above-mentioned (meth) acrylic acid ester residue in the presence of a radical-polymerizable compound having a mass fraction of 30 to 99 mass%
, And is cured by irradiation of an ultraviolet light emitting diode.

Claim 2:

The composition of claim 1, wherein (A) the photo-radical initiator is

(A1) a ketone compound,

(A2) an acylphosphine compound,

(A3) a thioxanthone compound,

(A4) The metallocene compound

Or a combination of two or more thereof.

[Claim 3]

The photo-radical-curable resin composition according to claim 1 or 2, further comprising a solvent.

Claim 4:

A process for producing a photo-radical-curable resin composition according to any one of claims 1 to 3, which comprises a step of once dissolving and homogenizing only the photo-radical initiator (A) and the radical chain transfer agent (B) Way.

By using the photo-radical curable resin composition of the present invention, it is possible to obtain a cured product in a very short time regardless of the presence or absence of oxygen, which is a polymerization inhibitor, when the composition is cured using an ultraviolet light emitting diode, . From these properties, it has become possible to use the ultraviolet light-emitting diode as a low-dose photo-radical curable resin composition as a curing light source.

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

The photo-radical-curable resin composition of the present invention comprises

(A) a photo radical initiator which generates a polymerizable active species by light irradiation by an ultraviolet light emitting diode,

(B) a radical chain transfer agent which improves the reactivity of the polymerizable active species,

(C) a radically polymerizable compound, particularly a polymerizable compound containing at least one of an acryl group and / or a methacryl group in the molecule

And, if necessary,

(D) Solvent

.

(A) a photo radical initiator

As the photo radical initiator, any compound capable of generating a polymerizable active species by irradiation with light by an ultraviolet light emitting diode can be used. In particular,

(A1) a ketone compound,

(A2) an acylphosphine compound,

(A3) a thioxanthone compound,

(A4) The metallocene compound

Are used alone or in combination of two or more.

As the ketone compound (A1), there can be used any of those which can be used as a photo radical initiator. Specific examples thereof include? -Hydroxycyclohexyl phenyl ketone, 2-hydroxy-2-methyl- 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, 4-chlorobenzophenone, 4-bromobenzophenone, 2-carboxybenzophenone, 2-ethoxycarbonylbenzophenone, benzophenone tetracarboxylic acid or its tetramethyl ester, 4,4'-bis ) Benzophenones (for example, 4,4'-bis (dimethylamino) benzophenone, 4,4'-bis (dicyclohexylamino) benzophenone, 4,4'-bis (dihydroxyethyl 4-dimethylamino benzophenone, 4-dimethylamino benzophenone, 4-dimethylamino acetophenone, benzyl, anthraquinone, 2-t 1-butanone, 2-methyl-1- [4- (4-fluorophenyl) -1-butanone, (Methylthio) phenyl] -2-morpholino-1-propanone, 2-hydroxy-2-methyl- [4- (1-methylvinyl) phenyl] propanol oligomer, benzoin, benzoin ethers For example, benzoin methyl ether, benzoin ethyl ether, benzoin propyl ether, benzoin isopropyl ether, benzoin phenyl ether, benzyl dimethyl ketal), acridone, chloroacridone, N- N-butyl acridone, N-butyl-chloroacridone, and the like.

(A2) As the acylphosphine compound used as the photoradical initiator, there can be used any of those which can be used as the photoradical initiator. Specific examples thereof include 2,4,6-trimethylbenzoyldiphenylphosphine oxide, 2,6- Dimethoxybenzoyldiphenylphosphine oxide, 2,6-dichlorobenzoyldiphenylphosphine oxide, 2,4,6-trimethylbenzoylmethoxyphenylphosphine oxide, 2,4,6-trimethylbenzoylethoxyphenylphosphine oxide 2,3,5,6-tetramethylbenzoyldiphenylphosphine oxide, benzoyl di- (2,6-dimethylphenyl) phosphonate, and the like. Examples of bisacylphosphine oxides include bis- (2,6-dichlorobenzoyl) phenylphosphine oxide, bis- (2,6-dichlorobenzoyl) -2,5-dimethylphenylphosphine oxide, bis- (2,6-dichlorobenzoyl) -1-naphthylphosphine oxide, bis- (2,6-dimethoxybenzoyl) phenylphosphine oxide, bis- 2,6-dimethoxybenzoyl) -2,4,4-trimethylpentylphosphine oxide, bis- (2,6-dimethoxybenzoyl) -2,5-dimethylphenylphosphine oxide, bis- 6-trimethylbenzoyl) phenylphosphine oxide, and (2,5,6-trimethylbenzoyl) -2,4,4-trimethylpentylphosphine oxide.

As the thioxanthone compound (A3), there can be used any of those which can be used as a photo radical initiator. Specific examples thereof include 2-isopropylthioxanthone, 4-isopropylthioxanthone, 2-chlorothioxanthone, 1-chloro-4-propanedioxanthone, and the like.

(A4) The metallocene compound is a photopolymerization initiator that generates a radical by light irradiation at a wavelength of 400 to 700 nm. As the metallocene compound (A4), a transition element represented by Fe, Ti, V, Cr, Mn, Co, Ni, Mo, Ru, Rh, Lu, Ta, W, Among them, the titanocene compound is preferable, and among the titanocene compounds, bis (η ⁵ -2,4-cyclopentadien-1-yl) -bis [2,6-difluoro-3- - yl) phenyl] thiatanium is most preferred.

When the mass fraction of the photopolymerization initiators (A1) to (A4) used in the photo-radical-curable resin composition of the present invention is 0.05 to 15 mass%, the sensitivity to the ultraviolet light emitting diode light source becomes high and the thick film curability is improved. More preferably, the thick film curability is further improved within the range of from 0.5 to 6% by mass of (A1) to (A4). The photopolymerization initiators of (A1) to (A4) may be used alone or in combination of two or more.

(B) a radical chain transfer agent

As the radical chain transfer agent, a compound having a function of reactivating the polymerized active species caught by an inert radical supplement such as oxygen and contributing to improvement of the surface hardening property can be used without limitation. Examples of the chain transfer agent include N, N-dimethyl aniline, N, N-dimethyl-p-toluidine, N, N-dimethyl- Dimethylaniline, N, N-dimethyl-4-isopropylaniline, N, N-dimethyl- N, N-bis (2-hydroxyethyl) -3,5-dimethylaniline, N, N-dimethyl-3,5-di- Di (2-hydroxyethyl) -p-toluidine, N, N-bis (2-hydroxyethyl) -3,4-dimethyl aniline, N, Aniline, N, N-bis (2-hydroxyethyl) -4-isopropylaniline, N, N-bis (2-hydroxyethyl) 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- N-dimethylaminobenzoic acid, 2- (methacryloyloxy) ethyl ester, 4-N, N-dimethylaminobenzophenone, trimethylamine, triethylamine, N-methyldiethanolamine, N-ethyldiethanolamine, N-butyldiethanolamine, N-lauryldiethanolamine, triethanolamine, 2- (dimethylamino) ethylmethacrylate, N-methyldiethanolamine dimethacrylate, N- Diethanolamine dimethacrylate, triethanolamine monomethacrylate, triethanolamine dimethacrylate, triethanolamine trimethacrylate and the like. Of these, particularly preferred amines are 2-ethylhexyl-4-dimethylaminobenzoate .

When the mass fraction of the radical chain transfer agent (B) used in the photo-radical-curable resin composition of the present invention is 0.01 to 10 mass%, the sensitivity to the ultraviolet light-emitting diode light source is high and the surface hardenability in air is improved. More preferably, the surface hardenability is further improved within the range of 0.5 to 5% by mass of (B). These radical chain transfer agents may be used alone or in combination of two or more.

(C) a radical polymerizing compound

The radically polymerizable compound is preferably one or more kinds of radically polymerizable monomers selected from acrylic ester monomers and / or methacrylic acid ester monomers having a monofunctional, bifunctional, bifunctional or trifunctional (polyfunctional) (Meth) acrylic acid ester monomer and / or methacrylic acid ester residue derived from the acrylic acid ester monomer and / or methacrylic acid ester monomer in the presence of a polymerization initiator such as an organopolysiloxane (silicone), a polyurethane, A radically polymerizable high molecular compound in which at least one of (meth) acrylic acid ester moieties is introduced into at least one terminal or molecular chain of the polymer (polymer) chain is preferably used.

Specific examples of the radically polymerizable (monomer) compound include monofunctional, bifunctional, and trifunctional or more monofunctional (meth) acrylic compounds having an unsaturated bond and having a radical addition reactivity, Examples of the acrylates include methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, Acrylate, n-hexyl (meth) acrylate, cyclohexyl (meth) acrylate, tert-butylcyclohexyl (meth) acrylate, 2-ethylhexyl (Meth) acrylate, 2-methoxyethyl (meth) acrylate, 2-ethoxyethyl (meth) acrylate, - (2-methoxyethoxy) ethyl (meth) (Meth) acrylate, diethylene glycol monomethyl ether (meth) acrylate, diethylene glycol monoethyl ether (meth) acrylate, diethylene glycol monoethyl ether , 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 (Meth) acrylate, dicyclopentanyl (meth) acrylate, dicyclopentenyl (meth) acrylate, dicyclopentenyl (meth) acrylate, (Meth) acrylate, dicyclopentenyloxyethyl (meth) acrylate, trifluoroethyl (meth) acrylate, octafluoropentyl Rate, and the like perfluorooctyl (meth) acrylate, tribromo phenyl (meth) acrylate, tribromo phenyl oxyethyl (meth) acrylate.

Examples of bifunctional (meth) acrylate esters include 1,6-hexanediol diacrylate, 1,6-hexanediol dimethacrylate, ethylene glycol diacrylate, ethylene glycol dimethacrylate, neopentyl glycol diacrylate Triethylene glycol diacrylate, triethylene glycol dimethacrylate, bis (acryloyloxyethyl) ether of bisphenol A, 3-methylpentanediol diacrylate, 3-methyl Pentanediol dimethacrylate, and the like.

Examples of (meth) acrylic acid esters having three or more functionalities include trimethylolpropane triacrylate, trimethylolpropane trimethacrylate, pentaerythritol triacrylate, pentaerythritol trimethacrylate, pentaerythritol tetraacrylate, penta Trimethylolpropane trimethacrylate, erythritol tetramethacrylate, dipentaerythritol pentaacrylate, dipentaerythritol penta methacrylate, dipentaerythritol hexaacrylate, dipentaerythritol hexa methacrylate, and the like.

Further, a polymer obtained by chemically introducing a radical polymerizable monomer such as (meth) acrylate ester into a polymer material such as a polysiloxane, a polyurethane, or a polyether to chemically introduce the monomer into a radical polymerizable monomer ), Or a combination of the materials may be used.

The (meth) acrylic acid ester compounds may be used alone or in combination of two or more.

In the present invention, when the mass fraction of the (meth) acrylate ester (C) used in the photo-radical-curable resin composition is set to 30 to 99 mass%, the sensitivity to the ultraviolet light-emitting diode light source becomes high and the curing rate and thick- . More preferably, the curing rate and the thick film curing property are further improved within the range of 70 to 98% by mass of (C). These (meth) acrylate esters may be used alone or in combination of two or more.

As the component used in the photo-radical curable resin composition of the present invention, the functions of the respective components (A), (B) and (C) may be imparted to one or a plurality of compounds. Acrylic resins, urethane resins, ether resins and copolymers thereof modified by acrylic acid ester moieties and / or methacrylic acid ester moieties.

Further, in the photo-radical curable resin composition of the present invention, it is preferable to add an adhesion assisting agent to improve the adhesiveness after curing of the cured product. Specifically, a compound having a cyanoacrylate skeleton such as alkyl esters of cyanoacrylic acid such as methyl cyanoacrylate, ethyl cyanoacrylate, propyl cyanoacrylate and butyl cyanoacrylate, Glycidoxypropyltrimethoxysilane, -glycidoxypropyltrimethoxysilane,? -Glycidoxypropyltrimethoxysilane,? -Glycidoxypropyltrimethoxysilane,? -Glycidoxybutyltrimethoxysilane ,? -glycidoxybutyltrimethoxysilane,? -glycidoxybutyltrimethoxysilane,? -glycidoxybutyltrimethoxysilane, (3,4-epoxycyclohexyl) methyltrimethoxysilane, (3,4-epoxycyclohexyl) ethyltrimethoxysilane,? - (3,4-epoxycyclohexyl) propyltrimethoxysilane,? - And epoxy functional group-containing alkoxysilanes represented by these groups 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. The preferable amount of the photo-radical-curable resin composition to be added is, for example, in the range of about 0.1 to 10% by mass, preferably about 0.5 to 5% by mass, of the entire composition to improve the adhesion to the adherend of the photo- have.

A solvent may be added to the composition of the present invention if necessary. Examples of the solvent include 5 to 15 carbon atoms such as n-pentane, n-hexane, n-heptane, isooctane, cyclopentane, Non-polar hydrocarbon solvents may be used. (E.g., a solvent containing a heteroatom other than carbon and hydrogen) may be used. Examples of the solvent include ethanol, propanol, butanol, cyclohexanol, diethyl ether, tetrahydrofuran, 1,4-dioxane , Ethers, and esters, such as acetone, ethyl acetate, and butyl acetate, and silane-based or siloxane-based solvents such as hexamethyldisilane and hexamethyldisiloxane may also be used. Fluorine-containing solvents such as fluoroalkanes and fluoroalkyl ethers can also be used. The addition amount of the photo radical initiator in the range of, for example, 0.1 to 50 mass% of the entire composition can improve the solubility of the photo radical initiator.

Process for producing a photo-radical-curable resin composition

A compound which becomes a photo radical initiator often contains an aromatic compound or a polar group in the molecule in order to efficiently absorb light. These groups of compounds have high crystallinity and therefore may have low solubility in the base monomer. In this case, in the present invention, it is preferable to dissolve and homogenize the photo radical initiator and the radical chain transfer agent (initiator aid) at a high temperature of 50 to 150 ° C in advance, and dissolve the obtained liquid in the radical polymerizable compound. In this case, the liquid is stable even at room temperature, and therefore dissolution into the radical polymerizable compound can be performed at room temperature. Further, the photo-radical curable resin composition thus obtained is capable of inhibiting recrystallization of the photo radical initiator and the radical chain transfer agent.

Curing of the photo-radical curable resin composition

Conventionally, when ultraviolet light is irradiated to a photo-radical curable resin composition as an ultraviolet light emitting diode as a light source instead of a conventional light source such as a high-pressure mercury lamp or a xenon lamp, and these resins are cured, curing defects are generally caused. As a reason for this, a high-pressure mercury lamp or a xenon lamp light source has an ultraviolet luminescence spectrum in a wide wavelength range and exhibits a high resin curability, whereas the ultraviolet light emitting diode has a quasi-monochromatic color having an emission wavelength in any one of 220 to 370 nm It is a light source and can not sufficiently cure the ultraviolet ray curable resin. Therefore, in the conventional photo-radical curable resin composition, the curing is defective, and in particular, the curing property of the deep portion is defective. Further, when oxygen such as air is present, since it functions as a polymerization inhibitor, surface hardness is often poor. In contrast, the photo-radical curable resin composition according to the present invention can be cured under the irradiation conditions of an ultraviolet light emitting diode, which is conventionally poor in curing as well as existing light sources such as a high pressure mercury lamp or a xenon lamp, Curing property and deep curing property can be obtained. It is possible to obtain high curability by an ultraviolet light emitting diode light source having an emission wavelength of 365 nm. The irradiation of the ultraviolet light emitting diode can be performed well under any atmosphere such as under a non-oxygen atmosphere such as an inert gas such as nitrogen or argon under an oxygen-containing atmosphere such as the air or under a reduced pressure, At room temperature (for example, 25 占 폚).

<Examples>

Hereinafter, the present invention will be described in more detail with reference to examples and comparative examples, but the present invention is not limited to these examples. In the following description, parts means parts by mass.

[Example 1]

Preparation of photo-radical-curable resin composition:

(IRGACURE 379, manufactured by Ciba Specialty Chemicals, Inc.) was added to a solution of 2-dimethylamino-2- (4-methylbenzyl) 1 part of 2-hydroxy-2-methyl-1-phenyl-propan-1-one (manufactured by Ciba Specialty Chemicals, trade name DAROCURE 1173), 2 parts of 2-ethylhexyl-4-dimethylaminobenzoate , 0.1 part of 2,4-diethyl thioxanthone (manufactured by Nippon Kayaku Co., Ltd., trade name: DETX-S) were mixed and then heated and dissolved at 100 占 폚 for 15 minutes . The liquid was cooled to room temperature and added to 100 parts of acrylic-modified silicone (Formula 1), followed by stirring and defoaming to obtain a photo-radical curable resin composition.

[Example 2]

The procedure of Example 1 was repeated except that the amount of 2-dimethylamino-2- (4-methylbenzyl) -1- (4-morpholin-4-yl- 0.6 part of benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1 (Irgacure 369 available from Ciba Specialty Chemicals) A radical-curable resin composition was obtained.

[Example 3]

The same procedure as in Example 1 was carried out except that 0.15 part of 2,4-diethylthioxanthone (manufactured by Nippon Kayaku Co., Ltd., product name: DETX-S) was changed to the composition in Example 1 and the photo-radical curable resin composition .

[Example 4]

3 parts of 1-hydroxy-cyclohexyl-phenyl ketone (manufactured by Ciba Specialty Chemicals, trade name Irgacure 184) was added in the composition of Example 1 and the same operation as in Example 1 was carried out to obtain a photo-radical curable resin composition &Lt; / RTI &gt;

[Example 5]

In the composition of Example 1, 0.6 part of 2-dimethylamino-2- (4-methylbenzyl) -1- (4-morpholin- 0.6 parts of 1-hydroxy-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1 (Irgacure 369 available from Ciba Specialty Chemicals) Except that 3 parts of phenyl ketone (manufactured by Ciba Specialty Chemicals, trade name Irgacure 184) was added and p-dimethylamino (4-dimethylamino) was added instead of 2-ethylhexyl-4-dimethylaminobenzoate (manufactured by Ciba Specialty Chemicals, 1 part of benzoic acid-bisylester (trade name: KAYACURE DMBI, manufactured by Nippon Kayaku Co., Ltd.) was added and the same operation as in Example 1 was added to obtain a photo-radical curable resin composition.

[Example 6]

In the composition of Example 1, the photo-radical curable resin composition was obtained by changing the acrylic denatured silicone represented by Chemical Formula 1 to acryl denatured urethane (HX-620, manufactured by Nippon Kayaku Co., Ltd.) and then performing the same operation as in Example 1.

Each resin was evaluated for surface curability and deep part curability of the cured product when irradiated with an ultraviolet light emitting diode light source in air or at room temperature (25 캜) as described below. As an ultraviolet light emitting diode irradiating device, an ICEQUE (spot type, ANUJ-5010) 2 manufactured by Matsushita Electric Industrial Co., Ltd. was used at 10 mm intervals. These UV-LEDs were irradiated at a focal distance of 10 mm and a scanning speed of 80 mm / s. The evaluation results are shown in Table 1.

Evaluation of surface hardenability

A linear cured sample was prepared by introducing a photo-radical curable resin composition into a mold frame having a length of 5 cm, a width of 1 mm, and a thickness of 600 μm formed on a glass plate. Subsequently, the curing reaction was carried out by light irradiation with an ultraviolet light emitting diode under the above conditions, and the surface of the cured product immediately after irradiation was contacted with rubber gloves, and then the contact portion was pressed against the black polypropylene plate, It was judged as follows.

X: The surface of the cured product is sticky, and there is a transfer material.

B: The surface of the cured product is slightly tacky, and there is a trace amount of the transfer product.

○: The surface of the cured product has no tackiness and no migration product.

Evaluation of Deep Cure Properties

The photo-cured product was peeled from the glass plate immediately after the ultraviolet ray irradiation, and the deep-part curability was judged by the amount of the liquid uncured product remaining on the glass plate as follows.

X: Unconserved cargo on the glass plate after the release of the cured product.

?: There are some unclear cargoes on the glass plate after peeling off the hardened cargo.

○: Unconserved cargo does not exist on the glass plate after the release of the hardened cargo.

 [Comparative Example 1]

Preparation of photo-radical-curable resin composition:

4 parts of 2-methyl-1- [4- (methylthio) phenyl] -2 (2-hydroxy-2-methyl-1-phenylpropane- -Morpholinopropane-1-one (manufactured by Ciba Specialty Chemicals, trade name Irgacure 907) were mixed. This liquid was added to 100 parts of acryl denatured silicone (KJC-7807R, Shin-Etsu Chemical Co., Ltd.) and the same operation as in Example 1 was carried out to obtain a photo-radical curable resin composition.

Table 2 shows the results of curing the above comparative photo-radical curable resin composition by UV-LED irradiation, using the same technique as in the examples.

Next, evaluation of the storage stability of the resin at the time of storage was carried out for each resin. The light radical-curable resin compositions of Examples 1 to 6 and Comparative Example 1 were sealed in a brown polyethylene bottle containing 500 g of the resin, and the presence or absence of precipitation of each compounding agent dissolved at -40 占 폚 for 168 hours was determined. The results are shown in Table 3.

From the results, it can not be said that the photo-radical curable resin composition of Comparative Example 1 satisfies the surface hardening property and the deep hardening property in the curing reaction using the ultraviolet light emitting diode light source. On the other hand, the photo-radical-curable resin composition of the present invention satisfies both of the curing properties, and it has been verified that sufficient curing performance is exhibited even at a low light amount. It was also found that the storage stability was improved as compared with the conventional resin composition.

Claims (4)

(A) a photo radical initiator, (B) a radical chain transfer agent, and (Polymer) chain comprising an organopolysiloxane (silicone), wherein the acrylic ester residue and / or the methacrylate ester residue derived from the bifunctional acrylic ester monomer and / or methacrylate ester monomer (C) (Meth) acrylic acid ester residue introduced by introducing at least one compound into the above-mentioned (meth) acrylic acid ester residue in the presence of a radical-polymerizable compound having a mass fraction of 30 to 99 mass% , And is cured by irradiation of an ultraviolet light emitting diode. The composition of claim 1, wherein (A) the photo-radical initiator is (A1) a ketone compound, (A2) an acylphosphine compound, (A3) a thioxanthone compound, (A4) The metallocene compound Or a combination of two or more thereof. The photo-radical-curable resin composition according to claim 1 or 2, further comprising a solvent. A process for producing a photo-radical-curable resin composition according to any one of claims 1 to 3, which comprises a step of once dissolving and homogenizing only the photo-radical initiator (A) and the radical chain transfer agent (B) Way.