JP2003238691A - Photocurable resin composition - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a photocurable resin composition which has good photocurability and can easily give a cured product being excellent in heat resistance as well as dimensional accuracy, etc., and being desirably used as a three-dimensional shaping such as a trial product of a machine part excellent in, especially, impact resistance, toughness such as folding resistance. <P>SOLUTION: The photocurable resin composition comprises (A) a cationically polymerizable organic compound, (B) an aromatic sulfonium compound represented by formula (1) (wherein R<SP>1</SP>is a p-phenylene group one or more of the hydrogen atoms of which are replaced by halogen atoms or alkyl groups; R<SP>2</SP>is a hydrocarbon group optionally containing an oxygen atom or a halogen atom; Y<SP>1</SP>and Y<SP>2</SP>, which may be the same as or different from each other, are each a hydrogen atom, a halogen atom, or a hydrocarbon group optionally containing an oxygen atom or a halogen atom; and X is an atomic group convertible into a monovalent anion; and (C) elastomer particles having a mean particle diameter of 10-700 nm. <P>COPYRIGHT: (C)2003,JPO

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention is excellent in photocurability,
And a liquid curable resin composition excellent in mechanical strength of a cured product, such as plastic, various films, wood, ceramics,
Glass, quartz fiber for communication, paper, metal, beverage can,
The present invention relates to a photocurable resin composition suitable as a coating material for fibers, a resin for optical three-dimensional modeling, a sealing agent for semiconductors, an adhesive for semiconductors, an underfill agent, an adhesive for optics, a printing plate material and the like. Of these, when used as a resin for optical three-dimensional molding, it exhibits excellent photocurability against various light sources such as lasers and ultraviolet lamps, and the three-dimensional object after curing has impact resistance and bending resistance. It relates to an excellent photocurable resin composition.

[0002]

2. Description of the Related Art In recent years, a photocurable liquid substance (liquid resin composition) is selectively irradiated with light to form a cured resin layer. An optical three-dimensional modeling method for forming the following three-dimensional object has been proposed (JP-A-60-247515, JP-A-62-35966, JP-A-62-101408).
Japanese Patent Laid-Open Publication No. 5-24119). Explaining a typical example of this optical three-dimensional modeling method, the liquid level of the photocurable resin composition contained in the container is selectively irradiated with light such as an ultraviolet laser to form a predetermined pattern. A cured resin layer having is formed. Then, on the cured resin layer, a photocurable resin composition for one layer is supplied, and the liquid surface thereof is selectively irradiated with light, whereby the cured resin layer formed in advance on the cured resin layer. A new cured resin layer is integrally laminated so as to be continuous. Then, by repeating the above steps a predetermined number of times with or without changing the pattern irradiated with light, a three-dimensional object in which a plurality of cured resin layers are integrally laminated is formed. This optical three-dimensional modeling method has attracted attention because it can be obtained easily and in a short time even if a target three-dimensional object has a complicated shape.

Conventionally, as the photocurable resin composition used in the optical three-dimensional molding method, the following resin compositions [a] to [c] have been introduced. [A] Resin composition containing a radically polymerizable organic compound such as urethane (meth) acrylate, oligoester (meth) acrylate, epoxy (meth) acrylate, thiol and ene compound, and photosensitive polyimide (for example, JP-A-1-204915). Japanese Patent Laid-Open No. 2-208
No. 305, Japanese Patent Laid-Open No. 3-160013). [B] A resin composition containing a cationically polymerizable organic compound such as an epoxy compound, a cyclic ether compound, a cyclic lactone compound, a cyclic acetal compound, a cyclic thioether compound, a spiro orthoester compound, a vinyl ether compound (for example, JP-A 1-213304). See the bulletin). [C] A resin composition containing a radically polymerizable organic compound and a cationically polymerizable organic compound (for example, JP-A-2-28).
261, Japanese Patent Application Laid-Open No. 2-75618, Japanese Patent Application Laid-Open No. H6-6
-228413 publication reference).

[0004]

However, photocurability, in particular, avoidance of deviation from a desired shape / dimension due to warpage or deformation of a modeled product due to curing shrinkage during photocuring, and curing obtained. Mechanical properties of objects, especially impact resistance,
In terms of toughness, bending resistance, etc., they have not been sufficiently satisfactory. Therefore, an object of the present invention is to provide a photocurable resin composition which is excellent in both photocurability and mechanical properties of the cured product obtained.

[0005]

Means for Solving the Problems The present inventor has combined a cationically polymerizable organic compound with a specific cationic polymerization initiator represented by the general formula (1) described below, and by blending elastomer particles therein, both of the above We found that the problem could be solved.

That is, the present invention provides the following component (A),
(B) and (C): (A) cationically polymerizable organic compound, (B) the following general formula (1)

[0007]

[Chemical 2]

(Wherein R ¹ represents a p-phenylene group in which one or more of its hydrogen atoms are replaced by a halogen atom or an alkyl group, and R ² may contain an oxygen atom or a halogen atom. Represents a hydrocarbon group, Y ¹
And Y ² represent a hydrogen atom, a halogen atom, or a hydrocarbon group which may contain an oxygen atom or a halogen atom, which may be the same or different, and X represents an atomic group capable of becoming a monovalent anion). A photocurable resin composition comprising an aromatic sulfonium compound and (C) elastomer particles having an average particle diameter of 10 to 700 nm.

[0009]

BEST MODE FOR CARRYING OUT THE INVENTION (A) Cationic polymerizable organic compound (hereinafter also referred to as "(A) component") used in the photocurable resin composition of the present invention. ] Is an organic compound that causes a polymerization reaction or a crosslinking reaction by irradiation with light in the presence of a cationic photopolymerization initiator, and is, for example, an epoxy compound, an oxetane compound, an oxolane compound, a cyclic acetal compound, a cyclic lactone compound, or a thiirane compound. , A thietane compound, a vinyl ether compound, a spiro orthoester compound which is a reaction product of an epoxy compound and a lactone, an ethylenically unsaturated compound, a cyclic ether compound, a cyclic thioether compound, a vinyl compound and the like.

Examples of the epoxy compound which can be used as the component (A) include bisphenol A diglycidyl ether, bisphenol F diglycidyl ether, bisphenol S diglycidyl ether, brominated bisphenol A diglycidyl ether, and brominated bisphenol F diester. Glycidyl ether, brominated bisphenol S diglycidyl ether, epoxy novolac resin, hydrogenated bisphenol A diglycidyl ether, hydrogenated bisphenol F diglycidyl ether, hydrogenated bisphenol S diglycidyl ether, 3,4-epoxycyclohexylmethyl-3 ', 4'-epoxycyclohexanecarboxylate, 2- (3,4-epoxycyclohexyl-
5,5-spiro-3,4-epoxy) cyclohexane-
Meta-dioxane, bis (3,4-epoxycyclohexylmethyl) adipate, vinylcyclohexene oxide, 4-vinylepoxycyclohexane, bis (3,3
4-epoxy-6-methylcyclohexylmethyl) adipate, 3,4-epoxy-6-methylcyclohexyl-3 ', 4'-epoxy-6'-methylcyclohexanecarboxylate, methylenebis (3,4-epoxycyclohexane), di Cyclopentadiene diepoxide,
Di (3,4-epoxycyclohexylmethyl) ether of ethylene glycol, ethylenebis (3,4-epoxycyclohexanecarboxylate), dioctyl epoxyhexahydrophthalate, di-2-ethylhexyl epoxyhexahydrophthalate, 1,4- Butanediol diglycidyl ether, 1,6-hexanediol diglycidyl ether, glycerin triglycidyl ether, trimethylolpropane triglycidyl ether,
Polyethylene glycol diglycidyl ether, polypropylene glycol diglycidyl ethers; Polyglycidyl of polyether polyol obtained by adding one or more alkylene oxides to an aliphatic polyhydric alcohol such as ethylene glycol, propylene glycol and glycerin Ethers; Diglycidyl esters of aliphatic long-chain dibasic acids; Monoglycidyl ethers of higher aliphatic alcohols; Phenol, cresol, butylphenol or monoglycidyl ethers of polyether alcohols obtained by adding alkylene oxides to these; Glycidyl esters of higher fatty acids; epoxidized soybean oil; butyl epoxy stearate; octyl epoxy stearate; epoxidized linseed oil; It can be exemplified butadiene.

Other cationically polymerizable organic compounds that can be used as the component (A) include trimethylene oxide, 3,3-dimethyloxetane, 3,3-dichloromethyloxetane and 3-ethyl-3-phenoxymethyl. Oxetane, bis (3-ethyl-3-methyloxy)
Oxetanes such as butane; tetrahydrofuran, 2,
Oxolanes such as 3-dimethyltetrahydrofuran;
Cyclic acetals such as trioxane, 1,3-dioxolane, 1,3,6-trioxanecyclooctane; γ
-Cyclic lactones such as propiolactone and ε-caprolactone; thiiranes such as ethylene sulfide, 1,2-propylene sulfide and thioepichlorohydrin;
Thietanes such as 3,3-dimethylthietane; vinyl ethers such as ethylene glycol divinyl ether, triethylene glycol divinyl ether and trimethylolpropane trivinyl ether; spiro orthoesters obtained by reaction of an epoxy compound with a lactone; vinylcyclohexane , Ethylenically unsaturated compounds such as isobutylene and polybutadiene; and derivatives of each of the above compounds.

Among these cationically polymerizable organic compounds, bisphenol A diglycidyl ether, bisphenol F diglycidyl ether, hydrogenated bisphenol A
Diglycidyl ether, hydrogenated bisphenol F diglycidyl ether, 3,4-epoxycyclohexylmethyl-3 ', 4'-epoxycyclohexanecarboxylate, bis (3,4-epoxycyclohexylmethyl) adipate, 1,4-butanedioldi Glycidyl ether, 1,6-hexanediol diglycidyl ether,
Glycerin triglycidyl ether, trimethylolpropane triglycidyl ether, neopentyl glycol diglycidyl ether, polyethylene glycol diglycidyl ether and polypropylene glycol diglycidyl ether are preferred.

Particularly preferred cationically polymerizable organic compounds as the component (A) are 3,4-epoxycyclohexylmethyl-3 ', 4'-epoxycyclohexanecarboxylate, bis (3,4-epoxycyclohexylmethyl) adipate and the like. 1. An epoxy compound having two or more alicyclic epoxy groups in one molecule, and when this epoxy compound is contained in the component (A) in a proportion of 50% by weight or more, a resin composition obtained The cationic polymerization reaction rate (curing rate) of the product can be increased to shorten the modeling time, and the curing shrinkage rate can be decreased to suppress the time-dependent deformation of the three-dimensional object.

UVR-610 is commercially available as a cationically polymerizable organic compound which can be preferably used as the component (A).
0, UVR-6105, UVR-6110, UVR-6
128, UVR-6200, UVR-6216 (above,
Union Carbide), Celoxide 2021, Celoxide 2021P, Celoxide 2081, Celoxide 2083, Celoxide 2085, Celoxide 2000, Celoxide 3000, Glycidol, AO.
EX24, Cyclomer A200, Cyclomer M10
0, Eporide GT-300, Eporide GT-30
1, Eporide GT-302, Eporide GT-40
0, Epolide 401, Epolide 403 (all manufactured by Daicel Chemical Industries Ltd.), Epicoat 828, Epicoat 812, Epicoat 1031, Epicoat 872, Epicoat CT508 (all manufactured by Yuka Shell Co., Ltd.), K
RM-2100, KRM-2110, KRM-219
9, KRM-2400, KRM-2410, KRM-2
408, KRM-2490, KRM-2200, KRM
-2720, KRM-2750 (above, Asahi Denka Kogyo KK), Rapi-Cure DVE-3, CHV
E, PEPC (above, manufactured by ISP), VECTOMER
Examples include 2010, 2020, 4010, 4020 (all manufactured by Allied Signal Co., Ltd.). The above-mentioned cationically polymerizable compounds can be used alone or in combination of two or more to form the component (A).

The content of the component (A) in the photocurable resin composition of the present invention is usually 2 based on the total composition.
0 to 85% by weight, preferably 30 to 80% by weight,
More preferably, it is 40 to 75% by weight. When the content ratio of the component (A) is too small, the dimensional accuracy of the three-dimensional object by the obtained resin composition is lowered, and the three-dimensional object tends to be deformed with time. On the other hand, when the content ratio is too large, the photocurability of the obtained resin composition is deteriorated and the molding efficiency is deteriorated.

The aromatic sulfonium compound as the component (B) used in the present invention includes ultraviolet rays, electron beams, X-rays, radiation,
It acts as a cationic photopolymerization initiator by irradiation with active energy rays such as high frequency.

In the above general formula (1), R ¹ is a p-phenylene group in which one or more of its hydrogen atoms are substituted with a halogen atom or an alkyl group. For example, one or more hydrogen atoms are fluorine atom, chlorine atom, bromine atom, iodine atom, methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group,
Tertiarybutyl group, pentyl group, isopentyl group, tertiarypentyl group, neopentyl group, hexyl group, isohexyl group, heptyl group, octyl group, 2-ethylhexyl group, nonyl group, decyl group, undecyl group, dodecyl group, tridecyl group. , P substituted with an isotridecyl group, myristyl group, palmityl group, stearyl group, etc.
A phenylene group. The number of these substituents is preferably in the range of 1 to 4, and the place is not particularly limited.

R ² represents a hydrocarbon group which may contain an oxygen atom or a halogen atom. Examples thereof include an alkyl group, a halogenated alkyl group, a hydroxyalkyl group, an alkoxy group, a phenyl group, an alkylphenyl group, a halogenated phenyl group, a phenoxy group, a hydroxyphenyl group and an alkoxycarbonyl group.

Examples of the alkyl group include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a tertiary butyl group, a pentyl group, an isopentyl group, a tertiary pentyl group, a neopentyl group, a hexyl group and an isohexyl group. Group, heptyl group, octyl group, 2-
Examples thereof include ethylhexyl group, nonyl group, decyl group, undecyl group, dodecyl group, tridecyl group, isotridecyl group, myristyl group, palmityl group and stearyl group. Moreover, one or more hydrogen atoms of these groups may be substituted with a phenyl group or an acyl group.

Examples of the halogenated alkyl group include those obtained by substituting one or more hydrogen atoms of the alkyl group with a halogen atom.

The alkoxy group is a methoxy group,
Ethoxy group, propyloxy group, butyloxy group, pentyloxy group, hexyloxy group, heptyloxy group,
Octyloxy group, nonyloxy group, decyloxy group,
Examples thereof include an undecyloxy group, a dodecyloxy group, a tridecyloxy group, a myristyloxy group, a palmityloxy group and a stearyloxy group.

The hydroxyalkyl group, halogenated alkyl group, hydroxyalkyl group, alkoxy group and alkoxycarbonyl group preferably have 1 to 12 carbon atoms.

When the hydrocarbon group has a phenyl group, one or more hydrogen atoms in the phenyl group are a halogen atom, an alkyl group, a hydroxyalkyl group,
It may be substituted with an alkoxy group, a hydroxyl group, an ester group (alkoxycarbonyl group), an acyl group or the like, and one or more hydrogen atoms in these substituents may be substituted with a halogen atom, a hydroxyl group or the like. These alkyl groups,
The hydroxyalkyl group, alkoxy group, hydroxyl group, ester group (alkoxycarbonyl group), acyl group and the like may be the above groups.

Y ¹ and Y ² represent the same or different hydrogen atom, halogen atom, or hydrocarbon group which may contain oxygen atom or halogen atom. In the hydrocarbon group which may contain an oxygen atom or a halogen atom, R ²
It may be a group described in the section 1), or may be a polyoxyalkylene group. The positions of Y ¹ and Y ² are not particularly limited.

X is an atomic group capable of becoming a monovalent anion. Among them, X is SbF ₆ ⁻ , PF ₆ ⁻ , A
^{_{sF 6 -, BF 4 -,}} SbCl 6 -, ClO 4 -, CF 3 S
O ₃ ⁻ , CH ₃ SO ₃ ⁻ , FSO ₃ ⁻ , F ₂ PO ₂ ⁻ , p-toluenesulfonate, camphorsulfonate, nonafluorobutanesulfonate, adamantanecarboxylate, tetraarylborate and the like are synthetically synthesized. Particularly preferred, SbF ₆ ⁻ is particularly preferred in terms of sensitivity.

The preferred aromatic sulfonium compound represented by the general formula (1) is 4- (2-chloro-4).
-Benzoylphenylthio) phenyldiphenylsulfonium hexafluoroantimonate, 4- (2-chloro-4-benzoylphenylthio) phenylbis (4-
Fluorophenyl) sulfonium hexafluoroantimonate, 4- (2-chloro-4-benzoylphenylthio) phenylbis (4-chlorophenyl) sulfonium hexafluoroantimonate, 4- (2-chloro-
4-benzoylphenylthio) phenylbis (4-methylphenyl) sulfonium hexafluoroantimonate, 4- (2-chloro-4-benzoylphenylthio)
Phenylbis (4- (α-hydroxyethoxy) phenyl) sulfonium hexafluoroantimonate, 4-
(2-Methyl-4-benzoylphenylthio) phenylbis (4-fluorophenyl) sulfonium hexafluoroantimonate, 4- (3-methyl-4-benzoylphenylthio) phenylbis (4-fluorophenyl) sulfonium hexafluoroantimonate Nate, 4-
(2-Fluoro-4-benzoylphenylthio) phenylbis (4-fluorophenyl) sulfonium hexafluoroantimonate, fluorofluoro 4- (2,
3,5,6-Tetramethyl-4-benzoylphenylthio) phenylbis (4-fluorophenyl) sulfonium hexafluoroantimonate, 4- (2,6-dichloro-4-benzoylphenylthio) phenylbis (4
-Fluorophenyl) sulfonium hexafluoroantimonate, 4- (2,6-dimethyl-4-benzoylphenylthio) phenylbis (4-fluorophenyl)
Sulfonium hexafluoroantimonate, 4-
(2,3-Dimethyl-4-benzoylphenylthio) phenylbis (4-fluorophenyl) sulfonium hexafluoroantimonate, 4- (2-methyl-4-benzoylphenylthio) phenylbis (4-chlorophenyl) sulfonium hexafluoro Antimonate, 4
-(3-Methyl-4-benzoylphenylthio) phenylbis (4-chlorophenyl) sulfonium hexafluoroantimonate, 4- (2-fluoro-4-benzoylphenylthio) phenylbis (4-chlorophenyl) sulfonium hexafluoroantimonate , Fluoro 4- (2,3,5,6-tetramethyl-4-benzoylphenylthio) phenylbis (4-chlorophenyl) sulfonium hexafluoroantimonate, 4-
(2,6-Dichloro-4-benzoylphenylthio) phenylbis (4-chlorophenyl) sulfonium hexafluoroantimonate, 4- (2,6-dimethyl-4
-Benzoylphenylthio) phenylbis (4-chlorophenyl) sulfonium hexafluoroantimonate, 4- (2,3-dimethyl-4-benzoylphenylthio) phenylbis (4-chlorophenyl) sulfonium hexafluoroantimonate, 4- (2 -Chloro-
4-Acetylphenylthio) phenyldiphenylsulfonium hexafluoroantimonate, 4- (2-chloro-4- (4-methylbenzoyl) phenylthio) phenyldiphenylsulfonium hexafluoroantimonate, 4- (2-chloro-4- (4 -Fluorobenzoyl) phenylthio) phenyldiphenylsulfonium hexafluoroantimonate, 4- (2-chloro-4-)
(4-methoxybenzoyl) phenylthio) phenyldiphenylsulfonium hexafluoroantimonate,

4- (2-chloro-4-dodecanoylphenylthio) phenyldiphenylsulfonium hexafluoroantimonate, 4- (2-chloro-4-acetylphenylthio) phenylbis (4-fluorophenyl)
Sulfonium hexafluoroantimonate, 4- (2
-Chloro-4- (4-methylbenzoyl) phenylthio) phenylbis (4-fluorophenyl) sulfonium hexafluoroantimonate, 4- (2-chloro-
4- (4-fluorobenzoyl) phenylthio) phenylbis (4-fluorophenyl) sulfonium hexafluoroantimonate, 4- (2-chloro-4- (4-
Methoxybenzoyl) phenylthio) phenylbis (4
-Fluorophenyl) sulfonium hexafluoroantimonate, 4- (2-chloro-4-dodecanoylphenylthio) phenylbis (4-fluorophenyl) sulfonium hexafluoroantimonate, 4- (2-chloro-4-acetylphenylthio ) Phenylbis (4-
Chlorophenyl) sulfonium hexafluoroantimonate, 4- (2-chloro-4- (4-methylbenzoyl) phenylthio) phenylbis (4-chlorophenyl) sulfonium hexafluoroantimonate, 4-
(2-chloro-4- (4-fluorobenzoyl) phenylthio) phenylbis (4-chlorophenyl) sulfonium hexafluoroantimonate, 4- (2-chloro-4- (4-methoxybenzoyl) phenylthio) phenylbis (4- Chlorophenyl) sulfonium hexafluoroantimonate, 4- (2-chloro-4-dodecanoylphenylthio) phenylbis (4-chlorophenyl) sulfonium hexafluoroantimonate,

4- (2-chloro-4-benzoylphenylthio) phenyldiphenylsulfonium hexafluorophosphate, 4- (2-chloro-4-benzoylphenylthio) phenyldiphenylsulfonium tetrafluoroborate, 4- (2-chloro- 4-benzoylphenylthio) phenyldiphenylsulfonium perchlorate, 4- (2-chloro-4-benzoylphenylthio) phenyldiphenylsulfonium trifluoromethanesulfonate, 4- (2-chloro-4-benzoylphenylthio) phenylbis (4- Fluorophenyl) sulfonium hexafluorophosphate, 4- (2-chloro-4-benzoylphenylthio) phenylbis (4
-Fluorophenyl) sulfonium tetrafluoroborate, 4- (2-chloro-4-benzoylphenylthio) phenylbis (4-fluorophenyl) sulfonium perchlorate, 4- (2-chloro-4-benzoylphenylthio) phenylbis ( 4-fluorophenyl)
Sulfonium trifluoromethanesulfonate, 4-
(2-chloro-4-benzoylphenylthio) phenylbis (4-fluorophenyl) sulfonium p-toluenesulfonate, 4- (2-chloro-4-benzoylphenylthio) phenylbis (4-fluorophenyl)
Sulfonium camphor sulfonate, 4- (2-chloro-4-benzoylphenylthio) phenylbis (4
-Fluorophenyl) sulfonium nonafluorobutane sulfonate, 4- (2-chloro-4-benzoylphenylthio) phenylbis (4-chlorophenyl) sulfonium hexafluorophosphate, 4- (2-chloro-4-benzoylphenylthio) Phenylbis (4-
(Chlorophenyl) sulfonium tetrafluoroborate, 4- (2-chloro-4-benzoylphenylthio)
Examples thereof include phenylbis (4-chlorophenyl) sulfonium perchlorate and 4- (2-chloro-4-benzoylphenylthio) phenylbis (4-chlorophenyl) sulfonium trifluoromethanesulfonate.

The content of the component (B) in the photocurable resin composition of the present invention is usually 0.1 to 10% by weight, preferably 0.2 to 5% by weight, based on the entire composition. More preferably, it is 0.3 to 3% by weight. (B)
If the content ratio of the components is too small, the photocurability of the obtained resin composition is lowered, and a three-dimensional object having sufficient mechanical strength cannot be molded. On the other hand, when the content ratio is excessively large, when the obtained resin composition is subjected to an optical three-dimensional modeling method, it is difficult to control the curing depth because it is not possible to obtain appropriate light transmittance. There is a tendency that the modeling accuracy of the three-dimensional object is reduced.

Elastomer particles (C) having an average particle diameter of 10 nm to 700 nm used in the photocurable resin composition of the present invention [hereinafter also referred to as "(C) component"]. ] Is polybutadiene, polyisoprene, butadiene / acrylonitrile copolymer, styrene / butadiene copolymer, styrene / isoprene copolymer, ethylene / propylene copolymer, ethylene / α-olefin copolymer, ethylene / α- Olefin / polyene copolymer, acrylic rubber,
Examples thereof include elastomer particles such as a butadiene / (meth) acrylic acid ester copolymer, a styrene / butadiene block copolymer, and a styrene / isoprene block copolymer. Acrylate /
Examples thereof include core / shell type particles coated with a glycidyl methacrylate copolymer or the like. The elastomer particles may have a crosslinked structure and can be crosslinked by a commonly used means. Examples of the crosslinking agent used in this case include divinylbenzene, ethylene glycol di (meth) acrylate, diallyl maleate, triallyl cyanurate, triallyl isocyanurate, diallyl phthalate, trimethylolpropane triacrylate, and allyl methacrylate. Can be mentioned.

Elastomer particles that can be preferably used as the component (C) include, for example, polybutadiene, polyisoprene, styrene / butadiene copolymer, styrene /
Isoprene copolymer, ethylene / propylene copolymer,
Ethylene / α-olefin copolymer, ethylene / α-
Examples thereof include olefin / polyene copolymer, acrylic rubber, butadiene / (meth) acrylic acid ester copolymer, styrene / butadiene block copolymer, and styrene / isoprene block copolymer-based elastomer particles. .

Further, as core / shell type particles which can be preferably used, polybutadiene, polyisoprene, styrene / butadiene copolymer, styrene / isoprene copolymer, ethylene / propylene copolymer, ethylene / α-olefin -Based copolymer, ethylene / α-olefin / polyene copolymer, acrylic rubber, butadiene /
(Meth) acrylic ester copolymer, styrene / butadiene block copolymer, styrene / isoprene block copolymer, etc. partially cross-linked core coated with methyl methacrylate polymer elastomer particles, methyl methacrylate / glycidyl methacrylate Examples thereof include particles coated with a copolymer. In addition,
In the case of core / shell type particles, the ratio of the radius of the core to the thickness of the shell is usually 1/2 to 1000/1, preferably 1/1 to
200/1 (for example, 35/1 with a core radius of 350 nm and a shell thickness of 10 nm).

Among these elastomer particles, polybutadiene, polyisoprene, styrene / butadiene copolymer, styrene / isoprene copolymer, butadiene / (meth) acrylic acid ester copolymer, styrene / butadiene block copolymer, styrene Particularly preferred are elastomer particles coated with a methylmethacrylate polymer and particles coated with a methylmethacrylate / glycidylmethacrylate copolymer on a core partially crosslinked with a / isoprene block copolymer. These elastomer particles can be produced by a commonly used method, for example, an emulsion polymerization method. As the emulsion polymerization method, for example, a method of charging and polymerizing all of the monomer components at once, a method of polymerizing a part of the monomer components, and then continuously or intermittently adding the rest, monomer components Can be continuously added from the beginning of the polymerization, or a method using seed particles can be adopted.

The elastomer particles thus obtained have an average particle size of 10 nm to 700 nm. If it is less than 10 nm, the impact resistance of the obtained three-dimensional object will be reduced, or the viscosity of the resin liquid will increase, affecting the productivity and modeling accuracy of the three-dimensional object. On the other hand, if it exceeds 700 nm, the surface will be sufficiently smooth. A solid three-dimensional object cannot be obtained, or the molding accuracy decreases. Examples of commercially available core / shell type elastomer particles as described above include Resinus Bond RKB (manufactured by Resinus Kasei Co., Ltd.), Techno MBS-61, MBS-69 (manufactured by Techno Polymer Co., Ltd.) and the like. be able to. These (C) component elastomer particles can be used alone or in combination of two or more kinds.

The content ratio of the component (C) in the photocurable resin composition of the present invention is usually 1 with respect to the entire composition.
Is about 35% by weight, preferably 3 to 30% by weight, particularly preferably 5 to 20% by weight. If the content ratio of the component (C) is too small, the impact resistance is lowered, while if the content ratio is too large, the molding accuracy of the obtained three-dimensional object tends to be lowered.

The photocurable resin composition of the present invention preferably further contains (D) an ethylenically unsaturated monomer. (D) Ethylenically unsaturated monomer [hereinafter referred to as "(D)
Also called "ingredient". ] Is an ethylenically unsaturated bond (C =
Examples of the compound having C) in the molecule include a monofunctional monomer having one ethylenically unsaturated bond in one molecule and a polyfunctional monomer having two or more ethylenically unsaturated bonds in one molecule. be able to.

Examples of monofunctional monomers that can be preferably used as the component (D) include, for example, isobornyloxyethyl (meth) acrylate, isobornyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, ethyldiethylene glycol (meth) acrylate. , Lauryl (meth) acrylate, dicyclopentadiene (meth) acrylate, dicyclopentenyloxyethyl (meth) acrylate, dicyclopentenyl (meth) acrylate, 2-tetrachlorophenoxyethyl (meth) acrylate, tetrahydrofurfuryl (meth) Acrylate, tetrabromophenyl (meth) acrylate, 2-tetrabromophenoxyethyl (meth) acrylate, 2-trichlorophenoxyethyl (meth) acrylate, tribromophenyl Sulfonyl (meth) acrylate,
2-tribromophenoxyethyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-
Hydroxypropyl (meth) acrylate, phenoxyethyl (meth) acrylate, butoxyethyl (meth)
Acrylate, pentachlorophenyl (meth) acrylate, pentabromophenyl (meth) acrylate, polyethylene glycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate, bornyl (meth) acrylate, methyltriethylenediglycol (meth) acrylate, and The following general formula (2)
The compounds represented by (4) to (4) can be exemplified.

[0038]

[Chemical 3]

(In the above formula, R ³ independently represents a hydrogen atom or a methyl group, R ⁴ represents an alkylene group having 2 to 6 carbon atoms, preferably 2 to 4 carbon atoms, and R ⁵ represents a hydrogen atom or a carbon atom. C 1 -C 12, preferably an 1-9 alkyl group, R ⁶ is 2 to 8 carbon atoms, preferably .r showing an alkylene group having 2 to 5 0 to 12, preferably an integer of 1 to 8 And q is an integer of 1 to 8, preferably 1 to 4.)

Of these monofunctional monomers, isobornyl (meth) acrylate, lauryl (meth) acrylate and phenoxyethyl (meth) acrylate are particularly preferable. As commercial products of these monofunctional monomers,
For example, Aronix M-101, M-102, M-11
1, M-113, M-117, M-152, TO-12
10 (all manufactured by Toagosei Co., Ltd.), KAYARAD T
C-110S, R-564, R-128H (Nippon Kayaku Co., Ltd.), viscoat 192, viscoat 220,
Screw coat 2311HP, screw coat 2000, screw coat 2100, screw coat 2150, screw coat 8F,
Viscoat 17F (above, manufactured by Osaka Organic Chemical Industry Co., Ltd.)
And so on.

As the polyfunctional monomer which can be suitably used as the component (D), for example, ethylene glycol di (meth) acrylate, dicyclopentenyl di (meth) acrylate, triethylene glycol diacrylate, tetraethylene glycol di (meth) acrylate can be used. Acrylate, tricyclodecanediyldimethylene di (meth) acrylate, tris (2-hydroxyethyl) isocyanurate di (meth) acrylate, tris (2-hydroxyethyl) isocyanurate tri (meth) acrylate, caprolactone-modified tris (2-hydroxy) Ethyl) isocyanurate tri (meth) acrylate, trimethylolpropane tri (meth) acrylate, ethylene oxide (hereinafter referred to as "EO") modified trimethylolpropane tri (meth) acrylate , Propylene oxide (hereinafter referred to as “PO”) modified trimethylolpropane tri (meth) acrylate, tripropylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, and both ends of bisphenol A diglycidyl ether ( (Meth) acrylic acid adduct, 1,4-butanediol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, polyester di ( (Meth) acrylate, polyethylene glycol di (meth) acrylate, dipentaerythritol hexa (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol tetra ( Data) acrylate, caprolactone-modified dipentaerythritol hexa (meth) acrylate, caprolactone-modified dipentaerythritol penta (meth) acrylate, ditrimethylolpropane tetra (meth) acrylate, EO-
Modified bisphenol A di (meth) acrylate, PO modified bisphenol A di (meth) acrylate, EO modified hydrogenated bisphenol A di (meth) acrylate, PO modified hydrogenated bisphenol A di (meth) acrylate, EO
Examples thereof include modified bisphenol F di (meth) acrylate and (meth) acrylate of phenol novolac polyglycidyl ether.

Commercially available products of these polyfunctional monomers include, for example, SA1002 (manufactured by Mitsubishi Chemical Corporation),
Screw coat 195, screw coat 230, screw coat 26
0, viscoat 215, viscoat 310, viscoat 214HP, viscoat 295, viscoat 300, viscoat 360, viscoat GPT, viscoat 40
0, viscoat 700, viscoat 540, viscoat 3000, viscoat 3700 (all manufactured by Osaka Organic Chemical Industry Co., Ltd.), Kayarad R-526, HDDA, NP
GDA, TPGDA, MANDA, R-551, R-7
12, R-604, R-684, PET-30, GPO
-303, TMPTA, THE-330, DPHA, D
PHA-2H, DPHA-2C, DPHA-2I, D-
310, D-330, DPCA-20, DPCA-3
0, DPCA-60, DPCA-120, DN-007
5, DN-2475, T-1420, T-2020, T
-2040, TPA-320, TPA-330, RP-
1040, RP-2040, R-011, R-300,
R-205 (Nippon Kayaku Co., Ltd.), Aronix M-210, M-220, M-233, M-240, M
-215, M-305, M-309, M-310, M-
315, M-325, M-400, M-6200, M-
6400 (above, manufactured by Toagosei Co., Ltd.), light acrylate BP-4EA, BP-4PA, BP-2EA, BP
-2PA, DCP-A (above, Kyoeisha Chemical Co., Ltd.),
New Frontier BPE-4, BR-42M, GX-
8345 (above, Dai-ichi Kogyo Seiyaku Co., Ltd.), ASF-4
00 (above, Nippon Steel Chemical Co., Ltd.), Lipoxy SP-1
506, SP-1507, SP-1509, VR-7
7, SP-4010, SP-4060 (above, Showa Highpolymer Co., Ltd. product), NK ester A-BPE-4 (above, Shin Nakamura Chemical Co., Ltd. product), etc. can be mentioned.

The above-mentioned monofunctional monomers and polyfunctional monomers may be used either individually or in combination of two or more, or by combining at least one monofunctional monomer and at least one polyfunctional monomer (D). The component can be constituted, but the component (D) contains at least 60% by weight of a polyfunctional monomer having three or more functional groups, that is, three or more ethylenically unsaturated bonds in one molecule. Is preferred. The content of the trifunctional or higher polyfunctional monomer is more preferably 70% by weight or more, particularly preferably 80% by weight or more, and most preferably 100% by weight.
Is. The content ratio of trifunctional or higher polyfunctional monomer is 60
If it is less than wt%, the photocurability of the obtained resin composition may be deteriorated, and the three-dimensional object to be molded may be easily deformed with time.

The polyfunctional monomer having three or more functional groups is selected from the above-exemplified tri (meth) acrylate compounds, tetra (meth) acrylate compounds, penta (meth) acrylate compounds, and hexa (meth) acrylate compounds. Of these, trimethylolpropane tri (meth) acrylate, EO
Modified trimethylolpropane tri (meth) acrylate, dipentaerythritol hexa (meth) acrylate, dipentaerythritol penta (meth) acrylate, ditrimethylolpropane tetra (meth) acrylate are particularly preferred.

The content ratio of the component (D) in the photocurable resin composition of the present invention is usually 5 based on the whole composition.
Is 45% by weight, preferably 7 to 35% by weight, more preferably 10 to 25% by weight. When the content ratio of the component (D) is too small, the photocurability of the obtained resin composition tends to decrease, and the mechanical strength also tends to decrease.
On the other hand, when the content ratio is too large, the resulting resin composition tends to shrink due to photocuring, and the obtained three-dimensional object tends to have reduced heat resistance, moisture resistance and the like.

The photocurable resin composition of the present invention preferably further contains (E) a radical photopolymerization initiator. (E) Radical photopolymerization initiator [hereinafter also referred to as "component (E)". ] Is a compound which is decomposed by receiving an energy ray such as light and initiates a radical polymerization reaction of the component (D) by the generated radical.

Specific examples of the radical photopolymerization initiator that can be used as the component (E) include, for example, acetophenone, acetophenone benzyl ketal, anthraquinone, 1- (4-isopropylphenyl) -2-hydroxy-2-methyl. Propan-1-one, carbazole, xanthone, 4-chlorobenzophenone, 4,4 '
-Diaminobenzophenone, 1,1-dimethoxydeoxybenzoin, 3,3'-dimethyl-4-methoxybenzophenone, thioxanthone compound, 2-methyl-1
-[4- (Methylthio) phenyl] -2-morpholino-propan-2-one, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butane-1
-One, triphenylamine, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, bis (2,6-dimethoxybenzoyl) -2,4,4-tri-methylpentylphosphine oxide, benzyldimethylketal, 1-hydroxy Cyclohexyl phenyl ketone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, fluorenone, fluorene, benzaldehyde, benzoin ethyl ether, benzoin propyl ether, benzophenone, Michler's ketone,
3-methylacetophenone, 3,3 ', 4,4'-tetra (t-butylperoxycarbonyl) benzophenone (BTTB), and combinations of BTTB with xanthene, thioxanthene, coumarin, ketocoumarin and other dye sensitizers Can be mentioned. Of these,
Benzyl dimethyl ketal, 1-hydroxycyclohexyl phenyl ketone, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, 2-benzyl-2
-Dimethylamino-1- (4-morpholinophenyl)
-Butan-1-one and the like are particularly preferable. The above radical photopolymerization initiators may be used either individually or in combination of two or more as the component (E).

The content of the component (E) in the photocurable resin composition of the present invention is usually 0.01 to 10% by weight, preferably 0.1 to 8% by weight, based on the entire composition. is there. When the content ratio of the component (E) is too small, the radical polymerization reaction rate (curing rate) of the obtained resin composition tends to be low, which requires a long time for modeling and a decrease in resolution. . On the other hand, when the content ratio of the component (E) is too large, an excessive amount of the polymerization initiator may rather deteriorate the curing characteristics of the resin composition, or may adversely affect the moisture resistance and heat resistance of the three-dimensionally shaped product. There is.

The photocurable resin composition of the present invention may further contain (F) a polyether polyol having at least one hydroxyl group in the molecule. (F) Polyether polyol [hereinafter also referred to as "component (F)". ] Is
Included in order to develop photocurability of resin composition, shape stability (suppression performance of deformation over time) and shape stability (suppression performance of change in mechanical properties over time) of a three-dimensional object obtained by stereolithography. It is a component that is The polyether polyol used as the component (F) preferably has 3 or more hydroxyl groups in one molecule, and more preferably 3 to 6 hydroxyl groups in one molecule. When a polyether polyol (polyether diol) having less than 3 hydroxyl groups in one molecule is used, the effect of improving photocurability is decreased,
In addition, the mechanical properties of the obtained three-dimensional object, especially the elastic modulus, tend to be lowered. On the other hand, when more than 6 polyether polyols are contained in one molecule, the elongation of the obtained three-dimensionally shaped product tends to decrease and a problem with moisture resistance tends to occur.

Examples of the component (F) include 3 such as trimethylolpropane, glycerin, pentaerythritol, sorbitol, sucrose and quadrol.
A polyhydric alcohol having a valency of more than
O), propylene oxide (PO), butylene oxide, and polyether polyols obtained by modification with a cyclic ether compound such as tetrahydrofuran. Specific examples include EO-modified trimethylolpropane and PO-modified trimethylolpropane. , Tetrahydrofuran modified trimethylolpropane, EO modified glycerin, PO modified glycerin, tetrahydrofuran modified glycerin, EO modified pentaerythritol, PO modified pentaerythritol, tetrahydrofuran modified pentaerythritol, EO modified sorbitol, PO modified sorbitol, EO modified sucrose, PO modified sucrose,
Examples thereof include EO-modified sucrose and EO-modified quadol. Of these, EO-modified trimethylolpropane, PO-modified trimethylolpropane, PO-modified glycerin, and PO-modified sorbitol are preferable.

The polyether polyol used as the component (F) preferably has a molecular weight of 100 to 2,000, more preferably 160 to 1,000. When a polyether polyol having an excessively small molecular weight is used as the component (F), depending on the resin composition obtained,
It may be difficult to obtain a three-dimensional object having shape stability and physical property stability. On the other hand, when a polyether polyol having an excessively large molecular weight is used as the component (F),
The obtained resin composition may have an excessively high viscosity, and the elastic modulus of a three-dimensional object obtained by stereolithography may decrease.

Commercially available products of the polyether polyol which can be used as the component (F) include Sannix TP-40.
0, Sannix GP-600, Sannix GP-1
000, Sannix SP-750, Sannix GP
-250, Sannix GP-400, Sannix G
P-600 (above, Sanyo Kasei Co., Ltd.), TMP-3G
lycol, PNT-4 Glycol, EDA-P-
4, EDA-P-8 (Nippon Emulsifier Co., Ltd.), G
-300, G-400, G-700, T-400, ED
P-450, SP-600, SC-800 (above, Asahi Denka Kogyo KK) etc. can be mentioned. The above-mentioned polyether polyols can be used either individually or in combination of two or more as the component (F).

The content of the component (F) in the photocurable resin composition of the present invention is usually 1 with respect to the total composition.
Is about 35% by weight, preferably 3 to 30% by weight, particularly preferably 5 to 25% by weight. When the content ratio of the component (F) is too small, the effect of improving the photocurability of the obtained resin composition decreases, and the shape stability and the physical property stability tend to decrease depending on the resin composition. There is.
On the other hand, when the content ratio of the component (F) is too large, the photocurability of the obtained resin composition tends to decrease, and the elastic modulus of the three-dimensional object obtained by stereolithography tends to decrease.

The photocurable resin composition of the present invention contains water, a photosensitizer (polymerization accelerator), a reactive diluent and the like as optional components other than those mentioned above, as long as the effects of the present invention are not impaired. Can be included. Examples of the photosensitizer include amine compounds such as triethanolamine, methyldiethanolamine, triethylamine, and diethylamine; thioxanthone, thioxanthone derivatives, anthraquinone, anthraquinone derivatives, anthracene, anthracene derivatives, perylene, perylene derivatives, benzophenone, benzoin. Isopropyl ether and the like, and reactive diluents include vinyl ethers, vinyl sulfides, vinyl urethanes, urethane acrylates, vinyl ureas and the like. The content of water is preferably 0.1 to 2% by weight based on 100% by weight of the entire resin composition from the viewpoint of stability of sensitivity. If the water content is less than 0.1% by weight, the sensitivity of the resin tends to change over time,
It tends to be difficult to perform stable modeling. Also,
If the water content exceeds 2%, the elastic modulus of the cured product may decrease.

Further, the photocurable resin composition of the present invention may contain various additives as other optional components as long as the objects and effects of the present invention are not impaired.
Such additives include epoxy resin, polyamide, polyamideimide, polyurethane, polybutadiene, polychloroprene, polyether, polyester, styrene-butadiene block copolymer, petroleum resin, xylene resin, ketone resin, cellulose resin, fluorine-based oligomer, Polymers or oligomers such as silicone-based oligomers and polysulfide-based oligomers; polymerization inhibitors such as phenothiazine and 2,6-di-t-butyl-4-methylphenol; polymerization initiation aids; leveling agents; wettability improvers; surfactants Agents; plasticizers; ultraviolet absorbers; silane coupling agents; inorganic fillers; pigments; dyes and the like. The photocurable resin composition of the present invention can be produced by uniformly mixing the above components.
The viscosity of the photocurable resin composition thus obtained (2
5 ° C.) is preferably 50 to 2,000 mPa · s, more preferably 70 to 1,500 mPa · s.
Is.

The photocurable liquid resin composition of the present invention obtained as described above is suitably used as a photocurable liquid resin substance in an optical three-dimensional molding method. That is, for the photocurable resin composition of the present invention, visible light, ultraviolet light,
A three-dimensional object having a desired shape can be manufactured by an optical three-dimensional modeling method that selectively irradiates light such as infrared light to supply energy required for curing.

The means for selectively irradiating the photocurable resin composition with light is not particularly limited, and various means can be adopted. For example, a means for irradiating the composition while scanning laser light or a convergent light obtained by using a lens, a mirror, or the like, a mask having a light transmitting portion of a predetermined pattern is used, and non-converging is performed through this mask. Adopting a means for irradiating the composition with light, a means for irradiating the composition with light through a light guide member formed by bundling a large number of optical fibers, and corresponding to a predetermined pattern in the light guide member. You can In the means using a mask, a mask that electro-optically forms a mask image composed of a light transmission region and a light non-transmission region according to a predetermined pattern is used as a mask according to the same principle as a liquid crystal display device. You can also In the above, when the intended three-dimensional object has a fine portion or requires high dimensional accuracy, a laser beam having a small spot diameter is used as a means for selectively irradiating the composition with light. It is preferable to employ a means for scanning. The light irradiation surface of the resin composition contained in the container (for example, the scanning plane of the convergent light) is either the liquid surface of the resin composition or the contact surface with the container wall of the translucent container. May be. When the liquid surface of the resin composition or the contact surface with the container wall is used as the light irradiation surface, light can be irradiated from the outside of the container directly or through the container wall.

In the above-mentioned optical three-dimensional molding method, usually, after the specific portion of the resin composition is cured, the light irradiation position (irradiation surface) is continuously or stepwise from the uncured portion to the uncured portion. By moving the film, the cured parts are laminated to form a desired three-dimensional shape. Here, the irradiation position can be moved by various methods. For example, any one of the light source, the container for the resin composition, and the uncured portion of the resin composition can be moved, or the resin composition can be additionally supplied to the container. And the like. A typical example of the above-mentioned optical three-dimensional modeling method will be described. By lowering (precipitating) a small amount (precipitation) from a liquid level of a resin composition, a supporting stage provided in an accommodating container so as to move up and down Then, the resin composition is supplied to form a thin layer (1). Then, by selectively irradiating the thin layer (1) with light, a solid cured resin layer (1) is formed. Then, a photocurable resin composition is supplied onto the cured resin layer (1) to form a thin layer (2) thereof, and the thin layer (2) is selectively irradiated with light, whereby A new cured resin layer (2) is formed on the cured resin layer (1) so as to be continuously and integrally laminated. Then, with or without changing the pattern irradiated with light,
By repeating this step a predetermined number of times, a three-dimensional object having a plurality of cured resin layers (n) integrally laminated is formed.

The three-dimensional object thus obtained is taken out of the container, the unreacted resin composition remaining on the surface thereof is removed, and then washed as required. Here, as the cleaning agent, an alcohol-based organic solvent represented by alcohols such as isopropyl alcohol and ethyl alcohol; a ketone-based organic solvent represented by acetone, ethyl acetate, methyl ethyl ketone and the like; an aliphatic represented by terpenes Examples of the organic solvents include low-viscosity thermosetting resins and photocurable resins. In the case of producing a three-dimensional object having good surface smoothness, it is preferable to wash by using the thermosetting resin or the photocurable resin, and in this case, the curable resin used for washing. Depending on the type, it is necessary to perform post cure by heat irradiation or light irradiation. In addition, since the post cure can cure not only the resin on the surface but also the unreacted resin composition that may remain inside the three-dimensional object, even when washed with an organic solvent. It is preferable to perform post cure.

The three-dimensional product thus obtained has high mechanical strength and dimensional accuracy, and also has excellent heat resistance. Further, the three-dimensionally shaped article has excellent shape stability and physical property stability, exhibits excellent impact resistance and bending resistance when used as a prototype of a mechanical component, and can be suitably used. Furthermore, in order to improve the surface strength and heat resistance of the three-dimensional object, after performing a cleaning treatment,
It is preferable to use a thermosetting or photocurable hard coat material. As such a hard coating material, an organic coating material made of an acrylic resin, an epoxy resin, a silicone resin or the like, or an inorganic hard coating material can be used. These hard coating materials can be used alone or in combination of two or more kinds. Can be used.

The composition of the present invention is useful for optical three-dimensional modeling as described above, and since the cured product has excellent mechanical strength, plastics, various films,
Wood, ceramics, glass, quartz fiber for communication, paper, metal, beverage cans, coating materials for fibers, optical three-dimensional modeling resin, semiconductor encapsulant, semiconductor adhesive, underfill agent, optical adhesive It is useful as an agent and a printing plate material.

[0062]

EXAMPLES Examples of the present invention will be described below, but the present invention is not limited to these examples.

Example 1 According to the formulation shown in Table 1, 25 parts by weight of 3,4-epoxycyclohexylmethyl-3 ', 4'-epoxycyclohexanecarboxylate "UVR-6110" (manufactured by Union Carbide Co.) and bis (3,4-Epoxycyclohexylmethyl) adipate "UVR-6199"
30 parts by weight (manufactured by Union Carbide) and 4- (2-
2 parts by weight of chloro-4-benzoylphenylthio) phenylbis (4-fluorophenyl) sulfonium hexafluoroantimonate and 8 parts by weight of trimethylolpropane triacrylate "biscoat TMP-3A" (Osaka Organic Chemical Industry Co., Ltd.) And 5 parts by weight of dipentaerythritol hexaacrylate "Kayarad DPHA" (manufactured by Nippon Kayaku Co., Ltd.) and 2 parts by weight of 1-hydroxycyclohexyl phenyl ketone "Irgacure 184" manufactured by Ciba Specialty Chemicals Co., Ltd. 18 parts by weight of elastomer particles (resinus bond RKB manufactured by Resinus Kasei Co., Ltd.) having an average particle diameter of 50 nm, having a partially cross-linked styrene / butadiene copolymer in the core part and methyl methacrylate / glycidyl methacrylate in the shell, and 1 part by weight of distilled water , Polyoxy Propylene glyceryl ether "Sannicx GP-400" (Sanyo Chemical Co., Ltd.)
9 parts by weight) were charged in a stirring container and stirred at 60 ° C. for 3 hours to obtain a uniform liquid composition (resin composition of the present invention).

Examples 2 to 5 According to the formulation shown in Table 1, a uniform liquid composition (resin composition of the present invention was prepared by charging in a stirring container in the same manner as in Example 1 and stirring at 60 ° C. for 3 hours. ) Got.

Comparative Example 1 As component B, phenylthiophenyldiphenylsulfonium hexafluoroantimonate was used in place of 4- (2-chloro-4-benzoylphenylthio) phenylbis (4-fluorophenyl) sulfonium hexafluoroantimonate. A liquid composition (resin composition other than the present invention) was obtained in the same manner as in Example 1 except for the above.

Comparative Example 2 Example 2 was repeated except that elastomer particles having an average particle size of 50 nm and having a partially crosslinked styrene / butadiene copolymer as the essential C component in the core portion and methyl methacrylate / glycidyl methacrylate as the shell were removed. Similarly, a liquid composition (resin composition other than the present invention) was obtained.

Comparative Example 3 A resin composition containing no cation-polymerizable organic compound which is an essential A component and an aromatic sulfonium compound represented by the general formula (1) which is an essential B component in a ratio shown in Table 1. Were mixed in the same manner as in Example 1 to obtain a liquid composition (resin composition other than the present invention).

<Evaluation of Resin Composition> The physical properties of each of the resin compositions obtained in Examples 1 to 4 and Comparative Examples 1 to 3 were measured according to the following evaluation methods.

Using a stereolithography apparatus "Solid Creator SCS300P" (manufactured by Sony Corporation) equipped with an ultraviolet laser having a critical sensitivity (Ec) wavelength of 355 nm, a laser spot diameter on the irradiation surface (liquid level) was 200 μm and a laser power was The laser was scanned under the condition of 100 mW. The scanning speed was changed from 100 mm / sec to 1000 mm / sec, and the cross section of the cured resin was observed with a microscope to determine the curing depth. The relationship between the scanning depth and the curing depth was determined, the scanning velocity at which the curing depth was 0 was determined by extrapolation, and the irradiation energy at that time was defined as the critical sensitivity (Ec).

Rate of Change in Sensitivity The critical sensitivity of the resin composition immediately after preparation is defined as Ec0, and this resin composition is subjected to high temperature and high humidity conditions of 23 ° C. and 50% humidity for 3 times.
After standing for 0 day, the critical sensitivity measured again was taken as Ec1. The rate of change in sensitivity was calculated from the following formula. Sensitivity change rate = | Ec1-Ec0 | ÷ Ec0 × 100 (%)

Cured Material Elastic Modulus A test piece (length 150 mm, width 10 mm, thickness 4 mm) having the shape described in JIS K7171 was formed at a scanning speed that gives a laminated film thickness of 200 μm and a curing depth of 300 μm. After washing the molded article, it was left in a constant temperature bath at 120 ° C. for 2 hours and then left to cool to room temperature. Using this test piece, a bending test was performed under the conditions of a fulcrum distance of 65 mm and a bending speed of 2 mm / min. The test was performed 3 times, the elastic modulus was calculated from the tangent line of the stress curve of each test piece, and the average value was used as the elastic modulus of the cured product.

Izod Impact Strength A test piece (length 63.5 mm, width 12.7 mm, thickness 6.4 m) having a shape described in JIS K7110 at a scanning speed that provides a laminated film thickness of 200 μm and a curing depth of 300 μm.
m) was modeled. After washing the molded article, it was left in a constant temperature bath at 120 ° C. for 2 hours and then left to cool to room temperature. A notch having a depth of 2.5 mm was made on this test piece using a milling machine. Tozo Seimitsu Kogyo Co., Ltd. Izod impact tester model CIT
-Using 401, swing-up angle 150 degrees, 20 kg weight-
It was measured under the condition of cm. The measurement was performed 10 times, and the average value was calculated to be the Izod impact strength of the cured product.

Amount of Warp A laminated film thickness is 200 μm, and a length of 150 mm, a width of 150 mm, and a thickness of 3 at a scanning speed that can obtain a curing depth of 300 μm.
A mm flat plate was formed. This flat plate was raised on a flat surface and left for 1 week in a room at a temperature of 23 ° C. and a humidity of 50%. After one week, the height at which the four corners of the flat plate floated from the flat surface was measured, and the average value was defined as the amount of warpage.

Heat resistance A test piece (length 150 mm, width 4 mm, thickness 10 mm) having the shape described in JIS K7191 was formed at a scanning speed that gives a laminated film thickness of 200 μm and a curing depth of 300 μm. After washing the molded article, it was left in a constant temperature bath at 120 ° C. for 2 hours and then left to cool to room temperature. This test piece was tested with JIS Yasuda's heat resistance evaluation tester model HD-PC3, according to JIS
Load 18.5k by edgewise method described in K7191
It was evaluated under the condition of g / cm ² and the deflection temperature under load was determined.

Table 1 shows the compounding formulation of the obtained photocurable resin composition, and Table 2 shows the evaluation results of the physical properties of these compositions or cured products thereof.

[0076]

[Table 1]

[0077]

[Table 2]

A-1: 3,4-epoxycyclohexylmethyl-3 ', 4'-epoxycyclohexanecarboxylate "UVR-6110" (manufactured by Union Carbide) A-2: bis (3,4-epoxycyclohexylmethyl) ) Adipate "UVR-6199" (manufactured by Union Carbide) A-3: butanediol diglycidyl ether "Araldite DY-022" (manufactured by Ciba Specialty Chemicals) A-4: neopentyl glycol diglycidyl ether "Eporite 1500NP" (Kyoeisha Chemical Co., Ltd.) A-5: 1,4-bis [(3-ethyl-3-oxetanylmethoxy) methyl] benzene "Aronix XDO"
(Manufactured by Toagosei Co., Ltd.) A-6: Epoxy-modified polybutadiene "Epolide PB"
3600 "(manufactured by Daicel Chemical Industries, Ltd.) B-1: 4- (2-chloro-4-benzoylphenylthio) phenylbis (4-fluorophenyl) sulfonium hexafluoroantimonate B-2: 4- (2- Chloro-4-benzoylphenylthio) phenyldiphenylsulfonium hexafluoroantimonate B-3: phenylthiophenyldiphenylsulfonium hexafluoroantimonate C-1: core / shell type elastomer particles (resinus bond RKB manufactured by Resinus Kasei Co., Ltd.) D- 1: trimethylolpropane triacrylate D-2: dipentaerythritol hexaacrylate D-3: acrylic acid adduct of bisphenol A diglycidyl ether E-1: 1-hydroxycyclohexyl phenyl ketone E-2: 2-methyl 1- (4-methylthiophenyl)
-2-Morpholinopropan-1-one F-1: Caprolactone modified triol "TONE-0
301 "(manufactured by Union Carbide Co.) F-2: polyoxypropylene glyceryl ether" Sannix GP-400 "(manufactured by Sanyo Kasei Co., Ltd.) G-1: distilled water

[0079]

According to the photocurable resin composition of the present invention,
It has good photo-curability and easily has high dimensional accuracy.
A cured product with excellent heat resistance can be molded, and the obtained cured product is suitable for use as a three-dimensional object such as a prototype of machine parts, which has excellent toughness such as impact resistance and bending resistance. can do.

Front page continuation (51) Int.Cl. ⁷ identification code FI theme code (reference) G03F 7/027 515 G03F 7/027 515 4J036 7/029 7/029 (72) Inventor Takaro Yatsushiro Tsukijiji, Tokyo 11-21 24 JSR Co., Ltd. (72) Inventor Ryoji Tada 2-11-24 Tsukiji, Chuo-ku, Tokyo J-SR Co., Ltd. (72) Inventor Takashi Ukaji 2-chome Tsukiji, Chuo-ku, Tokyo No. 24 F term in JSR Corporation (reference) 2H025 AA10 AB01 AB17 AB20 AC01 AC08 AD01 BC14 BC32 BC42 CA01 CA20 CA41 CA48 CB11 CB54 CC20 4J011 PA25 PA64 PA65 PA69 PA76 PA86 PC08 QA03 QA34 RA10 UA01 WA01 WA02 WA07 WA04 WA06 WA06 WA06 WA015 EA05 EA06 4J026 AA12 AA17 AA45 AA68 AA69 AB04 AC01 AC02 AC09 AC10 AC11 BA27 BA29 BA30 BA44 DB11 DB36 GA07 4J031 BB01 BB02 BB04 BC07 BC11 BD12 BD13 BD16 CA06 CA36 CA83 CB06 CE03 4J036 AB01 AB02 AE02 A08 AB02 AB10 AB02 AB10 AB02 AB10 AB02 AB10 AB02 AB10 AB02 AB10 AB02 AB10 AB02 AB10 AB02 AB10 AB02 AB10 JA01 JA02 JA 06 JA07 KA01

Claims (4)

[Claims] 1. The following components (A), (B) and (C): (A) cationically polymerizable organic compound, (B) the following general formula (1): (In the formula, R ¹ represents a p-phenylene group in which one or more of its hydrogen atoms are substituted with a halogen atom or an alkyl group, and R ² is a hydrocarbon group which may contain an oxygen atom or a halogen atom. And Y ¹ and Y ² represent the same or different hydrogen atom, halogen atom, or hydrocarbon group which may contain oxygen atom or halogen atom, and X represents an atomic group capable of becoming a monovalent anion. ] The aromatic sulfonium compound represented by these, and (C) elastomer particle | grains with an average particle diameter of 10-700 nm are contained, The photocurable resin composition characterized by the above-mentioned. 2. The photocurable resin composition according to claim 1, further comprising (D) an ethylenically unsaturated monomer and (E) a radical photopolymerization initiator. 3. The photocurable resin composition according to claim 1, which further comprises (F) a polyether polyol compound having one or more hydroxyl groups in the molecule. 4. The photocurable resin composition according to claim 1, which further contains (G) water.