JPH11310626A - Photocurable liquid resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a photocurable liquid resin composition having slight change of mechanical characteristics with time and deformation amount (bending) with time, excellent mechanical strength and toughness such as flexural resistance, etc., high dimensional accuracy and also excellent heat resistance, capable of forming a cured material suitable as a three-dimensional formed material such as a trial product of mechanical part. SOLUTION: This photocurable liquid resin composition comprises (A) a cationic polymerizable organic compound, (B) a cationic photopolymerization initiator, (C) an ethylenic unsaturated monomer, (D) a radical photopolymerization initiator (E) a polyether polyol compound containing one or more hydroxyl groups in one molecule and (F) elastomer particles having 10 mm to 700 mm average particle diameter. Preferably the composition has 20-85 wt.% of the component A, 5-45 wt.% of the component C, 5-35 wt.% of the component E and 1-35 wt.% of the component F based on the whole composition.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

TECHNICAL FIELD The present invention has excellent photocurability,
And liquid curable resin composition excellent in mechanical strength of cured product, plastic, various films, wood, ceramics,
Glass, quartz fiber for communication, paper, metal, beverage cans,
The present invention relates to a photocurable resin composition suitable as a coating material such as a fiber, a resin for optical three-dimensional modeling, a sealant for a semiconductor, an adhesive for a semiconductor, an underfill agent, an optical adhesive, a printing plate material, and the like. Particularly when used as a resin for optical three-dimensional modeling, it exhibits excellent photocurability to various light sources such as lasers and ultraviolet lamps, and the three-dimensional shape after curing has improved impact resistance and bending resistance. The present invention relates to an excellent photocurable resin composition.

[0002]

2. Description of the Related Art In recent years, by repeatedly irradiating a photocurable liquid material (liquid resin composition) with light to form a cured resin layer, the cured resin layer is integrally laminated. There has been proposed an optical three-dimensional molding method for forming a three-dimensional object (Japanese Patent Application Laid-Open Nos. 60-247515, 62-35966, and 62-101408).
And Japanese Patent Application Laid-Open No. H5-24119). To explain a typical example of this optical three-dimensional molding method, a predetermined pattern is formed by selectively irradiating light such as an ultraviolet laser to a liquid surface of a photocurable resin composition contained in a container. To form a cured resin layer. Next, on this cured resin layer, one layer of the photocurable resin composition is supplied, and by selectively irradiating the liquid surface with light, the cured resin layer formed on the previously formed cured resin layer is A new cured resin layer is integrally formed so as to be continuous. Then, the above process is repeated a predetermined number of times while changing or not changing the pattern to be irradiated with light, whereby a three-dimensional object formed by integrally laminating a plurality of cured resin layers is formed. This optical three-dimensional shaping method has attracted attention because it can easily and quickly obtain a target three-dimensional object having a complicated shape.

Conventionally, the following resin compositions (a) to (c) have been introduced as photocurable resin compositions used for optical three-dimensional molding. [A] A resin composition containing a radical 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) JP, JP-A-2-208
305, JP-A-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 spiroorthoester compound, a vinyl ether compound (for example, JP-A-1-213304) Gazette). [C] A resin composition containing a radically polymerizable organic compound and a cationically polymerizable organic compound (for example, JP-A-2-28
No. 261; Japanese Patent Application Laid-Open No. 2-75618;
-228413).

However, from the viewpoint of efficient stereolithography, the photocurable resin composition used in such a three-dimensional molding method has a low viscosity and can immediately form a smooth liquid surface. It is required that the material be rapidly cured by light irradiation. In addition, the photocurable resin composition does not swell the cured product constituting the three-dimensional object, and the amount of deformation such as warpage, shrinkage, or lifting of the overhang due to curing shrinkage during photocuring. It is required to be small. Furthermore, three-dimensional objects obtained by the optical three-dimensional molding method are used as models for studying designs, prototypes of mechanical parts, etc. It is required that the microfabrication faithful to the above is performed with high precision, and that it has sufficient mechanical strength and heat resistance to withstand the use conditions. It is also important that such mechanical properties are stable without changing over time.

[0005] However, conventionally known resin compositions cannot meet the above-mentioned requirements, and a three-dimensional product obtained by stereolithography of the resin composition has a residual strain due to curing shrinkage. There is a problem that the three-dimensional object is deformed with time (warp, shrinkage, lifting of the overhang). In particular, 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 shown in the above [A]. When used as a photocurable resin, the resulting three-dimensional object is not sufficiently improved in terms of molding accuracy and the stability over time of the molded shape despite its relatively excellent mechanical properties. It has already been pointed out that there is room for this (Molding Processing Journal Vol. 9, No. 5, pp. 330-335, 1997).
As a method aiming at improving the molding accuracy, a resin composition containing particles composed of a core-shell polymer (Japanese Patent Laid-Open No. 3-114733)
Scattered light in the photocurable resin by controlling the scattering of light in the photocurable resin by mixing particles composed of a deflecting material having a different refractive index from that of the photocurable resin (see JP-A-3-103415). Although a method of controlling the depth of light reaching the resin has been proposed, it is difficult to say that a sufficiently satisfactory molding accuracy has been obtained.

Also, a resin 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 spiroorthoester compound, a vinyl ether compound, etc. When the composition was used for a photocurable resin, there was a problem that the curability was not sufficient and modeling could not be performed efficiently. Although the molding accuracy of the three-dimensional shape obtained by molding is relatively good, the mechanical properties of the obtained three-dimensional shape deteriorate with time due to the use environment (temperature and humidity). Over a long period of time, it cannot be used under conditions where mechanical strength is required. Furthermore, it was pointed out that the mechanical strength of the three-dimensional object, particularly the toughness (impact resistance, bending resistance, etc.) was not sufficient, and that when a functional component was formed, it was not durable for practical use.

In view of these points, resin compositions containing a radically polymerizable organic compound and a cationically polymerizable organic compound as described in the above item (c) have been proposed. In terms of mechanical properties, particularly toughness, of a three-dimensionally shaped article, none has yet been obtained that can withstand practical use. As a method for improving the mechanical properties, particularly toughness, of a three-dimensional object, it has been proposed to blend fine particles having a specific gravity difference of less than 0.2 with the photocurable resin (JP-A-2-145616). Although the improvement in toughness is recognized by such a method, the disadvantage of being particularly vulnerable to repeated bending deformation when a three-dimensional object is actually used as a functional component has not been overcome, Further improvements were required.

[0008]

SUMMARY OF THE INVENTION The present invention has been made based on the above circumstances. A first object of the present invention is to provide a novel photocurable liquid resin composition. A second object of the present invention is to provide a photocurable liquid resin composition for optical three-dimensional molding, which has high mechanical strength and dimensional accuracy and can form a three-dimensional object suitable as a prototype of a mechanical part. Is to provide. A third object of the present invention is to provide a photocurable liquid resin composition for optical three-dimensional modeling, which is capable of modeling a three-dimensional object in which the shape of the obtained three-dimensional object has a small temporal change. . A fourth object of the present invention is to provide a photocurable liquid resin composition for optical three-dimensional modeling, which is capable of modeling a three-dimensional object having little change over time in mechanical properties. A fifth object of the present invention is to provide a photocurable liquid resin composition for optical three-dimensional modeling, which has excellent mechanical properties, especially excellent toughness including impact resistance. A sixth object of the present invention is to provide a photocurable liquid resin composition for optical three-dimensional modeling having excellent bending resistance.

[0009]

Means for Solving the Problems The photocurable liquid resin composition of the present invention comprises (A) a cationically polymerizable organic compound, and (B)
Cationic photopolymerization initiator, (C) ethylenically unsaturated monomer, (D) radical photopolymerization initiator, (E) polyether polyol compound having one or more hydroxyl groups in one molecule, and (F) average It is characterized by containing elastomer particles having a particle diameter of 10 nm to 700 nm.

[0010]

DESCRIPTION OF THE PREFERRED EMBODIMENTS <(A) Cationic polymerizable organic compound> (A) Cationic polymerizable organic compound (hereinafter also referred to as "component (A)") constituting the photocurable resin composition of the present invention. Is an organic compound that causes a polymerization reaction or a crosslinking reaction by irradiating light in the presence of a cationic photopolymerization initiator, such as an epoxy compound, an oxetane compound, an oxolane compound, a cyclic acetal compound, a cyclic lactone compound, and a thiirane compound. A thiethane compound, a vinyl ether compound, a spiroorthoester 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,
Vinyl compounds and the like can be mentioned.

Examples of the epoxy compound that 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 diglycidyl ether. Glycidyl ether, brominated bisphenol S diglycidyl ether, epoxy novolak 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 (3,4-epoxy-6-methylcyclohexylmethyl) adipate, 3,4-epoxy-6-methylcyclohexyl-3 ', 4'-Epoxy-6'-methylcyclohexanecarboxylate, methylenebis (3,4-epoxycyclohexane), dicyclopentadiene 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; by adding one or more alkylene oxides to aliphatic polyhydric alcohols such as ethylene glycol, propylene glycol and glycerin Polyglycidyl ethers of the obtained polyether polyol; diglycidyl esters of aliphatic long-chain dibasic acids; Glycidyl ethers; phenol, cresol, butylphenol or monoglycidyl ethers of polyether alcohols obtained by adding alkylene oxide thereto; glycidyl esters of higher fatty acids; epoxidized soybean oil; butyl epoxy stearate; octyl epoxy stearate Epoxidized linseed oil; and epoxidized polybutadiene.

Other cationically polymerizable organic compounds that can be used as 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-dioxolan, 1,3,6-trioxanecyclooctane; β
Cyclic lactones such as propiolactone and ε-caprolactone; thiirane such as ethylene sulfide, 1,2-propylene sulfide and thioepichlorohydrin;
Thiethanes such as 3,3-dimethylthiethane; vinyl ethers such as ethylene glycol divinyl ether, triethylene glycol divinyl ether, and trimethylolpropane trivinyl ether; spiro ortho esters obtained by reacting an epoxy compound with a lactone; vinylcyclohexane And ethylenically unsaturated compounds such as isobutylene and polybutadiene; and derivatives 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. An epoxy compound having two or more alicyclic epoxy groups in one molecule, and when the epoxy compound is contained in the component (A) in a proportion of 50% by weight or more, the obtained resin composition The cation polymerization reaction rate (curing rate) of the product is increased, so that the molding time can be shortened, and the curing shrinkage rate is reduced, and the temporal deformation of the three-dimensional object can be suppressed.

A commercially available cationic polymerizable organic compound which can be suitably used as the component (A) is UVR-610.
0, UVR-6105, UVR-6110, UVR-6
128, UVR-6200, UVR-6216 (or more,
Union Carbide Co., Ltd.), Celloxide 2021, Celloxide 2021P, Celloxide 2081, Celloxide 2083, Celloxide 2085, Celloxide 2000, Celloxide 3000, Glycidol, AO
EX24, Cyclomer A200, Cyclomer M10
0, Eporide GT-300, Eporide GT-30
1, Eporide GT-302, Eporide GT-40
0, Eporide 401, Eporide 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 (all manufactured by Asahi Denka Kogyo), Rapi-Cure DVE-3, CHV
E, PEPC (all made by ISP), VECTOMER
2010, 2020, 4010, 4020 (all manufactured by Allied Signal Inc.) and the like. The above-mentioned cationically polymerizable compounds can constitute the component (A) alone or in combination of two or more.

The content of the component (A) in the photocurable resin composition of the present invention is usually 20 to 85% by weight, preferably 30 to 80% by weight, more preferably 40% by weight.
~ 75% by weight. When the content ratio of the component (A) is too small, the dimensional accuracy of the three-dimensional object made of the obtained resin composition is reduced, and the three-dimensional object is easily deformed with time. On the other hand, when this content ratio is too large, the photocurability of the obtained resin composition is reduced, and the molding efficiency is reduced.

<(B) Cationic photopolymerization initiator> The present invention
(B) Cationic light weight constituting the photocurable resin composition of (1)
Copolymerization initiator [hereinafter also referred to as “component (B) component”. ] Is light
(A) component by receiving the energy ray of
Can release the substance that initiates cationic polymerization of
Compound. Here, energy rays such as light are
Visual light, ultraviolet light, infrared light, X-ray, α-ray, β-ray, γ-ray, etc.
means. Particularly preferred compounds of component (B) include
The general formula (1):  [R¹ _aR^Two _bR^Three _cR^Four _dW]^{+ m} [MX_{n + m}]^-m (1) wherein the cation is an onium ion and W is S, S
e, Te, P, As, Sb, Bi, O, I, Br, Cl
Or -N≡N and R¹, R^Two, R^ThreeAnd R^FourAre the same
Or different organic groups, wherein a, b, c and d are each
An integer from 0 to 3, where (a + b + c + d) is the valence of W
be equivalent to. M is a halide complex [MX_{n + m}] Central atom
A metal or metalloid constituting, for example, B,
P, As, Sb, Fe, Sn, Bi, Al, Ca, I
n, Ti, Zn, Sc, V, Cr, Mn, Co, etc.
You. X is a halogen atom such as F, Cl, Br, etc.
Where m is the net charge of the halide complex ion
And n is the valence of M. ] Has the structure represented by
Onium salts can be mentioned. This onium salt
A compound that releases a Lewis acid when exposed to light
You. The anion [MX in the above general formula (1)_{n + m}]of
As a specific example, tetrafluoroborate (B
F_Four ^-), Hexafluorophosphate (PF₆ ^-), F
Xafluoroantimonate (SbF₆ ^-), Hexaf
Luoro arsenate (AsF₆ ^-), Hexachloroanti
Monate (SbCl₆ ^-).

An onium salt having an anion represented by the general formula [MX _n OH) ⁻ ] can be used. Further, perchlorate ion (ClO ₄ ⁻ ), trifluoromethanesulfonic acid ion (CF ₃ SO ₃ ⁻ ), fluorosulfonic acid ion (FSO ₃ ⁻ ), toluenesulfonic acid ion, trinitrobenzenesulfonic acid anion,
Onium salts with other anions, such as the trinitrotoluenesulfonate anion, can also be used.

Among such onium salts, an onium salt particularly effective as the component (B) is an aromatic onium salt. Among them, aromatic halonium salts described in JP-A-50-151996, JP-A-50-158680 and the like, JP-A-50-151997, JP-A-52-1
No. 30899, JP-A-56-55420, JP-A-55-125105, etc., and VIA-aromatic onium salts described in JP-A-50-158698 and the like. JP-A-56-842
No. 8, JP-A-56-149402, JP-A-5-149402
Oxosulfoxonium salts described in JP-A-7-192429 and the like, aromatic diazonium salts described in JP-A-49-17040 and the like, US Pat. No. 4,139,655.
And the like. Further, an iron / allene complex, an aluminum complex / photolytic silicon compound-based initiator and the like can also be mentioned.

Commercially available cationic photopolymerization initiators which can be suitably used as the component (B) include UVI-695.
0, UVI-6970, UVI-6974, UVI-6
990 (all manufactured by Union Carbide), Adeka Optomer SP-150, SP-151, SP-170, S
P-171 (all manufactured by Asahi Denka Kogyo Co., Ltd.), Irgac
ure 261 (all manufactured by Ciba Specialty Chemicals Co., Ltd.), CI-2481, CI-2624, CI-
2639, CI-2064 (Nippon Soda Co., Ltd.)
Manufactured), CD-1010, CD-1011, CD-101
2, DTS-102, DTS
-103, NAT-103, NDS-103, TPS-
103, MDS-103, MPI-103, BBI-1
03 (all manufactured by Midori Kagaku Co., Ltd.), PCI-061
T, PCI-062T, PCI-020T, PCI-0
22T (all manufactured by Nippon Kayaku Co., Ltd.) and the like. Among them, UVI-6970, UVI-6
974, Adeka Optomer SP-170, SP-17
1, CD-1012 and MPI-103 are particularly preferable since a resin composition containing them can exhibit high photocuring sensitivity. The above-mentioned cationic photopolymerization initiators can constitute the component (B) alone or in combination of two or more.

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, more preferably 0.1 to 5% by weight.
3 to 3% by weight. When the content ratio of the component (B) is too small, the photocurability of the obtained resin composition decreases,
A three-dimensional object having sufficient mechanical strength cannot be formed. On the other hand, if this content ratio is excessive,
When subjecting the obtained resin composition to the optical three-dimensional molding method, it is difficult to control the curing depth because it is impossible to obtain appropriate light transmittance, and the molding accuracy of the obtained three-dimensional object tends to decrease. .

<(C) Ethylenically unsaturated monomer> (C) Ethylenically unsaturated monomer (hereinafter also referred to as "component (C)") constituting the photocurable resin composition of the present invention. Is a compound having an ethylenically unsaturated bond (C = C) in a molecule, a monofunctional monomer having one ethylenically unsaturated bond in one molecule, and two or more ethylene atoms in one molecule. And polyfunctional monomers having an unsaturated bond.

Monofunctional monomers which can be suitably used as component (C) include, for example, acrylamide, (meth)
Acryloyl morpholine, 7-amino-3,7-dimethyloctyl (meth) acrylate, isobutoxymethyl (meth) acrylamide, isobornyloxyethyl (meth) acrylate, isobornyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, Ethyl diethylene glycol (meth) acrylate, t-octyl (meth) acrylamide, diacetone (meth) acrylamide, dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate, lauryl (meth) acrylate, dicyclopentadiene (meth) acrylate, Dicyclopentenyloxyethyl (meth) acrylate, dicyclopentenyl (meth)
Acrylate, N, N-dimethyl (meth) acrylamide tetrachlorophenyl (meth) acrylate, 2-tetrachlorophenoxyethyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, tetrabromophenyl (meth) acrylate, 2-tetrabromophenoxy Ethyl (meth) acrylate, 2-trichlorophenoxyethyl (meth) acrylate, tribromophenyl (meth) acrylate, 2-tribromophenoxyethyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) ) Acrylate, vinylcaprolactam, N-vinylpyrrolidone, 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 ( Examples thereof include (meth) acrylate and compounds represented by the following general formulas (2) to (4).

[0024]

Embedded image

Of these monofunctional monomers, isobornyl (meth) acrylate, lauryl (meth) acrylate and phenoxyethyl (meth) acrylate are particularly preferred. Commercial products of these monofunctional monomers include:
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.), Biscoat 192, Biscoat 220,
VISCOAT 2311HP, VISCOAT 2000, VISCOAT 2100, VISCOAT 2150, VISCOAT 8F,
VISCOAT 17F (all manufactured by Osaka Organic Chemical Industry Co., Ltd.)
And the like.

Examples of the polyfunctional monomer that can be suitably used as the component (C) include ethylene glycol di (meth) acrylate, dicyclopentenyl di (meth) acrylate, triethylene glycol diacrylate, and tetraethylene glycol di (meth) acrylate. Acrylate, tricyclodecanediyl dimethylene 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) acryl Propylene oxide (hereinafter referred to as “PO”) modified trimethylolpropane tri (meth) acrylate, tripropylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, 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 include modified bisphenol F di (meth) acrylate and (meth) acrylate of phenol novolak polyglycidyl ether.

Commercially available products of these polyfunctional monomers include, for example, SA1002 (all manufactured by Mitsubishi Chemical Corporation),
VISCOAT 195, VISCOAT 230, VISCOAT 26
0, Bis coat 215, Bis coat 310, Bis coat 214HP, Bis coat 295, Bis coat 300, Bis coat 360, Bis coat GPT, Bis coat 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 (all manufactured by 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 (all manufactured by Toagosei Co., Ltd.), Light Acrylate BP-4EA, BP-4PA, BP-2EA, BP
-2PA, DCP-A (manufactured by Kyoeisha Chemical Co., Ltd.),
New Frontier BPE-4, BR-42M, GX-
8345 (all manufactured by Daiichi Kogyo Seiyaku Co., Ltd.), ASF-4
00 (all manufactured by Nippon Steel Chemical Co., Ltd.), Lipoxy SP-1
506, SP-1507, SP-1509, VR-7
7, SP-4010, SP-4060 (all manufactured by Showa Polymer Co., Ltd.) and NK ester A-BPE-4 (all manufactured by Shin-Nakamura Chemical Co., Ltd.).

The above monofunctional monomer and polyfunctional monomer may be used alone or in combination of two or more.
Alternatively, the component (C) can be constituted by combining at least one kind of a monofunctional monomer and at least one kind of a polyfunctional monomer.
That is, it is preferable that a polyfunctional monomer having three or more ethylenically unsaturated bonds in one molecule is contained in a proportion of 60% by weight or more. The content ratio 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. When the content ratio of the trifunctional or higher polyfunctional monomer is less than 60% by weight, the photocurability of the obtained resin composition is reduced, and the three-dimensional product to be formed may be easily deformed with time. .

The trifunctional or higher polyfunctional monomer is selected from the above-listed tri (meth) acrylate compounds, tetra (meth) acrylate compounds, penta (meth) acrylate compounds, and hexa (meth) acrylate compounds. And among these, trimethylolpropane tri (meth) acrylate, EO
Modified trimethylolpropane tri (meth) acrylate, dipentaerythritol hexa (meth) acrylate, dipentaerythritol penta (meth) acrylate, and ditrimethylolpropanetetra (meth) acrylate are particularly preferred.

The content of the component (C) in the photocurable resin composition of the present invention is usually 5 to 45% by weight,
Preferably 7 to 35% by weight, more preferably 10 to 25% by weight.
% By weight. When the content ratio of the component (C) is too small, the photocurability of the obtained resin composition is reduced, and a three-dimensional article having sufficient mechanical strength cannot be formed. On the other hand, when the content ratio is excessively large, the obtained resin composition tends to shrink due to photocuring, and the obtained three-dimensionally shaped article tends to have reduced heat resistance, moisture resistance and the like.

<(D) Radical Photopolymerization Initiator> (D) Radical photopolymerization initiator (hereinafter also referred to as “(D) component”) constituting the photocurable resin composition of the present invention. ] Is a compound that is decomposed by receiving an energy ray such as light, and causes a radical polymerization reaction of the component (C) to be started by generated radicals.

Specific examples of the radical photopolymerization initiator that can be used as the component (D) 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 a combination of BTTB with xanthene, thioxanthene, coumarin, ketocoumarin and other dye sensitizers Can be mentioned. Among them, benzyldimethyl ketal, 1-hydroxycyclohexylphenyl ketone, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butane-1- On is particularly preferred. The above radical photopolymerization initiators can constitute the component (D) alone or in combination of two or more.

The content of the component (D) in the photocurable resin composition of the present invention is usually 0.01 to 10% by weight, preferably 0.1 to 8% by weight. When the content ratio of the component (D) is too small, the radical polymerization reaction rate (curing rate) of the obtained resin composition tends to be low, so that it takes a long time for molding or the resolution tends to be low. . On the other hand, when the content ratio of the component (D) is too large, an excessive amount of the polymerization initiator may rather deteriorate the curing properties of the resin composition or adversely affect the moisture resistance and heat resistance of the three-dimensional object. There is.

<(E) Polyether polyol> (E) Polyether polyol (hereinafter also referred to as "component (E)") constituting the photocurable resin composition of the present invention. ] Develops the photocurability of the resin composition, the shape stability of the three-dimensional object obtained by stereolithography (the ability to suppress temporal deformation) and the shape stability (the ability to inhibit mechanical properties from changing over time). It is an essential component contained for. The polyether polyol used as the component (E) preferably has 3 or more hydroxyl groups in one molecule, and more preferably has 3 to 6 hydroxyl groups in one molecule. When a polyether polyol (polyether diol) having less than three hydroxyl groups in one molecule is used, the effect of improving photocurability is not sufficient, and the mechanical properties, particularly elasticity, of the resulting three-dimensional object are not sufficient. Rates tend to decrease. On the other hand, when more than 6 polyether polyols are contained in one molecule, there is a tendency that elongation of the obtained three-dimensionally shaped product tends to decrease and there is a tendency to cause a problem in moisture resistance.

The component (E) includes, for example, trimethylolpropane, glycerin, pentaerythritol, sorbitol, sucrose, quadrol and the like.
Polyhydric alcohols having a valency of at least
O), polyether polyols obtained by modification with cyclic ether compounds such as propylene oxide (PO), butylene oxide, and 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 molecular weight of the polyether polyol used as the component (E) is preferably from 100 to 2,000, more preferably from 160 to 1,000. When a polyether polyol having an excessively low molecular weight is used as the component (E), depending on the obtained resin composition,
It may be difficult to obtain a three-dimensionally shaped object having shape stability and physical property stability. On the other hand, when a polyether polyol having an excessively high molecular weight is used as the component (E),
There is a possibility that the viscosity of the obtained resin composition becomes excessive and the elastic modulus of the three-dimensional object obtained by stereolithography is reduced.

As a commercially available polyether polyol usable as the component (E), Sanix TP-40 can be used.
0, Sanix GP-600, Sanix GP-1
000, SANNIX SP-750, SANNIX GP
-250, SANNIX GP-400, SANNIX G
P-600 (above, manufactured by Sanyo Chemical Co., Ltd.), TMP-3G
lycol, PNT-4 Glycol, EDA-P-
4, EDA-P-8 (all manufactured by Nippon Emulsifier Co., Ltd.), G
-300, G-400, G-700, T-400, ED
P-450, SP-600, SC-800 (all manufactured by Asahi Denka Kogyo KK) and the like. The above-mentioned polyether polyols can constitute the component (E) alone or in combination of two or more.

The content of the component (E) in the photocurable resin composition of the present invention is usually from 5 to 35% by weight.
Preferably 7 to 30% by weight, particularly preferably 10 to 25%
% By weight. When the content ratio of the component (E) is too small, the effect of improving the photocurability of the obtained resin composition cannot be sufficiently achieved, and depending on the resin composition, the shape stability and the physical property stability may not be improved. A three-dimensional object having good properties cannot be obtained. On the other hand, even when the content ratio of the component (E) is excessive, 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.

<(F) Average particle size 10 nm to 700 nm
Elastomer particles> (E) Elastomer particles constituting the photocurable resin composition of the present invention having an average particle diameter of 10 nm to 700 nm [hereinafter also referred to as “(F) component”. ]
Are polybutadiene, polyisoprene, butadiene / acrylonitrile copolymer, styrene / butadiene copolymer, styrene / isoprene copolymer, ethylene / propylene copolymer, ethylene / α-olefin copolymer,
Elastomer particles such as ethylene / α-olefin / polyene copolymer, acrylic rubber, butadiene / (meth) acrylate copolymer, styrene / butadiene block copolymer, and styrene / isoprene block copolymer can be exemplified. And core / shell particles obtained by coating these elastomer particles with a methyl methacrylate polymer, a methyl methacrylate / glycidyl methacrylate copolymer, or the like.
The elastomer particles may have a crosslinked structure, and can be crosslinked by a commonly used means. In this case, as a crosslinking agent, divinylbenzene,
Examples include ethylene glycol di (meth) acrylate, diallyl maleate, triallyl cyanurate, triallyl isocyanurate, diallyl phthalate, trimethylolpropane triacrylate, and allyl methacrylate.

The elastomer particles which can be suitably used as the component (F) include, for example, polybutadiene, polyisoprene, styrene / butadiene copolymer, styrene /
Isoprene copolymer, ethylene / propylene copolymer,
Ethylene / α-olefin copolymer, ethylene / α-
Elastomer particles having olefin / polyene copolymer, acrylic rubber, butadiene / (meth) acrylate copolymer, styrene / butadiene block copolymer, and styrene / isoprene block copolymer as base components can be exemplified. .

Further, core / shell type particles include polybutadiene, polyisoprene, styrene / butadiene copolymer, styrene / isoprene copolymer, ethylene / propylene copolymer, ethylene / α-olefin copolymer. A core partially crosslinked with ethylene / α-olefin / polyene copolymer, acrylic rubber, butadiene / (meth) acrylate copolymer, styrene / butadiene block copolymer, styrene / isoprene block copolymer, Elastomer particles coated with methyl methacrylate polymer, methyl methacrylate /
Examples include particles coated with a glycidyl methacrylate copolymer. In the case of core / shell particles, the ratio of the radius of the core to the thickness of the shell is usually 1/2 to 2
It is 1000/1, preferably 1/1 to 200/1 (for example, 35/1 for a core radius of 350 nm and a shell thickness of 10 nm).

Of these elastomer particles, polybutadiene, polyisoprene, styrene / butadiene copolymer, styrene / isoprene copolymer, butadiene / (meth) acrylate copolymer, styrene / butadiene block copolymer, styrene Elastomer particles coated with a methyl methacrylate polymer and particles coated with a methyl methacrylate / glycidyl methacrylate copolymer on a core partially crosslinked with an / isoprene block copolymer or the like are particularly preferred. 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 in which all monomer components are charged at once and a polymerization is performed, a method in which a part of the monomer components is polymerized, and then the remaining portion is continuously or intermittently added, Can be continuously added from the beginning of the polymerization, or a method using seed particles can be employed.

The average particle diameter of the thus obtained elastomer particles is from 10 nm to 700 nm. If the thickness is less than 10 nm, the impact resistance of the obtained three-dimensional object is reduced, or the viscosity of the resin liquid is increased, which affects the productivity and the molding accuracy of the three-dimensional object, while if it exceeds 700 nm, the surface is sufficiently smooth. A three-dimensional object cannot be obtained, or the modeling accuracy decreases. Commercially available core / shell type elastomer particles as described above include, for example, Reginas Bond RKB (manufactured by Reginas Kasei Co., Ltd.), Techno MBS-61, and MBS-69.
(Above, manufactured by Techno Polymer Co., Ltd.). These elastomer particles of the component (F) alone are
Alternatively, two or more kinds can be used in combination.

The content of the component (F) in the photocurable resin composition of the present invention is usually 1 to 35% by weight,
It is preferably from 3 to 30% by weight, particularly preferably from 5 to 20% by weight. When the content of the component (F) is too small, the impact resistance is reduced. On the other hand, when the content is too large, the modeling accuracy of the obtained three-dimensionally shaped article tends to be reduced.

<Optional Components> In the photocurable resin composition of the present invention, as long as the effects of the present invention are not impaired, optional components other than the above-mentioned essential components [components (A) to (F)] may be used. A sensitizer (polymerization accelerator), a reactive diluent and the like can be contained. 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.

Further, the photocurable resin composition for stereolithography of the present invention has a composition within a range that does not impair the objects and effects of the present invention.
Various additives may be contained as other optional components. Such additives include epoxy resins, polyamides, polyamideimides, polyurethanes, polybutadienes, polychloroprenes, polyethers, polyesters,
Polymers or oligomers such as styrene-butadiene block copolymer, petroleum resin, xylene resin, ketone resin, cellulose resin, fluorine-based oligomer, silicone-based oligomer, and polysulfide-based oligomer; phenothiazine, 2,6-di-t-butyl-4 A polymerization inhibitor such as methylphenol; a polymerization initiation aid; a leveling agent;
Surfactants; plasticizers; ultraviolet absorbers; silane coupling agents; inorganic fillers; pigments; The photocurable resin composition of the present invention can be produced by uniformly mixing the above components (A) to (F) and, if necessary, the above optional components. The viscosity (25 ° C.) of the photocurable resin composition thus obtained is preferably from 50 to 2,000 cps, more preferably from 70 to 1,500 cps.

<Optical three-dimensional molding method> The photocurable liquid resin composition of the present invention obtained as described above is suitably used as a photocurable liquid resin material in an optical three-dimensional molding method. That is, the photocurable resin composition of the present invention is selectively irradiated with light such as visible light, ultraviolet light, or infrared light to supply necessary energy for curing, thereby achieving desired optical solidification. Can be manufactured.

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

In the above-mentioned optical three-dimensional molding method, usually, after a specific portion of the resin composition is cured, a light irradiation position (irradiation surface) is continuously or stepwise changed from a cured portion to an uncured portion. By moving the hardened parts, the hardened portions are laminated to form a desired three-dimensional shape. Here, the irradiation position can be moved by various methods, for example, by moving any one of a light source, a container for storing the resin composition, and a cured portion of the resin composition, or additionally supplying the resin composition to the container. And the like. A typical example of the above-described optical three-dimensional modeling method will be described. By lowering (settling) a small amount of a supporting stage provided in a storage container from the liquid surface of the resin composition, the supporting stage is placed on the supporting stage. To form a thin layer (1). Next, the thin layer (1) is selectively irradiated with light to form a solid cured resin layer (1). Next, a photo-curable resin composition is supplied on the cured resin layer (1) to form a thin layer (2), 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 thereon. And, with or without changing the pattern irradiated with light,
By repeating this process a predetermined number of times, a three-dimensional object formed by integrally laminating a plurality of cured resin layers (n) is formed.

The thus obtained three-dimensionally shaped object is taken out of the container, and after removing the unreacted resin composition remaining on the surface thereof, washing is performed as necessary. Here, as the cleaning agent, alcohol-based organic solvents represented by alcohols such as isopropyl alcohol and ethyl alcohol; ketone-based organic solvents represented by acetone, ethyl acetate, and methyl ethyl ketone; aliphatics represented by terpenes System organic solvent; low-viscosity thermosetting resin and photocurable resin. In the case of producing a three-dimensional object having good surface smoothness, it is preferable to wash using the thermosetting resin or the photocurable resin. In this case, the curable resin used for washing is preferably used. Depending on the type, post-curing by heat irradiation or light irradiation needs to be performed. In addition, the post cure not only hardens the resin on the surface, but also can harden the unreacted resin composition that may remain inside the three-dimensional object, so that even when the organic resin is washed with an organic solvent. It is preferable to perform post cure.

The three-dimensional object obtained in this manner has high mechanical strength and dimensional accuracy, and also has excellent heat resistance. In addition, the three-dimensional object has excellent shape stability and physical property stability, and exhibits excellent impact resistance and bending resistance when used as a prototype of a mechanical part, 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 process,
It is preferable to use a thermosetting or photocurable hard coat material. As such a hard coat material, an organic coat material made of an acrylic resin, an epoxy resin, a silicone resin or the like, or an inorganic hard coat can be used. These hard coat materials may be used alone or in combination of two or more. Can be used.

Utility The composition of the present invention is useful for optical three-dimensional modeling as described above. In addition, since the cured product has excellent mechanical strength, plastics, various films, wood, ceramics, glass, etc. , Quartz fiber for communication, paper, metal, cans for beverages, coating materials such as fibers, resin for optical three-dimensional molding, sealant for semiconductor, adhesive for semiconductor, underfill agent, optical adhesive, printing plate material It is useful as such.

[0053]

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, 30 parts by weight of 3,4-epoxycyclohexylmethyl-3 ′, 4′-epoxycyclohexanecarboxylate “UVR-6110” (manufactured by Union Carbide) and bis (3,4 -Epoxycyclohexylmethyl) adipate "UVR-6199"
5 parts by weight (manufactured by Union Carbide Co., Ltd.) and 1,6-hexanediol diglycidyl ether “Epolite 160
0 "(manufactured by Kyoeisha Chemical Co., Ltd.) and triallylsulfonium hexafluoroantimonate" UVI-6 "
974 "(manufactured by Union Carbide) and 2 parts by weight of trimethylolpropane triacrylate" Biscoat 29 "
5 "(manufactured by Osaka Organic Chemical Industry Co., Ltd.), 25 parts by weight,
Hydroxycyclohexyl phenyl ketone “Irgacure 184” (Ciba Specialty Chemicals Co., Ltd.)
4 parts by weight) and PO-modified glycerin “Sannicks G
P-400 "(manufactured by Sanyo Chemical Industries, Ltd.), 15 parts by weight,
16 parts by weight of elastomer particles having an average particle diameter of 50 nm (Reginas Bond RKB manufactured by Reginas Kasei Co., Ltd.) having a partially crosslinked styrene / butadiene copolymer in the core and methyl methacrylate / glycidyl methacrylate in the shell were charged in a stirring vessel. By stirring at ℃ for 3 hours,
A liquid composition (the resin composition of the present invention) was produced. The viscosity of the obtained liquid composition was measured by a B-type viscometer (25 ° C.).
Was 820 cps. Examples 2 to 7 A liquid composition (the photocurable resin composition of the present invention) was prepared in the same manner as in Example 1 except that the components (A) to (F) were stirred and mixed in accordance with the formulation shown in Table 1. Manufactured. Table 1 also shows the viscosity (25 ° C.) of each of the obtained liquid compositions measured by a B-type viscometer. Comparative Examples 1 to 3 Liquid compositions (comparative photocurable resin compositions) were produced in the same manner as in Example 1 except that the components were stirred and mixed in accordance with the formulation shown in Table 1. Table 1 also shows the viscosity (25 ° C.) of each of the obtained liquid compositions measured by a B-type viscometer.

[0054]

[Table 1]

(Note) 1) "UVR-6110" (manufactured by Union Carbide) 2) "UVI-6199" (manufactured by Union Carbide) 3) "Epolite 1600" (manufactured by Kyoeisha Chemical Co., Ltd.) 4) "Epolite" 1500NP "(Kyoeisha Chemical Co., Ltd.)
5) "UVI-6974" (manufactured by Union Carbide) 6) "Viscoat 295" (Osaka Organic Chemical Industry Co., Ltd.)
7) "Irgacure 184" (manufactured by Ciba Specialty Chemicals Co., Ltd.) 8) "Sunnics GP-400" (Sanyo Chemical Co., Ltd.)
9) Reginas Bond RKB manufactured by Regina Kasei Co., Ltd. 10) Particles manufactured by emulsion polymerization method As shown in Table 1, all of the compositions according to Examples 1 to 7 are used for optical three-dimensional modeling. It had a suitable viscosity as a resin composition.

<Evaluation of Photocurable Resin Composition>
7 and each of the photocurable resin compositions obtained in Comparative Examples 1 to 3, the curability was evaluated using an Ar laser according to the following evaluation method. The results are shown in Table 2.
Further, the elastic modulus of the cured product and its change with time, and the amount of deformation of the cured product with time were measured by the following methods, and the results are shown in Table 2. Further, the Izod impact strength and bending resistance of the cured product were measured by the methods described below, and the results are shown in Table 2.

[Evaluation of Curability by Ar Laser] Ar
Using a solid-state molding machine “Solid Creator JSC-2000” (manufactured by Sony Corporation) equipped with an irradiation light source consisting of an ion laser (wavelength 351 nm, 365 nm),
Laser spot diameter on irradiation surface (liquid surface) is 200μ
m, the laser power is set to 100 mW, the scanning speed is changed from 100 mm / sec to 1000 mm / sec, and the laser beam is selectively irradiated to the photocurable resin composition, and the minimum energy for curing the resin composition is obtained. The value was measured. It can be determined that the smaller the minimum curing energy, the better the curability of the resin. The curability of each of the resin compositions obtained in the above Examples and Comparative Examples was measured, and the resin compositions were evaluated in the order of superiority, in the order of excellent / good / improper. [Measurement of elastic modulus and change with time of elastic modulus] (1) Preparation of test piece: A coating film having a thickness of 200 µm was formed by applying a composition on a glass plate using an applicator, and a metal halide lamp was prepared. The surface of the coating film was irradiated with ultraviolet rays (irradiation amount: 0.5 J / cm ² ) using an equipped conveyor curing device to prepare a semi-cured resin film. Next, the semi-cured resin film is peeled from the glass plate, placed on a release paper, and irradiated with ultraviolet rays from the side opposite to the side where the ultraviolet rays were first irradiated (irradiation amount 0.5 J / c).
m ² ) to produce a cured resin film. The cured resin film thus produced was allowed to stand under the following environmental conditions to produce two types of test pieces. Test piece: allowed to stand in a thermo-hygrostat at a temperature of 23 ° C. and a relative humidity of 50% for 24 hours. Test piece: allowed to stand in a thermo-hygrostat at a temperature of 23 ° C. and a relative humidity of 50% for 30 days. (2) Measurement: In a thermo-hygrostat at a temperature of 23 ° C. and a relative humidity of 50%, a tensile speed of 1 mm / min was determined for each of a test piece (for initial value measurement) and a test piece (for time-dependent change measurement).
The elastic modulus was measured under the condition of a mark line distance of 25 mm.

[Time Deformation Amount] (1) Preparation of Test Specimen: Solid Creator JSC-2
000, the laser power on the irradiation surface (liquid surface) is 100 mW, and the curing depth is 0.3 mm for each composition.
The photocurable resin composition is selectively irradiated with a laser beam under the conditions of a scanning speed such that the cured resin layer (thickness 0.20)
1) by repeating the process of
Measurement model as shown in (1) (hereinafter referred to as “warp model”)
That. ). Next, the warped model was taken out of the optical shaping apparatus, the resin composition adhering to the outer surface was wiped off, and the excess resin composition was washed and removed with a terpene-based solvent. (2) Measurement: As shown in FIG. 1 (2), the lower end of the leg 11 in the obtained warped model 10 is fixed to the horizontal base 20, and the distance from this horizontal base 20 to the lower end of the leg 12 [lift Amount] was evaluated as the amount of warpage (initial value), and was evaluated as excellent / good / improper in ascending order of the amount of warpage. Further, this warped model was stored in a constant temperature and humidity room at a temperature of 23 ° C. and a relative humidity of 50%.
After standing for 0 days, the amount of warpage was evaluated in the same manner as above.

[Measurement of Impact Strength] (1) Preparation of Test Specimen: Solid Creator JSC-2
000, the laser power on the irradiation surface (liquid surface) is 100 mW, and the curing depth is 0.3 mm for each composition.
The photocurable resin composition is selectively irradiated with a laser beam under the conditions of a scanning speed such that the cured resin layer (thickness 0.20)
mm), a test piece in accordance with JIS K7110 was formed. (2) Measurement: The test piece prepared in this way was measured at 23 ° C.
After standing for 24 hours in a thermo-hygrostat at a relative humidity of 50%, the Izod impact strength was measured according to the method described in JIS K7110.

[Bending resistance test] (1) Preparation of test piece: A coating film having a thickness of 200 μm was formed by applying the composition on a glass plate using an applicator, and curing was performed on a conveyor equipped with a metal halide lamp. Using a device, the surface of the coating film was irradiated with ultraviolet rays (irradiation amount: 0.5 J / cm ² ) to produce a semi-cured resin film. Next, the semi-cured resin film is peeled from the glass plate, placed on a release paper, and irradiated with ultraviolet rays from the side opposite to the side where the ultraviolet rays were first irradiated (irradiation amount 0.5 J / c).
m ² ) to produce a cured resin film. (2) Measurement: The cured resin film thus produced was placed in a constant temperature and humidity room at a temperature of 23 ° C. and a relative humidity of 50%.
After allowing to stand for 4 hours, 1
While applying a constant load of kgf, the number of bending 60 times /
The bending test was repeatedly performed in seconds, and the number of times until the test piece was broken at the bending position was measured. If the number of breaks at the bending position was 30 or more, it was judged as pass, and if less than 30 times, it was rejected.

[Evaluation of Modeling Accuracy] The evaluation of the modelability of the three-dimensional object was performed by measuring the dimensions of the three-dimensional object molded from each resin liquid. (1) 3D modeling: Solid Creator JCS
According to −2000, an H-shaped three-dimensional object was formed as shown in FIG. 2 according to the following molding conditions. The state of the formed three-dimensionally shaped object was adjusted by leaving it in a constant temperature and humidity room at a temperature of 23 ° C. and a relative humidity of 50% for 24 hours. <Molding conditions> Same conditions as in the preparation of test pieces with time-dependent deformation (laser light intensity on liquid surface: 100 mW, scanning speed: appropriate scanning speed at which curing depth is 0.30 mm in each composition, curing to be formed) (Thickness of resin layer: 0.2mm)
It is. (2) Measurement of dimensional accuracy of three-dimensional object: In the three-dimensional object obtained as described above, the distance between A, B, and C in FIG. 2 is measured using a caliper capable of measuring up to 0.01 mm. The distances A and B, C and B are calculated by the following equations (I) and (II).
The dimensional difference between them was determined. Dimensional difference AB = (AB) (I) Dimensional difference CB = (CB) (II) The evaluation of the dimensional accuracy of the three-dimensional object is as follows. -When both absolute values of the dimensional differences AB and CB are less than 0.1 mm: dimensional accuracy [〕]-One of the absolute values of the dimensional differences AB and CB is less than 0.1 mm,
When the other is 0.1 mm or more and less than 0.2 mm: dimensional accuracy [○] • When both absolute values of dimensional differences AB and CB are 0.1 mm or more and less than 0.2 mm: dimensional accuracy [△] • dimensional difference AB , CB when any of the absolute values is 0.2 mm or more or when a shaped object cannot be obtained: Dimensional accuracy [×]

[0062]

[Table 2]

As is evident from Table 2, the cured products of the compositions according to Examples 1 to 7 all had high molding accuracy, a large elastic modulus, and excellent stability over time. Furthermore, the cured product of the composition had a small amount of deformation (warpage) due to curing shrinkage and was excellent in shape stability. Further, a cured product of the composition has excellent impact resistance and bending resistance. On the other hand, the cured product of the composition of Comparative Example 1 using no component (F) is inferior in impact resistance and bending resistance, and the composition of Comparative Example 2 not using the component (A) has poor curability. The cured product of the composition of Comparative Example 3 which was inferior, could not be molded, and did not use the component (C) had an appropriate viscosity, but could not be molded.

[0064]

According to the photocurable resin composition of the present invention,
It can produce a cured product with little change in mechanical properties over time and deformation over time (warpage), high mechanical strength and high dimensional accuracy, and excellent heat resistance. In particular, it can be suitably used as a three-dimensional object such as a prototype of a mechanical part, which has excellent toughness such as impact resistance and bending resistance.

[Brief description of the drawings]

FIG. 1 is an explanatory view schematically showing the shape of a model for measuring the amount of temporal deformation of a cured product of a photocurable composition produced in Examples and Comparative Examples and an outline of a measuring method.

FIG. 2 is a schematic view of a model for measuring the modeling (dimensional) accuracy of the cured products of the photocurable compositions produced in Examples and Comparative Examples.

[Explanation of symbols]

 10 Warp model 11, 12 Leg 20 Horizontal table

──────────────────────────────────────────────────続 き Continued on front page (51) Int.Cl. ⁶ Identification code FI G03F 7/027 502 G03F 7/027 502 7/033 7/033 7/038 503 7/038 503 // B29C 35/08 B29C 35 / 08 67/00 67/00 (72) Inventor Takeshi Watanabe 2-11-24 Tsukiji, Chuo-ku, Tokyo Inside JSR Corporation (72) Inventor Takashi Ukaji 2-11-24 Tsukiji, Chuo-ku, Tokyo Inside JSR Co., Ltd.

Claims (2)

[Claims] (A) a cationically polymerizable organic compound,
(B) a cationic photopolymerization initiator, (C) an ethylenically unsaturated monomer, (D) a radical photopolymerization initiator, (E) 1
A polyether polyol compound having one or more hydroxyl groups in the molecule, and (F) an average particle diameter of 10 nm to 700
A photo-curable liquid resin composition comprising: 2. The content of the component (A) is 20 to 85% by weight, the content of the component (C) is 5 to 45% by weight, and the content of the component (E) is 5 to 35% based on the total composition. The photocurable liquid resin composition according to claim 1, wherein the content of the component (F) is 1 to 35% by weight.