JPH09316111A - Photocurable composition and production of mold made of resin - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a resin composition suitable as a photocurable material, which can be used for forming a cured substance having high mechanical strength and excellent thermal resistance, and a production method for a mold made of a resin which enables production with ease of a resin mold having not only excellent dimensional accuracy, but also excellent durability for repeated use. SOLUTION: This resin composition comprises a monomer component comprising 30 to 70wt.% of a multi-functional unsaturated monomer A having a cyclic structure and 70 to 30wt.% of a mono-functional unsaturated monomer B which has a cyclic structure and a homopolymer of which has a Tg of 70 deg.C or higher; a photopolymerization initiator C; and an inorganic filler D having an average particle diameter or an average fiber length of 1 to 50μm. The inorganic filler is contained in an amount of 100 to 160 pts.wt. relative to 100 pts.wt. of the total amount of the monomer component and the photopolymerization initiator. A cured resin obtained from the composition has a distortion temperature of 100 deg.C or higher. This production method for a mold made of a resin comprises subjecting the photopolymerizable resin composition to stereo lithography by means of a stereo LASER apparatus.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a photocurable resin composition and a method for producing a resin mold by an optical molding method using the same.

[0002]

2. Description of the Related Art Recently, stereolithography for forming a three-dimensional object in which cured resin layers are integrally laminated by repeating a step of selectively irradiating a photocurable material with light to form a cured resin layer. A method has been proposed [JP-A-60-24751]
5, U.S. Pat. No. 4,575,330 (JP-A-62-35966), JP-A-62-1014.
08, JP-A-5-24119]. This stereolithography method has attracted attention because it can easily and quickly obtain a target three-dimensional object having a complicated three-dimensional shape.

A typical example of such an optical molding method will be described. A thin layer of a liquid photocurable resin composition is formed, and the thin layer is selectively irradiated with light, for example, by an ultraviolet laser, to thereby cure the resin. Form a layer. Next, on this cured resin layer, a layer of the photocurable resin composition was supplied to form a thin layer, and the thin layer was selectively irradiated with light, thereby forming the thin layer in advance. A new cured resin layer is integrally formed on the cured resin layer so as to be continuous therewith. 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.

[0004] The photocurable resin composition used in the stereolithography method has a low viscosity, is rapidly cured by light irradiation, and does not swell the cured product due to the photocurable resin composition. A small amount of deformation such as warpage, shrinkage, or lifting of an overhang (overhang) due to curing shrinkage during light curing; high dimensional accuracy of the cured product; a cured product having a complicated and fine shape However, it is required that modeling is possible.

Heretofore, three-dimensional objects obtained by stereolithography have been used as design models, medical models, and master models of resin molding dies. In recent years, attempts have been made to directly manufacture mounted components such as connectors and plugs, and built-in test components such as heaters, motors, and engines by a stereolithography method. Such components require not only high dimensional accuracy, but also sufficient mechanical strength and heat resistance to withstand use conditions. However, a conventional photolithography method using a photocurable resin composition has high mechanical strength and cannot obtain a cured product having high heat resistance, and has sufficient mechanical strength and heat resistance for mounting parts and embedded parts. It is difficult to manufacture a three-dimensional object having both properties.

On the other hand, attempts have been made to manufacture a "mold" used in various molding methods such as an injection molding method, a press molding method, a vacuum molding method, a pressure molding method, and a foam molding method by a stereolithography method.

However, when performing stereolithography using a conventionally known photocurable resin composition, the obtained stereolithography product does not have the pressure resistance and heat resistance required for the “mold”. Especially in the injection molding method of engineering plastics that is executed under high temperature and high pressure conditions,
A resin composition that gives a stereolithography (mold) that can withstand the above conditions is not known, and thus it has been difficult to manufacture a resin mold having excellent repeated durability by the stereolithography method.

[0008]

DISCLOSURE OF THE INVENTION The present invention has been made based on the above circumstances, and its object is to provide:
An object of the present invention is to provide a photocurable resin composition which can form a cured product having high mechanical strength and excellent heat resistance, and which is suitable as a photocurable material used in a stereolithography method. Another object of the present invention is to provide a resin mold manufacturing method capable of obtaining a molded product having high dimensional accuracy and easily manufacturing a resin mold having excellent repeated durability.

[0009]

The photocurable resin composition of the present invention comprises (A) a polyfunctional unsaturated monomer 3 having a cyclic structure.
A single amount of 0 to 70% by weight and (B) 70 to 30% by weight of a monofunctional unsaturated monomer having a cyclic structure and a homopolymer glass transition temperature (Tg) of 70 ° C. or higher. A body component, (C) a photopolymerization initiator, and (D) an inorganic filler having an average particle diameter or an average fiber length of 1 to 50 μm. The total amount of the monomer component and the photopolymerization initiator is 100 to 160 parts by volume with respect to 100 parts by volume, and the heat distortion temperature of the cured resin obtained by curing this is 100 ° C. or higher.

In the method of manufacturing a resin mold according to the present invention, a plurality of cured resin layers are integrally laminated by repeating a process of selectively irradiating a photocurable material with light to form a cured resin layer. In the method for producing a resin mold, the photocurable resin composition is used as a photocurable material.

[0011]

BEST MODE FOR CARRYING OUT THE INVENTION The present invention will be described in detail below. The photocurable resin composition of the present invention comprises a monomer component containing the components (A) and (B), a component (C) which is a photopolymerization initiator, and an inorganic filler (D). ) Component as an essential component.

<Monomer component> The monomer component constituting the photocurable resin composition of the present invention is a polyfunctional unsaturated monomer having a cyclic structure (hereinafter referred to as "specific polyfunctional monomer (a ) ”As a component (A), has a cyclic structure, and has a homopolymer glass transition temperature (Tg) of 70 ° C. or higher (hereinafter referred to as“ specific monofunctional monomer ”). The monomer (b) is also included as the component (B).

Specific polyfunctional monomers (a) include, for example, tricyclodecanediyldimethylene di (meth) acrylate, tris (2-hydroxyethyl) isocyanurate di (meth) acrylate, tris (2-hydroxyethyl). Isocyanurate tri (meth) acrylate,
Caprolactone modified tris (2-hydroxyethyl) isocyanurate tri (meth) acrylate, bisphenol A di (meth) acrylate, EO modified bisphenol A di (meth) acrylate, PPO modified bisphenol A di (meth) acrylate, bisphenol F di (meth) ) Acrylate, EO-modified bisphenol F di (meth) acrylate, PPO-modified bisphenol F di (meth) acrylate, bisphenol S di (meth) acrylate, EO-modified bisphenol S di (meth) acrylate, PPO-modified bisphenol S di (meth) acrylate , Hydrogenated bisphenol A di (meth) acrylate,
EO-modified hydrogenated bisphenol A di (meth) acrylate, EO-modified brominated bisphenol A di (meth) acrylate, PPO-modified brominated bisphenol A di (meth) acrylate
Acrylate, PPO modified hydrogenated bisphenol A di (meth) acrylate, hydrogenated bisphenol F di (meth) acrylate, EO modified hydrogenated bisphenol F di (meth)
Acrylate, PPO modified hydrogenated bisphenol F di (meth) acrylate, hydrogenated bisphenol S di (meth) acrylate, EO modified hydrogenated bisphenol S di (meth) acrylate
Acrylate, PPO-modified hydrogenated bisphenol S di (meth) acrylate, bisphenol A diglycidyl ether di (meth) acrylate, bisphenol F diglycidyl ether di (meth) acrylate, bisphenol S diglycidyl ether di (meth) acrylate, hydrogenated bisphenol A diglycidyl ether di (meth) acrylate, hydrogenated bisphenol F diglycidyl ether di (meth) acrylate, hydrogenated bisphenol S diglycidyl ether di (meth) acrylate, phenol novolac polyglycidyl ether (meth) acrylate 1,3 -Di (meth) acrylamidomethyl-2-
Imidazolidone, cardo epoxy (meth) acrylate, trimethylolpropane (meth) acrylic acid benzoate, allylated cyclohexyl di (meth) acrylate, methoxylated cyclohexyl di (meth) acrylate, epichlorohydrin modified phthalic acid di (meth) acrylate, aromatic Group polyester (meth) acrylate,
Examples thereof include polyfunctional (meth) acrylates such as alicyclic polyester acrylate and neopentyl glycol-modified trimethylolpropane di (meth) acrylate, and these can be used alone or in combination of two or more kinds.

Of these, particularly tricyclodecanediyldimethylene di (meth) acrylate, tris (2-hydroxyethyl) isocyanurate tri (meth) acrylate, bisphenol A diglycidyl ether di (meth) acrylate, bisphenol F diglycidyl ether. Di (meth) acrylate and the like are preferable.

Examples of commercially available products of the specific polyfunctional monomer (a) include SA1002 (manufactured by Mitsubishi Chemical Corporation), Viscoat 700, 540, 3000, 3700.
(Made by Osaka Organic Chemical Industry Co., Ltd.), Kayarad R-
551, R-712, R-604, R-684, HBA
-024E, HBA-240P (all manufactured by Nippon Kayaku Co., Ltd.), Aronix M-210, M-215, M-31.
5, M-325, M-6200, M-6400 (all manufactured by Toagosei Co., Ltd.), light acrylate BP-4E
A, BP-4PA, BP-2EA, BP-2PA, DC
PA (all manufactured by Kyoeisha Yushi Kagaku Kogyo Co., Ltd.), New Frontier BPE-4, TEICA, BR-42M,
GX-8345 (all manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd.), AS
F-400 (Nippon Steel Chemical Co., Ltd.), Lipoxy SP-
1506, SP-1507, SP-1509, VR-7
7, SP-4010, SP-4060 (all manufactured by Showa High Polymer Co., Ltd.), NK ester A-BPE-4 (all manufactured by Shin Nakamura Chemical Co., Ltd.) and the like can be used.

The proportion of component (A) in the monomer components is
The amount is 30 to 70% by weight, preferably 35 to 65% by weight, and more preferably 40 to 60% by weight. (A)
When the proportion of the components is less than 30% by weight, the resulting composition does not have sufficient photocurability, and a cured product of the composition may exhibit high mechanical strength and heat resistance. Can not. On the other hand, when the ratio of the component (A) exceeds 70% by weight, the viscosity of the obtained composition becomes excessive, and the curing shrinkage ratio of the composition becomes large, so that a cured product with high dimensional accuracy can be obtained. Can not.

The specific monofunctional monomer (b) is a monofunctional monomer having a cyclic structure and an ethylenically unsaturated bond, and is a homopolymer obtained by homopolymerizing the monomer. The glass transition temperature (Tg) is 70 ° C. or higher, preferably 90 ° C. or higher. By using a monomer having a glass transition temperature (Tg) of the homopolymer of 70 ° C. or higher as the component (B), a cured product obtained from the composition is a heat-resistant product used under high temperature conditions (for example, “mold The heat resistance required for ")" is sufficiently satisfied.

Here, the glass transition temperature (Tg) of the homopolymer of the specific monofunctional monomer (b) is a value measured based on the differential scanning calorimetry (DSC). Specifically, 1-hydroxycyclohexyl phenyl ketone was added to the specific monofunctional monomer (b) at a ratio of 3% by weight and dissolved, and then the homopolymer was irradiated with 5 J / cm ² of ultraviolet rays. Of the homopolymer D
SC measurement (heating rate 20 ° C./min) is performed, and the temperature of the second-order transition point of the differential thermal curve is taken as the glass transition temperature (Tg).

Specific examples of the specific monofunctional monomer (b) include (meth) acryloylmorpholine, morpholinoethyl (meth) acrylate, isobornyl (meth) acrylate, N-vinylcaprolactam and N-vinylpyrrolidone. , Tricyclo [5,2,1,0 ^2,6 ] decanyl (meth) acrylate, dicyclopentenyl (meth) acrylate, (meth) acrylated hydrogenated naphthol, o-phenylphenol glycidyl ether (meth) acrylate, p- Phenylphenol (meth) acrylate, (meth) acrylated cyclohexene oxide, 2- (meth) acryloyloxyethyl hydrogen phthalate, 2- (meth) acryloyloxypropyl hydrogen phthalate, 2- (meth) acryloyloxypropyl hex Mention may be made of hydroperoxides hydrogensulfate phthalate. These may be used alone or in combination of two or more. Of these,
Especially (meth) acryloylmorpholine, isobornyl (meth) acrylate, N-vinylcaprolactam, N
-Vinylpyrrolidone, tricyclo [5,2,1,
[0 ^2,6 ] Decanyl (meth) acrylate, dicyclopentenyl (meth) acrylate and the like are preferable.

Commercially available products of the specific monofunctional monomer (b) include ACMO (all manufactured by Kojin Co., Ltd.) and FA-5.
13A, FA-511A (all manufactured by Hitachi Chemical Co., Ltd.),
Aronix TO-1316, TO-1225, TO-
1317, TO-1315 (all manufactured by Toagosei Co., Ltd.), IBXA, Viscoat 2000, 2100, 21.
50 (above Osaka Organic Chemical Industry Co., Ltd.) and the like can be used.

The proportion of the component (B) in the monomer components is
The amount is 30 to 70% by weight, preferably 35 to 65% by weight, and more preferably 40 to 60% by weight. (B)
When the ratio of the components is less than 30% by weight, the curing shrinkage rate of the composition becomes large and a cured product with high dimensional accuracy cannot be obtained. On the other hand, when the ratio of the component (B) exceeds 70% by weight, the resulting composition does not have sufficient photocurability, and the cured product of the composition has high mechanical strength and heat resistance. Can not be expressed.

<Photopolymerization Initiator> The photopolymerization initiator which is the component (C) is an ethylenic unsaturated monomer contained in the specific polyfunctional monomer (a) and the specific monofunctional monomer (b). It is for starting the polymerization reaction of the bond, and is not particularly limited as long as it is decomposed by irradiation of light to generate a radical or a cation and initiates the polymerization of the monomer. .

Specific examples of such a photopolymerization initiator include acetophenone, acetophenone benzyl ketal, anthraquinone, 1- (4-isopropylphenyl) -2-hydroxy-2-methylpropan-1-one, carbazole and xanthone. , 4-chlorobenzophenone, 4,4'-diaminobenzophenone, 1,1-dimethoxydeoxybenzoin, 3,3'-dimethyl-4
-Methoxybenzophenone, a thioxanthone compound,
2-methyl-1- [4- (methylthio) phenyl] -2
-Morpholino-propan-2-one, 2-benzyl-
2-dimethylamino-1- (4-morpholinophenyl) -butan-1-one, triphenylamine, 2,
4,6-trimethylbenzoyldiphenylphosphine oxide, bis (2,6-dimethoxybenzoyl)-
2,4,4-tri-methylpentylphosphine oxide, benzyl dimethyl ketal, 1-hydroxycyclohexyl phenyl ketone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, fluorenone,
Fluorene, benzaldehyde, benzoin ethyl ether, benzoin propyl ether, benzophenone,
Michler's ketone, 2-benzyl-2-dimethylamino-
1- (4-morpholinophenyl) -butan-1-one, 3-methylacetophenone, 3,3 ', 4,4'-
Tetra (t-butylperoxycarbonyl) benzophenone (BTTB), and combinations of BTTB with xanthene, thioxanthene, coumarin, ketocoumarin, and other dye sensitizers, 1- (4-dodecylphenyl) -2
-Hydroxy-2-methylpropan-1-one, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholino-propan-1-one, benzoin, benzoin methyl ether, benzoin isobutyl ether, benzoin benzoic acids , 4-phenoxydichloroacetophenone-containing chloroacetophenones and the like, and these can be used alone or in combination of two or more kinds.

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 preferable.

The content ratio of the component (C) in the photocurable resin composition of the present invention is 0. 0 based on 100 parts by weight of the total amount of the component (A) and the component (B) which are monomer components.
It is preferably from 01 to 10 parts by weight, more preferably from 0.1 to 8 parts by weight. When this ratio is less than 0.01 part, the curing rate and resolution of the resulting composition tend to be lowered. On the other hand, when this ratio exceeds 10 parts by weight, the curing characteristics of the obtained composition, the physical properties of the cured product of the composition, heat resistance, handling and the like may be adversely affected.

<Inorganic Filler> The inorganic filler used as the component (D) may be in the form of particles or fibers. The average particle diameter in the particulate inorganic filler or the average fiber length in the fibrous inorganic filler is 1 to 50 μm, preferably 3 to 40 μm. When this average particle diameter (average fiber length) is 1 μm, the viscosity of the obtained composition becomes excessive and the curing speed becomes low, and a cured product with high dimensional accuracy can be obtained depending on the composition. Can not. On the other hand, when the average particle diameter (average fiber length) exceeds 50 μm, a cured product having a smooth surface cannot be obtained by the obtained composition, and even if the cured product is used as a “mold”, it is smooth. It is impossible to obtain a molded product having a smooth surface.

Specific examples of such an inorganic filler include aluminum oxide, aluminum hydroxide, diatomaceous earth, glass beads, hollow glass beads, magnesium oxide, magnesium hydroxide, magnesium carbonate, silica particles, shirasu balloon, glass fiber, Examples thereof include potassium titanate whiskers, carbon whiskers, sapphire whiskers, beryllia whiskers, boron carbide whiskers, silicon carbide whiskers, silicon nitride whiskers, and the like. Among these, glass beads, hollow glass beads, potassium titanate whiskers and the like are preferable.
These inorganic fillers can be used alone or in combination of two or more.

The inorganic filler may be surface-treated with a silane coupling agent or the like.
Examples of the silane coupling agent used as a surface treatment agent for the inorganic filler include vinyltrichlorosilane, vinyltris (βmethoxyethoxy) silane, vinyltriethoxysilane, vinyltrimethoxysilane, γ- (methacryloxypropyl) trimethoxy. Silane, β- (3,
4-epoxycyclohexyl) ethyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ
-Glycidoxypropylmethyldiethoxysilane, N-
β (aminoethyl) γ-aminopropyltrimethoxysilane, N-β (aminoethyl) γ-aminopropylmethyldimethoxysilane, γ-aminopropyltriethoxysilane, N-phenyl-γ-aminopropyltrimethoxysilane, γ- Examples thereof include mercaptopropyltrimethoxysilane and γ-chloropropyltrimethoxysilane.

Commercially available products of these inorganic fillers include, for example, glass beads GB210, GB210A, GB21.
0B, GB210C, GB045Z, GB045ZA,
GB045ZB, GB045ZC, GB731, GB7
31A, GB731B, GB731C, GB731M,
GB301S, EGB210, EGB210A, EGB
210B, EGB210C, EGB045Z, EGB0
45ZA, EGB045ZB, EGB045ZC, MB
-10, MB-20, EMB-10, EMB-20, H
SC-070Q, HSC-024X, HSC-080
S, HSC-070G, HSC-075L, HSC-1
10, HSC-110A, HSC-110B, HSC-
110C (above, manufactured by Toshiba Ballotini Co., Ltd.); Radio Light # 100, Radio Light Fine Flow B,
Radio Light Fine Flow A, Radio Light Sparkle Flow, Radio Light Special Flow, Radio Light # 300, Radio Light # 200, Radio Light Clear Flow, Radio Light # 500, Radio Light # 600, Radio Light # 2000, Radio Light # 700 , Radio Light # 500S, Radio Light # 800, Radio Light # 900, Radio Light # 800S, Radio Light # 3000, Radio Light Ace, Radio Light Super Ace, Radio Light High Ace, Radio Light PC-1, Radio Light Deluxe P-5, Radio Light Deluxe W-50, Radio Light Micro Fine, Radio Light F, Radio Light SPF, Radio Light G
C (above, Showa Chemical Industry Co., Ltd.); Heidilite
H-X, Heidilite H-21, Heidilite H-
31, Heidilite H-32, Heidilite H-4
2, Heidilite H-42M, Heidilite H-4
3, Heidilite H-32ST, Heidilite H-4
2STV, Heidilite H-42T, Heidilite
H-34, Heidilite H-34HL, Heidilite H-32I, Heidilite H-42I, Heidilite H-42S, Heidilite H-210, Heidilite H-310, Heidilite H-320, Heidilite H- 141, Heidilite H-241, Heidilite H-341, Heidilite H-320I,
Heidilite H-320ST, Heidilite HS-
310, Heidilite HS-320, Heidilite
HS-341, Alumina A-42-6, Alumina A-
42-1, Alumina A-42-2, Alumina A-4
2-3, Alumina A-420, Alumina A-43-
M, alumina A-43-L, alumina A-50-K,
Alumina A-50-N, Alumina A-50-F, Alumina AL-45-H, Alumina AL-45-2, Alumina AL-45-1, Alumina AL-43-M,
Alumina AL-43-L, Alumina AL-43P
C, Alumina AL-150SG, Alumina AL-1
70, alumina A-172, alumina A-173,
Alumina AS-10, Alumina AS-20, Alumina AS-30, Alumina AS-40, Alumina A
S-50 (above, Showa Denko KK); Star Mag-
U, Star Mag-M, Star Mag-L, Star Mag-
P, Star Mag-C, Star Mag-CX, High Purity Magnesia HP-10, High Purity Magnesia HP-10N, High Purity Magnesia HP-30, Star Brand-200, Star Brand-10, Star Brand-10A, Star Magnesium Carbonate Venus, star magnesium carbonate 2 star, star magnesium carbonate 1 star, star magnesium carbonate S, star magnesium carbonate for feed, star magnesium carbonate heavy, high purity magnesium carbonate GP-1
0, high-purity magnesium carbonate 30, Starbrand light calcium carbonate for general use, Starbrand light calcium carbonate EC, Starbrand light calcium carbonate K
FW-200 (above, Kamijima Chemical Co., Ltd.), MK
C silica GS50Z, MKC silica SS-15 (above, Mitsubishi Chemical Corporation make), Admafine SO-E
3, Admafine SO-C3, Admafine A
O-800, Admafine A0-809, Admafine AO-500, Admafine AO-509
(Above, manufactured by Admatex Co., Ltd.); XM-220
(Mitsui Petrochemical Co., Ltd.); Tismo-D, Tismo-L, Tofikar Y, Tofikar YN, Tofikar Y
B, Dendor WK-200, Dendor WK-200
B, Dendor WK-300, Dendor BK-20
0, Dendor BK-300, Suwanite, Bali Hai B
Superdentol (above, Otsuka Chemical Co., Ltd.) etc. are mentioned.

The content ratio of the component (D) in the photocurable resin composition of the present invention is 100 to 16 per 100 parts by volume of the total amount of the components (A), (B) and (C).
The volume is 0 parts by volume, and preferably 120 to 155 parts by volume. Here, the “capacity of the inorganic filler” means a value (w / d) obtained by dividing the weight (w) of the inorganic filler by the true specific gravity (d) of the inorganic filler.

When the content ratio of the component (D) is less than 100 parts by volume, the storage stability of the resulting photocurable resin composition is low, and the floating or sedimentation of the inorganic filler is likely to occur, resulting in a homogeneity. Is likely to be impaired, and it becomes difficult to obtain a cured product having high strength and excellent heat resistance.
On the other hand, when the content ratio of the component (D) exceeds 160 parts by volume, the viscosity of the composition tends to be high, and it becomes difficult to obtain a cured product with high dimensional accuracy.

<Optional Components> The photocurable resin composition of the present invention contains the above-mentioned components (A), (B), (C) and (D) as essential components. As an optional ingredient other than the ingredients, triethanolamine,
Sensitizers (polymerization accelerators) composed of amine compounds such as methyldiethanolamine, triethylamine and diethylamine, diluents such as vinyl ethers, vinyl sulfides, vinyl urethanes, urethane acrylates and vinyl ureas, epoxy resins, polyamides, polyamides Imide, polyurethane, polybutadiene, polychloroprene, polyether, polyester, styrene-butadiene-styrene block copolymer, petroleum resin, xylene resin, ketone resin, cellulose resin, fluorine-based oligomer, silicone-based oligomer, polysulfide-based oligomer, etc. Resin additive, phenothiazine, 2,6-di-
Polymerization inhibitors such as t-butyl-4-methylphenol, polymerization initiation aids, leveling agents, wettability improvers, surfactants, plasticizers, ultraviolet absorbers, silane coupling agents, inorganic fillers, resin particles, Pigments, dyes and the like can be included. The content ratio of these optional components can be appropriately adjusted within a range that does not impair the curability of the photocurable resin composition.

The photocurable resin composition of the present invention can be prepared by uniformly mixing the above-mentioned essential components and optional components used as necessary. Viscosity of photocurable resin composition thus prepared (25 ° C.)
Is preferably in the range of 100 to 50,000 cps, and more preferably in the range of 500 to 20,000 cps.

<Manufacture of Three-dimensional Object> The photocurable resin composition of the present invention thus obtained can be suitably used as a photocurable material in a stereolithography method. That is, for the photocurable resin composition of the present invention, visible light,
By repeating the process of selectively irradiating light such as ultraviolet light or infrared light to form a cured resin layer, a three-dimensional object having a desired shape in which the cured resin layers are integrally laminated is manufactured. be able to.

More specifically, the photocurable resin composition is supplied onto an appropriate support stage to form the thin layer (1), and the thin layer (1) is selectively irradiated with light. By doing so, a solid cured resin layer (1) is formed. Then
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, thereby obtaining the cured resin. A new cured resin layer (2) is formed on the layer (1) so as to be continuously and integrally laminated thereon. Then, by repeating this process a predetermined number of times with or without changing the pattern to be irradiated with light, a three-dimensional object formed by integrally laminating a plurality of cured resin layers (n) is formed.

The means for selectively irradiating the photocurable resin composition with light is not particularly limited, and various means can be adopted. For example, laser light,
Alternatively, means for irradiating the composition while scanning the convergent light obtained using a lens, a mirror, or the like, and irradiating the composition with non-convergent light via this mask using a mask having a light transmitting portion of a predetermined pattern A light guide member formed by bundling a large number of optical fibers, and a means for irradiating the composition with light through optical fibers corresponding to a predetermined pattern on the light guide member. 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 target three-dimensionally shaped object has a fine shape and when high dimensional accuracy is required, as a means for selectively irradiating light to the composition, laser light is used. It is preferable to employ scanning means.

After removing the unreacted photocurable resin composition remaining on the surface of the three-dimensional object thus obtained, a washing process is carried out if necessary.
In this cleaning treatment, alcohols such as isopropyl alcohol and ethyl alcohol as cleaning agents,
Among the organic solvents represented by esters such as ethyl acetate, ketones such as acetone and methyl ethyl ketone, thermosetting resin compositions and photocurable resin compositions, resin compositions having low viscosity can be used.

In order to obtain a three-dimensional object having excellent surface smoothness, after washing with the above resin composition, post treatment by heat treatment or light irradiation treatment is performed depending on the type of the resin composition. It is preferable to perform curing. This post-cure not only cures the resin composition existing on the surface of the three-dimensional object, but also cures the resin composition remaining inside, so that even when washed with an organic solvent. It is preferable to perform post cure.

Further, regarding the three-dimensional object subjected to the washing treatment, from the viewpoint of improving the surface strength and heat resistance,
Surface coating treatment is preferably performed using a thermosetting or photocurable hard coat material. As such a hard coat material, an acrylic resin, an epoxy resin,
An organic coating material made of a silicone resin or the like and various inorganic coating materials can be used, and two or more hard coating materials can be used in combination.

The three-dimensional product (cured product of the composition of the present invention) obtained as described above has high dimensional accuracy,
In addition, it has a heat deformation temperature of 100 ° C. or more and has sufficient mechanical strength and heat resistance required for a “mold” used under high temperature and high pressure conditions. Therefore, the three-dimensional object is particularly suitable as a resin mold used for various molding methods such as an injection molding method, a press molding method, a vacuum molding method, a pressure molding method, and a foam molding method.

[0041]

EXAMPLES The present invention will be described below with reference to examples, but the present invention is not limited to these examples.

<Examples 1 to 4> According to the formulation shown in Table 1, the components (A), (B), (C) and optional components (additives) were charged in a stirring vessel and heated at 50 ° C for 2 hours. A uniform resin liquid was obtained by stirring for a time. Next, this resin solution and the component (D) shown in Table 1 were mixed, charged in a stirring container equipped with a high-speed stirring device, and stirred at room temperature for 10 minutes (rotation speed: 3000 rpm),
The photocurable resin composition (composition [1] to composition [4]) of the present invention in which the component (D) was uniformly dispersed was prepared.
All of the compositions of the present invention prepared as described above were opaque and uniform viscous liquids. Table 1 also shows the viscosities (25 ° C.) measured by the B-type viscometer for each of the compositions [1] to [4].

<Comparative Examples 1 to 3> According to the formulation shown in Table 1, the components (A), (B), (C) and optional components (additives) were charged in a stirring vessel and heated at 50 ° C. for 2 hours. A uniform resin liquid was obtained by stirring for a time. Next, this resin solution and the component (D) shown in Table 1 were mixed, charged in a stirring container equipped with a high-speed stirring device, and stirred at room temperature for 10 minutes (rotation speed: 3000 rpm),
Comparative photocurable resin compositions (composition [5] to composition [7]) in which the component (D) was uniformly dispersed were prepared.
Here, Comparative Example 1 is an example in which the content ratio of the component (D) is too small, Comparative Example 2 is an example in which the ratio of the component (B) in the monomer component is too small, and Comparative Example 3 is This is an example in which the proportion of the component (A) in the monomer components is too small. All comparative compositions prepared as described above were opaque and uniform viscous liquids. For each of composition [5] to composition [7], viscosity (25 ° C.) measured by a B-type viscometer
Are also shown in Table 1.

<Evaluation of Photocurable Resin Composition> Examples 1 to 1
For each of the compositions [1] to [4] prepared according to No. 4, and the compositions [5] to [7] prepared according to Comparative Examples 1 to 3, curing by the compositions as described below. The bending strength and heat distortion temperature of the product were measured. The results are shown in Table 1.

[Preparation of Test Piece] First, a glass plate was subjected to PET.
The film is fixed, and 120 mm in height and 1 in width
A mold for producing a test piece was prepared by sticking a silicone rubber plate having a 1 mm rectangular through hole and having a thickness of 4 mm. A certain amount of each composition was poured into this mold so that the thickness was about 1 mm, and ultraviolet rays were irradiated (irradiation amount 0.5 J / cm ² ) using a conveyor curing device equipped with a metal halide lamp to cure the composition. It was By repeating the above operations and 4 times, a rod-shaped cured product having a thickness of 4 mm was obtained. Further, post-curing is performed by irradiating the entire surface of the rod-shaped cured product with ultraviolet rays (irradiation amount of 10 J / cm ² ), and after annealing at 150 ° C. for 1 hour, a constant temperature and temperature of 23 ° C. and a relative humidity of 50% are used. A test piece was prepared by leaving it in a moist chamber for 24 hours.

[Measurement of Bending Strength] The bending strength of the test piece was measured in a constant temperature and humidity chamber at a temperature of 23 ° C. and a relative humidity of 50%. Here, the bending speed was 50 mm / min, and the distance between marked lines was 40 mm.

[Measurement of heat distortion temperature] JIS K7207
According to method A, the heat distortion temperature of the test piece was measured.

<Production of Resin Mold> Compositions [1] to [4] prepared in Examples 1 to 4 and compositions [5] to [7] prepared in Comparative Examples 1 to 3 were prepared. Argon ion laser (wavelength 351 nm, 3
The cavity mold and the core mold were respectively molded under the following conditions by an optical molding apparatus "Solid Creator JSC-2000" (manufactured by Sony Corporation) using 65 nm). FIG. 1 is a plan view (I) and a side view (II) showing a cavity mold. In the figure,
1 is a pin shape, 2 is a rib, 3 is a pin shape, 4 is a claw, and 5
Is a fixing screw hole, and 6 is a pin shape.

(1) Laser light intensity on liquid surface: 40
mW, (2) Scanning speed: 100 cm / sec, (3) Thickness of cured resin layer to be formed: 0.2 mm, (4) Cavity type lamination number of times: 306 times (5) Core type lamination number of times: 220 times

[Post-Treatment] The resin composition adhering to the surfaces of the molded cavity mold and core mold is wiped off, and post cure is carried out by an ultraviolet lamp under the conditions of irradiation light intensity of 20 mW / cm ² and irradiation time of 30 minutes. Done, 150 more
Annealing was performed at 1 ° C. for 1 hour.

<Evaluation of Resin Mold (Injection Molding)> ABS resin "S996-JB gray" (Japan Synthetic Rubber Co., Ltd.) is used for each of the resin molds (cavity type and core type) molded as described above. (Made by the company), mold clamping force 10 tons, cylinder temperature 230 ° C, mold temperature 40 ° C, injection speed 20 mm / sec, holding pressure (10%) 17
An injection-molded product was obtained by performing injection molding under the condition of 5 kg / cm ² . The dimensional accuracy of the obtained injection-molded product and the repeating durability of the resin mold were evaluated as follows. The results are shown in Table 1.

[Dimensional Accuracy of Injection-Molded Product] “Good” when the accuracy is less than 0.5% with respect to the design dimension of the injection-molded product.
The case where the accuracy was 0.5% or more was evaluated as "poor".

[Repeatability] Injection molding using a resin mold was continuously performed, and the number of times molding was possible without damaging the resin mold was measured.

[0054]

[Table 1]

The commercial names of the constituents noted in (a) to (l) in Table 1 are as follows. (A): "Yupimer UV SA1002" (manufactured by Mitsubishi Chemical Co., Ltd.) (b): "VR-77" [manufactured by Showa Polymer Co., Ltd.] (c): "Aronix M-315" [Toa Gosei Co., Ltd. )) (D): "SR259" [Sartomer] (e): "Vinylpyrrolidone" [BASF] (f): "Vinylcaprolactam" [BASF] (g): "ACMO" (Manufactured by KK) (h): "FA-513A" (manufactured by Hitachi Chemical Co., Ltd.) (i): "Viscoat 192" (manufactured by Osaka Organic Chemical Industry Co., Ltd.) (j): "Irgacure 369" [ Ciba Geigy] (k): “Irgacure 651” [Ciba Geigy] (l): “GBO45ZC” (Toshiba Ballotini Co., Ltd.)
Made)

As is clear from Table 1, the compositions [1] to [4] obtained in Examples 1 to 4 all have a viscosity suitable as a photocurable material used in the stereolithography method. However, it is understood that the cured product of each composition has a large bending strength and a high heat distortion temperature of 100 ° C. or higher, and has sufficient mechanical strength and heat resistance.
Further, according to the resin mold formed by using the compositions [1] to [4] as the photocurable material, a molded product with high dimensional accuracy can be obtained, and the resin mold has excellent repeated durability. Is understood.

On the other hand, in the composition [5] obtained in Comparative Example 1, since the content ratio of the component (D) was too small, the cured product of the composition had a low bending strength. . In addition, a molded product with high dimensional accuracy could not be obtained depending on the resin mold molded using the composition, and the resin mold was inferior in repeated durability.

Further, the cured products of the compositions [6] to [7] obtained in Comparative Examples 2 to 3 have low bending strength and heat distortion temperature, and resin molded using these compositions. With the mold, it was not possible to obtain a molded product with high dimensional accuracy, and these resin molds were also inferior in repeated durability.

[0059]

According to the first aspect of the present invention, a cured product having high mechanical strength and excellent heat resistance can be formed, and is preferably used as a photocurable material for use in stereolithography. Can be provided.

According to the second aspect of the present invention, a molded product having high dimensional accuracy can be obtained, and deformation and damage do not occur even when subjected to molding processing 100 times or more, and repeated durability. An excellent resin mold can be easily manufactured.

[Brief description of drawings]

FIG. 1 is an explanatory view showing a configuration of a resin mold manufactured in Examples and Comparative Examples.

[Explanation of symbols]

 1 Pin shape 2 Rib 3 Pin shape 4 Claw 5 Screw hole for fixing 6 Pin shape

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁶ Identification number Office reference number FI Technical indication location C08F 290/02 C08F 290/02 299/00 MRM 299/00 MRM (72) Inventor Yuichi Haruta Tokyo 2-11-24 Tsukiji, Chuo-ku, Japan Synthetic Rubber Co., Ltd. (72) Inventor Takashi Ukaji 2-11-24 Tsukiji, Chuo-ku, Tokyo Japan Synthetic Rubber Co., Ltd.

Claims (2)

[Claims] 1. A polyfunctional unsaturated monomer (A) having a cyclic structure in an amount of 30 to 70% by weight, and (B) a cyclic structure, and a homopolymer having a glass transition temperature (Tg) of 70 ° C. or higher. Monofunctional unsaturated monomer 70-
A monomer component containing 30% by weight, (C) a photopolymerization initiator, and (D) an inorganic filler having an average particle diameter or an average fiber length of 1 to 50 μm, The content ratio of the inorganic filler is 100 to 1 with respect to 100 parts by volume of the total amount of the monomer component and the photopolymerization initiator.
60 parts by volume, and the heat distortion temperature of the cured resin obtained by curing this is 100
A photocurable resin composition having a temperature of not less than ° C. 2. A method for producing a resin mold in which a plurality of cured resin layers are integrally laminated by repeating a step of forming a cured resin layer by selectively irradiating a photocurable material with light. A method for producing a resin mold, comprising using the photocurable resin composition according to claim 1 as a photocurable material.