JPH0859760A - Resin composition for optically stereoscopic molding - Google Patents

Abstract

PURPOSE: To provide the subject resin composition containing a specified oligomer mixture, an ethylenic unsaturated monomer and a photo-polymerization initiator, capable of forming a molding free from deformation with time and excellent in mechanical strength, impact resistance, heat resistance, dimensional stability, etc., and useful for a mechanical component, etc. CONSTITUTION: This is a resin composition containing (A) an urethane (meth) acrylate oligomer synthesized by reacting a diol of the formula [R<1> is a 1 to 12C (branched) divalent aliphatic hydrocarbon group or a 6 to 12C divalent aromatic hydrocarbon group; R<2> is a 1 to 10C (branched) divalent aliphatic hydrocarbon group or a 6 to 12C divalent aromatic hydrocarbon group; (n) is 1 to 20], a diisocyanate and an OH-containing (meth)acrylate, (B) a urethane (meth)acrylate oligomer synthesized by reacting a diisocyanate with an OH- containing (meth)acrylate, (C) an ethylenic unsaturated monomer and (D) a photopolymerization initiator.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention is to produce a molded article which is hardened by irradiation of light, has excellent impact resistance, can obtain a highly accurate molded article, and is less deformed by warpage after modeling. The present invention relates to a resin composition for optical three-dimensional modeling capable of producing

[0002]

2. Description of the Related Art An optical three-dimensional modeling method is disclosed in, for example, Japanese Patent Laid-Open No.
As disclosed in Japanese Unexamined Patent Publication No. 0-247515, it is a method of selectively supplying energy required for a photocurable liquid substance to form a shaped article having a desired shape. Such a method and its improved technique are disclosed in US Pat.
5, 330 (JP-A-62-35966), JP-A-62-101408, JP-A-5-24119 and the like.

As a typical example of this three-dimensional modeling method, light, for example, an ultraviolet laser is selectively used so that a cured layer having a desired pattern can be obtained on the liquid surface of a photocurable liquid substance contained in a container. Irradiation to obtain a cured layer, and then a layer of a photocurable liquid substance is supplied on the cured layer, and then, similarly to the above, light is selectively irradiated to form a cured layer continuous with the above-mentioned cured layer. Form. This is a method of finally obtaining a desired three-dimensional model by repeating this stacking operation. This three-dimensional modeling method has attracted attention because it can easily obtain a desired modeled object in a short time even when the shape of the modeled object to be manufactured is complicated.

[0004]

In the photocurable liquid substance used in such a three-dimensional modeling method, the viscosity in the uncured state is low in order to carry out the modeling rapidly, and when irradiated with various kinds of light. It is required to cure quickly. Further, it is desired that deformation of the molded product such as swelling due to the photocurable liquid substance itself and warpage, shrinkage, and lifting of the overhanging portion due to curing contraction during photocuring is small. Furthermore, the molded object manufactured by this three-dimensional modeling method is used for trial production of models and mechanical parts for studying the design,
In particular, in order to use it for the trial manufacture of mechanical parts, it is required to have fine processing faithful to the design drawing, dimensional accuracy, and sufficient mechanical strength and heat resistance to withstand the operating conditions.

However, a molded article obtained from the photocurable liquid substance up to now has residual strain due to curing shrinkage and the like even after molding, and the molded article after molding gradually deforms over time. was there. This time-dependent deformation has been avoided by correcting the input CAD data, etc., but it has become difficult to deal with it only by correcting the input CAD data as the shape becomes complicated and miniaturized. Further, there has been no photo-curable liquid substance capable of simultaneously achieving mechanical strength, heat resistance and dimensional accuracy of a molded article.

Therefore, the present invention satisfies the above-mentioned characteristics required for the photocurable liquid substance used in the three-dimensional molding method, does not deform the molded article with time after molding, and has mechanical strength, heat resistance and An object of the present invention is to provide a resin composition for optical three-dimensional modeling that can achieve dimensional accuracy at the same time.

[0007]

The present invention provides (A) general formula (1)

[0008]

Embedded image

(In the formula, R ¹ is a linear or branched divalent aliphatic hydrocarbon group having 1 to 12 carbon atoms or 6 to 12 carbon atoms.
12 represents a divalent aromatic hydrocarbon group, and R ² has 1 carbon atom
10 to a linear or branched divalent aliphatic hydrocarbon group or a divalent aromatic hydrocarbon group having 6 to 12 carbon atoms, and n represents a number of 1 to 20). , A urethane (meth) acrylate oligomer obtained by reacting a diisocyanate and a hydroxyl group-containing (meth) acrylate, (B) a urethane (meth) acrylate oligomer obtained by reacting a diisocyanate and a hydroxyl group-containing (meth) acrylate, (C ) A resin composition for optical stereolithography, which comprises an ethylenically unsaturated monomer and (D) a photopolymerization initiator.

The urethane (meth) acrylate oligomer of component (A) used in the present invention (hereinafter referred to as "urethane oligomer (A)") is a diol (a) represented by the general formula (1) or a diisocyanate (roth). ) And a hydroxyl group-containing (meth) acrylate (c) are reacted with each other. Examples of the diol (a) represented by the general formula (1) include ethylene glycol, trimethylene glycol, tetramethylene glycol, pentamethylene glycol, 1,6-hexanediol, 1,7-heptanediol, 1, 8-octanediol, 1,9-nonanediol, 1,10-decanediol, 1,11-undecanediol, 1,12
-Dodecanediol, propylene glycol, butylene glycol, neopentyl glycol, 3-methylpentanediol, 1-methyloctanediol, 1,4-
Dihydric alcohols such as cyclohexanedimethanol, 1,2-dihydroxybenzene, 1,3-dihydroxybenzene, 1,4-dihydroxybenzene and 4,4'-dihydroxybiphenyl, and phthalic acid, isophthalic acid, terephthalic acid, maleic acid , Fumaric acid, oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, sebacic acid and the like. These dihydric alcohols and dibasic acids may be used alone or in combination of two or more. Among these diols (a), a diol obtained by reacting 3-methylpentanediol or neopentyl glycol with isophthalic acid, terephthalic acid or adipic acid is particularly preferable. As the diol thus obtained,
The number average molecular weight (hereinafter, simply referred to as "number average molecular weight") by the hydroxyl group quantification method is 300 to 20,000, particularly 4
It is preferably from 00 to 5,000, more preferably from 500 to 3,000.

Examples of the diisocyanate (b) reacted with the diol (a) include 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate,
1,3-xylylene diisocyanate, 1,4-xylylene diisocyanate, 1,5-naphthalene diisocyanate, p-phenylene diisocyanate, 3,3'-
Dimethyl-4,4'-diphenylmethane diisocyanate, 4,4'-biphenylene diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, dicyclohexylmethane diisocyanate, methylenebis (4-cyclohexylisocyanate), hydrogenated diphenylmethane diisocyanate, 2,2,4-trimethyl Hexamethylene diisocyanate, bis (2-isocyanatoethyl) fumarate, 6-isopropyl-
1,3-phenyl diisocyanate, 4-diphenyl propane diisocyanate, lysine diisocyanate, etc. can be mentioned. Among these diisocyanates, 2,4-tolylene diisocyanate and 2,6-
Tolylene diisocyanate, isophorone diisocyanate, hydrogenated diphenylmethane diisocyanate and the like are preferable.

Examples of the hydroxyl group-containing (meth) acrylate (c) include 2-hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, hydroxybutyl (meth) acrylate,
Hydroxyoctyl (meth) acrylate, pentaerythritol (meth) acrylate, glycerin di (meth) acrylate, dipentaerythritol monohydroxy (meth) acrylate, 1,4-butanediol mono (meth) acrylate, 4-hydroxycyclohexyl (meth) Acrylate, trimethylolpropane di (meth) acrylate, trimethylolethanedi (meth) acrylate, etc. can be used. Further, a compound obtained by an addition reaction of a glycidyl group-containing compound such as alkyl glycidyl ether, allyl glycidyl ether, glycidyl acrylate and (meth) acrylic acid can also be used. Among these, especially 2-
Hydroxyethyl acrylate is preferred.

In addition to the diol (a), diisocyanate (b) and hydroxyl group-containing (meth) acrylate (c), for example, ethylenediamine, tetramethylenediamine, hexamethylenediamine, paraphenylenediamine, 4,4-diaminodiphenylmethane. , A diamine containing a hetero atom, a diamine such as a polyether diamine, and the like can be used in combination. When diamine is used, it is preferably 50% or less of the amount of diol (a) used.

Further, to the extent that the product does not gel, a polyol other than difunctional to diol (a), a polyisocyanate other than difunctional to diisocyanate (b) or a polyamine other than difunctional to diamine Can be used in combination with the diol,
It is 30 parts by weight or less based on 100 parts by weight of the diamine or diisocyanate compound. Examples of the non-bifunctional polyols include, for example, addition products of glycerin and propylene oxide, glycerin, 1,2,3-pentanetriol, 1,2,3-butanetriol, tri (2-hydroxypolyoxypropyl) polyol. Examples thereof include siloxane, polycaprolactone triol, polycaprolactone tetraol, liquid polybutadiene having two or more hydroxyl groups in one molecule, or a hydrogenated product of the polybutadiene. Examples of polyisocyanates other than bifunctional include polymethylene polyphenyl isocyanate, triphenylmethane 4,4 ′,
4 ″ -triisocyanate and the like can be mentioned, and examples of the polyamine other than bifunctional include diethylenetriamine, 1,2,3-triaminopropane, polyoxypropyleneamine and the like.

Urethane oligomer (A) used in the present invention
As a method for producing the above, for example, a diol (a) is reacted with a diisocyanate (b) to produce a polyurethane having an isocyanate group at the end, and a hydroxyl group-containing (meth) acrylate (ha) is reacted therewith. Method: Diisocyanate and hydroxyl group-containing (meth)
Examples thereof include a method in which an acrylate is reacted to produce an intermediate having an isocyanate group at the terminal, and a diol is reacted with this to produce.

The urethane oligomer (A) thus obtained has a number average molecular weight of 600 to 20,000.
0, especially 600 to 5,000, more preferably 800 to 3,000
Those of 0 are preferred.

The urethane oligomer (A) accounts for 10 to 80% by weight, especially 15 to 70% by weight, and further 3% by weight of the total composition.
It is preferable to add 0 to 50% by weight. If it is less than 10% by weight, the toughness of the shaped article is impaired and it tends to be brittle and easily cracked, or it tends to be deformed with time after molding.
If it exceeds 80% by weight, the viscosity of the composition becomes too high,
Deformation at the time of molding tends to be large, and the molded article tends to be soft.

The urethane (meth) acrylate oligomer of component (B) used in the present invention (hereinafter referred to as "urethane oligomer (B)") is a diisocyanate (B).
And hydroxyl group-containing (meth) acrylate (C)
Is obtained by reacting. Examples of the diisocyanate (b) and the hydroxyl group-containing (meth) acrylate (c) used here may be the same as those used in the synthesis of the urethane oligomer (A).

Examples of such urethane oligomer (B) include a reaction product of 2-hydroxyethyl (meth) acrylate and 2,4-tolylene diisocyanate, 2-
A reaction product of hydroxyethyl (meth) acrylate and isophorone diisocyanate, a reaction product of 2-hydroxyethyl (meth) acrylate and hydrogenated diphenylmethane diisocyanate, and the like are preferable. Further, the urethane oligomer (B) preferably has a number average molecular weight of 600 or less, and particularly preferably 300 to 500.

The urethane oligomer (B) accounts for 3 to 70% by weight, particularly 5 to 50% by weight, and further 10 to 10% by weight of the total composition.
It is preferable to add 30% by weight. Below 3% by weight,
This causes inconveniences such as large deformation during molding and softening of the molded article. On the other hand, if it exceeds 70% by weight, there is a tendency that the molded article becomes brittle and easily cracked, or that it is easily deformed with time after molding.

As the ethylenically unsaturated monomer of the component (C) used in the present invention, both a monofunctional monomer and a polyfunctional monomer can be used. Examples of monofunctional monomers include acrylamide, (meth) acryloylmorpholine, 7-amino-3,7-dimethyloctyl (meth) acrylate, isobutoxymethyl (meth) acrylamide, isobornyloxyethyl (meth) acrylate, isobornyl. (Meth) acrylate, 2-ethylhexyl (meth) acrylate, ethyldiethylene glycol (meth) acrylate, t-
Octyl (meth) acrylamide, diacetone (meth)
Acrylamide, dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate,
Lauryl (meth) acrylate, dicyclopentadiene (meth) acrylate, dicyclopentenyl oxyethyl (meth) acrylate, dicyclopentenyl (meth) acrylate, N, N-dimethyl (meth) acrylamidotetrachlorophenyl (meth) acrylate, 2- Tetrachlorophenoxyethyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, tetrabromophenyl (meth) acrylate, 2-tetrabromophenoxyethyl (meth) acrylate, 2-trichlorophenoxyethyl (meth) acrylate, tribromophenyl ( (Meth) acrylate, 2-tribromophenoxyethyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, Cycloalkenyl caprolactam, N- vinyl pyrrolidone, 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, methyl trimethylene diglycol ( Examples thereof include meth) acrylates and compounds represented by the following formulas (2) to (4).

[0022]

[Chemical 3]

(Wherein R ³ represents a hydrogen atom or a methyl group, R ⁴ represents an alkylene group having 2 to 6 carbon atoms, preferably 2 to 4 carbon atoms, R ⁵ represents a hydrogen atom or 1 to 12 carbon atoms,
It is preferably an alkyl group having 1 to 9 and R ⁶ has 2 carbon atoms.
~ 8, preferably 2 ~ 5 alkylene groups, r is 0
~ 12, preferably an integer of 1-8, q is 1-8,
(Preferably an integer of 1 to 4)

Of these, (meth) acryloylmorpholine, isobornyl (meth) acrylate, lauryl (meth) acrylate, vinylcaprolactam,
N-vinylpyrrolidone, phenoxyethyl (meth) acrylate and the like are preferable. As the monofunctional monomer, for example, Aronix M-111, M-113, M-
117 (above, manufactured by Toagosei Kagaku Co., Ltd.), KAYAR
AD TC110S, R-629, R-644 (above,
Commercially available products such as Nippon Kayaku Co., Ltd.) and Viscoat 3700 (Osaka Organic Chemical Co., Ltd.) can also be used.

Examples of polyfunctional monomers include ethylene glycol di (meth) acrylate, dicyclopentenyl di (meth) acrylate, triethylene glycol diacrylate, tetraethylene glycol di (meth) acrylate.
Acrylate, tricyclodecanediyldimethylene di (meth) acrylate, tris (2-hydroxyethyl) isocyanurate di (meth) acrylate, tris (2-hydroxyethyl) isocyanurate tri (meth) acrylate, trimethylolpropane tri (meth) acrylate Acrylate, trimethylolpropane trioxyethyl (meth) acrylate, tripropylene diacrylate, neopentyl glycol di (meth) acrylate, bisphenol A diglycidyl ether both-end (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 (Meth) acrylate, and polyethylene glycol di (meth) acrylate.

Of these, tricyclodecanediyldimethylene di (meth) acrylate, tetraethylene glycol di (meth) acrylate, tripropylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, polyethylene glycol di ( (Meth) acrylate and the like are preferable.

Examples of the polyfunctional monomer include Uupimer UV, SA1002 (all manufactured by Mitsubishi Petrochemical Co., Ltd.), Viscoat 700 (manufactured by Osaka Organic Chemical Co., Ltd.),
KAYARAD R-604, DPCA-20, DPC
A-30, DPCA-120, HX-620, D-31
0, D-330 (above, manufactured by Nippon Kayaku Co., Ltd.), Aronix M-210, Aronix M-215, Aronix M-315, Aronix M-325 (above, Toa Gosei Co., Ltd.) and the like. A commercially available product can also be used.

The ethylenically unsaturated monomer as the component (C) can be used alone or in combination of two or more,
It is preferable to add 20 to 70% by weight, particularly 30 to 50% by weight, and further 30 to 45% by weight in the total composition. Two
If it is less than 0% by weight, the viscosity of the composition becomes too high,
Curability tends to decrease, and if it exceeds 70% by weight,
The shrinkage at the time of hardening becomes large, the strength of the modeled object,
Mechanical properties such as heat resistance tend to decrease.

The photopolymerization initiator of the component (D) used in the present invention starts the polymerization reaction of the urethane oligomer (A), the urethane oligomer (B) and the ethylenically unsaturated bond contained in the ethylenically unsaturated monomer. It is for doing. Such a photopolymerization initiator decomposes upon irradiation with light to generate radicals to initiate polymerization, and examples thereof include acetophenone, acetophenone benzyl ketal, anthraquinone, and 1- (4-isopropylphenyl) -2-hydroxy-2-. Methylpropan-1-one, carbazole, xanthone, 4-chlorobenzophenone, 4,4'-diaminobenzophenone, 1,1-dimethoxydeoxybenzoin, 3,3'-dimethyl-4
-Methoxybenzophenone, thioxanthone compounds,
1- (4-dodecylphenyl) -2-hydroxy-2-
Methylpropan-1-one, 2-methyl-1- [4-
(Methylthio) phenyl] -2-morpholino-propan-1-one, triphenylamine, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, 1
-Hydroxycyclohexyl phenyl ketone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, fluorenone, fluorene, benzyl methyl ketal, benzaldehyde, benzoin ethyl ether, benzoin propyl ether, benzophenone, Michler's ketone, 2-methyl-1 -[4- (Methylthiophenyl)]-2-morpholino-propan-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 Can be mentioned. Of these, 1-hydroxycyclohexyl phenyl ketone, benzyl dimethyl ketal, 2,4,6-trimethylbenzoyldiphenylphosphine oxide and the like are particularly preferable.

The photopolymerization initiator as the component (D) is 0.01 to 10% by weight, particularly 1 to 8% by weight, and further 2% by weight in the total composition.
It is preferable to blend 6 to 6% by weight. If it is less than 0.01% by weight, the curing rate and resolution tend to be lowered, and if it exceeds 10% by weight, the curing characteristics of the composition, the physical properties of the molded article, handling, etc. may be adversely affected.

An epoxy (meth) acrylate oligomer can be further used in combination with the composition of the present invention.

Here, the epoxy (meth) acrylate oligomer is an oligomer obtained by an addition reaction of an epoxy group-containing compound having various skeletons and (meth) acrylic acid. As the epoxy group-containing compound,
For example, a diglycidyl ether type epoxy compound obtained by reacting bisphenol A with epichlorohydrin, a diglycidyl ether compound obtained by reacting hydrogenated bisphenol A with epichlorohydrin,
Examples thereof include phenol novolac polyglycidyl ether. Among these compounds, a glycidyl ether type epoxy compound obtained by reacting bisphenol A with epichlorohydrin is particularly preferable. Further, as the epoxy (meth) acrylate oligomer, for example, a commercially available product such as VISCOAT 540 (manufactured by Osaka Organic Chemical Co., Ltd.) can be used.

The molecular weight of such an epoxy (meth) acrylate oligomer is 100 to 2,000, especially 40.
It is preferably 0 to 1,000. Below 100,
Shrinkage during curing and deformation during molding become large, and the molded article tends to become brittle. When it exceeds 2,000, the viscosity of the composition becomes high, which may make it difficult to handle. This epoxy (meth) acrylate oligomer is preferably added in an amount of 30% by weight or less in the entire composition.

Further, the composition of the present invention contains, in addition to the above-mentioned components, a sensitizing agent containing an amine-based compound such as triethanolamine, methyldiethanolamine, triethylamine, diethylamine, etc., if necessary, within a range not impairing curability. An agent (polymerization accelerator) and a reactive diluent such as vinyl ethers, vinyl sulfides, vinyl urethanes and vinyl ureas can be added. Further, as other additives, epoxy resin, polyamide, polyamideimide, polyurethane, polybutadiene, polychloroprene, polyether, polyester, styrene /
Polymers or oligomers such as butadiene-styrene block copolymers, petroleum resins, xylene resins, ketone resins, fluorine-based oligomers, silicone-based oligomers, polysulfide-based oligomers, phenothiazine, 2,6-di-
Polymerization inhibitors such as t-butyl-4-methylphenol, leveling agents, wettability improvers, surfactants, plasticizers, UV absorbers, silane coupling agents, inorganic fillers, resin particles, pigments, dyes, etc. It can be blended.

The composition of the present invention is produced by uniformly mixing the components (A) to (D) and various additives to be added as necessary. In addition, 25 of the composition of the present invention
Viscosity at ℃ is 100 ~ 5,000cps, especially 30
It is preferably in the range of 0 to 4,000 cps, more preferably 500 to 3,000 cps.

The composition of the present invention as described above is preferably used as a photocurable liquid substance in an optical three-dimensional molding method. That is, visible light in a specific portion of the composition of the present invention,
By selectively irradiating light such as ultraviolet light or infrared light and supplying the energy required for curing, a molded article having a desired shape can be obtained.

The method of selectively irradiating a specific portion of the composition of the present invention with light for curing is not particularly limited, and various methods can be used. For example, a method of irradiating a specific portion with convergent light obtained by using a laser beam or a lens, a mirror, a method of irradiating non-convergent light through a mask having a fixed pattern, and the like can be adopted. However, when fine processing or processing accuracy is required, it is desirable to minimize the size of the converged light, and in such a case, it is preferable to use laser light.

Further, the specific portion of the composition of the present invention which is irradiated with light is the liquid surface of the composition contained in the container, the surface of the composition in contact with the side wall or the bottom wall of the container, or the composition surface. Either is fine. To irradiate the liquid surface of the composition or the contact surface with the container wall, the light may be directly irradiated from the outside or through a transparent container wall, and when irradiating a specific portion in the composition, the light may be irradiated. Irradiation may be performed using a light guide such as a fiber.

Further, in the above-mentioned optical three-dimensional molding method, usually, after curing a specific portion of the composition, the irradiated position is continuously or stepwise moved from the already cured portion to the uncured portion. By doing so, the cured portion can be grown into a desired three-dimensional shape. This irradiation position can be moved by various methods, such as a light source,
It can be carried out by a method of moving at least one of a container containing the composition and a cured portion of the composition, and adding an uncured composition to the container.

As a typical method for obtaining a three-dimensional object using the composition of the present invention, a liquid composition of the present invention is used.
A cured layer is formed by selectively irradiating light so that a cured layer having a desired pattern is obtained, and then the uncured composition adjacent to the cured layer is similarly irradiated with light to first form a cured layer. A method of forming a new cured layer continuous with the molded cured layer and repeating this stacking operation to finally obtain a desired shaped article can be mentioned.

The formed molded article is taken out of the container used for the reaction, and the unreacted composition remaining on the surface of the molded article is removed, and then washed as necessary. Examples of the cleaning agent include organic solvents represented by alcohols such as isopropyl alcohol and ethyl alcohol, and thermosetting or photocurable low viscosity (1000 cps or less, preferably 1
A liquid resin of 00 cps or less) can be used.

When it is desired to impart transparency to the molded article, it is desirable to use the thermosetting or photocurable liquid resin as a cleaning agent. Further, in this case, it is necessary to perform post-curing with heat or light after cleaning, depending on the type of liquid resin used for cleaning. Since the post-cure has the effect of curing not only the liquid resin on the surface but also the unreacted composition that may remain inside the molded article, it was washed with an organic solvent. It is preferable to do this in some cases.

[0043]

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

Production Example 1 100.0 g of isobornyl acrylate and 264.2 of isophorone diisocyanate were placed in a reaction vessel equipped with a stirrer.
g, dibutyltin laurate 1.000 g and 2,6-
1.500 g of di-t-butyl-4-methylphenol was charged. Next, while cooling the reaction vessel, 138.1 g of 2-hydroxyethyl acrylate was added at an internal temperature of 25 ° C.
The mixture was gradually added with stirring so as not to exceed the above. After the addition was completed, stirring was continued for another hour while maintaining the internal temperature at 15 to 35 ° C. Next, poly (3-methylpentane adipate) diol (Kuraray Co., Ltd., trade name Clapol P1
010) 597.7 g was added, and stirring was continued at 50 to 60 ° C. for 6 hours. After confirming that the residual isocyanate group content was 0.2% or less, the content was taken out to obtain a urethane oligomer (A) (number average molecular weight 1,676). The oligomer (A) obtained here is referred to as an oligomer (1). The weight ratio of the oligomer (1) and isobornyl acrylate is 100/10.

Production Example 2 In a reaction vessel equipped with a stirrer, 100.0 g of isobornyl acrylate and 21,4-tolylene diisocyanate 21 were added.
9.6 g, dibutyltin laurate 1.000 g and 2,6-di-t-butyl-4-methylphenol 1.5
00g was charged. Then, while cooling the reaction vessel, 2
146.4 g of -hydroxyethyl acrylate was gradually added while stirring so that the internal temperature did not exceed 25 ° C. After the addition was completed, stirring was continued for another hour while maintaining the internal temperature at 15 to 35 ° C. Next, 634.0 g of poly (3-methylpentane adipate) diol (Kuraray Co., Ltd., trade name Clapol P1010) was added, and 50 to 6 was added.
Stirring was continued at 0 ° C. for 6 hours. After confirming that the residual isocyanate group was 0.1% or less, the content was taken out to obtain a urethane oligomer (A) (number average molecular weight 1
580). The urethane oligomer (A) obtained here is referred to as an oligomer (2). The weight ratio of oligomer (2) to isobornyl acrylate is 100/10.

Production Example 3 In a reaction vessel equipped with a stirrer, 100.0 g of isobornyl acrylate and 489.0 of isophorone diisocyanate were added.
g, dibutyltin laurate 1.000 g and 2,6-
1.500 g of di-t-butyl-4-methylphenol was charged. Next, while cooling the reaction vessel, 255.5 g of 2-hydroxyethyl acrylate was added at an internal temperature of 25 ° C.
The mixture was gradually added with stirring so as not to exceed the above. After completion of the addition, stirring was continued for another hour while maintaining the internal temperature at 15 to 35 ° C. Then, 255.5 g of 2-hydroxyethyl acrylate was added, and stirring was continued at 60 ° C. for 5 hours. After confirming that the residual isocyanate group content was 0.2% or less, the content was taken out to obtain a urethane oligomer (B) (number average molecular weight 454). The urethane oligomer (B) obtained here is referred to as an oligomer (3).
The weight ratio of oligomer (3) to isobornyl acrylate is 100/10.

Production Example 4 100.0 g of isobornyl acrylate and 2,4-tolylene diisocyanate 42 were placed in a reaction vessel equipped with a stirrer.
8.6 g, dibutyltin laurate 1.000 g and 2,6-di-t-butyl-4-methylphenol 1.5
00g was charged. Then, while cooling the reaction vessel, 2
285.7 g of -hydroxyethyl acrylate was gradually added while stirring so that the internal temperature did not exceed 25 ° C. After the addition was completed, stirring was continued for another hour while maintaining the internal temperature at 15 to 35 ° C. Then, 285.7 g of 2-hydroxyethyl acrylate was added, and stirring was continued at 60 ° C. for 5 hours. After confirming that the residual isocyanate group content was 0.1% or less, the content was taken out to obtain a urethane oligomer (B) (number average molecular weight 406). The urethane oligomer (B) obtained here is converted into an oligomer (4)
And The weight ratio of oligomer (4) to isobornyl acrylate is 100/10.

Production Example 5 100.0 g of isobornyl acrylate and 22,4-tolylene diisocyanate 22 were placed in a reaction vessel equipped with a stirrer.
0.3 g, dibutyltin laurate 1.000 g and 2,6-di-t-butyl-4-methylphenol 1.5
00g was charged. Then, while cooling the reaction vessel, 2
146.8 g of -hydroxyethyl acrylate was gradually added while stirring so that the internal temperature did not exceed 25 ° C. After the addition was completed, stirring was continued for another hour while maintaining the internal temperature at 15 to 35 ° C. Next, polyoxytetramethylene diol (Hodogaya Chemical Co., Ltd., trade name PT
G1000) 632.9 g was added, and the mixture was mixed at 50 to 60 ° C. for 6 minutes.
Stirring was continued for hours. After confirming that the residual isocyanate group was 0.1% or less, the content was taken out to obtain a urethane oligomer (number average molecular weight 1580). The urethane oligomer obtained here is referred to as an oligomer (5). The weight ratio of oligomer (5) and isobornyl acrylate is 100/10.

Examples 1 to 4 and Comparative Examples 1 to 4 Each component having the composition shown in Table 1 was placed in a stirring vessel and heated at 50 ° C. for 2 hours.
The composition was obtained by stirring for a time. The compositions of Examples 1 to 4 and Comparative Examples 1 to 4 were all transparent liquids. In addition, Young's modulus, breaking strength and breaking elongation of the cured products of these compositions were measured. Further, the molded article of the composition was measured for warpage and Izod impact strength. The results are shown in Table 1, FIG. 3 and FIG.

Measurement of Young's modulus, breaking strength and breaking elongation: (1) Preparation of test piece Using an applicator, the composition was 250 μm on a glass plate.
A thick film was applied and a cured film was prepared by irradiating with ultraviolet rays of 0.5 J / cm ² with a conveyor curing device equipped with a metal halide lamp. Then, the cured film was peeled from the glass plate, placed on a release paper, and 0.5 J / cm ² of ultraviolet rays was irradiated from the surface opposite to the surface that was first irradiated with ultraviolet rays.
This film was adjusted to a test piece at a relative humidity of 50% for 24 hours. (2) Measurement The Young's modulus of the test piece was measured in a constant temperature and humidity room at 23 ° C. and 50% relative humidity under conditions of a pulling speed of 1 mm / min and a marked line distance of 25 mm. The breaking strength and breaking elongation of the test piece at 23 ° C. were measured under the conditions of a pulling speed of 50 mm / min and a marked line distance of 25 mm.

Warpage measurement: Using a stereolithography apparatus (Solid Creator JSC-2000: manufactured by Sony Corporation) using an Ar ion laser (wavelengths 351 and 365 nm) as a light source, a laser power of 40 mW on the liquid surface and a scanning speed. A model as shown in FIG. 1 (hereinafter referred to as a warpage model) was molded under the condition of 100 cm / sec.
2 mm). After molding, the resin was taken out from the stereolithography apparatus and the adhered resin was wiped off, and post cure was performed using an ultraviolet lamp (irradiation light amount 7.2 J / cm ² ). Then, FIG.
One of them was fixed on a horizontal table as described above, and the amount of lifting Δh (mm) at the other end was measured as the amount of warpage. Furthermore, this warpage model was left in the state of 23 ° C. and 50% relative humidity, and the time-dependent change of the warpage amount was obtained by the same method as above. Measurement of Izod impact strength: A test piece manufactured using the above-described stereolithography apparatus was measured using an ASTM D 256 impact tester.

[0052]

[Table 1]

[0053]

EFFECTS OF THE INVENTION The resin composition for optical three-dimensional modeling of the present invention is capable of simultaneously achieving mechanical strength, heat resistance, and dimensional accuracy of a molded article without deformation with time after molding.

[Brief description of drawings]

FIG. 1 is a diagram showing a warpage model used for measuring a warpage in Examples.

FIG. 2 is a diagram showing a warpage model used for measuring the warpage in Examples.

FIG. 3 is a diagram showing changes over time in the amount of warpage in Examples 1 to 4.

FIG. 4 is a diagram showing changes over time in the amount of warpage in Example 1 and Comparative Examples 1 to 4.

Front page continuation (72) Inventor Takashi Ukaji 2-11-24 Tsukiji, Chuo-ku, Tokyo Japan Synthetic Rubber Co., Ltd.

Claims (1)

[Claims] 1. (A) General formula (1): (In the formula, R ¹ represents a linear or branched divalent aliphatic hydrocarbon group having 1 to 12 carbon atoms or a divalent aromatic hydrocarbon group having 6 to 12 carbon atoms, and R ² represents the number of carbon atoms. 1 to 10 is a linear or branched divalent aliphatic hydrocarbon group or a divalent aromatic hydrocarbon group having 6 to 12 carbon atoms, and n is 1 to 2
A urethane (meth) acrylate oligomer obtained by reacting a diisocyanate and a hydroxyl group-containing (meth) acrylate, (B) diisocyanate and a hydroxyl group-containing (meth) acrylate. An optical three-dimensional modeling resin composition containing the resulting urethane (meth) acrylate oligomer, (C) an ethylenically unsaturated monomer, and (D) a photopolymerization initiator.