JP2811358B2 - Optical three-dimensional molding resin composition - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Application Field] The present invention relates to an optical device that provides a molded article having a low viscosity in an uncured state, a high curing rate upon light irradiation, and a small change in physical properties over a wide temperature range. And a resin composition for three-dimensional modeling.

(Prior art) Optical stereolithography is, for example, as described in JP-A-60-247515, by selectively performing energy supply necessary for curing a photocurable liquid material, This is a method of forming a three-dimensional structure having a desired shape. A similar method or an improved technique thereof is disclosed in US Pat. No. 4,575,330 (JP-A-6
2-35966) and JP-A-62-101408. A typical example of the three-dimensional molding method is to selectively irradiate light, for example, an ultraviolet laser, on a liquid surface of a photocurable liquid material placed in a container so as to obtain a cured layer having a desired pattern. And then supply a layer of the photocurable liquid material on the cured layer, and then selectively irradiate light as described above to obtain a laminated layer continuous with the cured layer. There is a method of finally obtaining a desired three-dimensional object by repeating the operation. This three-dimensional molding method has attracted attention because a desired molded object can be obtained easily and in a short time even when the shape of the molded object to be manufactured is complicated.

Conventionally, examples of the photocurable liquid substance used in the three-dimensional molding method include resins such as modified polyurethane methacrylate, oligoester acrylate, urethane acrylate, epoxy acrylate, photosensitive polyimide, and aminoalkyd (Japanese Patent Application Laid-Open No. 60-247515). No.).

[Problems to be solved by the invention]

In the resin used for such a three-dimensional molding method,
For rapid molding, the viscosity in the uncured state is low,
When irradiated with various kinds of light, it is required to be rapidly cured. Furthermore, molded objects manufactured by this three-dimensional molding method are used for prototypes of models and mechanical parts for examining designs, etc., especially when used for trial production of mechanical parts, these mechanical parts are widely used. Since it is used in a temperature range, it is required that a molded article can be used in a wide temperature range and that a change in physical properties is small.

However, none of the conventional optical three-dimensional modeling resins has a low viscosity when uncured, is quickly cured by light irradiation, and has a sufficiently small change in the physical properties of the molded article from a low temperature range to a high temperature range.

Accordingly, the present invention provides an optical three-dimensional modeling resin composition that satisfies all of the physical properties required for an optical three-dimensional modeling resin, and that has a small change in the elastic modulus of the molded article particularly over a wide temperature range. Aim.

[Means for solving the problem]

The present invention provides a resin composition for optical stereolithography, comprising: (A) a silicone urethane (meth) acrylate; (B) a compound having a polyfunctional ethylenically unsaturated bond; and (C) a polymerization initiator. Is provided.

The silicone urethane (meth) acrylate (hereinafter referred to as “compound (A)) as the component (A) used in the present invention is obtained, for example, by reacting a polyol having a polysiloxane structure, a diisocyanate, and a (meth) acrylate having a hydroxyl group. Can be obtained,
The following method is mentioned as a specific example.

(Production Method 1) A method of reacting a hydroxyl group-containing (meth) acrylate with an isocyanate group of an intermediate product obtained by reacting a polyol having a polysiloxane structure with a diisocyanate.

(Production Method 2) A method of reacting a polyol having a polysiloxane structure with an isocyanate group of an adduct obtained by reacting a diisocyanate with a (meth) acrylate having a hydroxyl group.

(Production Method 3) A method of simultaneously reacting a diisocyanate, a polyol having a polysiloxane structure, and a (meth) acrylate having a hydroxyl group.

As a polyol having a polysiloxane structure,
For example, the following compounds (1) and (2) are mentioned.

(Wherein, R ₁ represents a methyl group or a phenyl group; R ₂ and R ₃ each represent an alkylene group having 1 to 12 carbon atoms;
Represents 1 to 500, m represents 0 to 500, x represents 1 to 6, y represents
Represents 0 to 6) (Wherein R ₁ , R ₂ , l and m are as described above, n is 2 to 500, preferably l + m is 5 to 200, and n is 2 to 2
These polyols having a polysiloxane structure include, for example, FM4411, FM4421, and FM4425 (hereafter, Chisso Corporation), Q4-3367, Q2-8026 (hereafter, Toray Silicone Corporation) KF6001, KF6002, and KF6003. (Above, Shin-Etsu Silicone Co., Ltd.) and 1248 FLUID (Dow Corning Co., Ltd.).

As the diisocyanate, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate,
Isophorone diisocyanate, 1,3-xylylene diisocyanate, 1,4-xylylene diisocyanate, 1,5-
Naphthalene diisocyanate, m-phenylene diisocyanate, p-phenylene diisocyanate, 3,3'-
Dimethyl-4,4'-diphenylmethane diisocyanate, 4,4'-diphenylmethane diisocyanate, 3,3 '
-Dimethylphenylene diisocyanate, 4,4'-biphenylene diisocyanate, hexamethylene diisocyanate, dicyclohexylmethane diisocyanate, methylene bis (4-cyclohexyl isocyanate), hydrogenated diphenylmethane diisocyanate, hydrogenated bisphenol A diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate , Bis (2-isocyanatoethyl) fumarate, 6-isopropyl-1,3-phenyl diisocyanate, 4-diphenylpropane diisocyanate and the like. Among these diisocyanates, 2,4-tolylene diisocyanate, isophorone diisocyanate, hydrogenated bisphenol A diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate and the like are preferable, and particularly preferable are isophorone diisocyanate, 2,4 -Tolylene diisocyanate.

Examples of the (meth) acrylate having a hydroxyl group include 2-hydroxyethyl (meth) acrylate and 2-hydroxyethyl (meth) acrylate.
Hydroxyalkyl (meth) acrylates such as hydroxypropyl (meth) acrylate, polyethylene glycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate, trimethylolpropane di (meth) acrylate, trimethylolethanedi (meth) acrylate, penta Erythritol tri (meth) acrylate, dipentaerythritol tripenta (meth) acrylate, 1,4-butanediol mono (meth) acrylate, 4-hydroxycyclohexyl (meth) acrylate, 1,6-hexanediol mono (meth) acrylate, Neopentyl glycol mono (meth) acrylate, glycerin di (meth) acrylate, (meth) acrylate represented by the following structural formulas (3) to (5), and alkyl group Glycidyl ether, allyl glycidyl ether, and compounds obtained by addition reaction of glycidyl (meth) glycidyl group-containing compounds such as acrylates and (meth) acrylic acid.

(Wherein, R ₄ represents a hydrogen atom or a methyl group) (Wherein, R ₄ is the same as described above, and p is 1 to 5) (In the formula, R ₄ is the same as described above.) Among these (meth) acrylates having a hydroxyl group, preferred is hydroxyethyl (meth)
Examples include acrylate, hydroxypropyl (meth) acrylate, hydroxybutyl (meth) acrylate, and (meth) acrylate represented by the structural formula (4).

 A preferred embodiment of the production method 1 will be described.

Hydroxyl group 1 of polyol having polysiloxane structure
The amount of diisocyanate used per equivalent is about 0.5 to
Preferably it is 1 mole. In this reaction, the reaction is usually performed using a catalyst such as copper naphthenate, cobalt naphthenate, zinc naphthenate, dibutyltin dilaurate, triethylamine or the like in an amount of 0.01 to 1 part by weight based on 100 parts by weight of the total amount of the reactants. The reaction temperature in this reaction is usually 0 to 80 ° C. In addition, the amount of the (meth) acrylate having a hydroxyl group is such that the hydroxyl group is about 0.8 to 1.2 equivalent relative to 1 equivalent of the isocyanate group of the intermediate product, and the reaction conditions are the same as the synthesis conditions of the intermediate product. The same is true.

 Next, a preferred embodiment of the production method 2 will be described.

0.5 to 1.0 mol of a (meth) acrylate having a hydroxyl group is reacted with 1 mol of the diisocyanate under the same reaction conditions as in Production Method 1. With respect to 1 equivalent of the isocyanate group of the adduct obtained, the hydroxyl group of the diol having a polysiloxane structure is reacted. And the reaction is carried out under the same reaction conditions as in Production Method 1.

 Next, a preferred embodiment of the production method 3 will be described.

The amount of the diisocyanate used per equivalent of the hydroxyl group of the diol having a polysiloxane structure is 0.5 to 1 mol, and the amount of the (meth) acrylate having a hydroxyl group is the total amount of the diol having a polysiloxane structure including the hydroxyl group. The amount of hydroxyl groups is adjusted to 0.9 to 1.1 times the equivalent of all isocyanate groups of the diisocyanate.

In the present invention, the compound (A) obtained as described above has a weight average molecular weight (hereinafter referred to as “「 ”).
Is usually from 500 to 30,000, preferably from 1,000 to 10,000. When the ▲ ▼ of the compound (A) is less than 500,
The elongation at break of the cured product of the obtained composition is reduced, and the toughness is easily reduced. On the other hand, if the amount exceeds 00030,000, the viscosity of the resulting composition becomes high, making it difficult to handle, and the fluidity is impaired, so that the production speed of the shaped article is reduced.

The proportion of the polysiloxane structure in the compound (A) is usually from 50 to 99% by weight, preferably from 60 to 98% by weight.

In the present invention, the compounding ratio of the compound (A) in the resin composition is usually 10 to 80% by weight, preferably 15 to 70% by weight.
It is. If the amount is less than 10% by weight, the elongation at break of the obtained cured product tends to decrease, and if it exceeds 80% by weight, the elastic modulus of the cured product near room temperature tends to decrease.

In the composition of the present invention, a urethane (meth) acrylate other than the compound (A) can be used in combination as long as the effects of the present invention are not impaired. As the urethane (meth) acrylate other than the compound (A), a compound selected from polytetramethylene polyol, polypropylene polyol, polybutylene polyol, polyethylene polyol, polycaprolactone polyol, polycarbonate polyol and polyester polyol has the diisocyanate and the hydroxyl group. Urethane (meth) acrylate obtained by reacting with (meth) acrylate can be mentioned.

Examples of the compound having a polyfunctional ethylenically unsaturated bond (hereinafter, referred to as “compound (B)”) of the component (B) used in the present invention include ethylene glycol di (meth) acrylate and dicyclopentenyl di (meth). ) Acrylate, tetraethylene glycol di (meth) acrylate, tris (2-hydroxyethyl) isocyanurate di (meth) acrylate, tris (2-
(Hydroxyethyl) isocyanurate tri (meth) acrylate, trimethylolpropane tri (meth) acrylate, trimethylolpropane trioxyethyl (meth) acrylate, neopentyl glycol di (meth)
Acrylate, bisphenol A diglycidyl ether at both ends (meth) acrylic acid adduct, 1,4-butanediol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, pentaerythritol tri (meth) acrylate, Examples include pentaerythritol tetra (meth) acrylate, polyester di (meth) acrylate, and polyethylene glycol di (meth) acrylate. Commercial products include Copimer UV, SA20
07 (Mitsubishi Yuka Co., Ltd.), Viscort 700 (Osaka Organic Chemical Co., Ltd.), KAYARAD R-604, DPCA-20, -30, -60,
-120, HX-620, D-310, D-330 (Nippon Kayaku Co., Ltd.), Aronix M-210, M-215, M-315, M-325
(Above, Toa Gosei Chemical Co., Ltd.).

In the present invention, the compounding ratio of the compound (B) in the resin composition is usually 10 to 80% by weight, preferably 15 to 70% by weight.
It is. If it is less than 10% by weight, the curability tends to decrease and the elastic modulus at around room temperature tends to decrease.
If the content exceeds 10% by weight, the elongation at break of the cured product tends to decrease.

The polymerization initiator of the component (C) in the present invention (hereinafter, referred to as “compound (C)”) is not particularly limited, but a photopolymerization initiator or a thermal polymerization initiator can be used.

Compound (C) includes acetophenone, acetophenone diethyl ketal, anthraquinone, 1- (4-isopropylphenyl) -2-hydroxy-2-methylpropan-1-one, carbazole, xanthone, 4-chlorobenzophenone, 4,4 ′ -Diaminobenzophenone, 3,3-dimethyl-4-methoxybenzophenone, 2,2
-Dimethoxy-2-phenylacetophenone, 4,4'-
Dimethoxybenzophenone, thioxanthone compounds,
1- (4-dodecylphenyl) -2-hydroxy-2-
Methylpropan-1-one, 2-methyl-1- (4-methylthio) phenyl) 2-morpholino-propane-1
-One, triphenylamine, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, 1-hydroxycyclohexylphenyl ketone, 2-hydroxy-2
-Methyl-1-phenylpropan-1-one, fluorenone, fluorene, benzyldimethyl 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 BTTB with xanthene, thioxanthene, coumarin, ketocoumarin and other Photopolymerization initiators such as combinations of dye sensitizers; benzoin peroxide, t-butylperoxybenzoate, dicumyl peroxide, 2,4-dichlorobenzoyl peroxide, t-butyl peroxide, azobisisobutyronitrile And the like.

Of these, 1-hydroxycyclohexylphenyl ketone, benzyldimethyl ketal, 2,4,6-trimethylbenzoylphenylphosphine oxide and the like are preferable.

When a thermal polymerization initiator is used, it is preferable to use infrared rays as radiation.

The compounding ratio of the compound (C) in the resin composition of the present invention is usually 0.05 to 10% by weight, preferably 0.1 to 8% by weight, particularly preferably 0.5 to 5% by weight. 10% by weight
If it exceeds 30, the properties of the cured product, cured properties, handleability, etc. may be adversely affected, and if it is less than 0.05% by weight, the curing speed may decrease.

If necessary, a sensitizer (polymerization accelerator) such as an amine compound such as triethanolamine, methyldiethanolamine, triethylamine or diethylamine may be used in combination with the compound (C) as long as the curing of the present invention is not hindered. Can be.

In the composition of the present invention, a reactive diluent having a monofunctional ethylenically unsaturated group can be used, if necessary, in addition to the compound (A), the compound (B) and the compound (C). Examples of the monofunctional compound used here include acrylamide, 7-amino-3,7-dimethyloctyl (meth) acrylate, isobutoxymethyl (meth) acrylamide, isobornyloxyethyl (meth) acrylate, isobornyl (meth) A) acrylate, 2-ethylhexyl (meth) acrylate, ethyldiethylene glycol (meth) acrylate, t-octyl (meth) acrylamide, diacetone (meth) acrylamide, dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate, dicyclopentadiene (Meth) acrylate, dicyclopentenyloxyethyl (meth) acrylate, dicyclopentenyl (meth) acrylate, N, N-dimethyl (meth) acrylamide, tetrachlorophen Le (meth) acrylate, 2-tetrachloro-phenoxyethyl (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, 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, (meth) acryloylmorpholine, methyltriethylenediglycol (meth) ) Acrylate and compounds represented by the following structural formulas (6) to (8).

(Wherein, R ₄ is the same as described above, R ₅ represents an alkylene group having 2 to 6 carbon atoms, preferably 2 to 4 carbon atoms, and R ₆ represents a hydrogen atom or 1 to 12 carbon atoms, preferably 1 to 9 carbon atoms. And r represents 0 to 12, preferably 1 to 8) (Wherein, R ₄ is the same as described above, R ₇ represents an alkylene group having 2 to 8, preferably 2 to 5 carbon atoms, and q represents 1 to 8, preferably 1 to 4) (In the formula, R ₄ , R ₇ and q are the same as described above.) As commercial products, Aronics M111, M113, M114, M
117 (Toa Gosei Chemical Co., Ltd.), KAYARAD TC110S, R6
29, R644 (Nippon Kayaku Co., Ltd.), Viscort 3700
(Osaka Organic Chemical Co., Ltd.).

Further, as a reactive diluent, vinyl ethers, vinyl sulfides, vinyl urethanes, vinyl ureas and the like can also be used.

In addition, the resin composition of the present invention may further include an epoxy resin, polyamide, polyamide imide, polyurethane, polybutadiene, polychloroprene, polyether, polyester, styrene / butadiene / styrene block copolymer as necessary as other additives. And a polymer or oligomer such as styrene / isoprene / styrene block copolymer. Petroleum resins, xylene resins, ketone resins, fluorine oligomers, silicone oligomers, polysulfide oligomers and the like can also be blended. A polymerization inhibitor such as phenothiazine and 2,6-di-t-butyl-4-methylphenol may be added. Furthermore, various additives other than the above, for example, sensitizers, polymerization initiators, leveling agents, wetting improvers, surfactants, plasticizers, ultraviolet absorbers, silane coupling agents, inorganic fillers, resin particles, pigments , A dye or the like.

The viscosity of the resin composition of the present invention is usually 20 to 5000 cps (2
5 ° C.), preferably 20 to 2000 cps, particularly preferably 20 to 50 cps.
It is 0cps.

The resin composition of the present invention can be suitably used as a curable liquid substance in an optical three-dimensional printing method. That is, the resin composition of the present invention is selectively irradiated with light such as visible light, ultraviolet light, or infrared light to a specific portion to supply energy required for curing, thereby obtaining a three-dimensional molded article having a desired shape. be able to. The method of selectively irradiating light to a specific portion of the resin composition is not limited. For example, a method of irradiating a specific portion with laser light, a focused light obtained using a lens, a mirror, or the like, a method of irradiating a specific portion, Through a mask having a fixed pattern. However, it is preferable to minimize the size of the converging light when emphasizing micro-processability, which is a part of the characteristics of the resin composition of the present invention, and processing accuracy. It is preferred to use. Further, the specific portion to be irradiated with light may be a liquid surface of the resin composition placed in the container, a surface in contact with a side wall or a low wall of the container, or a liquid. To irradiate the liquid surface of the resin composition or the contact surface with the container wall, the light may be irradiated directly from the outside or through a transparent container wall, and to irradiate a specific portion of the liquid with light, For example, the light can be emitted by a light guide such as an optical fiber.

In this optical three-dimensional molding method, usually, after a desired specific portion is cured, the irradiated position is continuously and stepwise moved from the cured portion to the uncured portion adjacent thereto, thereby curing the cured portion. Can be grown into a desired three-dimensional shape. Various methods of moving the irradiation position are possible,
For example, a method of moving one or more of the light source, the container, and the cured portion, or adding an uncured liquid curable substance to the container may be used.

As a typical method for obtaining a molded article from the resin composition of the present invention, the cured layer is selectively irradiated with light so as to obtain a cured layer having a desired pattern on the liquid composition of the present invention. Formed, then repeat the laminating operation to newly form a cured layer continuous with the cured layer by irradiating light to the uncured composition layer adjacent to the cured layer in the same manner as described above. To obtain a three-dimensional, that is, a three-dimensionally shaped object.

The following are examples of more specific embodiments of the above method.

After the first cured layer is formed, the uncured composition for the next cured layer is additionally supplied on the obtained first cured layer,
A method of repeating the operation of irradiating light to form the next cured layer.

Submerging the bottom plate in the composition by the depth of the first hardened layer,
After the first cured layer is formed, the bottom plate is further submerged by a further depth to allow one layer of the uncured composition to flow onto the first cured layer, and further irradiate light. A method of repeating the operation of forming the next cured layer.

A box having a transparent bottom plate is submerged in the composition contained in the container, and the composition layer formed in the gap between the bottom plate and the bottom surface of the container is made to have the same thickness as the first cured layer. Irradiating the composition layer with light through a transparent bottom plate of a box,
After forming a cured layer, the box is raised to allow the composition to flow into the gap between the first cured layer and the transparent bottom plate of the box,
A method of repeating the operation of forming the next cured layer by irradiating light in the same manner.

The plate is submerged in a composition placed in a container having a transparent bottom, and the composition layer formed in the gap between the plate and the bottom surface of the container is made to have the same thickness as the first cured layer. Irradiating the composition layer with light through a transparent bottom of a container to form a first cured layer, and then raising the plate by one thickness to obtain one layer of the uncured composition. In the gap between the first hardened layer and the plate, and then irradiating with light in the same manner as described above to form a next hardened layer.

The three-dimensional object formed by the above methods 1 to 3 is removed from the container used for the reaction, and after removing unreacted compounds remaining on the surface of the three-dimensional object, washing is performed as necessary. As a cleaning agent used for cleaning, an organic solvent typified by alcohols such as isopropyl alcohol or a thermosetting or photocurable low-viscosity resin can be used. If you want to give transparency to three-dimensional objects,
It is preferable to use the above-mentioned thermosetting or photosetting resin for cleaning. In this case, it is necessary to perform post-curing by heat or light after cleaning, depending on the type of resin used for cleaning. In addition, since the post cure not only cures the resin on the surface but also cures the unreacted resin composition that may remain inside the three-dimensional structure, the post cure is also effective in the case of washing with an organic solvent. It is preferred to do so.

〔Example〕

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

Production Example 1 25.8 g of tricyclodecane dimethanol diacrylate, 34.8 g of 2,4-tolylene diisocyanate, 0.4 g of dibutyltin dilaurate, 0.3 g of phenothiazine and 2,6-di-t-butyl-4-methylphenol were placed in a reaction vessel. 0.2g was charged. Then, while cooling the reaction vessel with ice water, 23.2 g of hydroxyethyl acrylate was added thereto at an internal temperature of 25 ° C.
The internal solution was added while stirring so as not to exceed.

After completion of the addition, stirring was continued for 1 hour while maintaining the internal temperature at 5 to 25 ° C., and then silicone diol (（2,000) (K
200 g of F6001 (Shin-Etsu Silicone) were added while stirring the internal solution so that the internal temperature did not exceed 60 ° C. After completion of the addition, stirring was continued until the residual isocyanate groups became 0.1% by weight or less of the charged amount, to obtain a silicone urethane acrylate of 2600. The obtained silicone urethane acrylate solution of tricyclodecane dimethanol diacrylate is referred to as oligomer (1). The weight ratio of silicone urethane acrylate to tricyclodecane dimethanol diacrylate is 10: 1.

Production Example 2 Isobornyl acrylate 56.8 g, isophorone diisocyanate 44.4 g, silicone diol (▲
▼ 5,000) (FM4421 Chisso Corporation) 500 g, phenothiazine 0.6 g and 2,6-di-t-butyl-4-methylphenol 0.4 g were charged. Next, 0.8 g of dibutyl dilaurate was added to the reaction vessel while cooling the reaction vessel with ice water.
The internal solution was added with stirring so as not to exceed 30 ° C.

After completion of the addition, stirring was continued for 1 hour while maintaining the internal temperature at 40 to 50 ° C, and then 23.2 g of hydroxyethyl acrylate was added while stirring the internal solution so that the internal temperature did not exceed 60 ° C. Thereafter, the internal temperature was maintained at 60 ° C., and stirring was continued until the residual isocyanate groups became 0.1% by weight or less of the charged amount, to obtain a silicone urethane acrylate of ▲ ▼ 5700. The resulting solution of silicone urethane acrylate in isobornyl acrylate is referred to as oligomer (2).
The weight ratio of silicone urethane acrylate to isobornyl acrylate is 10: 1.

Production Example 3 109.9 g of isobornyl acrylate, 66.46 g of isophorone diisocyanate, silicone diol (▲
(5,000) (1000 g of FM4421 Chisso Corporation, 0.8 g of phenothiazine and 0.5 g of 2,6-di-t-butyl-4-methylphenol.) Then, while cooling the reaction vessel with ice water, dibutyltin was added thereto. 1.0 g of dilaurate was added while stirring the internal solution so that the internal temperature did not exceed 30 ° C.

After completion of the addition, stirring was continued for 1 hour while maintaining the internal temperature at 40 to 50 ° C, and then 23.2 g of hydroxyethyl acrylate was added while stirring the internal solution so that the internal temperature did not exceed 60 ° C. Thereafter, the internal temperature was maintained at 60 ° C., and stirring was continued until the residual isocyanate groups became 0.1% by weight or less of the charged amount, to obtain 10,900 syringurethane acrylate. The resulting solution of silicone urethane acrylate in isobornyl acrylate is referred to as oligomer (3). The weight ratio of silicone urethane acrylate to isobornyl acrylate is 10: 1.

Production Example 4 Isobornyl acrylate 200 g, 2,4-toe
79 g of rearylene diisocyanate, hydroxyl-containing polymer
Cylsiloxane (▲ ▼ 5,700) (DOW CORNING  128
4 FLUID, Dow Corning Co., Ltd.) 868 g, Phenocia
0.8 g of gin and 2,6-di-t-butyl-4-methylphen
0.5 g of knoll was charged. The reaction vessel is then cooled with ice water
While adding 1.0 g of dibutyltin dilaurate to the internal temperature
The internal solution was added with stirring so as not to exceed 20 ° C.

After completion of the addition, the internal temperature was maintained at 20 to 30 ° C., and stirring was continued for 1 hour. Then, 53 g of hydroxyethyl acrylate was added while stirring the internal solution so that the internal temperature did not exceed 60 ° C.
Thereafter, the internal temperature was maintained at 60 ° C., and stirring was continued until the residual isocyanate groups became 0.1% by weight or less of the charged amount.
▼ 6,600 silicone urethane acrylates were obtained. The obtained isobornyl acrylate solution of silicone urethane acrylate is referred to as oligomer (4). The weight ratio of silicone urethane acrylate to isobornyl acrylate is 5: 1.

Comparative Production Example 1 25.8 g of tricyclodecane dimethanol diacrylate, 34.8 g of 2,4-toluene diisocyanate, 0.4 g of dibutyltin dilaurate, 0.3 g of phenothiazine and 2,6-di-t-butyl-4-methylphenol were placed in a reaction vessel. 0.2g was charged. Then, while cooling the reaction vessel with ice water, 23.2 g of hydroxyethyl acrylate was added thereto at an internal temperature of 25 ° C.
The internal solution was added while stirring so as not to exceed.

After completion of the addition, stirring was continued for 1 hour while maintaining the internal temperature at 5 to 25 ° C., and then polytetramethylene glycol (▲ ▼)
2,000) 200 g was added while stirring the internal solution so that the internal temperature did not exceed 60 ° C. Thereafter, stirring was continued until the residual isocyanate groups became 0.1% by weight or less of the charged amount. The resulting solution of the polytetramethylene glycol urethane acrylate oligomer of 2600 in tricyclodecane dimethanol diacrylate is designated as oligomer (5). The weight ratio of polytetramethylene glycol urethane acrylate to tricyclodecane dimethanol diacrylate is 10: 1.

Examples 1 to 5 and Comparative Examples 1 and 2 The components shown in Table 1 below were stirred at 40 to 50 ° C. for 2 hours to obtain a transparent resin composition.

Test Example Using each of the resin compositions obtained in Examples 1 to 5 and Comparative Examples 1 and 2, a test piece was prepared according to the following method, and Young's modulus, elongation at break, and dynamic viscoelasticity were measured. .
Table 2 shows the results.

(1) Preparation of test piece A resin composition was placed on a glass plate using an applicator.
The composition was applied to a thickness of 0 μm and irradiated with ultraviolet rays of 0.5 J / cm ² (wavelength: 350 nm) to obtain a cured film. Next, the cured film was peeled off from the glass plate, and the condition was adjusted at 23 ° C. and a relative humidity of 50% for 24 hours to obtain a test piece.

(2) Measurement of Young's modulus and elongation at break The Young's modulus of the test piece at −40 ° C., 23 ° C. and 60 ° C. was measured by a tensile tester equipped with a thermostatic chamber at a pulling speed of 1 mm / min and a gap of 25 mm between marked lines. And the breaking elongation of the test piece at 23 ° C. was measured at a tensile speed of 50 mm / min and a mark line of 25 mm.
It measured on condition of.

(3) Dynamic Viscoelasticity Measurement The test specimen was measured for storage elastic modulus (E ′) using a dynamic viscoelasticity tester (Vibron, Toyo Baldwin Co., Ltd.). The heating rate was 2 ° C./min, and the frequency was 35 Hz.

(Effect of the Invention) The resin composition for optical three-dimensional modeling of the present invention has a characteristic that the viscosity is low and the molded article has little change in physical properties in a wide temperature range, and is suitable as the resin composition for optical three-dimensional modeling. It is.

Continued on the front page (72) Inventor Fumie Nozawa 2-11-24 Tsukiji, Chuo-ku, Tokyo Japan Synthetic Rubber Co., Ltd. (72) Inventor Katsutoshi 2-11-24 Tsukiji, Chuo-ku, Tokyo Japan Synthetic Rubber Stock In-company (72) Inventor Edward Jay. Murphy United States 60005 South Michelle, Arlington Heights, Illinois 742 (56) References JP-A-3-199216 (JP, A) (58) Fields studied (Int. Cl. ⁶ , DB name) C08F 290/00 -290/06 C08F 299/08

Claims (1)

(57) [Claims] 1. A resin composition for optical stereolithography comprising: (A) a silicone urethane (meth) acrylate; (B) a compound having a polyfunctional ethylenically unsaturated bond; and (C) a polymerization initiator. Stuff.