JP2731363B2 - Optical three-dimensional molding resin composition - Google Patents

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 cured by light irradiation, has excellent impact resistance, can obtain a highly accurate molded article, and has less deformation due to warpage after molding. The present invention relates to a resin composition for optical three-dimensional shaping that can be used.

[0002]

2. Description of the Related Art Optical stereolithography is described in, for example,
As disclosed in Japanese Patent Application Laid-Open No. 0-247515, this is a method of selectively supplying energy required for a photocurable liquid material to form a shaped article having a desired shape. Such a method and its improved technology are described in US Pat.
No. 5,330 (JP-A-62-35966), JP-A-62-101408, JP-A-5-24119, and the like.

As a typical example of the three-dimensional molding method, light, for example, an ultraviolet laser is selectively applied to a liquid surface of a photocurable liquid material placed in a container so as to obtain a cured layer having a desired pattern. Irradiation to obtain a cured layer, then supply a photocurable liquid material on the cured layer in a layered form, and then selectively irradiate light as described above to form a cured layer continuous with the cured layer. Form. This is a method of finally obtaining a desired three-dimensional structure by repeating this laminating operation. This three-dimensional molding method has attracted attention because a target molded object can be easily and quickly obtained even when the shape of the molded object to be produced is complicated.

[0004]

The photocurable liquid material used in such a three-dimensional molding method has a low viscosity in an uncured state in order to rapidly perform the molding, and has a low viscosity when irradiated with various lights. It is required to cure quickly. Further, it is desired that deformation such as warping, shrinkage, or lifting of the overhang portion due to swelling of the molded article due to the photocurable liquid material itself or curing shrinkage during photocuring is small. In addition, molded objects manufactured by this three-dimensional molding method are used for prototypes of models and mechanical parts for studying designs, etc.
In particular, in order to use it for trial production of mechanical parts, it is required to have fine mechanical processing faithful to a design drawing, sufficient dimensional accuracy, and sufficient mechanical strength and heat resistance to withstand use conditions.

[0005] However, a molded product obtained from a conventional photocurable liquid material still has a residual strain due to curing shrinkage and the like even after molding, and the molded product after molding gradually deforms over time. was there. This temporal deformation has been avoided by, for example, correcting the input CAD data, but it has become difficult to cope with only the correction of the input CAD data as the shape becomes complicated and miniaturized. Further, there has not been a photocurable liquid material capable of simultaneously realizing the mechanical strength, heat resistance, and dimensional accuracy of a molded article.

Accordingly, the present invention satisfies the above-mentioned properties required for a photocurable liquid material used in a three-dimensional molding method, does not cause temporal deformation of the molded article after molding, and provides a mechanical strength, heat resistance and heat resistance of the molded article. It is an object of the present invention to provide an optical three-dimensional modeling resin composition that can simultaneously achieve dimensional accuracy.

[0007]

According to the present invention, there is provided (A) a compound represented by the following general formula (1):

[0008]

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Wherein R represents a linear or branched divalent aliphatic hydrocarbon group having 1 to 12 carbon atoms, and n represents 1 to 2
5), a urethane (meth) acrylate oligomer obtained by reacting a diisocyanate and a hydroxyl group-containing (meth) acrylate, (B) diisocyanate, hydroxyl group-containing (meth) acrylate and monofunctional alcohol Urethane (meth) acrylate oligomer obtained by reacting an equimolar mixture of (E), (C) an ethylenically unsaturated monomer, and (D) a formula (2)

[0010]

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[0011] It is an object of the present invention to provide a resin composition for optical stereolithography containing a photopolymerization initiator represented by the following formula:

The urethane (meth) acrylate oligomer (hereinafter referred to as "urethane oligomer (A)") as the component (A) used in the present invention comprises a diol (a) and a diisocyanate (b) represented by the above general formula (1). ) And a hydroxyl group-containing (meth) acrylate (c).

Here, as the diol (a) represented by the general formula (1), as R, for example, ethylene glycol, trimethylene glycol, tetramethylene glycol, pentamethylene glycol, 1,6-hexanediol, 1,7- Heptamethylenediol, 1,8-octanediol, 1,9-nonanediol, 1,10-decanediol, 1,11-undecanediol, 1,12-dodecanediol, propylene glycol, butylene glycol, diethylene glycol, neopentyl glycol Coat, 2-methyl-2-propylpropanediol, 3-
Examples thereof include polycarbonate esters of dihydric alcohols such as methylpentanediol and 1-methyloctanediol. Even if these dihydric alcohols are used alone,
More than one species may be used in combination. Among these diols, in particular, 1,6-hexanediol, 1,9-nonanediol, 3
Diols obtained from polycarbonates of dihydric alcohols such as -methylpentanediol are preferred.

The diol thus obtained has a number-average molecular weight (hereinafter, simply referred to as "number-average molecular weight") of 300 to 20,000, particularly 400 to 5,000, and more preferably 500 to 3,000 as determined by the method for determining hydroxyl terminal ends. Is preferred. Commercial products of these diols include Nipporan 980, Nipporan 981, and Nipporan 98
2, Nipporan 983 (above, manufactured by Nippon Polyurethane Industry Co., Ltd.), PNOC, PMD (above, manufactured by Kuraray Co., Ltd.) and the like.

Examples of the diisocyanate (b) to be reacted with the diol (a) include, for example, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate,
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, methylene bis (4-cyclohexyl isocyanate), hydrogenated diphenylmethane diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, bis (2-isocyanato Ethyl) fumarate, 6-isopropyl-1,3
-Phenyl diisocyanate, 4-diphenylpropane diisocyanate, lysine diisocyanate and the like. Among these diisocyanates, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, isophorone diisocyanate, hydrogenated diphenylmethane diisocyanate and the like are particularly preferable.

Examples of the hydroxyl group-containing (meth) acrylate (C) include, for example, 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, and the like 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 the like with (meth) acrylic acid can also be used. Of these, in particular 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'-diamino Diphenyl methane, diamines containing hetero atoms, diamines such as polyether diamines and the like can be used in combination. When a diamine is used, it is preferably 50% or less of the amount of the diol (a) used.

Further, a polyol other than difunctional with respect to the diol (a), a polyisocyanate other than difunctional with respect to the diisocyanate (b) or a polyamine other than difunctional with respect to the diamine may be used in such a degree that the product does not gel. Can be used in combination, usually, the amount of the diol,
30 parts by weight or less based on 100 parts by weight of the diamine or diisocyanate compound. Examples of the non-bifunctional polyol herein include, for example, an addition product of glycerin and propylene oxide, glycerin, 1,2,3-pentanetriol, 1,2,3-butanetriol, and tri (2-hydroxypolyoxypropyl) polyol. Examples thereof include siloxane, polycaprolactone triol, polycaprolactone tetraol, liquid polybutadiene having more than two hydroxyl groups in one molecule, and hydrogenated products of the polybutadiene. Examples of the non-bifunctional polyisocyanate include polymethylene polyphenyl isocyanate and triphenylmethane 4,4 ', 4 "-
Triisocyanates and the like can be mentioned. Examples of the polyamine other than bifunctional include diethylene triamine,
Examples thereof include 1,2,3-triaminopropane and polyoxypropyleneamine.

Urethane oligomer (A) used in the present invention
Is produced by, for example, reacting a diol (a) with a diisocyanate (b) to produce a polyurethane having an isocyanate group at a terminal, and reacting the polyurethane with a hydroxyl group-containing (meth) acrylate (c). Method: diisocyanate and hydroxyl group-containing (meth)
A method of producing an intermediate having an isocyanate group at the terminal by reacting an acrylate and reacting the intermediate with a diol can be exemplified.

The urethane oligomer (A) thus obtained has a number average molecular weight of 600 to 20,000.
0, especially 600-5,000, and even 800-3,000
Is preferred.

The urethane oligomer (A) is used in an amount of 10 to 80% by weight, preferably 15 to 70% by weight, more preferably 3 to 80% by weight in the total composition.
It is preferable to mix 0 to 50% by weight. If the content is less than 10% by weight, the toughness of the molded article tends to be impaired and brittle and easily cracked, and the molded article 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 the component (B) used in the present invention (hereinafter referred to as "urethane oligomer (B)") is a diisocyanate (II)
And an equimolar mixture of a hydroxyl group-containing (meth) acrylate (c) and a monofunctional alcohol (d).

Diisocyanate (b) used here
And hydroxyl group-containing (meth) acrylate (c)
Examples thereof include those similar to those used in the synthesis of the urethane oligomer (A). The monofunctional alcohol (d) may be a straight-chain or branched-chain hydrocarbon compound containing one hydroxyl group, an alicyclic hydrocarbon compound containing one hydroxyl group, or an aromatic compound containing one hydroxyl group. A group hydrocarbon compound can be used. For example, methanol, ethanol,
Isopropanol, n-propanol, butanol, pentanol, hexanol, heptanol, octanol, nonaol, decanol, undecanol, lauryl alcohol, cetyl alcohol, stearyl alcohol, cyclobutanol, cyclopentanol, cyclohexanol, cyclohexanemethanol, cycloheptanol, menthol , Isoborneol, phenol,
Examples include naphthol and benzyl alcohol. Of these, methanol, ethanol, isopropanol and n-propanol are particularly preferred.

Examples of the urethane oligomer (B) include a reaction product of an equimolar mixture of 2-hydroxyethyl (meth) acrylate, 2,4-tolylene diisocyanate and methanol, and 2-hydroxyethyl (meth) acrylate. Reaction product of an equimolar mixture of isophorone diisocyanate and methanol, reaction product of an equimolar mixture of 2-hydroxyethyl (meth) acrylate, 2,4-tolylene diisocyanate and ethanol, 2-hydroxyethyl (meth) acrylate and isophorone A reaction product of an equimolar mixture of diisocyanate and ethanol is preferred. Further, the urethane oligomer (B) preferably has a number average molecular weight of 600 or less, particularly 300 to 50.
0 is preferred.

The urethane oligomer (B) is used in an amount of 3 to 70% by weight, preferably 5 to 50% by weight, more preferably 10 to 50% by weight in the total composition.
It is preferable to mix 30% by weight. If it is less than 3% by weight,
Inconveniences such as large deformation at the time of molding and softening of the formed object occur. On the other hand, when the content exceeds 70% by weight, there is a tendency that disadvantages such as the molded article becoming brittle and liable to be broken, and the occurrence of temporal deformation after molding tend to occur.

As the ethylenically unsaturated monomer (C) used in the present invention, any of a monofunctional monomer and a polyfunctional monomer can be used.

Examples of the monofunctional monomer 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, dicyclopentenyloxyethyl (meth) acrylate, dicyclopentenyl (meth) acrylate, N, N-diethyl (meth) acrylamide, tetrachlorophenyl (meth) acrylate , 2-tetrachlorophenoxyethyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, tetrabromophenyl (meth) acrylate, 2-tetrabromophenoxyethyl (meth) acrylate, 2-trichlorophenoxyethyl (meth) acrylate, tri Bromophenyl (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, methyltrimethylene diglycol (meth) acrylate, the following formulas (3) to (5)

[0028]

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

Of these, (meth) acryloylmorpholine, isobornyl (meth) acrylate, lauryl (meth) acrylate, vinylcaprolactam,
N-vinylpyrrolidone, phenoxyethyl (meth) acrylate and the like are preferred. Examples of the monofunctional monomer include, for example, Aronics M-111, M-113, and M-113.
117 (manufactured by Toa Gosei Chemical Co., Ltd.), KAYARAD TC
110S, R-629, R-644 (all manufactured by Nippon Kayaku Co., Ltd.), Viscort 3700 (Osaka Organic Chemical Co., Ltd.)
) Can also be used.

Examples of the polyfunctional monomer include ethylene glycol di (meth) acrylate, dicyclopentenyl di (meth) acrylate, triethylene glycol diacrylate and tetraethylene glycol di (meth).
Acrylate, tricyclodecanediyl dimethylene di (meth) acrylate, tris (2-hydroxyethyl) isocyanurate di (meth) acrylate, tris (2-hydroxyethyl) isocyanurate tri (meth) acrylate, trimethylolpropane tri (meth) Acrylate, trimethylolpropanetrioxyethyl (meth) acrylate, tripropylene diacrylate, 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, pentaerythritol tetra (meth) acrylate, polyester di Meth) acrylate, polyethylene glycol di (meth) acrylate.

Of these, in particular, tricyclodecanediyl dimethylene di (meth) acrylate, tetraethylene glycol di (meth) acrylate, tripropylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, polyethylene glycol di ( Meth) acrylates and the like are preferred.

Examples of the polyfunctional monomer include, for example, Ubimer UV, SA1002 (Mitsubishi Chemical Corporation)
Manufactured), VISCOAT 700 (manufactured by Osaka Organic Chemical Co., Ltd.), KA
YARAD R-604, DPCA-20, DPCA-30,
DPCA-120, HX620, D-310, D-33
0 (all manufactured by Nippon Kayaku Co., Ltd.), Aronix M-21
0, Arrownics M-215, Arrownics M-31
5. Commercial products such as Aronix M-325 (all manufactured by Toa Gosei Chemical Co., Ltd.) can also be used.

The ethylenically unsaturated monomer as the component (C) can be used alone or in combination of two or more, and accounts for 20 to 70% by weight, particularly 30 to 50% by weight, more preferably 30 to 45% by weight in the total composition. It is preferable to mix by weight%.
If it is less than 20% by weight, the viscosity of the composition becomes too high,
Curability tends to decrease, and if it exceeds 70% by weight,
The shrinkage during curing increases, the strength of the shaped object,
Mechanical properties such as heat resistance tend to decrease.

The photopolymerization initiator of the component (D) used in the present invention is represented by the above formula (2), and is contained in the urethane oligomer (A), the urethane oligomer (B) and the ethylenically unsaturated monomer (C). This is for initiating the polymerization reaction of the contained ethylenically unsaturated bond.

The photopolymerization initiator of the component (D) is preferably contained in the total composition in an amount of 0.01 to 10% by weight, particularly 1 to 18% by weight, and more preferably 2 to 5% by weight. If the content is less than 0.01% by weight, the curing speed and the resolution tend to decrease, and
If the amount is more than 10% by weight, the curing properties of the composition,
This may have an adverse effect on handling.

The photopolymerization initiator (D) may be used alone or in combination with another photopolymerization initiator. Any photopolymerization initiator that can be used in combination may be any as long as it is decomposed by light irradiation to generate a radical to initiate polymerization. For example, acetophenone, acetophenone benzyl ketal, anthraquinone, 1- (4-isopropylphenyl) -2-hydroxy-2-methylpropan-1-one, carbazole, xanthone, 4-chlorobenzophenone, 4,4'-diaminobenzophenone, 1,1'-dimethoxydeoxybenzoin, 3,3'-dimethyl-4
-Methoxybenzophenone, a thioxanthone compound,
1- (4-dodecylphenyl) -2-hydroxy-2-
Methylpropan-1-one, 2-methyl-1- [4-
(Methylthio) phenyl] -2-morpholinopropan-1-one, triphenylamine, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, 1-hydroxycyclohexylphenyl ketone, 2-hydroxy-2-methyl-1-phenyl Propan-1-one, fluorenone, fluorene, benzaldehyde, benzoin ethyl ether, benzoin propyl ether, benzophenone, mechyl ketone, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butan-1-one, 3-methylacetophenone, 3,3 ', 4,
4′-tetra (t-butylperoxycarbonyl) benzophenone (BTTB) and BTTB and xanthene;
Examples thereof include combinations with thioxanthene, coumarin, ketocoumarin and other dye sensitizers. Of these,
Especially 1-hydroxycyclohexyl phenyl ketone,
2,4,6-trimethylbenzoyldiphenylphosphine oxide, 2-benzyl-2-dimethylamino-1-
(4-morpholinophenyl) -butan-1-one and the like are preferred.

The composition of the present invention may further contain an epoxy (meth) acrylate oligomer.

The epoxy (meth) acrylate oligomer is an oligomer obtained by an addition reaction between an epoxy group-containing compound having various skeletons and (meth) acrylic acid. As this epoxy group-containing compound,
For example, a diglycidyl ether type epoxy compound obtained by reacting epichlorohydrin with bisphenol A, a diglycidyl ether compound obtained by reacting hydrogenated bisphenol A with epichlorohydrin,
Phenol novolak polyglycidyl ether and the like can be mentioned. Among these compounds, a diglycidyl ether type epoxy compound obtained by reacting bisphenol A with epichlorohydrin is particularly preferable.

Examples of the epoxy (meth) acrylate oligomer include commercially available products such as Viscoat 540 (manufactured by Osaka Organic Chemical Co., Ltd.), SP-1509, and VR-77 (all manufactured by Showa Kogaku KK). They can be used together.

The molecular weight of such an epoxy (meth) acrylate oligomer is usually from 100 to 2,000, preferably from 400 to 1,000. If it is less than 100, the shrinkage at the time of curing and the deformation at the time of molding tend to be large, and the molded article tends to be brittle. If it exceeds 2,000, the viscosity of the composition becomes high and it may be difficult to handle. This epoxy (meth) acrylate oligomer is preferably blended in an amount of 30% by weight or less in the whole composition.

The composition of the present invention may further comprise, if necessary, a sensitizer comprising an amine compound such as triethanolamine, methyldiethanolamine, triethylamine, diethylamine, etc., as long as the curability is not impaired. An agent (polymerization accelerator) and a reactive diluent such as vinyl ethers, vinyl sulfides, vinyl urethanes and vinyl ureas can be blended. Furthermore, as other additives, epoxy resin, polyamide, polyamide imide, polyurethane, polybutadiene, polychloroprene, polyether, polyester, styrene /
Butadiene styrene block copolymer, petroleum resin, xylene resin, ketone resin, polymers or oligomers such as fluorine-based oligomer, silicone-based oligomer, polysulfide-based oligomer, phenothiazine, 2,6-di-
Polymerization inhibitors such as t-butyl-4-methylphenol, leveling agents, leakage improvers, surfactants, plasticizers, ultraviolet absorbers, silane coupling agents, inorganic fillers, resin particles, pigments, dyes, etc. 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 required. The composition of the present invention 2
The viscosity at 5 ° C is 100 to 10,000 cps, especially 30
It is preferably in the range of 0 to 7,000 cps, more preferably 500 to 5,000 cps.

Such a composition of the present invention is suitably used as a photocurable liquid substance in an optical three-dimensional molding method. That is, at a specific portion of the composition of the present invention, visible light,
By selectively irradiating light such as ultraviolet light or infrared light and supplying energy necessary 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 can be carried out by various methods. For example, a method of irradiating convergent light obtained by using a laser beam or a lens, a mirror, or the like to a specific portion, a method of irradiating non-convergent light through a mask having a fixed pattern, or the like can be adopted. However, when fine processing or processing accuracy is required, it is desirable to minimize the size of the convergent light. In such a case, it is preferable to use laser light.

Further, the specific portion of the composition of the present invention to be irradiated with light may be at the liquid level 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 in the composition. Either may be used. In order to irradiate light to the liquid surface of the composition or the surface in contact with the container wall, the light may be irradiated directly from the outside or through a transparent vessel wall. Irradiation may be performed using a light guide such as a fiber.

In the above-mentioned optical three-dimensional molding method, usually, after a specific portion of the composition is cured, the irradiation position is moved continuously or stepwise from an already cured portion to an uncured portion. By doing so, the cured portion can be grown into a desired three-dimensional shape. The movement of the irradiation position can be performed by various methods, for example, a light source,
The method can be carried out by moving at least one of the container containing the composition and the cured portion of the composition, or 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 as to obtain a cured layer having a desired pattern, and then irradiating the uncured composition adjacent to the cured layer with light in the same manner. A method in which a new cured layer that is continuous with the molded cured layer is formed, and this lamination operation is repeated to finally obtain a target object can be given.

The molded article is taken out of the container used for the reaction, and after removing the unreacted composition remaining on the surface of the molded article, washing is performed if necessary. Examples of the detergent include organic solvents typified by alcohols such as isopropyl alcohol and ethyl alcohol, and thermosetting or photocuring low viscosities (1,000 csp or less, preferably 1 csp or less).
(Less than 00 csp).

When it is desired to impart transparency to a molded article, it is desirable to use the above-mentioned thermosetting or photocurable liquid resin as a cleaning agent. In this case, it is necessary to perform post-curing by heat or light after cleaning, depending on the type of liquid resin used for cleaning. In addition, the post cure not only hardens the liquid resin on the surface, but also has the effect of hardening the unreacted composition that may remain in the inside of the molded article. It is preferable to carry out also in the case.

[0051]

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 Isobornyl acrylate 5 was placed in a reaction vessel equipped with a stirrer.
2.9 g, 2,4-tolylene diisocyanate 172.9
g, dibutyltin laurate 1.8 g and 2,6-di-t
0.9 g of -butyl-4-methylphenol was charged.
Then, 115.3 g of 2-hydroxyethyl acrylate was gradually added to the reaction vessel while stirring so that the internal temperature did not exceed 25 ° C while cooling the reaction vessel. After the addition was completed, stirring was continued for another hour while maintaining the internal temperature at 15 to 35 ° C. Next, polycarbonate diol (Nipporan 983, manufactured by Nippon Polyurethane Co., Ltd., liquid product at room temperature) 2
37.6 g was added and stirring was continued at 50-60 ° 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 oligomer (1). The weight ratio of the oligomer (1) to isobornyl acrylate is 100/10.

Production Example 2 Isobornyl acrylate 6 was placed in a reaction vessel equipped with a stirrer.
0.0 g, 220.6 g of isophorone diisocyanate, 1.8 g of dibutyltin laurate and 0.9 g of 2,6-di-t-butyl-4-methylphenol were charged. Then, 115.3 g of 2-hydroxyethyl acrylate was gradually added to the reaction vessel while stirring so that the internal temperature did not exceed 25 ° C while cooling the reaction vessel. After the addition is completed, the internal temperature is adjusted to 15
Stirring was continued for another 1 hour while maintaining the temperature at ３５35 ° C.
Next, polycarbonate diol (Nipporan 983, manufactured by Nippon Polyurethane Co., Ltd., liquid product at room temperature) 23
7.6 g was added and stirring was continued at 50-60 ° 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 1,676). The urethane oligomer (A) obtained here is referred to as oligomer (2). The weight ratio of the oligomer (2) to isobornyl acrylate is 100/10.

Production Example 3 Isobornyl acrylate 6 was placed in a reaction vessel equipped with a stirrer.
0.0 g, 220.6 g of isophorone diisocyanate, 1.8 g of dibutyltin laurate and 0.9 g of 2,6-di-t-butyl-4-methylphenol were charged. Then, 115.3 g of 2-hydroxyethyl acrylate was gradually added to the reaction vessel while stirring so that the internal temperature did not exceed 25 ° C while cooling the reaction vessel. After the addition is completed, the internal temperature is adjusted to 15
Stirring was continued for another 1 hour while maintaining the temperature at ３５35 ° C.
Then, 237.6 g of polycarbonate diol (Nipporan 981, trade name solid product, manufactured by Nippon Polyurethane Co., Ltd.), which was previously heated to 60 ° C. and melted, was added.
Stirring was continued at 50-60 ° 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 1,676). The urethane oligomer (A) obtained here is referred to as oligomer (3). The weight ratio of the oligomer (3) to isobornyl acrylate is 100/10.

Production Example 4 Isobornyl acrylate 8 was placed in a reaction vessel equipped with a stirrer.
3.0 g, 2,4-tolylene diisocyanate 428.6
g, 1.0 g of dibutyltin laurate and 2,6-di-t
1.5 g of -butyl-4-methylphenol were charged.
Next, while cooling the reaction vessel, 285.7 g of 2-hydroxyethyl acrylate was gradually added with 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, 113.3 g of ethanol was added, and the internal temperature was adjusted to 2
After stirring for 1 hour while maintaining the temperature at 0 to 40 ° C, stirring was continued at 60 ° C for 5 hours. 0.2% of residual isocyanate groups
After confirming the following, the content was taken out to obtain a urethane oligomer (B) (number average molecular weight: 336).
The urethane oligomer (B) obtained here is referred to as oligomer (4). The weight ratio of the oligomer (4) to isobornyl acrylate is 100/10.

Production Example 5 Isobornyl acrylate 8 was placed in a reaction vessel equipped with a stirrer.
6.7 g, 500.0 g of isophorone diisocyanate, 1.0 g of dibutyltin laurate and 1.5 g of 2,6-di-t-butyl-4-methylphenol were charged. Then, while cooling the reaction vessel, 261.3 g of 2-hydroxyethyl acrylate was gradually added while stirring such that the internal temperature did not exceed 25 ° C. After the addition is completed, the internal temperature is adjusted to 15
Stirring was continued for another 1 hour while maintaining the temperature at ３５35 ° C.
Then, 103.6 g of ethanol was added, and the internal temperature was adjusted to 20 to
After stirring at 40 ° C. for 1 hour, stirring was continued at 60 ° C. for 5 hours. After confirming that the residual isocyanate group was 0.2% or less, the content was taken out to obtain a urethane oligomer (B) (number average molecular weight: 384). The urethane oligomer (B) obtained here is referred to as oligomer (5). The weight ratio of oligomer (5) to isobornyl acrylate is 100/10.

Production Example 6 Isobornyl acrylate 1 was placed in a reaction vessel equipped with a stirrer.
0.0g, 2,4-tolylene diisocyanate 220.
3 g, 1.8 g of dibutyltin laurate and 2,6-di-
1.5 g of t-butyl-4-methylphenol was charged. Then, while cooling the reaction vessel, 146.8 g of 2-hydroxyethyl acrylate was gradually added while stirring such 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, polyoxytetramethylene diol (trade name: PTG1000, manufactured by Hodogaya Chemical Industry Co., Ltd.) 63
2.9 g was added and stirring was continued at 50-60 ° 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 (number-average molecular weight: 1,580). The urethane oli obtained here is referred to as an oligomer (6). Oligomer (6)
And the weight ratio of isobornyl acrylate is 100/10.

Production Example 7 Isobornyl acrylate 1 was placed in a reaction vessel equipped with a stirrer.
0.0g, 2,4-tolylene diisocyanate 428.
6 g, 11.0 g of dibutyltin laurate and 1.5 g of 2,6-di-t-butyl-4-methylphenol were charged. Next, while cooling the reaction vessel, 285.7 g of 2-hydroxyethyl acrylate was gradually added with 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 2-hydroxyethyl acrylate 28
5.7 g was added and stirring was continued at 60 ° C. for 5 hours. After confirming that the residual isocyanate group was 0.2% or less, the content was taken out to obtain a urethane oligomer (number average molecular weight 406). The urethane oligomer obtained here is referred to as oligomer (7). The weight ratio of oligomer (7) to 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.degree.
After stirring for an hour, a composition was obtained. The compositions of Examples 1 to 4 and Comparative Examples 1 to 4 were all transparent liquids. The viscosities of these compositions were measured. Further, the cured products of these compositions were measured for Young's modulus, breaking strength and breaking elongation. Further, regarding the shaped object of the composition,
Warpage and Izod impact strength were measured. The results are shown in Table 1, FIG. 3 and FIG.

Measurement of viscosity: A liquid temperature of 25 was measured using a B-type viscometer.
Measured in ° C. Measurement of Young's Modulus, Breaking Strength and Breaking Elongation: (1) Preparation of Test Specimen 200 μm of the composition was placed on a glass plate using an applicator.
The film was thickly applied and irradiated with ultraviolet rays of 0.5 J / cm ² by a conveyor curing device equipped with a metal halide lamp to produce a cured film. Next, the cured film was peeled from the glass plate, placed on release paper, and irradiated with 0.5 J / cm ² of ultraviolet light from the surface opposite to the surface to which the ultraviolet light was first applied.
The film was conditioned at a relative humidity of 50% for 24 hours to obtain a test piece. (2) Measurement In a constant temperature and humidity room at 23 ° C. and a relative humidity of 50%, the Young's modulus of the test piece was measured at a pulling speed of 1 mm / min and a mark interval of 25.
mm. Further, the breaking strength and the breaking elongation of the test piece at 23 ° C. were measured at a tensile speed of 50 mm /
It was measured under the conditions of min and 25 mm between the marked lines.

Measurement of warpage: Stereolithography apparatus (Solid Creator JSC-2000: Sony Corporation) using an Ar ion laser (wavelength 351 and 365 nm) as a light source
Was formed under the conditions of a laser power on the liquid surface of 40 mW and a scanning speed of 100 cm / sec (hereinafter, referred to as a warpage model) (0.2 mm thickness for one lamination). After molding, the resin was taken out from the optical shaping apparatus to remove the adhered resin, and then post-cured using an ultraviolet lamp (irradiation amount: 7.2 J / cm ² ). Next, as shown in FIG. 2, one was fixed to a horizontal table, and the lift amount Δh (mm) at the other end was measured as the warpage amount. Further, the warped model was left in a state of 23 ° C. and a relative humidity of 50%, and the change with time in the amount of warpage was determined in the same manner as described above.

Measurement of Izod impact strength: A test piece produced by using the above-mentioned stereolithography apparatus was subjected to ASTM D 2
It was measured using a 56 impact tester.

[0063]

[Table 1]

[0064]

The resin composition for optical three-dimensional modeling according to the present invention can realize the mechanical strength, heat resistance and dimensional accuracy of the molded article at the same time without deformation of the molded article with time.

[Brief description of the drawings]

FIG. 1 is a diagram showing a warpage evaluation model used for measuring warpage in an example.

FIG. 2 is a schematic diagram showing an evaluation of a warpage amount in an example.

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

FIG. 4 is a diagram showing a change with time in the amount of warpage of Example 2 and Comparative Examples 1 to 4.

 ──────────────────────────────────────────────────続 き Continuation of front page (72) Inventor Takashi Ukaji 2-11-24 Tsukiji, Chuo-ku, Tokyo Japan Synthetic Rubber Co., Ltd. (56) References JP-A-8-92342 (JP, A) JP JP-A-5-255461 (JP, A) JP-A-6-145276 (JP, A) JP-A-6-313022 (JP, A) JP-A-7-13173 (JP, A) JP-A-5-105747 (JP) , A) JP-A-6-166737 (JP, A) JP-A-62-129306 (JP, A) JP-A-63-308018 (JP, A) JP-A-62-45613 (JP, A)

Claims (1)

(57) [Claims] (A) General formula (1) (Wherein, R represents a linear or branched 2
A divalent isocyanate and a hydroxyl group-containing (meth) acrylate, and a urethane (meth) acrylate oligomer obtained by reacting a diol represented by
(B) diisocyanate, hydroxyl group-containing (meth)
A urethane (meth) acrylate oligomer obtained by reacting an equimolar mixture of an acrylate and a monofunctional alcohol, (C) an ethylenically unsaturated monomer, and (D) a formula (2) A resin composition for optical three-dimensional modeling containing a photopolymerization initiator represented by the formula: