JPH08231849A - Optically relief forming resin composition - Google Patents

Abstract

PURPOSE: To obtain an optically relief forming resin composition by mixing two specified urethane (meth)acrylate oligomers with an ethylenically unsaturated monomer and a photopolymerization initiator. CONSTITUTION: This composition comprises a urethane (meth)acrylate oligomer obtained by reacting a diol represented by formula I (wherein R is a 1-12 C bivalent aliphatic hydrocarbon group, and n is an integer of 1-25) with a diisocyanate and a hydroxyalkyl (meth)acrylate, a urethane (meth)acrylate oligomer obtained by reacting an equimolar mixture of a diisocyanate, a hydroxyalkyl (meth)acrylate and a monohydric alcohol, an ethylenically unsaturated monomer and a photopolymerization initiator represented by formula II.

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.
No. 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 so far by correcting the input CAD data, 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 heat resistance of the molded article. 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 represents a linear or branched divalent aliphatic hydrocarbon group having 1 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, a hydroxyl group-containing (meth) acrylate, and a monofunctional alcohol. Urethane (meth) acrylate oligomer obtained by reacting an equimolar mixture of the above, (C) ethylenically unsaturated monomer, and (D) formula (2)

[0010]

[Chemical 4]

The present invention provides a resin composition for optical three-dimensional molding containing a photopolymerization initiator represented by:

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).

As the diol (a) represented by the general formula (1), R is, 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 polycarbonic acid esters of dihydric alcohols such as methylpentanediol and 1-methyloctanediol. Even if these dihydric alcohols are used alone, 2
You may use together 1 or more types. Of these diols, 1,6-hexanediol, 1,9-nonanediol, 3
A diol obtained from a polycarbonate of a dihydric alcohol such as methylpentanediol is 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 further 500 to 3 by a hydroxyl group terminal quantification method. Those of 1,000 are preferred. Commercially available products of these diols include Nippon 980, Nippon 981 and Nippon 98.
2, Nippon Polan 983 (all manufactured by Nippon Polyurethane Industry Co., Ltd.), PNOC, PMD (all manufactured by Kuraray Co., Ltd.) and the like.

Examples of the diisocyanate (b) to be reacted with the diol (a) include 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, and 1,2.
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-trimethylhexamethylene diisocyanate, bis (2-isocyanato) Ethyl) fumarate, 6-isopropyl-1,3
-Phenyl diisocyanate, 4-diphenyl propane diisocyanate, lysine diisocyanate, etc. can be mentioned. Of 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 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'-diamino. Diphenyl such as diphenylmethane, diamine containing a hetero atom, and polyether diamine 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, and 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 as the polyamine other than bifunctional, for example, diethylenetriamine,
Examples thereof include 1,2,3-triaminopropane and polyoxypropyleneamine.

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 600-5,000, and even 800-3,000
Are preferred.

The urethane oligomer (A) accounts for 10 to 80% by weight, particularly 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).
It is obtained by reacting 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 of the same include those used in the synthesis of the urethane oligomer (A). As the monofunctional alcohol (d), a linear or branched hydrocarbon compound containing one hydroxyl group, an alicyclic hydrocarbon compound containing one hydroxyl group, or an aroma containing one hydroxyl group. Group hydrocarbon compounds 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 thereof include naphthol and benzyl alcohol. Of these, methanol, ethanol, isopropanol, and n-propanol are particularly preferable.

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

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, 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]

Embedded image

(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,
It preferably represents 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 preferable. As the monofunctional monomer, for example, Aronix M-111, M-113, M-
117 (above, manufactured by Toagosei Kagaku Co., Ltd.), KAYARAD TC
110S, R-629, R-644 (all manufactured by Nippon Kayaku Co., Ltd.), Viscoat 3700 (Osaka Organic Chemical Co., Ltd.)
It is also possible to use a commercially available product such as a product manufactured by K.K.

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, both-end (meth) acrylic acid adduct of bisphenol A diglycidyl ether, 1,4-butanediol di (Meth) acrylate, 1,6-hexanediol di (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, polyester diester Meth) acrylate, 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.

As the polyfunctional monomer, for example, Ubimar UV, SA1002 (above Mitsubishi Chemical Co., Ltd.)
), Viscoat 700 (Osaka Organic Chemical Co., Ltd.), KA
YARAD R-604, DPCA-20, DPCA-30,
DPCA-120, HX620, D-310, D-33
0 (above, Nippon Kayaku Co., Ltd.), Aronix M-21
0, Aronix M-215, Aronix M-31
5, a commercial product such as Aronix M-325 (above, manufactured by Toagosei Kagaku 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 is 20 to 70% by weight, especially 30 to 50% by weight, and further 30 to 45% by weight in the total composition. It is preferable to add the composition in a weight percentage.
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 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 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). It is for starting the polymerization reaction of the contained ethylenically unsaturated bond.

The photopolymerization initiator as the component (D) is preferably added in an amount of 0.01 to 10% by weight, particularly 1 to 18% by weight, and further preferably 2 to 5% by weight in the entire composition. If the amount is less than 0.01% by weight, the curing speed and resolution tend to decrease, and
If the content exceeds 100% by weight, the curing characteristics of the composition and the physical properties of the molded article,
It may adversely affect the handling.

The photopolymerization initiator as the component (D) may be used alone or in combination with other photopolymerization initiators. The photopolymerization initiator that can be used in combination may be any as long as it is decomposed by light irradiation to generate radicals 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, thioxanthone compounds,
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, Mechler ketone, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butan-1-one, 3-methylacetophenone, 3,3 ', 4,
4'-tetra (t-butylperoxycarbonyl) benzophenone (BTTB) and BTTB with xanthene,
Examples 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 preferable.

An epoxy (meth) acrylate oligomer may 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 diglycidyl ether type epoxy compound obtained by reacting bisphenol A with epichlorohydrin is particularly preferable.

As the epoxy (meth) acrylate oligomer, commercially available products such as VISCOAT 540 (manufactured by Osaka Organic Chemical Co., Ltd.), SP-1509, VR-77 (manufactured by Showa Polymer Co., Ltd.) are available. It can also be used together.

The molecular weight of such an epoxy (meth) acrylate oligomer is usually 100 to 2,000, preferably 400 to 1,000. When it is less than 100, the shrinkage upon curing and the deformation at the time of molding become large, and the molded article tends to be more brittle, and when 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 added in an amount of 30% by weight or less in the entire composition.

In addition to the above-mentioned components, the composition of the present invention may be sensitized with an amine-based compound such as triethanolamine, methyldiethanolamine, triethylamine, diethylamine, etc., if necessary, within the range not impairing the 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, leak 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, 2 of the composition of the present invention
Viscosity at 5 ° C is 100-10,000 cps, especially 30
It is preferably in the range of 0 to 7,000 cps, more preferably 500 to 5,000 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 for 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, etc., a method of irradiating non-convergent light through a mask of a constant 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 portions of the composition of the present invention which are irradiated with light are 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. 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.

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 detergent include organic solvents represented by alcohols such as isopropyl alcohol and ethyl alcohol, and thermosetting or photocurable low-viscosity (1,000 csp or less, preferably 1
A liquid resin of 00 csp or less) can be used.

When it is desired to impart transparency to the molded article, it is desirable to use the above-mentioned thermosetting or photocurable liquid resin as a cleaning agent. Further, in this case, post-curing needs to be performed with heat or light after the cleaning, depending on the type of the liquid resin used for the 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.

[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
-Butyl-4-methylphenol 0.9 g was charged.
Then, while cooling the reaction vessel, 115.3 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. Polycarbonate diol (Nippon Polyurethane Co., Ltd., trade name Nipporan 983, normal temperature liquid) 2
37.6 g was added and stirring was continued at 50-60 ° C. for 6 hours. After confirming that the residual isocyanate group content 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 (1). The weight ratio of the oligomer (1) and isobornyl acrylate is 100/10.

Production Example 2 Isobornyl acrylate 6 was placed in a reaction vessel equipped with a stirrer.
0.0 g, isophorone diisocyanate 220.6 g, dibutyltin laurate 1.8 g and 2,6-di-t-butyl-4-methylphenol 0.9 g were charged. Then, while cooling the reaction vessel, 115.3 g of 2-hydroxyethyl acrylate was gradually added with stirring so that the internal temperature did not exceed 25 ° C. After the addition is complete, increase the internal temperature to 15
Stirring was continued for another 1 hour while maintaining at ~ 35 ° C.
Polycarbonate diol (Nippon Polyurethane Co., Ltd., trade name Nipporan 983, normal temperature liquid) 23
7.6g was added and stirring was continued at 50-60 ° C for 6 hours. After confirming that the residual isocyanate group content 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 an oligomer (2). The weight ratio of 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, isophorone diisocyanate 220.6 g, dibutyltin laurate 1.8 g and 2,6-di-t-butyl-4-methylphenol 0.9 g were charged. Then, while cooling the reaction vessel, 115.3 g of 2-hydroxyethyl acrylate was gradually added with stirring so that the internal temperature did not exceed 25 ° C. After the addition is complete, increase the internal temperature to 15
Stirring was continued for another 1 hour while maintaining at ~ 35 ° C.
Next, 237.6 g of a polycarbonate diol (manufactured by Nippon Polyurethane Co., Ltd., trade name: Nipolan 981, solid product at room temperature) that has been heated and melted at 60 ° C. in advance is added,
Stirring was continued for 6 hours at 50-60 ° C. After confirming that the residual isocyanate group content 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 an oligomer (3). The weight ratio of 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, dibutyltin laurate 1.0 g and 2,6-di-t
-Butyl-4-methylphenol 1.5 g was charged.
Then, 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 maintaining the temperature at 0 to 40 ° C. for 1 hour, stirring was continued at 60 ° C. for 5 hours. 0.2% residual isocyanate groups
After confirming the following, the contents were taken out to obtain a urethane oligomer (B) (number average molecular weight 336).
The urethane oligomer (B) obtained here is referred to as an oligomer (4). The weight ratio of 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, isophorone diisocyanate 500.0 g, dibutyltin laurate 1.0 g and 2,6-di-t-butyl-4-methylphenol 1.5 g were charged. Then, while cooling the reaction vessel, 261.3 g of 2-hydroxyethyl acrylate was gradually added while stirring so that the internal temperature did not exceed 25 ° C. After the addition is complete, increase the internal temperature to 15
Stirring was continued for another 1 hour while maintaining at ~ 35 ° C.
Next, 103.6 g of ethanol was added, and the internal temperature was 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 content 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 an oligomer (5). The weight ratio of oligomer (5) and isobornyl acrylate is 100/10.

Production Example 6 Isobornyl acrylate 1 was placed in a reaction vessel equipped with a stirrer.
0.00 g, 2,4-tolylene diisocyanate 220.
3 g, dibutyltin laurate 1.8 g and 2,6-di-
1.5 g of t-butyl-4-methylphenol was charged. Next, while cooling the reaction vessel, 146.8 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. Next, polyoxytetramethylene diol (Hodogaya Chemical Co., Ltd., trade name PTG1000) 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 precipitate obtained here is referred to as an oligomer (6). Oligomer (6)
And the isobornyl acrylate are in a weight ratio of 100/10.

Production Example 7 Isobornyl acrylate 1 was placed in a reaction vessel equipped with a stirrer.
0.00 g, 2,4-tolylene diisocyanate 428.
6 g, dibutyltin laurate 11.0 g and 2,6-di-t-butyl-4-methylphenol 1.5 g were charged. Then, 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 content 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 an 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 container 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. The viscosity of these compositions was measured. In addition, Young's modulus, breaking strength and breaking elongation of the cured products of these compositions were measured. Furthermore, regarding the molded article of the composition,
The warpage and Izod impact strength were measured. The results are shown in Table 1, FIG. 3 and FIG.

Viscosity measurement: using a B type viscometer, liquid temperature 25
It was measured at ° C. Measurement of Young's modulus, breaking strength and breaking elongation: (1) Preparation of test piece Using an applicator, the composition was 200 μm on a glass plate.
A thick film was applied and a cured film was prepared by irradiating it with 0.5 J / cm ² of ultraviolet light using 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 irradiated with 0.5 J / cm ² of ultraviolet light from the surface opposite to the surface irradiated with ultraviolet light for the first time.
This film was conditioned at a relative humidity of 50% for 24 hours to prepare a test piece. (2) Measurement The Young's modulus of the test piece was measured at a pulling speed of 1 mm / min and a marked line distance of 25 in a constant temperature and humidity room at 23 ° C. and a relative humidity of 50%.
It was measured under the condition of mm. In addition, the breaking strength and breaking elongation of the test piece at 23 ° C. were measured at a tensile speed of 50 mm /
The measurement was performed under the conditions of min and 25 mm between marked lines.

Warpage measurement: Stereolithography apparatus (solid creator JSC-2000: Sony Corporation) using an Ar ion laser (wavelengths 351 and 365 nm) as a light source.
1) was molded under the conditions of a laser power of 40 mW on the liquid surface and a scanning speed of 100 cm / sec (hereinafter, referred to as a warpage model) (lamination thickness of once 0.2 mm). After molding, the resin was taken out from the stereolithography apparatus to remove the adhered resin, and post-cured using an ultraviolet lamp (irradiation light amount 7.2 J / cm ² ). Next, as shown in FIG. 2, one side was fixed to a horizontal table, and the lift amount Δh (mm) at the other end was measured as the warp amount. 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 produced by using the above-mentioned stereolithography apparatus was tested according to ASTM D 2
It measured using the 56 impact tester.

[0063]

[Table 1]

[0064]

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 evaluation model used for measuring warpage in Examples.

FIG. 2 is a schematic diagram showing evaluation of a warp amount 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 2 and Comparative Examples 1 to 4.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁶ Identification number Reference number within the agency FI technical display location // B29K 105: 24 (72) Inventor Takashi Ukaji 2-11-24 Tsukiji, Chuo-ku, Tokyo Within Nippon Synthetic Rubber Co., Ltd.

Claims (1)

[Claims] 1. (A) General formula (1): (In the formula, R is a linear or branched 2 having 1 to 12 carbon atoms.
A urethane (meth) acrylate oligomer obtained by reacting a diol represented by a valent aliphatic hydrocarbon group, n is a number of 1 to 25) with a diisocyanate and a hydroxyl group-containing (meth) acrylate,
(B) Diisocyanate, hydroxyl group-containing (meth)
Urethane (meth) acrylate oligomer obtained by reacting equimolar mixture of acrylate and monofunctional alcohol, (C) ethylenically unsaturated monomer and (D) formula (2) An optical three-dimensional modeling resin composition containing a photopolymerization initiator represented by: