JP4293535B2 - Active energy ray-curable epoxy resin composition for optical three-dimensional modeling and optical three-dimensional modeling method - Google Patents

Description

  The present invention relates to an active energy ray-curable epoxy resin composition for optical three-dimensional modeling that can be cured by irradiation with active energy rays such as ultraviolet rays and electron beams, and an optical three-dimensional modeling method. More specifically, the present invention relates to an active energy ray-curable epoxy resin composition for optical three-dimensional modeling and an optical three-dimensional modeling method that give a cured product that is excellent in chemical resistance, water resistance, moisture resistance, and adhesiveness and has little curing shrinkage.

In recent years, resin compositions that are cured by irradiation with active energy rays such as ultraviolet rays and electron beams have been used in various fields as paints, coating agents, adhesives, sealants and the like. As one of such active energy ray curable resin compositions, a photocurable epoxy resin composition is known.
(For example, JP-B-63-113022, JP-B-3-77210, JP-A-1-149848, JP-A2-114022, JP-A-4-266985, etc.).

Photo-curing epoxy resin, like radical polymerization photo-curing resin, has the characteristics that it is not affected by curing by oxygen and has excellent physical properties and adhesiveness of cured products, and its application range is also widely expected. It is what has been.
This photocurable epoxy resin composition is basically obtained by adding a photopolymerization initiator to an epoxy resin. It is already known that an onium salt is used as a photopolymerization initiator.
Examples of the epoxy resin to be cured with a photopolymerization initiator include 3,4-epoxycyclomethyl-3,4-epoxycyclohexanecarboxylate (Syracure UVR-6110 manufactured by Union Carbide, Celoxide 2021 manufactured by Daicel Chemical Industries), bis (3 A so-called alicyclic epoxy ester compound represented by 4-epoxycyclohexylmethyl) adipate (Syracure UVR-6128, manufactured by Union Carbide Corporation) is preferred in terms of reaction rate and physical properties, and is used as the main component of the resin. .

  In addition, as described in JP-A-60-247515, optical three-dimensional modeling means that various resins having photocurability are placed in a container, and an argon laser, helium cadmium laser, semiconductor laser, etc. By irradiating an arbitrary portion of the resin with a beam and continuously performing irradiation, the beam irradiation portion of the resin is cured, thereby creating a target plane to form a cured layer. Subsequently, another layer of the above-mentioned photo-curing resin is supplied onto the cured layer and cured in the same manner as described above, and a lamination operation is performed to obtain a cured layer continuous with the above-described cured layer. This is a method of obtaining a target three-dimensional solid object by repeating this operation.

  Conventionally, as the resin that has been used for the above-mentioned optical three-dimensional modeling, there is first a radical polymerizable resin composition. For example, JP-A-2-228312 and JP-A-5-279436 disclose (meth) acrylic resin. The resin composition for three-dimensional modeling centering on is disclosed. Further, Japanese Patent Laid-Open No. 2-145616 discloses a resin for optical three-dimensional modeling including fine particles having an apparent specific gravity difference of less than 0.2 with a liquid resin for the purpose of reducing deformation. In order to improve the accuracy of the molded article, JP-A-3-15520 discloses a composition comprising an ethylenically unsaturated monomer, a photoinitiator and an insoluble latent radiation polarizing material, and JP-A-3-41126. Discloses a composition comprising an ethylenically unsaturated monomer, a photoinitiator and a soluble latent radiation polarizer, respectively. Furthermore, JP-A-4-85314 discloses a resin composition containing silicone urethane acrylate, a compound having a polyfunctional ethylenically unsaturated bond, and a polymerization initiator.

  As other optical three-dimensional modeling resin compositions, cationically polymerizable resin compositions are known. For example, JP-A-1-213304 describes a cationic polymerizable resin composition comprising an active energy ray-curable cationic polymerizable organic compound and an active energy ray-sensitive cationic polymerization initiator. Yes. Japanese Patent Application Laid-Open No. 2-28261 discloses a resin having a low shrinkage and a high resolution in which an active energy ray-curable radically polymerizable organic compound is partially blended with an active energy ray-curable cationically polymerizable organic compound. JP-A-2-80423 discloses a resin composition comprising a vinyl ether resin, an active energy ray sensitive cationic polymerization initiator, a radical curable resin, and an active energy ray sensitive radical polymerization initiator in an epoxy resin. Is disclosed. Further, JP-A-2-75618 discloses an active energy ray-curable cationic polymerizable organic compound, an active energy ray-sensitive cationic polymerization initiator, an active energy ray-curable radical polymerizable organic compound, and an active energy ray-sensitive radical polymerization start. The resin composition for optical modeling characterized by containing an agent and hydroxyl-containing polyester is disclosed.

Among the above-mentioned conventional resin compositions for optical three-dimensional modeling, the cured product of a photocurable epoxy resin composition mainly composed of an alicyclic epoxy ester compound is generally glossy, heat resistant, and chemical resistant. Although it has excellent performance and low curing shrinkage and is used in paints, coating agents, adhesives, sealants, etc., further improvements are required in terms of alkali resistance, water resistance, and adhesiveness of cured products. In addition, sufficient products such as a dimensional change of the cured product due to moisture absorption have not been obtained yet.
In addition, since radically polymerizable resins and resin compositions for optical three-dimensional modeling that use them as a main component use radical polymerization, any resin (composition) is used, and curing inhibition occurs due to oxygen. Since the curing rate at the time will be low, it is necessary to perform "post-curing treatment" that always gives light or heat involved in curing at the time of modeling, and there is a defect that the molded object tends to deform during this post-curing treatment It was. Further, these resins have a large shrinkage at the time of curing, and it has been difficult to obtain a molded article having a desired size.

  Further, cationic curing type optical three-dimensional modeling resins such as those described in JP-A-1-213304, JP-A-2-28261, and JP-A-2-75618 do not cause curing inhibition by oxygen and are not contained in the resin. Since the curing proceeds even after light blocking by the activator, it has excellent characteristics that no post-curing treatment is required and deformation is small, and shrinkage at the time of curing is small, and a molded article of a desired size is obtained. Although it is easy, the sensitivity to the irradiation energy is not sufficient, and since the obtained shaped article has hygroscopicity, it has a drawback of deformation due to moisture absorption.

  JP-A-58-172387 provides a process for producing 2,2-dicyclohexenylpropane diepoxide, and JP-A-48-29899 discloses methylene bis (3,4-epoxycyclohexane) and Although the epoxy resin composition by thermosetting comprising polycarboxylic acid anhydrides is disclosed, it has not been known at all whether these alicyclic epoxy compounds are suitable for photocuring or optical modeling. It was.

JP-A-1-213304 (Claims, Examples) JP-A-2-28261 (Claims and Examples) Japanese Patent Laid-Open No. 2-75618 (Claims, Examples) JP 58-172387 A (Claims) JP-A-48-29899 Japanese Patent Application No. 2002-260490 (Claims, Examples) Neftekhimiya, 1972, 12, 353

  Accordingly, an object of the present invention is to provide an active energy ray-curable epoxy resin composition for optical three-dimensional modeling and an optical three-dimensional modeling method that give excellent cured products having excellent physical properties and little dimensional change due to moisture absorption. It is in.

  The present inventors have found that such problems can be solved by using an alicyclic epoxy compound having a specific structure, and have completed the present invention.

That is, the first of the present invention is an active energy ray-curable epoxy resin for optical three-dimensional modeling characterized by containing bis (3,4-epoxycyclohexyl) and (2) an active energy ray-sensitive cationic polymerization initiator. A composition is provided.
The second of the present invention is: (1) General formula (I)
[In formula, R < ¹ > -R < ¹⁸ > may be same or different, respectively. These are a hydrogen atom, a halogen atom, an oxygen atom, a hydrocarbon group that may contain a halogen atom, or an alkoxy group that may have a substituent, and an alicyclic epoxy compound represented by (2) An active energy ray-curable optical three-dimensional modeling comprising an active energy ray-sensitive cationic polymerization initiator, (4) a radical polymerizable organic compound, and (5) an active energy ray sensitive radical polymerization initiator An epoxy resin composition is provided.
A third aspect of the present invention is the active energy ray-curable epoxy resin for optical three-dimensional modeling according to the second aspect, wherein the alicyclic epoxy compound represented by the formula (I) is bis (3,4-epoxycyclohexyl). A composition is provided.
A fourth aspect of the present invention is the energy ray-curable epoxy resin composition for optical three-dimensional modeling according to any one of the first to third aspects of the present invention, and (3) an alicyclic epoxy represented by the general formula (I). An active energy ray-curable epoxy resin composition for optical three-dimensional modeling, comprising a cationically polymerizable organic compound other than a compound .
The fifth of the present invention is as follows: (2) The active energy ray-sensitive cationic polymerization initiator is any one of an aromatic iodonium salt, an aromatic sulfonium salt, or an iron-arene complex. The active energy ray-curable epoxy resin composition for optical three-dimensional modeling described above is provided.
A sixth aspect of the present invention is the active energy ray-curable epoxy resin composition for optical three-dimensional modeling according to any one of the above inventions 2 to 5, wherein 50% by weight or more of the above (4) radical polymerizable organic compound Provides an active energy ray-curable epoxy resin composition for optical three-dimensional modeling, which is a compound having a (meth) acryloyl group in the molecule .
The seventh of the present invention is (5) the activity according to any one of the above inventions 2 to 6, wherein the active energy ray sensitive radical polymerization initiator is any one of an acetophenone compound, a benzyl compound, and a ketone compound. An energy ray-curable epoxy resin composition for optical three-dimensional modeling is provided.
In the eighth aspect of the present invention, an active energy ray is irradiated on an arbitrary portion of the active energy ray-curable resin composition, and the energy irradiation portion of the resin composition is cured to form a cured layer having a desired thickness. The active energy ray-curable resin composition described above is further supplied onto the cured layer, and this is cured in the same manner to obtain a cured product continuous with the cured layer. In the optical three-dimensional modeling method for obtaining an original three-dimensional object, the active energy ray-curable resin composition is the active energy ray-curable epoxy resin composition for optical three-dimensional modeling according to any one of the above inventions 1 to 7. An optical three-dimensional modeling method is provided.
9th of this invention provides the three-dimensional solid object obtained by the optical three-dimensional modeling method of the said invention 8.

  In the present invention, an excellent cured product having excellent physical properties such as chemical resistance, water resistance, moisture resistance, and adhesiveness, less curing shrinkage, and less expansion in the cured product, that is, less dimensional change due to moisture absorption. An active energy ray-curable epoxy resin composition for optical three-dimensional modeling, and an optical three-dimensional modeling method using the same are obtained.

(1) In the alicyclic epoxy compound represented by the general formula (I) used in the present invention, R ^{1 to} R ¹⁸ in the formula (I) may be the same or different. These are a hydrogen atom, a halogen atom, an oxygen atom, a hydrocarbon group that may contain a halogen atom, or an alkoxy group that may have a substituent.
In the present invention, in addition to the alicyclic epoxy compound represented by the general formula (I), one or more cationically polymerizable organic compounds can be used in combination.
The alicyclic epoxy compound represented by the above formula (I), which is an essential resin component in the epoxy resin composition for active energy ray-curable optical three-dimensional modeling of the present invention, is known, for example, Japanese Patent Application 2002-2002. It can be produced by the method described in the specification of 260490 or Russian literature (Neftekhimiya, 1972, 12, 353). In particular, as described in the former, a product produced by epoxidation of a corresponding diolefin compound using a peracid having a low water content is preferable because the content of the diepoxy compound is high. Specific examples of the alicyclic epoxy compound represented by the above formula (I) include bis (3,4-epoxycyclohexyl) in which R ^{1 to} R ¹⁸ are all hydrogen atoms, and are particularly preferably used. .

The (2) active energy ray-sensitive cationic polymerization initiator used in the present invention is a compound capable of releasing a substance that initiates cationic polymerization by irradiation with active energy rays, and particularly preferred is a Lewis acid by irradiation. Is a double salt which is an onium salt which releases bismuth or its derivative. Representative examples of such compounds include the following general formula:
[A] ^{m +} [B] ^m-
And cation and anion salts represented by the formula:

Here, the cation [A] ^{m +} is preferably onium, and the structure thereof is, for example, the following general formula:
[(R ¹⁹ ) _a Q] ^{m +}
Can be expressed as

Further, here, R ¹⁹ is an organic group having 1 to 60 carbon atoms and may contain any number of atoms other than carbon atoms. a is an integer of 1 to 5. The a R ^{19 s} are independent and may be the same or different. Further, at least one is preferably an organic group as described above having an aromatic ring. Q is an atom or atomic group selected from the group consisting of S, N, Se, Te, P, As, Sb, Bi, O, I, Br, Cl, F, and N = N. Further, when the valence of Q in the cation [A] ^{m +} is q, it is necessary that the relationship m = a−q holds (however, N = N is treated as a valence of 0).

The anion [B] ^m− is preferably a halide complex, and the structure thereof is, for example, the following general formula:
[LX _b ] ^m-
Can be expressed as

Here, L is a metal or metalloid which is a central atom of a halide complex, and B, P, As, Sb, Fe, Sn, Bi, Al, Ca, In, Ti, Zn, Sc, V, Cr, Mn, Co and the like. X is a halogen atom. b is an integer of 3-7. Further, when the valence of L in the anion [B] ^m− is p, it is necessary that the relationship m = b−p holds.

Specific examples of the anion [LX _b ] ^m− represented by the above general formula include tetrafluoroborate (BF ₄ ) ⁻ , hexafluorophosphate (PF ₆ ) ⁻ , hexafluoroantimonate (SbF ₆ ) ⁻ , Hexafluoroarsenate (AsF ₆ ) ⁻ , hexachloroantimonate (SbCl ₆ ) ^{− and the} like can be mentioned.

Also, the anion B ^m−
[LX _b-1 (OH)] ^m−
The thing of the structure represented by can also be used preferably. L, X, and b are the same as described above. Other anions that can be used include perchlorate ion (ClO ₄ ) ⁻ , trifluoromethylsulfite ion (CF ₃ SO ₃ ) ⁻ , fluorosulfonate ion (FSO ₃ ) ⁻ , and toluenesulfonate anion. And trinitrobenzenesulfonic acid anion.

  In the present invention, among these onium salts, it is particularly effective to use the following aromatic onium salts (a) to (c). Among these, one of them can be used alone, or two or more of them can be mixed and used.

(A) Aryldiazonium salts such as phenyldiazonium hexafluorophosphate, 4-methoxyphenyldiazonium hexafluoroantimonate, 4-methylphenyldiazonium hexafluorophosphate, (b) diphenyliodonium hexafluoroantimonate, di (4-methylphenyl) iodonium Diaryl iodonium salts such as hexafluorophosphate and di (4-tert-butylphenyl) iodonium hexafluorophosphate (c) Triphenylsulfonium hexafluoroantimonate, tris (4-methoxyphenyl) sulfonium hexafluorophosphate, diphenyl-4-thio Phenoxyphenylsulfonium hexafluoroantimonate, diphenyl-4-thiophenoxy Enylsulfonium hexafluorophosphate, 4,4′-bis (diphenylsulfonio) phenyl sulfide-bis-hexafluoroantimonate, 4,4′-bis (diphenylsulfonio) phenyl sulfide-bis-hexafluorophosphate, 4 , 4′-bis [di (β-hydroxyethoxy) phenylsulfonio] phenyl sulfide-bis-hexafluoroantimonate, 4,4′-bis [di (β-hydroxyethoxy) phenylsulfonio] phenyl sulfide-bis- Hexafluorophosphate, 4- [4 '-(benzoyl) phenylthio] phenyl-di- (4-fluorophenyl) sulfonium hexafluoroantimonate, 4- [4'-(benzoyl) phenylthio] phenyl-di- (4-fluoro Phenyl) Triarylsulfonium salts such as phosphonium hexafluorophosphate are preferred.

Other preferable examples include (η ⁵ -2,4-cyclopentadien-1-yl) [(1,2,3,4,5,6, -η)-(1-methylethyl) benzene]- Iron-arene complexes such as iron-hexafluorophosphate, aluminum complexes such as tris (acetylacetonato) aluminum, tris (ethylacetonatoacetato) aluminum, tris (salicylaldehyde) aluminum, and silanols such as triphenylsilanol And a mixture thereof.

  Among these, it is preferable to use an aromatic iodonium salt, an aromatic sulfonium salt, or an iron-arene complex from the viewpoints of practical use and photosensitivity.

(3) The cationically polymerizable organic compound other than the alicyclic epoxy compound represented by the general formula (I) used in the present invention is an active energy ray sensitive cationic polymerization initiator activated by active energy ray irradiation. It is a compound that causes a high molecular weight or a crosslinking reaction, and refers to a compound having a structure other than the alicyclic epoxy compound represented by the general formula (I).
For example, an epoxy compound having a structure other than the alicyclic epoxy compound represented by the general formula (I), a cyclic ether compound, a cyclic lactone compound, a cyclic acetal compound, a cyclic thioether compound, a spiro orthoester compound, a vinyl compound, etc. Yes, one or more of these can be used. Among them, an epoxy compound that is easy to obtain and convenient for handling is suitable. Examples of such epoxy compounds include aromatic epoxy compounds, alicyclic epoxy compounds, and aliphatic epoxy compounds.
Specific examples of the aromatic epoxy resin include polyhydric phenol having at least one aromatic ring, or polyglycidyl ether of an alkylene oxide adduct thereof, such as bisphenol A, bisphenol F, or further alkylene oxide. Examples thereof include glycidyl ether and epoxy novolac resin of the added compound.

  Specific examples of the alicyclic epoxy resin include cyclohexane obtained by epoxidizing a polyglycidyl ether of a polyhydric alcohol having at least one alicyclic ring or a cyclohexene or cyclopentene ring-containing compound with an oxidizing agent. Examples thereof include oxides and cyclopentene oxide-containing compounds. For example, hydrogenated bisphenol A diglycidyl ether, 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate, 3,4-epoxy-1-methylcyclohexyl-3,4-epoxy-1-methylcyclohexanecarboxylate 6-methyl-3,4-epoxycyclohexylmethyl-6-methyl-3,4-epoxycyclohexanecarboxylate, 3,4-epoxy-3-methylcyclohexylmethyl-3,4-epoxy-3-methylcyclohexanecarboxylate 3,4-epoxy-5-methylcyclohexylmethyl-3,4-epoxy-5-methylcyclohexanecarboxylate, 2- (3,4-epoxycyclohexyl-5,5-spiro-3,4-epoxy) cyclohexane Meta Oxane, bis (3,4-epoxycyclohexylmethyl) adipate, vinylcyclohexene dioxide, 4-vinylepoxycyclohexane, bis (3,4-epoxy-6-methylcyclohexylmethyl) adipate, 3,4-epoxy-6-methyl Cyclohexyl carboxylate, methylene bis (3,4-epoxycyclohexane), dicyclopentadiene diepoxide, ethylene glycol di (3,4-epoxycyclohexylmethyl) ether, ethylene bis (3,4-epoxycyclohexanecarboxylate), epoxy hexahydro Examples include dioctyl phthalate and di-2-ethylhexyl epoxyhexahydrophthalate.

  Further, specific examples of the aliphatic epoxy resin include polyglycidyl ether of an aliphatic polyhydric alcohol or an alkylene oxide adduct thereof, polyglycidyl ester of an aliphatic long-chain polybasic acid, vinyl polymerization of glycidyl acrylate or glycidyl methacrylate. Homopolymers, glycidyl acrylates, or copolymers synthesized by vinyl polymerization of glycidyl methacrylate and other vinyl monomers. Typical compounds include 1,4-butanediol diglycidyl ether, 1,6-hexanediol diglycidyl ether, glycerin triglycidyl ether, trimethylolpropane triglycidyl ether, sorbitol tetraglycidyl ether, dipentaerythritol. One or more of glycidyl ethers of polyhydric alcohols such as hexaglycidyl ether of polyethylene glycol, diglycidyl ether of polyethylene glycol, diglycidyl ether of polypropylene glycol, and aliphatic polyhydric alcohols such as propylene glycol, trimethylolpropane and glycerin Polyglycidyl ether of polyether polyol, diglycidyl ester of aliphatic long-chain dibasic acid obtained by adding an alkylene oxide of And the like. In addition, monoglycidyl ethers of higher aliphatic alcohols, phenols, cresols, butylphenols, monoglycidyl ethers of polyether alcohols obtained by adding alkylene oxides to these, glycidyl esters of higher fatty acids, epoxidized soybean oil, epoxy Examples include octyl stearate, butyl epoxy stearate, epoxidized linseed oil, and epoxidized polybutadiene.

  Specific examples of the cationically polymerizable organic compound other than the epoxy compound that can be used in the present invention include oxetane compounds such as trimethylene oxide, 3,3-dimethyloxetane and 3,3-dichloromethyloxetane, tetrahydrofuran, 2,3 -Trioxane such as dimethyltetrahydrofuran, cyclic ether compounds such as 1,3-dioxolane, 1,3,6-trioxacyclooctane, cyclic lactone compounds such as β-propiolactone, γ-butyrolactone, ε-caprolactone, ethylene sulfide Thirane compounds such as trimethylene sulfide, 3,3-dimethylthietane, etc., cyclic thioether compounds such as tetrahydrothiophene derivatives, spiro orthoester compounds obtained by reaction of epoxy compounds with lactones Vinyl ethers such as spiro ortho carbonate compounds, cyclic carbonate compounds, ethylene glycol divinyl ether, alkyl vinyl ethers, 3,4-dihydropyran-2-methyl (3,4-dihydropyran-2-carboxylate), triethylene glycol divinyl ether Examples thereof include ethylenically unsaturated compounds such as compounds, styrene, vinylcyclohexene, isobutylene and polybutadiene, and the above derivatives.

In the present invention, (3) the amount of the cationically polymerizable organic compound other than the alicyclic epoxy compound represented by the general formula (I) is (1) the alicyclic represented by the general formula (I). The amount is 500 parts by weight or less, preferably 300 parts by weight or less, and more preferably 100 parts by weight or less with respect to 100 parts by weight of the epoxy compound.
When the compounding amount of the cationically polymerizable organic compound other than the alicyclic epoxy compound represented by the general formula (I) exceeds 500 parts by weight, excellent moisture absorption resistance by the alicyclic epoxy compound represented by the general formula (I) Is killed.

  Moreover, the compounding quantity of (2) active energy ray sensitive cationic polymerization initiator is (1) with respect to the alicyclic epoxy compound shown with the said general formula (I), or (1) with the said general formula (I). 0.05 to 30% by weight based on the total amount of the alicyclic epoxy compound shown and (3) a cationically polymerizable organic substance other than the alicyclic epoxy compound represented by the general formula (I), Preferably, it is 0.5 to 10% by weight. When the blending amount is less than 0.05% by weight, the sensitivity is deteriorated. On the other hand, when it exceeds 30% by weight, the curability is deteriorated, and problems such as a decrease in adhesiveness and coloring of a cured product are easily caused.

The radically polymerizable organic compound (4) used in the present invention is a radically polymerizable organic compound that undergoes a high molecular weight or a crosslinking reaction by irradiation with active energy rays in the presence of an active energy ray sensitive radical polymerization initiator. A compound having at least one unsaturated double bond in the molecule.
Examples of such compounds include acrylate compounds, methacrylate compounds, allyl urethane compounds, unsaturated polyester compounds, and styrene compounds.
Among such radically polymerizable organic compounds, a compound having a (meth) acryloyl group is preferable because it is easy to synthesize and obtain and is easy to handle. For example, epoxy (meth) acrylate, urethane (meth) acrylate, polyester (meth) acrylate, polyether (meth) acrylate, and (meth) acrylic acid esters of alcohols can be used.

  Here, the epoxy (meth) acrylate is, for example, an acrylate obtained by reacting a conventionally known aromatic epoxy resin, alicyclic epoxy resin, aliphatic epoxy resin or the like with (meth) acrylic acid. Among these epoxy acrylates, particularly preferred is an acrylate of an aromatic epoxy resin, and a polyglycidyl ether of a polyhydric phenol having at least one aromatic nucleus or an alkylene oxide adduct thereof is combined with (meth) acrylic acid. It is (meth) acrylate obtained by making it react. For example, (meth) acrylate, epoxy novolac resin and (meth) acrylic obtained by reacting glycidyl ether obtained by reaction of bisphenol A or its alkylene oxide adduct with epichlorohydrin with (meth) acrylic acid. Examples include (meth) acrylates obtained by reacting acids.

  Preferred as the urethane (meth) acrylate is a (meth) acrylate obtained by reacting a hydroxyl group-containing (meth) acrylic acid ester and an isocyanate group with one or two or more hydroxyl group-containing polyesters or hydroxyl group-containing polyethers, or a hydroxyl group. And (meth) acrylates obtained by reacting the containing (meth) acrylic acid ester with isocyanates.

  What is preferable as a hydroxyl-containing polyester used here is obtained by reaction with 1 type, or 2 or more types of polyhydric alcohol, 1 type or 2 or more types of polybasic acid, or 1 type or 2 or more types of lactones. Examples of the polyhydric alcohol that is a hydroxyl group-containing polyester include 1,3-butanediol, 1,4-butanediol, 1,6-hexanediol, diethylene glycol, triethylene glycol, neopentyl glycol, polyethylene glycol, and polypropylene. Examples include glycol, polybutylene glycol, trimethylolpropane, glycerin, pentaerythritol, dipentaerythritol and the like. Examples of the polybasic acid include adipic acid, terephthalic acid, phthalic anhydride, trimellitic acid, and the like. Examples of lactones include β-propiolactone, γ-butyrolactone, and ε-caprolactone.

  Preferred as the hydroxyl group-containing polyether is a hydroxyl group-containing polyether obtained by adding one or more alkylene oxides to a polyhydric alcohol, and the polyhydric alcohol is the same as the compound described above. Can be illustrated. Examples of the alkylene oxide include ethylene oxide, propylene oxide, and butylene oxide.

What is preferable as the hydroxyl group-containing (meth) acrylic acid ester is a hydroxyl group-containing (meth) acrylic acid ester obtained by an esterification reaction between a polyhydric alcohol and (meth) acrylic acid. The same thing can be illustrated.
Of such hydroxyl group-containing (meth) acrylic acid, a hydroxyl group-containing (meth) acrylic acid ester obtained by esterification reaction of a dihydric alcohol and (meth) acrylic acid is particularly preferred, for example, 2-hydroxyethyl (meth) acrylate. Is mentioned.

  As the isocyanates, compounds having at least one isocyanate group in the molecule are preferable, and divalent isocyanate compounds such as tolylene diisocyanate, hexamethylene diisocyanate, and isophorone diisocyanate are particularly preferable.

  The polyester (meth) acrylate is preferably a polyester (meth) acrylate obtained by reacting a hydroxyl group-containing polyester with (meth) acrylic acid. Preferred as the hydroxyl group-containing polyester used here is a hydroxyl group-containing polyester obtained by an esterification reaction of one or more polyhydric alcohols with one or more monobasic acids or polybasic acids. And as a polyhydric alcohol, the thing similar to the compound mentioned above can be illustrated. Examples of monobasic acids include formic acid, acetic acid, butyric acid, and benzoic acid. Examples of the polybasic acid include adipic acid, terephthalic acid, phthalic anhydride, and trimellitic acid.

  A preferable polyether (meth) acrylate is a polyether (meth) acrylate obtained by reacting a hydroxyl group-containing polyether with meth (acrylic) acid. Preferred as the hydroxyl group-containing polyether used here is a hydroxyl group-containing polyether obtained by adding one or more alkylene oxides to a polyhydric alcohol, and the polyhydric alcohol includes the compounds described above. The same thing can be illustrated. Examples of the alkylene oxide include ethylene oxide, propylene oxide, and butylene oxide.

  What is preferable as a (meth) acrylic acid ester of alcohols is obtained by reacting an aromatic or aliphatic alcohol having at least one hydroxyl group in the molecule and an alkylene oxide adduct thereof with (meth) acrylic acid. (Meth) acrylate, for example, 2-ethylhexyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, isoamyl (meth) acrylate, lauryl (meth) acrylate, stearyl (meta ) Acrylate, isooctyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, isobornyl (meth) acrylate, benzyl (meth) acrylate, 1,3-butanediol di (meth) acrylate, 1,4-butanedio Di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate , Polypropylene glycol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, ethylene oxide modified trimethylolpropane tri (meth) acrylate, propylene oxide modified trimethylolpropane tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, Dipentaerythritol hexa (meth) acrylate, ε-caprolactone modified, dipentaerythritol hexa (meth) acrylate I can get lost.

In the present invention, 50 parts by weight or more out of 100 parts by weight of the (4) radical polymerizable organic compound is preferably a compound having a (meth) acryloyl group in the molecule. The reason is that if the ratio of the compound having an unsaturated group other than the (meth) acryloyl group is increased, the curability by the active energy ray may be lowered. Among the compounds having a (meth) acryloyl group, it is preferable to use a poly (meth) acrylate having two or more (meth) acryloyl groups.
The blending amount of the radically polymerizable organic compound (4) used in the present invention is the alicyclic epoxy compound represented by the above general formula (I) or a mixture of the alicyclic epoxy compound and other cationically polymerizable organic compounds. The amount is preferably 200 parts by weight or less, particularly preferably 100 parts by weight or less, based on 100 parts by weight. When the compounding amount of the radical polymerizable organic compound exceeds 200 parts by weight, the excellent moisture absorption resistance by the alicyclic epoxy compound is diminished.

(5) The active energy ray-sensitive radical polymerization initiator used in the present invention is a compound capable of initiating radical polymerization by irradiation with active energy rays, and is a ketone such as an acetophenone compound, a benzyl compound, or a thioxanthone compound. System compounds are preferred.
Examples of the acetophenone compound include diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 4′-isopropyl-2-hydroxy-2-methylpropiophenone, and 2-hydroxymethyl-2. -Methylpropiophenone, 2,2-dimethoxy-1,2-diphenylethane-1-one, p-dimethylaminoacetophenone, p-tertiarybutyldichloroacetophenone, p-tertiarybutyltrichloroacetophenone, p-azidobenzal Acetophenone, 1-hydroxycyclohexyl phenyl ketone, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropanone-1, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -Butanone-1, benzoin Benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin-n-butyl ether, benzoin isobutyl ether and the like.
Examples of benzyl compounds include benzyl and anisyl.
Examples of the benzophenone compounds include benzophenone, methyl o-benzoylbenzoate, Michler's ketone, 4,4′-bisdiethylaminobenzophenone, 4,4′-dichlorobenzophenone, 4-benzoyl-4′-methyldiphenyl sulfide.
Examples of the thioxanthone compound include thioxanthone, 2-methylthioxanthone, 2-ethylthioxanthone, 2-chlorothioxanthone, 2-isopropylthioxanthone, and 2,4-diethylthioxanthone.
Other energy ray sensitive radical polymerization initiators include 2,4,6-trimethylbenzoyldiphenylphosphine oxide, bis (cyclopentadienyl) -bis [2,6-difluoro-3- (py-1-yl) ] Titanium etc. are mentioned.

These (5) active energy ray-sensitive radical polymerization initiators may be used alone or in combination of two or more according to the desired performance.
The compounding amount of the active energy ray-sensitive radical polymerization initiator is 0.05 to 30 parts by weight, preferably 0.5 to 10 parts by weight with respect to 100 parts by weight of the radical polymerizable organic compound. When the blending amount is less than 0.05 parts by weight, curing failure may occur. Conversely, when it exceeds 30 parts by weight, the cured product may be colored or the mechanical properties of the cured product may be deteriorated.

  Although not essential, the active energy ray-curable epoxy resin composition for optical three-dimensional modeling of the present invention can be blended with a photosensitizer as desired within the scope of the object of the present invention. For example, when a photosensitizer such as an anthracene derivative or pyrene derivative is used in combination, the curing rate is further improved as compared with the case where they are not blended, and it becomes preferable as an active energy ray-curable epoxy resin composition. The photosensitizer may be about 20 to 300% by weight with respect to (2) the energy ray-sensitive cationic polymerization initiator.

  The active energy ray-curable epoxy resin composition for optical three-dimensional modeling of the present invention is not essential, but is an organic compound having two or more hydroxyl groups in one molecule as desired within the scope of the present invention. Can be blended. For example, a flexible cured product can be obtained by blending an organic compound having two or more hydroxyl groups in one molecule, such as a polyhydric alcohol, a hydroxyl group-containing polyether, a hydroxyl group-containing polyester, or a polyhydric phenol.

Examples of polyhydric alcohols include ethylene glycol, propylene glycol, neopentyl glycol, trimethylolpropane, glycerin, pentaerythritol, dipentaerythritol, 1,3-butanediol, 1,4-butanediol, 1,6 -Hexanediol etc. are mentioned.
Further, the hydroxyl group-containing polyether is a compound obtained by adding one or more kinds of alkylene oxides to one or more kinds of polyhydric alcohols or polyhydric phenols. Examples of polyhydric alcohols used in this are ethylene glycol, propylene glycol, neopentyl glycol, trimethylolpropane, glycerin, pentaerythritol, dipentaerythritol, 1,3-butanediol, 1,4-butanediol 1,6-hexanediol and the like. Examples of the polyhydric phenol include bisphenol A, bisphenol F, phenol novolac resin, cresol novolac resin, and the like. Examples of the alkylene oxide include butylene oxide, propylene oxide, ethylene oxide and the like.
Furthermore, the hydroxyl group-containing polyester is a hydroxyl group-containing polyester obtained by an esterification reaction of one or more polyhydric alcohols or polyhydric phenols with one or two or more monobasic acids or polybasic acids, and It is a hydroxyl group-containing polyester obtained by an esterification reaction of one or more polyhydric alcohols or polyhydric phenols with one or two or more lactones. Examples of polyhydric alcohols and polyhydric phenols are the same as those described above. Examples of monobasic acids include formic acid, acetic acid, butyric acid, benzoic acid and the like. Examples of the polybasic acid include adipic acid, terephthalic acid, trimellitic acid and the like. Examples of lactones include β-propiolactone, γ-butyrolactone, and ε-caprolactone.
The polyhydric phenol is a compound containing two or more hydroxyl groups bonded directly to an aromatic ring in one molecule, and examples thereof include the same ones as described above.

  Organic compounds having two or more hydroxyl groups in one molecule are generally represented by (1) the alicyclic epoxy compound represented by the general formula (I) or (1) the general formula (I). What is necessary is just about 1 to 50 weight% with respect to the total amount of the alicyclic epoxy compound and cation polymerizable organic compounds other than the alicyclic epoxy compound represented by the said general formula (I).

In addition, the active energy ray-curable epoxy resin composition for optical three-dimensional modeling of the present invention can be blended with a thermoplastic polymer compound as desired within the scope of the object of the present invention, although it is not essential. The thermoplastic polymer compound is a polymer compound that is liquid or solid at room temperature and is uniformly mixed with the resin composition at room temperature.
Typical examples of such thermoplastic polymer compounds include polyester, polyvinyl acetate, polyvinyl chloride, polybutadiene, polycarbonate, polystyrene, polyvinyl ether, polyvinyl butyral, polyacrylate, polymethyl methacrylate, polybutene, and styrene butadiene block copolymer. Examples include hydrogenated products. Moreover, the thing which introduce | transduced functional groups, such as a hydroxyl group, a carboxyl group, a vinyl group, an epoxy group, into these thermoplastic polymer compounds can also be used. The desirable number average molecular weight of the thermoplastic polymer compound for the present invention is 1,000 to 500,000, and the more preferable number average molecular weight is 5,000 to 100,000.

The active energy ray-curable epoxy resin composition for optical three-dimensional modeling of the present invention blended with a thermoplastic polymer compound is preferable because the mechanical properties of the cured product are further increased as compared with the case where these are not blended. . The thermoplastic polymer compound generally includes (1) an alicyclic epoxy compound represented by the above general formula (I) or (1) an alicyclic epoxy compound represented by the above general formula (I) ( 3) with respect to the total amount of the cation polymerizable organic compound other than the alicyclic epoxy compound represented by the general formula (I), or (1) the alicyclic epoxy compound represented by the general formula (I) (3) If it is about 3 to 100% by weight based on the total amount of the cationically polymerizable organic compound other than the alicyclic epoxy compound represented by the general formula (I) and the radically polymerizable organic compound (4) Good.
Moreover, the active energy ray-curable epoxy resin composition for optical three-dimensional modeling of the present invention can be blended with a filler as desired within the scope of the object of the present invention, although it is not essential. Fillers are inorganic and organic powders, flakes, and fibrous materials.
Examples of inorganic fillers include glass powder, mica powder, silica or quartz powder, carbon powder, calcium carbonate powder, alumina powder, aluminum hydroxide powder, aluminum silicate powder, zirconium silicate powder, iron oxide powder, sulfuric acid Barium powder, kaolin, dolomite, metal powder, glass fiber, carbon fiber, asbestos, metal whisker, calcium carbonate whisker, hollow glass balloon or these surfaces are treated with a coupling agent, and organic groups are added to the surface. Can be mentioned.
Examples of organic fillers include pulp powder, nylon powder, polyethylene powder, crosslinked polystyrene powder, crosslinked acrylic resin powder, crosslinked phenol resin powder, crosslinked urea resin powder, crosslinked melamine resin powder, crosslinked epoxy resin powder, rubber powder or Those having reactive groups such as an epoxy group, an acrylic group, and a hydroxyl group on these surfaces can be mentioned. The filler is generally (1) the alicyclic epoxy compound represented by the general formula (I) or (1) the alicyclic epoxy compound represented by the general formula (I) and (3) the above Or (1) the alicyclic epoxy compound represented by the above general formula (I) and (3) with respect to the total amount with the cationically polymerizable organic substance other than the alicyclic epoxy compound represented by the general formula (I) About 0.5 to 30% by weight, preferably 1 with respect to the total amount of the cationically polymerizable organic material other than the alicyclic epoxy compound represented by the general formula (I) and the radically polymerizable organic compound (4) It may be about ˜20% by weight. When the blending amount of the filler exceeds 30% by weight, the curability by the active energy ray may be lowered.

  In addition, as long as the effect of the present invention is not impaired, a heat-sensitive cationic polymerization initiator, a colorant such as a pigment and a dye, a leveling agent, an antifoaming agent, a thickener, a flame retardant, an antioxidant, and a stabilizer. Various resin additives such as these can be added within the range of the usual use amount. Examples of the heat-sensitive cationic polymerization initiator include 2-butynyltetramethylenesulfonium hexafluoroantimonate and 3-methyl-2 described in JP-A-57-49613 and JP-A-58-37004. -Onium salts such as butynyltetramethylenesulfonium hexafluoroantimonate.

Examples of the active energy ray for curing the active energy ray-curable epoxy resin composition for optical three-dimensional modeling of the present invention include ultraviolet rays, electron beams, X-rays, radiation, and high frequencies, and ultraviolet rays are most preferable economically. Examples of the ultraviolet light source include an ultraviolet laser, a mercury lamp, a xenon lamp, a sodium lamp, and an alkali metal lamp.
The active energy ray-curable epoxy resin composition for optical three-dimensional modeling of the present invention can be used for metals, rubbers, plastics, molded products, films, paper, wood, glass, concrete, ceramic products and the like.
Moreover, as a specific use of the active energy ray-curable epoxy resin composition for optical three-dimensional modeling of the present invention, other than the optical three-dimensional modeling resin composition, paint, coating agent, ink, resist, adhesive, Examples include molding materials, casting materials, putty, and impregnating agents.

Next, the active energy ray-curable epoxy resin composition for optical three-dimensional modeling and the optical three-dimensional modeling method of the present invention will be described in detail.
In order to perform the optical three-dimensional modeling method of the present invention, first, it is necessary to prepare an active energy ray-curable epoxy resin composition for optical three-dimensional modeling.
This preparation process is preferably performed by a well-known process. For example, the constituent materials are sufficiently mixed. Specific examples of the mixing method include a stirring method using a stirring force accompanying rotation of a propeller and a roll kneading method. The above-mentioned components (1) and (2), (1) and (2) and (3), or (1) and (2) and (1) required for the active energy ray-curable epoxy resin composition for optical three-dimensional modeling The preferred blending ratios of 3), (4) and (5), the types of additives blended as necessary, and blending ratios thereof are as described above. The active energy ray-curable epoxy resin composition for optical three-dimensional modeling thus obtained is generally liquid at ordinary temperature.

Next, the active energy ray-curable epoxy resin composition for optical three-dimensional modeling is irradiated with an energy ray on any surface, and the active energy ray-irradiated surface of the resin composition is cured to have a desired thickness. A layer is formed, and the active energy ray-curable resin composition is further supplied onto the cured layer, and this is cured in the same manner to obtain a cured layer continuous with the cured layer. By repeating the operation, a three-dimensional solid molded product is obtained.
The work procedure for carrying out the optical three-dimensional modeling method of the present invention is specifically shown below. First, as described in, for example, JP-A-60-247515, a container having one (upper part) opened is filled with the resin composition up to about half of its height, and then into the container. A box with a bottom made of a material transparent to the active energy rays is submerged so that the resin composition does not flow into the box, and a light guide (having a condensing lens) is placed on the top of the box. And having a structure capable of irradiating active energy rays in the downward direction), moving the box or container relative to the light guide relative to the active energy rays of the box from the light guide A solid having a desired shape is formed by selectively irradiating a predetermined portion inside the resin composition with an active energy ray necessary for curing through a bottom made of a transparent material. In addition, the method of irradiating the active energy ray directly with respect to the predetermined part inside the said resin composition with which the inside of the container was filled from the light guide without using the said box.

  The kind of the active energy ray used for the optical three-dimensional modeling method of the present invention is the same as the active energy ray for curing the aforementioned active energy ray-curable resin composition of the present invention. That is, there are ultraviolet rays, electron beams, X-rays, radiation, high frequencies, etc., and ultraviolet rays having a wavelength of about 1800 to 5000 mm are most preferable economically. Examples of the ultraviolet light source include an ultraviolet laser, a mercury lamp, a xenon lamp, a sodium lamp, and an alkali metal lamp, and a laser beam is particularly preferable because of its good light condensing property. The active energy ray-curable epoxy resin composition for optical three-dimensional modeling of the present invention is very excellent for creating a three-dimensional three-dimensional model by stacking layered products, and without using a mold. It can be creatively processed, and by combining with CAD / CAM, various shapes such as free phases can be created with high precision, and its industrial value is extremely high. For example, as an application field of the epoxy resin composition for active energy ray-curable optical three-dimensional modeling of the present invention, a model for examining the appearance design in the middle of the design, a model for checking the inconvenience of the combination of parts It can be used for a wide range of applications such as a wooden mold for producing a mold and a model for copying for producing a mold.

(Example)
EXAMPLES Hereinafter, the present invention will be specifically described with reference to examples, but the present invention is not limited thereto.

[Examples 1 to 12, Comparative Examples 1 to 10]
The active energy ray-curable composition was blended according to the blending composition shown in Table 1 and Table 2 below (numerical values are parts by weight) and mixed uniformly.
In addition, the epoxy resin and energy ray sensitive cationic polymerization initiator as a cationically polymerizable organic substance used in the examples and comparative examples in each table are as follows.
Epoxy resin A: bis (3,4-epoxycyclohexyl) synthesized in Synthesis Example 1 below
Epoxy resin B: 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate Epoxy resin C: Bis (3,4-epoxycyclohexylmethyl) adipate Epoxy resin D: 1,4-butanediol diglycidyl ether

Initiator 1: Di- (4-tert-butylphenyl) iodonium hexafluorophosphate Initiator 2: Diphenyl-4-thiophenoxyphenylsulfonium hexafluoroantimonate Initiator 3: 4- [4 ′-(benzoyl) phenylthio] phenyl -Di- (4-fluorophenyl) sulfonium hexafluoroantimonate initiator 4: 4,4'bis- (diphenylsulfonio) phenyl sulfide-bis-hexafluoroantimonate initiator 5: 4,4'-bis- [ Di (β-hydroxyethoxy) phenylsulfonio] phenyl sulfide-bis-hexafluoroantimonate

Epoxy resin A was synthesized in Synthesis Example 1 below.
(Synthesis Example 1)
The starting material alicyclic olefin compound bicyclohexyl-3,3'-diene (406 g) and ethyl acetate (1217 g) were charged, nitrogen was blown into the gas phase, and the temperature in the reaction system was 37.5 ° C. In this manner, 457 g of a 30 wt% peracetic acid ethyl acetate solution (water content 0.41 wt%) was added dropwise over about 3 hours. After the peracetic acid solution was dropped, the reaction was terminated by aging at 40 ° C. for 1 hour. Further, the crude liquid at the end of the reaction was washed with water at 30 ° C., and the low boiling point compound was removed at 70 ° C./20 mmHg to obtain 415 g of an epoxy compound. The yield at this time was 85%.
The resulting epoxy compound had an oxirane oxygen concentration of 14.7% by weight (theoretical value: 16.5% by weight).
Further, in ¹ HNMR measurement, a peak derived from an internal double bond in the vicinity of δ4.5-5 ppm disappeared, and a proton peak derived from an epoxy group was confirmed in the vicinity of δ2.9-3.1 ppm. It was confirmed to be an alicyclic epoxy compound (referred to as epoxy compound A) represented by the general formula (I).

Moreover, evaluation of each performance in Table 1 and Table 2 was measured by the following method.
[transparency]
The transparency of the composition was visually determined. ○: completely transparent, Δ: slightly turbid, x: cloudy.
[Finger dryness]
The test composition was applied on an aluminum test panel to a thickness of 5 microns, irradiated with ultraviolet rays from a distance of 10 cm with a 80 W / cm high-pressure mercury lamp, and the amount of irradiation until the coating surface was dry to the touch when cured. mJ / cm ² ).
○: Less than 50 mJ / cm ² , Δ: 50 mJ / cm ² or more and less than 100 mJ / cm ² , X: 100 mJ / cm ² or more [gloss]
After irradiating with ultraviolet rays until dry to the touch, the surface of the cured coating film was visually determined.
○: Good gloss, Δ: Slightly cloudy, ×: No gloss [alkali resistance]
The composition is applied to a bonde-treated steel sheet with a thickness of 20 μm, and a cured coating film is obtained by irradiation with 100 mJ / cm ² with an 80 W / cm high-pressure mercury lamp. It was fixed horizontally so as not to move, covered with a petri dish to prevent evaporation of moisture, allowed to stand for 24 hours, washed with running water, and the change in the cured film was judged visually.
○: No change, Δ: Whitening of coating film, ×: Disappearance of coating film [water absorption]
A test composition was injected between two glass plates sandwiching a spacer having a thickness of 3 mm, irradiated with ultraviolet rays to prepare a test piece having a size of 30 mm × 30 mm × 3 mm, and measured according to JIS-K6911. Ultraviolet rays were irradiated at 2000 mJ / cm ² under an 80 W / cm high-pressure mercury lamp.

[Examples 13 to 15]
In the following, optical three-dimensional modeling was performed.
According to the composition shown in Table 3 below (the numerical values are parts by weight), each member was sufficiently mixed to obtain an active energy ray-curable epoxy resin composition for optical three-dimensional modeling. The obtained resin composition was a pale yellow transparent liquid.

[Comparative Examples 11 and 12]
Various resin compositions were prepared according to the composition shown in the following Table 3 (numerical values are parts by weight) and tested in the same manner as in Examples 13-15. Each test result is shown in Table 3 together with Examples 13-15. In addition, the compounds used for the test other than the above are as follows.
The following radical resins 1 to 3 were used as the radical polymerizable organic substance (hereinafter abbreviated as “radical resin”).
Radical resin 1: Bisphenol A diglycidyl ether diacrylate Radical resin 2: Trimethylolpropane triacrylate Radical resin 3: Dipentaerythritol hexaacrylate

The following radical initiators 1 and 2 were used as energy ray-sensitive radical polymerization initiators (hereinafter abbreviated as “radical initiators”).
Radical initiator 1: 1-hydroxy-cyclohexyl-phenyl-ketone Radical initiator 2: 2,2-dimethoxy-1,2-diphenylmethane-1-one

  Next, focusing on a three-dimensional NC (numerical control) table on which a container for containing a resin composition is placed, an ultraviolet Ar ion laser (wavelengths 333, 351, 364 nm multi-line, output 100 mW), an optical system, and a control computer. Using a three-dimensional modeling experiment system consisting of a control unit, the resin composition obtained in Examples 13 to 15 and Comparative Examples 11 and 12, based on CAD data, is laminated with a pitch of 0.1 mm, a height of 9 cm, a diameter A 5 cm hollow cylindrical model was prepared. The time required to produce this model was 55 minutes. The accuracy with respect to the design dimension was 0.05% in the height direction and 0.03% in the radial direction. Moreover, in order to investigate the change of the resin due to water absorption, a hollow test piece having a size of 3 mm × 10 mm × 50 mm was prepared, and this was left in a desiccator for 5 days to be completely dried. This test piece was left in a constant temperature and humidity chamber at a temperature of 30 ° C. and a humidity of 90% RH for 5 days, and the expansion rate due to moisture was measured from the length of the side of 50 mm before and after humidification. As a result, the expansion coefficient was 0.01%.

Claims (9)

An active energy ray-curable epoxy resin composition for optical three-dimensional modeling, comprising bis (3,4-epoxycyclohexyl) and (2) an active energy ray-sensitive cationic polymerization initiator . (1) General formula (I)
[In formula, R < ¹ > -R < ¹⁸ > may be same or different, respectively. These are a hydrogen atom, a halogen atom, an oxygen atom, a hydrocarbon group that may contain a halogen atom, or an alkoxy group that may have a substituent.
An alicyclic epoxy compound represented by: (2) an active energy ray sensitive cationic polymerization initiator , (4) a radical polymerizable organic compound, and (5) an active energy ray sensitive radical polymerization initiator. An active energy ray-curable epoxy resin composition for optical three-dimensional modeling. The active energy ray-curable epoxy resin composition for optical three-dimensional modeling according to claim 2, wherein the alicyclic epoxy compound represented by the formula ( I ) is bis (3,4-epoxycyclohexyl). 4. An energy ray-curable epoxy resin composition for optical three-dimensional modeling according to any one of claims 1 to 3 , and (3) a cationically polymerizable organic other than the alicyclic epoxy compound represented by the general formula (I) An active energy ray-curable epoxy resin composition for optical three-dimensional modeling, comprising a compound. (2) an active energy ray sensitive cationic polymerization initiator is an aromatic iodonium salts, aromatic sulfonium salts or iron, - active energy ray-curable according to any one of claims 1 to 4 which is one of arene complexes An epoxy resin composition for optical three-dimensional modeling. The active energy ray-curable epoxy resin composition for optical three-dimensional modeling according to any one of claims 2 to 5, wherein 50% by weight or more of the (4) radical polymerizable organic compound is (meta ) An active energy ray-curable epoxy resin composition for optical three-dimensional modeling, which is a compound having an acryloyl group. ( 5 ) The active energy ray-curable radical polymerization initiator is any one of an acetophenone compound, a benzyl compound, and a ketone compound. 7. The active energy ray-curable optical steric structure according to any one of claims 2 to 6. An epoxy resin composition for modeling.   The active energy ray-curable resin composition is irradiated with an active energy ray at an arbitrary portion, the energy-irradiated portion of the resin composition is cured to form a cured layer having a desired thickness, and the above-described cured layer is formed on the cured layer. Optically obtained by further supplying an active energy ray-curable resin composition and curing it in the same manner to obtain a cured product continuous with the aforementioned cured layer, and repeating this operation to obtain a three-dimensional solid object In an optical three-dimensional modeling method, the active energy ray-curable resin composition is the active energy ray-curable epoxy resin composition for optical three-dimensional modeling according to any one of claims 1 to 7. Solid modeling method. A three-dimensional solid object obtained by the optical three-dimensional modeling method according to claim 8.