JP2015131927A - Liquid resin composition for inkjet stereolithography - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a liquid resin composition for inkjet stereolithography, which can be colored in a full-color manner with a simple configuration of an apparatus and which gives a molded article excellent in hardness, strength, and storage property with light fastness.SOLUTION: The liquid resin composition for inkjet stereolithography essentially comprises the following components (A), (B), and (C): (A) an active ray-polymerizable organic compound; (B) a compound that generates an acid by irradiation with active rays; and (C) an acid-induced color developing dye precursor. For the active ray-polymerizable organic compound, a radical polymerizable organic compound and/or a cation polymerizable organic compound is used; for the compound that generates an acid by irradiation with active rays, a cationic photopolymerization initiator is used; and for the acid-color developing dye precursor, a color former is used. Visible rays are used as active rays. The liquid resin composition preferably further contains an ultraviolet ray absorbent.

Description

The present invention relates to a chromogenic liquid resin composition used in an inkjet stereolithography method.
Specifically, it is almost uncolored before use, is cured by actinic radiation at the time of modeling, and forms a colored modeled product by coloring the dye precursor, enabling full-color coloring and a fast curing speed. The present invention relates to a resin composition.

  There are a wide variety of stereolithography methods for creating a desired three-dimensional model by irradiating a liquid photo-curable resin with light such as laser light or ultraviolet light to cure it into a certain pattern and repeating this process as a 3D printer. It is known and various resin compositions are used. (Patent Documents 1 to 4)

In recent years, an optical modeling method using an inkjet method has been proposed. This is a method for forming a cured thin film by ejecting fine droplets of a photocurable liquid resin composition from a nozzle so as to draw a predetermined shape pattern, and irradiating with ultraviolet rays. There is an advantage that it is not necessary to install a resin liquid tank or a dark room. (Patent Document 5)
And various compositions are proposed also about the resin composition used for the inkjet-type optical modeling method. (Patent Documents 6 to 8)

In such an ink jet optical modeling method, in order to color a modeled object, it is usually cured after modeling using a liquid resin composition containing a colorant, or an uncolored modeled article after curing. A method of coloring by discharging a colorant is used. As the colorant, resin-soluble dyes, water-soluble dyes, finely dispersed pigments, and the like are used.
However, in the method of curing after shaping using a liquid resin composition containing a colorant, the resin composition itself is colored, so that it is difficult for light to reach the curable resin or polymerization initiator during curing. There is a drawback that it takes time.
In addition, the method of discharging and coloring a colorant onto an uncolored shaped article after curing requires a solution (ink) containing the colorant and a dedicated inkjet head, which has a drawback that the structure of the inkjet printer becomes complicated. . Furthermore, the manufacturing process also requires two steps of modeling hardening and coloring.

Patent Documents 9 and 10 disclose a photosensitive resin composition containing a photopolymerization initiator that generates free radicals upon irradiation with actinic radiation, a leuco dye, and a compound that generates acid upon irradiation with actinic radiation. The resin composition is a photosensitive resin composition for casting that is used for producing a replication model by casting, and a mold is made of an ultraviolet transparent silicone rubber, and the photosensitive resin composition is placed in the mold. By injecting and irradiating with ultraviolet rays, a duplication model colored in black can be produced. The inventions disclosed in Patent Documents 9 and 10 are different in use and configuration from the present invention, and since the used photosensitive resin composition has a high viscosity, it is difficult to use for inkjet. is there.

JP-A-62-35966 JP-A-1-204915 Japanese Patent Laid-Open No. 5-24119 JP-A-8-59760 JP 2002-067174 A JP 2008-50407 A JP 2010-155926 A JP 2012-111226 A Japanese Patent Laid-Open No. 11-60962 JP 2000-273109 A

INDUSTRIAL APPLICABILITY The present invention provides a liquid resin for ink jet photofabrication with a novel coloring system and composition that has a fast curing speed, enables each desired color and full-color coloring, has excellent light-resistant storage stability, and can simplify the equipment structure used for modeling. An object is to provide a composition.

As a result of various studies, the present inventors have found that the above-described problems can be achieved by a liquid resin composition for ink jet optical modeling containing the following components, and have completed the present invention.
That is, the present invention
(I) A liquid resin composition for inkjet optical modeling, comprising the following components (A), (B) and (C) as essential components.
(A) Actinic ray polymerizable organic compound (B) Compound that generates acid upon irradiation with actinic ray (C) Acid coloring dye precursor

(Ii) The liquid resin composition for inkjet optical modeling according to (i), wherein the (A) actinic ray polymerizable organic compound is the following (A-1) and / or (A-2).
(A-1) Radical polymerizable organic compound (A-2) Cationic polymerizable organic compound (iii) The radical polymerizable organic compound (A-1) is an organic compound having at least one unsaturated double bond. (Ii) Liquid resin composition for inkjet optical modeling.
(Iv) The liquid resin composition for inkjet photofabrication according to any one of (i) to (iii), further comprising (D) a radical photopolymerization initiator.

(V) The liquid resin composition for inkjet optical modeling according to any one of (ii) to (iv), wherein the cationically polymerizable organic compound (A-2) is an organic compound having two or more epoxy groups.
(Vi) The liquid resin composition for inkjet photofabrication according to any one of (i) to (v), wherein the compound that generates acid upon irradiation with actinic radiation of (B) is a cationic photopolymerization initiator.
(Vii) The (C) acid color-forming dye precursor is a fluorane compound, a phthalide compound, an azaphthalide compound, a fluorene spirophthalide compound system, a triphenylmethane compound, a diphenylmethane compound, a thiazine compound, or a lactam compound. The liquid resin composition for inkjet optical modeling according to any one of (i) to (vi), which is at least one color former selected from a compound and a diketone compound.
(Viii) The liquid resin composition for ink-jet photofabrication according to any one of (i) to (vii), which exhibits curing / coloring properties using visible light as an active ray.
(Ix) The liquid resin composition for inkjet optical modeling according to any one of (i) to (viii), further comprising (E) an ultraviolet absorber.
About.
(X) The liquid resin composition for inkjet optical modeling according to any one of claims 1 to 9, wherein the viscosity at 80 ° C or lower is 1 to 30 mPa · s.

The liquid resin composition for inkjet optical modeling of the present invention is not substantially colored before use, and is quickly cured by irradiation with active rays at the time of modeling, and is colored to a desired color by irradiation with the active rays. Can be colored. For this reason, it is possible to create 3D models of each color and full color with an inkjet 3D printer that uses a CAD (Computer Aided Design) system based on electronic data, and to freely create a 3D model of the desired shape and color. It can be manufactured at a high degree. Furthermore, since the head and ink dedicated to the colorant are not required, the ink jet modeling apparatus can be made small and simple. Moreover, since the liquid resin composition for inkjet optical modeling of the present invention is not substantially colored before use, the active ray easily reaches the inside of the resin composition, and the curing rate is fast.
Furthermore, in an embodiment in which visible light, particularly blue LED light is used as the active ray for curing, and the ultraviolet light absorber is contained in the resin composition, the apparatus for the light source can be set simply and inexpensively, and the cured shaped article Especially excellent in light-preserving property.

The liquid resin composition for inkjet stereolithography of the present invention contains the following components (A), (B) and (C) as essential components.
(A) Actinic ray-polymerizable organic compound (B) Compound that generates an acid upon irradiation with actinic rays (C) Acid coloring pigment precursor Hereinafter, each component will be described in detail.

[(A) Active-line polymerizable organic compound]
An actinically polymerizable organic compound is an organic compound having a group that polymerizes in the molecule upon irradiation with actinic radiation. From the polymerization type, (A-1) a radically polymerizable organic compound and (A-2) a cationically polymerizable organic A distinction can be made between compounds.
When the actinic polymerizable organic compound is (A-1) a radical polymerizable organic compound, it is preferable that the liquid resin composition for inkjet photofabrication of the present invention simultaneously contains (D) a radical photopolymerization initiator. . However, (A-1) radically polymerizable organic compound and (A-2) cationically polymerizable organic compound are used in combination, and (B) (A-1) and (A-2) are generated by a compound that generates an acid upon irradiation with active rays. ) Can be copolymerized, the content of (D) radical photopolymerization initiator is low or may not be contained.
For example, (A-1) contains a group having an active hydrogen such as a hydroxyl group and a compound having an ethylenically unsaturated bond at the same time, and (A-2) contains a compound having two or more epoxy groups, When (B) is copolymerizable with a compound that generates an acid upon irradiation with actinic radiation, the content of (D) radical photopolymerization initiator may be small or may not be contained.

[(A-1) Radical polymerizable organic compound]
The radical-polymerizable organic compound is a radical-polymerizable compound that is polymerized or cross-linked by actinic ray irradiation, and preferably a compound having at least one unsaturated double bond in one molecule. Examples of these compounds include acrylate compounds, methacrylate compounds, allyl urethane compounds, unsaturated polyester compounds, and polythiol compounds.

As a compound having one unsaturated double bond in one molecule, linear or branched alkyl (meth) acrylate, alicyclic ring-containing (meth) acrylate, heterocyclic ring-containing (meth) acrylate, styrene, vinylcyclohexene, Examples include isobutylene and butadiene, with (meth) acrylates being preferred.

Examples of linear or branched alkyl (meth) acrylates include methyl (meth) acrylate, ethyl (meth) acrylate, isobutyl (meth) acrylate, lauryl (meth) acrylate, stearyl (meth) acrylate, and isostearyl (meth) acrylate. , T-butyl (meth) acrylate and the like.
Examples of the alicyclic ring-containing (meth) acrylate include cyclohexyl (meth) acrylate, 4-t-cyclohexyl (meth) acrylate, isobornyl (meth) acrylate, dicyclopentanyl (meth) acrylate, and the like. Examples of the heterocycle-containing (meth) acrylate include tetrahydrofurfuryl (meth) acrylate, 4- (meth) acryloyloxymethyl-2-methyl-2-ethyl-1,3-dioxolane, and 4- (meth) acryloyloxymethyl. -2-cyclohexyl-1,3-dioxolane, adamantyl (meth) acrylate] and the like.

  Examples of the compound having one unsaturated double bond per molecule that can be suitably used 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, dimethyl Aminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate, lauryl (meth) acrylate, dicyclopentadiene (meth) acrylate, dicyclopentenyloxyethyl (meth) acrylate, disi Lopentanyl (meth) acrylate, dicyclopentenyl (meth) acrylate, N, N-dimethyl (meth) acrylamide tetrachlorophenyl (meth) acrylate, 2-tetrachlorophenoxyethyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, tetra Bromophenyl (meth) acrylate, 2-tetrabromophenoxyethyl (meth) acrylate, 2-trichlorophenoxyethyl (meth) acrylate, tribromophenyl (meth) acrylate, 2-tribromophenoxyethyl (meth) acrylate, 2-hydroxy Ethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, vinylcaprolactam, N-vinylpyrrolidone, phenoxyethyl (meth) acrylate, butoxye (Meth) acrylate, pentachlorophenyl (meth) acrylate, pentabromophenyl (meth) acrylate, polyethylene glycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate, bornyl (meth) acrylate, methyltriethylene diglycol (meta ) An acrylate etc. can be illustrated.

Of these compounds having one unsaturated double bond in one molecule, isobornyl (meth) acrylate, lauryl (meth) acrylate, and phenoxyethyl (meth) acrylate are particularly preferable. Examples of commercially available products of these compounds include Aronix M-101, M-102, M-111, M-113, M-117, M-152, TO-1210 (above, manufactured by Toagosei Co., Ltd.), KAYARAD.
TC-110S, R-564, R-128H (above, Nippon Kayaku Co., Ltd.), Biscote 192, Biscote 220, Biscote 2311HP, Biscote 2000, Biscote 2100, Biscote 2150, Biscote 8F, Biscote 17F (above, Osaka Organic) Chemical Industry Co., Ltd.).
In addition, in order to adjust the viscosity of the resin composition, to adjust the water solubility of the stereolithography product, as a copolymerization component with a compound having two or more epoxy groups, or as described later, In the case of the support material, it is preferable to contain a compound having a hydroxyl group and one unsaturated double bond.

Examples of the compound having a hydroxyl group and having one unsaturated double bond include a hydroxyl group-containing (meth) acrylate having 5 to 15 carbon atoms, a hydroxyl group-containing (meth) acrylate having a number average molecular weight of 200 to 2,000, and a hydroxyl group ( A meta) acrylamide derivative and the like are preferable.
Examples of the hydroxyl group-containing (meth) acrylate having 5 to 15 carbon atoms include hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, and the like. Examples of the hydroxyl group-containing (meth) acrylate having a number average molecular weight of 200 to 2,000 include polyethylene glycol mono (meth) acrylate, methoxypolyethylene glycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate, methoxypolypropylene glycol mono ( And a mono (meth) acrylate of a polyethylene glycol-polypropylene glycol block polymer. Examples of the hydroxyl group-containing (meth) acrylamide derivative include N-hydroxyethyl (meth) acrylamide, N-hydroxypropyl (meth) acrylamide, N-hydroxybutyl (meth) acrylamide and the like.
The content of the compound having a hydroxyl group and having one unsaturated double bond varies depending on the composition of the other active-line polymerizable organic compound.
However, when the stereolithography product is a support material, the compound having one unsaturated double bond having a water-soluble group such as a hydroxyl group is usually 3 to 50% by weight, more preferably 3 to 40% by weight. Use (when the support material is removed by washing with water).

The compound having two or more unsaturated double bonds in one molecule is preferably a compound having two or more (meth) acryl groups in one molecule. Examples include epoxy (meth) acrylate, urethane (meth) acrylate, polyester (meth) acrylate, polyether (meth) acrylate, and (meth) acrylic acid esters of alcohols.
The epoxy (meth) acrylate is an acrylate obtained by reacting, for example, an aromatic epoxy resin, an alicyclic epoxy resin, an aliphatic epoxy resin, and (meth) acrylic acid. Among these epoxy (meth) acrylates, a particularly preferred one is a (meth) 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, It is (meth) acrylate obtained by making it react with (meth) acrylic acid. For example, (meth) acrylate, epoxy novolac resin and (meth) obtained by reacting glycidyl ether obtained by reaction of bisphenol A or its alkylene oxide adduct and epichlorohydrin with (meth) acrylic acid. Examples thereof include (meth) acrylate obtained by reacting acrylic acid.

Preferred as the urethane (meth) acrylate is a (meth) acrylate obtained by reacting a hydroxyl group-containing (meth) acrylic acid ester and an isocyanate 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.
Preferred as the hydroxyl group-containing polyester used here is a hydroxyl group-containing polyester obtained by reaction of one or more fatty acid polyhydric alcohols with one or more polybasic acids, and is aliphatic. Examples of the polyhydric alcohol include 1,3-butanediol, 1,4-butanediol, 1,6-hexanediol, diethylene glycol, triethylene glycol, neopentyl glycol, polyethylene glycol, polypropylene glycol, trimethylolpropane, glycerin, Examples include pentaerythritol and dipentaerythritol. Examples of the polybasic acid include adipic acid, terephthalic acid, phthalic anhydride, and trimellitic acid.

Preferred as the hydroxyl group-containing polyether is a hydroxyl group-containing polyether obtained by adding one or more alkylene oxides to an aliphatic polyhydric alcohol, and the aliphatic polyhydric alcohol includes the compounds described above. The same thing can be illustrated. Examples of the alkylene oxide include ethylene oxide and propylene oxide.
What is preferable as a hydroxyl group-containing (meth) acrylic acid ester is a hydroxyl group-containing (meth) acrylic acid ester obtained by esterification reaction of an aliphatic polyhydric alcohol and (meth) acrylic acid, The same compounds as those described above can be exemplified.

Among such hydroxyl group-containing (meth) acrylic acids, a hydroxyl group-containing (meth) acrylic acid ester obtained by an esterification reaction between an aliphatic dihydric alcohol and (meth) acrylic acid is particularly preferred. ) Acrylates.
As the isocyanate, a compound having at least one isocyanate group in the molecule is desirable, 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 an esterification reaction of one or more aliphatic polyhydric alcohols with one or more monobasic acids, polybasic acids, and phenols. In the obtained hydroxyl group-containing polyester, examples of the aliphatic polyhydric alcohol include the same compounds as those described above. Examples of monobasic acids include formic acid, acetic acid, butyl carboxylic acid, benzoic acid and the like. Examples of the polybasic acid include adipic acid, terephthalic acid, phthalic anhydride, and trimellitic acid. Examples of phenols include phenol, p-nonylphenol, bisphenol A, and the like.
A preferred polyether (meth) acrylate is a polyether (meth) acrylate obtained by reacting a hydroxyl group-containing polyether with (meth) acrylic acid. What is preferable as the hydroxyl group-containing polyether used here is a hydroxyl group-containing polyether obtained by adding one or more alkylene oxides to an aliphatic polyhydric alcohol, The same compounds as those described above can be exemplified. Examples of the alkylene oxide include ethylene oxide and propylene oxide.

Preferable (meth) acrylic acid esters of alcohols are 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 (meta) ) Acrylate, for example, 2-ethylhexyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, isoamyl (meth) acrylate, lauryl (meth) acrylate, stearyl (meth) acrylate , Isooctyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, isobornyl (meth) acrylate, benzyl (meth) acrylate, 1,3-butanediol di (meth) acrylate, 1,4-butanediol di (meth) acrylate 1,6-he Sundiol 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 Examples include tri (meth) acrylate, pentaerythritol tri (meth) acrylate, dipentaerythritol hexa (meth) acrylate, and ε-caprolactone-modified dipentaerythritol hexa (meth) acrylate.

Examples of compounds having two or more unsaturated double bonds that can be suitably used include, for example, ethylene glycol di (meth) acrylate, dicyclopentenyl di (meth) acrylate, triethylene glycol diacrylate, and tetraethylene glycol. Di (meth) acrylate, tricyclodecanediyldimethylene di (meth) acrylate, trimethylolpropane tri (meth) acrylate, ethylene oxide (hereinafter referred to as “EO”) modified trimethylolpropane tri (meth) acrylate, propylene oxide (hereinafter referred to as “ PO ”) modified trimethylolpropane tri (meth) acrylate, tripropylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, bisphenol A diglycidyl a (Meth) acrylic acid adducts at both terminals of 1,4 butanediol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) Acrylate, polyester di (meth) acrylate, polyethylene glycol di (meth) acrylate, dipentaerythritol hexa (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol tetra (meth) acrylate, caprolactone modified dipentaerythritol hexa (Meth) acrylate, caprolactone-modified dipentaerythritol penta (meth) acrylate, ditrimethylolpropane tetra (meth) acrylate, EO-modified bisphenol A di (meth) acrylate, PO modified bisphenol A di (meth) acrylate, EO modified hydrogenated bisphenol A di (meth) acrylate, PO modified hydrogenated bisphenol A di (meth) acrylate, EO modified bisphenol F di (meth) acrylate And (meth) acrylate of phenol novolac polyglycidyl ether.
Of these (meth) acrylates, poly (meth) acrylates of polyhydric alcohols are particularly preferred.

  Examples of commercially available compounds having two or more unsaturated double bonds in one molecule include SA1002 (above, manufactured by Mitsubishi Chemical Corporation), biscoat 195, biscoat 230, biscoat 260, biscoat 215, and biscoat 310. Biscoat 214HP, biscoat 295, biscoat 300, biscoat 360, biscoat GPT, biscoat 400, biscoat 700, biscoat 540, biscoat 3000, biscoat 3700 (manufactured by Osaka Organic Chemical Industry Co., Ltd.), Kayrad R-526, HDDA, NPGDA, TPGDA, MANDA, R-551, R-712, R-604, R-684, PET-30, GPO-303, TMPTA, THE-330, DPHA, DPHA-2H, DPHA-2C, DPHA-2I, D-310 , D-330, DPCA-20, DPCA-30, DPCA-60, DPCA-120, DN-0075, DN-2475, T-1420, T-2020, T-2040, TPA-320, TPA-330, RP -1040, RP-2040, R-011, R-300, R-205 (manufactured by Nippon Kayaku Co., Ltd.), Aronix M-210, M-220, M-233, M-240, M-305 , M-309, M-310, M-400, M-6200, M-6400 (above, manufactured by Toagosei Co., Ltd.), light acrylate BP-4EA, BP-4PA, BP-2EA, BP-2PA, DCP -A (above, Kyoeisha Chemical Co., Ltd.), New Frontier BPE-4, BR-42M, GX-8345 (above, Daiichi Kogyo Seiyaku Co., Ltd.), ASF-400 (above, Nippon Steel Chemical) Manufactured by Co., Ltd.), lipoxy SP-1506, SP-1507, SP-1509, VR-77, SP-4010, SP-4060 (manufactured by Showa Polymer Co., Ltd.), NK ester A-BPE-4 ( As mentioned above, Shin-Nakamura Chemical Co., Ltd.) can be mentioned.

In the liquid resin composition for inkjet optical modeling of the present invention, in order to increase photocurability, dimensional stability at the time of curing, and physical / chemical strength of the molded article, as a radical polymerizable organic compound, in one molecule A compound having one unsaturated double bond and a compound having two or more unsaturated double bonds in one molecule may be combined in two or more, or one unsaturated double bond in one molecule It is preferable to constitute a combination of at least one compound having a compound and at least one compound having two or more unsaturated double bonds in one molecule. In addition, it is also preferable to further combine the compounds having three or more unsaturated double bonds in one molecule. Examples of the compound having 3 or more unsaturated double bonds in one molecule include tri (meth) acrylate compounds, tetra (meth) acrylate compounds, penta (meth) acrylate compounds, hexa (meth) acrylate compounds, and the like. Specifically, trimethylolpropane tri (meth) acrylate, EO-modified trimethylolpropane tri (meth) acrylate, dipentaerythritol hexa (meth) acrylate, dipentaerythritol penta (meth) acrylate, ditrimethylolpropane tetra (meth) Acrylate is preferred.
When the radically polymerizable organic compound is contained in the liquid resin composition for inkjet stereolithography of the present invention, the curing rate of the composition becomes faster.

[(A-2) Cationic polymerizable organic compound]
The cationically polymerizable organic compound is a cationically polymerizable compound that is polymerized or crosslinked by irradiation with actinic radiation in the presence of a cationic photopolymerizable initiator, preferably an epoxy compound, an oxetane compound, an oxolane compound, a cyclic acetal compound, A cyclic lactone compound, a thiirane compound, a thietane compound, a spiro orthoester compound that is a reaction product of an epoxy compound and a lactone compound, a vinyl ether compound, and the like can be given.
Examples of the epoxy compound include bisphenol A diglycidyl ether, bisphenol F diglycidyl ether, bisphenol S diglycidyl ether, brominated bisphenol A diglycidyl ether, brominated bisphenol F diglycidyl ether, brominated bisphenol S diglycidyl ether, and epoxy novolac. Resin, hydrogenated bisphenol A diglycidyl ether, hydrogenated bisphenol F diglycidyl ether, hydrogenated bisphenol S diglycidyl ether, 3,4-epoxycyclohexylmethyl-3 ′, 4′-epoxycyclohexanecarboxylate, 2- (3 4-epoxycyclohexyl-5,5-spiro-3,4-epoxy) cyclohexane-meta-dioxane, bis (3,4-epoxycyclohexylmethyl) azi Bis (3,4-epoxy-6-methylcyclohexylmethyl) adipate, 3,4-epoxy-6-methylcyclohexyl-3 ′, 4′-epoxy-6′-methylcyclohexanecarboxylate, ε-caprolactone modified 3,4-epoxycyclohexylmethyl-3 ′, 4′-epoxycyclohexanecarboxylate, trimethylcaprolactone modified 3,4-epoxycyclohexylmethyl-3 ′, 4′-epoxycyclohexanecarboxylate, β-methyl-δ-valerolactone modified 3,4-epoxycyclohexylmethyl-3 ′, 4′-epoxycyclohexanecarboxylate, methylene bis (3,4-epoxycyclohexane), di (3,4-epoxycyclohexylmethyl) ether of ethylene glycol, ethylene bis (3,4 Epoxycyclohexanecarboxylate), epoxycyclohexahydrophthalate dioctyl, epoxycyclohexahydrophthalate di-2-ethylhexyl, 1,4-butanediol diglycidyl ether, 1,6-hexanediol diglycidyl ether, neopentyl glycol Diglycidyl ether, trimethylolpropane triglycidyl ether, polyethylene glycol diglycidyl ether, glycerin triglycidyl ether, polypropylene glycol diglycidyl ethers; one or more of aliphatic polyhydric alcohols such as ethylene glycol, propylene glycol and glycerin Polyglycidyl ethers of polyether polyols obtained by adding an alkylene oxide of Diglycidyl esters of acids; monoglycidyl ethers of higher aliphatic alcohols; monoglycidyl ethers of polyether alcohols obtained by adding phenol, cresol, butylphenol or alkylene oxide; glycidyl esters of higher fatty acids; Examples include soybean oil; butyl epoxy stearate; octyl epoxy stearate; epoxidized linseed oil; epoxidized polybutadiene and the like.

Examples of oxetane compounds include trimethylene oxide, 3,3-dimethyloxetane, 3,3-dichloromethyloxetane, 3-ethyl-3-phenoxymethyloxetane, and bis (3-ethyl-3-methyloxy) butane. It can be illustrated.
Examples of oxolane compounds include tetrahydrofuran and 2,3-dimethyltetrahydrofuran.
Examples of the cyclic acetal compound include trioxane, 1,3-dioxolane, 1,3,6-trioxane cyclooctane, and the like.
Examples of cyclic lactone compounds include β-propiolactone and ε-caprolactone.

Examples of thiirane compounds include ethylene sulfide, 1,2-propylene sulfide, thioepichlorohydrin, and the like.
An example of the thietane compound is 3,3-dimethylthietane.
Examples of the vinyl ether compound include ethylene glycol divinyl ether, triethylene glycol divinyl ether, trimethylolpropane trivinyl ether, oxygen-containing alicyclic divinyl ether, and the like.
Examples of the ethylenically unsaturated compound include vinylcyclohexane, isobutylene, polybutadiene and the like.

  Among these cationically polymerizable organic compounds, 3,4-epoxycyclohexylmethyl-3 ′, 4′-epoxycyclohexanecarboxylate, bis (3,4-epoxycyclohexylmethyl) adipate, ε-caprolactone modified 3,4-epoxycyclohexyl Methyl-3 ′, 4′-epoxycyclohexanecarboxylate, trimethylcaprolactone modified 3,4-epoxycyclohexyl methyl-3 ′, 4′-epoxycyclohexanecarboxylate, β-methyl-δ-valerolactone modified 3,4-epoxycyclohexyl Methyl-3 ′, 4′-epoxycyclohexanecarboxylate, bisphenol A diglycidyl ether, bisphenol F diglycidyl ether, hydrogenated bisphenol A diglycidyl ether, hydrogenated bisphenol F diglycidyl ether, 1,4-butanediol diglycidyl ether, 1,6-hexanediol diglycidyl ether, trimethylolpropane triglycidyl ether, glycerin triglycidyl ether, polyethylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether Oxygen-containing alicyclic divinyl ether and the like are preferable.

More preferably, it has two or more alicyclic epoxy groups in one molecule such as 3,4-epoxycyclohexylmethyl-3 ′, 4′-epoxycyclohexanecarboxylate, bis (3,4-epoxycyclohexylmethyl) adipate. A compound.
In addition, oxygen-containing alicyclic divinyl ethers are copolymerized with epoxy compounds and (meth) acrylate compounds, which are radically polymerizable organic compounds, to provide heat resistance, fastness, adhesion, and flexibility to the model. Can be granted.

In the liquid resin composition for inkjet stereolithography of the present invention, it is also preferable to use a combination of two or more of the above cationic polymerizable organic compounds.
Examples of commercially available cationically polymerizable organic compounds that can be suitably used include UVR-6100, UVR-6105, UVR-6110, UVR-6128, UVR-6200, UVR-6216 (manufactured by Union Carbide), Celoxide 2021, Celoxide 2021P, Celoxide 2081, Celoxide 2083, Celoxide 2085, Epolide GT-300, Epolide GT-301, Epolide GT-302, Epolide GT-400, Epolide 401, Epolide 403, ONB-DVE, OXT-DVE, ISB-DVE ( As described above, manufactured by Daicel Chemical Industries, Ltd.), KRM-2100, KRM-2110, KRM-2199, KRM-2400, KRM-2410, KRM-2408, KRM-2490, KRM-2200 KRM-2720, KRM-2750 (manufactured by Asahi Denka Kogyo Co., Ltd.), Rapi-cureDVE-3, CHVE, PEPC (manufactured by ISP) Epicoat 828, Epicoat 812, Epicoat 1031, Epicoat 872, Epicoat CT508 ( As mentioned above, Japan Epoxy Resin Co., Ltd.), XDO (above, manufactured by Toagosei Co., Ltd.), VECOMER 2010, 2020, 4010, 4020 (above, Allied Signal Co., Ltd.) and the like can be mentioned.

  In addition, the above-mentioned compounds having an epoxy group may have a slightly high viscosity when used as a liquid resin composition for inkjet optical modeling. In such a case, the viscosity can be lowered by blending a liquid ethylenically unsaturated compound. In particular, a liquid ethylenically unsaturated compound having a small molecular weight has a large effect of reducing the viscosity. It is also effective to reduce the viscosity by adding liquid plasticizers within a range that does not affect other properties such as curability.

[(B) Compound that generates acid upon irradiation with actinic radiation]
A cationic photopolymerization initiator can be used as the compound that generates an acid upon irradiation with actinic radiation. Examples of particularly preferred cationic photopolymerization initiators include onium salts having a structure represented by the following general formula (1).

_{^{[R 1 a R 2 b R}} 3 c R 4 d W] + p [MX p + q] -q (1)

[In the formula (1), the cation is an onium ion, W is S, Se, Te, P, As, Sb, Bi, O, I, Br, Cl, or —N═N, and R ¹ , R ² , R ³ and R ⁴ are the same or different organic groups, a, b, c and d are each an integer of 0 to 3, and (a + b + c + d) is equal to the valence of W.
M is a halide complex [MX _{p + q} ]
X is a halogen atom, q is the net charge of the halide complex ion, and p is the valence of M. An onium salt having a structure represented by the formula:
M is preferably B, P, As, Sb, Fe, Sn, Bi, Al, Ca, In, Ti, Zn, Sc, V, Cr, Mn,
Co.
X is preferably F, Cl, Br, or I.
Specific examples of the anion [MX _{p + q} ] include tetrafluoroborate (BF ₄ ⁻ ), hexafluorophosphate (PF ₆ ⁻ ), hexafluoroantimonate (SbF ₆ ⁻ ), hexafluoroarsenate (AsF ₆ ⁻ ), hexachloro Antimonate (SbCl ₆ ⁻ ) and the like can be mentioned.

In the structure represented by the general formula (1), an onium salt having an anion represented by the general formula [MX _p (OH) ⁻ ] may be used instead of the anion [MX _{p + q} ].
Furthermore, instead of the anion [MX _{p + q} ], perchlorate ion (ClO ₄ ⁻ ), trifluoromethane sulfonate ion (CF ₃ SO ₃ ⁻ ), fluorosulfonate ion (FSO ₃ ⁻ ), toluene sulfonate ion, Onium salts having other anions such as nitrobenzene sulfonate anion and trinitrotoluene sulfonate anion can also be used.

The onium salt represented by the general formula (1) releases a Lewis acid by actinic ray irradiation.
An onium salt particularly effective as a cationic photopolymerization initiator as a compound that generates an acid upon irradiation with actinic rays is an aromatic onium salt. Of these, aromatic halonium salts described in JP-A-50-151996, JP-A-50-158680, JP-A-50-151997, JP-A-52-30899, JP-A-56. Group VIA aromatic onium salts described in JP-A-55420, JP-A-55-125105, etc., Group VA aromatic onium salts described in JP-A-50-158698, etc., JP-A-56-8428 Oxosulfoxonium salts described in JP-A-56-149402 and JP-A-57-192429, aromatic diazonium salts described in JP-A-49-17040, US Pat. , 139,655, and the like. Moreover, an iron / allene complex, an aluminum complex / photolytic silicon compound-based initiator, and the like can also be mentioned.

Particularly preferred cationic photopolymerization initiators are triarylsulfonium salts, diaryliodonium salts, aryldiazonium salts having BF ₄ ⁻ , PF ₆ ⁻ , ASF ₆ ⁻ , SBF ₆ ⁻ or the like as a counter ion, and triphenylsulfonium. hexafluorophosphate, p- thio phenoxy diphenyl sulfonium hexafluorophosphate, triphenylsulfonium tetrafluoroborate, 4-morpholino-2,5-dimethoxyphenyl diazonium fluoroborate, counterion BF ₄ ^- in which diphenyl iodide salt and di Tolyliodonium salt, phenyldiazonium tetrafluoroborate, tolyldiazonium tetrafluoroborate, tolyldiazonium hexafluorophosphate, bis (4-t-butylpheny ), Such as iodine hexafluorophosphate, and the like.

Examples of commercially available cationic photopolymerization initiators that can be suitably used as a compound that generates an acid upon irradiation with actinic radiation include UVI-6950, UVI-6970, UVI-6974, and UVI-6990 (manufactured by Union Carbide). Adekaoptomer SP-150, SP-151, SP-170, SP-172 (above, manufactured by Asahi Denka Kogyo Co., Ltd.), Irgacure 261 (above, made by Ciba Specialty Chemicals Co., Ltd.), CI-2481, CI- 2624, CI-2639, CI-2064 (above, manufactured by Nippon Soda Co., Ltd.), CD-1010, CD-1011, CD-1012 (above, made by Sartomer), DTS-102, DTS-103, NAT-103 , NDS-103, TPS-103, MDS-103, MPI-103, BBI-103 Gaku Co., Ltd.), PCI-061T, PCI-062T, PCI-020T, PCI-022T (above, Nippon Kayaku Co., Ltd.), CPI-110A (above, San Apro Co., Ltd.), t-BuDPI (Manufactured by Tokyo Chemical Industry Co., Ltd.). Among these, UVI-6970, UVI-6974, Adekaoptomer SP-170, SP-172, CD-1012, MPI-103, CPI-110A, and t-BuDPI are resin compositions containing these. It is particularly preferable because high photocuring sensitivity can be expressed. Said cationic photoinitiator can be used individually by 1 type or in combination of 2 or more types.

[(C) Acid coloring dye precursor]
A color former (leuco dye) can be used as the acid color-forming dye precursor.
A color former is an organic compound that is usually colorless but develops various colors with an acid, and is widely used in heat-sensitive recording materials, pressure-sensitive recording materials, thermochromic materials, and the like.
The color former that can be used as the acid-color-forming dye precursor in the liquid resin composition for inkjet stereolithography of the present invention is not particularly limited, and is a fluorane-based, phthalide-based, azaphthalide-based, fluorene spirophthalide-based, triphenylmethane-based, Examples include diphenylmethane, thiazine, lactam, and diketone.
In particular, fluoran, phthalide, azaphthalide, fluorene spirophthalide, triphenylmethane compound, lactam, and diketone are preferable.

Examples of color formers that develop blue color include 3,3-bis (4-dimethylaminophenyl) -6-dimethylaminophthalide, N-benzoylleucomethylene blue, and 3- (4-diethylamino-2-ethoxyphenyl) -3. -(1-ethyl-2-methylindol-3-yl) phthalide, 3- (4-diethylamino-2-methylphenyl) -3- (4-dimethylaminophenyl) -6-dimethylaminophthalide, 3- ( 4-diethylamino-2-ethoxyphenyl) -3- (1-ethyl-2-methylindol-3-yl) -4-azaphthalide, 3- (4- (N-ethyl-N-phenylamino) -2-ethoxy Phenyl) -3- (1-ethyl-2-methylindol-3-yl) -4-azaphthalide, 3- (4-diethylamino-2-methylphenol) ) -3- (1-ethyl-2-methylindol-3-yl) phthalide, 3- (1-ethyl-2-methylindol-3-yl) -3- (2-n-hexyloxy-4-) Diethylaminophenyl) -4-azaphthalide, 3- (4-diethylamino-2-ethoxyphenyl) -3- (1-ethyl-2-methylindol-3-yl) -4,7-diazaphthalide, 3-diphenylamino-6 -Diphenylaminofluorane etc. can be mentioned.

Examples of color formers that develop a green color include 2-anilino-6- (N-ethyl-Nn-hexylamino) fluorane, 2-dibenzylamino-6-diethylaminofluorane, 3,3-bis (4- Diethylamino-2-ethoxyphenyl) -4-azaphthalide, 2- (N-phenyl-N-methylamino) -6- (N-ethyl-Np-tolylamino) fluorane, 2-chloro-3-methyl-6- [P- (p-anilinoanilino) anilino] fluorane, 3- (4-diethylaminophenyl) -3- (2,2-bis (1-ethyl-2-methylindol-3-yl) -1-ethenyl) phthalide, Examples include 3,6-bis (dimethylamino) fluorene-9-spiro-3 ′-(6′-dimethylamino) phthalide.

Color formers that develop red color include 3,6-bis (diethylamino) fluorane-γ-anilinolactam, 3,6-bis (diethylamino) fluorane-γ- (p-nitro) anilinolactam, 3,6 -Bis (diethylamino) fluorane-γ- (o-chloro) anilinolactam, 2-bromo-6-diethylaminofluorane, 6-diethylaminofluorane, 3-methyl-6-diethylaminofluorane, 2-methyl-6- Diethylaminofluorane, 2-chloro-6-diethylaminofluorane, 1,2-benzo-6-diethylaminofluorane, 1,2-benzo-6-di-n-butylaminofluorane, 1,3-dimethyl-6 -Diethylaminofluorane, 2-chloro-3-methyl-6-diethylaminofluorane, 2-methyl- -(N-ethyl-Np-tolylamino) fluorane, 2-chloro-3-methyl-6- (N-ethyl-N-isobutylamino) fluorane, 1,2-benzo-6- (N-ethyl-N -Isoamylamino) fluorane, 3,3-bis (1-butyl-2-methylindol-3-yl) phthalide, 3,3-bis (1-octyl-2-methylindol-3-yl) phthalide, 7- (N-ethyl-N-isoamylamino) -3-methyl-1-phenylspiro [(1,4-dihydrochromeno [2,3-c] pyrazole) -4,3′-phthalide], 7- (N -Ethyl-Nn-hexylamino) -3-methyl-1-phenylspiro [(1,4-dihydrochromeno [2,3-c] pyrazole) -4,3′-phthalide] and the like. it can.

Examples of color formers that develop a yellow color include 3,6-dimethoxyfluorane, 3,6-di-n-butoxyfluorane, 2-chloro-6-cyclohexylaminofluorane, and 2,6-bis [4-di (). -N-butylaminobenzoyl] pyridine (diketone compound), 2,6-bis [4- [N-methyl-N-cyclohexyl] aminobenzoyl] pyridine (diketone compound), 2,6-diphenyl-4- ( 4-dimethylaminophenyl) -pyridine, 2,2-bis (4- (2- (4-diethylaminophenyl) quinazolyl) oxyphenyl) propane, N, N-dimethyl-4- [2- (2-octyloxyphenyl) ) -6-phenyl-4-pyridinyl] -benzenamine, N, N-dimethyl-4- [2- (2-butoxyphenyl) -6-phenyl-4 Pyridinyl] -benzeneamine, 4-chloro-N- (4- (N- (4-methylbenzyl) -N-methylamino) benzylidene) aniline, 1- (2-quinolyl) -2- (3-methoxy-4 -Dodecyloxyphenyl) ethene, 1- (4-n-dodecyloxy-3-methoxyphenyl) -2- (2-quinolyl) ethylene and the like.

Examples of color formers that develop black color include 2-anilino-3-methyl-6-diethylaminofluorane, 2-anilino-3-methyl-6-di-n-butylaminofluorane, 2- (3-methylanilino) -3-methyl-6-diethylaminofluorane, 2- (2,4-dimethylanilino) -3-methyl-6-diethylaminofluorane, 2-anilino-3-methyl-6- (N-methyl-N- (Cyclohexylamino) fluorane, 2-anilino-3-methyl-6- (N-ethyl-N-isoamylamino) fluorane, 2- (o-chloroanilino) -6-diethylaminofluorane, 2-anilino-3-chloro-6 -Diethylaminofluorane, 2- (2-carbomethoxy-phenylamino) -6-diethylaminofluorane, 2-anilino- -Methyl-6-dipentylaminofluorane, 2-anilino-3-methyl-6- (N-ethyl-N-tetrahydrofurfuryl) aminofluorane, 2-anilino-3-methyl-6-pyrrolidinofluorane, etc. Can be mentioned.
In addition, as a color former that develops orange, 3-chloro-6-cyclohexylaminofluorane, 3-chloro-6-anilinofluorane, etc. As a color former that develops vermilion, 2-chloro-6-diethylamino Fluorane, 2-bromo-3-methyl-6- (di-n-butyl) aminofluorane, 2-phenoxy-6- (N-ethyl-N-isoamyl) aminofluorane, etc. Examples of the former include rhodamine B anilinolactam.
In the liquid resin composition for inkjet stereolithography of the present invention, one type of color former or a color former of the same color may be mixed in one type of resin composition, and a mixed color may be obtained. In addition, one type of resin composition may be used by mixing color formers exhibiting different colors.

[(D) radical photopolymerization initiator]
As described above, in the liquid resin composition for inkjet optical modeling according to the present invention, when (A-1) a radical polymerizable organic compound is contained, it is preferable to simultaneously contain (D) a radical photopolymerization initiator. However, (A-1) a radically polymerizable organic compound and (A-2) a cationically polymerizable organic compound are used in combination, and (B) a compound that generates an acid upon irradiation with actinic radiation (A-1) and (A-2). This is not the case when) is copolymerizable.
The radical photopolymerization initiator is not particularly limited as long as it generates radical active species by irradiation with actinic radiation in order to increase the molecular weight of the (A-1) radical polymerizable organic compound by radical polymerization.
Preferably, acetophenone compounds, benzophenone compounds, benzoin compounds, benzyl compounds, thioxanthone compounds, acylphosphine compounds, and the like are used.

Examples of acetophenone compounds include diethoxyacetophenone, 2-hydroxymethyl-1-phenylpropan-1-one, 4′-isopropyl-2-hydroxy-2-methylpropiophenone, 2-hydroxy-2-methylpropio Phenone, 2,2-dimethoxy-1,2-diphenylethane-1-one, p-dimethylaminoacetophenone, p-tert. -Butyldichloroacetophenone, p-tert. -Butyltrichloroacetophenone, 2,2-diethoxyacetophenone, p-azidobenzalacetophenone, 1-hydroxycyclohexyl phenyl ketone, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropanone-1, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1 and the like.

Examples of the benzophenone compounds include benzophenone, methyl o-benzoylbenzoate, Michler's ketone, 4,4′-bis (dimethylamino) benzophenone, 4,4′-bis (diethylamino) benzophenone, 4,4′-dichlorobenzophenone, 4 -Benzoyl-4'-methyldiphenyl sulfide, 3,3 ', 4,4'-tetra (t-butylperoxycarbonyl) benzophenone (BTTB) and the like.
Examples of the benzoin compound include benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin-n-butyl ether, benzoin isobutyl ether, α-methoxybenzoin methyl ether, and the like.

Examples of the benzyl compound include benzyl, anisyl, benzylmethyl ketal, benzyl-β-methoxyethyl acetal, and the like.
Examples of the thioxanthone compound include thioxanthone, 2-methylthioxanthone, 2-ethylthioxanthone, 2-chlorothioxanthone, 2-isopropylthioxanthone, and 2,4-diethylthioxanthone.
Examples of the acylphosphine compound include acylphosphine compounds such as monoacylphosphine oxide, bisacylphosphine oxide, and 2,4,6-trimethylbenzoyldiphenylphosphine oxide.
Others, xanthones, fluorenones, benzaldehydes, fluorenes, anthraquinones, naphthacenediones, triphenylamines, carbazoles, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, bis (cyclopentadienyl) -Bis [2,6-difluoro-3- (py-1-yl)] titanium, and combinations of BTTB and xanthenes, thioxanthenes, coumarins, ketocoumarins and other dye sensitizers . In particular, naphthacenediones such as 5,11-bis (silyloxy) naphthacene-6,12-dione, and combinations of these with sensitizers of anthraquinone compounds and anthracene compounds have high sensitivity to blue LED light. Have
Among these, benzyldimethyl ketal, 1-hydroxycyclohexyl phenyl ketone, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, α-methoxybenzoin methyl ether, 2-benzyl-2-dimethylamino-1- (4-morpholino Particularly preferred are phenyl) -butan-1-one, 5,11-bis (silyloxy) naphthacene-6,12-dione, and the like.
Commercially available product names of radical photopolymerization initiators include IRGACURE 184, 369, 651, 500, 819, 907, CGI 1700, CGI 1750, CGI 1850, CG 24-61, DAROCUR 1116, 1173 (above, manufactured by Ciba Specialty Chemicals); LUCIRIN TPO ( BASF); Ubekrill P36 (UCB) and the like. These radical photopolymerization initiators can be used singly or in combination of two or more.

[Other additives]
The liquid resin composition for inkjet optical modeling of the present invention may contain various additives as other components as necessary within a range not impairing the object and effects of the present invention.
Such additives include polymers or oligomers, (thermal) polymerization inhibitors, chain transfer agents, antioxidants, photosensitizers, leveling agents, wettability improvers, surfactants, plasticizers, UV absorbers. , Silane coupling agents, inorganic fillers, pigments, dyes and the like.
Among these, an ultraviolet absorber is very useful especially in the aspect which hardens the liquid resin composition for inkjet optical shaping | molding of this invention using visible light, and it demonstrates separately by the postscript as a component (E).
A polymer or an oligomer can be added in order to adjust the viscosity of the liquid resin composition for inkjet optical modeling of the present invention and the properties of the resulting cured model.
Examples of polymers or oligomers include epoxy resins, polyamides, polyamideimides, polyurethanes, polybutadienes, polychloroprenes, polyethers, polyesters, styrene-butadiene block copolymers, petroleum resins, xylene resins, ketone resins, cellulose resins, fluorine-based polymers. Examples thereof include polymers such as oligomers, silicone oligomers, and polysulfide oligomers, and oligomers.

Examples of (thermal) polymerization inhibitors include phenol compounds [hydroquinone, hydroquinone monomethyl ether, 2,6-di-t-butyl-p-cresol, 2,2-methylene-bis- (4-methyl-6-t- Butylphenol), 1,1,3-tris- (2-methyl-4-hydroxy-5-t-butylphenyl) butane, etc.], sulfur compounds [dilauryl thiodipropionate, etc.], phosphorus compounds [triphenyl phosphite Etc.], amine compounds [phenothiazine etc.] and the like.

Examples of chain transfer agents include hydrocarbons [C6-24 compounds such as aromatic hydrocarbons (toluene, xylene, etc.) and unsaturated aliphatic hydrocarbons (1-butene, 1-nonene, etc.)]; halogenated hydrocarbons (C1-24 compounds such as dichloromethane, carbon tetrachloride); alcohols (C1-24 compounds such as methanol, 1-butanol); thiols (C1-24 compounds such as ethylthiol, 1-octylthiol); ketones (C3-24 compounds such as acetone, methyl ethyl ketone); aldehydes (C2-18 compounds such as 2-methyl-2-propylaldehyde, 1-pentylaldehyde); phenols (C6-36 compounds such as phenol, m- , P- and o-cresol); quinones (C6-24 compounds such as hydrides) Quinone); amine (compound of C3～24, such as diethyl methyl amine, diphenylamine); Compound of and disulfides (C2～24, such as diethyl disulfide, di-1-octyl disulfide) and the like.

Examples of the antioxidant include phenol compounds [monocyclic phenol (2,6-di-t-butyl-p-cresol, etc.), bisphenol [2,2′-methylenebis (4-methyl-6-t-butylphenol), etc. ], Polycyclic phenol [1,3,5-trimethyl-2,4,6-tris (3,5-di-t-butyl-4-hydroxybenzyl) benzene etc.], etc.], sulfur compound (dilauryl 3,3 '-Thiodipropionate etc.), phosphorus compounds (triphenyl phosphite etc.), amine compounds (octylated diphenylamine etc.) and the like. Commercial products of these antioxidants include IRGANOX 1010, 1035, 1076, 1222 (above, manufactured by Ciba Specialty Chemicals), ANTIGENE P, 3C, Sumilizer GA-80, GP
(Manufactured by Sumitomo Chemical Co., Ltd.).

Examples of the photosensitizer (polymerization accelerator) include amine compounds such as triethanolamine, methyldiethanolamine, triethylamine, and diethylamine; thioxanthone, thioxanthone derivatives; anthraquinone, 2- (2-hydroxyethylthio) -9,10. Anthraquinone derivatives such as anthraquinone, 2- (n-butyloxycarbonylmethylthio) anthraquinone, 2- (3-methylbutylthio) anthraquinone and 2- [2- (diethylaminocarbonylethyl) thio] anthraquinone; anthracene and anthracene derivatives; Perylene, derivatives of perylene; benzophenone; benzoin isopropyl ether; pigments such as coumarins and ketocoumarins;

Examples of the surfactant include a molecular weight of 264 or more and Mn of 5,000 or less. For example, a PEG type nonionic surfactant [nonylphenol ethylene oxide (hereinafter abbreviated as EO) 1 to 40 mol adduct, stearic acid EO 1 to 40 mol adduct Etc.], polyhydric alcohol type nonionic surfactant (sorbitan palmitic acid monoester, sorbitan stearic acid monoester, sorbitan stearic acid triester, etc.), fluorine-containing surfactant (perfluoroalkyl EO 1-50 mol adduct, per Fluoroalkylcarboxylate, perfluoroalkylbetaine, etc.), modified silicone oils [polyether-modified silicone oil, (meth) acrylate-modified silicone oil, etc.] and the like.

Examples of the inorganic filler include metal powder (aluminum powder, copper powder, etc.), metal oxide (alumina, silica, talc, mica, clay, etc.), metal hydroxide (aluminum hydroxide, etc.), metal salt (calcium carbonate, etc.) , Magnesium hydroxide, magnesium carbonate, zinc oxide, calcium silicate, etc.), fiber [inorganic fiber (carbon fiber, glass fiber, asbestos, etc.), organic fiber (cotton, nylon, acrylic, rayon fiber, etc.), etc.], microballoon (Glass, shirasu, phenol resin, etc.), carbons (carbon black, graphite, coal powder, etc.), metal sulfides (molybdenum disulfide, etc.) and the like.
As the pigment and dye, various known organic / inorganic pigments and dyes are used. In the liquid resin composition for inkjet photo-molding of the present invention, it is used for the purpose of toning, and the curing speed is greatly reduced by coloring. It is not preferable to contain such a large amount.

[(E) UV absorber]
As the ultraviolet absorber, benzotriazole, benzophenone, triazine derivatives, salicylic acid derivatives, hindered amines and the like are preferable.
Examples of the benzotriazole series include 2- (2′-hydroxy-5′-methylphenyl) benzotriazole, 2- (2′-hydroxy-5′-tert-butylphenyl) benzotriazole, 2- (2′-hydroxy- 5'-tert-butylphenyl) -5-chlorobenzotriazole, 2- (2'-hydroxy-3 ', 5'-di-tert-butylphenyl) benzotriazole, 2- (2'-hydroxy-3'- tert-butyl-5′-methylphenyl) -5-chlorobenzotriazole, 2- (2′-hydroxy-3 ′, 5′-ditert-butylphenyl) -5-chlorobenzotriazole, 2- (2′- Hydroxy-3 ′, 5′-ditert-amylphenyl) benzotriazole, 2- (2′-hydroxy-4′-octylphenyl) benzotriazol 2- (2′-hydroxy-5′-methacryloxyethylphenyl) -2H-benzotriazole, 2-{(2′-hydroxy-3 ′, 3 ″, 4 ″, 5 ″, 6 ′ And '-tetrahydrophthalimidomethyl) -5'-methylphenyl} benzotriazole.
Examples of the benzophenone series include 2-hydroxybenzophenone, 5-chloro-2-hydroxybenzophenone, 2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-octyloxybenzophenone, 2-hydroxy- 4-dodecyloxybenzophenone, 2-hydroxy-4-octadecyloxybenzophenone, 2,2′-dihydroxy-4-methoxybenzophenone, 2,2′-dihydroxy-4,4′-dimethoxybenzophenone, 2-hydroxy-4- And methoxy-5-sulfobenzophenone.
Examples of triazine derivatives include 2- [4-{(2-hydroxy-3-dodecyloxy-propyl) oxy} -2-hydroxyphenyl] -4,6-bis (2,4-dimethylphenyl) -1,3. 5-triazine, 2- [4-{(2-hydroxy-3-tridecyloxy-propyl) oxy} -2-hydroxyphenyl] -4,6-bis (2,4-dimethylphenyl) -1,3,5- Triazine, 2- {4- (octyl-2-methylethanoate) oxy-2-hydroxyphenyl-4,6- {bis (2,4-dimethylphenyl)}-1,3,5-triazine [Ciba Special Manufactured by Tea Chemicals, trade name Tinuvin 479], tris [2,4,6- [2- {4- (octyl-2-methylethanoate) oxy-2-hydroxyphenyl}]]-1, 3,5-triazine [manufactured by Ciba Specialty Chemicals, trade name “Tinubin 777] and the like.

Examples of the salicylic acid derivative include phenyl salicylate, p-tert-butylphenyl salicylate, p-octylphenyl salicylate, p- (1,1,3,3-tetramethylbutyl) phenyl salicylate, and the like.
Examples of hindered amines include bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate, bis (1,2,2,6,6-pentamethyl-4-piperidyl) sebacate, and bis (1 , 2,2,6,6-pentamethyl-4-piperidyl) [{3,5-bis (1,1-dimethylethyl) -4-hydroxyphenyl} methyl] butyl malonate.
Of these, 2- [4-{(2-hydroxy-3-dodecyloxy-propyl) oxy} -2-hydroxyphenyl] -4,6-bis (2,4-dimethylphenyl) -1,3,5- Triazine, 2- {4- (octyl-2-methylethanoate) oxy-2-hydroxyphenyl-4,6- {bis (2,4-dimethylphenyl)}-1,3,5-triazine, 2- ( 2'-hydroxy-5'-tert-butylphenyl) benzotriazole is particularly preferred.

As commercially available products of these ultraviolet absorbers, in addition to those described above, for example, TINUVIN P, 234, 320, 326, 327, 328, 329, 213 (above, manufactured by Ciba Specialty Chemicals), Seesorb 102, 103, 501, 202, 712 and 704 (manufactured by Sipro Kasei Co., Ltd.) and the like, but are not limited thereto.
These ultraviolet absorbers can be used singly or in combination of two or more.
In the liquid resin composition for inkjet stereolithography of the present invention, in the case of curing using ultraviolet rays as active rays, it is not preferable to use a large amount of an ultraviolet absorber because it affects the curing speed and the cured film thickness.
On the other hand, in the mode of curing using visible light, there is almost no effect on curing, and the durability of the molded article after curing and color development is improved, so the liquid resin composition for inkjet optical modeling of the present invention is used. It is preferable to contain a UV absorber

[Liquid resin composition for inkjet optical modeling]
In the case of forming a three-dimensional model (model) having a complicated shape by the inkjet stereolithography method, a support that temporarily supports the model in order to prevent the model from being deformed by its own weight or the like before curing. (Support) is often formed. After the three-dimensional structure is formed, the support is removed by means such as physical peeling or dissolution with an appropriate solvent.
Therefore, it is preferable that the composition is different between the case where the liquid resin composition for inkjet optical modeling is the target three-dimensional object material (model material) and the case of the support material (support material). . The liquid resin composition for inkjet stereolithography of the present invention can be used as a model material or a support material, but a model material having excellent design properties such as full color coloring can be produced. It is more preferable to use as.

Hereinafter, the case where the liquid resin composition for inkjet stereolithography of the present invention is a model material will be mainly described. In addition, when it is a support material, it has the characteristics that 3-50 weight% of the resin composition contains the compound which has one water-soluble unsaturated double bond as mentioned above, for example.
The liquid resin composition for inkjet stereolithography of the present invention contains (A) an active ray polymerizable organic compound, (B) a compound that generates an acid upon irradiation with an active ray, and (C) an acid coloring dye precursor as essential components. To do. The contents (% by weight) of the components (A) to (C) in the resin composition are shown below.
(A) Content of actinic-ray polymerizable organic compound is 15 to 99% in a resin composition, Preferably it is 20 to 98%, More preferably, it is 30 to 97%.

In addition, in order to preferably adjust the viscosity, curing speed, strength and durability of the cured product of the liquid resin composition for inkjet stereolithography of the present invention, it is also preferable to use a plurality of compounds as the actinically polymerizable organic compound. For example, (1) 30-80% of a compound having one ethylenically unsaturated group and 20-60% of a compound having two or more ethylenically unsaturated groups are used. (2) Epoxy group in the molecule For example, 10 to 60% of a compound having two or more of the above and 50 to 90% of an ethylenically unsaturated compound having a hydroxyl group and an ethylenically unsaturated bond in the molecule can be used. Furthermore, it is also preferable to use a plurality of types of compounds having different structures for each of a compound having an ethylenically unsaturated group and a compound having two or more epoxy groups in the molecule.
In addition, the liquid resin composition for inkjet optical modeling of the present invention can also be used as an aqueous inkjet optical modeling ink, and in that case, the content of the actinic polymerizable organic compound is preferably 10% to 70%.
(B) The content of the compound that generates an acid upon irradiation with actinic radiation differs depending on (A) the type of actinic radiation polymerizable organic compound and (D) whether or not it further contains a radical photopolymerization initiator, Usually, it is 0.1 to 20% in the resin composition, preferably 0.5 to 15%, more preferably 1 to 10%. When the radically polymerizable organic compound (A-1) is 50% or more of the active ray polymerizable organic compound as the active ray polymerizable organic compound and further contains a radical photopolymerization initiator, 0.1 to 15%, preferably 0.5 to 10%, more preferably 1 to 8%.
If the content of the compound that generates an acid upon irradiation with actinic radiation is less than the lower limit of the above range, the color density of the acid color-forming dye precursor may not be sufficient, and if it exceeds the upper limit, the curable thickness of the resin composition The strength of the cured model may be adversely affected.
The content of the (C) acid color-forming dye precursor is 0.3 to 15% in the resin composition, preferably 0.5 to 12%, and more preferably 1 to 10%. If the content of the acid color-forming dye precursor is less than the lower limit of the above range, the color density may not be sufficient. If the upper limit is exceeded, the resin composition may have a curable thickness and the strength of the cured model. There is. The optimal content of the acid color-forming dye precursor varies depending on the color tone (absorption wavelength) and the wavelength of the active ray used for curing.

The acid color-forming dye precursor is preferably compatible with the (A) actinic ray polymerizable organic compound, but can be mixed using a solvent or finely pulverized for use.
Next, contents (% by weight) of components other than the components (A) to (C) in the resin composition are shown below.
The content of the (D) radical photopolymerization initiator depends on the content of the (A-1) radical polymerizable organic compound in the (A) active ray polymerizable organic compound. The content is 0.1 to 10%, preferably 0.3 to 8%. However, even when a radical polymerizable organic compound is not contained, it is preferable from the viewpoint of improving the curing rate to contain a small amount of a radical photopolymerization initiator.
(E) Content of a ultraviolet absorber changes with kinds (wavelength) of the actinic radiation used for hardening. When ultraviolet rays are used as the actinic radiation, it is preferable that no ultraviolet absorber is contained or the amount thereof is small.
When using actinic rays other than ultraviolet rays, for example, visible light, the content is 0.1 to 10% in the resin composition, preferably 0.2 to 5%, more preferably 0.3% to 3%. . When the content is less than the lower limit of the above range, the effect is not sufficient, and when the content exceeds the upper limit, physical properties after curing of the resin composition, particularly heat resistance, may be lowered.
The cured product of the resin composition containing an appropriate amount of the ultraviolet absorber improves not only the durability of the resin but also the durability of the colored pigment, and therefore can maintain the quality during curing modeling for a long period of time.
(A) Polymers or oligomers other than the actinically polymerizable organic compound are added as necessary in order to adjust the viscosity of the liquid resin composition for inkjet optical modeling of the present invention and the properties of the resulting cured molded article. The content thereof is 10% or less, preferably 5% or less in the resin composition.

Polymerization inhibitors, chain transfer agents, antioxidants, leveling agents, wettability improvers, surfactants, plasticizers, silane coupling agents, pigments, and dye contents are the composition of the liquid resin composition for inkjet photofabrication. Although it varies depending on the purpose of use, it is usually 0.1 to 3%, preferably 0.1 to 2% in the resin composition. Moreover, the case where it does not contain at all is also included.
A photosensitizer is contained as required depending on the type of polymerization initiator and the type (wavelength) of active rays used for curing. Content is 0.1 to 5% normally in a resin composition, Preferably it is 0.1 to 3%.
The inorganic filler is used to make the cured molded article opaque or to modify the physical properties, and the content thereof is 20% or less, preferably 15% or less in the resin composition. However, since it affects the color tone of the acid color-forming dye precursor, it is preferably contained in a small amount in order to obtain a cured molded article having a vivid color tone. Further, it may not be contained at all.
The liquid resin composition for inkjet optical modeling according to the present invention can be manufactured by uniformly mixing the above-described essential components and components contained as desired using a mixing and stirring device or the like.
In order to assist the mixing and dissolution of each component, an arbitrary amount of an aliphatic solvent, an aromatic solvent, an alcohol solvent, an aqueous solvent, or the like may be used as long as the effects of the present invention are not hindered.
The liquid resin composition used in the inkjet stereolithography method is slightly different from the resin composition used in the conventional stereolithography method and needs to be smoothly ejected from a fine nozzle, so it is a low viscosity resin composition. Is preferred. The viscosity of the liquid resin composition for inkjet optical modeling according to the present invention is preferably 1 to 30 mPa · s, more preferably 2 to 20 mPa · s at 80 ° C. or less from the viewpoint of dischargeability from an inkjet nozzle.
Moreover, it is preferable that the Young's modulus of the hardened | cured material of the liquid resin composition for inkjet optical modeling of this invention is 700-2200 MPa, and it is more preferable that it is 1000-1500 MPa.

[Activity line used for curing]
In the liquid resin composition for inkjet stereolithography of the present invention, the active ray used for curing is not particularly limited, and far infrared rays, infrared rays, and visible rays are selected depending on the compound that generates acid upon irradiation with active rays and the active ray polymerizable organic compound. It can be appropriately selected from light, near ultraviolet, ultraviolet and the like. In particular, near ultraviolet rays, ultraviolet rays, blue LED light, blue laser light, argon laser light with wavelengths of 488 nm and 514.5 nm, YAG laser light with 532 nm as the second harmonic, and the like are preferable.
When visible light is used as the actinic ray, the resin composition can easily contain an ultraviolet absorber as described above, and thus there is an advantage that the durability of the cured shaped article can be increased. In particular, blue LED light is preferable in that it has a good balance in terms of high active energy and contains an ultraviolet absorber, and that a light source can be obtained easily and inexpensively.

[Manufacturing method of three-dimensional modeled object by ink jet stereolithography]
Inkjet stereolithography is a method of stereolithography in which fine droplets of a photocurable liquid resin composition are ejected from a nozzle so as to draw a predetermined shape pattern by an inkjet method and then irradiated with active rays to form a cured thin film. Is the law.
Specifically, the optical modeling apparatus used for the inkjet optical modeling method includes at least a plane stage for optical modeling of a target three-dimensional model and an inkjet nozzle that can move on a plane at least parallel to the plane stage. One and a light source for irradiating the active ray for hardening of the liquid resin composition for optical modeling are provided.
Based on the CAD data, etc., the liquid resin composition for optical modeling is ejected from the inkjet nozzle in a desired pattern according to the cross-sectional shape data obtained by dividing the shape of the target three-dimensional model into a plurality of cross-sectional shapes. After the resin thin layer made of the composition is formed, the resin thin layer is cured by irradiating active rays from a light source. Next, on the cured resin thin layer, a liquid resin composition for optical modeling is supplied from an inkjet nozzle according to the following cross-sectional shape. By repeating the above, a cured resin layer corresponding to each cross-sectional shape is laminated to form a target three-dimensional structure.
In the liquid resin composition for inkjet optical modeling according to the present invention, the color development of the acid-colorable dye precursor is also achieved by irradiation with actinic radiation used for curing the resin composition, and a colored three-dimensional modeled product can be obtained. Even when the film thickness of the resin composition is large, the curing of the resin composition is completed prior to the color development of the acid color-forming dye precursor, and the curing rate and the cured film thickness of the resin composition are blocked by shielding the active ray by color development. There is little reduction. If necessary, after the curing of the resin composition is completed, the active color can be further irradiated to complete the color development of the acid color-forming dye precursor.

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

Example 1
Isobornyl acrylate [radical polymerizable organic compound, trade name Light Acrylate IB-XA, manufactured by Kyoeisha Chemical Co., Ltd., average number of functional groups 1] 70 parts by weight, tripropylene glycol diacrylate [radical polymerizable organic compound, trade name APG -200, manufactured by Shin-Nakamura Chemical Co., Ltd., average functional group number 2] 30 parts by weight, 1-hydroxycyclohexyl phenyl ketone [radical photopolymerization initiator] 2 parts by weight, triarylsulfonium hexafluorophosphate [by actinic radiation irradiation Compound generating acid] 3 parts by weight, 3- (4-diethylamino-2-ethoxyphenyl) -3- (1-ethyl-2-methylindol-3-yl) -4-azaphthalide [acid coloring dye precursor 3 parts by weight were sufficiently mixed and stirred using a stirrer to obtain a uniform liquid resin composition. This resin composition was not colored.
This resin composition was uniformly applied to a thickness of about 100 μm on a 200 mm × 200 mm glass plate using an applicator bar. This was irradiated with ultraviolet rays for 1 minute using a metal halide lamp to obtain a cured resin film colored blue.

Example 2
In Example 1, 3 parts by weight of 3- (4-diethylamino-2-ethoxyphenyl) -3- (1-ethyl-2-methylindol-3-yl) -4-azaphthalide was used as the acid color-forming dye precursor. Instead, application was performed on a glass plate in the same manner as in Example 1 except that 3 parts by weight of 3,3-bis (1-n-butyl-2-methylindo-luoyl) phthalide was used. A liquid resin composition was obtained. This was irradiated with ultraviolet rays for 1 minute in the same manner as in Example 1 to obtain a cured resin film colored red.

Example 3
In Example 1, 3 parts by weight of 3- (4-diethylamino-2-ethoxyphenyl) -3- (1-ethyl-2-methylindol-3-yl) -4-azaphthalide was used as the acid color-forming dye precursor. Instead, 3- [4- (N-ethyl-N-phenylamino) -2-ethoxyphenyl] -3- (1-ethyl-2-methylindol-3-yl) -4,7-diazaphthalide 1.5 A liquid applied on a glass plate in the same manner as in Example 1 except that 1.5 parts by weight of 2,6-bis [4-di-n-butylaminobenzoyl] pyridine was used. A resin composition was obtained. This was irradiated with ultraviolet rays for 1 minute in the same manner as in Example 1 to obtain a cured resin film colored green.

Example 4
Dicyclopentanyl acrylate [radical polymerizable organic compound, trade name FA-513AS, manufactured by Hitachi Chemical Co., Ltd., average functional group number 1] 65 parts by weight, dicyclopentane dimethylol diacrylate [radical polymerizable organic compound, trade name Light acrylate DCP-A, manufactured by Kyoeisha Chemical Co., Ltd., average functional group number 2] 10 parts by weight, urethane acrylate oligomer [radical polymerizable organic compound, product name Photomer 6010, manufactured by Cognis Co., Ltd., average functional group number 2] 25 parts by weight 1,3,5-trimethylbenzoyldiphenylphosphine oxide [radical photopolymerization initiator, trade name Lucillin TPO, manufactured by BASF Corp.] 2 parts by weight, 4-isopropylphenyl-4′-methylphenyliodonium tetrakispentafluorophenyl Borate [Generates acid upon irradiation with actinic radiation Compound, trade name RHODORSIL PHOTOINITIATOR 2074, manufactured by Rhodia Japan Ltd.] 3 parts by weight, Coumarin 6 [photosensitizer, also known as 3- [2-benzothiazolyl] -7- [diethylamino] coumarin] 1 part by weight, 2- 1 part by weight of hydroxy-4-methoxybenzophenone [ultraviolet absorber] and 3 parts by weight of 2-anilino-3-methyl-6-di-n-butylaminofluorane [acid-coloring dye precursor] were used with a stirrer. The mixture was sufficiently mixed and stirred to obtain a uniform liquid resin composition.
This resin composition was uniformly applied to a thickness of about 100 μm on a 200 mm × 200 mm glass plate using an applicator bar. This was irradiated with blue LED light (peak wavelength about 460 nm) for 1 minute to obtain a cured resin film colored black.

Example 5
In Example 4, 3,3-bis (4-diethylamino-2-ethoxy) was used instead of 3 parts by weight of 2-anilino-3-methyl-6-di-n-butylaminofluorane as the acid color-forming dye precursor. Example 3 except that 3 parts by weight of phenyl) -4-azaphthalide and 1 part by weight of 2- (n-butyloxycarbonylmethylthio) anthraquinone instead of 1 part by weight of coumarin 6 were used as a photosensitizer. The liquid resin composition apply | coated on the glass plate was obtained. This was irradiated with blue LED light for 1 minute in the same manner as in Example 4 to obtain a cured resin film colored green.

Example 6
In Example 4, 3 parts by weight of 3-chloro-6-cyclohexylaminofluorane instead of 3 parts by weight of 2-anilino-3-methyl-6-di-n-butylaminofluorane was used as the acid color-forming dye precursor. As a compound that generates an acid upon irradiation with actinic radiation, 6 parts by weight of bis (4-tert-butylphenyl) iodonium hexafluorophosphate instead of 3 parts by weight of 4-isopropylphenyl-4′-methylphenyliodonium tetrakispentafluorophenylborate The liquid resin composition apply | coated on the glass plate was performed like Example 4 except having used the part. This was irradiated with blue LED light for 1 minute in the same manner as in Example 4 to obtain a cured resin film colored orange.

Example 7
3 ′, 4′-epoxycyclohexylmethyl-3,4-epoxycyclohexylcarboxylate [cationic polymerizable organic compound] 70 parts by weight, 2-hydroxyethyl methacrylate [viscosity reducing copolymer] 30 parts by weight, bis (4-t-Butylphenyl) iodonium hexafluorophosphate [compound that generates acid upon irradiation with actinic radiation] 8 parts by weight, 1,2-benzo-6-di-n-butylaminofluorane [acid coloring dye precursor 3 parts by weight were sufficiently mixed and stirred using a stirrer to obtain a uniform liquid resin composition. This resin composition was not colored.
In the same manner as in Example 1, this resin composition was uniformly applied to a thickness of about 100 μm on a 200 mm × 200 mm glass plate using an applicator bar. This was irradiated with ultraviolet rays for 1 minute using a metal halide lamp to obtain a cured resin film colored red.

Example 8
3 ′, 4′-epoxycyclohexylmethyl-3,4-epoxycyclohexylcarboxylate [cationic polymerizable organic compound] 70 parts by weight, 2-hydroxyethyl methacrylate [viscosity reducing copolymer] 30 parts by weight, bis (4-t-butylphenyl) iodonium hexafluorophosphate [compound that generates acid upon irradiation with active rays] 8 parts by weight, coumarin 6 [photosensitizer] 1 part by weight, 2-hydroxy-4-methoxybenzophenone [ultraviolet absorption Agent] 1 part by weight, 3,6-di-n-butoxyfluorane [acid coloring dye precursor] 3 parts by weight was sufficiently mixed and stirred using a stirrer to obtain a uniform liquid resin composition. This resin composition was not colored.
This resin composition was uniformly applied to a thickness of about 100 μm on a 200 mm × 200 mm glass plate using an applicator bar. This was irradiated with blue LED light for 1 minute in the same manner as in Example 4 to obtain a cured resin film colored yellow.

Example 9
In Example 8, instead of 3 parts by weight of 3,6-di-n-butoxyfluorane as an acid color-forming dye precursor, 2- (2,4-dimethylanilino) -3-methyl-6-diethylaminofluor A liquid resin composition coated on a glass plate was obtained in the same manner as in Example 8 except that 3 parts by weight of oran was used. This was irradiated with blue LED light for 1 minute in the same manner as in Example 4 to obtain a cured resin film colored black.

Example 10
In Example 8, 3 parts by weight of 2-N, N-dibenzylamino-6-diethylaminofluorane was used in place of 3 parts by weight of 3,6-di-n-butoxyfluorane as the acid color-forming dye precursor. A liquid resin composition coated on a glass plate was obtained in the same manner as in Example 8 except that. This was irradiated with blue LED light for 1 minute in the same manner as in Example 4 to obtain a cured resin film colored green.

Evaluation The viscosity at 70 ° C. of the liquid resin compositions prepared in Examples 1 to 10 was measured using a viscometer BLII (manufactured by Toki Sangyo Co., Ltd.). The results are shown in Table 1 below. Moreover, about the obtained cured resin film, sclerosis | hardenability and light preservability were confirmed as follows. The results are shown in Table 1 below. In addition, all the cured resin films had clear colors and sufficient strength.
Curability:
The cured resin film was touched with a finger to confirm the presence or absence of stickiness. The case where there was no stickiness was indicated by ○, and the case where there was stickiness was indicated by ×.
Light storage stability:
Using a xenon fade meter (Suntest XLS +, manufactured by Toyo Seiki Co., Ltd.) using a xenon arc lamp, irradiation was continued for 72 hours from the glass plate surface side at 310 W, and the presence or absence of fading was confirmed.
The case where no fading was observed was indicated by ◎, the case where slight fading was observed, ○, the case where there was a moderate fading, and the case where apparently fading was indicated by ×.

As shown in Table 1, the liquid resin composition for inkjet optical modeling of the present invention had a viscosity suitable for inkjet optical modeling and had sufficient curability. Moreover, the light-resistant storage stability was good, and especially the hardened | cured material which contained the ultraviolet absorber and was hardened | cured by blue LED light irradiation was very excellent in light-resistant storage stability. Furthermore, the cured product has a clear color and sufficient strength, and is very suitable as a liquid resin composition for inkjet optical modeling that can be colored in full color.

The liquid resin composition for inkjet optical modeling of the present invention can be quickly cured by active ray irradiation during modeling, and can be colored vividly to a desired color by this active ray irradiation. In addition, since the molded article is excellent in curability, strength, and light-resistant storage stability, it is very suitable as a liquid resin composition for ink jet type optical modeling capable of full color coloring with a simple structure.

Claims (10)

A liquid resin composition for inkjet optical modeling, comprising the following components (A), (B) and (C) as essential components.
(A) Actinic ray polymerizable organic compound (B) Compound that generates acid upon irradiation with actinic ray (C) Acid coloring dye precursor The liquid resin composition for inkjet optical modeling according to claim 1, wherein the (A) active ray polymerizable organic compound is the following (A-1) and / or (A-2).
(A-1) Radical polymerizable organic compound (A-2) Cationic polymerizable organic compound The liquid resin composition for inkjet optical modeling according to claim 2, wherein the radical polymerizable organic compound (A-1) is an organic compound having at least one unsaturated double bond. Furthermore, (D) The liquid resin composition for inkjet optical modeling in any one of Claims 1-3 containing a radical photopolymerization initiator. The liquid resin composition for inkjet optical modeling according to any one of claims 2 to 4, wherein the cationic polymerizable organic compound (A-2) is an organic compound having two or more epoxy groups. The liquid resin composition for inkjet photofabrication according to any one of claims 1 to 5, wherein the compound that generates an acid upon irradiation with actinic radiation (B) is a cationic photopolymerization initiator. The (C) acid coloring dye precursor is a fluorane compound, a phthalide compound, an azaphthalide compound, a fluorene spirophthalide compound, a triphenylmethane compound, a diphenylmethane compound, a thiazine compound, a lactam compound, or a diketone. The liquid resin composition for inkjet optical modeling according to any one of claims 1 to 6, wherein the liquid resin composition is at least one color former selected from system compounds. The liquid resin composition for inkjet optical modeling according to any one of claims 1 to 7, wherein the liquid resin composition exhibits curing / coloring properties using visible light as an active ray. Furthermore, (E) Liquid resin composition for inkjet optical modeling in any one of Claims 1-8 containing a ultraviolet absorber. The liquid resin composition for inkjet optical modeling according to any one of claims 1 to 9, wherein the viscosity at 80 ° C or lower is 1 to 30 mPa · s.