WO2019167895A1 - Resin composition and production method for three dimensional shaped object using same, and three dimensional shaped object - Google Patents

Abstract

The present invention addresses the problem of providing a three dimensional shaped object having few warps, high strength, and good light resistance. To solve the aforementioned problem, this resin composition is used in a production method for a three-dimensional shaped object comprising a cured product of the resin composition obtained by selectively irradiating a liquid form of the resin composition with visible light. The resin composition includes a photopolymerizable compound, a thermally polymerizable compound, a visible light polymerization initiator, and an ultraviolet light absorbent.

Description

Resin composition, manufacturing method of three-dimensional model using the same, and three-dimensional model

The present invention relates to a resin composition, a method for producing a three-dimensional structure using the resin composition, and a three-dimensional structure.

In recent years, various methods have been developed that can manufacture a three-dimensional object having a complicated shape relatively easily. One of the methods for producing a three-dimensional model is a method of selectively irradiating a resin composition that is cured by active energy rays with active energy rays (for example, ultraviolet light) to cure the resin composition to a desired shape. Are known.

However, when three-dimensional modeling is performed using a resin composition mainly containing a photopolymerizable compound, there is a problem that it is easily contracted during curing and warpage is likely to occur. For such problems, for example, it has been proposed to suppress warpage by mixing a photopolymerizable compound and a thermopolymerizable compound and further performing thermosetting after photocuring (for example, Patent Document 1). .

In recent years, a method of continuously or intermittently curing a liquid resin composition containing a photopolymerizable compound has been proposed as a method for producing a new three-dimensional structure (Patent Documents 2 and 3). In this method, first, a buffer region in which the resin composition is not cured even when irradiated with active energy rays and a curing region in which the resin composition is cured by irradiation with active energy rays are provided in the molded article tank. At this time, each area | region is formed so that a buffer area | region may be located in the modeling tank bottom part side, and the area | region for hardening may be located in the modeling tank upper part side. Then, a carrier serving as a base point for three-dimensional modeling is disposed in the curing region, and active energy rays are selectively irradiated from the buffer region (modeling tank bottom) side to the curing region. Thereby, a part of solid modeling thing (hardened material of a resin composition) is formed in the career surface. Further, by continuously irradiating the active energy rays while pulling up the carrier to the upper side of the modeling tank, a cured product of the resin composition is continuously formed below the carrier, and the three-dimensional modeled product is seamless. Is produced.

Japanese Patent Laid-Open No. 2-24127 Special table 2016-509962 gazette Special table 2016-509964

Generally, thermopolymerizable compounds often have a molecular structure that is easily decomposed or cut by ultraviolet light or the like. Therefore, as in Patent Document 1 described above, when a photopolymerizable compound and a thermopolymerizable compound are mixed and the resin composition is cured with ultraviolet light, the thermopolymerizable compound is easily decomposed, and a desired warpage suppressing effect is obtained. It was difficult to obtain. Moreover, in order to improve the light resistance of a thermopolymerizable resin, it is possible to add an ultraviolet light absorber to a resin composition. However, in the method of producing a three-dimensional structure by selectively irradiating active energy rays such as Patent Literature 2 and Patent Literature 3, the resin composition is required to have high sensitivity to active energy rays. Therefore, when an ultraviolet light absorber is included in the resin composition, there is a problem that the curing of the photopolymerizable compound tends to be insufficient, and the strength of the three-dimensional structure to be obtained is likely to be reduced.

The present invention has been made in view of such problems. That is, an object of the present invention is to provide a shaped article with less warpage, high strength, and good light resistance.

The first of the present invention is the following resin composition.
[1] A resin composition used in a method for producing a three-dimensional structure made of a cured product of the resin composition by selectively irradiating a liquid resin composition with visible light, which is photopolymerizable. A resin composition comprising a compound, a thermally polymerizable compound, a visible light polymerization initiator, and an ultraviolet light absorber.

[2] The photopolymerizable compound and / or the thermopolymerizable compound includes in its molecule at least one structure selected from the group consisting of an aromatic ring, a triazine ring, an ester bond, a urethane bond, and a urea bond. The resin composition according to [1].
[3] The resin composition according to [1] or [2], wherein the visible light polymerization initiator has an absorption maximum in a wavelength region of 400 nm or more.
[4] The resin composition according to any one of [1] to [3], further comprising a light stabilizer.
[5] The resin composition according to any one of [1] to [4], further comprising a filler.

2nd of this invention exists in the manufacturing method of the following three-dimensional molded items, and a three-dimensional molded item.
[6] An optical modeling step of selectively irradiating the resin composition according to any one of [1] to [5] with visible light to form a primary cured product including a cured product of the photopolymerizable compound. The manufacturing method of the three-dimensional molded item containing.
[7] The manufacturing method of the three-dimensional molded item according to [6], further including a thermosetting step of thermosetting the primary cured product.
[8] The method for manufacturing a three-dimensional structure according to [7], further including a light irradiation step of irradiating the primary cured product with visible light before the thermosetting step.

[9] The stereolithography step includes the resin composition and oxygen, includes at least a buffer region in which curing of the photopolymerizable compound is inhibited by oxygen, and the resin composition, and the oxygen concentration is higher than that of the buffer region. A first step of forming a low curing region capable of curing the photopolymerizable compound adjacent to the inside of the molded article tank, and selectively irradiating the resin composition with visible light from the buffer region side Then, the second step of curing the photopolymerizable compound in the curing region, in the second step, while moving the formed cured product to the opposite side of the buffer region, The method for producing a three-dimensional structure according to any one of [6] to [8], wherein visible light is continuously applied to the curing region to form the primary cured product.
[10] A three-dimensionally shaped article, which is a cured product of the resin composition according to any one of [1] to [5].

According to the resin composition of the present invention, it is possible to provide a three-dimensionally shaped article with less warpage, high strength, and excellent light resistance.

FIG. 1 is a schematic diagram of an apparatus for manufacturing a three-dimensional structure according to an embodiment of the present invention. FIG. 2 is a schematic view of a three-dimensional object manufacturing apparatus according to another embodiment of the present invention.

1. Resin Composition The resin composition of the present invention is in a liquid form and is used in a method for producing a three-dimensional model by selectively irradiating visible light to the resin composition. In the present invention, visible light refers to a wavelength range of 400 nm to 780 nm. As described above, when the photopolymerizable compound is mainly contained in such a resin composition, there is a problem that the resulting three-dimensional structure is likely to be warped. Conventionally, it has also been proposed to add a thermopolymerizable resin to such a resin composition. However, since the thermopolymerizable resin deteriorates due to ultraviolet light irradiation at the time of modeling, etc. The warp could not be sufficiently suppressed. In addition, when an ultraviolet light absorber is added to such a resin composition, the curing of the photopolymerizable compound is hindered, and the strength of the three-dimensional structure to be obtained tends to be lowered. Therefore, it has been desired to provide a resin composition that can produce a three-dimensional structure with little warpage, high strength, and good light resistance.

In contrast, the resin composition of the present invention contains a photopolymerizable compound, a thermopolymerizable compound, a visible light polymerization initiator, and an ultraviolet light absorber. Since the visible light polymerization initiator is contained in the resin composition, it can be cured with visible light. At this time, light for curing (visible light) is not easily absorbed by the ultraviolet light absorber, and the photocurability tends to be good. Also, even if the thermopolymerizable compound or the like has a structure that is easily photodegraded, it is difficult to photodegrade by irradiation with visible light, so that it is easy to obtain a desired warpage suppressing effect, and three-dimensional modeling with high dimensional accuracy. A thing is obtained. Moreover, since the ultraviolet light absorber is contained in the resin composition of this invention, it is also possible to suppress the light degradation with time after a three-dimensional molded item.

When the photopolymerizable compound and / or the thermopolymerizable compound has a structure selected from the group consisting of an aromatic ring, a triazine ring, an ester bond, a urethane bond, and a urea bond in the molecule, Things are subject to light degradation. On the other hand, if it is a composition of the resin composition of this invention, even if a photopolymerizable compound and a thermopolymerizable compound have such a structure, the light resistance of a three-dimensional molded item over a long period of time. Has the advantage of becoming better.

The resin composition contains components other than a curing agent, a light stabilizer, a filler, a photopolymerizable compound, a thermopolymerizable compound, a visible light polymerization initiator, and an ultraviolet light absorber as necessary. May be. Hereinafter, each component will be described.

1-1. Photopolymerizable compound The photopolymerizable compound contained in the resin composition may be a compound that is liquid at room temperature and can be polymerized by irradiation with visible light, and may be a monomer or an oligomer. It may be a prepolymer or a mixture thereof. The photopolymerizable compound may be a radical polymerizable compound or a cationic polymerizable compound. However, as will be described later, in a resin composition used for a method of producing a three-dimensional structure (hereinafter also referred to as “CLIP method”) while adding oxygen to the resin composition, the photopolymerizable compound is a radical polymerizable compound. Need to be. The resin composition may contain only one type of photopolymerizable compound, or may contain two or more types.

The radically polymerizable compound is not particularly limited as long as it has a group capable of radical polymerization by irradiation with visible light in the presence of a visible light polymerization initiator (radical polymerization initiator) described later. Examples of radically polymerizable compounds include ethylene group, propenyl group, butenyl group, vinylphenyl group, allyl ether group, vinyl ether group, maleyl group, maleimide group, (meth) acrylamide group, acetyl vinyl group, vinyl amide group, (meta ) Compounds having one or more acryloyl groups in the molecule are included.

Among these, the radical polymerizable compound is an unsaturated carboxylic acid ester compound containing one or more unsaturated carboxylic acid ester structures in the molecule or an unsaturated compound described later containing one or more unsaturated carboxylic acid amide structures in the molecule. A carboxylic acid amide compound is preferred. Furthermore, a (meth) acrylate-based compound and / or a (meth) acrylamide-based compound containing a (meth) acryloyl group, which will be described later, are particularly preferable. In the present specification, the description “(meth) acryl” represents methacryl and / or acryl, the description “(meth) acryloyl” represents methacryloyl and / or acryloyl, and “(meth) acrylate” "Represents methacrylate and / or acrylate.

Examples of “compound having an allyl ether group” which is one of radically polymerizable compounds include phenyl allyl ether, o-, m-, p-cresol monoallyl ether, biphenyl-2-ol monoallyl ether, biphenyl- 4-ol monoallyl ether, butyl allyl ether, cyclohexyl allyl ether, cyclohexanemethanol monoallyl ether, phthalic acid diallyl ether, isophthalic acid diallyl ether, dimethanol tricyclodecane diallyl ether, 1,4-cyclohexanedimethanol diallyl ether, alkylene (C2-5) Glycol diallyl ether, polyethylene glycol diallyl ether, glycerol diallyl ether, trimethylolpropane diallyl ether, pentaerythritol dia Ether, polyglycerol (degree of polymerization 2-5) diallyl ether, trimethylolpropane triallyl ether, glycerol triallyl ether, pentaerythritol tetraallyl ether and tetraallyloxyethane, pentaerythritol triallyl ether, diglycerol triallyl ether, sorbitol Triallyl ether and polyglycerin (degree of polymerization 3 to 13) polyallyl ether and the like are included.

Examples of the “compound having a vinyl ether group” include butyl vinyl ether, butyl propenyl ether, butyl butenyl ether, hexyl vinyl ether, 1,4-butanediol divinyl ether, ethyl hexyl vinyl ether, phenyl vinyl ether, benzyl vinyl ether, ethyl ethoxy vinyl ether. , Acetylethoxyethoxy vinyl ether, cyclohexyl vinyl ether, tricyclodecane vinyl ether, adamantyl vinyl ether, cyclohexane dimethanol divinyl ether, tricyclodecane dimethanol divinyl ether, EO adduct divinyl ether of bisphenol A, cyclohexanediol divinyl ether, cyclopentadiene vinyl ether, nor Bornyldimethanol divini Ether, divinyl resorcin, divinyl hydroquinone, ethylene glycol divinyl ether, diethylene glycol divinyl ether, triethylene glycol divinyl ether, propylene glycol divinyl ether, dipropylene glycol vinyl ether, butylene divinyl ether, dibutylene glycol divinyl ether, 4-cyclohexane divinyl ether, oxa Norbonane divinyl ether, neopentyl glycol divinyl ether, glycerin trivinyl ether, oxetane divinyl ether, glycerin ethylene oxide adduct trivinyl ether (addition mole number of ethylene oxide 6), trimethylolpropane trivinyl ether, trivinyl ether ethylene oxide adduct trivinyl ether ( Added mole number 3 Chiren'okishido), pentaerythritol trivinyl ether, includes such ditrimethylolpropane hexa ether and their oxyethylene adduct.

Examples of the “compound having a maleimide group” include phenylmaleimide, cyclohexylmaleimide, n-hexylmaleimide and the like.

Examples of “compounds having a (meth) acrylamide group”, that is, (meth) acrylamide compounds include (meth) acrylamide, N, N-dimethyl (meth) acrylamide, N-ethyl (meth) acrylamide, N- Isopropyl (meth) acrylamide, N-hydroxyethyl (meth) acrylamide, N-butyl (meth) acrylamide, isobutoxymethyl (meth) acrylamide, diacetone (meth) acrylamide, bismethyleneacrylamide, di (ethyleneoxy) bispropylacrylamide, And tri (ethyleneoxy) bispropylacrylamide, (meth) acryloylmorpholine, and the like.

On the other hand, examples of the above-mentioned “compound having a (meth) acryl group”, that is, a (meth) acrylate-based compound include isoamyl (meth) acrylate, stearyl (meth) acrylate, lauryl (meth) acrylate, butyl (meth) acrylate, Pentyl (meth) acrylate, octyl (meth) acrylate, isooctyl (meth) acrylate, isononyl (meth) acrylate, decyl (meth) acrylate, isodecyl (meth) acrylate, tridecyl (meth) acrylate, isomyristyl (meth) acrylate, isostearyl (Meth) acrylate, dicyclopentenyloxyethyl (meth) acrylate, dicyclopentenyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, dimethylaminoethyl (meth) acrylate Lilate, diethylaminoethyl (meth) acrylate, 2-ethylhexyl-diglycol (meth) acrylate, 2- (meth) acryloyloxyethyl hexahydrophthalic acid, methoxyethoxyethyl (meth) acrylate, butoxyethyl (meth) acrylate, ethoxy Diethylene glycol (meth) acrylate, methoxydiethylene glycol (meth) acrylate, methoxypolyethylene glycol (meth) acrylate, methoxypropylene glycol (meth) acrylate, phenoxyethyl (meth) acrylate, pentachlorophenyl (meth) acrylate, pentabromophenyl (meth) acrylate , Tetrahydrofurfuryl (meth) acrylate, dicyclopentanyl (meth) acrylate, cyclohexyl ( (Meth) acrylate, isobornyl (meth) acrylate, polyethylene glycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate, glycerin (meth) acrylate, 7-amino-3,7-dimethyloctyl (meth) acrylate, 2-hydroxy Ethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 2-hydroxy-3-phenoxypropyl (meth) acrylate, benzyl (meth) acrylate, 2- (2-ethoxyethoxy) ) Ethyl (meth) acrylate, 2-ethylhexyl carbitol (meth) acrylate, 2- (meth) acryloyloxyethyl succinic acid, 2- (meth) acryloyloxyethyl phthalic acid, 2- (meth) Acryloyloxyethyl-2-hydroxyethyl - phthalic acid, 2- (meth) acryloyloxyethyl hexahydrophthalic acid, and t- butyl cyclohexyl (meth) monofunctional containing acrylate (meth) acrylate monomer;
Triethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, tripropylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, 1,4-butanediol di (Meth) acrylate, 1,6-hexanediol di (meth) acrylate, 1,9-nonanediol di (meth) acrylate, cyclohexanedi (meth) acrylate, cyclohexanedimethanol di (meth) acrylate, neopentylglycol di ( (Meth) acrylate, tricyclodecanediyldimethylene di (meth) acrylate, dimethylol-tricyclodecane di (meth) acrylate, polyester di (meth) acrylate, bisphenol PO adduct di (meth) acrylate, hydroxypivalate neopentyl glycol di (meth) acrylate, polytetramethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, tripropylene glycol di (meth) acrylate , And bifunctional (meth) acrylate monomers including tricyclodecane dimethanol di (meth) acrylate and the like;
Trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, ditrimethylolpropane tetra (meth) A tri- or higher functional (meth) acrylate monomer including acrylate, dipentaerythritol monohydroxypenta (meth) acrylate, glycerin propoxytri (meth) acrylate, pentaerythritol ethoxytetra (meth) acrylate, and the like;
And oligomers thereof.

Further, the “(meth) acrylate compound” may be a product obtained by further modifying various (meth) acrylate monomers or oligomers thereof (modified product). Examples of modified products include triethylene glycol diacrylate, polyethylene glycol diacrylate, ethylene oxide modified trimethylolpropane tri (meth) acrylate, ethylene oxide modified pentaerythritol tetraacrylate, ethylene oxide modified bisphenol A di (meth) acrylate, ethylene Ethylene oxide modified (meth) acrylate monomers such as oxide modified nonylphenol (meth) acrylate; tripropylene glycol diacrylate, polypropylene glycol diacrylate, propylene oxide modified trimethylolpropane tri (meth) acrylate, propylene oxide modified pentaerythritol tetraacrylate, propylene Oxide-modified glycerin tri (meth) ac Propylene oxide modified (meth) acrylate monomers such as caprate; Caprolactone modified (meth) acrylate monomers such as caprolactone modified trimethylolpropane tri (meth) acrylate; Caprolactam modified (meth) acrylates such as caprolactam modified dipentaerythritol hexa (meth) acrylate Monomer; and the like.

The “(meth) acrylate-based compound” may be a compound (hereinafter also referred to as “modified (meth) acrylate-based compound”) in which various oligomers are (meth) acrylated. Examples of such modified (meth) acrylate compounds include polybutadiene (meth) acrylate compounds, polyisoprene (meth) acrylate compounds, epoxy (meth) acrylate compounds, urethane (meth) acrylate compounds, silicone ( A meth) acrylate compound, a polyester (meth) acrylate compound, a linear (meth) acrylic compound, and the like are included. Among these, epoxy (meth) acrylate compounds, urethane (meth) acrylate compounds, and silicone (meth) acrylate compounds can be preferably used. When an epoxy (meth) acrylate compound, a urethane (meth) acrylate compound, or a silicone (meth) acrylate compound is included in the resin composition, the strength of the three-dimensional structure to be obtained easily increases.

The epoxy (meth) acrylate compound may be a compound containing at least one epoxy group and one (meth) acrylate group in one molecule. Examples thereof include bisphenol A type epoxy (meth) acrylate and bisphenol. Novolak type epoxy such as F type epoxy (meth) acrylate, bisphenyl type epoxy (meth) acrylate, triphenolmethane type epoxy (meth) acrylate, cresol novolac type epoxy (meth) acrylate, phenol novolac type epoxy (meth) acrylate, etc. (Meth) acrylate and the like are included.

A urethane (meth) acrylate compound is obtained by reacting an aliphatic polyisocyanate compound having two isocyanate groups or an aromatic polyisocyanate compound having two isocyanate groups with a (meth) acrylic acid derivative having a hydroxyl group. And a compound having a urethane bond and a (meth) acryloyl group.

Examples of the isocyanate compound used as a raw material for the urethane (meth) acrylate compound include isophorone diisocyanate, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, hexamethylene diisocyanate, trimethylhexamethylene diisocyanate, diphenylmethane-4 , 4'-diisocyanate (MDI), hydrogenated MDI, polymeric MDI, 1,5-naphthalene diisocyanate, norbornane diisocyanate, tolidine diisocyanate, xylylene diisocyanate (XDI), hydrogenated XDI, lysine diisocyanate, triphenylmethane triisocyanate, tris (Isocyanatephenyl) thiophosphate, tetramethylxylylene diisocyanate, 1,6,11-undecantri Isocyanate and the like.

Examples of the isocyanate compound that is a raw material for the urethane (meth) acrylate compound include ethylene glycol, propylene glycol, glycerin, sorbitol, trimethylolpropane, carbonate diol, polyether diol, polyester diol, polycaprolactone diol, and the like. Also included are chain-extended isocyanate compounds obtained by reaction of polyols with excess isocyanate compounds.

On the other hand, examples of the (meth) acrylic acid derivative having a hydroxyl group as a raw material for the urethane (meth) acrylate compound include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxy Hydroxyalkyl (meth) acrylates such as butyl (meth) acrylate and 4-hydroxybutyl (meth) acrylate; ethylene glycol, propylene glycol, 1,3-propanediol, 1,3-butanediol, 1,4-butanediol, Mono (meth) acrylates of dihydric alcohols such as polyethylene glycol; mono (meth) acrylates and di (meth) acrylates of trivalent alcohols such as trimethylolethane, trimethylolpropane and glycerin; It includes epoxy (meth) acrylate of rates.

The urethane (meth) acrylate compound having the above structure may be commercially available, and examples thereof include M-1100, M-1200, M-1210, and M-1600 (all manufactured by Toagosei Co., Ltd.). ), EBECRYL210, EBECRYL220, EBECRYL230, EBECRYL270, EBECRYL1290, EBECRYL2220, EBECRYL4827, EBECRYL4842, EBECRYL4858, EBECRYL5129, EBECRYL6700, EBECRYL8402, EBECRYL8803, EBECRYL8804, EBECRYL8807, EBECRYL9260 (all manufactured by Daicel-Orunekusu Co., Ltd.), Art resin UN-330, Art Resin SH-500B, Art Resin UN-12 0TPK, Art Resin UN-1255, Art Resin UN-3320HB, Art Resin UN-7100, Art Resin UN-9000A, Art Resin UN-9000H (all manufactured by Negami Kogyo Co., Ltd.), U-2HA, U-2PHA, U- 3HA, U-4HA, U-6H, U-6HA, U-6LPA, U-10H, U-15HA, U-108, U-108A, U-122A, U-122P, U-324A, U-340A, U-340P, U-1084A, U-2061BA, UA-340P, UA-4000, UA-4100, UA-4200, UA-4400, UA-5201P, UA-7100, UA-7200, UA-W2A (all Shin-Nakamura Chemical Co., Ltd.), AH-600, AI-600, AT-600, UA-101I, UA-1 1T, UA-306H, UA-306I, include UA-306T (all manufactured by Kyoeisha Chemical Co., Ltd.) and the like.

On the other hand, the urethane (meth) acrylate compound may be a blocked isocyanate obtained by blocking the isocyanate group of polyisocyanate with a blocking agent having a (meth) acrylate group.

The polyisocyanate used for obtaining the blocked isocyanate may be the aforementioned “isocyanate compound”, or a compound obtained by reacting these compounds with a polyol or polyamine. Examples of the polyol include conventionally known polyether polyols, polyester polyols, polymer polyols, vegetable oil polyols, and flame retardant polyols such as phosphorus-containing polyols and halogen-containing polyols. One of these polyols may be contained in the blocked isocyanate, or two or more thereof may be contained.

Examples of the polyether polyol to be reacted with isocyanate and the like include compounds having at least two active hydrogen groups (specifically, polyhydric alcohols such as ethylene glycol, propylene glycol, glycerin, trimethylolpropane, pentaerythritol, etc.) A compound prepared by an addition reaction of an alkylene oxide (specifically, ethylene oxide, propylene oxide, etc.) with an amine such as ethylenediamine; an alkanolamine such as ethanolamine or diethanolamine; Methods for preparing polyether polyols are described, for example, in Gunter Oertel, “Polyurethane Handbook” (1985) Hanser ｕ Publishers (Germany), p. 42-53.

Examples of the polyester polyol include a condensation reaction product of a polyvalent carboxylic acid such as adipic acid or phthalic acid and a polyhydric alcohol such as ethylene glycol, 1,4-butanediol, or 1,6-hexanediol, or nylon. Includes waste from manufacturing, waste from trimethylolpropane, pentaerythritol, waste from phthalic polyester, polyester polyol derived from the treatment of waste (eg, Keiji Iwata “Polyurethane Resin Handbook” (1987) Nikkan Kogyo Shimbun) (See description of company p. 117).

Examples of the polymer polyol include a polymer polyol obtained by reacting the polyether polyol with an ethylenically unsaturated monomer (for example, butadiene, acrylonitrile, styrene, etc.) in the presence of a radical polymerization catalyst. The polymer polyol preferably has a molecular weight of about 5000 to 12000.

Examples of vegetable oil polyols include hydroxyl group-containing vegetable oils such as castor oil and palm oil. A castor oil derivative polyol obtained using castor oil or hydrogenated castor oil as a raw material can also be suitably used. The castor oil derivative polyol includes castor oil polyester obtained by reaction of castor oil, polyvalent carboxylic acid and short chain diol, and an alkylene oxide adduct of castor oil and castor oil polyester.

Examples of flame retardant polyols include phosphorus-containing polyols obtained by adding alkylene oxide to phosphoric acid compounds; halogen-containing polyols obtained by ring-opening polymerization of epichlorohydrin and trichlorobutylene oxide; alkylenes for active hydrogen compounds having aromatic rings An aromatic ether polyol obtained by adding an oxide; an aromatic ester polyol obtained by a condensation reaction of a polyvalent carboxylic acid having an aromatic ring and a polyhydric alcohol;

The hydroxyl value of the polyol to be reacted with isocyanate or the like is preferably 5 to 300 mgKOH / g, and more preferably 10 to 250 mgKOH / g. The hydroxyl value can be measured by the method defined in JIS-K0070.

Examples of polyamines to be reacted with isocyanates include ethylenediamine, diethylenetriamine, triethylenetetraamine, hexamethylenepentamine, bisaminopropylpiperazine, tris (2-aminoethyl) amine, isophoronediamine, polyoxyalkylenepolyamine, diethanolamine. , Triethanolamine and the like.

On the other hand, the blocking agent for blocking the isocyanate group of the polyisocyanate may be any one that has a (meth) acryloyl group, reacts with the isocyanate group, and can be eliminated by heating.

Specific examples of such blocking agents include t-butylaminoethyl methacrylate (TBAEMA), t-pentylaminoethyl methacrylate (TPAEMA), t-hexylaminoethyl methacrylate (THAEMA), t-butylaminopropyl methacrylate (TPAEMA). ), T-hexylaminoethyl methacrylate (THAEMA), t-butylaminopropyl methacrylate (TBAPMA) and the like.

The blocking reaction of polyisocyanate can be generally carried out at −20 to 150 ° C., preferably 0 to 100 ° C. If it is 150 ° C. or lower, side reactions can be prevented, while if it is −20 ° C. or higher, the reaction rate can be in an appropriate range. The blocking reaction between the polyisocyanate compound and the blocking agent can be performed regardless of the presence or absence of a solvent. When using a solvent, it is preferable to use a solvent inert to the isocyanate group. In the blocking reaction, a reaction catalyst can be used. Specific examples of the reaction catalyst include organometallic salts such as tin, zinc and lead, metal alcoholates, and tertiary amines.

When the blocked isocyanate prepared as described above is used as a radical polymerizable compound, first, the acryloyl group portion is polymerized by light irradiation. Thereafter, by removing the blocking agent by heating, the produced isocyanate compound can be newly polymerized with polyol, polyamine, or the like, and a three-dimensional structure including polyurethane, polyurea, or a mixture thereof can be obtained.

On the other hand, the silicone (meth) acrylate compound can be a compound in which (meth) acrylic acid is added to the terminal and / or side chain of the silicone having a polysiloxane bond in the main chain. The silicone used as a raw material for the silicone (meth) acrylate compound is an organopolysiloxane obtained by polymerizing a known monofunctional, bifunctional, trifunctional, or tetrafunctional silane compound (for example, alkoxysilane) in any combination. Can do. Specific examples of silicone acrylates include commercially available TEGORad 2500 (trade name: manufactured by Tego Chemie Service GmbH) and organic compounds having —OH groups such as X-22-4015 (trade name: manufactured by Shin-Etsu Chemical Co., Ltd.). A product obtained by esterifying a modified silicone and acrylic acid in the presence of an acid catalyst; reacting an organically modified silane compound such as epoxy silane such as KBM402 and KBM403 (both trade names: manufactured by Shin-Etsu Chemical Co., Ltd.) with acrylic acid Etc. are included.

On the other hand, the type of the cationically polymerizable compound, which is another example of the photopolymerizable compound, is not particularly limited as long as it has a group capable of cationic polymerization by irradiation with visible light in the presence of an acid catalyst. Examples thereof include a cyclic hetero compound, and a compound having a cyclic ether group is preferable from the viewpoint of reactivity and the like.

Specific examples of the cationic polymerizable compound include oxirane compounds such as oxirane, methyl oxirane, phenyl oxirane, and 1,2-diphenyl oxirane, or a hydrogen atom of an oxirane ring such as glycidyl ether, glycidyl ester, and glycidyl amine. And epoxy group-containing compounds substituted with a methine linking group; 2- (cyclohexylmethyl) oxirane, 2-ethoxy-3- (cyclohexylmethyl) oxirane, [(cyclohexyloxy) methyl] oxirane, 1,4-bis ( An epoxy group-containing compound having a cycloalkane ring, such as oxiranylmethoxymethyl) cyclohexane, 7-oxabicyclo [4.1.0] heptane, 3-methyl-7-oxabicyclo [4.1.0] heptane, 7-Oxabicyclo [4.1.0] heptane-3-y Aliphatic epoxy group-containing compounds having no aromatic ring, such as rumethanol and 7-oxabicyclo [4.1.0] heptane-3-methoxymethyl; 3-phenyl-7-oxabicyclo [4.1. 0] heptane-3-carboxylate, 4-ethylphenyl 7-oxabicyclo [4.1.0] heptane, benzyl 7-oxabicyclo [4.1.0] heptane-3-carboxylate, 4-ethylphenyl 7 An alicyclic epoxy group-containing compound having an aromatic ring such as oxabicyclo [4.1.0] heptane-3-carboxylate;
3-ethyl-3-hydroxymethyloxetane, 1,4-bis [(3-ethyl-3-oxetanyl) methoxymethyl] benzene, di (1-ethyl-3-oxetanyl) methyl ether, 3-ethyl-3- ( Oxetanyl group-containing compounds such as phenoxymethyl) oxetane, 3-ethyl-3- (2-ethylhexyloxymethyl) oxetane, phenol novolac oxetane, 3-ethyl-{(3-triethoxysilylpropoxy) methyl} oxetane;
2-methyltetrahydrofuran, 2,5-diethoxytetrahydrofuran, tetrahydrofuran-2,2-dimethanol 3-methyl-2,4 (3H, 5H) -furandone, 2,4-dioxotetrahydrofuran-3-carboxylate, 1,5-di (tetrahydrofuran-2-yl) pentan-3-yl propanoate, 4- (2,5-dioxotetrahydrofuran-3-yl) -1,2,3,4-tetrahydronaphthalene-1,2 -5 or more-membered cyclic ether compounds such as dicarboxylic acid anhydride and methoxytetrahydropyran are included.

The total amount of the photopolymerizable compound contained in the resin composition is preferably 10 to 90% by mass, more preferably 30 to 70% by mass, and more preferably 40 to 60% by mass with respect to the total mass of the resin composition. % Is more preferable. When the amount of the photopolymerizable compound is within the above range, a three-dimensional model with high strength is easily obtained.

1-2. Thermopolymerizable compound The thermopolymerizable compound contained in the resin composition may be any compound that can be polymerized and cured by heating. Usually, the thermopolymerizable compound is used in combination with a curing agent described later.

Examples of such a thermally polymerizable compound include a compound containing at least one group selected from the group consisting of a cyclic ether group, a cyanate group, an isocyanate group, and a hydrosilyl group.

Examples of “compound having a cyclic ether group” include compounds containing epoxide, oxetane, tetrahydrofuran, tetrahydropyran and the like. Among these, from the viewpoint of polymerizability and the like, a compound having an epoxy group (hereinafter also referred to as “epoxy compound”) is preferable. Examples of the epoxy compound include an epoxy compound having one or more epoxy groups in the molecule. Examples of epoxy compounds include biphenyl type epoxy compounds, bisphenol A type epoxy compounds, bisphenol F type epoxy compounds, stilbene type epoxy compounds, hydroquinone type epoxy compounds, and the like; cresol novolac type epoxy compounds, phenol novolac type Novolak type epoxy compounds such as epoxy compounds and naphthol novolak type epoxy compounds; Phenol aralkyl type epoxy compounds such as phenylene skeleton-containing phenol aralkyl type epoxy compounds, biphenylene skeleton containing phenol aralkyl type epoxy compounds, phenylene skeleton containing naphthol aralkyl type epoxy compounds; Phenolmethane type epoxy compound, alkyl-modified triphenolmethane type epoxy compound, glycidylamine, Polyfunctional epoxy compounds such as functional naphthalene type epoxy compounds; modified phenol type epoxy compounds such as dicyclopentadiene modified phenol type epoxy compounds, terpene modified phenol type epoxy compounds, silicone modified epoxy compounds; heterocycles such as triazine nucleus-containing epoxy compounds Containing epoxy compound; naphthylene ether type epoxy and the like are included.

In addition, the “compound having a cyanate group” may be a compound having one or more cyanate groups in the molecule. Examples include 1,3- or 1,4-dicyanatobenzene; 1,3,5-tricyanatobenzene; 1,3-, 1,4-, 1,6-, 1,8-, 2, 6- or 2,7-dicyanatonaphthalene; 1,3,6-tricyanatonaphthalene; 2,2′- or 4,4′-dicyanatobiphenyl; bis (4-cyanatophenyl) methane; 2,2 -Bis (4-cyanatophenyl) propane; 2,2-bis (3,5-dichloro-4-cyanatophenyl) propane; 2,2-bis (3-dibromo-4-dicyanatophenyl) propane; bis (4-cyanatophenyl) ether; bis (4-cyanatophenyl) thioether; bis (4-cyanatophenyl) sulfone; tris (4-cyanatophenyl) phosphite; tris (4-cyanatophenyl) phos Bis (3-chloro-4-cyanatophenyl) methane: 4-cyanatobiphenyl; 4-cumylcyanatobenzene; 2-t-butyl-1,4-dicyanatobenzene; 2,4-dimethyl-1 2,5-dicyanatobenzene; 2,5-di-tert-butyl-1,4-dicyanatobenzene; tetramethyl-1,4-dicyanatobenzene; 4-chloro-1,3-dicyanatobenzene; 3 ′, 5,5′-tetramethyl-4,4 ′ dicyanatodiphenylbis (3-chloro-4-cyanatophenyl) methane: 1,1,1-tris (4-cyanatophenyl) ethane; 1-bis (4-cyanatophenyl) ethane; 2,2-bis (3,5-dichloro-4-cyanatophenyl) propane; 2,2-bis (3,5-dibromo-4-cyanatophenyl) Propane; bi (P- cyanophenoxy aminophenoxy) benzene; di (4-cyanatophenyl) ketone; cyan oxide novolak; cyan oxide bisphenol polycarbonate oligomer is contained.

The “compound having an isocyanate group” is not particularly limited as long as it is a compound having one or more isocyanate groups in the molecule, and examples thereof include tolylene diisocyanate, xylylene diisocyanate, naphthylene diisocyanate, diphenylmethane. Aromatic diisocyanates such as diisocyanates; alicyclic diisocyanates such as isophorone diisocyanate, dicyclohexylmethane diisocyanate, cyclohexylene diisocyanate, diisocyanate methylcyclohexane; aliphatic diisocyanates such as hexamethylene diisocyanate; triphenylmethane triisocyanate, tris (isocyanatephenyl) thiophosphate 1 to 3 adduct of trimethylolpropane and hexamethylene diisocyanate, hexa Trifunctional or higher functional polyisocyanates such as cyclic trimers of tylene diisocyanate; blocking agents for isocyanate groups of these compounds (for example, alcohols, phenols, lactams, oximes, alkyl acetoacetates, alkyl malonates) , Phthalimides, imidazoles, hydrogen chloride, hydrogen cyanide, sodium hydrogen sulfite and the like) and the like.

In addition, the “compound having a hydrosilyl group” may be a compound having one or more hydrosilyl groups in the molecule, and examples thereof include a methylhydrosiloxane-dimethylsiloxane copolymer and the like. These “compounds having a hydrosilyl group” can be obtained by addition reaction with a polyorganosiloxane having a vinyl group at the terminal or side chain. Examples of polysiloxanes having vinyl groups include polydimethylsiloxanes in which vinyl groups are substituted at each terminal silicon atom, dimethylsiloxane-diphenylsiloxane copolymers in which vinyl groups are substituted at each terminal silicon atom, and vinyls at each terminal silicon atom. Examples include polyphenylmethylsiloxane having a substituted group, vinylmethylsiloxane-dimethylsiloxane copolymer having a trimethylsilyl group at each end, and the like.

The total amount of the thermopolymerizable compound and the curing agent described below is preferably 20 to 90% by mass, more preferably 30 to 80% by mass, and more preferably 40 to 40% by mass with respect to the total amount in the resin composition. More preferably, 60% by mass is contained. When the total amount of the thermopolymerizable compound and the curing agent is included in the range, the dimensional accuracy of the three-dimensional structure to be obtained is likely to be increased.

1-3. Visible light polymerization initiator A visible light polymerization initiator will not be restrict | limited especially if it is a compound which can be excited by visible light and can superpose | polymerize the said photopolymerizable compound. The resin composition may contain only one type of visible light polymerization initiator, or two or more types of visible light polymerization initiators.

Specific examples of visible light polymerization initiators for radical polymerization include α-diketones (for example, camphorquinone, 9,10-phenanthrenequinone, 1-phenyl-propane-1,2-dione, diacetyl, 4,4′- Dichlorobenzyl or derivatives thereof), hydrogen abstraction-type initiators such as aromatic ketones and ketocoumarins; halogen compounds such as tris (trichloromethyl) triazine, organic peroxide-based initiators such as benzoyl peroxide; hexaaryls Bisimidazole compounds, boron compounds such as cyanine borate, organometallic compound initiators such as bispentadienyltitanium-di (pentafluorophenyl); 2-methylthioxanthone, 2,4-diethylthioxanthone, 2,4,6- Trimethylbenzoyl and diphenylphosphine oxide, mono Silgermanium compounds and diacylgermanium compounds (for example, benzoyltrimethylgermanium, dibenzoyldiethylgermanium or bis (4-methoxybenzoyl) -diethylgermanium), titanocene (for example, bis- (η5-2,4-cyclopentadiene-1- Yl) -bis- [2,6-difluoro-3- (1H-pyrrol-1-yl) phenyl] -titanium, etc.), N-phenylglycine and the like. Specific examples of the visible light polymerization initiator for cationic polymerization include 9,10-dibutoxyanthracene.

Of these, camphorquinone and 9,10-phenanthrenequinone are preferred from the viewpoint of absorbance in the visible region.

The visible light polymerization initiator preferably has an absorption maximum at a wavelength of 400 nm or more, more preferably in a wavelength range of 420 to 550 nm, and even more preferably in a range of 450 to 500 nm. When the maximum absorption wavelength of the visible light polymerization initiator is within this range, the wavelength of visible light that is irradiated when the three-dimensional model is manufactured can be set to a relatively long wavelength side. Therefore, deterioration of a thermopolymerizable compound etc. at the time of three-dimensional molded item preparation can be suppressed.

The visible light polymerization initiator is preferably contained in an amount of 0.025 to 5% by mass, more preferably 0.05 to 1% by mass, and more preferably 0.25 to 1% by mass with respect to the total amount in the resin composition. More preferably it is included. In particular, it is preferably contained in an amount of 0.1 to 3 parts by mass, more preferably 0.5 to 2 parts by mass with respect to 100 parts by mass of the photopolymerizable compound. When the visible light polymerization initiator is included in the range, the photocurability of the resin composition tends to be good.

1-4. Ultraviolet light absorber The ultraviolet light absorber is not particularly limited as long as it is a compound capable of absorbing ultraviolet light. In this specification, the ultraviolet light is light having a wavelength of less than 400 nm. The ultraviolet light absorber is particularly preferably a compound capable of absorbing light having a wavelength of 260 to 380 nm, and more preferably a compound capable of absorbing light having a wavelength of 300 to 360 nm. Moreover, it is preferable that the said ultraviolet light absorber has little absorption of light with a wavelength of 400 nm or more, and it is more preferable not to absorb light with a wavelength of 400 nm or more substantially.

The ultraviolet light absorber may be an organic ultraviolet light absorber or an inorganic ultraviolet light absorber. Moreover, these may be combined. The resin composition may contain only one type of ultraviolet light absorber, or two or more types.

Examples of organic ultraviolet light absorbers include thiazolidone-based, benzotriazole-based, acrylonitrile-based, benzophenone-based, aminobutadiene-based, triazine-based, phenyl salicylate-based, benzoate-based compounds, and the like. Among these, triazine-based, benzotriazole-based, and benzophenone-based organic ultraviolet light absorbers are preferable from the viewpoint of sufficiently absorbing ultraviolet light and hardly inhibiting excitation of the visible light polymerization initiator. .

Examples of the thiazolidone-based ultraviolet light absorber include thiazolidone or a derivative thereof.
Examples of benzotriazole ultraviolet absorbers include 2- (2′-hydroxy-5-methylphenyl) benzotriazole, 2- (2′-hydroxy-3 ′, 5′-di-t-butylphenyl) benzo Triazole, 2- (2′-hydroxy-3′-t-butyl-5′-methylphenyl) benzotriazole, 2,2′-methylenebis [6- (2H-benzotriazol-2-yl) -4- (1 , 1,3,3-tetramethylbutyl) phenol] (molecular weight 659; for example LA31 from ADEKA), 2- (2H-benzotriazol-2-yl) -4,6-bis (1-methyl-1-phenyl) Ethyl) phenol (molecular weight 447.6; for example, Tinuvin 234 from BASF Japan Ltd.) and the like.
Examples of the acrylonitrile ultraviolet absorber include ethyl 2-cyano-3,3-diphenylacrylate, 2-ethylhexyl 2-cyano-3,3-diphenylacrylate, and the like.

Examples of benzophenone ultraviolet absorbers include 2,4-dihydroxy-benzophenone, 2-hydroxy-4-methoxy-benzophenone, 2-hydroxy-4-n-octoxy-benzophenone, 2-hydroxy-4-dodecyloxy-benzophenone 2-hydroxy-4-octadecyloxy-benzophenone, 2,2′-dihydroxy-4-methoxy-benzophenone, 2,2′-dihydroxy-4,4′-dimethoxy-benzophenone, 2,2 ′, 4,4 '-Tetrahydroxy-benzophenone and the like are included.
Examples of aminobutadiene-based ultraviolet absorbers include known aminobutadiene-based ultraviolet absorbers.

Examples of triazine ultraviolet absorbers include 2,4-diphenyl-6- (2-hydroxy-4-methoxyphenyl) -1,3,5-triazine, 2,4-diphenyl-6- (2-hydroxy -4-ethoxyphenyl) -1,3,5-triazine, 2,4-diphenyl- (2-hydroxy-4-propoxyphenyl) -1,3,5-triazine, 2,4-diphenyl- (2-hydroxy -4-butoxyphenyl) -1,3,5-triazine, 2,4-diphenyl-6- (2-hydroxy-4-butoxyphenyl) -1,3,5-triazine, 2,4-diphenyl-6- (2-hydroxy-4-hexyloxyphenyl) -1,3,5-triazine, 2,4-diphenyl-6- (2-hydroxy-4-octyloxyphenyl) -1,3,5-tria 2,4-diphenyl-6- (2-hydroxy-4-dodecyloxyphenyl) -1,3,5-triazine, 2,4-diphenyl-6- (2-hydroxy-4-benzyloxyphenyl)- 1,3,5-triazine, [2- (4,6-diphenyl-1,3,5-triazin-2-yl) -5- (hexyl) oxyphenol] (for example, Tinuvin 1577FF manufactured by BASF Japan), [2- [4,6-bis (2,4-dimethylphenyl) -1,3,5-triazin-2-yl] -5- (octyloxy) phenol] (for example, CYASORB UV-1164 manufactured by Cytec Industries, Inc. ) Etc. are included.

Examples of phenyl salicylate ultraviolet light absorbers include phenylsulcylate, 2-4-di-t-butylphenyl-3,5-di-t-butyl-4-hydroxybenzoate, and the like.

Examples of benzoate ultraviolet light absorbers include 2,4-di-tert-butylphenyl-3,5-di-tert-butyl-4-hydroxybenzoate (molecular weight 438.7; for example, Sumisorb 400 from Sumitomo Chemical Co., Ltd.) Is included.

Examples of the hindered amine ultraviolet absorber include bis (2,2,6,6-tetramethylpiperidin-4-yl) sebacate and the like.

Among the above, the organic photopolymerization initiator is preferably a compound having a molecular weight of 400 or more. When the molecular weight is 400 or more, it is difficult to volatilize from the resin composition, and it is difficult to volatilize even during heat curing. Therefore, it is possible to improve light resistance with a relatively small amount.

On the other hand, examples of inorganic ultraviolet light absorbers include metal oxide pigments. Specifically, titanium oxide, zirconium oxide, tin oxide, zinc oxide, antimony oxide, or a mixture thereof can be used.

The ultraviolet light absorber is preferably contained in an amount of 0.05 to 5% by weight, more preferably 0.1 to 2% by weight, and more preferably 0.2 to 1% by weight based on the total amount in the resin composition. More preferably. When the ultraviolet light absorber is included in the above range, the light resistance of the three-dimensional structure to be obtained tends to be good.

1-5. Curing Agent The resin composition usually further includes a curing agent and a curing accelerator for curing the above-mentioned thermopolymerizable compound. The kind of the curing agent and the curing accelerator is appropriately selected according to the kind of the above-mentioned thermopolymerizable compound.

Examples of curing agents and curing accelerators include linear aliphatic diamines having 2 to 20 carbon atoms such as ethylenediamine, trimethylenediamine, tetramethylenediamine, hexamethylenediamine, metaphenylenediamine, paraphenylenediamine, paraxylenediamine, 4,4'-diaminodiphenylmethane, 4,4'-diaminodiphenylpropane, 4,4'-diaminodiphenyl ether, 4,4'-diaminodiphenyl sulfone, 4,4'-diaminodicyclohexane, bis (4-aminophenyl) Aminos such as phenylmethane, 1,5-diaminonaphthalene, metaxylenediamine, paraxylenediamine, 1,1-bis (4-aminophenyl) cyclohexane, N, N-dimethyl-n-octylamine, dicyanodiamide; aniline Modified resole resin and di Resol type phenol resins such as chill ether resol resin; Novolak type phenol resins such as phenol novolak resin, cresol novolak resin, tert-butylphenol novolak resin, nonylphenol novolak resin; phenylene skeleton containing phenol aralkyl resin, biphenylene skeleton containing phenol aralkyl resin Phenol aralkyl resin; phenol resin having a condensed polycyclic structure such as naphthalene skeleton and anthracene skeleton; polyoxystyrene such as polyparaoxystyrene; alicyclic ring such as hexahydrophthalic anhydride (HHPA) and methyltetrahydrophthalic anhydride (MTHPA) Aromatics such as aromatic anhydride, trimellitic anhydride (TMA), pyromellitic anhydride (PMDA), benzophenone tetracarboxylic acid (BTDA) Acid anhydrides including acid anhydrides; Polymercaptan compounds such as polysulfides, thioesters, thioethers; Isocyanate compounds such as isocyanate prepolymers and blocked isocyanates; Organic acids such as carboxylic acid-containing polyester resins; Zinc naphthenate, Naphthenic acid Organic metal salts such as cobalt, tin octylate, cobalt octylate, bisacetylacetonate cobalt (II), trisacetylacetonate cobalt (III), and zinc acetylacetonate are included. The resin composition may contain only one type of curing agent or curing accelerator, or two or more types. The amount of the curing agent and curing accelerator is appropriately selected according to the type and amount of thermal polymerization.

The amount of the curing agent and curing accelerator is appropriately selected according to the amount of the above-mentioned thermopolymerizable compound.

1-6. Light Stabilizer The resin composition may contain a light stabilizer. Examples of the light stabilizer include a photo-antioxidant, a photo-aging inhibitor, a singlet oxygen quencher, a superoxide anion quencher, an ozone quencher, and an infrared absorber.

Of these, hindered amine light stabilizers are preferably used. For example, poly [[6- (N-morpholino) -1,3,5-triazine-2,4-diyl] [(2,2,6,6- Tetramethyl-4-piperidyl) imino] hexamethylene [(2,2,6,6-tetramethyl-4-piperidyl) imino] (Sumitomo Chemical Co., Sumisolv 500), 1,2,3,4-butane Tetracarboxylic acid tetra (2,2,6,6-tetramethyl-4-piperidyl) (manufactured by Adeka Argus), poly [[6-1,1,3,3-tetramethylbutyl) imino-1,3 5-triazine-2,4-diyl] (2,2,6,6-tetramethyl-4-piperidyl) imino] hexamethylene [(2,2,6,6-tetramethyl-4-piperidyl) imino] ( Ciba Geigy, Nubin 944-LD), dimethyl succinate-1- (2-hydroxyethyl) -4-hydroxy-2,2,6,6-tetramethylpiperidine polycondensate (Ciba Geigy, Tinuvin 622LD), 2- (3 , 5-Di-t-butyl-4-hydroxybenzyl) -2-n-butylmalonate bis (1,2,2,6,6-pentyl-4-piperidyl) (manufactured by Ciba Geigy, Tinuvin 144), N N, -bis (3-aminopropyl) ethylenediamine-2,4-bis [N-butyl-N- (1,2,2,6,6-pentamethyl-4-piperidyl) amino] -6-chloro-1 , 3,5-triazine condensate, bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate (Sankyo LS770), bis (N-methyl-2,2,6,6- Te Ramethyl-4-piperidyl) sebacate (Sankyo LS292), 4-benzoyloxy-2,2,6,6-tetramethyl-4-piperidine (Sankyo LS-744), 8-acetyl- 3-dodecyl-7,7,9,9-tetramethyl-1,3,8-triazaspiro [4.5] decane-2,4-dione (manufactured by Sankyo, Sanol LS-440), 1- [2- [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionyloxy] ethyl] -4- [3-3,5-di-tert-butyl-4-hydroxyphenyl) propionyloxy] -2 , 2,6,6-tetramethylpiperidine (manufactured by Sankyo), 2,2,4,4-tetramethyl-20- (β-lauryl-oxycarbonyl) -ethyl-7-oxa-3,20-diazaday Pio (5,1,11,2) heneicosan-21-one (Sanduvor 305, manufactured by Sand Corp.), [N- (2,2,6,6-tetramethyl-4-piperidyl) -β-alanine] dodecyl ester, Myristyl ester mixture (Sanduvor 3052 manufactured by Sand Corp.), 5-norbornene-2,3-dicarboxylic acid bis (2,2,6,6-tetramethyl-4-piperidyl) ester, 5-norbornene-2,3- And dicarboxylic acid bis (N-methyl-2,2,6,6-tetramethyl-4-piperidyl) ester.

The light stabilizer is preferably contained in an amount of 0.05 to 5% by weight, more preferably 0.1 to 2% by weight, and more preferably 0.2 to 1% by weight based on the total amount in the resin composition. More preferably. When the light stabilizer is included in the above range, the light resistance of the resulting three-dimensional structure tends to be good.

1-7. Filler The filler contained in the resin composition is not particularly limited, and may be an organic filler or an inorganic filler. The resin composition may contain only one kind of filler, or may contain two or more kinds.

Conventionally, when a filler is included in a resin composition for selectively irradiating and curing actinic light energy, light having a short wavelength such as ultraviolet light is likely to be scattered, resulting in reduced or obtained curability. The dimensional accuracy of the three-dimensional model was easy to decrease. On the other hand, since the resin composition of the present invention is cured by visible light, such light scattering hardly occurs even if a relatively large amount of filler is contained. Therefore, the amount of filler can be increased sufficiently, and the strength of the three-dimensional structure can be increased.

Examples of fillers include glass fillers made of soda-lime glass, silicate glass, borosilicate glass, aluminosilicate glass, quartz glass, etc .; alumina, zirconium oxide, titanium oxide, lead zirconate titanate, silicon carbide, silicon nitride, nitriding Ceramic filler made of aluminum, tin oxide, etc .; Metal filler made of simple metals such as iron, titanium, gold, silver, copper, tin, lead, bismuth, cobalt, antimony, cadmium, or alloys thereof; graphite, graphene, Carbon filler made of carbon nanotubes; organic polymer fiber made of polyester, polyamide, polyaramid, polyparaphenylenebenzobisoxazole, polysaccharides, etc .; potassium titanate whisker, silicone carbide whisker, silicon nitride Whisker-like inorganic compounds (such as the above-mentioned ceramic filler needles) composed of scallers, α-alumina whiskers, zinc oxide whiskers, aluminum borate whiskers, calcium carbonate whiskers, magnesium hydroxide whiskers, basic magnesium sulfate whiskers, calcium silicate whiskers, etc. Including single crystals); talc, mica, clay, wollastonite, hectorite, saponite, stevensite, hydelite, montmorillonite, nontrinite, bentonite, Na-type tetralithic fluoromica, Li-type tetralithic fluoromica, Na-type Examples include swellable mica such as fluorine teniolite and Li-type fluorine teniolite, clay mineral made of vermiculite, and the like. Furthermore, examples of fillers include polyolefin fillers made of polyethylene, polypropylene, etc .; FEP (tetrafluoroethylene-hexafluoropropylene copolymer), PFA (tetrafluoroethylene-perfluoroalkoxyethylene copolymer), A fluororesin filler made of ETFE (tetrafluoroethylene-ethylene copolymer) or the like is also included.

Among these, organic polymer fibers are preferable, and nanofibers made of polysaccharides are particularly preferable. Examples of polysaccharides include cellulose, hemicellulose, lignocellulose, chitin and chitosan. Among these, cellulose and chitin are preferable, and cellulose is more preferable from the viewpoint of further increasing the strength of the three-dimensional structure to be obtained.

A fibrous filler composed of cellulose, ie, cellulose nanofiber (hereinafter also simply referred to as “nanocellulose”), is a plant-derived fiber or mechanical defibrillation of plant cell walls, biosynthesis by acetic acid bacteria, 2, Cellulose nanofibers mainly composed of fibrous nanofibrils obtained by oxidation with an N-oxyl compound such as 2,6,6-tetramethylpiperidine-1-oxyl radical (TEMPO) or electrospinning may be used. . Nanocellulose is cellulose mainly composed of nanofibrils crystallized in whisker-like (needle-like) obtained by mechanically defibrating plant-derived fibers or plant cell walls. It may be a nanocrystal or any other shape. Nanocellulose should just have cellulose as a main component and may contain lignin, hemicellulose, etc. Nanocellulose containing lignin which is hydrophobic without performing delignification treatment is preferable because of its high affinity with photopolymerizable compounds and thermopolymerizable compounds.

The shape of the filler is not particularly limited, and may be, for example, fibrous (including whisker-like) or particulate, but is fibrous from the viewpoint of improving the strength of the three-dimensional model. Is preferred.

When the filler is particulate, the average particle size is preferably 0.005 to 200 μm, more preferably 0.01 to 100 μm, and further preferably 0.1 to 50 μm. When the average particle size of the particulate filler is 0.1 μm or more, the strength of the three-dimensional structure is easily increased. On the other hand, when the average particle size is 50 μm or less, it becomes easy to form a three-dimensional modeled object with high definition. The average particle diameter can be measured by analyzing an image obtained by imaging the resin composition with a transmission electron microscope (TEM).

On the other hand, when the filler is fibrous, the average fiber diameter is preferably 0.002 μm or more and 20 μm or less. When the average fiber diameter is 0.002 μm or more, the strength of the three-dimensional structure is easily increased. When the average fiber diameter is 20 μm or less, the filler does not excessively increase the viscosity of the resin composition, and the accuracy of the three-dimensional structure tends to be good. The average fiber diameter of the filler is more preferably 0.005 μm or more and 10 μm or less, further preferably 0.01 μm or more and 8 μm or less, and particularly preferably 0.02 μm or more and 5 μm or less.

The average fiber length of the filler is preferably 0.2 μm or more and 200 μm or less. When the average fiber length is 0.2 μm or more, the strength of the three-dimensional structure is easily increased. When the average fiber length is 100 μm or less, the filler is less likely to settle due to the entanglement between the fillers. The average fiber length of the filler is more preferably from 0.5 μm to 100 μm, further preferably from 1 μm to 60 μm, and particularly preferably from 1 μm to 40 μm.

The aspect ratio of the filler is preferably 10 or more and 10,000 or less. If the aspect ratio is 10 or more, the strength of the three-dimensional structure tends to be higher. When the aspect ratio is 10,000 or less, the filler is hardly precipitated due to the entanglement between the fillers. The aspect ratio of the filler is more preferably 12 or more and 8000 or less, further preferably 15 or more and 2000 or less, and particularly preferably 18 or more and 800 or less.

The average fiber diameter, average fiber length, and aspect ratio of the filler can be measured by analyzing an image obtained by imaging the resin composition with a transmission electron microscope (TEM).

Here, the amount of the filler contained in the resin composition is preferably 1 to 50% by mass, and more preferably 5 to 40% by mass with respect to the total mass of the resin composition. When the amount of the filler is within the above range, a three-dimensional model with high strength is easily obtained.

Here, the filler may be surface-treated with various surface treatment agents such as a known silane coupling agent. When the filler is surface-treated, the adhesion between the filler and the photopolymerizable compound or the thermopolymerizable compound is increased, and a three-dimensional molded article with higher strength is easily obtained.

1-8. Other components In the resin composition, as long as it enables formation of a three-dimensional structure by irradiation with visible light, and the resulting three-dimensional structure does not significantly cause unevenness in strength, a photosensitizer, a polymerization inhibitor, Optional additives such as antioxidants, coloring materials such as dyes and pigments, antifoaming agents, and surfactants may be further included.

1-9. Physical Properties of Resin Composition The resin composition of the present invention has a viscosity at 25 ° C. of 0.2 to 100 Pa · s as measured using a rotary viscometer in accordance with JIS K-7117-1. It is preferably 1 to 10 Pa · s. When the viscosity of the resin composition is within the above range, moderate fluidity can be obtained in the method for producing a three-dimensional structure to be described later. As a result, it is possible to improve the modeling speed, and it is difficult for the filler or the like to settle in the resin composition, and as a result, the strength of the three-dimensional model is easily increased.

1-10. Preparation method of resin composition The resin composition contains the photopolymerizable compound, the thermopolymerizable compound, a visible light polymerization initiator, an ultraviolet light absorber, and a filler, a curing agent, a light stabilizer and the like as necessary. It can be prepared by mixing in any order.

As the apparatus used for mixing the resin composition, a known apparatus can be used. For example, Ultra Turrax (manufactured by IKA Japan), TK homomixer (manufactured by Primix), TK pipeline homomixer (manufactured by Primics), TK Philmix (manufactured by Primix), Claremix (manufactured by M Technique), Medialess stirrers such as Claire SS5 (manufactured by M Technique), Cavitron (manufactured by Eurotech), Fine Flow Mill (manufactured by Taiheiyo Kiko), Viscomill (manufactured by IMEX), Apex Mill (manufactured by Kotobuki Industries), Star mill (Ashizawa, manufactured by Finetech), DCP Super Flow (manufactured by Nihon Eirich), MP Mill (manufactured by Inoue Mfg.), Spike mill (manufactured by Inoue Mfg.), Mighty mill (manufactured by Inoue Mfg.), SC mill (Mitsui Media stirrers such as mining) and optimizers ( Ginomashin Inc.), manufactured by Starburst (Sugino Machine Limited), Nanomizer (manufactured by Yoshida Kikai), and a high-pressure impact type dispersing device such as NANO 3000 (manufactured by Bitsubusha).

Also, revolving mixers such as Awatori Nerita (Shinky) and Kaku Hunter (Photochemical), planetary mixers such as Hibismix (Primics) and Hibis Disper (Primics), Nanouptor An ultrasonic dispersion apparatus such as (manufactured by Sonic Bio) can also be suitably used.

2. Manufacturing method of three-dimensional molded article The liquid resin composition described above includes a step of selectively irradiating visible light to form a primary cured product including a cured product of the photopolymerizable compound. It can be used for manufacturing methods.

In the manufacturing method of the three-dimensional molded article using the above-mentioned resin composition, first, the resin composition is selectively irradiated with visible light, and the above-mentioned photopolymerizable compound is cured into a desired shape to form a primary cured product. An optical modeling process is performed. And after formation of a primary hardened | cured material, the thermosetting process which heat-polymerizes the thermopolymerizable compound contained in the said primary hardened | cured material is performed, and a three-dimensional molded item is obtained. In addition, you may perform the visible light irradiation process of irradiating visible light after preparation of a primary cured material.

The following two embodiments are included in examples of the manufacturing method of such a three-dimensional structure, but the method of the present invention is not limited to these methods.

2-1. Additive manufacturing method (SLA method)
FIG. 1 is a schematic diagram illustrating an example of an apparatus (manufacturing apparatus for a three-dimensional structure) for producing a primary cured product by an additive manufacturing method. The manufacturing apparatus 500 supports the modeling tank 510 that can store the liquid resin composition 550, the modeling stage 520 that can reciprocate in the vertical direction (depth direction) inside the modeling tank 510, and the modeling stage 520. A base 521, a visible light source 530, and a galvano mirror 531 for guiding visible light to the inside of the modeling tank 510 are included.

The modeling tank 510 only needs to have a size that can accommodate the primary cured product to be manufactured. Moreover, a well-known thing can be used for the light source 530 for irradiating visible light. Examples of light sources for irradiating visible light include metal halide lamps, halogen lamps, xenon lamps, LEDs, sunlight, ultra-high pressure mercury lamps, and the like. Among these light sources, an LED is particularly preferable because an arbitrary wavelength can be selected. About light sources other than LED, since ultraviolet light is contained, it is preferable to remove ultraviolet light through a filter. The wavelength of visible light to be irradiated is preferably 400 to 550 nm, and more preferably 420 to 500 nm.

In this method, first, the resin composition 550 is filled in the modeling tank 510. At this time, the modeling stage 520 is disposed below the liquid surface of the resin composition 550 by the thickness of the modeled object layer (first modeled object layer) to be produced. In this state, the visible light emitted from the light source 530 is guided and scanned by the galvano mirror 531 or the like, and is irradiated to the resin composition 550 on the modeling stage 520. At this time, a 1st model object layer is formed in a desired shape by selectively irradiating visible light only to the field which forms the 1st model object layer.

Thereafter, the modeling stage 520 is lowered (moved in the depth direction) by the thickness of one layer (the thickness of the second modeling object layer to be produced next), and the first modeling object layer is placed in the resin composition 550. Let it sink. Thereby, the resin composition is supplied onto the first modeled object layer. Subsequently, in the same manner as described above, the visible light emitted from the light source 530 is guided by the galvano mirror 531 or the like, and irradiated to the resin composition 550 positioned above the first modeled object layer. Also at this time, visible light is selectively irradiated only to the region where the second shaped article layer is formed. Thereby, a 2nd modeling thing layer is laminated | stacked on the above-mentioned 1st modeling thing layer.

Then, the primary cured product is formed into a desired shape by repeating the lowering of the modeling stage 520 (supply of the resin composition) and irradiation with visible light. In addition, let the shape of the primary cured material produced by the said method be the same as the shape of the three-dimensional molded item finally produced.

If necessary, the obtained primary cured product may be further irradiated with visible light. Irradiation with visible light may be performed only in a desired range or may be performed on the entire primary cured product. When such visible light irradiation is performed, the polymerizability increases to the inside of the primary cured product, and warpage of the resulting three-dimensional model is easily suppressed. The reason why the warpage is suppressed when cured to the inside is that the thermosetting component in the primary cured product is in an uncured state, and curing shrinkage occurs in the process of polymerization by heating. At this time, if the primary cured product is subjected to shrinkage stress at a high temperature, warping tends to occur. Therefore, by further irradiating the primary cured product with visible light and increasing the internal polymerization degree, the strength of the primary cured product is increased and deformation due to curing shrinkage of the thermosetting component can be reduced, so that warpage is suppressed. .

Thereafter, the thermopolymerizable compound contained in the primary cured product is heated and cured by a known method. When heating the primary cured product, the temperature is preferably such that the primary cured product is not deformed. For example, the temperature is preferably lower than the glass transition temperature (Tg) of the cured product of the photopolymerizable compound.

2-2. Continuous molding method (CLIP method)
FIG. 2 is a schematic diagram illustrating an example of an apparatus (manufacturing apparatus for a three-dimensional model) for producing a primary cured product by a continuous modeling method. As shown in FIG. 2, the manufacturing apparatus 600 irradiates visible light with a modeling tank 610 that can store a liquid resin composition, a modeling stage 620 that can reciprocate in the vertical direction (depth direction), and the like. Light source 660 and the like. The modeling tank 610 has a window portion 615 that does not allow the resin composition to pass therethrough and allows visible light and oxygen to pass therethrough. In addition, the material etc. will not be restrict | limited especially if the modeling tank 610 has a width | variety wider than the three-dimensional molded item to manufacture, and does not interact with a resin composition. Further, the material of the window portion 615 is not particularly limited as long as it does not impair the purpose and curing of the present embodiment.

Further, a known light source 660 for irradiating visible light can be used, and can be the same as the light source used in the additive manufacturing method. Further, by using an SLM projection optical system having a spatial light modulator (SLM) such as a liquid crystal panel or a digital mirror device (DMD) as the light source 660, even if a desired area is irradiated with visible light, Good. In the CLIP method, in particular, a light source capable of irradiating light with a wavelength of 420 to 550 nm is preferable, and a light source capable of irradiating light with a wavelength of 440 to 500 nm is more preferable.

In this method, first, the molding tank 610 is filled with the above-described resin composition. And oxygen is introduce | transduced into the bottom part side of the modeling tank 610 from the window part 615 provided in the bottom part of the modeling tank 610. FIG. The method for introducing oxygen is not particularly limited, and for example, the outside of the modeling tank 610 may be an atmosphere having a high oxygen concentration and a pressure may be applied to the atmosphere.

By supplying oxygen from the window 615 into the modeling tank 610 in this manner, in the region on the window 615 side, the oxygen concentration increases, and the buffer region 642 where the photopolymerizable compound is not cured even when irradiated with visible light. Is formed. On the other hand, in the region above the buffer region 642, the concentration of oxygen is sufficiently lower than that of the buffer region 642, and becomes a curing region 644 where the photopolymerizable compound can be cured by irradiation with visible light.

Subsequently, a step of selectively irradiating visible light from the buffer region side 642 to form a cured product of the photopolymerizable compound in the curing region 644 is performed. Specifically, the modeling stage 620 that is the base point for producing the primary cured product is disposed in the vicinity of the interface between the curing region 644 and the buffer region 642. Then, visible light is selectively irradiated from the light source 660 arranged on the buffer region 642 side to the bottom surface side of the modeling stage 620. Thereby, the photopolymerizable compound in the vicinity of the bottom surface of the modeling stage 620 (curing region 644) is cured, and the uppermost portion of the primary cured product is formed.

Thereafter, the modeling stage 620 is raised (moved away from the buffer area 642). As a result, the uncured resin composition is newly supplied from the cured product 651 to the curing region 644 on the bottom side of the modeling tank 610. Then, visible light is irradiated continuously and selectively (a region to be cured) from the light source 660 while the modeling stage 620 and the cured product 651 are continuously raised. As a result, a cured product is continuously formed from the bottom surface of the modeling stage 620 to the bottom side of the modeling tank 610, and a primary modeled object having no seam and high strength is manufactured. In this embodiment as well, the shape of the primary cured product is the same as the shape of the three-dimensional model to be finally produced.

Thereafter, if necessary, the obtained primary cured product may be further irradiated with visible light. Irradiation with visible light may be performed only in a desired range or may be performed on the entire primary cured product. As described above, when such visible light irradiation is performed, the polymerizability of the photopolymerizable compound inside the primary cured product is increased, and warping of the resulting three-dimensional model is easily suppressed.

Thereafter, the thermopolymerizable compound contained in the primary cured product is heated and cured by a known method. When heating the primary cured product, the temperature is preferably such that the primary cured product is not deformed. For example, the temperature is preferably lower than the glass transition temperature (Tg) of the cured product of the photopolymerizable compound.

In the CLIP method described above, if the viscosity of the resin composition is high, it is difficult to fill the curing region 644 of the modeling tank 610 with a new resin composition. For this reason, it may be difficult to lift the formed cured product 651, or the resin composition may not be uniformly filled in the curing region 644 if it is forcibly lifted, and the strength of the resulting three-dimensional model may be reduced. On the other hand, if the thickness of the buffer region 642 is increased, it is considered that the curing region 644 is easily filled with a new resin composition. However, conventional light having a short wavelength, such as ultraviolet light, cannot reach the curing region 644 sufficiently when the thickness of the buffer region 642 is increased, and conventionally the thickness of the buffer region 642 cannot be increased.

On the other hand, since the wavelength of visible light is long, even if the buffer region 642 is thick, it can easily reach the curing region 644. Therefore, according to the manufacturing method of the present invention, it is possible to increase the thickness of the buffer region 642, and it is possible to produce a three-dimensional model with high strength.

Hereinafter, specific examples of the present invention will be described. These examples do not limit the scope of the present invention.

1. Materials Upon preparation of the resin compositions in Examples and Comparative Examples, the following materials were prepared.
(Photopolymerizable compound)
Acrylate compounds: trimethylpropane triacrylate and diacrylate (CN120Z manufactured by Sartomer)
Silicone acrylate compound: (manufactured by Bluestar Silicones, UV RCA 170)

(Thermopolymerizable compound)
Epoxy compound: poly [2- (chloromethyl) oxirane-alt-4,4 ′-(propane-2,2-diyl) diphenol] (Araldite 506 manufactured by Huntsman) and its curing agent (4, 4 '-Methylenebis (2,6-dimethylaniline)
Silicone compound: One-component addition-curable silicone (manufactured by Shin-Etsu Chemical Co., Ltd., KE-1056) and its curing agent (N, N-dimethyloctylamine)
-Urethane compounds: isophorone diisocyanate and its curing agent (polytetramethylene oxide)
Cyanate ester compounds: 1-bis (4-cyanatophenyl) ethane and its curing agent (isobornyl acrylate solution containing 1500 ppm of zinc (II) acetylacetonate monohydrate and 2- (5-chloro -2-benzotriazolyl) -6-tert-butyl-p-cresol)

(Visible light polymerization initiator)
・ Camphorquinone (manufactured by Tokyo Chemical Industry Co., Ltd., maximum absorption 470 nm)
・ 3-Ketocoumarin (manufactured by Tokyo Chemical Industry Co., Ltd., maximum absorption 460 nm)

(Ultraviolet photopolymerization initiator)
・ Alkylphenone photopolymerization initiator (BASF, IRGACURE184, maximum absorption 330 nm)

(Ultraviolet light absorber)
Benzophenone ultraviolet absorber: ADEKA, ADK STAB 1413
Benzotriazole ultraviolet absorber: ADEKA, ADK STAB LA-32
Triazine ultraviolet light absorber: ADEKA, ADK STAB LA-46
・ Benzoate UV absorber: Sumitomo Chemical 400, manufactured by Sumitomo Chemical Co., Ltd.

(Light stabilizer)
・ Hindered amine light stabilizer: Sumitomo Chemical Co., Ltd.

(Filler)
・ Magnesium sulfate whisker: Ube Materials, Moss Heidi ・ Cellulose nanofiber: Sugino Machine, BiNFis

2. Preparation of resin composition (Examples 1 to 9 and Comparative Examples 1 to 5)
With the materials and mass ratios shown in Table 1 below, each component was mixed to obtain a resin composition. The mixing was performed for 5 minutes at a revolution speed of 60 rpm and a rotation speed of 180 rpm using a planetary kneading machine (Hibismix 2P-1 manufactured by PRIMIX Corporation).

3. Production of a three-dimensional modeled object Using the above-mentioned resin composition, a three-dimensional modeled object was manufactured by the method shown below, respectively.

(Comparative Examples 1 to 5, Examples 1 to 3)
Each of the resin compositions prepared above was put into a modeling tank 510 of the three-dimensional modeled manufacturing apparatus having the configuration shown in FIG. In Comparative Examples 1 to 5, a laser diode having a wavelength of 370 nm and an output of 70 mW is used as the light source 530 (NDU 4116 manufactured by Nichia Corporation), and in Examples 1 to 3, the light source 530 is having a wavelength of 460 nm and an output of 100 mW. Using a laser diode (NDB4216 manufactured by Nichia Corporation), light irradiation and lowering of the modeling stage 520 were repeated to obtain a primary cured product of the test piece shape of JIS K7161-2 (ISO 527-2) type 1A Obtained. In addition, the primary hardened | cured material from which the longitudinal direction of a tensile test piece turns into a modeling direction (down direction of a stage) and the primary hardened | cured material from which the longitudinal direction of a tensile test piece becomes horizontal in a modeling direction were each produced. The obtained primary cured product was washed with isopropyl alcohol.
About the comparative examples 1 and 4, the said primary cured material was made into the three-dimensional molded item as it was.
On the other hand, the primary cured products of Comparative Examples 2, 3, and 5 and Examples 1 and 2 were thermally cured under the conditions shown in Table 1 below.
In addition, for the primary cured product of Example 3, light having a wavelength of 400 to 700 nm was irradiated by a xenon lamp on both surfaces of the three-dimensional modeled object (test piece) for 5 minutes so that the irradiation intensity was 5 mW / cm ^2. did. Thereafter, it was thermoset under the conditions shown in Table 1 below.

(Examples 4 to 9)
For the production of the three-dimensional model, the resin composition was put into the model tank 610 of the manufacturing apparatus 600 shown in FIG. At the bottom of the modeling tank 610, a Teflon (registered trademark) AF2400 film (window 615) having a thickness of 0.0025 inches manufactured by Biogeneral, which can transmit oxygen as a polymerization inhibitor, is disposed. And after making the atmosphere outside the modeling tank 610 into an oxygen atmosphere, it pressurized moderately. Thereby, the buffer region 642 containing the resin composition and oxygen was formed on the bottom side of the modeling tank 610, and the upper part of the buffer region 642 became a curing region 644 having a lower oxygen concentration than the buffer region.
Then, the modeling stage 620 was raised while irradiating light from a visible light source 660: DLP projector (HD 142X manufactured by Optoma) in a planar shape. At this time, the irradiation intensity of visible light was 5 mW / cm ² . The pulling speed of the modeling stage 620 was 50 mm / hr. Then, a three-dimensionally shaped object was prepared so as to have a test piece shape of JIS K7161-2 (ISO 527-2) type 1A. By the said method, the primary hardened | cured material from which the longitudinal direction of a tensile test piece becomes a horizontal direction and a modeling direction (drawing direction of the modeling stage 620), and also the primary cured | curing material from which the longitudinal direction of a tensile test piece becomes horizontal in a modeling direction Were prepared. The obtained three-dimensional model was washed with isopropyl alcohol.
The primary cured products of Examples 4, 5, and 7 to 9 were thermally cured under the conditions shown in Table 1 below.
On the other hand, the primary cured product of Example 6 was irradiated with light of a wavelength of 400 to 700 nm from a xenon lamp on both surfaces of the three-dimensional structure (test piece) for 5 minutes so that the irradiation intensity was 5 mW / cm ^2. did. Thereafter, it was thermoset under the conditions shown in Table 1 below.

4). Evaluation The obtained three-dimensional molded item was evaluated by the following method. The obtained results are shown in Table 2.

(Strength)
Tensile strength was evaluated by a tensile test in accordance with JIS K7161-1 for a three-dimensional object whose longitudinal direction is the modeling direction and a three-dimensional object whose longitudinal direction is horizontal to the modeling direction. At this time, the distance between the gripping tools was 115 mm, and the test speed was 5 mm / min. Moreover, the value which divided the stress at the time of a fracture | rupture by the cross-sectional area of the test piece was computed as each tensile strength.

About the three-dimensional molded item whose longitudinal direction is horizontal to the modeling direction, the following criteria were evaluated.
A: Horizontal tensile strength is 100 MPa or more. O: Horizontal tensile strength is 20 MPa or more and less than 100 MPa. X: Horizontal tensile strength is less than 20 MPa.

About the three-dimensional molded item whose longitudinal direction is the modeling direction, the following modeling strength ratio was evaluated.
Modeling direction strength ratio = Tensile strength in the modeling direction / Tensile strength in the horizontal direction in the modeling direction ◎: Modeling direction strength ratio is 0.9 or more ○: Modeling direction strength ratio is 0.6 or more and less than 0.9 ×: Modeling direction strength Ratio is less than 0.6

(warp)
The above-described three-dimensional model (the longitudinal direction is horizontal to the modeling direction) was placed on a metal surface plate, and scanned in the thickness direction using a laser displacement meter (LK-G5000 manufactured by Keyence Corporation). And the curvature amount of the three-dimensional molded item was calculated as follows.
Warpage amount = maximum value of specimen height-minimum value of specimen height

A: Less than 0.5 mm O: 0.5 mm or more and less than 2 mm X: 2 mm or more

(Light resistance)
A light resistance test was performed on the above-mentioned three-dimensional modeled object (the longitudinal direction is horizontal to the modeling direction) using a 7.5 kW super xenon weather meter SX75 manufactured by Suga Test Instruments Co., Ltd. according to JIS D0205. The light resistance test was performed using a xenon arc lamp in an environment of a black panel temperature of 60 ° C. and a relative humidity of 50%. Further, light having a wavelength range of 300 to 400 nm was irradiated for 300 hours through an outer glass filter made of silicate glass and an inner filter made of quartz glass so that the sample surface radiation intensity became 75 W / m ² . Thereafter, the strength retention after the light resistance test was calculated and evaluated as follows.
Strength retention ratio = tensile strength after light resistance test / tensile strength before light resistance test ◎: Strength retention ratio is 0.9 or more ○: Strength retention ratio is 0.8 or more and less than 0.9 △: Strength retention ratio is 0 .6 or more and less than 0.8 ×: Strength retention ratio of 0.4 or more and less than 0.6 XX: Strength retention ratio of less than 0.4

As shown in Table 2 above, when the thermopolymerizable resin was not included, the obtained three-dimensional model was easy to warp (Comparative Examples 1 and 4). Moreover, when a heat-polymerizable resin was included and an ultraviolet light absorber was not included (Comparative Examples 2 and 5), the light resistance was likely to be low. In particular, in Comparative Example 2 cured with ultraviolet light, the evaluation of warpage was low. Since this deteriorated by light at the time of producing the primary cured product, it is considered that the effect of adding the thermopolymerizable compound could not be obtained. On the other hand, when the resin composition containing an ultraviolet light absorber was cured with ultraviolet light, the resin composition could not be sufficiently cured and the strength was very low (Comparative Example 3).

In contrast, a resin composition containing a photopolymerizable compound, a thermopolymerizable compound, a visible light polymerization initiator, and an ultraviolet light absorber had high light resistance and high strength in both the horizontal direction and the molding direction. Even if an ultraviolet light absorber was included, it was presumed that since it was cured with visible light, the curing was hardly inhibited and the strength was high (Examples 1 to 9). Moreover, since these Examples contained a thermopolymerizable compound, it was difficult for warpage to occur.

In particular, when a light irradiation step was further included after the production of the primary cured product, the cured product was hardly warped (Examples 3 and 6). On the other hand, when the filler was included, the strength of the resulting three-dimensional model was likely to increase (Examples 2 and 7). Furthermore, when a light stabilizer was included, the light resistance was particularly likely to increase (Example 5). As a three-dimensional modeling method, the CLIP method had higher strength in the modeling direction than the SLA method. In the CLIP method, it is considered that the strength in the modeling direction is increased because a three-dimensional model is produced without a seam.

This application claims priority based on Japanese Patent Application No. 2018-036684 filed on Mar. 1, 2018. The contents described in the application specification and the drawings are all incorporated herein.

According to the resin composition of the present invention, it is possible to provide a molded article with little warpage, high strength, and good light resistance. Therefore, the present invention is expected to broaden the application range of the three-dimensional structure using the resin composition and contribute to the progress and spread of the technology in the same field.

500, 600 Manufacturing apparatus 510, 610 Modeling tank 615 Window unit 520, 620 Modeling stage 521 Base 530, 660 Light source 531 Galvano mirror 550 Resin composition 642 Buffer region 644 Curing region 651 Cured product

Claims (10)

1. A resin composition used in a method of producing a three-dimensional structure formed of a cured product of the resin composition by selectively irradiating a liquid resin composition with visible light,
   A photopolymerizable compound;
   A thermopolymerizable compound;
   A visible light polymerization initiator;
   An ultraviolet light absorber;
   A resin composition comprising:
2. The photopolymerizable compound and / or the thermopolymerizable compound includes in its molecule at least one structure selected from the group consisting of an aromatic ring, a triazine ring, an ester bond, a urethane bond, and a urea bond.
   The resin composition according to claim 1.
3. The visible light polymerization initiator has an absorption maximum in a wavelength region of 400 nm or more,
   The resin composition according to claim 1 or 2.
4. Further comprising a light stabilizer,
   The resin composition according to any one of claims 1 to 3.
5. Further including a filler,
   The resin composition according to any one of claims 1 to 4.
6. An optical modeling step of selectively irradiating the resin composition according to any one of claims 1 to 5 with visible light to form a primary cured product including a cured product of the photopolymerizable compound;
   Manufacturing method of a three-dimensional molded item.
7. Including a thermosetting step of further thermosetting the primary cured product,
   The manufacturing method of the three-dimensional molded item of Claim 6.
8. Before the thermosetting step, including a light irradiation step of further irradiating the primary cured product with visible light,
   The manufacturing method of the three-dimensional molded item of Claim 7.
9. The stereolithography process
   A buffer region containing the resin composition and oxygen, wherein the curing of the photopolymerizable compound is inhibited by oxygen; and at least the resin composition, wherein the oxygen concentration is lower than the buffer region, and the photopolymerizable compound is cured. A first step of forming an area for curing adjacent to the molded article tank;
   A second step of selectively irradiating the resin composition with visible light from the buffer region side and curing the photopolymerizable compound in the curing region;
   Including
   In the second step, while moving the formed cured product to the side opposite to the buffer region, the curing region is continuously irradiated with visible light to form the primary cured product,
   The method for manufacturing a three-dimensional structure according to any one of claims 6 to 8.
10. A three-dimensionally shaped article, which is a cured product of the resin composition according to any one of claims 1 to 5.

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