WO2019193961A1

WO2019193961A1 - Resin composition, method for manufacturing three-dimensionally shaped article using same, and three-dimensionally shaped article

Info

Publication number: WO2019193961A1
Application number: PCT/JP2019/011126
Authority: WO
Inventors: 有由見米▲崎▼
Original assignee: コニカミノルタ株式会社
Priority date: 2018-04-02
Filing date: 2019-03-18
Publication date: 2019-10-10
Also published as: JP7163956B2; JPWO2019193961A1

Abstract

The present invention addresses the problem of providing: a three-dimensionally shaped article which has high mechanical strength, and excellent durability and dimensional accuracy; a method for manufacturing the same; and a resin composition which is used for same. To solve the problem, this resin composition is used in a method for manufacturing a three-dimensionally shaped article comprising a cured product of the resin composition by selectively irradiating a liquid resin composition with active energy. Said resin composition includes a photopolymerizable compound, a thermopolymerizable compound, and a functional group-containing filler having a functional group capable of binding to the thermally polymerizable compound at the surface.

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. As one of the methods for producing a three-dimensional model, there is known a method of selectively irradiating a resin composition that is cured by active energy with active energy to cure the resin composition into a desired shape (for example, Patent Document 1). In recent years, attempts have been made to make various three-dimensional shaped objects produced by such a method into various final products.

However, when three-dimensional modeling is performed using a resin composition mainly containing a photopolymerizable compound, the mechanical strength may not be sufficient, or desired dimensional accuracy may not be obtained due to curing shrinkage. Therefore, it is known to add fillers such as glass beads for the purpose of improving the mechanical strength and improving the dimensional accuracy of the three-dimensional structure to be obtained (for example, Patent Documents 2 and 3). However, there is a problem that it is difficult to obtain sufficient mechanical strength required for the final product only by adding a filler.

In recent years, a method for 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 4 and 5). In the method, first, a buffer region in which the resin composition is not cured even when irradiated with active energy and a curing region in which the resin composition is cured by irradiation with active energy 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. And the carrier used as the base point of three-dimensional modeling is arrange | positioned in the area | region for hardening, and active energy is selectively irradiated to the area | region for hardening from the buffer area | region (modeling tank bottom part) side. Thereby, a part of solid modeling thing (hardened material of a resin composition) is formed in the career surface. Further, by irradiating active energy 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 a seamless three-dimensional modeled object is produced. .

JP-A-8-174680 Japanese Unexamined Patent Publication No. 7-26060 JP 2016-138180 A Special table 2016-509962 gazette International Publication No. 2017/044381

Here, in order to increase the mechanical strength of the three-dimensional structure, it has been studied to add a thermopolymerizable compound and a filler to the resin composition for modeling. However, when the filler is simply mixed with the thermopolymerizable compound, the initial mechanical strength is improved, but the mechanical strength is lowered due to deterioration over time. This is because the filler is likely to be localized simply by mixing, cracks are generated from the portion where the filler is not present, and the deterioration of the three-dimensional structure is promoted. Moreover, although the dimensional accuracy is improved by mixing the thermopolymerizable compound as compared with the case of only the photopolymerizable compound, there is a problem that it is insufficient when a precision instrument application is assumed.

The present invention has been made in view of such problems. That is, an object of the present invention is to provide a three-dimensionally shaped product that is excellent in mechanical strength and durability, and further excellent in dimensional accuracy, a method for producing the same, and a resin composition used therefor.

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 active energy to a liquid resin composition, which is photopolymerizable A resin composition comprising a compound, a thermopolymerizable compound, and a functional group-containing filler having a functional group capable of binding to the thermopolymerizable compound on the surface.

[2] The resin composition according to [1], wherein the thermopolymerizable compound is an epoxy resin or a precursor thereof, or a urethane resin or a precursor thereof.
[3] The resin composition according to [1] or [2], wherein the functional group-containing filler is a cellulose nanofiber having a functional group capable of binding to the thermopolymerizable compound.

2nd of this invention exists in the manufacturing method of the following three-dimensional molded items, or a three-dimensional molded item.
[4] An optical modeling step of selectively irradiating the resin composition according to any one of [1] to [3] with active energy to form a primary cured product including a cured product of the photopolymerizable compound. And the manufacturing method of the three-dimensional molded item including the thermosetting process which further thermosets the said primary cured material.
[5] 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 molded article tank, and selectively irradiating the resin composition with active energy 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 [4], wherein the curing region is irradiated with active energy to form the primary cured product.
[6] A three-dimensionally shaped article, which is a cured product of the resin composition according to any one of [1] to [3].

According to the resin composition of the present invention, it is possible to provide a three-dimensional modeled object having high mechanical strength, durability, and dimensional accuracy.

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 state, and is used in a method for producing a three-dimensional structure by selectively irradiating the resin composition with active energy. As described above, it has been studied to add a filler or a thermopolymerizable compound to such a resin composition. However, even if the addition of the filler alone can increase the initial mechanical strength of the three-dimensional structure, the filler is likely to be localized, and the resin in the region not containing the filler is likely to deteriorate over time. It was. Therefore, it was difficult to obtain high mechanical strength over a long period of time. Moreover, although the dimensional accuracy is improved by mixing the thermopolymerizable compound as compared with the case of using only the photopolymerizable compound, there is a problem that it is insufficient when a precision instrument application is assumed.

On the other hand, the resin composition of the present invention includes a photopolymerizable compound, a thermopolymerizable compound, and a functional group-containing filler having a functional group capable of binding to the thermopolymerizable compound on the surface. When the resin composition is selectively irradiated with active energy, the photopolymerizable compound is polymerized to produce a primary cured product having a desired shape. Furthermore, the thermopolymerizable compound in the primary cured product is polymerized by heating the primary cured product. At this time, the functional group of the functional group-containing filler is bonded to the thermopolymerizable compound, whereby the filler is taken into the polymerized product (cured product) of the thermopolymerizable compound via a chemical bond. As a result, the filler is uniformly distributed in the three-dimensional structure, the mechanical strength of the three-dimensional structure is increased, and deterioration with time is suppressed. Further, the filler is excellent in strength without any dimensional change due to heat change. Therefore, the dimensional change of the three-dimensional molded article obtained is further suppressed by a filler being taken in into a resin frame | skeleton via a chemical bond.

The resin composition may contain a photopolymerization initiator, a thermosetting agent, a thermosetting accelerator, various additives, and the like as necessary, as long as the object and effect of the present invention are not impaired. . Hereinafter, each component will be described.

1-1. Photopolymerizable compound The photopolymerizable compound contained in the resin composition may be any compound that can be polymerized and cured by irradiation with active energy. For example, it may be a monomer, an oligomer, 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 for producing a three-dimensional structure (hereinafter also referred to as “CLIP method”) while adding a polymerization inhibitor such as oxygen to the resin composition, a photopolymerizable compound is used. Needs to be a radically polymerizable compound.

The resin composition may contain only one type of photopolymerizable compound or two or more types. Examples of the active energy for curing the photopolymerizable compound include ultraviolet rays, X-rays, electron beams, γ rays, visible light, and the like.

The type of radically polymerizable compound, which is one of the photopolymerizable compounds, is not particularly limited as long as it has a group that can be radically polymerized by irradiation with active energy in the presence of a radical polymerization initiator or the like. Photopolymerizable compounds include, for example, ethylene, propenyl, butenyl, vinylphenyl, allyl ether, vinyl ether, maleyl, maleimide, (meth) acrylamide, acetylvinyl, vinylamide, (meth) A compound having one or more acryloyl groups and the like in the molecule can be obtained. Among these, the unsaturated carboxylic acid ester compound containing one or more unsaturated carboxylic acid ester structures in the molecule, or the unsaturated carboxylic acid amide compound containing one or more unsaturated carboxylic acid amide structures in the molecule. preferable. More specifically, a (meth) acrylate-based compound and / or (meth) acrylamide-based compound containing a (meth) acryloyl group, which will be described later, is 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 the “compound having an allyl ether group” which is one of the above radical 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, cyclohexane methanol monoallyl ether, phthalic acid diallyl ether, isophthalic acid diallyl ether, dimethanol tricyclodecane diallyl ether, 1,4-cyclohexanedimethanol diallyl ether, Alkylene (2-5 carbon atoms) glycol diallyl ether, polyethylene glycol diallyl ether, glycerol diallyl ether, trimethylolpropane diallyl ether, pentaerythritol Diallyl ether, polyglycerin (degree of polymerization 2-5) diallyl ether, trimethylolpropane triallyl ether, glycerin triallyl ether, pentaerythritol tetraallyl ether and tetraallyloxyethane, pentaerythritol triallyl ether, diglyceryl triallyl ether, Examples include sorbitol triallyl ether and polyglycerin (polymerization degree 3 to 13) polyallyl ether.

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, cyclohexanedimethanol divinyl ether, tricyclodecane dimethanol divinyl ether, EO adduct divinyl ether of bisphenol A, cyclohexanediol divinyl ether, cyclopentadiene vinyl ether, Norbornyl dimethanol di Nyl ether, 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, oxanorbonane divinyl ether, neo Pentyl glycol divinyl ether, glycerin trivinyl ether, oxetane divinyl ether, glycerin ethylene oxide adduct trivinyl ether (ethylene oxide addition mole number 6), trimethylolpropane trivinyl ether, trivinyl ether ethylene oxide adduct trivinyl ether (ethylene oxide addition mole number 3), Penta Risuri tall trivinyl ether, includes such ditrimethylolpropane hexa ether and their oxyethylene adduct.

Examples of the “compound having a vinyl phenyl group” include divinyl resorcin, divinyl hydroquinone and the like.

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

Examples of the “compound having a (meth) acrylamide group” include (meth) acrylamide, N, N-dimethyl (meth) acrylamide, N-ethyl (meth) acrylamide, N-isopropyl (meth) acrylamide, N-hydroxy. Ethyl (meth) acrylamide, N-butyl (meth) acrylamide, isobutoxymethyl (meth) acrylamide, diacetone (meth) acrylamide, bismethylene acrylamide, 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) acryloyl group” 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, dicyclo Pentenyloxyethyl (meth) acrylate, dicyclopentenyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, dimethylaminoethyl (meth) acrylate, diethylaminoethyl (Meth) acrylate, 2-ethylhexyl-diglycol (meth) acrylate, 2- (meth) acryloyloxyethyl hexahydrophthalic acid, methoxyethoxyethyl (meth) acrylate, butoxyethyl (meth) acrylate, ethoxydiethylene 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, isobol (Meth) acrylate, polyethylene glycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate, glycerin (meth) acrylate, 7-amino-3,7-dimethyloctyl (meth) acrylate, 2-hydroxyethyl (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) acryloyloxyethylphthalic acid, 2- (meth) acryloyloxyethyl-2- Monofunctional (meth) acrylate monomers including hydroxyethyl-phthalic acid, 2- (meth) acryloyloxyethyl hexahydrophthalic acid, and t-butylcyclohexyl (meth) acrylate;
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 “compound having a (meth) acryloyl group” 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 “compound having a (meth) acryloyl group” may further be a compound obtained by (meth) acrylate-converting various oligomers (hereinafter also referred to as “modified (meth) acrylate-based compound”). 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 is likely to increase. Moreover, when these resins are used, the functional group-containing filler described later bonds not only to the thermopolymerizable compound but also to the photopolymerizable compound. As a result, the cured product of the thermopolymerizable compound and the cured product of the photopolymerizable compound are bonded via the filler, and a three-dimensional modeled product having higher strength is obtained.

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 epoxies 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 isocyanate or polyisocyanate with a blocking agent having a (meth) acrylate group.

The isocyanate used for obtaining the blocked isocyanate may be the above-mentioned “isocyanate compound”, and the polyisocyanate may be a polymer of the “isocyanate compound”. These compounds and polyols or polyamines may be used. The compound etc. which made this react may be sufficient. 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; For example, Gunter Oertel, “Polyurethane Handbook” (1985), Hanser 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) (Refer to 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 irradiation with active energy. 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 the silicone acrylate compound include a commercially available TEGORAD 2500 (trade name: manufactured by Tego Chemie Service GmbH) and an —OH group such as X-22-4015 (trade name: manufactured by Shin-Etsu Chemical Co., Ltd.). An organically modified silicone and acrylic acid esterified under an acid catalyst; an organically modified silane compound such as epoxy silane such as KBM402 and KBM403 (both trade names: manufactured by Shin-Etsu Chemical Co., Ltd.) and acrylic acid are reacted. 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 that can be cationically polymerized by irradiation with active energy 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 ( Epoxy group-containing compounds 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] heptan-3-ylmethanol, 7-oxabicyclo [4.1.0] heptane-3-methoxymethyl and the like alicyclic epoxy group-containing compounds having no aromatic ring; 3-phenyl-7-oxa Bicyclo [4.1.0] heptane-3-carboxylate, 4-ethylphenyl 7-oxabicyclo [4.1.0] heptane, benzyl 7-oxabicyclo [4.1.0] heptane-3-carboxylate An alicyclic epoxy group-containing compound having an aromatic ring such as 4-ethylphenyl 7-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, the curability of the primary cured product described later is improved.

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 thermally polymerizable compounds include cyanate ester compounds, urethane resins or precursors thereof, epoxy resins or precursors thereof, silicone resins, unsaturated polyester resins, and phenol resins.

Examples of cyanate ester compounds that are thermopolymerizable compounds 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 Bis (4-cyanatophenyl) ether; bis (4-cyanatophenyl) thioether; bis (4-cyanatophenyl) sulfone; tris (4-cyanatophenyl) phos Tris (4-cyanatophenyl) phosphate; bis (3-chloro-4-cyanatophenyl) methane: 4-cyanatobiphenyl; 4-cumylcyanatobenzene; 2-t-butyl-1,4- Dicyanatobenzene; 2,4-dimethyl-1,3-dicyanatobenzene; 2,5-di-t-butyl-1,4-dicyanatobenzene; tetramethyl-1,4-dicyanatobenzene; 4-chloro -1,3-dicyanatobenzene; 3,3 ′, 5,5′-tetramethyl-4,4 ′ dicyanatodiphenylbis (3-chloro-4-cyanatophenyl) methane: 1,1,1-tris 1,4-bis (4-cyanatophenyl) ethane; 2,2-bis (3,5-dichloro-4-cyanatophenyl) propane; 2,2-bis (3 , 5 Dibromo-4-cyanatophenyl) propane, bis (p- cyanophenoxy aminophenoxy) benzene; di (4-cyanatophenyl) ketone; cyan oxide novolak; cyan oxide bisphenol polycarbonate oligomer is contained.

Examples of the urethane resin that is a thermopolymerizable compound or a precursor thereof include a known urethane resin having one or more urethane bonds in the molecule, or a precursor thereof. Specifically, examples of the urethane resin include a polyester urethane resin, a polyether urethane resin, a polycarbonate urethane resin, and the like. On the other hand, examples of the precursor of the urethane resin include polyisocyanate, polyol, polyether polyol, polyester polyol, polymer polyol, and the like.

In addition, examples of the epoxy resin that is a thermally polymerizable compound or a precursor thereof include a known epoxy resin having one or more epoxy groups in the molecule or a precursor thereof. Examples of epoxy resins include biphenyl type epoxy resins, bisphenol A type epoxy resins, bisphenol F type epoxy resins, stilbene type epoxy resins, hydroquinone type epoxy resins and the like; cresol novolak type epoxy resins, phenol novolak type epoxy resins Resin, novolak type epoxy resin such as naphthol novolak type epoxy resin; phenol aralkyl type epoxy resin such as phenylene skeleton containing phenol aralkyl type epoxy resin, biphenylene skeleton containing phenol aralkyl type epoxy resin, phenylene skeleton containing naphthol aralkyl type epoxy resin; Methane type epoxy resin, alkyl-modified triphenol methane type epoxy resin, glycidylamine, tetrafunctional naphthalene type epoxy resin, etc. Functional epoxy resin; modified phenolic epoxy resin such as dicyclopentadiene modified phenolic epoxy resin, terpene modified phenolic epoxy resin, silicone modified epoxy resin; heterocyclic ring containing epoxy resin such as triazine nucleus-containing epoxy resin; naphthylene ether type Epoxy and the like are included.

Further, the silicone resin that is a thermopolymerizable compound may be any resin having an organopolysiloxane structure, and examples thereof include the following addition-curable silicone resins.

A typical addition-curable liquid silicone resin contains a silicone containing a vinylsilyl group, a silicone containing a hydrosilyl group, and an addition reaction catalyst as essential components. A cross-linked structure is formed and cured by an addition reaction occurring between them.

Examples of silicones having vinyl silyl groups include polydimethylsiloxane having vinyl groups substituted at each terminal silicon atom, dimethylsiloxane-diphenylsiloxane copolymer having vinyl groups substituted at each terminal silicon atom, and vinyl groups at each terminal silicon atom. Are substituted polyphenylmethylsiloxane, vinylmethylsiloxane-dimethylsiloxane copolymer having a trimethylsilyl group at each end, and the like.

Examples of silicones containing hydrosilyl groups include methylhydrosiloxane-dimethylsiloxane copolymers having trimethylsilyl groups at each end. Further, polydimethylsiloxane having a hydrogen atom bonded to each end can be used in combination.

Examples of the addition reaction catalyst include platinum black, secondary platinum chloride, chloroplatinic acid, a reaction product of chloroplatinic acid and a monohydric alcohol, a complex of chloroplatinic acid and olefins, a platinum catalyst such as platinum bisacetoacetate, Platinum group metal catalysts such as palladium catalysts and rhodium catalysts are mainly used.

Furthermore, examples of the unsaturated polyester resin that is a thermopolymerizable compound include trade names PC-740, PC-184-C, PC-350-C (all manufactured by DIC Materials) and the like.

Further, examples of the phenol resin which is a thermopolymerizable compound include trade names MEH-8000H, MEH-8005 (both manufactured by Meiwa Kasei Co., Ltd.) and the like.

Among the above, the thermopolymerizable compound may be an epoxy resin or a precursor thereof, or a urethane resin or a precursor thereof from the viewpoint of easy chemical bonding with a functional group-containing filler described later and easy handling. preferable.

The thermopolymerizable compound is preferably contained in an amount of 10 to 90% by mass, more preferably 30 to 70% by mass, and further preferably 40 to 60% by mass with respect to the total amount of the resin composition. When the heat-polymerizable compound is included in the range, the heat resistance and the like of the obtained three-dimensional structure are easily increased.

1-3. Functional group-containing filler The functional group-containing filler only needs to have a functional group capable of binding to the above-described thermopolymerizable compound on the surface, and the resin composition may contain only one kind of filler. More than one species may be included.

Here, the functional group-containing filler is a surface of a known organic filler or inorganic filler by a surface modifier having a “functional group capable of binding to a thermally polymerizable compound” and a “functional group capable of binding or adsorbing to a filler”. It is obtained by processing. An example of the surface treatment method includes a method in which the following surface modifier and filler are dispersed in a solvent and the solution is stirred.

“Functional group capable of binding to thermopolymerizable compound” included in the surface modifier is a functional group that can be bonded to the functional group of the thermopolymerizable compound by ionic bond or covalent bond, or that can interact by intermolecular force. Any functional group may be used, and the functional group may be chemically bonded to a part of the functional group of the photopolymerizable compound. Examples of “functional group that can be bonded to the thermally polymerizable compound” include amino group, imino group, epoxy group, glycidyl group, oxetanyl group, isocyanate group, cyanate group, vinyl group, styryl group, hydrosilyl group, mercapto group, A ureido group, a (meth) acryloyl group, a hydroxy group, a phenyl group and the like are included.

In addition, it is preferable that the “functional group that can be bonded to the thermopolymerizable compound” is appropriately selected according to the type of the functional group of the thermopolymerizable compound. For example, when the thermally polymerizable compound has an epoxy group, the functional group-containing filler preferably has an amino group or a thiol group on the surface. Moreover, when a thermopolymerizable compound is an isocyanate ester type compound, it is preferable that a functional group containing filler has an amino group or a hydroxyl group on the surface. When the thermopolymerizable compound is a urethane resin or a precursor thereof, the functional group-containing filler preferably has an isocyanate group, a hydroxy group, or an amino group on the surface. Furthermore, when the thermopolymerizable compound is a silicone resin, it is preferable that the functional group-containing filler has a phenyl group or a hydroxy group on the surface. Moreover, when a thermopolymerizable compound is unsaturated polyester resin, it is preferable that a functional group containing filler has a (meth) acryloyl group and a phenyl group on the surface. Furthermore, when the thermopolymerizable compound is a phenol resin, the functional group-containing filler preferably has an amino group and a hydroxy group on the surface.

On the other hand, examples of the “group that can be bonded to or adsorbed to the filler” included in the surface modifier include Si atom, Ti atom, Zr atom, carboxyl group, amino group, imino group, cyano group, azo group, An azido group, a thiol group, a sulfo group, a (meth) acryloyl group, an epoxy group, an isocyanate group and the like are included. Of these, Si atoms, Ti atoms, and Zr atoms are preferable, and Si atoms are particularly preferable from the viewpoint of reactivity to the filler.

Specific examples of the surface modifier include a silane coupling agent, a titanium coupling agent, or a zirconium coupling agent, and among these, a silane coupling agent is particularly preferable.

Examples of silane coupling agents include vinyltrimethoxysilane, vinyltriethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropyl Trimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 3-glycidoxypropyltriethoxysilane, p-styryltrimethoxysilane, N-2- (aminoethyl) -3-aminopropylmethyldimethoxysilane, N -2- (Aminoethyl) -3-aminopropyltrimethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-triethoxysilyl-N- (1,3-dimethyl-butylidene) propyl Amine, N-phenyl-3- Minopropyltrimethoxysilane, tris- (trimethoxysilylpropyl) isocyanurate, 3-ureidopropyltrialkoxysilane, 3-mercaptopropylmethyldimethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-isocyanatopropyltriethoxysilane, 3 -Compounds having reactive functional groups such as (meth) acryloxypropyltrimethoxysilane are included.

In this specification, examples of the silane coupling agent include not only a silane compound having a reactive functional group such as a vinyl group or an epoxy group, but also an amino group, an imino group, a glycidyl group, an oxetanyl group, an isocyanate. A silane compound having a reactive functional group such as a group, a cyanate group, a styryl group, a hydrosilyl group, a mercapto group, a ureido group, a (meth) acryloyl group, a phenyl group or a hydroxy group, or a silazane is also included.

Specific examples of the titanium coupling agent include phenyltrimethoxytitanium, 3-aminopropyltrimethoxytitanium, 3-aminopropyltriethoxytitanium, 3- (2-aminoethyl) -aminopropyltrimethoxytitanium, 3- (2-aminoethyl) -aminopropyltriethoxytitanium, 3- (2-aminoethyl) -aminopropylmethyldimethoxytitanium, 3-anilinopropyltrimethoxytitanium, 3-mercaptopropyltriethoxytitanium, 3-isocyanatopropyltri Examples include trialkoxytitanium diphenyldimethoxytitanium such as methoxytitanium, 3-glycidoxypropyltriethoxytitanium, and 3-ureidopropyltrimethoxytitanium.

Furthermore, specific examples of the zirconium-based coupling agent include tri-n-butoxy ethylacetoacetate zirconium, di-n-butoxy bis (ethylacetoacetate) zirconium, n-butoxy tris (ethylacetoacetate) zirconium, Tetrakis (n-propylacetoacetate) zirconium, tetrakis (acetylacetoacetate) zirconium, tetrakis (ethylacetoacetate) zirconium, di-n-butoxy bis (acetylacetonate) zirconium and the like are included.

On the other hand, examples of fillers treated with the surface modifier include glass fillers made of soda-lime glass, silicate glass, borosilicate glass, aluminosilicate glass, quartz glass, etc .; alumina, zirconium oxide, titanium oxide, titanate Ceramic filler composed of lead zirconate, silicon carbide, silicon nitride, aluminum nitride, tin oxide, magnesium sulfate, etc .; simple metals such as iron, titanium, gold, silver, copper, tin, lead, bismuth, cobalt, antimony, cadmium, Or a metal filler made of these alloys, etc .; a carbon filler made of graphite, graphene, carbon nanotubes, etc .; an organic polymer fiber made of polyester, polyamide, polyaramid, polyparaphenylene benzobisoxazole, polysaccharides, etc .; potassium titanate whisker Whisker-like inorganic compounds composed of silicone carbide whisker, silicon nitride whisker, α-alumina whisker, zinc oxide whisker, aluminum borate whisker, calcium carbonate whisker, magnesium hydroxide whisker, basic magnesium sulfate whisker, calcium silicate whisker, etc. (Including the needle-shaped single crystal of the above ceramic filler); talc, mica, clay, wollastonite, hectorite, saponite, stevensite, hydride, montmorillonite, nontrite, bentonite, Na-type tetralithic fluoric mica, Li-type Examples include tetrasilicic fluorine mica, swelling mica such as Na-type fluorine teniolite, Li-type fluorine teniolite, and clay mineral made of vermiculite.

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, magnesium sulfate and organic polymer fibers are used from the viewpoint that the aspect ratio is high and the strength of the resulting three-dimensional molded article is likely to be increased, and that the dimensional change of the resulting three-dimensional molded article is likely to be reduced. Nanofibers made of polysaccharides are particularly preferable. Examples of polysaccharides include cellulose, hemicellulose, lignocellulose, chitin and chitosan. Among these, cellulose and chitin are preferable from the viewpoint that the strength of the obtained three-dimensional model is further increased, and cellulose is more preferable from the viewpoint that availability and the strength of the three-dimensional model are easily increased.

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 functional group-containing filler contained in the resin composition is preferably 1 to 70% by mass, more preferably 5 to 60% by mass with respect to the total mass of the resin composition. Most preferred is ˜40 mass%. When the amount of the functional group-containing filler is within the above range, a three-dimensional model with high strength is easily obtained.

1-4. Thermosetting agent and thermosetting accelerator The resin composition usually further includes a thermosetting agent and a thermosetting accelerator for curing the above-mentioned thermopolymerizable compound. The kind of thermosetting agent or thermosetting accelerator is appropriately selected according to the kind of the above-mentioned thermopolymerizable compound.

Examples of thermosetting agents and accelerators include linear aliphatic diamines having 2 to 20 carbon atoms such as ethylenediamine, trimethylenediamine, tetramethylenediamine, hexamethylenediamine, metaphenylenediamine, paraphenylenediamine, and paraxylene. Diamine, 4,4'-diaminodiphenylmethane, 4,4'-diaminodiphenylpropane, 4,4'-diaminodiphenyl ether, 4,4'-diaminodiphenyl sulfone, 4,4'-diaminodicyclohexane, bis (4-amino Phenyl) phenylmethane, 1,5-diaminonaphthalene, metaxylenediamine, paraxylenediamine, 1,1-bis (4-aminophenyl) cyclohexane, N, N-dimethyl-n-octylamine, aminos such as dicyanodiamide Aniline modified resole resin Resol type phenol resins such as dimethyl ether resol resin; Novolak type phenol resins such as phenol novolak resin, cresol novolak resin, tert-butylphenol novolak resin, nonylphenol novolak resin; Phenol such as phenylene skeleton-containing phenol aralkyl resin and biphenylene skeleton-containing phenol aralkyl resin Aralkyl resins; Phenol resins having a condensed polycyclic structure such as naphthalene skeleton and anthracene skeleton; Polyoxystyrenes such as polyparaoxystyrene; Alicyclics such as hexahydrophthalic anhydride (HHPA) and methyltetrahydrophthalic anhydride (MTHPA) Good acid anhydride, trimellitic anhydride (TMA), pyromellitic anhydride (PMDA), benzophenone tetracarboxylic acid (BTDA), etc. Acid anhydrides including aromatic acid anhydrides; Polymercaptan compounds such as polysulfides, thioesters and thioethers; Isocyanate compounds such as isocyanate prepolymers and blocked isocyanates; Organic acids such as carboxylic acid-containing polyester resins; Zinc naphthenates and naphthenic acids 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 kind of thermosetting agent or thermosetting accelerator, or may contain two or more kinds. The amount of the thermosetting agent and the thermosetting accelerator is appropriately selected according to the type and amount of the thermopolymerizable compound.

The amount of the thermosetting agent and the thermosetting accelerator is appropriately selected according to the amount of the above-mentioned thermopolymerizable compound, and is, for example, 30 to 100 parts by mass with respect to 100 parts by mass of the thermopolymerizable compound. The amount is preferably 40 to 90 parts by mass, more preferably 50 to 80 parts by mass.

1-5. Photopolymerization initiator The resin composition usually contains a photopolymerization initiator for initiating the polymerization of the photopolymerizable compound. The type of the photopolymerization initiator is appropriately selected according to the type of the photopolymerizable compound. For example, when the photopolymerizable compound is a radical polymerizable compound, a radical polymerization initiator is included. On the other hand, when the photopolymerizable compound is a cationic polymerizable compound, a cationic polymerization initiator such as a photoacid generator is included.

The radical polymerization initiator is not particularly limited as long as it is a compound capable of generating radicals by irradiation with active energy, and can be a known radical polymerization initiator.

Examples of radical polymerization initiators include 2-hydroxy-2-methyl-1-phenylpropan-1-one (manufactured by BASF, IRGACURE 1173 (“IRGACURE” is a registered trademark of the company), etc.), 2-hydroxy-1 -{4- [4- (2-hydroxy-2-methyl-propionyl) -benzyl] phenyl} -2-methyl-propan-1-one (manufactured by BASF, IRGACURE 127 etc.), 1- [4- (2 -Hydroxyethoxy) -phenyl] -2-hydroxy-2-methyl-1-propan-1-one (BASF, IRGACURE 2959, etc.), 2,2-dimethoxy-1,2-diphenylethane-1-one (BASF) (IRGACURE 651, etc.), benzyl dimethyl ketal, 1- (4-isopropylphenyl) -2-hy Roxy-2-methylpropan-1-one, 4- (2-hydroxyethoxy) phenyl- (2-hydroxy-2-propyl) ketone, 1-hydroxycyclohexyl-phenylketone, 2-methyl-2-morpholino (4- Thiomethylphenyl) propan-1-one, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone, benzoin, benzoin methyl ether, benzoin isopropyl ether, diphenyl (2,4,6-trimethylbenzoyl) ) Phosphine oxide, bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide, benzyl, methylphenylglyoxyester, benzophenone, methyl-4-phenylbenzophenone o-benzoylbenzoate, 4,4'-dichlorobenzo Enone, hydroxybenzophenone, 4-benzoyl-4′-methyl-diphenyl sulfide, acrylated benzophenone, 3,3 ′, 4,4′-tetra (t-butylperoxycarbonyl) benzophenone, 3,3′-dimethyl-4- Methoxybenzophenone, 2-isopropylthioxanthone, 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, 2,4-dichlorothioxanthone, Michler-ketone, 4,4'-diethylaminobenzophenone, 10-butyl-2-chloroacridone 2-ethylanthraquinone, 9,10-phenanthrenequinone, camphorquinone, 2,4-diethyloxanthen-9-one and the like.

The radical polymerization initiator is preferably contained in an amount of 0.01 to 10% by weight, more preferably 0.1 to 5% by weight, based on the total amount of the photopolymerizable compound (radical polymerizable compound). More preferably 5 to 3% by mass is contained. When the radical polymerization initiator is included in the range, the above-described photopolymerizable compound can be polymerized sufficiently efficiently.

On the other hand, the cationic polymerization initiator is not particularly limited as long as it is a compound capable of generating an acid by irradiation of active energy and polymerizing a photopolymerizable compound (cationic polymerizable compound). An agent can be used. Examples of the photoacid generator include sulfonium salt-based or iodonium salt-based onium salt-based photoacid generators.

Examples of the anionic component in the onium salt photoacid generator include phosphate ions such as PF ₆ ⁻ and PF ₄ (CF ₂ CF ₃ ) ₂ ^— , antimonate ions such as SbF ₆ ^— , trifluoromethanesulfonate, and the like. Fluoroalkylsulfonic acid ions, perfluoroalkylsulfonamides, perfluoroalkylsulfone methides and the like.

On the other hand, as the cation component in the onium salt photoacid generator, for example, sulfonium such as aromatic sulfonium, iodonium such as aromatic iodonium, phosphonium such as aromatic phosphonium, sulfoxonium such as aromatic sulfoxonium, etc. Is included.

Examples of such onium salt photoacid generators include sulfonium salts such as aromatic sulfonium salts, iodonium salts such as aromatic iodonium salts, phosphonium salts such as aromatic phosphonium salts, having an anion component as a counter anion, Examples include sulfoxonium salts such as aromatic sulfoxonium salts.

The photoacid generator is preferably contained in an amount of 0.01 to 10% by weight, more preferably 0.1 to 5% by weight, based on the total amount of the photopolymerizable compound (cationic polymerizable compound). More preferably 5 to 3% by mass is contained. When the photoacid generator is included in this range, the above-mentioned photopolymerizable compound (cationic polymerizable compound) can be polymerized sufficiently efficiently.

1-6. Other components In the resin composition, a photosensitizer, a polymerization inhibitor, and the like, as long as it enables formation of a three-dimensional structure by irradiation of active energy and does not cause unevenness in strength in the resulting three-dimensional structure. Optional additives such as antioxidants, coloring materials such as dyes and pigments, antifoaming agents, and surfactants may be further included.

1-7. 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, the modeling speed can be improved, and the functional group-containing filler or the like is less likely to settle in the resin composition, and as a result, the strength of the three-dimensional model is easily increased.

1-8. Preparation Method of Resin Composition The resin composition is composed of the photopolymerizable compound, the thermopolymerizable compound, the functional group-containing filler, the photopolymerization initiator, the thermosetting agent and the thermosetting accelerator, and optionally added as necessary. It can be prepared by mixing agents 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 active energy 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 active energy, 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 thermally 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 active energy irradiation process of irradiating active energy 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, an active energy irradiation source 530, and a galvano mirror 531 that guides the active energy into 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 active energy. For example, examples of the light source 530 for irradiating ultraviolet rays include a semiconductor laser, a metal halide lamp, a mercury arc lamp, a xenon arc lamp, a fluorescent lamp, a carbon arc lamp, a tungsten-halogen copying lamp, and sunlight.

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 active energy emitted from the irradiation source 530 is guided and scanned by the galvano mirror 531 or the like, and irradiated to the resin composition 550 on the modeling stage 520. At this time, the first shaped article layer is formed in a desired shape by selectively irradiating the active energy only to the region where the first shaped article layer is formed.

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 active energy emitted from the irradiation source 530 is guided by the galvanometer mirror 531 or the like, and irradiated to the resin composition 550 positioned above the first modeled object layer. Also at this time, active energy is selectively irradiated only to the area | region which forms a 2nd molded article layer. Thereby, a 2nd modeling thing layer is laminated | stacked on the above-mentioned 1st modeling thing layer.

Thereafter, the primary cured product is formed into a desired shape by repeatedly lowering the modeling stage 520 (supplying the resin composition) and irradiating with active energy. 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 active energy. Irradiation of active energy may be performed only in a desired range or may be performed on the entire primary cured product. When irradiation of such active energy is performed, the polymerizability increases to the inside of the primary cured product, and warpage of the resulting three-dimensional model is easily suppressed.

Thereafter, the primary cured product is heated by a known method to polymerize the thermopolymerizable compound contained in the primary cured product, or to react the functional group-containing filler with the functional group of the thermopolymerizable compound. The primary cured product is preferably heated at a temperature at which 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 a modeling tank 610 capable of storing a liquid resin composition, a stage 620 capable of reciprocating in the vertical direction (depth direction), and active energy. 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 but allows the active energy 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 active energy 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 the active energy is surface-irradiated to a desired region, Good.

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 way, in the region on the window 615 side, the oxygen concentration increases, and the buffer region 642 where the photopolymerizable compound does not cure even when irradiated with active energy. Is formed. On the other hand, in the region above the buffer region 642, the oxygen concentration is sufficiently lower than that of the buffer region 642, and the photopolymerizable compound can be cured by the irradiation with active energy.

Subsequently, a step of selectively irradiating active energy from the buffer region side 642 to form a cured product of the photopolymerizable compound in the curing region 644 is performed. Specifically, a stage 620 serving as a 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, active energy is selectively irradiated to the bottom surface side of the stage 620 from the light source 660 disposed on the buffer region 642 side. Thereby, the photopolymerizable compound in the vicinity of the bottom surface of the stage 620 (curing region 644) is cured, and the uppermost portion of the primary cured product is formed.

Thereafter, the stage 620 is moved up (moved away from the buffer area 642). Thereby, the uncured resin composition 650 is newly supplied from the cured product 651 to the curing region 644 on the bottom side of the modeling tank 610. Then, while continuously or intermittently raising the stage 620 and the cured product 651, the active energy is irradiated from the light source 660 continuously or intermittently and selectively (a region to be cured). As a result, a cured product is continuously formed from the bottom surface of the 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, the obtained primary cured product may be further irradiated with active energy as necessary. Irradiation of active energy may be performed only in a desired range or may be performed on the entire primary cured product. As described above, when such active energy irradiation is performed, the polymerizability of the photopolymerizable compound inside the primary cured product is increased, and warpage of the resulting three-dimensional model is easily suppressed.

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

1-1. Preparation of Resin Composition [Comparative Example 1]
360 g of photopolymerizable resin (Daicel Ornex, EBECRYL 600; bisphenol A type epoxy acrylate), and photopolymerization initiator (BASF, IRGACURE TPO; diphenyl (2,4,6-trimethylbenzoyl) phosphine oxide) 5 0.0 g was mixed to prepare a resin composition.

[Comparative Example 2]
360 g of a photopolymerizable resin (Daicel Ornex, EBECRYL 600), 40 g of glass beads, and 5.0 g of a photopolymerization initiator (BASF, IRGACURE TPO) were mixed to prepare a resin composition.

[Comparative Example 3]
60 g of glass beads, 0.6 g of 3-acryloxypropyltrimethoxysilane (Shin-Etsu Silicone, KBM-5103) as a surface modifier, and 1.0 g of hydrochloric acid (concentration 35 mass%) were added to 40 g of an aqueous ethanol solution. And stirred for 30 minutes at room temperature. After stirring, the reaction solution was filtered, and the filtrate was spread on a shallow tray or the like and dried at 120 ° C. for 90 minutes. After drying, the dried product was crushed with a ball mill to obtain 3-acryloxypropyltrimethoxysilane-modified glass beads.
Thereafter, 360 g of a photopolymerizable resin (Daicel Ornex Corporation, EBECRYL 600), the above-mentioned 3-acryloxypropyltrimethoxysilane-modified glass beads 40 g, and a photopolymerization initiator (BASF, IRGACURE TPO) 5.0 g were added. By mixing, a resin composition was prepared.

[Comparative Example 4]
240 g of thermopolymerizable resin (Mitsubishi Chemical Corporation, jER806; bisphenol F type epoxy resin) and 120 g of curing accelerator (Mitsubishi Chemical Corporation, jER Cure 113; modified alicyclic amine) are mixed to prepare a resin composition. did.

[Comparative Example 5]
240 g of thermopolymerizable resin (manufactured by Mitsubishi Chemical Corporation, jER806), 120 g of a curing accelerator (manufactured by Mitsubishi Chemical Corporation, jER Cure 113), and 40 g of glass beads were mixed to prepare a resin composition.

[Comparative Example 6]
60 g of glass beads, 0.6 g of 3-aminopropyltrimethoxysilane (manufactured by Shin-Etsu Silicone Co., Ltd., KBM-903) and 1.0 g of hydrochloric acid (concentration 35 mass%) were added to 40 g of an aqueous ethanol solution. And stirred at room temperature for 30 minutes. After stirring, the reaction solution was filtered, spread on a shallow tray, and dried at 120 ° C. for 90 minutes. After drying, it was crushed with a ball mill to obtain 3-aminopropyltrimethoxysilane-modified glass beads.
Thereafter, 240 g of a thermopolymerizable resin (Mitsubishi Chemical Corporation, jER806), 120 g of a curing accelerator (Mitsubishi Chemical Corporation, jER Cure 113), and 40 g of the above 3-aminopropyltrimethoxysilane-modified glass beads were mixed to obtain a resin composition. A product was prepared.

[Comparative Example 7]
180 g of photopolymerizable resin (Daicel Ornex, EBECRYL 600), 120 g of heat polymerizable resin (Mitsubishi Chemical, jER806), 2.5 g of photopolymerization initiator (IRGACURE TPO), and curing accelerator (Mitsubishi Chemical) Manufactured by jER Cure 113) and mixed with 60 g to prepare a resin composition.

[Comparative Example 8]
180 g of photopolymerizable resin (Daicel Ornex, EBECRYL 600), 120 g of thermopolymerizable resin (Mitsubishi Chemical, jER806), 2.5 g of photopolymerization initiator (BASF, IRGACURE TPO), curing accelerator ( Mitsubishi Chemical Co., Ltd., jER Cure 113) 60 g and glass beads 40 g were mixed to prepare a resin composition.

[Comparative Example 9]
60 g of glass beads, 0.6 g of methyltriethoxysilane (manufactured by Shin-Etsu Silicone Co., Ltd., KBE-13) as a surface modifier and 1.0 g of hydrochloric acid (concentration 35 mass%) were added to 40 g of an aqueous ethanol solution at room temperature. For 30 minutes. After stirring, the reaction solution was filtered, and the filtrate was spread on a shallow tray or the like and dried at 120 ° C. for 90 minutes. After drying, the dried product was crushed with a ball mill to obtain methyltriethoxysilane-modified glass beads.
180 g of photopolymerizable resin (Daicel Ornex, EBECRYL 600), 120 g of thermopolymerizable resin (Mitsubishi Chemical, jER806), 2.5 g of photopolymerization initiator (BASF, IRGACURE TPO), curing accelerator ( Mitsubishi Chemical Co., Ltd., jER Cure 113) 60 g and the above methyltriethoxysilane-modified glass beads 40 g were mixed to prepare a resin composition.

[Example 1]
180 g of photopolymerizable resin (Daicel Ornex, EBECRYL 600), 120 g of thermopolymerizable resin (Mitsubishi Chemical, jER806), 2.5 g of photopolymerization initiator (BASF, IRGACURE TPO), curing accelerator ( A resin composition was prepared by mixing 60 g of jER Cure 113) manufactured by Mitsubishi Chemical Corporation and 40 g of 3-aminopropyltrimethoxysilane-modified glass beads prepared in the same manner as in Comparative Example 6.

[Example 2]
60 g of glass beads, 0.6 g of surface modification agent 3-methacryloxypropyltrimethoxysilane (manufactured by Shin-Etsu Silicone, KBM-503), and 1.0 g of hydrochloric acid (concentration 35 mass%) were added to 40 g of an aqueous ethanol solution. And stirred at room temperature for 30 minutes. After stirring, the reaction solution was filtered, spread on a shallow tray, and dried at 120 ° C. for 90 minutes. After drying, it was crushed with a ball mill to obtain 3-methacryloxypropyltrimethoxysilane-modified glass beads.
180 g of photopolymerizable resin (Daicel Ornex, EBECRYL 600), 180 g of thermopolymerizable resin (DIC Material, PC740; unsaturated polyester resin), curing accelerator (DIC Material, RA; general-purpose amine accelerator) 2.0 g of auxiliary agent, 2.5 g of photopolymerization initiator (manufactured by BASF, IRGACURE TPO), and 40 g of the 3-methacryloxypropyltrimethoxysilane-modified glass beads were mixed to prepare a resin composition.

[Example 3]
180 g of photopolymerizable resin (Daicel Ornex, EBECRYL 600), 180 g of thermopolymerizable resin (Maywa Kasei, MEH-8000H; phenol resin), 2.5 g of photopolymerization initiator (BASF, IRGACURE TPO) Then, 40 g of 3-aminopropyltrimethoxysilane-modified glass beads produced by the same method as in Comparative Example 6 were mixed to prepare a resin composition.

[Example 4]
180 g of photopolymerizable resin (Daicel Ornex, EBECRYL 600), 60 g of thermopolymerizable resin (Sanyu REC, UF-110-1A), 120 g of thermopolymerizable resin (Sanyu REC, UF-110-1B), A resin composition was prepared by mixing 2.5 g of a photopolymerization initiator (manufactured by BASF, IRGACURE TPO) and 40 g of 3-aminopropyltrimethoxysilane-modified glass beads prepared in the same manner as in Comparative Example 6.

1-2. Production of 3D objects (SLA method)
The resin compositions (samples 1 to 63) were charged into a modeling tank 510 of a three-dimensional modeled manufacturing apparatus (NOBEL1.0 manufactured by XYZprinting) having a configuration as shown in FIG. Then, irradiation with semiconductor laser light (output 100 mW, wavelength 405 nm) from the light source 530 and lowering of the modeling stage 520 are repeated to obtain a primary cured product of the test piece shape of JIS K7161-2 (ISO 527-2) type 1A. It was. In the production, the longitudinal direction of the tensile test piece was made to be the modeling direction (the descending direction of the stage).

2-1. Preparation of Resin Composition [Comparative Examples 10 to 12]
Resin compositions were prepared in the same manner as in Comparative Examples 7-9.

[Examples 5 to 8]
Resin compositions were prepared in the same manner as in Examples 1 to 4.

[Comparative Example 13]
120 g of photopolymerizable resin (Daicel Ornex, EBECRYL 600), 80 g of thermopolymerizable resin (Mitsubishi Chemical, jER806), 1.7 g of photopolymerization initiator (BASF, IRGACURE TPO), curing accelerator ( Mitsubishi Chemical Co., Ltd., jER Cure 113) 40 g and cellulose nanofiber 5 mass% acetone dispersion 300 g were mixed to prepare a resin composition.
The obtained resin composition was stirred with a stirrer in an environment of 50 ° C. for 3 hours to sufficiently evaporate acetone.

[Comparative Example 14]
While stirring 1000 g of a cellulose nanofiber 2 mass% dispersion (Sugino Machine, BiNFi-s) with a stirrer, 0.3 g of methyltriethoxysilane (Shin-Etsu Silicone, KBE-13) was added. Thereafter, stirring was continued for 20 minutes, and the solvent was replaced with ethanol. Thereafter, the solvent was further replaced with acetone to produce methyl group-modified cellulose nanofibers.
120 g of photopolymerizable resin (Daicel Ornex, EBECRYL 600), 80 g of thermopolymerizable resin (Mitsubishi Chemical, jER806), 1.7 g of photopolymerization initiator (BASF, IRGACURE TPO), curing accelerator ( Mitsubishi Chemical Co., Ltd., jER Cure 113) 40 g and the above methyl group-modified cellulose nanofiber 2% by mass acetone dispersion 750 g were mixed to prepare a resin composition. The obtained resin composition was stirred with a stirrer in an environment of 50 ° C. for 3 hours to volatilize acetone sufficiently.

[Example 9]
While stirring 1000 g of a cellulose nanofiber 2 mass% dispersion (Sugino Machine, BiNFi-s) with a stirrer, 0.3 g of 3-aminopropyltrimethoxysilane (Shin-Etsu Silicone, KBM-903) was added. Thereafter, stirring was continued for 20 minutes, and the solvent was replaced with ethanol. Thereafter, the solvent was further replaced with acetone to produce amino group-modified cellulose nanofibers.
120 g of photopolymerizable resin (Daicel Ornex, EBECRYL 600), 80 g of thermopolymerizable resin (Mitsubishi Chemical, jER806), 1.7 g of photopolymerization initiator (BASF, IRGACURE TPO), curing accelerator ( Mitsubishi Chemical Co., Ltd., jER Cure 113) 40 g and the above amino group-modified cellulose nanofiber 2% by mass acetone dispersion 750 g were mixed to prepare a resin composition. The obtained resin composition was stirred with a stirrer in an environment of 50 ° C. for 3 hours to volatilize acetone sufficiently.

[Example 10]
While stirring 1000 g of cellulose nanofiber 2 mass% dispersion (Sugino Machine, BiNFi-s) with a stirrer, 0.3 g of 3-methacryloxypropyltrimethoxysilane (Shin-Etsu Silicone, KBM-503) was added. . Thereafter, stirring was continued for 20 minutes, and the solvent was replaced with ethanol. Thereafter, the solvent was further replaced with acetone to prepare methacrylic group-modified cellulose nanofibers.
120 g of photopolymerizable resin (Daicel Ornex, EBECRYL 600), 120 g of thermopolymerizable resin (DIC Material, PC740; unsaturated polyester resin), curing accelerator (DIC Material, RA; general-purpose amine accelerator) Auxiliary agent (1.5 g), a photopolymerization initiator (manufactured by BASF, IRGACURE TPO) (1.7 g), and methacrylic group-modified cellulose nanofiber 2 mass% acetone dispersion liquid (750 g) were mixed to prepare a resin composition. The obtained resin composition was stirred with a stirrer in an environment of 50 ° C. for 3 hours to volatilize acetone sufficiently.

[Example 11]
120 g of photopolymerizable resin (Daicel Ornex, EBECRYL 600), 120 g of thermopolymerizable resin (Maywa Kasei, MEH-8000H; phenol resin), 1.7 g of photopolymerization initiator (BASF, IRGACURE TPO) Then, 300 g of an amino group-modified cellulose nanofiber 5 mass% acetone dispersion prepared in the same manner as in Example 9 was mixed to prepare a resin composition. The obtained resin composition was stirred with a stirrer in an environment of 50 ° C. for 3 hours to volatilize acetone sufficiently.

[Example 12]
120 g of photopolymerizable resin (Daicel Ornex, EBECRYL 600), 40 g of thermopolymerizable resin (Sanyu REC, UF-110-1A), 80 g of thermopolymerizable resin (Sanyu REC, UF-110-1B), A resin composition was prepared by mixing 1.7 g of a photopolymerization initiator (IRGACURE TPO) and 300 g of an amino group-modified cellulose nanofiber 5 mass% acetone dispersion. The obtained resin composition was stirred with a stirrer in an environment of 50 ° C. for 3 hours to volatilize acetone sufficiently.

[Comparative Example 15]
180 g of photopolymerizable resin (Daicel Ornex, EBECRYL 600), 120 g of thermopolymerizable resin (Mitsubishi Chemical, jER806), 2.5 g of photopolymerization initiator (BASF, IRGACURE TPO), curing accelerator ( Mitsubishi Chemical Co., Ltd., jER Cure 113) 60 g and magnesium sulfate (Ube Materials Co., Ltd.) 40 g were mixed to prepare a resin composition.

[Comparative Example 16]
180 g of photopolymerizable resin (Daicel Ornex, EBECRYL 600), 120 g of thermopolymerizable resin (Mitsubishi Chemical, jER806), 2.5 g of photopolymerization initiator (BASF, IRGACURE TPO), curing accelerator ( Mitsubishi Chemical Co., Ltd., jER Cure 113) 60 g and methyl group-modified magnesium sulfate (Ube Materials Co., Ltd.) 40 g were mixed to prepare a resin composition.

[Example 13]
60 g of magnesium sulfate, 0.6 g of 3-aminopropyltrimethoxysilane (Shin-Etsu Silicone Co., Ltd., KBM-903) as a surface modifier and 1.0 g of hydrochloric acid (concentration 35 mass%) were added to 40 g of an aqueous ethanol solution. And stirred at room temperature for 30 minutes. After stirring, the reaction solution was filtered, spread on a shallow tray, and dried at 120 ° C. for 90 minutes. After drying, it was pulverized with a ball mill to produce 3-aminopropyltrimethoxysilane-modified magnesium sulfate.
180 g of photopolymerizable resin (Daicel Ornex, EBECRYL 600), 120 g of thermopolymerizable resin (Mitsubishi Chemical, jER806), 2.5 g of photopolymerization initiator (BASF, IRGACURE TPO), curing accelerator ( A resin composition was prepared by mixing 60 g of jER Cure 113) manufactured by Mitsubishi Chemical Corporation and 40 g of the above 3-aminopropyltrimethoxysilane-modified magnesium sulfate.

[Example 14]
Add 60 g of magnesium sulfate, 0.6 g of 3-methacryloxypropyltrimethoxysilane (Shin-Etsu Silicone Co., Ltd., KBM-503) and 1.0 g of hydrochloric acid (concentration 35% by mass) to 40 g of an aqueous ethanol solution. And stirred at room temperature for 30 minutes. After stirring, the reaction solution was filtered, spread on a shallow tray, and dried at 120 ° C. for 90 minutes. After drying, it was pulverized with a ball mill to produce 3-methacryloxypropyltrimethoxysilane-modified magnesium sulfate.
180 g of photopolymerizable resin (Daicel Ornex, EBECRYL 600), 120 g of thermopolymerizable resin (DIC Material, PC740; unsaturated polyester resin), 2.5 g of photopolymerization initiator (BASF, IRGACURE TPO) Then, 60 g of a curing accelerator (manufactured by Mitsubishi Chemical Co., Ltd., jER Cure 113) and 40 g of 3-methacryloxypropyltrimethoxysilane-modified magnesium sulfate were mixed to prepare a resin composition.

[Example 15]
180 g of photopolymerizable resin (Daicel Ornex, EBECRYL 600), 180 g of thermopolymerizable resin (Maywa Kasei, MEH-8000H; phenol resin), 2.5 g of photopolymerization initiator (BASF, IRGACURE TPO) And 40 g of 3-aminopropyltrimethoxysilane-modified magnesium sulfate prepared in the same manner as in Example 13 was mixed to prepare a resin composition.

[Example 16]
180 g of photopolymerizable resin (Daicel Ornex, EBECRYL 600), 60 g of thermopolymerizable resin (Sanyu REC, UF-110-1A), 120 g of thermopolymerizable resin (Sanyu REC, UF-110-1B), A resin composition was prepared by mixing 2.5 g of a photopolymerization initiator (manufactured by BASF, IRGACURE TPO) and 40 g of 3-aminopropyltrimethoxysilane-modified magnesium sulfate prepared in the same manner as in Example 13.

2-2. Production of 3D objects (CLIP method)
For the production of the three-dimensional modeled object, the resin compositions (samples 40 to 42) were respectively added to the modeling 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. As a result, a buffer region 642 containing the resin composition 650 and oxygen was formed on the bottom side of the modeling tank 610, and a curing region 644 having a lower oxygen concentration than the buffer region was formed above the buffer region 642.
Then, the stage 620 was raised while irradiating light in a planar shape from an ultraviolet ray source: LED projector (DLP (VISITECH LE4910H UV-388) manufactured by Texas Instruments). At this time, the irradiation intensity of ultraviolet rays was 5 mW / cm ² . The stage pulling speed was 50 mm / hr. Then, a primary cured product of JIS K7161-2 (ISO 527-2) type 1A test piece shape was produced. In the production, the longitudinal direction of the tensile test piece was set to the modeling direction (the pulling direction of the stage 620).

3. Evaluation About the three-dimensional molded item produced by the above-mentioned method, sclerosis | hardenability, tensile strength, durability, and dimensional accuracy were evaluated with the following method.

3-1. Curability About the obtained three-dimensional molded item, it was set as “◯” when cured by the above-mentioned SLA method or CLIP method, and “X” when not cured.

3-2. Tensile strength A tensile test was performed in accordance with JIS K7161. Specifically, the tensile strength was specified by a tensile tester, Tensilon RTC-1250, manufactured by A & D, and evaluated as follows.
◎: When the tensile strength is 70 MPa or more ◎: When the tensile strength is 50 MPa or more and less than 70 MPa 〇: When the tensile strength is 30 MPa or more and less than 50 MPa △: When the tensile strength is 10 MPa or more and less than 30 MPa ×: Tensile strength is less than 10 MPa in the case of

3-3. Durability (Change in tensile strength over time)
In the super xenon weather meter SX120, a light resistance test was conducted for one week under the conditions of irradiance of 150 W / m ² (300-400 nm), black panel temperature of 63 ° C., and humidity of the tank of 50% RH. The tensile strength was measured and evaluated as follows.
◎: When the tensile strength after the light resistance test is 70 MPa or more ◎: When the tensile strength after the light resistance test is 50 MPa or more and less than 70 MPa 〇: When the tensile strength after the light resistance test is 30 MPa or more and less than 50 MPa △: Light resistance When tensile strength after property test is 10 MPa or more and less than 30 MPa ×: When tensile strength after light resistance test is less than 10 MPa

3-4. Dimensional accuracy Evaluation of the dimensional accuracy of the three-dimensional structure was performed by measuring the dimensions of each three-dimensional structure. Specifically, the absolute value of the left-right dimension difference of the width (b2) of the grip part of the JIS K7161-2 (ISO 527-2) type 1A test piece is B, and the left-right dimension of the thickness (h) of the grip part The absolute value of the difference was set as H and evaluated as follows.
A: When B and H are each less than 0.1 mm O: When either B or H is less than 0.1 mm and the other is 0.1 mm or more and less than 0.2 mm Δ: B When both of H and H are 0.1 mm or more and less than 0.2 mm ×: When either B or H is 0.2 mm or more, or when a model is not obtained

As shown in Tables 1 and 2, when the resin composition does not contain a thermopolymerizable compound, the tensile strength tends to be low, and the durability (tensile strength after the light resistance test) was also poorly evaluated. (Comparative Examples 1 to 3). On the other hand, when the photopolymerizable compound was not included, it was not possible to form by the above method (Comparative Examples 4 to 6).

On the other hand, even if the resin composition contained a photopolymerizable compound and a thermopolymerizable compound, when no filler was contained, the tensile strength was not sufficiently increased and the dimensional accuracy was also low (Comparative Example 7). And Comparative Example 10). Furthermore, even if a filler is included, if it does not have a functional group capable of reacting with a thermopolymerizable resin (for example, a methyl group), it is difficult to sufficiently increase the tensile strength and dimensional accuracy, and the durability is low. (Comparative Examples 8, 9, and 11 to 16).

On the other hand, when the resin composition contains a photopolymerizable compound, a thermopolymerizable compound, and a filler having a functional group capable of reacting with the thermopolymerizable compound, curability, tensile strength, durability, and dimensional accuracy. However, all became good (Examples 1 to 16). In addition, the tensile strength was increased in the case where the three-dimensional object was prepared by the CLIP method (Examples 5 to 16) compared to the case where the three-dimensional object was prepared by the SLA method (Examples 1 to 4). According to the CLIP method, it is surmised that the three-dimensional model without a joint is produced, so that the tensile strength is increased.

In particular, when the filler is cellulose nanofiber or magnesium sulfate, when the filler is present in parallel to the tensile direction due to the high aspect ratio, the effect of reinforcing the molded product is produced, and the tensile strength is likely to increase (implementation). Examples 9-16).

This application claims priority based on Japanese Patent Application No. 2018-070959 filed on Apr. 2, 2018. All the contents described in the application specification are incorporated herein by reference.

According to the resin composition of the present invention, it is possible to provide a three-dimensionally shaped object having high dimensional accuracy and durability and high mechanical strength. 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 area 644 Curing area 651 Cured material

Claims

A resin composition used in a method for selectively irradiating a liquid resin composition with active energy to produce a three-dimensional structure made of a cured product of the resin composition,
A photopolymerizable compound;
A thermopolymerizable compound;
A functional group-containing filler having a functional group capable of binding to the thermopolymerizable compound on the surface,
Resin composition.
The thermally polymerizable compound is an epoxy resin or a precursor thereof, or a urethane resin or a precursor,
The resin composition according to claim 1.
The functional group-containing filler is a cellulose nanofiber having a functional group capable of binding to the thermopolymerizable compound,
The resin composition according to claim 1 or 2.
An optical modeling step of selectively irradiating the resin composition according to any one of claims 1 to 3 with active energy to form a primary cured product including a cured product of the photopolymerizable compound;
Including a thermosetting step of further thermosetting the primary cured product,
Manufacturing method of a three-dimensional molded item.
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 active energy from the buffer region side to cure 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 irradiated with active energy to form the primary cured product.
The manufacturing method of the three-dimensional molded item of Claim 4.
A three-dimensionally shaped article, which is a cured product of the resin composition according to any one of claims 1 to 3.