JP6574980B2 - Active energy ray-curable resin composition for model materials - Google Patents

Description

  The present invention relates to an active energy ray-curable resin composition for a model material for forming a three-dimensional object in addition manufacturing, particularly an ink jet three-dimensional stereolithography method, a model material obtained by curing the resin composition, and It relates to a three-dimensional model using it.

  Addition manufacturing technology is based on three-dimensional shape data, and melts thermoplastic resin, active energy ray curable resin, powder resin, powder metal, etc. using melt extrusion, inkjet, laser light, electron beam, etc. It is a technique for obtaining a desired three-dimensional model by stacking in a thin film by curing or the like.

  Manufacturing of 3D objects using additive manufacturing technology is possible directly from the shape data, and since complex shapes such as hollows and meshes can be integrally formed, test models that need to be manufactured in small lots or made to order. In addition to production, the use has expanded to a wide range of fields such as the automobile industry, aircraft industry, medical field, industrial robots, home appliances, architecture and food.

  With the expansion of the field of use, materials used for three-dimensional objects are expanding, such as metal, gypsum, concrete, resin, and food. Especially for resins, they can be easily molded by heating and melting and active energy ray curing, so they are used for additional manufacturing from early on, and are widely used in a variety of fields, from engineer plastics for aviation parts to flexible rubber-like resins. .

  An additive manufacturing apparatus called a 3D printer is generally used to obtain a three-dimensional modeled object, and various types of 3D printers are selectively used depending on a target field and a material to be used. Specifically, when an acrylic active energy ray curable resin is used, an inkjet ultraviolet curable 3D printer such as Objet made by Stratasys, AGLISTA made by Keyence, or a 3D printer made by stereolithography such as 3D Systems SLA series, DWS DigitalWax are used. On the other hand, when using high-strength thermoplastic resins such as acrylonitrile butadiene styrene resin, polycarbonate resin, polyphenylsulfone resin, polyetherimide resin, A 3D printer using a melt lamination method, for example, FORTUS, Dimension, uPrint, etc. manufactured by Stratasys is used. In addition, there is known a 3D printer of a powder modeling method in which nylon powder or the like is formed by fusing with a laser, for example, SLS series manufactured by 3D Systems.

  Among various types of 3D printers, the inkjet optical molding method is suitable for precise molding with a fine lamination pitch, and it is easy to use various active energy ray curable resins at the same time, with a wide range of physical properties from hard to soft. Therefore, there is an increasing demand in various fields such as the creation of a prototype model.

  In particular, because organ models for medical use need to be created in accordance with the results of each individual patient's examination, they are known as a field that is compatible with additive manufacturing technology. Since simulation and the like are possible, it is expected to contribute to future medical development. Since reproduction of such organs requires various textures, there is an increasing demand for not only conventional hard resins but also rubber-like resins having both flexibility and toughness.

  However, when three-dimensional molding is performed by an inkjet photomolding method using an active energy ray-curable resin, it is necessary to add a large amount of a crosslinking agent in order to ensure sufficient strength of the model material (Patent Documents 1 and 2). ) As a result, the elongation and flexibility were remarkably lowered, and it was difficult to obtain a tough molded product. Moreover, although the amount of addition of a crosslinking agent was reduced or a low Tg monomer was blended, a stretchable and flexible rubber-like resin was obtained, but the strength was not satisfactory ( Patent documents 3 to 5).

  Therefore, in order to obtain a flexible and tough active energy ray curable resin, a technique using a high molecular weight polyfunctional polymerizable compound as a crosslinking agent has been reported, and in particular, a polyrotaxane having an unsaturated group as a crosslinking agent capable of freely moving the crosslinking point. Has attracted attention as a resin material having a high Young's modulus and high extensibility, and having both flexibility and toughness (Patent Documents 6 to 9). However, the liquid viscosity of high molecular weight polyfunctional polymerizable compounds including the crosslinkable polyrotaxane is high, and by mixing them, the liquid viscosity of the active energy ray-curable resin composition increases rapidly, and the inkjet photoforming method There was an unsuitable problem.

  Under such circumstances, it is desired to develop an active energy ray-curable resin composition that can be molded into a flexible and tough rubber-like model material that is used in an inkjet photomolding method and that is suitable for an artificial organ. It was.

EP1274751B1 JP 2012-111226 A Japanese Patent Laid-Open No. 2015-0778255 WO2015-049873 WO2015-056614 WO2005-095493 WO2006-088200 JP 2011-046917 A JP 2014-224270 A

  The present invention provides an active energy ray-curable resin composition capable of forming a model material having both flexibility and toughness, and a photocurable ink used in an ink jet three-dimensional stereolithography method containing the same. Is an issue. Another object of the present invention is to provide a model material having both flexibility and toughness obtained by laminating and curing the photocurable ink, and a molded product using the model material.

  As a result of intensive studies to solve the above problems, the present inventors have blended polyrotaxane (A) having an unsaturated group and compound (B) having an ethylenically unsaturated group in a specific proportion. We have seen an active energy ray-curable resin composition capable of providing a cured resin having both flexibility and toughness, and a low-viscosity photocurable ink used in an inkjet three-dimensional stereolithography method containing the resin composition. This has led to the present invention.

That is, the present invention relates to (1) 1.0-20.0% by mass of polyrotaxane (A) having an unsaturated group and compound (B) having an ethylenically unsaturated group (excluding (A)) 80.0-99. An active energy ray-curable resin composition having 0.0 mass%, wherein the polyrotaxane (A) is composed of a cyclic molecule, a linear molecule that includes the cyclic molecule in a skewered manner, and the cyclic molecule is an unsaturated group An active energy ray-curable resin composition characterized by being a compound having
(2) Compound (B) having an ethylenically unsaturated group is a monofunctional unsaturated compound (b1) having a glass transition temperature (Tg) of 10 ° C. or higher of the homopolymer, and a glass transition temperature (Tg) of the homopolymer of less than 10 ° C. The active energy ray-curable resin composition according to (1) above, which is a monofunctional unsaturated compound (b2) and a polyfunctional unsaturated compound (b3),
(3) Polyrotaxane (A) having an unsaturated group 1.0 to 20.0% by mass, monofunctional unsaturated compound (b1) 10.0 to 80.0% by mass, monofunctional unsaturated compound (b2) The active energy ray-curable resin composition according to (1) or (2) above, having 0 to 60.0% by mass and 0 to 25.0% by mass of the polyfunctional unsaturated compound (b3) ,
(4) The active energy ray-curable resin composition according to any one of (1) to (3), wherein the polyfunctional unsaturated compound (b3) has a number average molecular weight of 400 to 20000. 5) The activity according to any one of (1) to (4) above, wherein the polyfunctional unsaturated compound (b3) is polyurethane di (meth) acrylamide having a number average molecular weight of 400 to 20,000. Energy ray curable resin composition,
(6) A photocurable ink containing the active energy ray-curable resin composition according to any one of (1) to (5), which is used in a three-dimensional photomolding method using an inkjet method.
(7) A model material obtained by curing the photocurable ink according to (6) with active energy rays,
(8) A three-dimensional structure characterized by using the model material described in (7) above is provided.

  According to the present invention, a flexible and tough cured resin can be obtained by curing an active energy ray-curable resin composition containing a polyrotaxane having an unsaturated group and a compound having an ethylenically unsaturated group. In addition, when the resin composition has a low viscosity and is used as a photocurable ink in an ink jet three-dimensional stereolithography method, a three-dimensional molded article composed of a model material having both flexibility and toughness can be obtained.

The present invention is described in detail below.
The polyrotaxane (A) having an unsaturated group used in the present invention is a pseudopolyrotaxane in which the opening of a cyclic molecule is skewered by a linear molecule, and the cyclic molecule is detached at both ends of the pseudopolyrotaxane. A polyrotaxane having at least one ethylenically unsaturated bond is a polyrotaxane cyclic molecule in which a blocking group is arranged so that there is no blocking group. These polyrotaxanes (A) may be used alone or in combination of two or more.

  It is preferable that content of the polyrotaxane (A) which has an unsaturated group used for this invention is 1.0-20.0 mass% with respect to the whole active energy ray-curable resin composition (E). When the content is 1.0% by mass or more, the model material obtained by polymerizing the active energy ray-curable resin composition (E) by irradiation with active energy rays has good tensile strength, elasticity, and the like. When the content is 0.0% by mass or less, the liquid viscosity of the active energy ray-curable resin composition (E) is low, and the discharge suitability when used in an inkjet ink can be sufficiently satisfied. Furthermore, since the cured resin has both flexibility and toughness as a model material for a three-dimensional molded article, it is more preferably 3.0 to 15.0% by mass.

  The linear molecule of the polyrotaxane (A) used in the present invention is not particularly limited as long as it can be clasped into the opening of the cyclic molecule. Specific examples of the linear molecule include polyethylene glycol, polypropylene glycol, polytetraethylene glycol, polyvinyl alcohol, polyvinyl pyrrolidone, polyvinyl acetal resin, polyvinyl methyl ether, polyamine, polyethylene imine, casein, gelatin, starch, and / or the like. These copolymers, cellulose resins (carboxymethyl cellulose, hydroxyethyl cellulose, hydroxypropyl cellulose, etc.), polyolefin resins such as polyethylene, polypropylene, and other copolymer resins with olefin monomers, polyester resins, polyvinyl chloride Resins, polystyrene resins such as polystyrene and acrylonitrile-styrene copolymer resins, poly (meth) acrylic acid, polyacrylamide, Acrylic resins such as methyl methacrylate, (meth) acrylic acid ester copolymer, acrylonitrile-methyl acrylate copolymer resin, polycarbonate resin, polyurethane resin, vinyl chloride-vinyl acetate copolymer resin, polyvinyl butyral resin, and derivatives thereof Or modified products, polyisobutylene, polytetrahydrofuran, polyaniline, acrylonitrile-butadiene-styrene copolymer (ABS resin), polyamides such as nylon, polyimides, polydienes such as polyisoprene and polybutadiene, polysiloxanes such as polydimethylsiloxane , Polysulfones, polyimines, polyacetic anhydrides, polyureas, polysulfides, polyphosphazenes, polyketones, polyphenylenes, polyhaloolefins, and the like And derivatives thereof. It is preferably selected from the group consisting of polyethylene glycol, polypropylene glycol, polytetrahydrofuran, polyisoprene, polyisobutylene, polybutadiene, polyethylene, polypropylene, polyvinyl alcohol, polyvinyl methyl ether, and polydimethylsiloxane, and more preferably polyethylene glycol. These linear molecules may be used alone or in combination of two or more. The molecular weight of the linear molecule is 3,000 to 1,000,000 in number average, preferably 5,000 to 100,000, more preferably 10,000 to 50,000.

  The cyclic molecule of the polyrotaxane (A) used in the present invention is preferably a cyclic molecule having a hydroxyl group, and specific examples include α-cyclodextrin, β-cyclodextrin and γ-cyclodextrin. -Cyclodextrins are particularly preferred. Moreover, a part of the hydroxyl group of the cyclic molecule may be substituted with another group. Examples of other groups include a hydrophilic group for making the polyrotaxane of the present invention hydrophilic, a hydrophobic group for making it hydrophobic, and the like. These cyclic molecules may be used alone or in combination of two or more.

  In the polyrotaxane (A) used in the present invention, when the amount of cyclic molecules to be maximally included when the cyclic molecules are skewered by linear molecules is 1.0, the cyclic molecule Is preferably included in a skewered manner in a linear molecule in an amount of 0.001 to 0.6, more preferably 0.01 to 0.5, and 0.05 to 0.4. More preferably. The maximum inclusion amount of the cyclic molecule can be determined by the length of the linear molecule and the thickness of the cyclic molecule.

  The blocking group of the polyrotaxane (A) used in the present invention is not particularly limited as long as it is a group that is arranged at both ends of the pseudopolyrotaxane and acts so as not to leave the cyclic molecule. Specific examples of blocking groups include adamantane groups, trityl groups, dinitrophenyl groups, cyclodextrins, fluoresceins, silsesquioxanes, pyrenes, steroids, substituted benzenes (alkyl groups as substituents, An alkyloxy group, a hydroxy group, a halogen group, a cyano group, a sulfonyl group, a carboxyl group, an amino group, a phenyl group, and the like. One or more substituents may be present. Polynuclear aromatics (as substituents there may be mentioned alkyl groups, alkyloxy groups, hydroxy groups, halogen groups, cyano groups, sulfonyl groups, carboxyl groups, amino groups, phenyl groups, etc. Or a plurality of them may be present). These blocking groups may be used alone or in combination of two or more. It is preferably selected from the group consisting of adamantane groups, trityl groups, dinitrophenyl groups, cyclodextrins, fluoresceins, silsesquioxanes, and pyrenes, and are adamantane groups or trityl groups. It is more preferable.

  The unsaturated group of the polyrotaxane (A) used in the present invention is bonded to the cyclic molecule directly or via a chain molecule. The unsaturated group is not particularly limited as long as it has radical polymerizability, and specific examples include a vinyl group, an allyl group, an acryloyl group, and a methacryloyl group. These unsaturated groups may be used alone or in combination of two or more. An acryloyl group and a methacryloyl group are preferable, and an acryloyl group is more preferable.

  The chain molecule is not particularly limited as long as it is bonded to a hydroxyl group of a cyclic molecule. Specific examples of the chain molecule include alkylenes, alkenylenes, alkylene glycols, polycaprolactones, polycarbonates, polyesters, polyamides, and polyurethanes. These chain molecules may be used alone or in combination of two or more, or two or more chain molecules may be combined and used as one chain molecule.

  Examples of alkylenes and alkenylenes include linear alkylene groups or linear alkenylene groups having 1 to 8 carbon atoms, branched alkylene groups or branched alkenylene groups having 3 to 20 carbon atoms.

  Examples of alkylene glycols include linear or branched alkylene glycols having 1 to 20 carbon atoms, dialkylene glycols, trialkylene glycols, and polyalkylene glycols.

  Polycaprolactones are ring-opening polymers of lactone monomers, and the number average molecular weight is preferably 200 to 10,000. Lactone monomers include β-propiolactone, β-methylpropiolactone, 4-membered ring lactones such as L-serine-β-lactone derivatives, γ-butyrolactone, γ-hexanolactone, γ-heptanolactone, γ -Octanolactone, γ-decanolactone, γ-dodecanolactone, α-hexyl-γ-butyrolactone, α-heptyl-γ-butyrolactone, α-hydroxy-γ-butyrolactone, γ-methyl-γ-decanolactone, α-methylene -Γ-butyrolactone, α, α-dimethyl-γ-butyrolactone, D-erythronolactone, α-methyl-γ-butyrolactone, γ-nonanolactone, DL-pantolactone, γ-phenyl γ-butyrolactone, γ-undecanolactone , Γ-valerolactone, 2,2-pentamethylene-1,3-dioxolane-4- ON, 5-membered ring lactones such as α-bromo-γ-butyrolactone, γ-crotonolactone, α-methylene-γ-butyrolactone, α-methacryloyloxy-γ-butyrolactone, β-methacryloyloxy-γ-butyrolactone, δ- Valerolactone, δ-hexanolactone, δ-octanolactone, δ-nonanolactone, δ-decanolactone, δ-undecanolactone, δ-dodecanolactone, δ-tridecanolactone, δ-tetradecanolactone, DL- Examples include 6-membered ring lactones such as mevalonolactone and 4-hydroxy-1-cyclohexanecarboxylic acid δ-lactone, 7-membered ring lactones such as ε-caprolactone, lactide, 1,5-dioxepan-2-one, and the like. Examples of the lactone monomer include ε-caprolactone, γ-butyllactone, α-methyl-γ-butyllactone, δ-valerolactone, and lactide.

  The polycarbonate is a polycarbonate composed of a diol component and a carbonyl component, and the number average molecular weight is preferably from 200 to 10,000. Examples of the carbonyl component include phosgene, chloroformate, dialkyl carbonate, diaryl carbonate, and alkylene carbonate. Examples of the diol component include ethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,4-cyclohexanedimethanol, 3-methyl-1,5-pentanediol, 1,9-nonanediol, neopentyl glycol, 2-ethyl-2- And butyl-1,3-propanediol.

  Polyesters are compounds obtained by polycondensation of a diol component and a polyvalent carboxylic acid, and the number average molecular weight is preferably 200 to 10,000. Examples of the polyvalent carboxylic acid component include terephthalic acid, isophthalic acid, succinic acid, adipic acid, azelaic acid, sebacic acid, dodecanedioic acid, and the like. Examples of the diol component include ethylene glycol, 1,2-propylene glycol, 1, 3-propylene glycol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,4-cyclohexanedimethanol, 3-methyl-1,5-pentanediol, 1,9-nonane Examples include diol, neopentyl glycol, 2-ethyl-2-butyl-1,3-propanediol.

  Polyamides are ring-opened polymers of a compound or lactam monomer obtained by polycondensation of a diamine component and a polyvalent carboxylic acid, and terephthalic acid, isophthalic acid, succinic acid, adipic acid can be used as the polyvalent carboxylic acid component. , Azelaic acid, sebacic acid, dodecanedioic acid and the like. Examples of the diamine component include ethylenediamine, 1,2-propylenediamine, 1,3-propylenediamine, 1,4-butanediamine, pentamethylenediamine, hexamethylenediamine. 1,4-cyclohexanediamine and the like, and examples of the lactam monomer include β-propiolactam, γ-butyrolactam, ε-caprolactam, undecaractam, lauryl lactam, and the like. The number average molecular weight is preferably 200 to 10,000.

  Polyurethanes are compounds obtained by an addition reaction between a diol and a polyisocyanate compound having two or more isocyanate groups in one molecule, and the number average molecular weight is preferably 200 to 10,000. As the diol component, ethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,4-cyclohexanedimethanol , 3-methyl-1,5-pentanediol, 1,9-nonanediol, neopentyl glycol, 2-ethyl-2-butyl-1,3-propanediol and the like, and having two or more isocyanate groups As polyisocyanate compounds, trimethylene diisocyanate, tetramethylene diisocyanate, pentamethylene diisocyanate, hexamethylene diisocyanate, 1,2-propylene diisocyanate, 1,2-butylene diisocyanate, 2,3-butylene diisocyanate, 1,3- Aliphatic isocyanates such as tylene diisocyanate, 2,4,4-trimethylhexamethylene diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, 1,3-phenylene diisocyanate, 1,4-phenylene diisocyanate, 2,4-triisocyanate Aromatic isocyanates such as diisocyanate, 2,6-tolylene diisocyanate, 4,4'-diphenylmethane diisocyanate, 2,4-diphenylmethane diisocyanate, xylylene diisocyanate, cyclopentylene diisocyanate, cyclohexylene diisocyanate, isophorone diisocyanate, 4, 4′-dicyclohexylmethane diisocyanate, methylcyclohexylene diisocyanate, 2,5-norbornane diisocyanate, 2, - alicyclic isocyanates such as norbornane diisocyanate, or, these adduct type, isocyanurate type, multimers such as biuret type and the like.

  The method for synthesizing the polyrotaxane (A) used in the present invention is not particularly limited, and can be obtained by a known method using the various raw material compounds. For details, the descriptions in Patent Documents 6 to 9 can be referred to. For example, first, an opening of a cyclic molecule is included in a skewered manner by a linear molecule, a blocking group is arranged at both ends of the linear molecule so that the cyclic molecule is not detached, and an unmodified polyrotaxane (a1 ) Second, using some or all of the hydroxyl groups in the cyclic molecule of polyrotaxane (a1), a chain molecule is introduced via an ether bond, ester bond, urethane bond, carbonate bond, etc. by a known synthetic reaction, and modified. A polyrotaxane (a2) is obtained. Third, an unsaturated group is introduced using a reactive group such as a hydroxyl group in the chain molecule of the modified polyrotaxane (a2) to obtain a polyrotaxane (A).

  Moreover, an unsaturated group and a cyclic molecule can be directly introduced into the unmodified polyrotaxane (a1) via an ether bond, an ester bond, a urethane bond, a silyl ether bond, or the like, without passing through the above reaction step.

  In order to introduce an unsaturated group into the polyrotaxane (A), a compound having both an unsaturated group and another reactive group can be used. Specifically, carboxylic acids having an unsaturated group such as (meth) acrylic acid, 2-carboxyethyl (meth) acrylate, (meth) acrylamide 2-carboxyethyl, maleic acid, itaconic acid, maleic anhydride, anhydrous Carboxylic anhydrides having an unsaturated group such as (meth) acrylic acid, carboxylic acid halides having an unsaturated group such as (meth) acrylic acid chloride, 3- (acryloyloxy) propionic acid chloride, (meth) acrylic Isocyanates having an unsaturated group such as Iroxyethyl isocyanate, Epoxys having an unsaturated group such as glycidyl (meth) acrylate, vinyl glycidyl ether, 4-hydroxybutyl (meth) acrylate glycidyl ether, vinyltrimethoxysilane, vinyl Triethoxysilane, p-styryltri Alkoxysilanes having an unsaturated group such as toxisilane, p-styryltriethoxysilane, 3- (meth) acryloxypropyltrimethoxysilane, 3- (meth) acryloxypropyltriethoxysilane, hydroxyethyl (meth) acrylate, Alcohols having an unsaturated group such as hydroxypropyl (meth) acrylate, hydroxybutyl (meth) acrylate, N- (2-hydroxyethyl) acrylamide, 2-vinyl-2-oxazoline, 2-isopropenyl-2-oxazoline, Examples thereof include oxazolines having an unsaturated group such as 2-allyl-2-oxazoline and 2- [2- (acryloylamino) phenyl] -4-methyl-2-oxazoline.

  Moreover, the polyrotaxane (A) used for this invention can provide the process of couple | bonding functional groups other than an unsaturated group with a cyclic molecule directly or via a chain molecule before and after the said reaction process.

  When producing the polyrotaxane (A) used in the present invention, it is common to use an organic solvent, and as the kind of organic solvent, there are a linear molecule, a blocking group, a chain molecule to be introduced and an unsaturated group. Depending on the type and amount of the solvent, examples include toluene, xylene, acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, ethyl acetate, butyl acetate, methylene chloride, N, N′-dimethylformamide, dimethylacetamide, dimethylsulfoxide, 2 -Pyrrolidone, N-methyl-2-pyrrolidone, 1,3-dimethyl-2-imidazolidinone and the like.

  The compound (B) having an ethylenically unsaturated group (excluding the polyrotaxane (A) having an unsaturated group) used in the present invention is a monofunctional unsaturated compound having a glass transition temperature (Tg) of 10 ° C. or higher of a homopolymer ( b1), a monofunctional unsaturated compound (b2) having a glass transition temperature (Tg) of less than 10 ° C. and a polyfunctional unsaturated compound (b3) having two or more functions. When the monofunctional unsaturated compounds (b1) and (b2) are blended in a certain proportion, the strength and flexibility of the model material obtained by active energy ray irradiation are good, and the polyfunctional unsaturated compound (b3 ), A model material having excellent flexibility and toughness can be obtained.

  The total content of the three compounds (b1), (b2) and (b3) constituting the compound (B) having an ethylenically unsaturated group is based on the whole active energy ray-curable resin composition (E). It is preferable that it is 80.0-99.0 mass%. If it is within this range, the liquid viscosity of the active energy ray-curable resin composition (E) is low, and can provide excellent ink jet discharge suitability, and at the same time, the strength of the model material obtained by polymerization by irradiation with active energy rays. Good elasticity. Furthermore, it is more preferable that it is 85.0-94.0 mass%.

  Monofunctional unsaturated compound (b1) having a glass transition temperature (Tg) of 10 ° C. or higher of the homopolymer of the present invention includes (meth) acrylate group, (meth) acrylamide group, vinyl group, allyl group, styrene group, acetylene group, etc. These compounds may be used, and these may be used alone or in combination of two or more.

  It is preferable that the usage-amount of a monofunctional unsaturated compound (b1) is 10.0-80.0 mass% with respect to the active energy ray-curable resin composition (E) whole. When it is 10.0% by mass or more, the obtained model material has good tensile strength, elasticity, and the like, and when it is 80.0% by mass or less, the elongation and flexibility of the model material can be maintained. Furthermore, it is more preferable that it is 20.0-60.0 mass%.

  Monofunctional unsaturated compound (b2) having a glass transition temperature (Tg) of less than 10 ° C. of homopolymer contains (meth) acrylate group, (meth) acrylamide group, vinyl group, allyl group, styrene group, acetylene group, etc. In addition, one compound may be used alone, or two or more compounds may be used in combination.

  It is preferable that the usage-amount of a monofunctional unsaturated compound (b2) is 0-65.0 mass% with respect to the whole active energy ray-curable resin composition (E). The blending of (b2) has the effect of improving the tensile elongation and flexibility of the model material after curing, but if the amount used exceeds 65.0% by mass, the rubber hardness of the model material is reduced and the strength is satisfactory. And hardness cannot be obtained. Furthermore, it is more preferable that it is 30.0-60.0 mass%.

  Of the monofunctional unsaturated compounds (b1) and (b2) used in the present invention, examples of the compound containing a (meth) acrylate group include (meth) acrylic acid, a straight chain having 1 to 22 carbon atoms, Alkyl (meth) acrylates having branched and cyclic alkyl groups, hydroxyalkyl (meth) acrylates having straight, branched and cyclic hydroxyalkyl groups having 1 to 18 carbon atoms, (meth) acrylic acid and (Meth) acrylic acid alkyl carboxylic acids such as (meth) acrylic acid ethyl carboxylic acid, (meth) acrylic acid ethyl succinic acid, (meth) acrylic acid ethyl phthalic acid, (meth) acrylic acid ethyl hexahydrophthalic acid and the like comprising hydroxyalkyl carboxylic acids Acids, (meth) acrylic acid groups having a linear, branched or cyclic alkylsulfonic acid group having 1 to 18 carbon atoms Killsulfonic acids, (meth) acrylic acid alkyl phosphates having 1 to 18 carbon atoms in which a linear, branched or cyclic alkyl phosphate group is introduced, alkyl groups having 1 to 18 carbon atoms and alkylene having 1 to 4 carbon atoms Alkoxyalkylene glycol (meth) acrylates, alkoxydialkylene glycol (meth) acrylates, alkoxytrialkylene glycol (meth) acrylates, alkoxypolyalkylene glycol (meth) acrylates, and phenoxy that have been introduced with a functional group comprising a glycol group Groups and phenoxyalkylene glycol (meth) acrylates, phenoxydialkylene glycol (meth) acrylates, phenoxytrialkylene glycol (meth) acrylates introduced with a functional group consisting of an alkylene glycol group having 1 to 4 carbon atoms Rate, phenoxypolyalkylene glycol (meth) acrylate, N-alkylamino (meth) acrylates having an aminoalkyl group having 1 to 6 carbon atoms, aminoalkyl group having 1 to 6 carbon atoms and carbon number N-alkylaminoalkyl (meth) acrylates introduced with an N-alkylaminoalkyl group consisting of 1 to 6 alkyl groups, or an aminoalkyl group having 1 to 6 carbon atoms and an alkyl group having 1 to 6 carbon atoms N, N-dialkylaminoalkyl (meth) acrylates introduced with N, N-dialkylaminoalkyl groups, benzyl (meth) acrylate, phenoxyethyl (meth) acrylate, dicyclopentanyl (meth) acrylate, dicyclopenta Nyloxyethyl (meth) acrylate, dicyclopentenyl (meth) a Introducing cyclic structures such as relate, dicyclopentenyloxyethyl (meth) acrylate, bornyl (meth) acrylate, isobornyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, 2-methyl-2-adamantyl (meth) acrylate Examples include (meth) acrylates into which an epoxy group has been introduced, such as (meth) acrylates, glycidyl (meth) acrylate, and 4-hydroxybutyl (meth) acrylate glycidyl ether.

  Among the monofunctional unsaturated compounds (b1) and (b2) used in the present invention, the compound containing a (meth) acrylamide group includes (meth) acrylamide, mono- or di-substituted (meth) acrylamide, and (meth) acrylic. In addition, examples of the mono- or di-substituted (meth) acrylamide include N-alkyl (meth) acrylamide introduced with a linear, branched, or cyclic alkyl group having 1 to 18 carbon atoms, N, N-dialkyl (meth) acrylamide, N-hydroxyalkyl (meth) acrylamide introduced with a hydroxyalkyl group having 1 to 6 carbon atoms, N, N-di (hydroxyalkyl) (meth) acrylamide, N- Hydroxyalkyl-N- (4-hydroxyphenyl) (meth) acrylamide, hydroxyalkyl having 1 to 6 carbon atoms N-alkyl-N-hydroxyalkyl (meth) acrylamide, N-alkyl-N- (4-hydroxyphenyl) (meth) acrylamide, and 4-hydroxyphenyl introduced with an alkyl group and an alkyl group having 1 to 6 carbon atoms (Meth) acrylamide, N, N-di (4-hydroxyphenyl) (meth) acrylamide, N-alkoxy introduced with an alkoxyalkyl group composed of an alkoxy group having 1 to 6 carbon atoms and an alkylene group having 1 to 6 carbon atoms Alkyl (meth) acrylamide, N, N-di (alkoxyalkyl) (meth) acrylamide, alkoxyalkyl group consisting of an alkoxy group having 1 to 6 carbon atoms and an alkylene group having 1 to 6 carbon atoms, 1 to 6 carbon atoms N-alkyl-N-alkoxyalkyl (meth) acrylamide introduced with an alkyl group of N-sulfoalkylacrylamide introduced with ~ 6 alkyl sulfonic acid groups, N-alkylamino (meth) acrylamide introduced with aminoalkyl groups having 1 to 6 carbon atoms, aminoalkyl groups with 1 to 6 carbon atoms and carbon N-alkylaminoalkyl (meth) acrylamide introduced with an N-alkylaminoalkyl group comprising an alkyl group having 1 to 6 carbon atoms, N comprising an aminoalkyl group having 1 to 6 carbon atoms and an alkyl group having 1 to 6 carbon atoms , N-N-dialkylaminoalkyl (meth) acrylamide introduced with N-dialkylaminoalkyl group.

  Among the monofunctional unsaturated compounds (b1) and (b2) used in the present invention, as a compound containing a vinyl group, a carboxylic acid vinyl ester introduced with a carboxylic acid having 1 to 22 carbon atoms, a carbon number of 1 Alkyl vinyl ether, vinyl chloride, N-vinyl pyrrolidone, N-vinyl caprolactam, N-vinyl oxazoline, maleic acid, maleic anhydride, fumaric acid, itaconic acid, itaconic, having a linear, branched or cyclic alkyl group of -22 Acid anhydrides, maleic acid monoalkyl esters, maleic acid dialkyl esters, maleic acid monoalkyl amides, maleic acid dialkyl amides, maleic acid alkyl imides, having introduced linear, branched or cyclic alkyl groups having 1 to 22 carbon atoms, Fumaric acid monoalkyl ester, fumaric acid dialkyl ester, fumaric acid Alkyl amide, dialkyl fumarate amide, itaconic acid monoalkyl esters, itaconic acid dialkyl esters, itaconic acid monoalkyl amides, itaconic acid dialkyl amides, itaconic acid alkyl imide, vinyl carboxylic acids, vinyl sulfonic acid, vinyl phosphoric acid.

  Of the monofunctional unsaturated compounds (b1) and (b2) used in the present invention, as the compound containing an allyl group, a carboxylic acid allyl ester into which a carboxylic acid having 1 to 22 carbon atoms is introduced, the carbon number is 1 Examples include alkylallyl ethers having a linear, branched or cyclic alkyl group of ˜22, phenyl allyl ether, alkylphenyl allyl ether, allylamine, mono- or dialkylallylamine having a branched or cyclic alkyl group.

  Of the monofunctional unsaturated compounds (b1) and (b2) used in the present invention, as a compound containing a styrene group, styrene, an α-alkylstyrene having an alkyl group having 1 to 18 carbon atoms introduced at the α-position, α-methyl styrene dimer, o-alkyl styrene, m-alkyl styrene, p-alkyl styrene, p-styrene sulfonic acid introduced with a sulfonic acid machine, etc., in which an alkyl group having 1 to 18 carbon atoms is introduced into the phenyl group.

Among the monofunctional unsaturated compounds (b1) and (b2) used in the present invention, monofunctional unsaturated compounds containing acid groups such as carboxylic acid groups, sulfonic acid groups, and phosphoric acid groups are neutralized. It can also be used. The cations used for neutralization include alkali metal ions such as Li ⁺ , Na ⁺ and K ⁺ , alkaline earth metal ions such as Ca ²⁺ and Mg ²⁺ , ammonium salts, alkylamine salts, dialkylamine salts, and trialkyls. It is at least one ion selected from inorganic cations such as amine salts and tetraalkylamine salts, or organic cations.

Of the monofunctional unsaturated compounds (b1) and (b2) used in the present invention, monofunctional unsaturated compounds containing an amino group, an alkylamino group, and a dialkylamino group can be neutralized and used. As anions used for neutralization, as anions, halogen ions such as Cl ⁻ , Br ⁻ and I ⁻ or OH ⁻ , CH ₃ COO ⁻ , NO ₃ ⁻ , ClO ₄ ⁻ , PF ₆ ⁻ and BF ₄ ^{− are used.} , HSO ₄ ⁻ , CH ₃ SO ₃ ⁻ , CF ₃ SO ₃ ⁻ , CH ₃ C ₆ H ₄ SO ₃ ⁻ , C ₄ F ₉ SO ₃ ⁻ , (CF ₃ SO ₂ ) ₂ N ⁻ , SCN ^{− and the} like At least one ion selected from an acid anion or an organic acid anion.

  Among the monofunctional unsaturated compounds (b1) and (b2) used in the present invention, the monofunctional unsaturated compound containing a tertiary amino group is a linear, branched or cyclic alkyl having 1 to 22 carbon atoms. An ammonium ion having an unsaturated group quaternized by adding a group, an alkenyl group, or an aryl group, for example, trimethylammonium ethyl acrylate, dimethylbenzyl ammonium ethyl acrylate, trimethyl ammonium propyl acrylamide, dimethyl propenyl ammonium propyl acrylamide, etc. it can. As the ammonium ion having an unsaturated group, at least one ion selected from the inorganic acid anions or organic acid anions described in the preceding paragraph is arbitrarily selected and used as an onium salt constituted by combining the anion and the cation. Can do.

  As the polyfunctional unsaturated compound (b3) used in the present invention, allyl (meth) acrylate, diallylamine, alkyl diallylamine having an alkyl group having 1 to 18 carbon atoms introduced, and alkyl group having 1 to 18 carbon atoms are introduced. Dialkyl diallyl ammonium chloride or dialkyl diallylammonium used as an onium salt constituted by arbitrarily selecting at least one ion selected from the inorganic acid anions or organic acid anions described in the preceding paragraph and combining the anion and cation Dialkyldiallylammonium salts such as p-toluenesulfonate, alkylene glycol di (meth) acrylates, polyalkylene glycol di (meth) acrylates, polyester di (meth) acrylates, polycarbonate di (meth) acrylate Examples of the polyfunctional unsaturated compound having 3 or more functional groups include pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meta). ) Acrylate, trimethylolpropane tri (meth) acrylate, dipentaerythritol tri (meth) acrylate, ditrimethylolpropane tetra (meth) acrylate, dipentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipenta Erythritol hexa (meth) acrylate, tri (meth) acryloyloxyethoxytrimethylolpropane, glycerin polyglycidyl ether poly (meth) acrylate, Ethylene oxide modified tri (meth) acrylate, ethylene oxide modified dipentaerythritol penta (meth) acrylate, ethylene oxide modified dipentaerythritol hexa (meth) acrylate, ethylene oxide modified pentaerythritol tri (meth) acrylate, ethylene oxide modified penta Examples include erythritol tetra (meth) acrylate and succinic acid-modified pentaerythritol tri (meth) acrylate. These polyfunctional unsaturated compounds (b3) may be used alone or in combination of two or more.

  The polyfunctional unsaturated compound (b3) preferably has a number average molecular weight of 400 to 20,000. When the number average molecular weight is 400 or more, the unsaturated bond equivalent is not too high, and the flexibility of the resulting model material is sufficiently satisfied. When the number average molecular weight is 20,000 or less, the active energy ray curability is obtained. The liquid viscosity of the resin composition (E) can be controlled to be low, and is excellent in ink jet discharge suitability. Further, the number average molecular weight is more preferably 1,000 to 10,000.

  As the unsaturated group of the polyfunctional unsaturated compound (b3), it is more preferable to use a (meth) acrylate group or a (meth) acrylamide group because the curability is good. Particularly when polyurethane di (meth) acrylamides are used, not only the curability of the active energy ray-curable composition (E) is further improved, but also the flexibility of the model material obtained by curing is improved. . In addition, the hydrogen bond derived from the urethane bond or the amide bond is particularly preferable because the tensile strength and elasticity of the model material are improved and a well-balanced molded article can be obtained.

  It is preferable that the usage-amount of a polyfunctional unsaturated compound (b3) is 0-25.0 mass% with respect to the whole active energy ray-curable resin composition (E). The tensile strength, elasticity, etc. of the model material obtained by adding the polyfunctional unsaturated compound (b3) are improved, and when it is 25.0% by mass or less, the active energy ray-curable resin composition The liquid viscosity of (E) is low and can provide excellent ink jet discharge aptitude. Furthermore, it is more preferable that it is 2.0-20.0 mass%.

  Examples of the alkylene glycol di (meth) acrylates include ethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, 3-methyl-1,5-pentanediol di ( (Meth) acrylate, 1,6-hexanediol di (meth) acrylate, 1,9-nonanediol di (meth) acrylate, 2-n-butyl-2-ethyl-1,3-propanediol di (meth) acrylate, Examples include dimethylol tricyclodecane di (meth) acrylate. These alkylene glycol di (meth) acrylates can be used alone or in combination of two or more.

  Examples of the polyalkylene glycol di (meth) acrylates include diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, diprolene glycol di (meth) acrylate, and triprolene glycol. Di (meth) acrylate, polyprolene glycol di (meth) acrylate, di (neopentyl glycol) di (meth) acrylate, tri (neopentyl glycol) di (meth) acrylate, poly (neopentyl glycol) di (meth) acrylate , Di (3-methyl-1,5-pentanediol) di (meth) acrylate, tri (3-methyl-1,5-pentanediol) di (meth) acrylate, poly (3-methyl-1,5-pentanediol ) Di (meth) acrylate, polyethylene glycol polypropylene glycol di (meth) acrylate. These polyalkylene glycol di (meth) acrylates can be used alone or in combination of two or more.

  As said polyester di (meth) acrylate, the polyester polyol which has a hydroxyl group in the both terminal or side chain which contains a polyester frame | skeleton in a molecule | numerator, and (meth) acrylic acid are ester-bonded. Examples of the polyvalent carboxylic acid component of the polyester polyol include terephthalic acid, isophthalic acid, succinic acid, adipic acid, azelaic acid, sebacic acid, and dodecanedioic acid. Examples of the diol component include ethylene glycol and 1,2-propylene glycol. 1,3-propylene glycol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,4-cyclohexanedimethanol, 3-methyl-1,5-pentanediol, 1, Examples include 9-nonanediol, neopentyl glycol, 2-ethyl-2-butyl-1,3-propanediol. These polyester di (meth) acrylates can be used alone or in combination of two or more.

  As said polycarbonate di (meth) acrylate, the polycarbonate polyol which has a hydroxyl group in the both terminal or side chain which contains a carbonate skeleton in a molecule | numerator, and (meth) acrylic acid are ester-bonded. Examples of the carbonyl component of the polycarbonate polyol include phosgene, chloroformate, dialkyl carbonate, diaryl carbonate, and alkylene carbonate. Examples of the diol component include ethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 1,4- Butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,4-cyclohexanedimethanol, 3-methyl-1,5-pentanediol, 1,9-nonanediol, neopentyl glycol, 2-ethyl -2-butyl-1,3-propanediol and the like. These polycarbonate di (meth) acrylates can be used alone or in combination of two or more.

  Examples of the polyurethane di (meth) acrylates include an alcohol compound having one or more hydroxyl groups in the molecule, a polyisocyanate compound having two or more isocyanate groups in one molecule, and a (meth) acrylate having a hydroxyl group. It is a compound obtained by addition reaction with a compound, and the synthesis method is not particularly limited, and can be synthesized by a known urethanization reaction technique. These polyurethane di (meth) acrylates can be used alone or in combination of two or more.

  Examples of the polyurethane di (meth) acrylamides include alcohol compounds having one or more hydroxyl groups in the molecule, polyisocyanate compounds having two or more isocyanate groups in one molecule, and (meth) acrylamides having hydroxyl groups. It is a compound obtained by addition reaction with a compound, and the synthesis method is not particularly limited, and can be synthesized by a known urethanization reaction technique. These polyurethane di (meth) acrylamides can be used alone or in combination of two or more.

  The alcohol compound having one or more hydroxyl groups in the molecule is ethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 1, 1-propylene glycol having one or more hydroxyl groups at the terminal or side chain of the main chain skeleton. 2-butylene glycol, 1,3-butylene glycol, 1,4-butylene glycol, 1,5-pentane glycol, 2-methyl-1,3-propylene glycol, 2-methyl-1,4-butylene glycol, 1, 6-hexanediol, 3-methyl-1,5-pentanediol, 1,9-nonanediol, neopentyl glycol, 2-ethyl-2-butyl-1,3-propanediol, glycerin, polyethylene glycol, polypropylene glycol, Polytetramethylene glycol, polymethylpentane glycol, poly Hexamethylene glycol, polyglycerol, polybutadiene polyol, hydrogenated polybutadiene polyol, polyisoprene polyol, hydrogenated polyisoprene polyol, polyester polyol, polycarbonate polyol, terminal carbinol-modified polydimethylsiloxane, and the like. These polyols can be used individually by 1 type or in combination of 2 or more types.

  Examples of the polyisocyanate compound having two or more isocyanate groups in one molecule include trimethylene diisocyanate, tetramethylene diisocyanate, pentamethylene diisocyanate, hexamethylene diisocyanate, 1,2-propylene diisocyanate, and 1,2-butylene. Aliphatic isocyanates such as diisocyanate, 2,3-butylene diisocyanate, 1,3-butylene diisocyanate, 2,4,4-trimethylhexamethylene diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, 1,3- Phenylene diisocyanate, 1,4-phenylene diisocyanate, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, 4,4'-diphenylmethane diisocyanate , Aromatic isocyanates such as 2,4-diphenylmethane diisocyanate, xylylene diisocyanate, cyclopentylene diisocyanate, cyclohexylene diisocyanate, isophorone diisocyanate, 4,4′-dicyclohexylmethane diisocyanate, methylcyclohexylene diisocyanate, 2,5- Examples thereof include alicyclic isocyanates such as norbornane diisocyanate and 2,6-norbornane diisocyanate, and multimers such as adduct type, isocyanurate type and burette type. These polyisocyanates can be used alone or in combination of two or more.

  Examples of the (meth) acrylate compound having a hydroxyl group and the (meth) acrylamide compound having a hydroxyl group include, for example, a hydroxyalkyl (meth) acrylate having a hydroxyalkyl group having 1 to 6 carbon atoms, 4-hydroxyphenyl (meta ) Acrylates, dialkylene glycol (meth) acrylates introduced with an alkylene glycol group having 1 to 6 carbon atoms, trialkylene glycol (meth) acrylates, polyalkylene glycol (meth) acrylates, glycerol mono (meth) acrylates, glycerol di ( (Meth) acrylate, N-hydroxyalkyl (meth) acrylamide introduced with a hydroxyalkyl group having 1 to 6 carbon atoms, N, N-di (hydroxyalkyl) (meth) acrylamide, N-hydroxyalkyl N- (4-hydroxyphenyl) (meth) acrylamide, N-alkyl-N-hydroxyalkyl (meth) acrylamide introduced with a hydroxyalkyl group having 1 to 6 carbon atoms and an alkyl group having 1 to 6 carbon atoms, N-alkyl-N- (4-hydroxyphenyl) (meth) acrylamide, 4-hydroxyphenyl (meth) acrylamide, N, N-di (4-hydroxyphenyl) (meth) acrylamide and the like are mentioned, and has a hydroxyl group. A (meth) acrylamide compound is preferable because of its high curability, and N- (2-hydroxyethyl) acrylamide is particularly preferable because of its low skin irritation (PII = 0) and high safety and easy handling.

  The active energy ray-curable resin composition (E) of the present invention is cured by irradiation with active energy rays. The active energy rays of the present invention are those having an energy quantum in electromagnetic waves or charged particle beams, that is, visible. It refers to light energy rays such as light, electron beam, ultraviolet ray, infrared ray, X ray, α ray, β ray, γ ray and the like. For example, radiation sources such as a high-pressure mercury lamp, a halogen lamp, a xenon lamp, a metal halide lamp, an LED lamp, an electron beam accelerator, and a radioactive element can be used. When an electron beam is used as the active energy ray source, it is usually unnecessary to contain a photoinitiator, but when another active energy ray source is used, a photopolymerization initiator (C) may be added. preferable. As the active energy ray to be irradiated, ultraviolet rays are preferable because of the storage stability, curing speed and low toxicity of the active energy ray-curable resin composition (E).

  Examples of the photopolymerization initiator (C) used in the present invention are ordinary ones such as acetophenone series, benzoin series, benzophenone series, α-aminoketone series, xanthone series, anthraquinone series, acylphosphine oxide series, and polymer photoinitiator series. May be selected as appropriate. For example, as acetophenones, diethoxyacetophenone, 2,2-dimethoxy-1,2-diphenylethane-1-one, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 1- (4- Isopropylphenyl) -2-hydroxy-2-methylpropan-1-one, 4- (2-hydroxyethoxy) -phenyl- (2-hydroxy-2-propyl) ketone, 1-hydroxycyclohexylphenylketone, 2-methyl- Examples of 1- (4-methylthiophenyl) -2-morpholinopropane-1 and benzoins include benzoin, α-methylbenzoin, α-phenylbenzoin, α-allylbenzoin, α-benzoylbenzoin, benzoin methyl ether, benzoin ethyl ether , Benzoin isopropyl ether, As zoin isobutyl ether, benzyldimethyl ketal, and benzophenones, benzophenone, benzoylbenzoic acid, methyl benzoylbenzoate, and α-aminoketones as 2-methyl-1- (4-methylthiophenyl) -2- (4-morpholinyl) ) -1-propanone, 2-benzyl-2- (dimethylamino) -1- (4- (4-morpholinyl) phenyl) -1-butanone, 2- (dimethylamino) -2- (4-methylphenyl) methyl As -1- (4- (4-morpholinyl) phenyl) -1-butanone and xanthones, xanthone, thioxanthone, and anthraquinones as anthraquinone, 2-methylanthraquinone, 2-ethylanthraquinone, and acylphosphine oxides Is bis (2,4,6-tri Tylbenzoyl) -phenylphosphine oxide, 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide, polymer photoinitiator includes 2-hydroxy-2-methyl-1- (4- (1-methylvinyl) And polymers of) phenyl) propan-1-one. These photopolymerization initiators can be used alone or in combination of two or more.

  When an active energy ray source other than an electron beam is used, the content of the photopolymerization initiator (C) is 0.1 to 5.0% by mass with respect to the entire active energy ray curable resin composition (E). preferable. When it is 0.1% by mass or more, the active energy ray-curable resin composition (E) is sufficiently polymerized by irradiation with active energy rays, and the amount of residual monomer in the resulting model material is small, and the cured product Have good tensile strength, elasticity and the like. When the amount is 5.0% by mass or less, the pot life of the active energy ray-curable resin composition (E) is long, and troubles such as gelation during storage do not occur. Furthermore, 0.5-3.0 mass% is more preferable.

The amount of active energy ray irradiation (integrated light amount) is not particularly limited. Depending on the type and amount of polyrotaxane (A) having an unsaturated group, compound (B) having an ethylenically unsaturated group, and photopolymerization initiator (C) used in the active energy ray-curable resin composition (E) Although it fluctuates, it is preferably 50 to 2000 mJ / cm ² . When the integrated light quantity is 50 mJ / cm ² or more, sufficient curing proceeds, the cured product has good tensile strength, elasticity, and the like, and when the integrated light quantity is 2000 mJ / cm ² or less, the active energy ray It is more preferable that the irradiation time is short, which leads to an improvement in productivity in addition production, hardly causes coloration with time of the obtained molded product, and is 100 to 1000 mJ / cm ² .

  The active energy ray-curable resin composition (E) of the present invention includes, as necessary, other components (D) such as a polyurethane resin, a polyester resin, a polyamide resin, a polyimide resin, a polyether resin, a polyvinyl acetate, an epoxy resin, Polymers such as polyacrylamide, starch, and carboxymethyl cellulose, various additives, and the like can be mixed and used. Additives include thermal polymerization inhibitors, antioxidants, antioxidants, UV sensitizers, preservatives, phosphate esters and other flame retardants, surfactants, wetting and dispersing materials, antistatic agents, and coloring agents. Plasticizers, surface lubricants, leveling agents, softeners, pigments, organic fillers, inorganic fillers, and the like can be added. The amount of addition of these other components (D) is not particularly limited as long as it does not adversely affect the characteristics expressed by the active energy ray-curable resin composition (E) according to the present invention, and is based on the whole (E) A range of 5% by mass or less is preferred.

  Examples of the thermal polymerization inhibitor include hydroquinone, p-methoxyphenol, 2,6-di-tert-butyl-p-cresol, 2,2,6,6-tetramethylpiperidine-1-oxyl, 4-hydroxy- 2,2,6,6-tetramethylpiperidine-1-oxyl, phenothiazine, pyrogallol, β-naphthol and the like can be mentioned.

  Examples of the anti-aging agent include hindered phenol-based compounds such as butylated hydroxytoluene and butylhydroxyanisole, benzotriazole-based compounds, and hindered amine-based compounds.

  Surfactants include, for example, nonylphenol polyethylene oxide adducts, lauric acid polyethylene oxide adducts, alkylene oxide addition nonionic surfactants such as stearic acid polyethylene oxide adducts, sorbitan palmitic acid monoester, sorbitan stearic acid monoester , Polyhydric alcohol type nonionic surfactant such as sorbitan stearic acid triester, acetylene glycol compound type nonionic surfactant, acetylene type polyalkylene glycol compound type nonionic surfactant, perfluoroalkyl polyethylene oxide adduct, Fluorine-containing surfactants such as perfluoroalkyl carboxylates and perfluoroalkyl betaines, polyether-modified silicone oils, (meth) acrylate-modified silicon Modified silicone oils such N'oiru, amphoteric polymeric surfactant (BYK chemie Japan Ltd., such as BYKJET-9150, BYKJET-9151) can be mentioned.

  The active energy ray-curable resin composition (E) of the present invention is preferably used for three-dimensional modeling by a photomolding method, and is used for a three-dimensional photomolding method that is ejected by an ink jet method and cured by irradiation with active energy rays. Is more preferable. From the viewpoint of stably discharging the active energy ray-curable resin composition (E), the liquid viscosity is preferably 1 to 100 mPa · s at 25 ° C., and the discharge temperature is preferably in the range of 20 to 80 ° C. When the discharge temperature is set to a high temperature, the liquid viscosity of the active energy ray-curable resin composition (E) decreases, and a high-viscosity resin composition can be discharged, but heat denaturation and polymerization tend to occur. Therefore, it is more preferable to discharge the active energy ray-curable resin composition (E) at a liquid viscosity at 25 ° C. of 80 mPa · s or less and at a temperature lower than 70 ° C. The liquid viscosity at 25 ° C. is more preferably 10 mPa · s or more in order to suppress the spread of the droplet after landing of the active energy ray-curable resin composition (E).

  The cured product of the active energy ray-curable resin composition (E) of the present invention can be suitably used as a model material for three-dimensional photomolding. The hardness Shore A of the cured product is 0 to 90, the elongation at break is preferably 100% or more, and the break strength is preferably 3 MPa or more. If the Shore A hardness is 0 or more, sufficient strength as a model material can be obtained, and if it is 90 or less, rubber properties rich in flexibility can be obtained. When it has a breaking elongation of 100% or more, it becomes possible to bend and elongate as a flexible model material, and when it has a breaking strength of 3 MPa or more, it is preferable because it is difficult to break when it is bent or stretched. More preferably, it has a breaking strength of 5 MPa or more.

  The three-dimensional photomolding of the active energy ray-curable resin composition (E) of the present invention by the ink jet method draws a predetermined shape pattern from the ink discharge nozzles of the fine droplets of (E) and irradiates the active energy rays. A method of forming a cured thin film is preferable. Moreover, a three-dimensional molding can be obtained by repeatedly repeating lamination and curing on the cured thin film.

  In manufacturing a three-dimensional modeled object by the three-dimensional stereolithography method of the present invention, a support material can be used to support the model material made of the active energy ray-curable resin composition (E) of the present invention. The support material to be used is not particularly limited, and examples thereof include a heat-meltable wax and resin, or a photocurable resin. However, a photocurable resin is preferable from the viewpoint that the model material can be formed simultaneously with an ink jet method. Furthermore, as the support material, a cured product having a water-soluble property, a water-dispersible property, or a water-swellable property is more preferable because it is easy to peel from the model material.

  Examples of the heat-melting wax and resin include waxes such as paraffin wax, microcrystalline wax, carbana wax, ester wax and amide wax, and polymers such as polyethylene glycol and low-melting crystalline polyester resin. It is not limited.

  As a photocurable, water-soluble, water-dispersible or water-swellable cured product, for example, a support material AR-S1 (manufactured by Keyence Co., Ltd.) used in Keyence AGLISTA, a support material used in Objet made by Stratasys Examples thereof include SUP707 and SUP705 (manufactured by Stratasys Ltd.), but are not particularly limited.

  EXAMPLES Hereinafter, although an Example and a comparative example are given and this invention is demonstrated further more concretely, this invention is not limited to these Examples. In the following, “part” and “%” are all based on mass unless otherwise specified.

  Polyrotaxanes (A-1) to (A-4) were used after the solvent was distilled off from the commercially available product of Celm Superpolymer (manufactured by Admanst Soft Materials) and dried. Their physical property values are shown in Table 1.

  The monofunctional unsaturated compound (b1) comprises (b1-1) isobornyl acrylate (Tg 94 ° C.), (b1-2) 1,4-cyclohexanedimethanol monoacrylate (Tg = 18 ° C.), ( b1-3) acroylmorpholine (Tg = 145 ° C.), (b1-4) diethyl acrylamide (Tg = 81 ° C.), (b1-5) cyclohexyl acrylate (Tg = 15 ° C.), (b1-6) N- (2-hydroxyethyl) acrylamide (Tg = 98 ° C.) was used.

  The monofunctional unsaturated compound (b2) has methoxydipropylene glycol acrylate (Tg = −44 ° C.) as (b2-1), methoxytriethylene glycol acrylate (Tg = −50 ° C.) as (b2-2), ( b2-3) as methoxypolyethylene glycol acrylate (polyethylene glycol average molecular weight 400) (Tg = −71 ° C.), (b2-4) as phenoxyethyl acrylate (Tg = −22 ° C.), and (b2-5) as methyl acrylate Isostearyl acrylate (Tg = −18 ° C.) was used as (Tg = 8 ° C.) and (b2-6).

  Tricyclodecane dimethanol diacrylate (trade name “A-DCP” manufactured by Shin-Nakamura Chemical Co., Ltd.) as the polyfunctional unsaturated compound (b3-1), and ditrimethylolpropane tetraacrylate (trade name) as (b3-3) “AD-TMP” manufactured by Shin-Nakamura Chemical Co., Ltd.) and 1,6-hexanediol diacrylate (trade name “A-HD-N” manufactured by Shin-Nakamura Chemical Co., Ltd.) were used as (b3-4).

Production Example 1 Production of Polyfunctional Unsaturated Compound (b3-2) Polydimethylsiloxane having a terminal hydroxyl group having a hydroxyl value of 120 mgKOH / g and a number average molecular weight of 930 in a 300 mL Separ flask equipped with a stirrer, thermometer and reflux condenser. Brand name Shin-Etsu Silicone KF-6000: manufactured by Shin-Etsu Chemical Co., Ltd.) 100.0 g, trilene diisocyanate 27.9 g and dibutyltin dilaurate 0.04 g as a catalyst were added, and the mixture was stirred at 60 ° C. while stirring in a nitrogen atmosphere. Reacted for hours. Further, 13.5 g of N- (2-hydroxyethyl) acrylamide, 0.20 g of methylhydroquinone as a polymerization inhibitor and 0.02 g of dibutyltin dilaurate as a catalyst were added to this reaction product, and reacted at 60 ° C. for 2 hours. Thereafter, the reaction vessel was cooled, and it was confirmed by IR measurement that the absorption peak of the isocyanate group at 2230 cm ⁻¹ disappeared. The polyfunctional unsaturated compound (b3-2) which is polyurethane diacrylamide having a number average molecular weight of 2,800 )

Production Example 2 Production of Polyfunctional Unsaturated Compound (b3-5) Polytetratetrahydrofuran having a hydroxyl group value of 112 mgKOH / g and a terminal hydroxyl group having a number average molecular weight of 1,000 in a 300 mL Separ flask equipped with a stirrer, thermometer and reflux condenser 100.0 g of methylene glycol, 33.3 g of isophorone diisocyanate and 0.04 g of dibutyltin dilaurate as a catalyst were added, and the mixture was reacted at 80 ° C. for 4 hours with stirring in a nitrogen atmosphere. Furthermore, 11.6 g of 2-hydroxyethyl acrylate, 0.01 g of methylhydroquinone as a polymerization inhibitor and 0.02 g of dibutyltin dilaurate as a catalyst were added to this reaction system, reacted at 80 ° C. for 3 hours, and measured by IR measurement to 2230 cm ^−. It was confirmed that the absorption peak of ¹ isocyanate group disappeared. Thereafter, the reaction vessel was cooled to obtain a polyfunctional unsaturated compound (b3-5) which is a polyurethane diacrylate having a number average molecular weight of 1,800.

Production Example 3 Production of Polyfunctional Unsaturated Compound (b3-6) Polypropylene glycol having a terminal hydroxyl group with a hydroxyl value of 112 mgKOH / g and a number average molecular weight of 1,000 in a 300 mL Separa flask equipped with a stirrer, thermometer and reflux condenser 100.0 g, 26.1 g of tolylene diisocyanate and 0.04 g of dibutyltin dilaurate as a catalyst were added and reacted at 60 ° C. for 3 hours with stirring in a nitrogen atmosphere. Further, 12.2 g of N- (2-hydroxyethyl) acrylamide, 0.20 g of methylhydroquinone as a polymerization inhibitor and 0.02 g of dibutyltin dilaurate as a catalyst were added to this reaction product, reacted at 60 ° C. for 2 hours, IR It was confirmed by measurement that the absorption peak of the isocyanate group at 2230 cm ⁻¹ disappeared. Thereafter, the reaction vessel was cooled to obtain a polyfunctional unsaturated compound (b3-6) which is polyurethane diacrylamide having a number average molecular weight of 2,500.

Production Example 4 Production of polyfunctional unsaturated compound (b3-7) Polycarbonate diol having a hydroxyl value of 224 mgKOH / g and a terminal hydroxyl group with a number average molecular weight of 500 in a 300 mL Separ flask equipped with a stirrer, thermometer and reflux condenser Name Kuraray polyol C-590: manufactured by Kuraray Co., Ltd.) 100.0 g, isophorone diisocyanate 88.8 g and dibutyltin dilaurate 0.04 g as a catalyst were added and reacted at 60 ° C. for 3 hours while stirring in a nitrogen atmosphere. Further, 48.8 g of N- (2-hydroxyethyl) acrylamide, 0.20 g of methylhydroquinone as a polymerization inhibitor and 0.02 g of dibutyltin dilaurate as a catalyst were added to this reaction product, reacted at 60 ° C. for 2 hours, IR It was confirmed by measurement that the absorption peak of the isocyanate group at 2230 cm ⁻¹ disappeared. Thereafter, the reaction vessel was cooled to obtain a polyfunctional unsaturated compound (b3-7) which is polyurethane diacrylamide having a number average molecular weight of 1,200.

Production Example 5 Production of polyfunctional unsaturated compound (b3-8) Caprolactone-modified hydroxyethyl acrylate (trade name PLACCEL FA4D: manufactured by Daicel Chemical Industries, Ltd.) 100 in a 300 mL Separ flask equipped with a stirrer, thermometer, and reflux condenser 1.0 g, 0.01 g of methylhydroquinone as a polymerization inhibitor, 64.0 g of isocyanurate type isophorone diisocyanate (trade name VESTANAT T1890: manufactured by Degussa Japan Co., Ltd.) and 0.02 g of dibutyltin dilaurate as a catalyst were added and stirred in a nitrogen atmosphere. The reaction was carried out at 80 ° C. for 12 hours. It was confirmed by IR measurement that the absorption peak of the isocyanate group at 2230 cm ⁻¹ disappeared. Thereafter, the reaction vessel was cooled to obtain a trifunctional compound (b3-8).

Molecular weight measurement The number average molecular weight of the obtained polyfunctional unsaturated compounds (b3-2), (b3-5), (b3-6), and (b3-7) was measured by high performance liquid chromatography (manufactured by Shimadzu Corporation). Using LC-10A, the column was Shodex GPC KF-806L (exclusion limit molecular weight: 2 × 10 ⁷ , separation range: 100 to 2 × 10 ⁷ , theoretical plate number: 10,000 plates / bar, packing material: styrene- Divinylbenzene copolymer, filler particle size: 10 μm), and tetrahydrofuran was used as the eluent.), And calculated in terms of standard polystyrene molecular weight.

Example 1 Preparation of Active Energy Ray-Curable Resin Composition (E-1) 19.5 parts by mass of an acrylic group-introduced polyrotaxane (A1-1), 40.0 parts by mass of isobornyl acrylate (b1-1), methoxy Dipropylene glycol acrylate (b2-1) 40.0 parts by mass, IRGACURE 184 (1-hydroxycyclohexyl phenyl ketone (manufactured by BASF Japan Ltd.)) (C-1) 0.5 parts by mass are respectively charged in a container at 25 ° C. By stirring for 1 hour, a uniform transparent active energy ray-curable resin composition (E-1) of Example 1 was obtained.

Examples 2 to 9 Preparation of active energy ray-curable resin compositions (E-2) to (E-9) Examples 2 to 9 were carried out in the same manner as in Example 1 with the compositions shown in Table 2. The active energy ray-curable resin compositions (E-2) to (E-9) corresponding to the above were obtained.

Comparative Examples 1-9 Preparation of Active Energy Ray Curable Resin Compositions (F-1) to (F-9) Comparative Examples 1-9 were carried out in the same manner as in Example 1 with the compositions shown in Table 2. The active energy ray-curable resin compositions (F-1) to (F-9) corresponding to the above were obtained. Here, Comparative Example 8 is Example 7 described in Patent Document 3 (Japanese Patent Laid-Open No. 2015-0778255), and Comparative Example 9 is Example 1-6 described in Patent Document 2 (Japanese Patent Laid-Open No. 2012-111226). Was referenced.

Explanation of abbreviations in Table 2 C: Photopolymerization initiator C-1: 1-hydroxycyclohexyl phenyl ketone (IRGACURE184, manufactured by BASF Japan Ltd.)
C-2: 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide (IRGACURE-TPO, manufactured by BASF Japan Ltd.)
C-3: 1-hydroxycyclohexyl phenyl ketone / benzophenone = 1/1 mixture (IRGACURE-500, manufactured by BASF Japan Ltd.)
D: Other components D-1: Polyethylene glycol having a number average molecular weight of 2,000 (PEG 2000, manufactured by Toho Chemical Industry Co., Ltd.)
D-2: Polydimethylsiloxane having a terminal hydroxyl group having a hydroxyl value of 22 mgKOH / g (trade name: Shin-Etsu Silicone KF-6003: manufactured by Shin-Etsu Chemical Co., Ltd.)
D-3: Polyether-modified silicone oil (trade name TSF-4442: manufactured by Momentive Performance Materials Japan GK)

  Evaluation using the active energy ray-curable resin composition for forming the support material obtained in Examples 1 to 9 and Comparative Examples 1 to 9 was carried out by the following method, and the results are shown in Table 3.

Viscosity measurement Cone plate type viscometer (device name: RE550 type viscometer manufactured by Toki Sangyo Co., Ltd.) was used and obtained in each example and comparative example at 25 ° C. according to JIS K5600-2-3. The liquid viscosity of the active energy ray-curable resin composition was measured.

Measurement of rubber hardness of the cured product A 75 μm thick heavy release PET film (polyester film E7001 manufactured by Toyobo Co., Ltd.) was adhered to a horizontally placed glass plate, and a spacer with a thickness of 1 mm and an interior of 60 mm × 90 mm was installed. After filling the inside of the spacer with the active energy ray-curable resin composition obtained in each Example and Comparative Example, a 50 μm-thick lightly peeled PET film (polyester film E7002 manufactured by Toyobo Co., Ltd.) is further formed thereon. , And irradiated with ultraviolet rays (apparatus: manufactured by Eye Graphics, inverter type conveyor device ECS-4011GX, metal halide lamp: M04-L41 manufactured by Eye Graphics, ultraviolet illuminance of 300 mW / cm ² , integrated light quantity 1000 mJ / cm ² ) and activated The energy ray curable resin composition was cured. Thereafter, six cured products prepared by removing the peeled PET films on both sides were stacked, and the Shore A hardness was measured according to JIS K6253 “Rubber Hardness Test Method”. Moreover, when Shore A hardness was larger than 90, it measured by Shore D hardness.

Measurement of elongation at break and strength at break of cured product A 75 μm-thick heavy release PET film (made by Toyobo Co., Ltd., polyester film E7001) was adhered to a horizontally placed glass plate, 2 mm thick, and 60 mm × 100 mm inside. The spacer was filled with the active energy ray-curable resin composition obtained in each Example and Comparative Example inside the spacer, and then a 50 μm-thick lightly peeled PET film (manufactured by Toyobo Co., Ltd.) , Polyester film E7002) and ultraviolet irradiation (apparatus: manufactured by iGraphics, inverter type conveyor device ECS-4011GX, metal halide lamp: M04-L41 manufactured by igraphics, ultraviolet illuminance of 300 mW / cm ² , integrated light quantity of 1000 mJ / cm ^2), curing the active energy ray curable resin composition It was. Thereafter, the elongation and strength of the cured product prepared by removing the peeled PET films on both sides were measured according to JIS K6732. The cured product was punched into a dumbbell shape in accordance with JIS K6732, and used as a test piece. The tensile elongation at break and the breaking strength of the test piece were measured using a tensile compression tester (Tensilon RTC-1250A manufactured by Orientec Co., Ltd.) The measurement was performed under conditions of a tensile speed of 50 mm / min and a distance between chucks of 100 mm under a temperature environment of 25 ° C.
Breaking elongation rate of cured product ◎: Breaking elongation rate of 200% or more ○: Breaking elongation rate of 100% or more and less than 200% Δ: Breaking elongation rate of 50% or more and less than 100% x: Breaking elongation rate of less than 50% Rupture strength ◎: rupture strength of 5 MPa or more ◯: rupture strength of 3 MPa or more and less than 5 MPa Δ: rupture strength of 1 MPa or more and less than 3 MPa × break strength of less than 1 MPa

Table 3

As is apparent from the results in Table 3, the active energy ray-curable resin compositions (E) of Examples 1 to 9 have a liquid viscosity of 100 mPa · s or less at 25 ° C., and are excellent in operability. Inkjet aptitude was shown. Further, it was curable with an integrated light quantity of 1000 mJ / cm ² or less even in the air, and showed excellent curability. The cured products obtained by curing the active energy ray-curable resin composition (E) all show a rubber hardness of Shore A 0 to 90, a good elongation of 100% or more, and a good breaking strength of 3 MPa or more. It was a resin suitable as a model material having both flexibility and toughness.

  When the polyrotaxane (A) having an unsaturated group is not included, the polyfunctional unsaturated compound (b3) has a low liquid viscosity of the resin composition in Comparative Example 1 using a low molecular weight crosslinking agent, and has good ink jet aptitude. As shown, the elongation of the cured product was low. On the other hand, the polyfunctional unsaturated compound (b3) in Comparative Example 2 using a high molecular weight crosslinking agent had good hardness, elongation and breaking strength of the cured product, but the liquid viscosity was high. Not applied. Moreover, in the comparative example 3 which contains the polyrotaxane (A) which has an unsaturated group excessively, although hardness, elongation rate, and breaking strength of hardened | cured material were satisfied, liquid viscosity was high. When the polyrotaxane (A) content was insufficient, in Comparative Example 4 not containing the polyfunctional unsaturated compound (b3), the liquid viscosity was low, but it was low with the elongation and breaking strength of the obtained cured product. . Therefore, based on the composition of Comparative Example 4, the polyfunctional unsaturated compound (b3) was added (Comparative Example 5), but the breaking strength was improved, but the elongation and breaking strength were still insufficient. It was in a state. In Comparative Example 6 where the content of the monofunctional unsaturated compound (b1) having a Tg of 10 ° C. or higher was small, a soft cured product was obtained, but the elongation rate and breaking strength of the cured product were low. On the contrary, in Comparative Example 7 in which (b1) is excessively contained, the elongation percentage of the cured product was insufficient. Further, in Comparative Example 8 of the present invention corresponding to Example 7 described in Patent Document 3 (Japanese Patent Application Laid-Open No. 2015-0778255), the liquid viscosity is 10 mPa · s, showing good ink jet aptitude, and flexible rubber-like curing. Although a polyrotaxane (A) having an unsaturated group was not contained, the addition amount of the polyfunctional unsaturated compound (b3) corresponding to the crosslinking agent was low, and the monofunctional having a Tg of 10 ° C. or higher Since only 5% of the unsaturated compound (b1) was contained, the cohesive strength of the cured product was low, and only a cured product having a low breaking strength and low elongation could be obtained. Comparative Example 9 of the present invention corresponding to Example 1-6 described in Patent Document 2 (Japanese Patent Application Laid-Open No. 2012-111226) had good inkjet suitability and curability, but the hardness of the cured product was high. Since it did not stretch, it lacked flexibility.

  From these facts, containing 1.0 to 20.0% by mass of the polyrotaxane (A) having an unsaturated group suppresses an increase in liquid viscosity, and an active energy ray-curable resin having good operability in ink jet printing. A composition (E) can be obtained. In addition, the cured product of the active energy ray-curable resin composition (E) exhibits high elongation and high breaking strength due to the mobility of the introduced polyrotaxane at the cross-linking point, and exhibits an unprecedented flexibility and toughness. Model material was obtained.

  As described above, the active energy ray-curable resin composition of the present invention can be suitably used for forming a model material for addition production. Further, since the active energy ray-curable resin composition has a low liquid viscosity and excellent operability, it can be suitably used for addition production by inkjet. Furthermore, the hardened | cured material of the active energy ray-curable resin composition of this invention can be used as a model material which has a softness | flexibility and toughness, and can be utilized for a flexible three-dimensional molded item.

Claims (5)

Having a polyrotaxane (A) 1.0 to 20.0% by weight having an ethylenically unsaturated group and a compound having an ethylenically unsaturated group (excluding (A)) (B) 80.0~99.0 wt% be an active energy ray curable resin composition, the polyrotaxane (a) consists of linear molecules clathrate cyclic molecules and cyclic molecules skewered shape, with a compound having a cyclic molecule having an ethylenically unsaturated group The compound (B) having an ethylenically unsaturated group is a compound (b1) having an ethylenically unsaturated group having a glass transition temperature (Tg) of 10 ° C. or higher of the homopolymer; compounds having an ethylenically unsaturated group of the glass transition temperature (Tg) of less than 10 ° C. the polymer (b2) 0-60.0 wt%, and poly as compound (b3) having a plurality of ethylenically unsaturated groups Retanji (meth) acrylamide 2-25.0 actinic radiation-curable resin composition, which is a mass%. 2. The active energy ray-curable resin composition according to claim 1, wherein the polyurethane di (meth) acrylamide has a number average molecular weight of 400 to 20000. The photocurable ink containing the active energy ray curable resin composition of Claim 1 or Claim 2 used for the three-dimensional photomolding method by an inkjet system. A model material obtained by curing the photocurable ink according to claim 3 with an active energy ray. A three-dimensional structure using the model material according to claim 4 .