WO2019230132A1

WO2019230132A1 - Photo-fabrication composition set

Info

Publication number: WO2019230132A1
Application number: PCT/JP2019/010942
Authority: WO
Inventors: 浩史太田; 圭介奥城
Original assignee: マクセルホールディングス株式会社
Priority date: 2018-05-29
Filing date: 2019-03-15
Publication date: 2019-12-05
Also published as: JP2021130724A

Abstract

The present invention relates to a photo-fabrication composition set that is for use in material jet photo-fabrication and includes a model material composition and a support material composition. The model material composition includes a monofunctional monomer (A) and a polyfunctional monomer (B) that has, in the molecule thereof, a plurality of polymerizable functional groups that include a carbon-carbon double bond. The molar fractions (monofunctional monomer (A)/polyfunctional monomer (B)) of the monofunctional monomer (A) and the polyfunctional monomer (B) are 99.9/0.1–92/8. The monofunctional monomer (A) contains, relative to the total mass of the monofunctional monomer (A), at least 85 mass% of a (meth)acrylate (A1) that has a molecular weight of at least 150 but less than 400 and, as a homopolymer, has a glass transition temperature of 5°C or lower. The support material composition contains, relative to 100 parts by mass of the support material composition, 15–75 parts by mass of a polyalkylene glycol (a) that includes an oxybutylene group and has a weight average molecular weight of at least 300, 19–80 parts by mass of a water-soluble monofunctional ethylenically unsaturated monomer (b), and a photopolymerization initiator.

Description

Stereolithography composition set

The present invention relates to an optical modeling composition set in which a composition for a model material and a composition for a support material used in a material jet optical modeling method are combined, and a method for manufacturing an optical modeling object using the same.

An optical molding method (hereinafter referred to as “the material jet (inkjet) method) for forming a cured layer having a predetermined shape by discharging a photocurable resin composition from a nozzle and immediately irradiating it with ultraviolet rays or the like to cure. Also known as “material jet stereolithography”. The material jet stereolithography has been attracting attention as a modeling method realized by a 3D printer that can freely create a three-dimensional model based on CAD (Computer Aided Design) data.

The material jet stereolithography method is easy to model complex shapes compared to the conventional method of obtaining stereolithography by irradiating a liquid photocurable composition with light, curing the irradiated part, and laminating it. . In addition, since the amount of the photocurable composition required is small and there are merits such as easy adjustment of mechanical properties by simultaneously emitting photocurable compositions with different properties from multiple nozzles, various prototypes are available. Used for applications.

In recent years, there has been an increasing demand for trial applications using rubber-like materials, and it is used for material jet stereolithography, which has rubber-like elongation and elasticity, and has excellent dimensional stability over time. Various model material compositions that can be produced have been proposed (Patent Documents 1 to 3).

JP2015-78255A International Publication No. 2015/056614 International Publication No. 2015/049873

The model material composition is usually used in the material jet stereolithography together with the support material composition. In recent years, from the viewpoint of handling and environment, a water-soluble composition for a support material has been developed, and the above-mentioned patent document also describes a composition for a model material described in the document as a water-soluble composition for a support material. It is described that it can be used in combination with a product. However, the conventionally widely known composition for a support material as exemplified in the above-mentioned patent document contains a water-soluble polymer such as polypropylene glycol having high hydrophilicity. Depending on the type and content of the contained components, the support material obtained may be less self-supporting, so that there is a problem in that the dimensional accuracy of an optically shaped product formed using such a support material composition decreases. It was. In particular, a model material formed from a composition for a model material having elongation and elasticity such as rubber tends to decrease in dimensional accuracy, and the composition accuracy for the support material to be combined easily has a large influence on the modeling accuracy. .

Therefore, the present invention proposes a combination of a composition for a model material having elongation and elasticity like rubber, and a composition for a support material having both high support power and excellent water removability for the model material composition. And it aims at providing the composition set for optical modeling which can model the optical modeling thing which has elongation and elasticity like rubber | gum with high precision.

As a result of intensive studies to solve the above problems, the present inventors have completed the present invention. That is, the present invention provides the following preferred embodiments.
[1] A composition set for stereolithography used in a material jet stereolithography method comprising a composition for model material and a composition for support material,
The composition for a model material comprises a monofunctional monomer (A) and a polyfunctional monomer (B) having a plurality of polymerizable functional groups containing a carbon-carbon double bond in the molecule, and the monofunctional monomer The molar fraction of (A) and the polyfunctional monomer (B) (monofunctional monomer (A) / polyfunctional monomer (B)) is 99.9 / 0.1 to 92/8,
As the monofunctional monomer (A), a (meth) acrylate (A1) having a molecular weight of 150 or more and less than 400 and having a glass transition temperature of 5 ° C. or less as a homopolymer is used as the monofunctional monomer (A). Contains 85% by mass or more based on the total mass,
The support material composition is based on 100 parts by mass of the support material composition.
15 parts by mass or more and 75 parts by mass or less of a polyalkylene glycol (a) containing an oxybutylene group and having a weight average molecular weight of 300 or more,
19 parts by weight or more and 80 parts by weight or less of a water-soluble monofunctional ethylenically unsaturated monomer (b), and
A composition set for optical modeling containing a photopolymerization initiator.
[2] The composition set for stereolithography according to [1], wherein the glass transition temperature of the cured product of the composition for model material is 5 ° C. or lower.
[3] The polymerizable functional group which the polyfunctional monomer (B) constituting the composition for model material has is selected from the group consisting of an acryl group, a methacryl group, a vinyl ether group and an allyl ether group, [1] or The composition set for stereolithography according to [2].
[4] The composition set for stereolithography according to any one of [1] to [3], wherein the composition for model material contains two or more kinds of the (meth) acrylates (A1).
[5] The composition set for optical modeling according to any one of [1] to [4], wherein the composition for a model material further contains a photopolymerization initiator.
[6] The composition set for optical modeling according to any one of [1] to [5], wherein the composition for a model material has a viscosity at 25 ° C. of 150 mPa · s or less.
[7] The content of the photopolymerization initiator in the composition for support material is 1 part by mass or more and 15 parts by mass or less with respect to 100 parts by mass of the composition for support material. The composition set for stereolithography in any one.
[8] The composition for a support material further contains a surface conditioner in an amount of 0.005 parts by mass to 3 parts by mass with respect to 100 parts by mass of the composition for a support material. The composition set for optical modeling according to crab.
[9] The support material composition contains a water-soluble organic solvent, and the content of the water-soluble organic solvent is 30 parts by mass or less with respect to 100 parts by mass of the support material composition. [8] The composition set for optical modeling according to any one of [8].
[10] The composition set for stereolithography according to any one of [1] to [9], wherein the composition for support material further contains a storage stabilizer.
[11] A model material obtained by photocuring the model material composition contained in the composition set for optical modeling according to any one of [1] to [10] by a material jet stereolithography method, Stereolithography.
[12] A method for producing an optically shaped article by a material jet stereolithography method using the optical shaping composition set according to any one of [1] to [10],
A step (I) of obtaining a model material by photocuring the composition for model material, and obtaining a support material by photocuring the composition for support material; and
Step (II) for removing the support material
A method for producing an optically shaped object.

According to the present invention, it is possible to provide an optical modeling composition set capable of modeling an optical modeling object having elongation and elasticity like rubber with high accuracy.

It is a schematic side view which shows the state which ejects the composition for model materials and the composition for support materials in the manufacturing method of the optical modeling thing which concerns on this embodiment, and has irradiated the energy beam. It is a schematic side view which shows the state which is discharging the composition for model materials and the composition for support materials in the manufacturing method of the optical modeling thing which concerns on this embodiment. It is a schematic side view which shows the state which has irradiated the energy beam to the composition for model materials and the composition for support materials in the manufacturing method of the optical modeling thing which concerns on this embodiment. It is a model side view of the optical modeling product precursor (optical modeling thing) which consists of a support material and a model material. It is a model side view of a stereolithography product.

Hereinafter, the present invention will be described with reference to embodiments, but the present invention is not limited to the following embodiments.

<Model material composition>
The optical modeling composition set of the present invention includes a model material composition. The composition for a model material included in the optical modeling composition set of the present invention includes a monofunctional monomer (A) and a polyfunctional monomer (B) having a plurality of polymerizable functional groups containing carbon-carbon double bonds in the molecule. ).

The monofunctional monomer (A) is a component having a property of being polymerized and cured by irradiation with active energy rays such as ultraviolet rays, and is a polymerizable compound having one radical polymerizable group in the molecule. The radically polymerizable group possessed by the monofunctional monomer (A) includes (meth) acryl group, vinyl ether group, allyl ether group, styrene group, (meth) acrylamide group, acetyl vinyl group, vinyl amide group and other ethylene groups and acetylene groups. Etc. In the present invention, “(meth) acrylate” is a general term for acrylate and methacrylate, and means one or both of acrylate and methacrylate. The same applies to “(meth) acryloyl”, “(meth) acryl” and the like.

In the present invention, the composition for a model material is a (meth) acrylate (A1) having a molecular weight of 150 or more and less than 400 as a monofunctional monomer (A) and a glass transition temperature of 5 ° C. or less as a homopolymer. Containing. When the model material composition contains (meth) acrylate (A1), the model material (photofabricated product) obtained by curing the model material composition is imparted with rubber-like elongation and elasticity. Can do.

(Meth) acrylate (A1) has a glass transition temperature of 5 ° C. or lower when it is a homopolymer. When the glass transition temperature is not more than the above upper limit, rubber-like properties can be imparted to the model material obtained by photocuring the clear composition for model material. The lower limit of the glass transition temperature in (meth) acrylate (A1) is not particularly limited, but is usually −55 ° C. or higher, preferably −50 ° C. or higher.

Specific examples of the (meth) acrylate (A1) having the above molecular weight and glass transition temperature include isoamyl acrylate, lauryl (meth) acrylate, octyl acrylate, isooctyl (meth) acrylate, isononyl acrylate, decyl acrylate, and isodecyl acrylate. , Tridecyl (meth) acrylate, isomyristyl acrylate, isostearyl acrylate, 2-ethylhexyl acrylate, 2-ethylhexyl-diglycol acrylate, 4-hydroxybutyl acrylate, methoxydiethylene glycol acrylate, methoxytriethylene glycol acrylate, ethoxydiethylene glycol acrylate, 2- (2-Ethoxyethoxy) ethyl acrylate, 2-ethylhexylcal Tall acrylate, phenoxyethyl acrylate, phenoxyethyl ethoxyethyl acrylate.

Content of the said (meth) acrylate (A1) in a composition for model materials is 85 mass% or more with respect to the total mass of the monofunctional monomer (A) which the composition for model materials contains, Preferably it is 90 mass%. That's it. When the content of (meth) acrylate (A1) is 85% by mass or more, dimensional stability can be improved while imparting sufficient rubber-like properties to the obtained model material. In the present invention, the upper limit of the content of (meth) acrylate (A1) contained in the model material composition is not particularly limited, and all of the monofunctional monomer (A) (that is, 100% by mass with respect to the total mass). (Meth) acrylate (A1) may be used, but from the viewpoint of imparting elasticity, it is, for example, 98% by mass or less, and preferably 95% or less.

The composition for model material may contain only one kind of (meth) acrylate (A1). However, the model material composition has a dimensional stability by accelerating stress relaxation that causes a range of curing speed and causes curing shrinkage. Since improvement can be expected, it is preferable to contain two or more (meth) acrylates (A1).

In the present invention, the model material composition may contain a monofunctional monomer other than (meth) acrylate (A1). Examples of such other monofunctional monomers include (meth) acrylates (A2) other than the (meth) acrylate (A1), such as methyl (meth) acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, and pentyl. Acrylate, n-stearyl acrylate, cyclohexyl acrylate, benzyl acrylate, 2- (meth) acryloyloxyethyl hexahydrophthalic acid, butoxyethyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, isobornyl (meth) acrylate, methoxyethyl acrylate 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 2-hydroxy-3-phenyl Kishipuropiru (meth) acrylate, 2- (meth) acryloyloxyethyl phthalate, 2- (meth) acryloyloxyethyl-2-hydroxyethyl - phthalic acid, such as t- butyl cyclohexyl (meth) acrylate.

The other monofunctional monomer includes a monofunctional monomer having a vinyl ether group, a monofunctional monomer having an allyl ether group, a monofunctional monomer having an acetyl vinyl group, a monofunctional monomer having a (meth) acrylamide group, and a vinylamide group. It may be a monofunctional monomer having, a monofunctional monomer having an acetylene group, or the like.

Examples of the monofunctional monomer having a vinyl ether group include butyl vinyl ether, butyl propenyl ether, butyl butenyl ether, hexyl vinyl ether, ethyl hexyl vinyl ether, phenyl vinyl ether, benzyl vinyl ether, ethyl ethoxy vinyl ether, acetyl ethoxy ethoxy vinyl ether, cyclohexyl vinyl ether, and adamantyl vinyl ether. Etc.

Monofunctional monomers having an allyl ether group include, for example, phenyl allyl ether, o-, (m-, p-cresol monoallyl ether, biphenyl-2-ol monoallyl ether, biphenyl-4-ol monoallyl ether, butyl Examples include allyl ether, cyclohexyl allyl ether, and cyclohexane methanol monoallyl ether.

Examples of the monofunctional monomer having an acetyl vinyl group include vinyl acetate. Examples of the monofunctional monomer having a (meth) acrylamide group include acrylamide, N, N-dimethylacrylamide, N-isopropylacrylamide, and methacrylamide. Examples of the monofunctional monomer having a vinylamide group include N-vinyl-ε-caprolactam, N-vinylformamide, N-vinylpyrrolidone and the like. Examples of the monofunctional monomer having an acetylene group include acetylene.

The polyfunctional monomer (B) is a component having a property of being polymerized and cured by irradiation with active energy rays such as ultraviolet rays, and has a polymerizable property having a plurality of polymerizable functional groups containing carbon-carbon double bonds in the molecule. Monomer. Examples of the polymerizable functional group containing a carbon-carbon double bond of the polyfunctional monomer (B) include a (meth) acryl group, a vinyl ether group, an allyl ether group, a styrene group, and a (meth) acrylamide group. Especially, since photopolymerization sensitivity becomes favorable, it is preferable that a polyfunctional monomer (B) contains the polymerizable functional group selected from the group which consists of an acryl group, a methacryl group, a vinyl ether group, and an allyl ether group. The polymerizable functional groups containing a plurality of carbon-carbon double bonds in the molecule may be the same as or different from each other. As a polyfunctional monomer (B), only 1 type may be used independently and you may use in combination of multiple types.

As polyfunctional (meth) acrylate, for example,
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, neopentyl glycol di (meth) acrylate, dimethylol-tricyclodecane di (meth) acrylate, bisphenol A bifunctional monomer such as PO adduct di (meth) acrylate of A, neopentyl glycol di (meth) acrylate hydroxypivalate, poly (tetramethylene glycol di (meth) acrylate);
Trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol hexa (meth) acrylate, ditrimethylolpropane tetra (meth) acrylate, glycerin propoxytri (meth) acrylate And trifunctional or higher polyfunctional monomers such as pentaerythritol ethoxytetra (meth) acrylate.

The (meth) acrylate compound may be a modified product. Examples of modified products include ethylene oxide-modified (meth) acrylate compounds such as ethylene oxide-modified trimethylolpropane tri (meth) acrylate and ethylene oxide-modified pentaerythritol tetraacrylate; caprolactone such as caprolactone-modified trimethylolpropane tri (meth) acrylate Modified (meth) acrylate compounds; and caprolactam-modified (meth) acrylate compounds such as caprolactam-modified dipentaerythritol hexa (meth) acrylate.

The polyfunctional vinyl ether compound may be difunctional, trifunctional, tetrafunctional or higher.
Examples of the bifunctional vinyl ether include 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, neopentyl glycol divinyl ether, and cyclohexane. Examples thereof include diol divinyl ether, cyclohexane dimethanol divinyl ether, norbornyl dimethanol divinyl ether, isovinyl divinyl ether, divinyl resorcin, and divinyl hydroquinone.
Examples of the trifunctional vinyl ether include glycerin trivinyl 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), and the like. included. Examples of tetrafunctional or higher functional vinyl ethers include pentaerythritol trivinyl ether, ditrimethylolpropane hexavinyl ether, and their oxyethylene adducts.

The polyfunctional allyl ether may be difunctional, trifunctional or higher.
Examples of the bifunctional allyl ether include 1,4-cyclohexanedimethanol diallyl ether, alkylene (2 to 5 carbon atoms) glycol diallyl ether, and polyethylene glycol (weight average molecular weight: 100 to 4000) diallyl ether. Further, glyceryl diallyl ether, trimethylolpropane diallyl ether, pentaerythritol diallyl ether, polyglycerol (degree of polymerization 2 to 5) diallyl ether and the like can be mentioned.
Examples of the trifunctional or higher functional allyl ether include trimethylolpropane triallyl ether, glyceryl triallyl ether, pentaerythritol tetraallyl ether, and tetraallyloxyethane. Further, pentaerythritol triallyl ether, diglycerin triallyl ether, sorbitol triallyl ether, polyglycerin (degree of polymerization 3 to 13) polyallyl ether and the like can be mentioned.

Furthermore, examples of other polyfunctional monomers include diallyl phthalate, diallyl isophthalate, divinylbenzene, and N, N-ethylenebisacrylamide.

In the present invention, the molar fraction (monofunctional monomer (A) / polyfunctional monomer (B)) of the monofunctional monomer (A) and the polyfunctional monomer (B) contained in the model material composition is 99.9 / It is preferably 0.1 to 92/8. When the molar fraction of the content of the monofunctional monomer (A) and the content of the polyfunctional monomer (B) is within the above range, the polyfunctional monomer (B) functions as a crosslinking agent, By appropriately cross-linking, high elongation and elasticity can be imparted to the obtained model material. In the present invention, the molar fraction is more preferably 99.5 / 0.5 to 92/8.

In the present invention, in particular, the (meth) acrylate (A1) is contained in an amount of 85% by mass or more based on the total mass of the monofunctional monomer (A) contained in the model material composition, and the polyfunctional monomer (B) is contained. By containing in the range of the said molar fraction in relation to a monofunctional monomer (A), the extensibility (rubber elasticity) and dimensional stability of the model material obtained can be made compatible. This is not limited, but for example, the monofunctional monomer having a low glass transition temperature of the cured product has a higher rate of viscosity increase during the curing reaction than the monofunctional monomer having a high glass transition temperature of the homopolymer. Therefore, when the composition for a model material containing a monofunctional monomer having a low glass transition temperature as a homopolymer is cured, it is possible to secure time for alleviating the curing shrinkage. It is considered that a model material having both rubber elasticity and dimensional stability can be obtained if the time for relaxing the curing shrinkage can be secured.

The composition for model material may further contain a photopolymerization initiator. Usually, when the actinic ray is an electron beam, the photopolymerization initiator may not be included. However, when the actinic ray is an ultraviolet ray, it is preferable to include a photopolymerization initiator.

The photopolymerization initiator includes a cleavage type and a hydrogen abstraction type. In the present invention, the model material composition preferably contains at least an open-type photopolymerization initiator. That is, the composition for model material may contain (i) both a cleavage type and a hydrogen abstraction type photopolymerization initiator, or (ii) contain only a cleavage type photopolymerization initiator. Good. What is necessary is just to use properly the aspect of a photoinitiator according to the desired effect.

When the composition for model material contains (i) both a cleavage type and a hydrogen abstraction type photopolymerization initiator, it is preferable to contain a large amount of the cleavage type initiator as a mass ratio. The ratio of the hydrogen abstraction type initiator in the photopolymerization initiator is preferably 30% by mass or less, more preferably 20% by mass or more and 30% by mass or less, based on the total mass of the photopolymerization initiator.

When the model material composition contains both a cleavage type and a hydrogen abstraction type polymerization initiator as a photopolymerization initiator, the curing rate of the stereolithography composition tends to increase. Although the reason is not clear, it is thought that when the photopolymerization initiator of the cleavage type and the hydrogen abstraction type coexist, the hydrogen abstraction type initiator plays a role as a sensitizer and thus the polymerization rate is improved. The improvement in the polymerization rate is more advantageous in a material jet stereolithography method for modeling a three-dimensional solid that requires much longer time than ordinary two-dimensional printing (inkjet printing).

When the model material composition contains (ii) only a cleavage type photopolymerization initiator (no hydrogen abstraction type initiator), both the cleavage type and hydrogen abstraction type light Compared to the case where a polymerization initiator is contained, the extensibility or elasticity of the model material formed from the model material composition may be improved. The reason for this is not clear, but is presumed as follows. Irregular crosslinking may occur when a graft reaction occurs between linear polymers obtained by polymerization of monofunctional monomers due to a hydrogen abstraction type initiator. When the cross-linking is regular, the cured product receives a uniform force when stretched, so that high stretchability can be maintained. However, if the cured product has irregular cross-linking, the cured product When the is stretched, stress concentrates on a specific part in the cured product. For this reason, it is considered that the crosslinking site or the linear polymer chain is easily broken, and the extensibility and elasticity are rather lowered.

Therefore, in order to improve the modeling speed of the three-dimensional stereolithography, it is preferable that the model material composition includes (i) both types of polymerization initiators, that is, a cleavage type and a hydrogen abstraction type. On the other hand, when importance is attached to the durability of the cured product, it is preferable to contain only (ii) a cleavage type photopolymerization initiator (substantially no hydrogen abstraction type).

Examples of the cleavage type photopolymerization initiator include diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, benzyldimethyl ketal, 1- (4-isopropylphenyl) -2-hydroxy- 2-methylpropan-1-one, 4- (2-hydroxyethoxy) phenyl- (2-hydroxy-2-propyl) ketone, 1-hydroxycyclohexyl-phenylketone, 2-methyl-2-morpholino (4-thiomethyl) Acetophenones such as phenyl) propan-1-one and 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone; benzoins such as benzoin, benzoin methyl ether and benzoin isopropyl ether; 6-Trimethylbenzoindiphenylphosphineoxy Acylphosphine oxide and the like; benzyl and methyl phenylglyoxylate esters.

Examples of hydrogen abstraction type photopolymerization initiators include benzophenones (benzophenone, N, N-diethylbenzophenone, etc.), thioxanthones (2,4-diethylthioxanthone, isopropylthioxanthone, chlorothioxanthone, isopropoxychlorothioxanthone, etc.) And anthraquinones (ethyl anthraquinone, benzanthraquinone, aminoanthraquinone, chloroanthraquinone, etc.), acridines (9-phenylacridine, 1,7-bis (9,9′-acridinyl) heptane, etc.) and the like.

The content of the photopolymerization initiator in the model material composition may be appropriately selected according to the type and amount of the polymerizable compound constituting the model material composition, the type of initiator used, the type of actinic rays, and the like. However, it is preferably 0.01% by mass to 10% by mass with respect to the total mass of the model material composition.

The composition for model material can contain other additives as necessary within the range not impairing the effects of the present invention. Other additives include, for example, photopolymerization initiation aids, storage stabilizers, surface conditioners, antioxidants, colorants, UV absorbers, light stabilizers, chain transfer agents, fillers, diluent solvents, thickening agents. Agents and the like.

The photopolymerization initiation assistant is, for example, a tertiary amine compound, and preferably an aromatic tertiary amine compound. Examples of the aromatic tertiary amine compound include N, N-dimethylaniline, N, N-diethylaniline, N, N-dimethyl-p-toluidine, N, N-dimethylamino-p-benzoic acid ethyl ester, N, N-dimethylamino-p-benzoic acid isoamyl ethyl ester, N, N-dihydroxyethylaniline, triethylamine, N, N-dimethylhexylamine and the like can be mentioned. Of these, N, N-dimethylamino-p-benzoic acid ethyl ester and N, N-dimethylamino-p-benzoic acid isoamyl ethyl ester are preferred. These compounds may be used alone or in combination of two or more.

The surface conditioner is a component that adjusts the surface tension of the model material composition to an appropriate range, and the type thereof is not particularly limited. By making the surface tension of the model material composition within an appropriate range, it is possible to stabilize the ejection properties and to suppress interfacial mixing between the model material composition and the support material composition. As a result, it is possible to obtain a shaped article with good dimensional accuracy.

Examples of the surface conditioner include silicone compounds. Examples of the silicone compound include a silicone compound having a polydimethylsiloxane structure. Specific examples include polyether-modified polydimethylsiloxane, polyester-modified polydimethylsiloxane, and polyaralkyl-modified polydimethylsiloxane. These include BYK-300, BYK-302, BYK-306, BYK-307, BYK-310, BYK-315, BYK-320, BYK-322, BYK-323, BYK-325, BYK-330, BYK-331, BYK-333, BYK-337, BYK-344, BYK-370, BYK-375, BYK-377, BYK-UV3500, BYK-UV3510, BYK-UV3570 (above, manufactured by BYK Chemie), TEGO-Rad2100 , TEGO-Rad2200N, TEGO-Rad2250, TEGO-Rad2300, TEGO-Rad2500, TEGO-Rad2600, TEGO-Rad2700 (above, manufactured by Degussa), Granol 100, Granol 115, Granol 400, Grano Le 410, Granol 435, Granol 440, Granol 450, B-1484, Polyflow ATF-2, KL-600, UCR-L72, UCR-L93 (manufactured by Kyoeisha Chemical Co., Ltd.) and the like may be used. Further, a surface conditioner other than the silicone compound (for example, a nonionic surface conditioner such as a fluorine-based surface conditioner) may be used. These may be used alone or in combination of two or more.

When the model material composition contains a surface conditioner, the content thereof is preferably 0.005 to 3 parts by mass, more preferably 0.01 to 3 parts by mass with respect to 100 parts by mass of the model material composition. 1 part by mass. When the content of the surface conditioner is within the above range, the surface tension of the model material composition is easily adjusted to an appropriate range.

The storage stabilizer is a component that can enhance the storage stability of the model material composition. Further, clogging of the head caused by polymerization of the polymerizable compound by thermal energy can be prevented. Examples of the storage stabilizer include hindered amine compounds (HALS), phenolic antioxidants, phosphorus antioxidants, nitrosamine compounds, and the like. Specifically, hydroquinone, methoquinone, benzoquinone, p-methoxyphenol, hydroquinone monomethyl ether, hydroquinone monobutyl ether, TEMPO, 4-hydroxy-TEMPO, TEMPOL, cuperon Al, IRGASTAB UV-10, IRGASTAB UV-22, FIRSTCURE ST- 1 (manufactured by ALBEMARLE), t-butylcatechol, pyrogallol, TINUVIN 111 FDL, TINUVIN 144, TINUVIN 292, TINUVIN XP40, TINUVIN XP60, TINUVIN 400, etc. manufactured by BASF. These may be used alone or in combination of two or more.

When the composition for a model material contains a storage stabilizer, the content thereof is preferably 0.05 to 3 parts by mass with respect to 100 parts by mass of the composition for a model material from the viewpoint of easily obtaining the above effect. More preferably, it is 0.1 to 2 parts by mass.

The viscosity of the composition for model material of the present invention is preferably 150 mPa · s or less at 25 ° C. from the viewpoint of improving dischargeability from the material jet nozzle. The above-mentioned viscosity can be measured using a rotational viscometer in accordance with JIS Z 8803. The viscosity of the composition for a model material can be controlled by adjusting the type of the polymerizable compound and the blending ratio thereof, the type of the diluent solvent and the thickener, the amount of addition thereof, and the like.

The glass transition temperature (Tg) of the cured product of the composition for model material of the present invention is preferably 5 ° C. or less. By setting the glass transition temperature of the cured product of the model material composition to 5 ° C. or less, good elasticity can be maintained even at low temperatures. The glass transition temperature of the cured product of the model material composition is more preferably 3 ° C. or lower. The glass transition temperature can be measured, for example, by differential thermal analysis (DTA) or differential scanning calorimetry (DSC).

The method for producing the model material composition of the present invention is not particularly limited. For example, the model material composition may be produced by uniformly mixing the components constituting the model material composition using a mixing stirrer, a disperser, or the like. it can.

<Composition for support material>
The optical modeling composition set of the present invention includes a support material composition. The composition for support material constituting the composition set for optical modeling of the present invention is based on 100 parts by mass of the composition for support material.
15 to 75 parts by mass of a polyalkylene glycol (a) containing an oxybutylene group and having a weight average molecular weight of 300 or more, and
19 parts by weight or more and 80 parts by weight or less of a water-soluble monofunctional ethylenically unsaturated monomer (b)
It is a composition containing this. When the composition for a support material contains the polyalkylene glycol (a) containing an oxybutylene group in the above content, a support material having both excellent water removal property and support capability can be provided. Moreover, the support material composition excellent in low-temperature stability can be provided. While the polyalkylene glycol (a) containing the oxybutylene group is water-soluble, it does not have hydrophilicity to reduce the support force of the support material when the support material is formed, while the oxybutylene group is Since the polyalkylene glycol (a) contained is water-soluble, the support material is excellent in water removability when the support material is formed. Here, water-soluble means a property that can be dissolved in water or dispersed in water. Moreover, the composition for a support material is not easily solidified (solidified) at low temperatures, and the fluidity is not easily lowered.

More specifically, in the present invention, the composition for a support material comprises the above polyalkylene glycol (a) containing an oxybutylene group, a water-soluble monofunctional ethylenically unsaturated monomer (b), and a photopolymerization initiator. Containing. Thereby, it is possible to provide a support material having both excellent water removability and support force, and can provide a support material composition having excellent low-temperature stability.

The polyalkylene glycol (a) containing an oxybutylene group that can be included in the support material composition may be either a linear type or a multi-chain type. Moreover, as long as it melt | dissolves in water, the alkyl group may be included in the terminal, for example, Preferably it may contain the C6 or less alkyl chain. These may be used alone or in combination of two or more.

The polyalkylene glycol (a) containing an oxybutylene group is a water-soluble resin for imparting appropriate hydrophilicity to a support material, and by adding this, a support material having both water removability and support power Can be obtained. The polyalkylene glycol containing an oxybutylene group is not particularly limited as long as it contains an oxybutylene group. For example, the polyalkylene glycol having only an oxybutylene group (oxytetramethylene group) is a single polybutylene glycol. Alternatively, it may be a polybutylene polyoxyalkylene glycol (for example, polybutylene polyethylene glycol) having both an oxybutylene group and another oxyalkylene group.

For example, the polybutylene glycol is represented by the following chemical formula (1), and the polybutylene polyethylene glycol is represented by the following chemical formula (2).

In the above chemical formula (2), m is preferably an integer of 5 to 300, and n is preferably an integer of 2 to 150. More preferably, m is 6 to 200, and n is 3 to 100. Further, the oxybutylene group in the chemical formula (1) and the chemical formula (2) may be a straight chain or may be branched. These may be used alone or in combination of two or more.
Since the composition for a support material contains the polyalkylene glycol (a) containing an oxybutylene group, the removability by water can be further improved without reducing the support force of the support material, It supports a model material having elasticity and becomes a support material suitable for modeling a model material with high accuracy. In particular, for model materials that have elasticity and elasticity like rubber and whose dimensional accuracy tends to decrease during molding, the support material can sufficiently support the model material during stereolithography, so modeling at the stage of stereolithography Accuracy can be improved. Furthermore, since the support material can be easily removed at the stage of removing the support material after that, the support material can be used while suppressing the decrease in accuracy even in the microstructure of the three-dimensional model molded with high accuracy during stereolithography. Can be removed. This not only prevents the reduction of dimensional accuracy when removing the support material by improving the removability of the support material with water, but also improves the dimensional accuracy of the model material during stereolithography by improving the self-supporting property of the support material. By increasing the height, it is possible to obtain an optically shaped article having better dimensional accuracy.

The weight average molecular weight (M _w ) of the polyalkylene glycol (a) containing an oxybutylene group is 300 or more. When the weight average molecular weight of the polyalkylene glycol (a) is less than 300, the compatibility with the components constituting the composition for a support material is lowered, and bleeding tends to occur. Therefore, the weight average molecular weight of the polyalkylene glycol (a) containing an oxybutylene group is more preferably 400 or more, and even more preferably 500 or more. The upper limit of the weight average molecular weight of the polyalkylene glycol (a) containing an oxybutylene group is not particularly limited, but is usually 3000 or less, preferably 2000 or less. When the weight average molecular weight is within the above range, the water-soluble monofunctional ethylenically unsaturated monomer (b) is easily compatible in the composition before curing, while the water-soluble monofunctional ethylenic monomer after light irradiation is easily compatible. It becomes difficult to be compatible with the cured product of the saturated monomer, and the support material can be easily removed with water or a water-soluble solvent.

As described above, the content of the polyalkylene glycol (a) containing an oxybutylene group in the support material composition is preferably 15 parts by mass or more and 75 parts by mass or less with respect to 100 parts by mass of the support material composition. Is 17 parts by mass or more, more preferably 20 parts by mass or more, preferably 72 parts by mass or less, more preferably 70 parts by mass or less. When the content of the polyalkylene glycol (a) containing an oxybutylene group is less than 15 parts by mass, the hydrophilicity of the support material decreases, so the water removability of the support material decreases, and the content is 75 masses. If the amount exceeds 50 parts, the amount of the water-soluble monofunctional ethylenically unsaturated monomer (b) that is a polymerizable component is reduced, and the support material is softened and the self-supporting property is lowered. To do.

In the present invention, the water-soluble monofunctional ethylenically unsaturated monomer (b) contained in the support material composition includes, for example, a hydroxyl group-containing (meth) acrylate having 5 to 15 carbon atoms [for example, hydroxyethyl (meta ) Acrylate, hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, etc.], hydroxyl group-containing (meth) acrylate having a number average molecular weight (Mn) of 200 to 1,000 [for example, polyethylene glycol mono (meth) acrylate, mono Alkoxy (1 to 4 carbon atoms) polyethylene glycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate, monoalkoxy (1 to 4 carbon atoms) polypropylene glycol mono (meth) acrylate, mono (meta) of PEG-PPG block polymer Acry Etc.], (meth) acrylamide derivatives [eg (meth) acrylamide, N-methyl (meth) acrylamide, N-ethyl (meth) acrylamide, N-propyl (meth) acrylamide, N-butyl (meth) acrylamide, N , N′-dimethyl (meth) acrylamide, N, N′-diethyl (meth) acrylamide, N-hydroxyethyl (meth) acrylamide, N-hydroxypropyl (meth) acrylamide, N-hydroxybutyl (meth) acrylamide, etc.] (Meth) acryloylmorpholine and the like can be mentioned. These may be used alone or in combination of two or more.

Content of the water-soluble monofunctional ethylenically unsaturated monomer (b) contained in the composition for support material is 19 parts by mass or more and 80 parts by mass or less with respect to 100 parts by mass of the composition for support material. The amount is preferably 22 parts by mass or more, more preferably 25 parts by mass or more, preferably 76 parts by mass or less, and more preferably 73 parts by mass or less. When the content of the water-soluble monofunctional ethylenically unsaturated monomer (b) is within the above range, the removability of the support material with water can be improved without reducing the support power of the support material.

Furthermore, the composition for support material may contain a water-soluble organic solvent. A water-soluble organic solvent is a component which improves the solubility to water of the support material obtained by photocuring the composition for support materials. Moreover, it has the function to adjust the composition for support materials to low viscosity.

As the water-soluble organic solvent, a glycol-based solvent is preferably used. Specifically, for example, ethylene glycol monoacetate, propylene glycol monoacetate, diethylene glycol monoacetate, dipropylene glycol monoacetate, triethylene glycol monoacetate, triethylene glycol monoacetate, and the like. Glycol ester solvents such as propylene glycol monoacetate, tetraethylene glycol monoacetate, tetrapropylene glycol monoacetate, ethylene glycol diacetate, propylene glycol diacetate; ethylene glycol monomethyl ether, propylene glycol monomethyl ether, triethylene glycol monomethyl ether, ethylene Glycol monoethyl ether, propylene glycol Ethyl ether, ethylene glycol monopropyl ether, propylene glycol monopropyl ether, ethylene glycol monobutyl ether, propylene glycol monobutyl ether, tetrapropylene glycol monobutyl ether, ethylene glycol dimethyl ether, propylene glycol dimethyl ether, ethylene glycol diethyl ether, propylene glycol diethyl ether, ethylene Glycol ether solvents such as glycol dipropyl ether, propylene glycol dipropyl ether, ethylene glycol dibutyl ether, propylene glycol dibutyl ether, diethylene glycol diethyl ether; ethylene glycol monomethyl ether acetate, propylene glycol monomer Ether ether, dipropylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, propylene glycol monoethyl ether acetate, ethylene glycol monopropyl ether acetate, propylene glycol monopropyl ether acetate, ethylene glycol monobutyl ether acetate, propylene glycol monobutyl ether acetate, etc. And glycol monoether acetate solvents. These may be used alone or in combination of two or more.

Among them, since it is easy to prepare a composition for a support material having a low viscosity and the support material obtained by curing is excellent in water solubility, examples of the water-soluble organic solvent include triethylene glycol monomethyl ether, diethylene glycol diethyl ether and Dipropylene glycol monomethyl ether acetate is preferred.

The content of the water-soluble organic solvent in the support material composition is preferably 30 parts by mass or less, more preferably 28 parts by mass or less, further preferably 100 parts by mass of the support material composition. 25 parts by mass or less. When the content of the water-soluble organic solvent is within the above range, the removability of the support material with water or a water-soluble solvent can be improved without reducing the support power of the support material. When the composition for a support material contains a water-soluble organic solvent, the content thereof is preferably 3 masses with respect to 100 parts by mass of the composition for a support material from the viewpoint that the composition for a support material can be adjusted to a low viscosity. More than a part.

As the photopolymerization initiator, the compounds described above as photopolymerization initiators that can be contained in the model material composition can be used in the same manner. The content of the photopolymerization initiator in the composition for support material is preferably 1 part by mass or more and 20 parts by mass or less, more preferably 2 parts by mass or more, with respect to 100 parts by mass of the composition for support material. Moreover, More preferably, it is 18 mass parts or less, More preferably, it is 15 mass parts or less. When the content of the photopolymerization initiator is within the above range, unreacted polymerization components can be sufficiently reduced, and the curability of the support material can be sufficiently enhanced.

By including each of the above components in a content within the above range, a composition for a support material that has both excellent water solubility and support ability can be obtained. In particular, since the support power is excellent, there is no concern that the moisture in the air is taken in during modeling and the support power is reduced, and an optical modeling product with good dimensional accuracy can be obtained.

The support material composition may contain other additives as necessary. Examples of other additives include surface conditioners, antioxidants, colorants, pigment dispersants, storage stabilizers, ultraviolet absorbers, light stabilizers, chain transfer agents, and fillers.

By adding a surface conditioner to the support material composition, the surface tension of the support material composition can be controlled within an appropriate range, and the model material composition and the support material composition are mixed at the interface. Can be suppressed. Thereby, a stereolithography thing with favorable dimensional accuracy can be obtained. As the surface conditioner that can be contained in the support material composition, the same as those exemplified as the surface conditioner that can be used in the previous model material composition can be used, the content of which is the composition for the support material It is preferable that it is 0.005 mass part or more and 3 mass parts or less with respect to 100 mass parts of things.

Moreover, the storage stability can be improved by blending a storage stabilizer into the support material composition. As the storage stabilizer that can be contained in the support material composition, those exemplified as the storage stabilizer that can be used in the previous model material composition can be used, and the content thereof can be determined by the support material composition. It is preferable that they are 0.05 mass part or more and 3 mass parts or less with respect to 100 mass parts.

In the present invention, the viscosity of the composition for a support material is preferably 30 to 200 mPa · s at 25 ° C., more preferably 35 mPa · s or more, from the viewpoint of improving dischargeability from a material jet nozzle. Preferably it is 40 mPa * s or more, More preferably, it is 170 mPa * s or less, More preferably, it is 150 mPa * s or less. In addition, the measurement of the said viscosity can be performed using R100 type | mold viscosity meter based on JISZ8803.

In the present invention, the surface tension of the support material composition is preferably 24 to 30 mN / m, more preferably 24.5 to 29.5 mN / m, and further preferably 25 to 29 mN / m. When the surface tension is within the above range, it is possible to normally form droplets ejected from the nozzle, to ensure an appropriate droplet amount and landing accuracy, and to suppress the occurrence of satellites, It becomes easy to ensure high modeling accuracy. In addition, the surface tension of the composition for support material can be measured in accordance with the method similar to the measuring method of the surface tension in the composition for model materials.

The method for producing the composition for a support material of the present invention is not particularly limited. For example, the composition for a support material can be produced by uniformly mixing the components constituting the composition for a support material using a mixing stirrer, a disperser, or the like. it can.

<Composition set for stereolithography>
The composition set for optical modeling of the present invention is excellent in a three-dimensional modeled object (model material) having high elongation and elasticity because the support material is excellent in self-supporting property and removability and does not impair the dimensional accuracy of the optical modeled object. Can be shaped with accuracy.

<Optical modeling product and its manufacturing method>
The manufacturing method of the optical modeling thing of this invention is a manufacturing method of the optical modeling thing using the composition set for optical modeling of this invention, and is a composition for model materials, and a support material using a material jet (inkjet) type printer. After discharging the composition for use, the model material composition is photocured to obtain a model material, the water soluble support material composition is photocured to obtain a water soluble support material, and the water soluble support material Is removed by contacting with water.

Since the manufacturing method of the present invention uses the optical modeling composition set of the present invention, an optical modeling object having rubber-like properties can be formed with high modeling accuracy.

Hereinafter, a method for manufacturing an optically shaped object of the present invention will be described with reference to the drawings. FIG. 1 is a schematic side view showing a state in which a support material composition and a model material composition are ejected by a material jet modeling method and irradiated with energy rays. In FIG. 1, the three-dimensional modeling apparatus 10 includes an inkjet head module 11 and a modeling table 12. The ink jet head module 11 includes an optical modeling ink unit 11a, a roller 11b, and a light source 11c. Furthermore, the optical modeling ink unit 11a includes a model material inkjet head 11aM filled with the model material composition 13, and a support material inkjet head 11aS filled with the support material composition 14.

The model material composition 13 is ejected from the model material inkjet head 11aM, the support material composition 14 is ejected from the support material inkjet head 11aS, and the energy beam 15 is irradiated and ejected from the light source 11c. The model material composition 13 and the support material composition 14 are cured to form the model material 13PM and the support material 14PS. FIG. 1 shows a state in which the first layer model material 13PM and the support material 14PS are formed.

Next, the method for manufacturing an optically shaped product of the present invention will be described in more detail based on the drawings. In the method for producing an optically shaped article of the present invention, first, as shown in FIG. 2, the inkjet head module 11 is scanned in the X direction (right direction in FIG. 2) with respect to the modeling table 12, and the inkjet head for model material is used. The composition 13 for model material is discharged from 11aM, and the composition 14 for support material is discharged from the inkjet head 11aS for support material. Thereby, on the modeling table 12, the layer which consists of the model material precursor 13M, and the layer which consists of the support material precursor 14S are arrange | positioned adjacently so that each interface may contact.

Next, as shown in FIG. 3, the inkjet head module 11 is scanned in the reverse X direction (left direction in FIG. 3) with respect to the modeling table 12, and the model material precursor 13 </ b> M and the support material precursor 14 </ b> S with the roller 11 b. After smoothing the surface of the layer made of the material, the energy beam 15 is irradiated from the light source 11c to cure the layer made of the model material precursor 13M and the support material precursor 14S, and the first model material 13PM and the support material 14PS. A layer consisting of is formed.

Subsequently, the modeling table 12 is lowered by one layer in the Z direction, and the same process as described above is performed to form a second layer of model material and support material. Thereafter, by repeating the above steps, as shown in FIG. 4, an optically shaped product precursor 16 composed of the model material 13PM and the support material 14PS is formed.

Finally, the optical modeling product precursor 16 shown in FIG. 4 is brought into contact with water, for example, by immersing in water, the support material 14PS is dissolved and removed to form the optical modeling product 17 as shown in FIG. Is done.

In the method for producing an optically shaped article of the present invention, for example, a high pressure mercury lamp, a metal halide lamp, a UV-LED, or the like can be used as the light source. From the viewpoint that the three-dimensional modeling apparatus 10 can be miniaturized and the power consumption is small, UV-LED is preferable. The amount of light is preferably 200 to 500 mJ / cm ² from the viewpoint of the hardness and dimensional accuracy of the shaped product. When a UV-LED is used as the light source, it is preferable to use a light having a center wavelength of 385 to 415 nm because light easily reaches a deep layer and the hardness and dimensional accuracy of the optically shaped product can be improved. As the energy rays 15 irradiated from the light source 11c, ultraviolet rays, near ultraviolet rays, visible rays, infrared rays, far infrared rays, electron beams, α rays, γ rays, X-rays, and the like can be used. And from a viewpoint of efficiency, ultraviolet rays or near ultraviolet rays are preferable.

In the manufacturing method of the present invention, for example, based on the three-dimensional CAD data of the object to be manufactured, the data of the composition for the model material that forms the three-dimensional structure by stacking by the material jet method, and the three-dimensional modeling in the process of preparation The data of the composition for the support material that supports the object is prepared, and further, the slice data for discharging each composition by the material jet type 3D printer is prepared, and each of the material for the model material and the support material is based on the prepared slice data. After discharging the composition, the photo-curing treatment is repeated for each layer to produce an optically shaped article composed of a cured product of the model material composition (model material) and a cured product of the composition for support material (support material). it can.

The thickness of each layer constituting the three-dimensional model is preferably thin from the viewpoint of modeling accuracy, but is preferably 5 to 30 μm from the balance with the modeling speed.

The obtained stereolithography is a combination of a model material and a support material. The support material is removed from the stereolithography product to obtain a stereolithography product as a model material. The support material can be removed by, for example, immersing an optical modeling object obtained in a removal solvent that dissolves the support material, softening the support material, and then removing the support material from the model material surface with a brush or the like. preferable. Water or a water-soluble solvent such as a glycol solvent or an alcohol solvent may be used as the solvent for removing the support material. These may be used alone or in combination.

The above-mentioned stereolithography product has suppressed water absorption and swelling when contacted with water, and is less likely to cause breakage and deformation of the fine structure portion. Further, the stereolithographic product is excellent in water and oil repellency and hardly contaminated.

The stereolithographic product obtained by the above steps has a relatively high surface hardness in an embodiment. For example, the stereolithographic product has a surface hardness of Shore-D hardness of 50 or more, preferably 60 or more, more preferably 70 or more. The optically shaped article has a high dimensional accuracy because water absorption and swelling are suppressed because it takes a short time to contact water when removing the support material.

Hereinafter, examples that more specifically disclose the present embodiment will be shown. In addition, this invention is not limited only to these Examples.

Hereinafter, the present invention will be described in more detail with reference to examples. Unless otherwise specified, “%” and “parts” in the examples are% by mass and parts by mass.

1. Model Material Composition Table 1 shows the details of the components constituting the model material composition used in the examples.

[Table 1]

(1) Preparation of Model Material Composition In the formulation shown in Table 2, the components constituting each model material composition were uniformly mixed using a mixing stirrer, and Examples M1 to M6 and Comparative Examples The composition for model materials of m1 and m2 was manufactured.

[Table 2]

(2) Physical properties of model material composition <Measurement of viscosity>
The viscosity of each composition for model materials was measured using a rotational viscometer. The results are shown in Table 2.

(3) Characteristics of the model material A frame is formed on a glass plate with a frame-shaped silicon rubber having a length of 100 mm, a width of 20 mm, and a thickness of 1 mm. The composition for each model material is poured into the frame, and a metal halide lamp is used. A model material was obtained by irradiating with an ultraviolet ray having an integrated light quantity of 600 mJ / cm ² . The obtained model material was measured and evaluated for the following characteristics. The results are shown in Table 2.

<Glass transition temperature (Tg)>
The glass transition degree was measured by DSC (differential scanning calorimetry).

<Rubber properties>
The breaking strength and breaking elongation were measured by applying a constant load at a tensile speed of 500 mm / min at room temperature. Curve A (40%, 6.8 MPa), (100%, 3 MPa), (300%, 1.1 MPa), curve B, where X-axis is elongation (%) and Y-axis is breaking strength (MPa) Evaluation was performed according to the following evaluation criteria with reference to a line connecting (40%, 5.2 MPa), (100%, 2.2 MPa), and (300%, 0.75 MPa).
Evaluation criteria:
○: On the opposite side of the origin from curve A Δ: Between curve A and curve B ×: Between curve B and origin

<Dimensional stability>
The dimensions immediately after curing of the cured product and the dimensions after 7 days were measured.
Evaluation criteria:
○: Dimensional difference is less than 1% △: Dimensional difference is less than 1-3% ×: Dimensional difference is 3% or more

2. Composition for Support Material Details of components constituting the composition for support material used in Examples are shown in Table 3.

[Table 3]

(1) Preparation of Support Material Composition In the formulation shown in Table 4, the components constituting each support material composition were uniformly mixed using a mixing and stirring device, respectively, and Examples S1 to S13 and Comparative Examples The composition for support material of s1 was manufactured.

[Table 4]

(2) Characteristics of Support Material Composition and Cured Product thereof With respect to the support material compositions of Examples S1 to S13 and Comparative Example s1, the low temperature stability of the support material composition and the support material are obtained by the following method. The high-temperature and high-humidity condition stability (supporting power) and water removability of the cured support material obtained by curing the composition were evaluated.

<Low temperature stability of support material composition>
The stability of the composition for the support material at low temperature was evaluated. Each composition for support material was put into a glass bottle, and the glass bottle with the composition for support material was stored in a thermostatic bath set at a temperature of 10 ° C. for 24 hours. Then, the state of the composition for support material after storage was confirmed visually, and the low temperature stability of the composition for support material was evaluated according to the following criteria.

When the composition for the support material is maintained in a liquid state: low temperature stability A (excellent)
When the support material composition is partially solidified (solidified): Low temperature stability B (good)
When the composition for the support material is solidified (solidified): low temperature stability C (poor)

<Supporting power of cured support material>
A frame is formed on a glass plate with a frame-shaped silicon rubber having a length of 30 mm, a width of 30 mm, and a thickness of 5 mm, each support material composition is poured into the frame, and an ultraviolet ray with an integrated light amount of 500 mJ / cm ² is obtained by a metal halide lamp. Was irradiated to produce a cured support material. Subsequently, the cured product was placed in a glass petri dish, and the petri dish containing the cured product was left in a thermostatic bath at a temperature of 40 ° C. and a relative humidity of 90% for 2 hours. Thereafter, the state of the cured product after standing was visually confirmed, and the support force of the cured support material was evaluated according to the following criteria.

When there is no generation of liquid substances on the surface of the cured product and no softening of the cured product is confirmed: Support strength A (excellent)
When a slight amount of liquid material is generated on the surface of the cured product and softening of the cured product is confirmed slightly: Support strength B (good)
When a liquid substance is generated on the surface of the cured product and softening of the cured product is confirmed: Support force C (defect)

<Water removability of the cured support material>
A cured support material was produced in the same manner as in the evaluation of the support force of the cured support material. Next, the cured product is placed in a beaker filled with 50 mL of ion exchange water, treated with an ultrasonic cleaner while maintaining the water temperature at 25 ° C., and the time until the cured product is dissolved is measured. The water removal property of the support material cured product was evaluated based on the standard.

The time until the cured product completely dissolved was less than 1 hour: water removability A (excellent)
The time until the cured product was completely dissolved was 1 hour or more and less than 2 hours: Water removability B (good)
The time until the cured product was completely dissolved was 2 hours or more: water removability C (poor)

The results are shown in Table 5.

[Table 5]

It can be seen that the support material compositions of Examples S1 to S13 obtained satisfactory results (excellent or good) in all evaluation items.

3. Stereolithographic Composition Set Examples 1 to 3 and Comparative Examples 1 and 2 were prepared by combining the model material composition and the support material composition as shown in Table 6.

A spacer having a thickness of 1 mm was arranged on the four upper surfaces of a glass plate (trade name “GLASS PLATE”, manufactured by ASONE, 200 mm × 200 mm × thickness 5 mm), and was partitioned into 10 cm × 10 cm squares. After casting the composition for the support material in the square, an ultraviolet LED (NCCU001E, manufactured by Nichia Corporation) is used as the irradiation means, and ultraviolet rays are irradiated so that the total irradiation light amount becomes 500 mJ / cm ^2. And cured to obtain a support material.

Next, spacers having a thickness of 1 mm were arranged on the four sides of the upper surface of the support material and partitioned into squares of 10 cm × 10 cm. After casting the composition for the model material in the square, an ultraviolet LED (NCCU001E, manufactured by Nichia Corporation) is used as the irradiation means, and ultraviolet rays are irradiated so that the total irradiation light amount becomes 500 mJ / cm ^2. And cured to obtain a model material.

<Evaluation of adhesion>
In this state, it was left in a thermostatic bath at 30 ° C. for 12 hours, the state of adhesion between the model material and the support material was visually confirmed, and evaluated according to the following criteria. The results are shown in Table 9.
○: The model material and the support material were in close contact.
Δ: The model material and the support material were in close contact with each other, but peeling occurred when the interface between the model material and the support material was scratched with a nail.
X: Peeling occurred at the interface between the model material and the support material, and the model material was peeled off so as to be warped by the curing shrinkage of the model material.

[Table 6]

As can be seen from the results in Table 6, the set of optical shaping compositions of Examples 1 to 3 satisfying the requirements of the present invention does not cause peeling at the interface between the model material and the support material, and the model material and the support material Was more closely attached. Thus, if the model material and the support material are in close contact with each other, an optically shaped product with good dimensional accuracy can be obtained.

DESCRIPTION OF SYMBOLS 10 3D modeling apparatus 11 Inkjet head module 11a Optical modeling ink unit 11aM Model material inkjet head 11aS Support material inkjet head 11b Roller 11c Light source 12 Modeling table 13 Model material composition 13M Model material precursor 13PM Model material 14 Support Material composition 14S Support material precursor 14PS Support material 15 Energy beam 16 Stereolithography product precursor (Optical fabrication product)
17 Stereolithography

Claims

A composition set for stereolithography used in a material jet stereolithography method comprising a composition for model material and a composition for support material,
The composition for a model material comprises a monofunctional monomer (A) and a polyfunctional monomer (B) having a plurality of polymerizable functional groups containing a carbon-carbon double bond in the molecule, and the monofunctional monomer The molar fraction of (A) and the polyfunctional monomer (B) (monofunctional monomer (A) / polyfunctional monomer (B)) is 99.9 / 0.1 to 92/8,
As the monofunctional monomer (A), a (meth) acrylate (A1) having a molecular weight of 150 or more and less than 400 and having a glass transition temperature of 5 ° C. or less as a homopolymer is used as the monofunctional monomer (A). Contains 85% by mass or more based on the total mass,
The support material composition is based on 100 parts by mass of the support material composition.
15 parts by mass or more and 75 parts by mass or less of a polyalkylene glycol (a) containing an oxybutylene group and having a weight average molecular weight of 300 or more,
19 parts by weight or more and 80 parts by weight or less of a water-soluble monofunctional ethylenically unsaturated monomer (b), and
A composition set for optical modeling containing a photopolymerization initiator.
The glass transition temperature of the hardened | cured material of the composition for model materials is 5 degrees C or less, The composition set for optical modeling of Claim 1.
The polymerizable functional group which the polyfunctional monomer (B) which comprises the composition for model materials has is selected from the group which consists of an acryl group, a methacryl group, a vinyl ether group, and an allyl ether group of Claim 1 or 2 Stereolithography composition set.
The composition set for optical modeling according to any one of claims 1 to 3, wherein the composition for a model material contains two or more kinds of the (meth) acrylates (A1).
The composition for optical modeling according to any one of claims 1 to 4, wherein the composition for model material further contains a photopolymerization initiator.
The composition set for optical modeling according to any one of claims 1 to 5, wherein the composition for a model material has a viscosity at 25 ° C of 150 mPa · s or less.
The light according to any one of claims 1 to 6, wherein the content of the photopolymerization initiator in the support material composition is 1 part by mass or more and 15 parts by mass or less with respect to 100 parts by mass of the composition for support material. Composition set for modeling.
The stereolithography according to any one of claims 1 to 7, wherein the support material composition further comprises 0.005 parts by mass or more and 3 parts by mass or less of a surface conditioner with respect to 100 parts by mass of the support material composition. Composition set.
The support material composition contains a water-soluble organic solvent, and the content of the water-soluble organic solvent is 30 parts by mass or less with respect to 100 parts by mass of the support material composition. The composition set for stereolithography according to 1.
The composition for optical modeling according to any one of claims 1 to 9, wherein the composition for a support material further contains a storage stabilizer.
An optically modeled article comprising a model material obtained by photocuring the model material composition contained in the composition for optical modeling according to any one of claims 1 to 10 by a material jet stereolithography method.
A method for producing an optically shaped object by using the composition set for optical modeling according to any one of claims 1 to 10 by a material jet stereolithography method,
A step (I) of obtaining a model material by photocuring the composition for model material, and obtaining a support material by photocuring the composition for support material; and
Step (II) for removing the support material
A method for producing an optically shaped object.