JPH1030002A - Photo curable fluid resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a photo curable fluid resin composition capable of forming a photo cured resin article containing inorganic substance free from crack fissure and film peeling, and a sintered molding. SOLUTION: This photo curable fluid resin composition polymerizes by the action of light, capable of insolubilizing in solvent or molding a structure changing from liquid to a solid. In this case, as the indispensable components, the composition consists of (a) a radically polymerizable monomer containing a hydrophilic group, (b) a photo polymerization initiator, (c) an inorganic substance. The hydrophilic group of the component (a) of this photo curable fluid resin composition has a character affording to this photo curable fluid resin, adhesive properties to the inorganic substance. By using the component (A) the adhesive properties between the inorganic substance and the resin increases because this composition contains the inorganic substance. Accordingly, the mold of the inorganic substance containing photo curable resin is capable of forming as a structure free from crack fissure and film peeling.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a photocurable fluid resin composition which can be polymerized by the action of light, insolubilized in a solvent or changed from a liquid to a solid to form a structure.

[0002]

2. Description of the Related Art In recent years, researches on micro machines have been actively conducted, and in particular, there is a great need for a three-dimensional component processing technique, and various types of fine processing techniques are being studied. As one of these fine processing techniques, a three-dimensional stereolithography method is known. Here, the three-dimensional stereolithography method is a method of irradiating a photocurable resin with light to form a photocurable layer, stacking a plurality of the photocurable layers, and forming a desired three-dimensional structure. . Regarding three-dimensional stereolithography, see "Yoji Maruyama, Kazuo Okawa, Seiji Hoshino, Naoichiro Saito, Takashi Nakai," Stereolithography "Nikkan Kogyo Shimbun, (199
0)).

As a method of processing a three-dimensional structure using this three-dimensional stereolithography method, a photocurable fluid resin containing a ceramic powder is used to pattern-irradiate light to produce a structure, which is then degreased and fired. A technique for obtaining a ceramic structure by tying the ceramic structure is known. For example, Japanese Patent Application Laid-Open No. Hei 6-329460 discloses that 100 parts by weight of a ceramic powder, 0.1 parts of a photo-curable resin,
A method of three-dimensionally forming a ceramic structure by three-dimensional stereolithography using a slurry composed of 5 to 50 parts by weight and 10 to 200 parts by weight of a solvent is described.

[0004]

When a structure is three-dimensionally formed by a three-dimensional stereolithography method using a photocurable resin mixed with an inorganic substance such as a ceramic powder, cracks or peeling are caused in the direction of the laminated surface. This causes a problem that a desired photocurable resin molded product cannot be obtained. This cracking and peeling is a problem that also occurs in a sintered molded article prepared by degrease and sintering the photocurable resin molded article.

The above-mentioned JP-A-6-329460 and "Yoji Maruyama, Kazuo Okawa, Seiji Hoshino, Naoichiro Saito, Takashi Nakai," Stereolithography "Nikkan Kogyo Shimbun, (1990)" describe the solution to the above problem. Is not specifically described.

Accordingly, the present invention has been made to solve the above problems, and an object of the present invention is to make it possible to produce a photocurable resin molded article containing an inorganic substance without cracking or peeling, and a sintered molded article. An object of the present invention is to provide a photocurable fluid resin composition.

[0007]

The above object can be attained by the following (1) to (3).

(1) In a photocurable fluid resin composition which can be polymerized by the action of light and insolubilized in a solvent or changed from a liquid to a solid to form a structure, (a) a hydrophilic group A photocurable fluid resin composition, comprising: a radical polymerizable monomer having the formula: (b) a photopolymerization initiator; and (c) an inorganic substance.

(2) The inorganic substance comprising (c) is:
(1) a surface treatment with an organic compound having a silane having a functional group capable of reacting with an inorganic substance on one side chain and having a functional group capable of radical polymerization on the other side chain; The photocurable fluid resin composition according to the above).

(3) The inorganic substance according to (1) or (2), wherein the inorganic substance comprising (c) is a powder, and the powder is a powder having two or more particle size distributions. Photocurable fluid resin composition.

Hereinafter, the present invention will be described in detail.

The present invention is a photocurable fluid resin composition which can be polymerized by the action of light and insolubilized in a solvent or changed from a liquid to a solid to form a structure.

The photocurable fluid resin composition according to the first invention comprises: (a) a radical polymerizable monomer having a hydrophilic group;
It contains (b) a photopolymerization initiator and (c) an inorganic substance as essential components.

In the photocurable fluid resin composition of the present invention, the “radical polymerizable monomer having a hydrophilic group” of the component (a) may be any one as long as the radical polymerizable monomer contains a hydrophilic group. There is no particular limitation. For example, there is a monomer having a hydrophilic group and one or more radically polymerizable functional groups. Specifically, there are a radical polymerizable monomer having a morpholino group as a hydrophilic group and a radical polymerizable monomer having a cationic ionic group. In the present invention,
Radical polymerizable monomers having a morpholino group are preferred, and morpholine acrylate is particularly preferred.

In the photocurable fluid resin composition of the present invention, for example, (meth)
Acrylic acid, vinyl acetic acid, styrene sulfonic acid, maleic anhydride, 2-acrylamido-2-methylpropane sulfonic acid, N, N-dimethylaminopropylacrylamide, N, N-dimethylaminoethyl (meth) acrylate, N, N- Dimethylaminopropylacrylamide, 2-acryloyloxyethyltrimethylammonium chloride, 3-acrylamidopropyltrimethylammonium chloride, morpholine acrylate, 2-hydroxyethyl (meth) acrylate, ethylene glycol (meth) acrylate, acrylamide, glycerol mono (meth) acrylate , Vinylpyrrolidone, N-isopropylacrylamide, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acryle DOO, morpholinoethyl (meth) acrylate, (meth) acrylate, (meth) acrylate, N, N-dimethylacrylamide, 2-sulfonium ethyl sodium methacrylate,
2-hydroxy-3-phenoxypropyl (meth) acrylate, (2- (meth) acryloyloxyethyl)
Acid phosphate, N-methacryloxy-N-carboxymethylpiperidine, N-methacryloxy-N,
N-dicarboxymethyl-p-phenylenediamine, hydroxynaphthoxypropyl methacrylate, methacryloxyethyl phosphorisphenyl, 4-methacryloxyethyl trimellitic anhydride, 4-methacryloxyethyl trimellitic acid, (meth) acryloxyethyl phthalate Radical polymerizable monomers containing a hydrophilic group, such as, 2- (meth) acryloyloxyethyl succinic acid, can be suitably used.

In the present invention, the term "hydrophilic group" means a hydroxyl group, a carboxyl group, a sulfonic acid group, a phosphoric acid group, a tertiary amine, a quaternary amine hydroxide, a sulfonium group,
It means a functional group such as an amide group, an amino group and a morpholino group.

Further, in the present invention, the term "cationic ionic group" means a functional group such as a tertiary amine and a quaternary amine hydroxide.

Further, in the photocurable fluid resin composition of the present invention, the component (a) may be used in combination of a plurality of the above compounds.

In the photocurable fluid resin composition of the present invention, the photopolymerization initiator of the component (b) is not particularly limited as long as it is a compound that generates a radical upon irradiation with light. For example, 2-hydroxy-2-methyl-1-phenylpropan-1-one can be suitably used, and benzophenone, 2,2-dimethoxy-1,2-
Diphenylethane-1-one, 1-hydroxycyclohexylphenyl ketone, 2,4,6-trimethylbenzoyldiphenylphosphon oxide, 1- [4-
(2-Hydroxyethoxy) -phenyl] -2-hydroxy-2-methyl-1-propan-1-one and the like can also be used. Specifically, the photopolymerization initiator is described in “Kiyomi Kato,“ Ultraviolet Curing System ”
(1989) ".

In the photocurable fluid resin composition of the present invention, the inorganic substance of the component (c) may be a powder or fiber of the inorganic substance. Specifically, the average particle size is 0.2
A μm alumina powder is applicable, but is not limited thereto. When the purpose is to form a sintered compact, the inorganic substance may be any powder that can be processed into a ceramic structure by powder sintering of the inorganic substance, and the type and particle size are not particularly limited. For example, porcelain, clay, white clay,
Examples include kaolin compositions, phosphates, silicates, carbides, glass, silica, alumina, zirconia, lead zirconate titanate, and the like. When the purpose is to produce a photocurable resin molded article, inorganic fiber such as glass fiber and asbestos can be used in addition to the above-mentioned inorganic substance powder. The particle size of the powder is not particularly limited, but may be 0.05
The thickness is preferably 100 μm, more preferably 0.1 μm to 10 μm. Although the size of the fiber is not particularly limited, the diameter is 0.05 to 10 μm and the length is 1 to 50.
0 μm is desirable, 0.1-5 μm in diameter and 5 in length.
Those having a thickness of 100 μm are more desirable.

The photocurable fluid resin composition of the present invention is used in an amount of from 0.5 to 10 based on the radical polymerizable monomer having a hydrophilic group.
It is desirable to prepare by mixing a photopolymerization initiator of wt%, preferably 2 wt%, and an inorganic substance of 10 vol% or more, preferably 28 vol% or more based on the radical polymerizable monomer having a hydrophilic group. In particular, when producing a sintered compact, the content of the inorganic substance is desirably as large as possible within a range where the photocurable fluid resin composition of the present invention is sufficiently cured by light irradiation.

The powder-mixed photocurable resin composition of the present invention is prepared by mixing the above components (a) and (b) by an appropriate method, adding a powder thereto, and kneading. The method of mixing the components (a) and (b) is not particularly limited as long as the resin and the like can be homogenized, but a method such as stirring using a stirrer in which a stirrer chip is put in the resin may be used. desirable. Next, the obtained photocurable fluid resin composition is kneaded with the powder of the component (c). The method of kneading is not particularly limited, but a method of kneading using a vacuum defoaming machine or the like that performs stirring while removing air bubbles by applying a vacuum may be used.

The hydrophilic group of the radically polymerizable monomer (a), which is a photocurable fluid resin component of the photocurable fluid resin composition of the present invention, can be added to the photocurable resin by using a metal or metal oxide. It has the property of providing adhesion to inorganic substances such as. Moreover, the photocurable fluid resin composition of the present invention contains an inorganic substance, and the adhesiveness between the inorganic substance and the resin is improved by using a radical polymerizable monomer having a hydrophilic group. Therefore, it is possible to produce a photocurable resin molded article containing an inorganic substance, which is produced by light irradiation or three-dimensional stereolithography, as a structure without cracks or peeling. In addition, it becomes possible to produce a sintered compact produced by sintering the inorganic substance-containing photocurable resin compact as a structure without cracks or peeling.

In the photocurable fluid resin composition according to the second invention, the inorganic substance comprising (c) described in the first invention has a functional group capable of reacting with the inorganic substance on one side chain. It is characterized by being surface-treated with an organic compound having silane and having a functional group capable of radical polymerization on the other side chain.

The “organic compound having a silane having a functional group capable of reacting with an inorganic substance on one side chain and having a functional group capable of radical polymerization on the other side chain” means that an organic compound having a functional group capable of reacting with an inorganic substance on one side chain. The organic compound is not particularly limited as long as it is an organic compound having a silane having a functional group capable of being formed and having a functional group capable of radical polymerization on the other side chain. For example, 3-trimethoxysilylpropyl methacrylate, vinyltrimethoxysilane,
Vinyltriacetoxysilane, 3-trimethoxysilylpropyl methacrylate, trichlorovinylsilane, and triethoxyvinylsilane can be used. In the present invention, 3-trimethoxysilylpropyl methacrylate can be suitably used.

In the present invention, the silane having a functional group capable of reacting with an inorganic substance means a silane group having a functional group capable of reacting with a hydroxyl group present on the surface of the powder.
Therefore, when a surface treatment of powder is performed using an organic compound having a functional group capable of reacting with an inorganic substance on one side chain and having a functional group capable of radical polymerization on the other side chain, The compound reacts with the OH group present on the inorganic substance, and the silane compound is firmly bound to the inorganic substance by a covalent bond. As a result, a monomolecular film having a radically polymerizable functional group on the surface of the inorganic substance is formed.
When the composition of the present invention containing the inorganic substance is irradiated with light such as ultraviolet rays, the functional group capable of radical polymerization on the surface of the inorganic substance and the component (a) are bonded by a chemical bond, and the inorganic substance is photo-cured. The resin and the resin are bonded by a chemical bond. Therefore, by performing the surface treatment, the affinity of the inorganic substance to the resin can be improved, sedimentation can be reduced, and the viscosity can be prevented from increasing. It is possible to improve the content of the inorganic substance with respect to the curable fluid resin. Therefore, the strength of the produced inorganic substance-containing photocurable resin molded article is improved, and the shape retention of the sintered molded article is improved.

Next, a surface treatment method for an inorganic substance will be described. First, a mineral acid such as hydrochloric acid is dropped into a solution obtained by mixing an organic solvent such as an alcohol (for example, ethanol) and water (preferably ion-exchanged water) to adjust the pH of the solution to 3.5 to 3.5.
Adjust to 4.5. To this solution, an organic compound having a silane containing a functional group capable of reacting with an inorganic substance in one side chain and a radically polymerizable functional group in the other side chain is added with stirring. The surface treatment solution is prepared by stirring for 2 hours, preferably 20 minutes to 1 hour. Next, the above-mentioned surface treatment solution is added dropwise while stirring, for example, alumina powder as an inorganic substance of the component (c), and after dropping the entire volume, the mixture is further added for 15 minutes to 2 hours, preferably 30 minutes to 1 hour.
Stirring was continued for hours. Next, it is dried by heating. The heat drying varies depending on the component (d) used, and the drying temperature is set within 10 ° C. before and after the boiling point of the component (d), and is performed for 1 to 5 hours. After drying, the alumina can be ground into a fine powder using an agate mortar.

The other conditions such as the mixing method are as described in the first invention.

The photocurable fluid resin composition according to the third invention is characterized in that the inorganic substance (c) is a powder, and the powder is a powder having two or more particle size distributions. I do.

"Powder having two or more particle size distributions"
The powder of the inorganic substance described in the first invention can be suitably used. The particle size distribution of the inorganic substance powder is not particularly limited, but it is desirable to use a powder having two or more particle size distributions including a particle size distribution of 0.1 to 1 μm. In the present invention, in particular, the average particle size is 5.5 μm.
m, 3 μm, 0.25 μm, and 0.2 μm alumina powders are preferred.

Further, as described in the second invention,
As the powder of the present invention, a powder of an inorganic substance surface-treated with an organic compound having a silane having a functional group capable of reacting with an inorganic substance on one side chain and having a functional group capable of radical polymerization on the other side chain. Can be used.

The other conditions such as the mixing method are the same as those described in the first invention.

[0033]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, a first embodiment of the photocurable fluid resin composition of the present invention will be described.

This embodiment is configured as follows.

In the photocurable fluid resin composition, (a) morpholine acrylate is used as a radical polymerizable monomer having a hydrophilic group, and (b) 2-hydroxy- is used as a photopolymerization initiator.
2-methyl-1-phenylpropan-1-one,
(C) Photocurable fluid resin composition 1 is prepared using alumina powder having an average particle size of 0.2 μm as an inorganic substance. The photocurable fluid resin composition is used in an amount of 0.5 to 10% by weight, preferably 2% by weight based on morpholine acrylate.
Hydroxy-2-methyl-1-phenylpropane-1-
ON and 10 vol for morpholine acrylate
% Or more, preferably 28 vol% or more of alumina powder.

The preparation method of the present invention will be described. First, morpholine acrylate is weighed and then 2-hydroxy-2
-Methyl-1-phenylpropan-1-one is weighed and added and stirred for about 10 minutes using a stirrer. Next, the alumina powder is weighed and added, and the solution is stirred for about 30 minutes using a device capable of stirring the solution while reducing the pressure to obtain a photocurable fluid resin composition.

Next, a method for preparing a photocurable resin molded article 1 containing an inorganic substance using the photocurable fluid resin composition 1 will be described.

Using the photocurable fluid resin composition 1, a photocurable resin molded body 1 is prepared by a three-dimensional stereolithography apparatus.

A specific method of forming a three-dimensional structure by the optical forming method is shown in a process flowchart of FIG.

1) A drawing of a three-dimensional structure is input to a three-dimensional CAD.

2) From the three-dimensional structure, a horizontal slice figure data group is created for each fixed layer thickness.

3) An elevator that moves in the vertical direction is installed in the photocurable fluid resin, and the photocurable fluid resin is positioned so as to have a constant lamination thickness.

4) A laser beam, for example, an excimer laser, a He—Cd laser, or an Ar laser having a wavelength region of ultraviolet rays is scanned along a horizontal section of a target shape to cure the photocurable fluid resin.

5) The elevator is moved again, and the elevator is positioned so as to have a constant lamination thickness, and the uncured photocurable fluid resin flows therein.

6) Steps 4) and 5) are repeated until a three-dimensional structure having the desired shape is completed.

7) The three-dimensional structure is taken out, and the uncured photocurable fluid resin adhering to the surface is washed.

8) Post-exposure is performed.

The three-dimensional structure is manufactured by the above steps.
By such a method, a three-dimensional structure can be manufactured without cutting.

Next, the stereolithography of a three-dimensional structure using the photocurable resin of the present invention will be specifically described with reference to FIG. FIG. 2 shows an example of stereolithography of a three-dimensional structure by a regulated liquid level method. However, the present invention is not limited to the method of the present invention. For example, stereolithography can be performed by a free liquid level method.

FIG. 2 is a conceptual view of the optical molding, in which 21 is a table which moves up and down, 22 is a glass plate which transmits light, 23
Is a tank containing a powder mixed photocurable fluid resin, 24 is a focused laser beam (eg, an ultraviolet laser beam), 25 is a powder mixed photocurable fluid resin, and 26 is a powder mixed resin molded by laser beam irradiation. Represents the body.
FIG. 2A is a diagram illustrating a state of forming a target layer of a three-dimensional structure. First, the 21 tables are arranged so that the 21 tables and the 22 glass surface are at a fixed interval, and 24 laser beams are irradiated. Thereby, the photocurable fluid resin composition is cured, and the first layer of the three-dimensional structure is formed. (B) is a diagram illustrating a state in which the first-layer stereolithography of the three-dimensional resin molded body has been completed. (C) is a diagram showing a state in which the irradiation of the laser beam is stopped and the elevator of 21 is raised at a constant interval in order to perform optical shaping of the second layer of the three-dimensional resin molded body. (D) is a diagram in which the second layer of the three-dimensional resin molded body is optically formed by a laser beam. These steps (A) to (D) are repeated to form the inorganic substance-containing photocurable resin molded article 1 having a desired shape while laminating and forming a three-dimensional resin molded article.

Next, a method for producing a sintered compact 1 using the photocurable resin compact 1 containing an inorganic substance will be described.

The photocurable resin molded article 1 is placed in a furnace, and preferably at a temperature increasing rate of 10 to 500 ° C./hour, more preferably 1 to 500 ° C./hour.
Degreasing is performed at a maximum temperature of 300 to 500 ° C, more preferably at 350 ° C at 00 ° C / hour, and then at a temperature of 1200 to 200
0 ° C., preferably raised to 1500 ° C., for 1-3 hours,
The sintered compact 1 is prepared by sintering for preferably 2 hours.

Morpholine acrylate, which is a photocurable fluid resin component of the above photocurable fluid resin composition, is a radical polymerizable monomer having a morpholino group. The morpholino group is a hydrophilic group and has a property of imparting adhesion to a metal or an inorganic substance to the photocurable resin. The photocurable fluid resin composition contains alumina powder as a metal oxide as an inorganic substance, and the adhesiveness between alumina and the resin is improved by using morpholine acrylate. Therefore, an inorganic substance-containing photocurable resin molded article created by light irradiation or three-dimensional stereolithography or the like, or a sintered molded article created by sintering the inorganic substance-containing photocurable resin molded article, cracks, It is possible to create a structure without peeling.

(A) morpholine acrylate as a radical polymerizable monomer having a hydrophilic group; (b) 2-hydroxy-2-methyl-1-phenylpropan-1-one as a photopolymerization initiator; ) An inorganic substance-containing photocurable resin molded article prepared by light irradiation or three-dimensional stereolithography by forming a photocurable fluid resin composition using an alumina powder having an average particle size of 0.2 μm as an inorganic substance. Alternatively, a sintered molded article produced by sintering the inorganic substance-containing photocurable resin molded article becomes a photocurable fluid resin composition that can be produced as a structure without cracks or peeling.

Each configuration of the embodiment of the present invention is as follows.
Naturally, various modifications and changes are possible.

For example, morpholine acrylate can be a radical polymerizable monomer having another hydrophilic group.

Examples of the radical polymerizable monomer having a hydrophilic group include a hydroxyl group, a carboxyl group, a sulfonic acid group, a phosphoric acid group, a tertiary amine, a quaternary amine hydroxide, a sulfonium group,
It is selected from monomers having a hydrophilic group such as an amide group, an amino group, and a morpholino group, and having at least one or more radically polymerizable functional groups. For example, (meth) acrylic acid, vinyl acetic acid, styrenesulfonic acid, maleic anhydride, 2-acrylamido-2-methylpropanesulfonic acid, N, N-dimethylaminopropylacrylamide,
N, N-dimethylaminoethyl (meth) acrylate,
2-acryloyloxyethyltrimethylammonium chloride, 3-acrylamidopropyltrimethylammonium chloride, morpholine acrylate,
-Hydroxyethyl (meth) acrylate, ethylene glycol (meth) acrylate, acrylamide, glycerol mono (meth) acrylate, vinylpyrrolidone, N-isopropylacrylamide, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, Morpholinoethyl (meth) acrylate, methyl (meth) acrylate, ethyl (meth) acrylate, N, N-dimethylacrylamide, 2-sulfoethyl methacrylate sodium salt, 2-hydroxy-3-phenoxypropyl (meth) ) Acrylate, (2- (meth) acryloyloxyethyl) acid phosphate, N-methacryloxy-N-carboxymethylpiperidine, N-methacryloxy-N, N-dicarboxymethyl-p Phenylenediamine, hydroxy naphthoxycarbonyl methacrylate, methacryloxyethyl phosphate Hollis phenyl, 4-methacryloxyethyl trimellitic anhydride, 4-methacryloxyethyl trimellitic acid, (meth) acryloxyethyl phthalate, 2
-(Meth) acryloyloxyethyl succinic acid and the like are worth it. Radical polymerizable monomer having a hydrophilic group,
It comprises one or more of the above monomers.
It is also possible to use a mixture of the radical polymerizable monomer having a hydrophilic group and the radical polymerizable monomer having no hydrophilic group. Specific examples of the radical polymerizable monomer having no hydrophilic group are described in detail in “Kiyomi Kato,“ Ultraviolet Curing System ”General Technology Center, (1989)” and are not particularly limited. . For example, benzyl (meth) acrylate, dicyclopentenyl (meth) acrylate, dicyclopentenyloxyethyl (meth) acrylate, isobonyl (meth) acrylate, phenoxyethyl (meth) acrylate and the like are worthy of mention.

The 2-hydroxy-2-methyl-1-phenylpropan-1-one can be changed to another photopolymerization initiator.

The photopolymerization initiator is selected from compounds having a function of generating a radical upon irradiation with light. Specifically, it is described in detail in "Seimi Kato," Ultraviolet Curing System "General Technology Center, (1989)", and is not particularly limited. For example, benzophenone,
2,2-dimethoxy-1,2-diphenylethane-1-
On, 1-hydroxycyclohexyl phenyl ketone,
2,4,6-trimethylbenzoyldiphenylphosphon oxide, 1- [4- (2-hydroxyethoxy) -phenyl] -2-hydroxy-2-methyl-1-methyl
Propan-1-one and the like are worth it.

The alumina powder can be changed to a powder or fiber of another inorganic substance.

For the purpose of producing a sintered compact, the inorganic substance may be any powder that can be processed into a ceramic structure by powder sintering of the inorganic substance, and the type and particle size are not particularly limited. is not. Examples include porcelain, clay, porcelain clay, kaolin composition, phosphate, silicate, carbide, glass, silica, alumina, zirconia, lead zirconate titanate, and the like. When the purpose is to produce a photocurable resin molded article, inorganic fiber such as glass fiber and asbestos can be used in addition to the above-mentioned inorganic substance powder. The particle size of the powder is not particularly limited, but is preferably 0.05 to 100 μm, and 0.1 to 100 μm.
10 μm is more desirable. Although the size of the fiber is not particularly limited, the diameter is 0.05 to 10 μm,
It is desirable that the length is 1 to 500 μm, and the diameter is 0.1 to 5
μm and a length of 5 to 100 μm are more desirable.

A radical polymerizable monomer having a hydrophilic group,
The photocurable fluid resin composition prepared by mixing a photopolymerization initiator and an inorganic substance has a photopolymerization ratio of 0.5 to 10% by weight, preferably 2% by weight, based on the radical polymerizable monomer having a hydrophilic group. It is desirable to contain an initiator and 10 vol% or more, preferably 28 vol% or more of an inorganic substance with respect to the radical polymerizable monomer having a hydrophilic group. In particular, when a sintered compact is produced, the content of the inorganic substance is desirably as large as possible within a range where the photocurable fluid resin composition is sufficiently cured by light irradiation.

Next, a second embodiment of the present invention will be described.

This embodiment is configured as follows.

The photocurable fluid resin composition of the present embodiment comprises methacrylic acid-3 as an inorganic component (c) contained in the photocurable fluid resin composition 1 described in the first embodiment. Using an alumina powder having a mean particle size of 0.2 μm surface-treated with trimethoxysilylpropyl.
That is, the surface-treated alumina powder is mixed with the components (a) and (b) described in the first embodiment to prepare a photocurable fluid resin composition 2. The photocurable fluid resin composition of the present embodiment is 0.5 to 10% by weight, preferably 2% by weight, of morpholine acrylate.
Hydroxy-2-methyl-1-phenylpropane-1-
ON and 10 vol for morpholine acrylate
%, Preferably 28 vol% or more of alumina powder.

Next, a method of surface treating alumina powder with 3-trimethoxysilylpropyl methacrylate will be described.

1) Based on the weight of the alumina powder to be treated, 2% by weight of 3-trimethoxysilylpropyl methacrylate, 20% by weight of ethanol, and 20% by weight of ion-exchanged water are weighed.

2) Ethanol and ion-exchanged water are mixed to prepare a mixed solution having a ratio of 1: 1. Further, hydrochloric acid is added dropwise to adjust the pH of the solution to 3.5 to 4.5.

2) To the mixed solution was added 3-trimethoxysilylpropyl methacrylate, and the mixture was stirred for about 20 minutes as a mixed solution having a concentration of 5 wt% of 3-trimethoxysilylpropyl methacrylate. Is prepared.

3) The surface treatment solution 1 was dropped while stirring the alumina powder, and after dropping the whole volume, the mixture was stirred for 30 minutes.

4) Spread the alumina powder thinly in a stainless steel vat, and heat dry in a dryer at 120 ° C. for 3 hours.

5) After drying, the hardened alumina powder is pulverized using an agate mortar and returned to a powder form.

The alumina powder having been subjected to the surface treatment in the above steps can be obtained.

The method for forming the inorganic substance-containing photocurable resin molded article 2 using the photocurable fluid resin composition 2 and the method for preparing the sintered molded article 2 are the same as those in the first embodiment.

The 3-trimethoxysilylpropyl methacrylate surface-treated with alumina powder of the photocurable fluid resin composition has a silane having a functional group capable of reacting with an inorganic substance on one side chain, and Is an organic compound having a radically polymerizable functional group on the side chain of When the surface treatment of a metal oxide such as alumina powder is performed using the organic compound, the silane compound reacts with the hydroxyl group of the metal oxide, and the silane compound is strongly bonded to the metal oxide by a covalent bond. Then, a monomolecular film is formed on the surface of the metal oxide with a radically polymerizable functional group exposed on the surface. When the composition containing the metal oxide is irradiated with light such as ultraviolet light, the radically polymerizable functional group on the surface of the metal oxide and the photocurable fluid resin are bonded by a chemical bond, and the metal oxide and the photocurable resin are cured. The bonded resin is joined by a chemical bond.
For this reason, the surface treatment can improve the affinity of the inorganic substance to the resin, reduce the precipitation, and also prevent the viscosity from increasing. Therefore, it is possible to improve the content of the inorganic substance in the photocurable fluid resin as compared with the case where an untreated inorganic substance is used. Thereby, the strength of the produced inorganic substance-containing photocurable resin molded body is improved, and the shape retention of the sintered molded body is improved.

The photocurable fluid resin composition of this embodiment is added to the inorganic substance component (c) contained in the photocurable fluid resin composition 1 described in the first embodiment, and to one side chain. Alumina powder which has a silane having a functional group capable of reacting with an inorganic substance and is surface-treated with 3-trimethoxysilylpropyl methacrylate, which is an organic compound having a functional group capable of radical polymerization on the other side chain, is used. Thereby, the photocurable fluid resin composition which can improve the strength of the photocured inorganic substance-containing photocurable resin molded article and improve the shape retention of the sintered molded article can be obtained.

The embodiments of the present invention can of course be variously modified and changed.

For example, as described in the first embodiment, the morpholine acrylate contained in the photocurable fluid resin composition can be changed to another radically polymerizable monomer having a hydrophilic group. It is. 2-hydroxy-2-
Methyl-1-phenylpropan-1-one can be changed to another photopolymerization initiator as described in the first embodiment.

The alumina powder can be changed to any other inorganic substance as long as it is an inorganic substance having a hydroxyl group on the surface. In the present embodiment, the powder or fiber of the inorganic substance can be used. It is not limited to powder. Examples of the inorganic substance having a hydroxyl group on its surface include metal oxides, and are selected from, for example, silica, alumina, lead zirconate titanate, and the like. The size of the inorganic substance can be changed as described in the first embodiment.

The 3-trimethoxysilylpropyl methacrylate is an organic compound having a silane having a functional group capable of reacting with inorganic powder on one side chain and a radically polymerizable functional group on the other side chain. If so, other compounds can be used. Specifically, vinyltrimethoxysilane, vinyltriacetoxysilane, methacrylic acid-3-
It is selected from trimethoxysilylpropyl, trichlorovinylsilane, triethoxyvinylsilane and the like.

A radical polymerizable monomer having a hydrophilic group,
The photocurable fluid resin composition of the present embodiment prepared by mixing a photopolymerization initiator and an inorganic substance has a content of 0.5 to 10% by weight, preferably 0.5 to 10% by weight, based on the radical polymerizable monomer having a hydrophilic group. Preferably contains 2 wt% of the photopolymerization initiator and 10 vol% or more, preferably 28 vol% or more of the inorganic substance based on the radical polymerizable monomer having a hydrophilic group. In particular, when a sintered compact is produced, the content of the inorganic substance is desirably as large as possible within a range where the photocurable fluid resin composition is sufficiently cured by light irradiation.

Next, a third embodiment of the photocurable fluid resin composition of the present invention will be described.

This embodiment is configured as follows.

The photocurable fluid resin composition of the present embodiment has an average particle size of 5.0 as the inorganic substance component (c) contained in the photocurable fluid resin composition 1 described in the first embodiment.
A mixture of alumina powders of 5 μm, 3 μm, 0.25 μm, and 0.2 μm in a weight ratio of 1.5: 2: 1: 1 is used. That is, the mixture of the above alumina powder is mixed with the components (a) and (b) described in the first embodiment to prepare the photocurable fluid resin composition 3. The photocurable fluid resin composition 3 contains 0.5 to 10% by weight, preferably 2% by weight, of 2-hydroxy-2-methyl-1-phenylpropan-1-one and morpholine acrylate based on morpholine acrylate. 10 vol%
As described above, preferably 28 vol% or more of the above-mentioned alumina powder is contained.

The method for forming the inorganic substance-containing photocurable resin molded body 3 using the photocurable fluid resin composition 3 and the method for preparing the sintered molded body 3 are the same as those in the first embodiment.

The photocurable fluid resin composition 3 contains alumina powder as an inorganic substance. The larger the particle size of the alumina powder, the larger the content of the resin can be reduced because the larger the viscosity of the resin can be reduced, the greater the strength of the inorganic material-containing photocurable resin molded product can be improved, and the better the shape retention of the sintered molded product can be improved. But,
Surface smoothness decreases. On the other hand, when the particle size is small, the surface smoothness is improved, but when a large amount of powder having a small particle size is mixed, the viscosity becomes high and processing becomes difficult.

The photocurable fluid resin composition 3 has good surface smoothness by using alumina powder having two or more particle size distributions as the component (c).
In addition, the strength of the inorganic substance-containing photocurable resin molded article can be improved, and the shape retention of the sintered molded article can be improved.

The photocurable fluid resin is used as the inorganic substance component (c) contained in the photocurable fluid resin composition 1 according to the first embodiment by using powders having two or more particle size distributions. By preparing the composition, it has a surface smoothness, and improves the strength of the produced inorganic substance-containing photocurable resin molded body, it is possible to improve the shape retention of the sintered molded body,
It becomes a photocurable fluid resin composition.

The embodiments of the present invention can of course be variously modified and changed.

For example, the morpholine acrylate contained in the photocurable fluid resin composition 3 can be changed to another radical polymerizable monomer having a hydrophilic group as described in the first embodiment. is there. As described in the first embodiment, 2-hydroxy-2-methyl-1-phenylpropan-1-one can be changed to another photopolymerization initiator.

The alumina powder can be changed to a powder of another inorganic substance as described in the first embodiment.
Further, as described in the second embodiment, the surface is formed by an organic compound having a silane having a functional group capable of reacting with an inorganic substance on one side chain and a radically polymerizable functional group on the other side chain. Conversion of the treated inorganic material to a powder is possible.

The particle size distribution of the alumina powder is not particularly limited, but is a particle size distribution of 0.1 to 1 μm, and a powder having two or more particle size distributions within the particle size distribution. It is desirable to use

The composition ratio of the photocurable fluid resin composition of the present embodiment can be changed as described in the first embodiment.

Next, a fourth embodiment of the photocurable fluid resin composition of the present invention will be described.

This embodiment is configured as follows.

The photocurable fluid resin composition of the present embodiment has an average particle diameter of 0.1 as the inorganic substance component (c) contained in the photocurable fluid resin composition 1 described in the first embodiment.
A mixture of alumina powder of 2 μm and silica powder of average particle diameter of 0.2 μm in a volume ratio of 10: 1 is used, that is, the components (a) and (b) described in the first embodiment are used. A photocurable fluid resin composition 4 is prepared using a mixture of the above alumina powder. The photocurable fluid resin composition 4 has a morpholine acrylate content of 0.5 to
10 wt%, preferably 2 wt% of 2-hydroxy-2
-Methyl-1-phenylpropan-1-one and a mixed powder of 10 vol% or more, preferably 28 vol% or more based on morpholine acrylate.

The method for producing the inorganic substance-containing photocurable resin molded article 4 using the photocurable fluid resin composition 4 and the method for producing the sintered molded article 4 are the same as those in the first embodiment. The curable fluid resin composition contains two types of ceramic powders having different sintering temperatures. When a sintered compact is produced, silica powder having a low sintering temperature is sintered first, and alumina powder is later formed. Sinter. Since the sintering is performed in a stepwise manner, distortion generated during sintering is reduced, and the shape retention of the sintered compact is improved.

[0098] The inorganic material component (c) contained in the photocurable fluid resin composition 1 described in the first embodiment is prepared by using two or more ceramic powders having different sintering temperatures. By preparing the resin composition, a photocurable fluid resin composition capable of improving the shape retention of the sintered compact is obtained.

It is to be noted that the embodiments of the present invention can of course be variously modified and changed.

For example, as described in the first embodiment, the morpholine acrylate contained in the photocurable fluid resin composition can be changed to another radical polymerizable monomer having a hydrophilic group. . 2-hydroxy-2-methyl-
1-phenylpropan-1-one can be changed to another photopolymerization initiator as described in the first embodiment.

The inorganic material powder is not particularly limited as long as it is at least two types of ceramic powders having different sintering temperatures. Therefore, the alumina powder and the silica powder can be changed to a powder of another inorganic substance as described in the first embodiment, and one side as described in the second embodiment. It is possible to change the inorganic material into a powder whose surface is treated with an organic compound having a silane having a functional group capable of reacting with an inorganic substance in the chain and having a functional group capable of radical polymerization on the other side chain. It is also possible to use a powder having two or more particle size distributions as described in the third embodiment.

The composition ratio of the photocurable fluid resin composition of the present embodiment can be changed as described in the first embodiment.

Next, a fifth embodiment of the photocurable fluid resin composition of the present invention will be described.

This embodiment is configured as follows.

The photocurable fluid resin composition of the present embodiment comprises morpholine acrylate and glycerol (mono) as the component (a) contained in the photocurable fluid resin composition 1 described in the first embodiment. ) A methacrylate is used at a weight ratio of 6: 4. That is, the components (b) and (c) described in the first embodiment are mixed with the monomer mixture 1 to prepare a photocurable fluid resin composition 5. The photocurable fluid resin composition 5
Is 0.5 to 10 with respect to the monomer mixture 1 of the component (a).
wt%, preferably 2 wt%, of 2-hydroxy-2-methyl-1-phenylpropan-1-one and at least 10 vol%, preferably 28 vol%, based on the monomer mixture 1.
1% or more of alumina powder.

The method for forming the inorganic substance-containing photocurable resin molded article 5 using the photocurable fluid resin composition 5 and the method for preparing the sintered molded article 5 are the same as those in the first embodiment.

The photocurable fluid resin composition contains two kinds of monomers as radical polymerizable monomers having a hydrophilic group. Since these two types of monomers have different decomposition temperatures, degreasing can be performed in a stepwise manner when degreasing in the step of producing a sintered compact. For this reason, distortion generated by thermal decomposition of the monomer mixture 1 having a hydrophilic group during degreasing is reduced,
Shape retention of the sintered compact is improved.

The photocurable fluid resin composition was prepared by using two radical polymerizable monomers having a hydrophilic group as the component (a) contained in the photocurable fluid resin composition 1 described in the first embodiment. By preparing the product, a photocurable fluid resin composition capable of improving the shape retention of the sintered compact is obtained.

The embodiments of the present invention can of course be variously modified and changed.

For example, morpholine acrylate and glycerol (mono) methacrylate contained in the photocurable fluid resin composition may be other radical polymerizable monomers having a hydrophilic group as described in the first embodiment. Can be changed. The monomer mixture 1 can be a mixture of radically polymerizable monomers having two or more hydrophilic groups. Although the composition ratio is not particularly limited, it is preferable that each of the monomers to be mixed has a mixing ratio of 10 mol% or more. 2-hydroxy-2-methyl-1-phenylpropan-1-one can be changed to another photopolymerization initiator as described in the first embodiment. Alumina powder is first
Other inorganic substances as described in the fourth to fourth embodiments can be changed.

The photocurable fluid resin composition of the present embodiment is 0.5 to 10% by weight, preferably 2% by weight, of 2-hydroxy-2-methyl-1-phenylpropane-based monomer mixture 1. 1-one and 10% by volume or more, preferably 28% by volume or more of alumina powder with respect to the monomer mixture 1 are mixed.

Next, a sixth embodiment of the photocurable fluid resin composition of the present invention will be described.

The present embodiment is configured as follows.

The photocurable fluid resin composition of the present embodiment comprises morpholine acrylate and pentaerythritol triacetate as component (a) contained in the photocurable fluid resin composition 1 described in the first embodiment. A monomer mixture 2 mixed with acrylate is used. That is, the monomer mixture 2
Then, the components (b) and (c) described in the first embodiment are mixed to prepare a photocurable fluid resin composition 6. The monomer mixture 2 was added in an amount of 0.1 to morpholine acrylate.
1-20 mol%, preferably 0.5-1 mol% of pentaerythritol triacrylate is mixed. The photocurable fluid resin composition 6 comprises 0.5 to 10% by weight, preferably 2% by weight of 2-hydroxy-2-methyl-1-phenylpropan-1-one based on the monomer mixture 2, It is constituted by mixing 10 vol% or more, preferably 28 vol% or more of alumina powder with respect to the monomer mixture 2.

The method for forming the inorganic substance-containing photocurable resin molded article 6 using the photocurable fluid resin composition 6 and the method for preparing the sintered molded article 6 are the same as those in the first embodiment.

The photocurable fluid resin composition contains two kinds of monomers as radical polymerizable monomers having a hydrophilic group. Since these two types of monomers have different decomposition temperatures, degreasing can be performed in a stepwise manner when degreasing in the step of producing a sintered compact. For this reason, at the time of degreasing, distortion generated by thermal decomposition of the monomer mixture 2 having a hydrophilic group is reduced,
Shape retention of the sintered compact is improved.

Since one of the two types of radically polymerizable monomers having a hydrophilic group is a monomer having two or more radically polymerizable functional groups, an inorganic substance-containing photocurable material prepared by light irradiation is used. The resin molded body is three-dimensionally cross-linked by the photocurable resin, and the material strength is improved.

The component (a) contained in the photocurable fluid resin composition 1 according to the first embodiment includes a monomer having a hydrophilic group and one radically polymerizable functional group, By preparing a photocurable fluid resin composition using two kinds of monomers having a hydrophilic group and having two or more radically polymerizable functional groups, the material of the inorganic substance-containing photocurable resin molded article is prepared. A photocurable fluid resin composition having improved strength and capable of improving the shape retention of the sintered compact.

The present embodiment is, of course, of various modifications,
Changes are possible.

For example, the morpholine acrylate contained in the photocurable fluid resin composition has another hydrophilic group as described in the first and fifth embodiments and has one radical polymerizable functional group. It is possible to change to a monomer having one. 2-hydroxy-2-methyl-1-phenylpropan-1-one can be changed to another photopolymerization initiator as described in the first embodiment. The alumina powder can be changed to another inorganic substance as described in the first to fourth embodiments.

Further, pentaerythritol triacrylate can be changed to a monomer having another hydrophilic group and two or more radically polymerizable functional groups. Examples of such monomers include glycerol di (meth) acrylate, 2-hydroxy-3-acryloyloxypropyl (meth) acrylate, N, N'-methylenebisacrylamide, and the like.

A monomer comprising a monomer having the hydrophilic group and one radically polymerizable functional group and a monomer having the hydrophilic group and two or more radically polymerizable functional groups The composition ratio of the mixture 2 is 0.1 to 20 mol with respect to the monomer having the hydrophilic group and one radically polymerizable functional group.
%, Preferably 0.5 to 1 mol%, of a monomer having two or more radically polymerizable functional groups.

The photocurable fluid resin composition is used in an amount of 0.5 to 10% by weight, preferably 2% by weight, based on the mixed monomer 2.
10 vol. With respect to the mixed monomer 2
%, Preferably 28 vol% or more of an inorganic substance. In particular, when a sintered compact is produced, the content of the inorganic substance is desirably as large as possible within a range where the photocurable fluid resin composition is sufficiently cured by light irradiation.

Next, a seventh embodiment of the photocurable fluid resin composition of the present invention will be described.

This embodiment is configured as follows.

The photocurable fluid resin composition of the present embodiment has a diameter of 0.5 to 0.5 as the inorganic substance component (c) contained in the photocurable fluid resin composition 1 described in the first embodiment.
A silica fiber having a length of 1 μm and a length of 10 to 30 μm is used. That is, the above-mentioned silica fibers are mixed with the components (a) and (b) described in the first embodiment to prepare the photocurable fluid resin composition 7. The photocurable fluid resin composition contains 0.5 to 10% by weight, preferably 2% by weight, of morpholine acrylate and 2-hydroxy-2-methyl-1-phenylpropan-1-one, and morpholine acrylate. On the other hand, it is constituted by mixing with 1 vol% or more, preferably 5 vol% or more of silica fibers. The content of the silica fiber is desirably as large as possible within a range where the photocurable fluid resin composition is sufficiently cured by light irradiation.

The method for producing the inorganic substance-containing photocurable resin molded article 7 using the photocurable fluid resin composition 7 is the same as in the first embodiment.

The above-mentioned photocurable fluid resin composition contains silica fiber as an inorganic substance, and has an inorganic substance-containing light produced by light irradiation, compared to a photocurable fluid resin composition containing powder as an inorganic substance. The material strength of the curable resin molded body is improved.

The photocurable fluid resin composition is prepared by using a fibrous inorganic substance as the component (c) contained in the photocurable fluid resin composition 1 described in the first embodiment. Thus, a photocurable fluid resin composition capable of improving the material strength of the inorganic substance-containing photocurable resin molded article is obtained.

It is to be noted that various modifications and changes can be made to the embodiment of the present invention.

For example, the morpholine acrylate contained in the photocurable fluid resin composition has another hydrophilic group as described in the first and fifth embodiments and has one radical polymerizable functional group. It is possible to change to a monomer having one. 2-hydroxy-2-methyl-1-phenylpropan-1-one can be changed to another photopolymerization initiator as described in the first embodiment. The silica fiber can be changed to another inorganic material fiber as described in the first embodiment. Although the size of the fiber is not particularly limited, the diameter is 0.05 to 10 μm and the length is 1 to 50.
0 μm is desirable, 0.1-5 μm in diameter and 5 in length.
Those having a thickness of 100 μm are more desirable.

The photocurable fluid resin composition prepared by mixing the radically polymerizable monomer having a hydrophilic group, the photopolymerization initiator, and the fibrous inorganic substance is a radical polymerizable monomer having the hydrophilic group. 0.5 to 10% by weight, preferably 2% by weight, of the photopolymerization initiator with respect to the polymerizable monomer, and 1 vol% or more, preferably 5 vol% or more with respect to the radical polymerizable monomer having a hydrophilic group. It is desirable to mix and mix the above fibrous inorganic substances. The content of the fibrous inorganic substance is desirably as large as possible within a range where the photocurable fluid resin composition is sufficiently cured by light irradiation.

Next, an eighth embodiment of the photocurable fluid resin composition of the present invention will be described.

This embodiment is configured as follows.

The photocurable fluid resin composition 8 of the present embodiment
Is contained in the photocurable fluid resin composition 6 according to the sixth embodiment, instead of the component (a) contained in the photocurable fluid resin composition 2 according to the second embodiment. Component (a), a monomer mixture 2 in which morpholine acrylate and pentaerythritol triacrylate are mixed
Is used. That is, the components (b) and (c) described in the second embodiment are mixed with the component (a) in the sixth embodiment to prepare the photocurable fluid resin composition 8. The photocurable fluid resin composition is used in an amount of 0.5 to 10% by weight, preferably 2% by weight based on the monomer mixture 2.
Hydroxy-2-methyl-1-phenylpropane-1-
ON and 10 vol% or more with respect to the monomer mixture 2;
Preferably, 28 vol% or more of alumina powder surface-treated with 3-trimethoxysilylpropyl methacrylate is mixed.

The method of forming the inorganic substance-containing photocurable resin molded article 8 using the photocurable fluid resin composition 8 and the method of preparing the sintered molded article 8 are the same as in the first embodiment.

The photo-curable fluid resin composition of this embodiment is a photo-curable fluid resin composition having both the functions and effects of the second embodiment and the functions and effects of the sixth embodiment. That is, the photocurable fluid resin composition can improve the material strength of the inorganic substance-containing photocurable resin molded article and improve the shape retention of the sintered molded article.

The embodiment of the present invention can be variously modified and changed in the same manner as those described in the second and sixth embodiments.

Next, a ninth embodiment of the photocurable fluid resin composition of the present invention will be described.

This embodiment is configured as follows.

The photocurable fluid resin composition of this example is the same as the photocurable fluid resin composition 8 described in the eighth embodiment, except that the inorganic substance component (c) contained in the resin composition of the fourth embodiment is used. And the inorganic substance component (C) contained in the photocurable fluid resin composition 4 described in (1). That is, a mixture in which alumina powder having an average particle diameter of 0.2 μm and silica powder having an average particle diameter of 0.2 μm are mixed with the components (a) and (b) of the eighth embodiment in a volume ratio of 10: 1, respectively. A powder, which has been surface-treated with 3-trimethoxysilylpropyl methacrylate, is mixed to prepare a photocurable fluid resin composition 9.

The photocurable fluid resin composition is used in an amount of 0.5 to 10% by weight, preferably 2% by weight, based on the monomer mixture 2.
Of 2-hydroxy-2-methyl-1-phenylpropan-1-one and 10 vol% based on the monomer mixture 2.
Or more, preferably 28 vol% or more of methacrylic acid-3
Mixing with the mixed powder surface-treated with trimethoxysilylpropyl.

The method for forming the inorganic substance-containing photocurable resin molded article 9 using the photocurable fluid resin composition 9 and the method for preparing the sintered molded article 9 are the same as those in the first embodiment.

The method of surface treatment of the powder is the same as in the second embodiment.

A photocurable fluid resin composition having the effects of the second embodiment, the effects of the fourth embodiment, and the effects of the sixth embodiment is obtained.

The embodiment of the present invention can be variously modified and changed as described in the second, fourth and sixth embodiments.

Next, a tenth embodiment of the photocurable fluid resin composition of the present invention will be described.

This embodiment is configured as follows.

The photocurable fluid resin composition according to the present embodiment includes, as (a) contained in the photocurable fluid resin composition 1 described in the first embodiment, a radical having a cationic ionic group. 2-acryloyloxyethyltrimethylammonium chloride which is a polymerizable monomer is used, and as the component (c), lead zirconate titanate powder having an average particle diameter of 0.2 μm is used. That is, the component (a) and (c) are mixed with the component (b) described in the first embodiment to form the photocurable fluid resin composition 10. The photocurable fluid resin composition is 0.5 to 10 wt% based on 2-acryloyloxyethyltrimethylammonium chloride.
%, Preferably 2% by weight of 2-hydroxy-2-methyl-1-phenylpropan-1-one and 10% by volume or more, preferably 28% by volume or more of zirconate titanate based on 2-acryloyloxyethyltrimethylammonium chloride Mix with lead powder.

The method for forming the inorganic substance-containing photocurable resin molded body 10 using the photocurable fluid resin composition 10 and the method for preparing the sintered molded body 10 are the same as those in the first embodiment.

Component (c) of the photocurable fluid resin composition
Since the lead zirconate titanate powder is a powder having piezoelectric characteristics, unlike a simple ceramic powder, the inorganic substance-containing photocurable resin molded article formed by using the photocurable fluid resin of the present embodiment or a sintered body The formed body can function as a piezoelectric body. However, since the photocurable fluid resin composition containing lead zirconate titanate powder has the property of absorbing ultraviolet light, the photocurable fluid resin cured with ultraviolet light contains an inorganic substance. It is difficult to produce a photocurable resin molded body. However, when the 2-acryloyloxyethyltrimethylammonium chloride of the present embodiment is used as the photocurable fluid resin, the inorganic substance-containing photocurable resin molded article can be formed.

The reason for this is not clear, but may be due to the interaction between the ionic group of 2-acryloyloxyethyltrimethylammonium chloride and lead zirconate titanate. 2-acryloyloxyethyltrimethylammonium chloride has a cationic ionic group, and the same effect is obtained when a radical polymerizable monomer having another cationic ionic group is used. On the other hand, a radical polymerizable monomer having no ionic group, a radical polymerizable monomer having an anionic ionic group,
When a radical polymerizable monomer having a nonionic ionic group is used, the above effect is not obtained.

The photocurable fluid resin composition 1 according to the first embodiment includes (a) 2-acryloyloxyethyltrimethylammonium, which is a radically polymerizable monomer having a cationic ionic group. By preparing a photocurable fluid resin composition using chloride and lead zirconate titanate powder having an average particle diameter of 0.2 μm in (c), an inorganic substance-containing photocurable resin molded product having piezoelectric properties is obtained, And a photocurable fluid resin composition capable of producing a sintered molded article.

Note that each configuration of the embodiment of the present invention
Naturally, various modifications and changes are possible.

For example, 2-acryloyloxyethyltrimethylammonium chloride contained in the photocurable fluid resin composition can be changed to another radically polymerizable monomer having a cationic ionic group. For example,
N, N-dimethylaminopropylacrylamide, N,
N-dimethylaminoethyl (meth) acrylate, N,
N-dimethylaminopropylacrylamide, 3-acrylamidopropyltrimethylammonium chloride and the like are worth it.

The particle size of the lead zirconate titanate powder is not particularly limited, but is preferably from 0.05 to 100 μm, more preferably from 0.1 to 10 μm.

The photocurable fluid resin composition prepared by mixing the radical polymerizable monomer having a cationic ionic group, the photopolymerization initiator, and the lead zirconate titanate powder has a hydrophilic property. 0.5 to 10 wt%, preferably 2 wt%, of the photopolymerization initiator based on the radical polymerizable monomer having a group, and 10 vol% or more, preferably, based on the radical polymerizable monomer having the hydrophilic group. Is desirably mixed with 28 vol% or more of the inorganic substance. In particular, when a sintered compact is produced, the content of the inorganic substance is desirably as large as possible within a range where the photocurable fluid resin composition is sufficiently cured by light irradiation.

Next, an eleventh embodiment of the photocurable fluid resin composition of the present invention will be described.

The present embodiment is configured as follows.

The photocurable fluid resin composition of this embodiment is a photopolymerization initiator composed of (b) contained in the photocurable fluid resin composition 10 described in the tenth embodiment.
Bis (cyclopentadienyl) -bis (2,6-difluoro-3- (pyr-1-yl) titanium is used, that is, the components (a) and (c) described in the tenth embodiment are replaced by components ( As b), photocurable fluid resin composition 11 using bis (cyclopentadienyl) -bis (2,6-difluoro-3- (pyr-1-yl) titanium)
Is prepared. The photocurable fluid resin composition contains 0.5 to 10% by weight, preferably 2% by weight, of bis (cyclopentadienyl) -bis (2,6-difluoro-3) based on 2-acryloyloxyethyltrimethylammonium chloride. -(Pyr-1-yl) titanium and 10 vol% or more, preferably 28 vol% or more of lead zirconate titanate powder based on 2-acryloyloxyethyltrimethylammonium chloride are mixed.

The method of forming the inorganic substance-containing photocurable resin molded article 11 using the photocurable fluid resin composition 11 and the method of preparing the sintered molded article 11 are the same as those in the first embodiment.

However, the light source used in the production apparatus is 3
A light source that can emit light having a wavelength of 60 nm or more is used.
For example, an Ar laser, a xenon laser, an ultra-high pressure mercury lamp, etc. are worthy of this.

As described in the tenth embodiment, the photocurable fluid resin composition containing the lead zirconate titanate powder has a property that the lead zirconate titanate absorbs ultraviolet light. It is difficult to produce a photocurable resin molded article containing an inorganic substance with a photocurable fluid resin that is cured by ultraviolet rays. The photo-curable fluid resin composition 11 uses the radically polymerizable monomer having a cationic ionic group described in the tenth embodiment, and is used as a photo-polymerization initiator that generates a radical in a visible light region. Since (cyclopentadienyl) -bis (2,6-difluoro-3- (pyr-1-yl) titanium is used, it is possible to prepare the inorganic substance-containing photocurable resin molded article.

(A) contained in the photocurable fluid resin composition 1 described in the first embodiment, 2-acryloyloxyethyltrimethylammonium chloride is used as a radical polymerizable monomer having a cationic ionic group. And (b) bis (cyclopentadienyl) -bis (2,6-difluoro-3- (pyr-1) as a photopolymerization initiator which generates a radical by light having a wavelength of 360 nm or more in (b).
-Yl) using titanium, and (c) having an average particle size of 0.2 μm.
m, by forming a photocurable fluid resin composition using lead titanate zirconate powder, an inorganic substance-containing photocurable resin molded product having piezoelectric properties, and a sintered molded product can be produced. , Resulting in a photocurable fluid resin composition.

Note that each configuration of the embodiment of the present invention
Various modifications and changes as described in the tenth embodiment are possible.

For example, bis (cyclopentadienyl) -bis (2,6-difluoro-3- (pyr-1-yl) titanium contained in the photocurable fluid resin composition has another wavelength of 360 nm or more. It is possible to change the compound to generate a radical by the light of, for example, 2,4-diethylthioxanthone, isopropylthioxanthone, 1-chloro-4-propoxythioxanthone, 2- (3-dimethylamino-2-hydroxypropoxy)- 3,4-dimethyl-9H-thioxanthone-9-one mesochloride, 2-methyl-1- [4- (methylthio) phenyl]
-2-morpholinopropane-1,2-benzyl-2-
Dimethylamino-1- (4-morpholinophenyl)-
Butanone-1 and the like are worth it. Also, 1,3-di (t-butyldioxycarbonyl) benzene, 3,3
Peroxyesters such as 3 ′, 4,4′-tetra- (t-butylperoxycarbonyl) benzophenone;
A mixture of a thiopyrylium salt, a merocyanine, a quinoline, and a stilquinoline dye can also be used.

Next, a twelfth embodiment of the photocurable fluid resin composition of the present invention will be described.

This embodiment is configured as follows.

As the lead titanate zirconate powder contained in the photocurable fluid resin composition 11 according to the eleventh embodiment, lead zirconate titanate surface-treated with 3-trimethoxysilylpropyl methacrylate Use powder. That is, the component (a) described in the eleventh embodiment
In (b), the photocurable fluid resin composition 12 is prepared using the surface-treated lead zirconate titanate powder.
The photocurable fluid resin composition has a ratio of 0.2 to 2-acryloyloxyethyltrimethylammonium chloride.
5-10 wt%, preferably 2 wt%, of bis (cyclopentadienyl) -bis (2,6-difluoro-3- (pyr-1-yl) titanium and 2-acryloyloxyethyltrimethylammonium chloride
vol% or more, preferably 28 vol% or more, is mixed with a surface-treated lead zirconate titanate powder.

The method for forming the inorganic substance-containing photocurable resin molded body 12 using the photocurable fluid resin composition 12 and the method for preparing the sintered molded body 12 are the same as those in the first embodiment.

However, the light source used in the production apparatus is 3
A light source that can emit light having a wavelength of 60 nm or more is used. For example, an Ar laser, a xenon laser, an ultra-high pressure mercury lamp, etc. are worthy of this.

The photo-curable resin composition of the present embodiment is a photo-curable fluid resin composition having the functions and effects of the second embodiment and the eleventh embodiment. That is, it is possible to improve the strength of the photocurable inorganic substance-containing photocurable resin molded article, improve the shape retention of the sintered molded article, and have the inorganic substance-containing photocurable resin molded article having piezoelectric characteristics. And a photocurable fluid resin composition capable of producing a sintered compact.

The embodiment of the present invention can be variously modified and changed as described in the second and eleventh embodiments.

Next, a thirteenth embodiment of the photocurable fluid resin composition of the present invention will be described.

This embodiment is configured as follows.

The photocurable fluid resin composition of the present embodiment is a radical polymerizable resin comprising 2-acryloyloxyethyltrimethylammonium chloride contained in the photocurable fluid resin composition 11 described in the eleventh embodiment. Instead of the monomer, a monomer mixture 3 in which 2-acryloyloxyethyltrimethylammonium chloride, N, N-dimethylaminopropylacrylamide and pentaerythritol triacrylate are mixed is used. That is,
The photocurable fluid resin composition 13 is formed by mixing the monomer mixture 3 with the components (b) and (c) of the eleventh embodiment. The monomer mixture 3 was prepared by adding 10 to 2-acryloyloxyethyltrimethylammonium chloride.
５０50 mol%, preferably 30-40 mol% of N,
N-dimethylaminopropylacrylamide and 0.1 to 30 mol%, preferably 10 to 30 mol%, based on 2-acryloyloxyethyltrimethylammonium chloride
It is constituted by mixing 20 mol% of pentaerythritol triacrylate.

The photocurable fluid resin composition is used in an amount of 0.5 to 10% by weight, preferably 2% by weight, based on the monomer mixture 3.
% Of bis (cyclopentadienyl) -bis (2,6-difluoro-3- (pyr-1-yl) titanium and 10 vol% or more, preferably 2 vol.
It is constituted by mixing with 8 vol% or more of lead zirconate titanate powder.

The method for producing the inorganic substance-containing photocurable resin molded article 13 using the photocurable fluid resin composition 13 and the method for producing the sintered molded article 13 are the same as in the first embodiment.

However, the light source used in the producing apparatus is 3
A light source that can emit light having a wavelength of 60 nm or more is used.
For example, an Ar laser, a xenon laser, an ultra-high pressure mercury lamp, etc. are worthy of this.

2 contained in the photocurable fluid resin composition
-Acryloyloxyethyltrimethylammonium chloride is not easy to handle due to the large stickiness of the resin, but the stickiness is reduced by mixing N, N-dimethylaminopropylacrylamide,
By mixing pentaerythritol triacrylate which is a cross-linking agent, the hardness of the cured product is improved. Accordingly, it is possible to produce an inorganic substance-containing photocurable resin molded article and a sintered molded article that are easy to handle and have high material strength and have piezoelectric characteristics.

Next, a fourteenth embodiment of the photocurable fluid resin composition of the present invention will be described.

This embodiment is configured as follows.

The photocurable fluid resin composition of the present embodiment is obtained by adding methacrylic acid-3- to lead zirconate titanate powder contained in the photocurable fluid resin composition 13 described in the thirteenth embodiment. Lead zirconate titanate powder surface-treated with trimethoxysilylpropyl is used. That is,
The surface-treated lead zirconate titanate powder is mixed with the components (a) and (b) of the thirteenth embodiment to prepare a photocurable fluid resin composition 14. The photocurable fluid resin composition is 0.5 to 10% by weight, preferably 2% by weight of bis (cyclopentadienyl) -bis (2) based on the monomer mixture 3 described in the thirteenth embodiment. , 6-Difluoro-3- (pyr-1-yl) titanium and 10 vol% or more, preferably 28 v, based on the monomer mixture 3.
ol% or more of the surface-treated lead zirconate titanate powder is mixed.

The method for producing the inorganic substance-containing photocurable resin molded article 14 using the photocurable fluid resin composition 14 and the method for producing the sintered molded article 14 are the same as those in the first embodiment.

However, the light source used in the production apparatus is 3
The light source can emit light having a wavelength of 60 nm or more. For example, an Ar laser, a xenon laser, an ultra-high pressure mercury lamp, etc. are worthy of this.

A photocurable fluid resin composition having both the functions and effects of the second embodiment and the functions and effects of the thirteenth embodiment is obtained. In other words, the photocuring properties that improve the material strength, improve the shape retention of the sintered molded body, and are easy to handle, and enable the production of an inorganic substance-containing photocurable resin molded body having piezoelectric properties and a sintered molded body It becomes a fluid resin composition.

[0187]

The present invention will be described in more detail with reference to the following examples.

Example 1 Example 1 was configured as follows.

A monomer mixture A obtained by mixing morpholine acrylate (produced by Kojin) and pentaerythritol triacrylate (produced by Nippon Kayaku) as a radical polymerizable monomer having a hydrophilic group was used as a photopolymerization initiator. Using 2-hydroxy-2-methyl-1-phenylpropan-1-one (manufactured by Ciba-Geigy) and alumina powder having an average particle diameter of 0.2 μm (manufactured by Daimei Chemical Industry) as an inorganic substance, a light containing powder A curable fluid resin composition A ′ was prepared. The monomer mixture A was formed by mixing 0.75 mol% of pentaerythritol triacrylate with respect to morpholine acrylate. The photocurable fluid resin composition A ′ was added to the monomer mixture A in an amount of 2 wt.
% Of 2-hydroxy-2-methyl-1-phenylpropan-1-one and 30 vol% of alumina powder based on the monomer mixture A were mixed.
The obtained photocurable fluid resin composition A ′ was first stirred for about 1 hour with a stirrer equipped with a vacuum pump, and then operated while operating a vacuum pump for further 1 hour or more while defoaming. Thus, a photocurable fluid resin composition A for three-dimensional stereolithography was prepared.

Next, a method for producing a photocurable resin molded article A containing alumina powder using the photocurable fluid resin composition A will be described.

In this embodiment, the three-dimensional optical shaping apparatus shown in FIG. 3A and the light source shown in FIG. 3B were used. In FIG. 3A, reference numeral 31 denotes an elevator which can move up and down freely, 32 denotes a glass plate which transmits light, 33 denotes a tank containing a photocurable fluid resin, 34 denotes a focused laser beam, and 35 denotes photocuring. Numeral flowable resin 36 is a cured powder-mixed resin molded product.
In addition, 37 is a stage for scanning the laser beam, and 38 is a stage for moving the elevator. The condensed laser beam (34) is condensed by the condensing unit 39. In FIG. 3B, reference numeral 41 denotes a He-Cd laser having a wavelength of 325 nm and an output of 15 mW, reference numeral 42 denotes an optical fiber, reference numeral 43 denotes an optical fiber adapter, and reference numeral 44 denotes an electromagnetic shutter for controlling exposure.

This device is used as follows.

First, the stage (3) is set so that the table (31) and the glass surface (34) are at a fixed interval.
8) is adjusted and the table (31) is fixed. Next, the laser beam is irradiated from the bottom surface of the storage tank (33) through glass that transmits light. At this time, based on slice data previously obtained from three-dimensional CAD data having a predetermined structure,
The stage (37) is controlled to scan with a laser beam.
Thereby, the photocurable fluid resin composition is cured, and the first layer of the three-dimensional structure is formed. Next, the laser beam irradiation was stopped in order to photoform the second layer of the three-dimensional resin molded product,
By operating the stage (38), the table (31) is raised at regular intervals. Next, based on the slice data of the second layer, a laser beam is irradiated to cure the second layer of the three-dimensional resin molded body. This procedure is repeated to form an inorganic substance-containing photocurable resin molded article having a desired shape while laminating and forming a three-dimensional resin molded article.

On the other hand, the laser beam is emitted from the bottom of the storage tank (33) as follows. Laser (4
The exposure amount of the laser beam emitted from 1) is adjusted by an electromagnetic shutter (44) for exposure control. The laser beam whose exposure has been adjusted is guided to an optical fiber (42) through an optical fiber adapter (43), and passes light from the bottom surface of a storage tank (33) shown in FIG. 3A through the optical fiber (42). The photocurable fluid resin (35) is irradiated through the transparent glass plate (32).

In this example, a photocurable resin molded article containing alumina powder was produced by the following steps and conditions.

1) A cylinder as a three-dimensional structure was modeled by three-dimensional CAD.

2) A horizontal slice figure data group was created from the cylindrical structure for each fixed layer thickness.

3) The table (31) was positioned so that the photocurable fluid resin 1 had a constant lamination thickness.

4) A 325 nm wavelength He-Cd laser beam was scanned in accordance with slice pattern data to cure one layer of the photocurable fluid resin.

5) The elevator was again positioned so as to have a constant lamination thickness.

6) By repeating steps 4) and 5) until a three-dimensional structure having the desired shape was completed, a modeled cylindrical structure was produced.

7) The cylindrical structure was taken out, and the uncured material adhering to the surface was washed.

8) Post-exposure was performed using an ultra-high pressure mercury lamp.

The powder-containing cylindrical structure A of this example had an outer diameter of 2.8 mm, a wall thickness of 0.45 mm, and an axial length of the cylinder of 2.2 mm. The lamination thickness was set to 0.028 mm, and the number of laminations was 80.
It took about 8 hours to produce the cylindrical structure.

Next, a sintered cylindrical structure A was prepared as follows using the powder-containing cylindrical structure A made of a photocurable resin containing alumina powder.

Thermal analysis using a thermogravimetric simultaneous analyzer (manufactured by Hitachi, Ltd.) confirmed that the temperature at which thermal decomposition of the monomer mixture A as a radical polymerizable monomer started was about 350 ° C. The cylindrical structure was placed in a furnace at 100 ° C /
The temperature was raised to the above-mentioned thermal decomposition starting temperature of 350 ° C. at a heating rate of time, and the furnace temperature was kept at 350 ° C. for about 10 hours. Next, the temperature was increased to 1500 ° C. at a rate of 50 ° C./hour, kept at 1500 ° C. for 2 hours, and sintered. Thus, a sintered cylindrical structure A was prepared.

The monomer mixture A, which is a photocurable fluid resin component of this example, contains a radical polymerizable monomer having a hydrophilic group as a constituent. The hydrophilic group of the polymerizable monomer,
It has the property of providing the photocurable resin with adhesion to inorganic substances such as metals and metal oxides. The photocurable fluid resin composition A contains alumina powder as an inorganic substance, and the adhesiveness between the inorganic substance and the resin is improved by using a radical polymerizable monomer having a hydrophilic group. Therefore, it has become possible to prepare an alumina powder-containing cylindrical structure formed by light irradiation, three-dimensional stereolithography, or the like as a structure free of delamination between layers and cracks. In addition, the alumina powder-containing cylindrical structure was degreased and sintered to produce a sintered body without peeling or cracking.

FIG. 4A shows an alumina powder-containing cylindrical structure A prepared by using the above monomer mixture A as a radical polymerizable monomer having a hydrophilic group and using an alumina powder having an average particle diameter of 0.2 μm. FIG. As shown,
Alumina powder-containing cylindrical structure A free from delamination and cracks
Could be created. Furthermore, by performing degreasing sintering of the cylindrical structure A, a cylindrical sintered body A free from peeling or cracking could be produced.

For comparison, FIG. 4B shows an acrylic photocurable resin having no hydrophilic group and an average particle size of 0.2.
Photocurable fluid resin composition B prepared by mixing with μm alumina powder (alumina powder content is 30 vol%)
Is used to show the prepared powder-containing cylindrical structure B. As shown in this figure, it was confirmed that the powder-containing cylindrical structure B was delaminated. In addition, it was confirmed that the delamination was left in the cylindrical sintered body B obtained by degreasing the powder-containing cylindrical structure B.

In this example, the rate of occurrence of delamination between the powder-containing cylindrical structures B produced using an acrylic photocurable resin (resin B) having no hydrophilic group and the hydrophilic group were determined. Powder-containing cylindrical structure A produced using the monomer mixture A (resin A) as a radical polymerizable monomer having
The rate of occurrence of delamination between layers was examined and compared as shown in FIG.
The vertical axis in FIG. 5 represents the rate of occurrence of delamination between layers when a large number of powder-containing cylindrical structures were produced, and the horizontal axis represents the volume content of the powder. As the powder, alumina powder having an average particle size of 0.2 μm was used. As can be seen from FIG. 5, when the photocurable resin having a hydrophilic group (resin A) described in this example was used, a cylindrical structure without delamination between layers could be efficiently produced. The results for the case where the powder content is 35 vol% or more in FIG. 5 are the results when the alumina powder treated by the surface treatment method described in Example 2 is used.

Example 2 Example 2 was configured as follows.

A monomer mixture A obtained by mixing morpholine acrylate and pentaerythritol triacrylate as a radical polymerizable monomer having a hydrophilic group was used, and 2-hydroxy-2-methyl-1-phenyl was used as a photopolymerization initiator. Photocurable fluid resin composition using propane-1-one and alumina powder having an average particle diameter of 0.2 μm, which is surface-treated with 3-trimethoxysilylpropyl methacrylate (manufactured by Kanto Chemical) as an inorganic substance. C ′ was prepared. 0.75 mol% of pentaerythritol triacrylate based on morpholine acrylate was mixed with the monomer mixture A. The photocurable fluid resin composition C ′ is composed of 2 wt% of 2-hydroxy-2-methyl-1-phenylpropan-1-one based on the monomer mixture A and 40 vol% of a photopolymerization initiator. It was prepared by mixing with a surface-treated alumina powder.

The photocurable fluid resin composition C ′ was stirred and defoamed while stirring to prepare a photocurable fluid resin composition C for three-dimensional stereolithography. The preparation method was the same as in Example 1. Further, a cylindrical structure C in which the alumina powder was 40 vol% with respect to the monomer mixture A was produced by the same three-dimensional stereolithography apparatus and the same process as in Example 1.
The method for producing the sintered cylindrical structure C was the same as that in the first embodiment.

In this example, the surface treatment of the alumina powder was performed using 3-trimethoxysilylpropyl methacrylate by the following method.

1) 2 wt% based on the weight of alumina powder
3-trimethoxysilylpropyl methacrylate,
20 wt% of ethanol and 20 wt% of ion-exchanged water were weighed.

2) Ethanol and ion-exchanged water are mixed, and hydrochloric acid is further added dropwise to adjust the pH of the solution to 3.5 to 4.5.
Was prepared.

2) To the mixed solution was added 3-trimethoxysilylpropyl methacrylate, and the mixture was stirred for about 20 minutes to obtain a surface treatment solution A.

3) While the alumina powder was being stirred, the surface treatment solution A was added dropwise, and after the total volume was added, the mixture was stirred for 30 minutes.

4) The alumina powder obtained in 3) was dried by heating at 120 ° C. for 3 hours in a dryer.

5) After drying, the alumina powder was pulverized using an agate mortar to obtain a powder. Thereby, a surface-treated alumina powder was obtained.

The 3-trimethoxysilylpropyl methacrylate surface-treated with alumina powder contained in the photocurable fluid resin composition C contains a silane having a functional group capable of reacting with an inorganic substance on one side chain. And an organic compound having a radically polymerizable functional group on the other side chain. When a surface treatment of a metal oxide such as alumina powder is performed using the organic compound, the silane compound reacts with a hydroxyl group of the metal oxide, and the silane compound is strongly bonded to the metal oxide by a covalent bond. A monomolecular film is formed on the surface of the metal oxide with a radically polymerizable functional group exposed on the surface. When the composition containing the metal oxide is irradiated with light such as ultraviolet light, the radically polymerizable functional group on the surface of the metal oxide and the photocurable fluid resin are bonded by a chemical bond, and the metal oxide and the photocurable resin are cured. The bonded resin is joined by a chemical bond. The surface treatment improves the affinity of the inorganic substance to the resin, makes it difficult to cause precipitation, and can prevent the viscosity from increasing. For this reason, it became possible to improve the content ratio of the inorganic substance to the photocurable fluid resin as compared with the case where an untreated inorganic substance was used. Accordingly, the strength of the produced inorganic substance-containing photocurable resin molded article was improved, and the shape retention of the sintered molded article was able to be improved.

FIG. 6 shows the result of preventing the viscosity of the photocurable fluid resin composition C from increasing by the surface treatment of the alumina powder. FIG. 6 shows the powder photocurable fluid resin composition C obtained by preparing the powder photocurable fluid resin composition C using the surface-treated alumina powder having an average particle diameter of 0.2 μm and the same powder having no surface treatment. FIG. 3 is a diagram showing a relationship between the volume content of alumina powder in the resin composition C and the viscosity of the powder photocurable fluid resin composition C.

A composition containing 40 vol% of alumina powder with respect to the resin containing the monomer mixture A as a main component was prepared, and the powder-containing cylindrical structure C having no peeling between layers and no cracks was prepared.
Could be produced. Further, the powder-containing cylindrical structure C was degreased and sintered in the same manner as in Example 1,
A sintered cylindrical structure C having good shape retention was obtained.

Example 3 Example 3 was configured as follows.

A monomer mixture A obtained by mixing morpholine acrylate and pentaerythritol triacrylate as a radical polymerizable monomer having a hydrophilic group was used, and 2-hydroxy-2-methyl-1-phenyl was used as a photopolymerization initiator. Using propan-1-one, inorganic particles having an average particle size of 5.5 μm, 3 μm, 0.25 μm, and 0.2 μm
The photocurable fluid resin composition D ′ was prepared using a mixed alumina powder A obtained by mixing alumina powders of m in a weight ratio of 1.5: 2: 1: 1. The monomer mixture A is
0.75 mol% of pentaerythritol triacrylate was mixed with morpholine acrylate. The photocurable fluid resin composition D ′ comprises a photopolymerization initiator composed of 2 wt% of 2-hydroxy-2-methyl-1-phenylpropan-1-one based on the monomer mixture A;
vol% of mixed alumina powder A was prepared.

The photocurable fluid resin composition D ′ for three-dimensional stereolithography was prepared by stirring and defoaming the photocurable fluid resin composition D ′. The preparation method was the same as in Example 1. Further, a cylindrical structure D in which the alumina powder was 38 vol% with respect to the monomer mixture A was produced by the same three-dimensional stereolithography apparatus and the same process as in Example 1.
The method for producing the sintered cylindrical structure D was the same as that in Example 1.

The larger the particle size of the alumina powder is, the lower the viscosity of the photocurable fluid resin composition can be. Therefore, a large amount of alumina powder can be contained, and the shape retention of the sintered compact can be improved. Precipitation of powder tends to occur in the curable fluid resin composition, and surface smoothness is reduced. On the other hand, when the particle size is small, the viscosity of the photocurable fluid resin composition becomes high, and processing becomes difficult. As shown in this example, the above problem could be solved by using alumina powder having two or more particle size distributions.

Table 1 shows the experimental results of this example. Powder 1, Powder 2, Powder 3, and Powder 4 in the table have an average particle size of 5.5 μm, 3 μm, 0.25 μm, and 0.2 μm, respectively.
Of alumina powder.

[0229]

[Table 1]

Experiments 1 and 2 are experiments using the monomer mixture A (resin A) as the photocurable fluid resin component.
The alumina powder content was 38 vol% and 40 vol, respectively.
The powder photocurable fluid resin composition D having 1% had sufficient fluidity for three-dimensional stereolithography. Using the powder photocurable fluid resin composition D, a powder-containing cylindrical structure free of peeling between layers and cracking could be produced by three-dimensional stereolithography. In addition, a sintered body without peeling or cracking could be obtained by degreasing and sintering the cylindrical structure containing alumina powder.

Experiment 3 is an experiment using an acrylic photocurable resin (resin B) having no hydrophilic group as the photocurable fluid resin component. In this experiment, the powder had an average particle size of 5.5 μm, 3 μm
Powdered photocurable fluid resin composition E was obtained using a mixture of alumina powders of m, 0.25 μm, and 0.2 μm in a weight ratio of 1.5: 2: 1: 1, respectively. Although the powder photocurable fluid resin composition E had sufficient fluidity for three-dimensional stereolithography when the powder content was 38%, it was laminated on the produced powder-containing cylindrical structure E. It was confirmed that peeling occurred between them.

In Experiment 4, the monomer mixture A (resin A) was used as the photocurable fluid resin component, and the alumina powder was treated by the surface treatment method described in Example 2 to have an average particle size of 5.5 μm.
This is an experiment using alumina powders of m, 3 μm, 0.25 μm, and 0.2 μm. The four powders were mixed at a weight ratio of 1.5: 2: 1: 1 to obtain a powdery photocurable fluid resin composition F. The powder photocurable fluid resin composition F has sufficient fluidity for three-dimensional stereolithography when the content of the powder is set to 48%. Then, a powder-containing cylindrical structure F having no peeling between layers and no crack was produced by the three-dimensional stereolithography described in Example 1. Further, under the conditions described in Example 1, degreasing sintering was performed to obtain a sintered cylindrical structure F having good shape retention without delamination between layers or cracks.

Example 4 Example 4 was constructed as follows.

A monomer mixture A obtained by mixing morpholine acrylate and pentaerythritol triacrylate as a radical polymerizable monomer having a hydrophilic group was used, and 2-hydroxy-2-methyl-1-phenyl was used as a photopolymerization initiator. Using propane-1-one, a mixed powder B obtained by mixing alumina powder having an average particle diameter of 0.2 μm and silica powder having an average particle diameter of 0.2 μm as inorganic substances in a volume ratio of 10: 1 was used. Thus, a photocurable fluid resin composition G ′ was prepared. The monomer mixture A was formed by mixing 0.75 mol% of pentaerythritol triacrylate with respect to morpholine acrylate. The photocurable fluid resin composition G ′ is 2 wt% based on the monomer mixture A.
% Of 2-hydroxy-2-methyl-1-phenylpropan-1-one and 30 vol% of mixed powder B were prepared.

The photocurable fluid resin composition G ′ was stirred and defoamed while stirring to prepare a photocurable fluid resin composition G for three-dimensional stereolithography. The preparation method was the same as in Example 1. Further, a cylindrical structure G in which the alumina powder was 30 vol% with respect to the monomer mixture A was produced by the same three-dimensional stereolithography apparatus and the same process as in Example 1.
The method for producing the sintered cylindrical structure G was the same as that in the first embodiment.

Since the photocurable fluid resin composition 4 contains an alumina powder and a silica powder, the photocurable fluid resin composition A described in Example 1 has transparency to ultraviolet rays.
Got better. For this reason, it became possible to set the lamination thickness in the three-dimensional stereolithography to be greater than 0.028 mm in Example A. In this embodiment, the lamination thickness is set to 0.035 mm. When a cylindrical structure having the same dimensions as in Example A was manufactured, the manufacturing time was reduced by 20%, and the molding speed was increased.

Example A produced by three-dimensional stereolithography
The cylindrical structure having the same dimensions as above was degreased and sintered to obtain a sintered compact having good shape retention. This is because the silica powder having a low sintering temperature is sintered first, and the alumina powder is sintered later. Was able to improve the shape retention.

Example 5 Example 5 was configured as follows.

As the radical polymerizable monomer having a cationic ionic group, 2-acryloyloxyethyltrimethylammonium chloride (produced by Kojin), N, N-dimethylaminopropylacrylamide (produced by Kojin), and pentaerythritol triacrylate (Nippon Kayaku Co., Ltd.) and bis (cyclopentadienyl) -bis (2,6-difluoro-3- (pyr-1-yl) titanium (Ciba Geigy) as a photopolymerization initiator Photocuring using a powder of lead zirconate titanate having an average particle diameter of 0.2 μm (manufactured by Sakai Chemical) surface-treated with 3-trimethoxysilylpropyl methacrylate (manufactured by Kanto Chemical) as an inorganic substance. A water-soluble resin composition H ′ was prepared, and the monomer mixture B was 2-acryloyloxyethyltrimethylanhydride. Benzalkonium chloride 3 with respect to Ride
It was prepared by mixing 0 mol% of N, N-dimethylaminopropylacrylamide with 15 mol% of pentaerythritol triacrylate based on 2-acryloyloxyethyltrimethylammonium chloride.
The photocurable fluid resin composition H ′ was prepared from bis (cyclopentadienyl) -bis (2,6-difluoro-3- (pyr-1-yl) titanium based on 2% by weight of the monomer mixture B. The resulting photopolymerization initiator was mixed with 28 vol% of lead zirconate titanate powder.

The surface treatment of the lead zirconate titanate powder using 3-trimethoxysilylpropyl methacrylate was performed in the same manner as in Example 1.

The photocurable fluid resin composition H ′ was stirred and defoamed while stirring to prepare a photocurable fluid resin composition H for three-dimensional stereolithography. The preparation method was the same as in Example 1. Further, in the same three-dimensional stereolithography apparatus and the same process as in Example 1, a cylindrical structure G in which the alumina powder was 28 vol% with respect to the monomer mixture A was produced.
The method for producing the sintered cylindrical structure G was the same as that in the first embodiment.

The powder-containing photocurable resin molded body H was prepared using a three-dimensional stereolithography apparatus having a structure similar to that of FIG. 3 using an argon laser having a wavelength of 488 nm (manufactured by NEC, output 25 mW). The lamination thickness was set to 0.02 mm, and a columnar structure H having a diameter of 1.6 mm and an axial height of 3 mm was produced. The method of forming the sintered cylindrical structure H was the same as that of the first embodiment.

The 3-trimethoxysilylpropyl methacrylate surface-treated with alumina powder contained in the photocurable fluid resin composition H contains a silane having a functional group capable of reacting with an inorganic substance on one side chain. And an organic compound having a radically polymerizable functional group on the other side chain. When the surface treatment of a metal oxide such as alumina powder is performed using the organic compound, the silane compound reacts with the hydroxyl group of the metal oxide, and the silane compound is strongly bonded to the metal oxide by a covalent bond. Then, a monomolecular film is formed on the surface of the metal oxide with a radically polymerizable functional group exposed on the surface. When the composition containing the metal oxide is irradiated with light such as ultraviolet light, the radically polymerizable functional group on the surface of the metal oxide and the photocurable fluid resin are bonded by a chemical bond,
The metal oxide and the photocured resin are joined by a chemical bond. The above surface treatment improves the affinity of the inorganic substance to the resin, prevents the formation of precipitates, and can prevent the increase in viscosity. It has become possible to increase the content of inorganic substances. As described above, in this example, the strength of the inorganic substance-containing photocurable resin molded product was improved, and the shape retention of the sintered molded product was improved.

The monomer mixture B is a radical polymerizable monomer having a cationic ionic group, 2-acryloyloxyethyltrimethylammonium chloride and N, N
-It has dimethylaminopropylacrylamide and shows good photocurability even when it contains lead zirconate titanate. In addition, compared with the case where 2-acryloyloxyethyltrimethylammonium chloride is used alone, the mixture of N, N-dimethylaminopropylacrylamide reduces the stickiness of the cured product, and the mixture of pentaerythritol triacrylate as a crosslinking agent. This improved the hardness of the cured product.

Since the photocurable fluid resin composition H contains lead zirconate titanate powder, it has low transparency to light having a wavelength of 325 nm, but has transparency to light of an argon laser having a wavelength of 488 nm. . Further, bis (cyclopentadienyl) -bis (2,6-difluoro-3- (pyr-1-yl) titanium contained in the photocurable fluid resin composition H reacts to a wavelength of 360 nm or more. Since this is a visible light polymerization initiator, the photocurable fluid resin composition H could be cured by irradiation with the argon laser.

By setting the lamination thickness to 0.02 mm using the three-dimensional stereolithography device and the photocurable fluid resin composition H, the diameter is 1.6 mm and the height in the axial direction is 3 mm.
Was produced.

The present invention includes the following inventions in addition to the inventions described in the above claims. In the following, in order to clarify the relationship with claims 1 to 3,
These are described together. In addition, Claims 1 to 3
This corresponds to (1) to (3) below.

(1) In a photocurable fluid resin composition which can be polymerized by the action of light to be insoluble in a solvent or change from a liquid to a solid to form a structure, (a) a hydrophilic group A photocurable fluid resin composition, comprising: a radical polymerizable monomer having the formula: (b) a photopolymerization initiator; and (c) an inorganic substance.

(Corresponding Embodiments of the Invention) Embodiments of the present invention correspond to the first to fourteenth embodiments. Embodiments corresponding to the present invention are Embodiments 1 to 5.

The “radical polymerizable monomer having a hydrophilic group” in the present invention corresponds to morpholine acrylate in the first embodiment, but includes (meth) acrylic acid, vinyl acetic acid, styrene sulfonic acid, Maleic anhydride, 2-acrylamido-2-methylpropanesulfonic acid, N, N
-Dimethylaminopropylacrylamide, N, N-dimethylaminoethyl (meth) acrylate, N, N-dimethylaminopropylacrylamide, 2-acryloyloxyethyltrimethylammonium chloride, 3
-Acrylamidopropyltrimethylammonium chloride, morpholine acrylate, 2-hydroxyethyl (meth) acrylate, ethylene glycol (meth) acrylate, acrylamide, glycerol mono (meth) acrylate, vinylpyrrolidone, N-isopropylacrylamide, 2-hydroxyethyl (meth )
Acrylate, 2-hydroxypropyl (meth) acrylate, morpholinoethyl (meth) acrylate,
Methyl (meth) acrylate, ethyl (meth) acrylate, N, N-dimethylacrylamide, methacrylic acid
2-sulfoethyl sodium salt, 2-hydroxy-3
-Phenoxypropyl (meth) acrylate, (2-
(Meth) acryloyloxyethyl) acid phosphate, N-methacryloxy-N-carboxymethylpiperidine, N-methacryloxy-N, N-dicarboxymethyl-p-phenylenediamine, hydroxynaphthoxypropyl methacrylate, methacryloxyethyl phosphorisphenyl , 4-methacryloxyethyl trimellitic anhydride, 4-methacryloxyethyl trimellitic acid,
(Meth) acryloxyethyl phthalate, 2- (meth)
Also includes acryloyloxyethyl succinic acid and the like. In this proposal, the term "hydrophilic group" refers to a functional group such as a hydroxyl group, a carboxyl group, a sulfonic acid group, a phosphoric acid group, a tertiary amine, a quaternary amine hydroxide, a sulfonium group, an amide group, an amino group, and a morpholino group. Means

The photopolymerization initiator in the present invention corresponds to 2-hydroxy-2-methyl-1-phenylpropan-1-one in the first embodiment, but includes benzophenone,
2,2-dimethoxy-1,2-diphenylethane-1-
On, 1-hydroxycyclohexyl phenyl ketone,
2,4,6-trimethylbenzoyldiphenylphosphon oxide, 1- [4- (2-hydroxyethoxy) -phenyl] -2-hydroxy-2-methyl-1-methyl
The compound is not particularly limited as long as it has a function of generating a radical upon irradiation with light, including propan-1-one and the like. Specifically, it is described in detail in "Kiyoshi Kato," Ultraviolet Curing System "General Technology Center, (1989)".

The inorganic substance in the present invention corresponds to alumina powder having an average particle diameter of 0.2 μm in the first embodiment, but may be other inorganic substance powder or fiber. When the purpose is to form a sintered compact, the inorganic substance may be any powder that can be processed into a ceramic structure by powder sintering of the inorganic substance, and the type and particle size are not particularly limited. For example, porcelain, clay, white clay,
Examples include kaolin compositions, phosphates, silicates, carbides, glass, silica, alumina, zirconia, lead zirconate titanate, and the like. When the purpose is to produce a photocurable resin molded article, inorganic fiber such as glass fiber and asbestos can be used in addition to the above-mentioned inorganic substance powder. The particle size of the powder is not particularly limited, but may be 0.05
The thickness is preferably from 100 to 100 µm, more preferably from 0.1 to 10 µm. The size of the fiber is not particularly limited, but the diameter is 0.05 to 10 μm and the length is 1 to 50.
0 μm is desirable, and the diameter is 0.1 to 5 μm and the length is 5 μm.
-100 μm is more desirable.

The photocurable fluid resin composition prepared by mixing the radical polymerizable monomer having a hydrophilic group, the photopolymerization initiator, and the inorganic substance is a radical polymerizable monomer having the hydrophilic group. 0.5 to 10% by weight, preferably 2% by weight, of the photopolymerization initiator and 10% by volume or more, preferably 28% by volume or more, of the radical polymerizable monomer having a hydrophilic group. It is desirable to constitute the mixture with a substance. In particular, when a sintered compact is produced, the content of the inorganic substance is desirably as large as possible within a range where the photocurable fluid resin composition is sufficiently cured by light irradiation.

(Operation) Next, the operation of the present invention will be described.

The (a) hydrophilic group of the radical polymerizable monomer having a hydrophilic group, which is a photocurable fluid resin component of the above photocurable fluid resin composition, can be added to a photocurable resin such as a metal or metal oxide. It has the property of providing adhesion to inorganic substances. The photocurable fluid resin composition contains an inorganic substance, and the adhesiveness between the inorganic substance and the resin is improved by using a radical polymerizable monomer having a hydrophilic group. Therefore, it is possible to produce a photocurable resin molded article containing an inorganic substance, which is produced by light irradiation or three-dimensional stereolithography, as a structure without cracks or peeling. In addition, it becomes possible to produce a sintered compact produced by sintering the inorganic substance-containing photocurable resin compact as a structure without cracks or peeling.

(Effect) (a) A radical polymerizable monomer having a hydrophilic group is
The photopolymerization initiator is composed of (c) an inorganic substance to form a photocurable fluid resin composition, whereby an inorganic substance-containing photocurable resin molded article prepared by light irradiation, three-dimensional stereolithography, or the like can be used. In addition, a sintered molded article produced by sintering the inorganic substance-containing photocurable resin molded article is a photocurable fluid resin composition that can be produced as a structure without cracks or peeling.

(2) The inorganic substance comprising (c) is
(1) a surface treatment with an organic compound having a silane having a functional group capable of reacting with an inorganic substance on one side chain and having a functional group capable of radical polymerization on the other side chain; The photocurable fluid resin composition according to the above).

(Corresponding Embodiments of the Invention) Embodiments of the present invention relate to the second, eighth, ninth, twelfth and fourteenth embodiments.
Corresponds to this embodiment. Embodiments corresponding to the present invention are Embodiments 2 and 5.

The “organic compound having a silane having a functional group capable of reacting with an inorganic substance on one side chain and a radically polymerizable functional group on the other side chain” in the present invention is referred to as an “organic compound” in this embodiment. Although 3-trimethoxysilylpropyl methacrylate is applicable, any organic compound having a silane having a functional group capable of reacting with an inorganic substance on one side chain and having a functional group capable of radical polymerization on the other side chain. If desired, other compounds can be used. Specifically, it is selected from vinyltrimethoxysilane, vinyltriacetoxysilane, 3-trimethoxysilylpropyl methacrylate, trichlorovinylsilane, triethoxyvinylsilane, and the like.

The photocurable fluid resin composition prepared by mixing the radical polymerizable monomer having a hydrophilic group, the photopolymerization initiator, and the inorganic substance is a radical polymerizable monomer having the hydrophilic group. 0.5 to 10% by weight, preferably 2% by weight, of the photopolymerization initiator and 10% by volume or more, preferably 28% by volume or more, of the radical polymerizable monomer having a hydrophilic group. It is desirable to constitute the mixture with a substance. In particular, when a sintered compact is produced, the content of the inorganic substance is desirably as large as possible within a range where the photocurable fluid resin composition is sufficiently cured by light irradiation.

Next, the operation of the present invention will be described.

The organic compound obtained by surface-treating the inorganic substance of the photocurable fluid resin composition has a silane having a functional group capable of reacting with the inorganic substance on one side chain and has a radical polymerizable on the other side chain. It is an organic compound having a functional group. When a surface treatment of an inorganic substance composed of a metal oxide is performed using the organic compound, the silane compound reacts with a hydroxyl group of the metal oxide, and the silane compound is strongly bonded to the metal oxide by a covalent bond. A monomolecular film is formed on the surface of the metal oxide with a radically polymerizable functional group exposed on the surface. When the composition containing the metal oxide is irradiated with light such as ultraviolet light, the radically polymerizable functional group on the surface of the metal oxide and the photocurable fluid resin are bonded by a chemical bond, and the metal oxide and the photocurable resin are cured. The bonded resin is joined by a chemical bond. For this reason, the above-mentioned surface treatment improves the affinity of the inorganic substance to the resin, reduces precipitation, and reduces the increase in viscosity. Can be improved. Therefore, the strength of the produced inorganic substance-containing photocurable resin molded article is improved, and the shape retention of the sintered molded article is improved.

(Effect) The inorganic substance comprising (c) is
Using an inorganic substance surface-treated with an organic compound having a silane having a functional group capable of reacting with an inorganic substance on one side chain and a radically polymerizable functional group on the other side chain, a photocurable fluid resin By making up the composition,
A photocurable fluid resin composition capable of improving the strength of the produced inorganic substance-containing photocurable resin molded article and improving the shape retention of the sintered molded article.

(3) The inorganic substance according to (1) or (2), wherein the inorganic substance comprising (c) is a powder, and the powder has two or more particle size distributions. Photocurable fluid resin composition.

(Corresponding Embodiment of the Invention) The embodiment relating to the present invention corresponds to the third embodiment. An embodiment corresponding to the present invention is the third embodiment.

In the present invention, “powder having two or more particle size distributions” refers to an average particle size of 5.5 μm,
Alumina powders of μm, 0.25 μm, and 0.2 μm correspond, but the alumina powder can be changed to a powder of another inorganic substance as described in the corresponding embodiment of the invention (1). Also, as described in the corresponding embodiment of the invention (2), one side chain has a silane having a functional group capable of reacting with an inorganic substance and the other side chain has a radical polymerizable functional group. It is possible to convert inorganic substances surface-treated with organic compounds into powders.

The particle size distribution of the alumina powder is not particularly limited, but may include a particle size distribution of 0.1 to 1 μm.
It is desirable to use a powder having more than one kind of particle size distribution.

The composition ratio of the photocurable fluid resin composition can be changed as described in the corresponding embodiment of the invention (1).

(Operation) Next, the operation of the embodiment of the present invention will be described.

The photocurable fluid resin composition contains an inorganic substance powder. The larger the particle size of the powder, the greater the viscosity of the resin can be reduced, so that it can be contained in a large amount and can improve the strength of the inorganic material-containing photocurable resin molded product and the shape retention of the sintered compact. The powder tends to precipitate inside, and the surface smoothness of the photocurable resin molded article is reduced. When the particle size is small, the distribution of the powder becomes uniform, and the surface smoothness of the molded body is improved, but when mixed in a large amount, the viscosity becomes high and processing becomes difficult.

The photocurable fluid resin composition has a surface smoothness and a strength of an inorganic substance-containing photocurable resin molded article by using the inorganic powder as a powder having two or more particle size distributions. And the powder content are improved, and the shape retention of the sintered compact can be improved.

Effect By forming a photocurable fluid resin composition by using powder having two or more particle size distributions as the inorganic substance (c), the inorganic material has surface smoothness and is produced. The photocurable fluid resin composition is capable of improving the strength and powder content of the inorganic substance-containing photocurable resin molded body and improving the shape retention of the sintered molded body.

(4) The inorganic substance comprising (c) is:
The photocurable fluid resin composition according to any one of (1) to (3), which is a powder that can be processed into a ceramic molded body by subsequent sintering.

(Corresponding Embodiments of the Invention) Embodiments of the present invention correspond to the first to fourteenth embodiments. Embodiments corresponding to the present invention are Embodiments 1 to 5.

The “powder that can be processed into a ceramic molded body by subsequent sintering” in the present invention corresponds to the alumina powder in the first embodiment, but the ceramic structure may be formed by powder sintering of another inorganic substance. Any type and particle size can be used as long as the powder can be processed into a powder. Examples thereof include porcelain, clay, clay, kaolin composition, phosphate, silicate, carbide, glass, silica, alumina, zirconia, lead zirconate titanate, and the like.

The composition ratio of the photocurable fluid resin composition can be changed as described in the corresponding embodiment of the invention (1).

(Function / Effect) By using a powder which can be processed into a ceramic molded body by the subsequent sintering for the inorganic substance comprising the above (c), it is possible to produce a sintered molded body without cracks and peeling. It becomes a photocurable fluid resin composition.

(5) The inorganic substance comprising (c) is:
The photocurable fluid resin composition according to any one of the above (1) to (4), wherein the composition is two or more types of ceramic powders having different sintering temperatures or different light transmittances.

(Corresponding Embodiments of the Invention) Embodiments according to the present invention correspond to the fourth and ninth embodiments. An embodiment corresponding to the present invention is the fourth embodiment.

The “two or more ceramic powders having different sintering temperatures or light transmittances” in the present invention correspond to alumina powder and silica powder in this embodiment, but differ in sintering temperature or light transmittance. There is no particular limitation as long as it is two or more types of ceramic powder. Therefore, the alumina powder and the silica powder can be changed to a powder of another inorganic substance as described in the embodiment corresponding to the above invention (1), and can be changed to an embodiment corresponding to the above invention (2). Inorganic substance powder surface-treated with an organic compound having a silane having a functional group capable of reacting with an inorganic substance on one side chain and having a functional group capable of radical polymerization on the other side chain as described in the embodiment. Changes to are possible. It is also possible to use a powder having two or more particle size distributions as described in the embodiment corresponding to the invention (3).

The composition ratio of the photocurable fluid resin composition can be changed as described in the corresponding embodiment of the invention (1).

(Operation) Next, the operation of the present invention will be described.

The photocurable fluid resin composition contains two types of ceramic powders having different light transmittances.
By changing the mixing ratio of the various types of ceramic powder, it is possible to change the thickness of the three-dimensional stereolithography. Further, when the photocurable fluid resin composition contains two types of ceramic powders having different sintering temperatures, when producing a sintered compact, the powder having a lower sintering temperature is sintered first, Later the powder sinters. Because of this sintering step by step,
Strain generated during sintering is reduced, and the shape retention of the sintered compact is improved.

(Effect) The inorganic substance comprising (c) is
By using two or more kinds of ceramic powders having different sintering temperatures or light transmittances to form the photocurable fluid resin composition, the efficiency of producing the photocurable resin molded body is improved, or the sintered molded body is improved. It is possible to improve the shape retention of
It becomes a photocurable fluid resin composition.

(6) The monomer according to (1), wherein the monomer comprising (a) comprises two or more monomers having a hydrophilic group and one radically polymerizable functional group. ) ~
The photocurable fluid resin composition according to (5).

(Corresponding Embodiment of the Invention) The embodiment relating to the present invention corresponds to the fifth embodiment.

The “monomer having a hydrophilic group and one radically polymerizable functional group” in the present invention corresponds to morpholine acrylate and glycerol monomethacrylate in the fifth embodiment. The radical polymerizable monomer having another hydrophilic group as described in the corresponding embodiment of (1) can be changed. The composition ratio of the two or more monomers is not particularly limited, but it is preferable that each of the monomers to be mixed has a mixing ratio of 10 mol% or more.

The photocurable fluid resin composition may be used in an amount of 0.5 to 10 w / w based on the monomer mixture composed of the two or more monomers.
t%, preferably 2 wt%, of a photopolymerization initiator and 10 vol% with respect to a monomer mixture comprising two or more monomers.
As described above, preferably 28 vol% or more of an inorganic substance is mixed.

(Operation) Next, the operation of the present invention will be described.

The photocurable fluid resin composition contains two kinds of radically polymerizable monomers having a hydrophilic group, and when degreased in the step of producing a sintered compact,
The decomposition temperatures of the two monomers are different. Therefore, since degreasing occurs step by step in the degreasing step, distortion generated during sintering is reduced, and the shape retention of the sintered compact is improved.

(Effect) The monomer composed of the above (a) has 2
Kind of, using a radical polymerizable monomer having a hydrophilic group,
By configuring the photocurable fluid resin composition, a photocurable fluid resin composition capable of improving the shape retention of the sintered molded article is obtained.

(7) The monomer composed of (a) is a monomer having a hydrophilic group and one radical polymerizable functional group, and a monomer having a hydrophilic group and two radical polymerizable functional groups. The photocurable fluid resin composition according to any one of the above (1) to (6), comprising two or more monomers of one or more monomers.

(Corresponding Embodiments of the Invention) The sixth, eighth, ninth, thirteenth, and fourteenth embodiments correspond to the embodiments of the present invention. Embodiments corresponding to the present invention are Embodiments 1 to 5.

The “monomer having a hydrophilic group and one radically polymerizable functional group” in the present invention corresponds to morpholine acrylate in this embodiment, but corresponds to the above-mentioned invention (1). Other radically polymerizable monomers having a hydrophilic group described in the embodiment can also be used. In the present invention, “a monomer having a hydrophilic group and two or more radically polymerizable functional groups” corresponds to pentaerythritol triacrylate in this embodiment, but has a different hydrophilic group and a radical It is possible to change to a monomer having two or more polymerizable functional groups. For example, glycerol di (meth) acrylate, 2-hydroxy-3-acryloyloxypropyl (meth) acrylate, N, N'-methylenebisacrylamide, and the like are worthy of mention.

A monomer comprising the monomer having the hydrophilic group and one radically polymerizable functional group and the monomer having the hydrophilic group and two or more radically polymerizable functional groups The composition ratio of the mixture is 0.1 to 20 mol with respect to the monomer having the hydrophilic group and one radically polymerizable functional group.
%, Preferably 0.5 to 1 mol% of a monomer having a hydrophilic group and two or more radically polymerizable functional groups.

The photocurable fluid resin composition accounts for 0.5 to 10% by weight, preferably 2% by weight, based on the monomer mixture.
Of the photopolymerization initiator and 10 vo
It is desirable that the composition be mixed with 1% or more, preferably 28% by volume or more of the inorganic substance. In particular, when a sintered compact is produced, the content of the inorganic substance is desirably as large as possible within a range where the photocurable fluid resin composition is sufficiently cured by light irradiation.

(Operation) Next, the operation of the present invention will be described.

The photocurable fluid resin composition contains two types of radically polymerizable monomers having a hydrophilic group, and when degreasing in the step of producing a sintered compact,
The decomposition temperatures of the two monomers are different. Therefore, since degreasing occurs step by step in the degreasing step, distortion generated during sintering is reduced, and the shape retention of the sintered compact is improved.

Since one of the two monomers is a monomer having two or more radically polymerizable functional groups, the inorganic substance-containing photocurable resin molded article produced by irradiation with light is The material is three-dimensionally crosslinked by the curable resin, and the material strength is improved.

Effects The (a) contained in the photocurable fluid resin composition 1 according to the first embodiment includes a monomer having a hydrophilic group and one radically polymerizable functional group, and a monomer having a hydrophilic group. Of the photocurable resin molded body containing inorganic substance is improved by forming the photocurable fluid resin composition using two kinds of monomers having two or more radical polymerizable functional groups. Thus, a photocurable fluid resin composition capable of improving the shape retention of a sintered molded article.

(8) The inorganic substance comprising (c) is
(1), (2), characterized in that it is made of fiber
(6) The photocurable fluid resin composition according to (7).

(Corresponding Embodiment of the Invention) The embodiment relating to the present invention corresponds to the seventh embodiment.

[0303] The fibers in the present invention correspond to silica fibers in this embodiment, but can be changed to other inorganic fibers as described in the corresponding embodiments of the invention (1). is there. The size of the fiber is not particularly limited, but a diameter of 0.05 to 10 μm and a length of 1 to 500 μm
Preferably, the diameter is 0.1 to 5 μm and the length is 5 to 10.
A thickness of 0 μm is more desirable.

The photocurable fluid resin composition prepared by mixing the radically polymerizable monomer having a hydrophilic group, the photopolymerization initiator, and the fibrous inorganic substance can be prepared by mixing the radicalizable polymerizable monomer having the hydrophilic group. 0.5 to 10% by weight, preferably 2% by weight, of the photopolymerization initiator with respect to the polymerizable monomer, and 1 vol% or more, preferably 5 vol% or more with respect to the radical polymerizable monomer having a hydrophilic group. It is desirable to mix and mix the above fibrous inorganic substances. The content of the fibrous inorganic substance is desirably as large as possible within a range where the photocurable fluid resin composition is sufficiently cured by light irradiation.

(Operation) Next, the operation of the present invention will be described.

The above-mentioned photocurable fluid resin composition contains fibers as an inorganic substance. Compared with a photocurable fluid resin composition containing powder as an inorganic substance, the photocurable fluid resin composition produced by irradiation with light is used. The material strength of the conductive resin molded body is improved.

Effect By forming a photocurable fluid resin composition by using a fibrous inorganic substance as the inorganic substance (c), the material strength of the inorganic substance-containing photocurable resin molded article is improved. It becomes a photocurable fluid resin composition that can be used.

(9) The photocurable fluid resin composition according to any one of (1) to (8), wherein the monomer comprising (a) comprises a monomer having a morpholino group.

(Corresponding Embodiments of the Invention) Embodiments relating to the present invention correspond to the first to fourth and seventh embodiments.

The “monomer having a morpholino group” in the present invention corresponds to morpholine acrylate in this embodiment. However, as described in the corresponding embodiment of the above invention (1), other monomers are used. And a radical polymerizable monomer having a hydrophilic group.

[0311] The composition ratio of the photocurable fluid resin composition can be changed as described in the corresponding embodiment of the invention (1).

(Effects) This is the same as the invention (1).

(10) The monomer comprising (a) is
Characterized by consisting of morpholine acrylate,
The photocurable fluid resin composition according to any one of (1) to (5), (8), and (9).

(Corresponding Embodiments of the Invention) Embodiments of the present invention correspond to the first to fourth and seventh embodiments.

The composition ratio of the photocurable fluid resin composition can be changed as described in the corresponding embodiment of the invention (1).

(Operation and structure) This is the same as the above-mentioned invention (1).

(11) The monomer comprising (a) is
Morpholine acrylate, and pentaerythritol triacrylate;
The photocurable fluid resin composition according to any one of the above (1) to (9).

(Corresponding Embodiments of the Invention) Embodiments relating to the present invention correspond to the sixth, eighth, and ninth embodiments. Embodiments corresponding to the present invention are Embodiments 1 to 4.

The composition ratio of the photocurable fluid resin composition can be changed as described in the corresponding embodiment of the invention (7).

(Operation and structure) This is the same as the invention (6).

(12) The above (1) to (4), (6), (7), (9) to (11), wherein the inorganic substance consisting of (c) is made of alumina powder. The photocurable fluid resin composition according to the above.

(Corresponding Embodiments of the Invention) Embodiments of the present invention correspond to the first to third, fifth, sixth and eighth embodiments. Embodiments corresponding to the present invention are Embodiments 1 to 3.

The composition ratio of the photocurable fluid resin composition can be changed as described in the corresponding embodiment of the invention (1).

(Operation and effect) The same as the invention (4).

(13) The photocurable composition according to any one of (1) to (7) and (9) to (11), wherein the inorganic substance comprising (c) comprises alumina powder and silica powder. Fluid resin composition.

(Corresponding Embodiments of the Invention) Embodiments of the present invention correspond to the fourth and ninth embodiments.
An embodiment corresponding to the present invention is the fourth embodiment.

The composition ratio of the photocurable fluid resin composition can be changed as described in the corresponding embodiment of the invention (1).

(Operation and effect) The same as the above invention (5).

(14) The monomer comprising the component (a) is
The above (1) to (1) to (1), wherein the inorganic substance comprising a radically polymerizable monomer having a cationic ionic group and comprising the above-mentioned (c) comprises a lead zirconate titanate powder.
The photocurable fluid resin composition according to (4).

(Corresponding Embodiments of the Invention) Embodiments of the present invention correspond to the tenth, eleventh, and twelfth embodiments.

The “radical polymerizable monomer having a cationic ionic group” in the present invention corresponds to 2-acryloyloxyethyltrimethylammonium chloride in the tenth embodiment. The radical polymerizable monomer having an ionic group can be changed.
For example, N, N-dimethylaminopropyl acrylamide, N, N-dimethylaminoethyl (meth) acrylate, N, N-dimethylaminopropyl acrylamide,
3-Acrylamidopropyltrimethylammonium chloride, etc., deserve it. The term "cationic ionic group" is used in this proposal to refer to tertiary amines, hydroxylated 4
It means a functional group such as a secondary amine.

The particle size of the lead zirconate titanate powder is not particularly limited, but is preferably from 0.05 to 100 μm, more preferably from 0.1 to 10 μm.

The photocurable fluid resin composition prepared by mixing the radical polymerizable monomer having a cationic ionic group, the photopolymerization initiator, and the lead zirconate titanate powder has a hydrophilic property. 0.1 for the radical polymerizable monomer having a group.
5 to 10 wt%, preferably 2 wt% of the photopolymerization initiator;
10 v for the radical polymerizable monomer having a hydrophilic group
ol% or more, preferably 28 vol% or more of the inorganic substance. In particular, when a sintered compact is produced, the content of the inorganic substance is desirably as large as possible within a range where the photocurable fluid resin composition is sufficiently cured by light irradiation.

(Operation) Next, the operation of the present invention will be described.

The lead zirconate titanate powder of the above-mentioned photocurable fluid resin composition is a powder having piezoelectric properties, unlike a simple ceramic powder. Can function as a piezoelectric body. However, since the photocurable fluid resin composition containing lead zirconate titanate powder has the property of absorbing ultraviolet light, the photocurable fluid resin cured with ultraviolet light contains an inorganic substance. It is difficult to produce a photocurable resin molded body. However, when a radically polymerizable monomer having a cationic ionic group is used as the photocurable fluid resin, the inorganic substance-containing photocurable resin molded article can be produced.

The reason for this is not clear, but may be due to the interaction between the cationic ionic group of the radical polymerizable monomer having a cationic ionic group and lead zirconate titanate. . When a radical polymerizable monomer having no ionic group, a radical polymerizable monomer having an anionic ionic group, or a radical polymerizable monomer having a nonionic ionic group is used, the above effect is not obtained. .

(Effect) A radically polymerizable monomer having a cationic ionic group is used for the monomer composed of (a), and a lead curable zirconate titanate is used for (c). By forming the fluid resin composition, a photocurable fluid resin composition capable of producing an inorganic substance-containing photocurable resin molded article having a piezoelectric property and a sintered molded article is obtained.

(15) The monomer comprising (a) is
The photopolymerization initiator comprising a radically polymerizable monomer having a cationic ionic group and comprising the above-mentioned (b) is 360n
(1) to (1) to (1), wherein the inorganic substance comprising (c) is a lead zirconate titanate powder.
(4) The photocurable fluid resin composition according to (14).

(Corresponding Embodiments of the Invention) Embodiments of the present invention correspond to the eleventh and twelfth embodiments. An embodiment corresponding to the present invention is the fifth embodiment.

The “radical polymerizable monomer having a cationic ionic group” in the present invention corresponds to 2-acryloyloxyethyltrimethylammonium chloride in the eleventh embodiment. As described in the corresponding embodiment of the invention, it is possible to change to a radical polymerizable monomer having another cationic ionic group. In the present invention, "radical is generated by light having a wavelength of 360 nm or more" The “compound” corresponds to bis (cyclopentadienyl) -bis (2,6-difluoro-3- (pyr-1-yl) titanium in the eleventh embodiment, but has another wavelength of 360 nm or more. Compounds that generate radicals by light can be changed, for example, 2,4-
Diethylthioxanthone, isopropylthioxanthone, 1-chloro-4-propoxythioxanthone, 2-
(3-dimethylamino-2-hydroxypropoxy)-
3,4-dimethyl-9H-thioxanthone-9-one mesochloride, 2-methyl-1- [4- (methylthio)
Phenyl] -2-morpholinopropane-1, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1 and the like are worth it. Also,
To peroxyesters such as 1,3-di (t-butyldioxycarbonyl) benzene and 3,3 ′, 4,4′-tetra- (t-butylperoxycarbonyl) benzophenone, thiopyrylium salts, merocyanines, quinolines, and stills A substance in which a quinoline dye is mixed can also be used.

The particle size of the lead zirconate titanate powder is not particularly limited, but is preferably from 0.05 to 100 μm, more preferably from 0.1 to 10 μm.

The composition ratio of the photocurable fluid resin composition prepared by mixing the radical polymerizable monomer having a cationic ionic group, the photopolymerization initiator, and the lead zirconate titanate powder is as follows. Modifications are possible as described in the corresponding embodiment of the invention (14).

(Operation) Next, the operation of the embodiment of the present invention will be described.

As described in the function of the invention (14), the photocurable fluid resin composition containing the lead zirconate titanate powder has a property that the lead zirconate titanate powder absorbs ultraviolet light. In addition, it is difficult to form a photocurable resin molded article containing an inorganic substance with a photocurable fluid resin that is cured by ultraviolet rays. The photocurable fluid resin composition of the present invention,
The radical polymerizable monomer having a cationic ionic group described in the operation of the invention (14) is used, and a radical is generated by light having a wavelength of 360 nm or more as a photopolymerization initiator that generates a radical in a visible light region. The use of such a compound makes it possible to produce the inorganic substance-containing photocurable resin molded article.

(Effect) A radical polymerizable monomer having a cationic ionic group is used as the monomer (a), and the photopolymerization initiator (b) is irradiated with light having a wavelength of 360 nm or more. Using a photopolymerization initiator that generates radicals, the inorganic substance comprising (c) has an average particle size of 0.2 μm.
m, by forming a photocurable fluid resin composition using lead titanate zirconate powder, an inorganic substance-containing photocurable resin molded product having piezoelectric properties, and a sintered molded product can be produced. , Resulting in a photocurable fluid resin composition.

(16) The monomer comprising the component (a) is
The photopolymerization initiator comprising a radically polymerizable monomer having a cationic ionic group and comprising the above-mentioned (b) is 360n
the inorganic substance (c) is made of a powder of lead zirconate titanate, and has a functional group capable of reacting with the inorganic substance on one side chain. (1) to (1), which are surface-treated with an organic compound having silane and having a functional group capable of radical polymerization on the other side chain.
(4) The photocurable fluid resin composition according to (14) or (15).

(Corresponding Embodiment of the Invention) The embodiment relating to the present invention corresponds to the twelfth embodiment. An embodiment corresponding to the present invention is the fifth embodiment.

The “radical polymerizable monomer having a cationic ionic group” in the present invention corresponds to 2-acryloyloxyethyltrimethylammonium chloride in the twelfth embodiment. As described in the corresponding embodiment of the invention, it is possible to change to a radical polymerizable monomer having another cationic ionic group. In the present invention, "radical is generated by light having a wavelength of 360 nm or more" The “compound” corresponds to bis (cyclopentadienyl) -bis (2,6-difluoro-3- (pyr-1-yl) titanium in the twelfth embodiment, but corresponds to the invention (15). As described in the embodiment of the present invention, a compound capable of generating a radical by another light having a wavelength of 360 nm or more can be changed.

The particle size of the lead zirconate titanate powder is not particularly limited, but is preferably from 0.05 to 100 μm, more preferably from 0.1 to 10 μm.

The “organic compound having a silane having a functional group capable of reacting with an inorganic substance on one side chain and a radically polymerizable functional group on the other side chain” in the present invention is referred to as the first compound.
In the second embodiment, 3-trimethoxysilylpropyl methacrylate is applicable, but as described in the corresponding embodiment of the invention (2), a functional group capable of reacting with an inorganic substance is provided on one side chain. Other compounds can also be used as long as they are organic compounds having a silane having a group and having a functional group capable of radical polymerization on the other side chain.

The composition ratio of the photocurable fluid resin composition prepared by mixing the radical polymerizable monomer having a cationic ionic group, the photopolymerization initiator, and the lead zirconate titanate powder is as follows: Modifications are possible as described in the corresponding embodiment of the invention (14).

(Operation and Effect) Next, the operation of the embodiment of the present invention will be described.

A photocurable fluid resin composition having the effects of the invention (2) and the effects of the invention (15) is obtained.

(17) The organic compound having a silane having a functional group capable of reacting with an inorganic substance on one side chain and a radically polymerizable functional group on the other side chain as described in the above (2) is methacrylic acid. A photocurable fluid resin composition, which is -3-trimethoxysilylpropyl.

(Corresponding Embodiment of the Invention) The embodiment relating to the present invention relates to the second, eighth, ninth, twelfth and fourteenth embodiments.
Corresponds to this embodiment. Embodiments corresponding to the present invention are Embodiment 2 and Embodiment 5.

The composition ratio of the photocurable fluid resin composition can be changed as described in the corresponding embodiment of the invention (1).

(Function and Effect) The same as the invention (2).

(18) The monomer comprising (a) is
Morpholine acrylate and pentaerythritol triacrylate, wherein the inorganic substance (c) is made of alumina powder, and the powder is surface-treated with 3-trimethoxysilylpropyl methacrylate. (1)-
(4), (6), (7), (9), (11), (1
2), The photocurable fluid resin composition according to (17).

(Corresponding Embodiment of the Invention) An embodiment relating to the present invention corresponds to the eighth embodiment. An embodiment corresponding to the present invention is the second embodiment.

The composition ratio of the photocurable fluid resin composition can be changed as described in the corresponding embodiment of the invention (1).

(Operation and Effect) Next, the operation of the embodiment of the present invention will be described.

A photocurable fluid resin composition having both the effects of the above invention (2) and the above invention (7) is obtained.

(19) The monomer comprising (a) is
Morpholine acrylate and pentaerythritol triacrylate, wherein the inorganic substance (c) comprises alumina powder and silica powder, and the powder is subjected to surface treatment with 3-trimethoxysilylpropyl methacrylate. Characterized by the fact that
(1) to (7), (9) to (11), (13),
(17) The photocurable fluid resin composition according to (17).

(Corresponding Embodiment of the Invention) The ninth embodiment corresponds to the embodiment relating to the present invention.

The composition ratio of the photocurable fluid resin composition can be changed as described in the corresponding embodiment of the invention (1).

(Operation and Effect) Next, the operation of the embodiment of the present invention will be described.

A photocurable fluid resin composition having the effects of the invention (2), the invention (5), and the invention (7) is obtained.

(20) The monomer consisting of the above (a) is
The inorganic substance consisting of 2-acryloyloxyethyltrimethylammonium chloride and comprising the above (c),
Characterized by being composed of lead zirconate titanate powder,
The photocurable fluid resin composition according to any one of (1) to (4) and (14) to (16).

Embodiments 10, 11, and 12 correspond to this.

(Corresponding Embodiments of the Invention) Embodiments relating to the present invention correspond to the tenth, eleventh, and twelfth embodiments.

The composition ratio of the photocurable fluid resin composition can be changed as described in the corresponding embodiment of the invention (14).

(Operation and effect) The same as the invention (14).

(21) The monomer consisting of the above (a) is
An inorganic substance comprising a monomer obtained by mixing 2-acryloyloxyethyltrimethylammonium chloride, N, N-dimethylaminopropylacrylamide and pentaerythritol triacrylate,
Characterized by being composed of lead zirconate titanate powder,
The photocurable fluid resin composition according to any one of (1) to (4) and (14) to (16).

(Corresponding Embodiment of the Invention) The thirteenth embodiment corresponds to the embodiment relating to the present invention. An embodiment corresponding to the present invention is the fifth embodiment.

The photocurable fluid resin composition is used in an amount of 10 to 50 mol%, preferably 30 to 40 mol%, based on 2-acryloyloxyethyltrimethylammonium chloride.
% of N, N-dimethylaminopropylacrylamide and 0.1 to 30 mol%, preferably 10 to 20 mol%, of pentaerythritol triacrylate based on 2-acryloyloxyethyltrimethylammonium chloride. And 0.5 to 10 wt%, preferably 2 wt%, of the photopolymerization initiator based on the monomer mixture, and 10 vol% based on the monomer mixture.
As described above, it is desirable that the composition be mixed with lead zirconate titanate powder of 28 vol% or more. In particular, when a sintered compact is produced, the content of the inorganic substance is desirably as large as possible within a range where the photocurable fluid resin composition is sufficiently cured by light irradiation.

(Operation and Effect) Next, the operation of the embodiment of the present invention will be described.

[0377] 2 contained in the photocurable fluid resin composition
-Acryloyloxyethyltrimethylammonium chloride is not easy to handle due to the large stickiness of the resin, but the stickiness is reduced by mixing N, N-dimethylaminopropylacrylamide,
By mixing pentaerythritol triacrylate which is a cross-linking agent, the hardness of the cured product is improved. Accordingly, it is possible to produce an inorganic substance-containing photocurable resin molded article and a sintered molded article that are easy to handle and have high material strength and have piezoelectric characteristics.

(22) The monomer consisting of the above (a) is
The photopolymerization initiator consisting of a monomer obtained by mixing 2-acryloyloxyethyltrimethylammonium chloride, N, N-dimethylaminopropylacrylamide and pentaerythritol triacrylate, wherein the photopolymerization initiator (b) is bis (cyclopentadienyl) -bis (2,6-difluoro-3- (pyr-1-yl) titanium, wherein the inorganic substance comprising (c) comprises lead zirconate titanate powder, and comprises 3-trimethoxysilylpropyl methacrylate The photocurable fluid resin composition according to any one of (1) to (4) and (14) to (16), which has been subjected to a surface treatment.

(Corresponding Embodiment of the Invention) The embodiment relating to the present invention corresponds to the fourteenth embodiment. An embodiment corresponding to the present invention is the fifth embodiment.

The photocurable fluid resin composition is 10 to 50 mol%, preferably 30 to 40 mol%, based on 2-acryloyloxyethyltrimethylammonium chloride.
% of N, N-dimethylaminopropylacrylamide and 0.1 to 30 mol%, preferably 10 to 20 mol%, of pentaerythritol triacrylate based on 2-acryloyloxyethyltrimethylammonium chloride. 0.5 to 10% by weight, preferably 2% by weight, based on the monomer mixture, of bis (cyclopentadienyl) -bis (2,6-difluoro-3- (pyr-1-yl) titanium; 10 vol% or more, preferably 28 vol%, based on the monomer mixture
It is desirable to mix and contain 1% or more of lead zirconate titanate powder. Especially when making a sintered compact,
The content of the inorganic substance is desirably as large as possible within a range where the photocurable fluid resin composition is sufficiently cured by light irradiation.

(Function and Effect) Next, the function of the present invention will be described.

A photocurable fluid resin composition having the effects of the invention (2) and the effects of the invention (21) is obtained.

[0383]

According to the photocurable fluid resin composition of the present invention, an inorganic substance-containing photocurable resin molded article prepared by light irradiation, three-dimensional stereolithography, or the like is formed as a structure without cracks or peeling. Composition. In addition, it becomes possible to produce a sintered compact produced by sintering the inorganic substance-containing photocurable resin compact as a structure without cracks or peeling.

[Brief description of the drawings]

FIG. 1 is a flowchart showing a procedure of an optical shaping method using a powder-mixed photocurable fluid resin composition of the present invention.

FIG. 2 is a schematic diagram illustrating each procedure of a molding process for irradiating a photocurable fluid resin composition with light to form a three-dimensional resin molded product, taking a regulated liquid level method as an example. .

FIG. 3 is a schematic view of an optical molding apparatus for curing a photocurable fluid resin composition of the present invention to form a three-dimensional structure.

FIG. 4A is a cylindrical three-dimensional structure obtained by curing the photocurable fluid resin composition of the present invention, and FIG. 4B is a photocurable resin composition of the present invention. It is a figure which shows the cylindrical three-dimensional structure obtained by hardening the photocurable resin composition using the acrylic photocurable resin which does not have a hydrophilic group as the component (a) of a fluid resin composition.

FIG. 5 shows components (a) of a photocurable resin fluid composition.
As a graph showing the rate of occurrence of delamination with respect to the content of alumina powder when a radical polymerizable monomer having a hydrophilic group is used and when a radical polymerizable monomer without a hydrophilic group is used as is there.

FIG. 6 is a diagram showing a change in viscosity of a photocurable fluid resin composition containing a surface-treated powder and a non-surface-treated powder with respect to a deposition content of alumina powder. is there.

[Explanation of symbols]

31: elevator, 32: glass plate that transmits light, 33
... Tank, 34: Focused laser beam, 35: Photocurable fluid resin, 36: Cured powder mixed resin molded product, 3
7 ... stage for scanning laser beam, 3
8: Stage for moving the elevator, 39: Condenser, 41: He-Cd laser, 42: Optical fiber,
43: Optical fiber adapter, 44: Electromagnetic shutter for exposure control, 51: Correlation-peeled part.

Continued on the front page (51) Int.Cl. ⁶ Identification number Office reference number FI Technical indication // C04B 35/622 C04B 35/00 E 35/632 108

Claims (3)

[Claims] 1. A photocurable fluid resin composition which can be polymerized by the action of light to be insolubilized in a solvent or changed from a liquid to a solid to form a structure, wherein (a) a hydrophilic group is used as an essential component thereof. Having a radical polymerizable monomer,
A photocurable fluid resin composition comprising: (b) a photopolymerization initiator; and (c) an inorganic substance. 2. An organic compound having a functional group capable of reacting with an inorganic substance on one side chain and a radically polymerizable functional group on the other side chain. The photocurable fluid resin composition according to claim 1, which has been surface-treated. 3. The photocurable fluid according to claim 1, wherein the inorganic substance (c) is a powder, and the powder is a powder having two or more particle size distributions. Resin composition.