JP2018199287A - Manufacturing method of ceramic body - Google Patents

Abstract

To provide a manufacturing method of a ceramic body with high purity and a ceramic particle dispersion element with high purity and high concentration applicable to the manufacturing method of the ceramic body where boehmite sol or binder component is not used as indispensable material and a dry process is not indispensable.SOLUTION: A manufacturing method of a ceramic body comprises a process (I) to cure ink liquid X including a solvent (A) and ceramic particles (B) modified with a reactive functional group and ink liquid Y including a chemical compound (C) as an essential component for crosslinking reaction with the ceramic particles (B) modified with the reactive functional group, by supplying and mixing both of them simultaneously or independently layer by layer or at one time to a support body, wherein the solvent (A) is a solvent of which a steam pressure at 20°C is equal to or lower than 1500 Pa and which has no reactivity with any of the ceramic particles (B) or the chemical compound (C).SELECTED DRAWING: None

Description

  The present invention relates to a method for producing a three-dimensional shaped object (ceramic body).

  In order to produce a three-dimensional structure, a technique for maintaining the shape is required. A well-known method is generally a method in which a mold is used to inject a thermoplastic resin, molten metal, or the like. However, producing a ceramic body by this method using a ceramic dispersion as a material requires a step of drying a solvent in a mold, which is practically difficult.

  In recent years, 3D printers have attracted attention as a low-volume production method. In an inkjet 3D printer, a solution containing a photocurable resin is ejected from an inkjet head and then cured by an ultraviolet lamp. Since this method can simultaneously supply various materials by increasing the number of nozzles, it is possible to produce a shaped article made of a plurality of materials. However, in this method, in order to maintain the shape, a photocurable resin is indispensable, and therefore the ceramic concentration in the modeled object has to be reduced accordingly.

  In Patent Document 1, a manufacturing process of a three-dimensional ceramic body is proposed by printing a suspension containing a ceramic layer by layer using an inkjet printer, and drying and curing the formed composite layer. Yes. In this process, a suspension containing 50 wt% to 80 wt% ceramic particles is used as an ink in a dispersion medium containing an aqueous boehmite sol, a low molecular weight alcohol, a drying inhibitor, and an organic fluidizing agent, and then ejected by inkjet. A three-dimensional ceramic body is formed by drying and sintering. However, in this process, it is essential to contain an aqueous boehmite sol (alumina monohydrate), and it was impossible to produce a shaped article that does not contain alumina. In addition, in order to maintain the shape, each layer must be dried at 80 ° C., and it takes a lot of time to produce a three-dimensional structure by stacking multiple layers.

  In Patent Document 2, an ink-jet ink capable of forming a thick film having a thickness of 10 μm is prepared, which contains 0.1 to 20 parts by weight of a semiconductor oxide. In this ink, the oxide particles are cured using a binder. However, since the oxide particle concentration is only mentioned up to 20 parts by weight, it is unclear whether it can be carried out at a higher concentration. is there. Moreover, although the 10-micrometer-thick thick film is formed, it is unknown whether it can model with the thickness beyond it.

International Publication No. 2007/112885 JP 2012-102308 A

  The problem to be solved by the present invention is to provide a method for producing a high-purity ceramic body, and without requiring a boehmite sol or a binder component and without requiring a drying step, the ceramic body An object of the present invention is to provide a high-purity and high-concentration ceramic particle dispersion that can be applied to the production method described above.

  As a result of various investigations, the present inventors have cured ceramic nanoparticles dispersed in a specific solvent using the surface modification group of the particles, thereby allowing a binder such as a resin or the main component of the target ceramic body. The present inventors completed the present invention by finding that a high-purity ceramic body that does not contain any other inorganic substance as an essential component can be formed while enclosing a solvent.

  That is, the present invention performs a cross-linking reaction between the ink X liquid containing the solvent (A) and the ceramic particles (B) modified with the reactive functional group, and the ceramic particles (B) modified with the reactive functional group. A step (I) in which the ink Y liquid containing the compound (C) to be awakened as an essential component is simultaneously or separately cured and supplied to the support layer by layer or at a time, and the solvent (A) comprises: The present invention relates to a method for producing a ceramic body, wherein the vapor pressure at 20 ° C. is 1500 Pa or less, and the solvent is not reactive with any of the ceramic particles (B) or the compound (C).

Moreover, this invention relates to the manufacturing method of a ceramic sintered compact which has the process of drying or sintering the ceramic body obtained by the said method.
The present invention also relates to an ink set used in the manufacturing method of the present invention described above. That is, the ink set includes an ink X solution containing a solvent (A) and a ceramic particle (B) modified with a reactive functional group, and a crosslink with the ceramic particle (B) modified with the reactive functional group. It consists of two or more inks of ink Y liquid containing a compound (C) that causes a reaction as an essential component, the solvent (A) has a vapor pressure at 20 ° C. of 1500 Pa or less, and the ceramic particles (B) Or it is a modeling ink set which is a solvent which is not reactive with any of the said compound (C).

  In the ink set for modeling according to the present invention, since the ceramic is dispersed in the solvent without requiring the boehmite sol and the binder component disclosed in Patent Document 1 and Patent Document 2, the change in viscosity with respect to temperature is slow. And the temperature stability of the ceramic dispersion is high. Moreover, since the solvent and ceramic fine particles are the main components and the other components are not essential, a high-purity ceramic fine particle dispersion can be prepared. Furthermore, a high-purity ceramic sintered body is produced by removing the solvent by drying or sintering from the ceramic body produced by using this dispersion in the steps in the above-described method for producing a ceramic body of the present invention. be able to. Furthermore, since the dispersion of the present invention can be applied to any kind of ceramic as long as it has particles having a surface modification group dispersed in a solvent, it can be applied to the production of a shaped article using a ceramic having various functions. Is possible.

Hereinafter, the present invention will be described in detail.
The present invention relates to a method for producing a ceramic body, comprising a step of curing the ink set of the present invention by supplying and mixing layers or at a time on a support simultaneously or separately.
Such an ink set of the present invention can be cured only by mixing ink.
Energy rays or thermal stimuli can also be used to promote curing. In addition, the ink set of the present invention uses a specific solvent, so that the ceramic particles can easily form a network structure while containing the solvent, and a three-dimensional shape cured product can be more suitably produced. The inventors have found such a property, paying attention to this, and manufacturing a ceramic body that is a shaped product (a method for maintaining the shape before removing the organic component) and a ceramic sintered body (drying or firing the organic component). By applying the present ink set to a method for producing a ceramic body obtained by removing by congealing, the above-described effects were obtained and the problem was solved.

  If the ink set of the present invention is used, when the ink is cured, the solvent can remain in the cured product (it can be cured while the solvent is contained), so that distortion due to the volatilization of the solvent is less likely to occur, and between the particles Therefore, a three-dimensional cured product can be suitably produced.

  The ink Y liquid may be mixed with a solvent (D) for the purpose of adjusting the viscosity, if necessary.

  In the cured product produced by curing the ink X liquid and the ink Y liquid simultaneously or separately by supplying them to the support layer by layer or once and mixing them, the solvent (A) and the solvent ( The total amount of D) preferably remains 80% by weight or more, more preferably 90% by weight or more of the total weight of the solvent before curing. In order to obtain such a result, the solvent (A) and the solvent (D) to be used are preferably solvents having a vapor pressure of 1500 Pa or less at 20 ° C., and are solvents having a vapor pressure of 1000 Pa or less at 20 ° C. It is more preferable. If it is in this range, the distortion of the network between the particles hardly occurs, and the network between the particles at the time of curing can be more suitably produced.

  As an example of the solvent (A) and the solvent (D) that satisfy such requirements, the compound represented by the following formula (1), the compound represented by the following formula (2), and the following formula (3) Compound, 3-methoxybutyl acetate, glycerin, 1,3-butylene glycol, 2-ethyl-1,3-hexanediol, 1,3-octylene glycol, 2-ethylbutanol, 2-ethylhexyl acetate, 3-methylbutyl acetate Benzyl acetate, methyl propionate, butyl propionate, dibutyl phthalate, methyl lactate, ethyl lactate, butyl lactate, nonane, decane, dodecane, methyl benzoate, ethyl benzoate, butyl benzoate, N-methyl-2-pyrrolidone , Dimethyl sulfoxide, N, N-dimethylformamide, N, N-dimethylacetamide, γ-butyrolactone δ- valerolactone, such as ε- caprolactone.

(In the formula (1), R ₁ is a hydrogen atom or a methyl group, R ₂ is a hydrogen atom or an alkyl group which may be branched having 1 to 12 carbon atoms, R ₃ is a hydrogen atom, a benzyl group, a phenyl group or carbon. (It is the alkyl group which may be branched of number 1-12. Moreover, n is an integer of 1-4.)

(In Formula (2), R ₄ is a hydrogen atom or a methyl group, R ₅ is a hydrogen atom, a benzyl group, or an alkyl group having 1 to 12 carbon atoms, and R ₆ is a methyl group or an ethyl group. Moreover, n is an integer of 1 to 4.)

(In the formula _(3), R 7, _{R 8} are each independently a methyl group or an ethyl group. Further, n represents an integer of 1 to 4.)

  More preferable examples of the solvent (A) and the solvent (D) include a compound represented by the formula (1), a compound represented by the formula (2), a compound represented by the formula (3), and N-methyl. -2-pyrrolidone, dimethyl sulfoxide and the like. These may use only 1 type and may mix and use 2 or more types.

  The solvent (A) and the solvent (D) may be the same or different types.

  In the ink set of the present invention, the ceramic particles (B) modified with reactive functional groups react with the ceramic particles (B) modified with reactive functional groups and a compound (C) that causes a crosslinking reaction, It is considered that a network structure is formed and cured while enclosing the solvent as described above. By finding such a curing system, the shape can be maintained without using a binder resin which has been considered as an essential component in the past, and a high-purity ceramic body can be obtained. That is, modeling using an ink set that substantially does not contain a binder component is possible. Note that “substantially free” means that the binder component is not contained in an amount that has been used in the field of the art so as to sufficiently exhibit, for example, photocuring performance. It is not meant to exclude the addition of a minute amount for the purpose.

  Crosslinking reaction to form network structure includes reaction of epoxy group and thiol group, reaction of epoxy group and amino group, reaction of epoxy group and carboxyl group, reaction of amino group and isocyanate group, reaction of isocyanate group and hydroxyl group, etc. Is mentioned.

  In order to produce the ceramic particles (B) modified with the reactive functional group, a reactive compound having a reactive group capable of coordinating and / or bonding to the surface of the ceramic and capable of the crosslinking reaction ( The ceramic particles may be modified with α). The reactive compound (α) can be used as a single component or as a mixture of two or more thereof.

  Examples of reactive compounds (α) include epoxy groups, amino groups, functional groups having reactive double bonds (methacryloyl groups, acryloyl groups, vinyl groups, etc.), isocyanate groups, hydroxyl groups, thiol groups, and carboxyl groups. And reactive compounds.

  Examples of reactive compounds containing epoxy groups include epichlorohydrin, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropyltri Examples include methoxysilane, 3-glycidoxypropylmethyldiethoxysilane, and 3-glycidoxypropyltriethoxysilane.

  Examples of reactive compounds containing a functional group having a reactive double bond include acrylic acid, methacrylic acid, maleic acid, fumaric acid, 2- (meth) acryloyloxyethyl succinic acid, 2- (meth) Acryloyloxyethyl hexahydrophthalic acid, 2- (meth) acryloyloxyethyl phthalic acid, vinyltrimethoxysilane, vinyltriethoxysilane, 3- (meth) acryloxypropylmethyldimethoxysilane, 3- (meth) acrylic Roxypropyltrimethoxysilane, 3- (meth) acryloxypropyltriethoxysilane, p-styryltrimethoxysilane, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) Acrylate, 2-hydroxybutyl (meth) acryl Over DOO, such as 4-hydroxybutyl (meth) acrylate.

  Examples of reactive compounds containing amino groups include N-2- (aminoethyl) -3-aminopropylmethyldimethoxysilane, N-2- (aminoethyl) -3-aminopropyltrimethoxysilane, 3-amino. Examples thereof include propyltrimethoxysilane and 3-aminopropyltriethoxysilane.

  In addition to the reactive compound (α), the ceramic particles (B) may be a compound (β) having no reactive functional group (hereinafter referred to as a compound) as long as it can be coordinated and / or bonded to the surface of the ceramic. (May be described as (β)), and may be further modified. The compound (β) is effective for improving the dispersibility of the ceramic particles in the solvent. Examples of the compound (β) include acetic acid, valeric acid, hexanoic acid, heptanoic acid, 2-ethylhexanoic acid, octanoic acid, 2-methylheptanoic acid, 4-methyloctanoic acid, nonanoic acid, decanoic acid, neodecane Acid, dodecanoic acid, tetradecanoic acid, hexadecanoic acid, octadecanoic acid, oleic acid, 12-hydroxystearic acid, cyclohexanol, 1-butanol, 2-butanol, oleic alcohol, methylcyclohexanol, ethylene glycol monoethyl ether . These may be used alone or in combination of two or more.

  In the present invention, the method for modifying the surface of the ceramic particles (B) may be a method usually employed for modifying the ceramic particles, and the method is not particularly limited. For example, ceramic nanoparticles such as metal oxides are placed in a reaction vessel in a nitrogen atmosphere and stirred while spraying the reactive compound (α) or compound (β), and then heated and stirred at 100 to 150 ° C. for 1 hour or longer for modification. Either a dry method to make the slurry, or a wet method in which the ceramic particles (B) are slurried, the reactive compound (α) and the compound (β) are added, and the mixture is modified by stirring while applying heat may be used. Further, surface modification may be performed when the ceramic nanoparticles are synthesized by a sol-gel method or a supercritical hydrothermal synthesis method.

The ceramic particles for producing the ceramic particles (B) modified with the reactive functional group used in the present invention may be single, a mixture of two or more ceramics, a solid solution or a composite oxide. Also good. Examples of single _{ceramic, SiO 2, Al 2 O 3} , TiO 2, ZrO 2, In 2 O 3, ZnO, SnO 2, La 2 O 3, Y 2 O 3, CeO 2, MgO, Si 3 such as N _4, and examples of solid solution or composite _{oxide, ITO, ATO, BaTiO 3,} CaTiO 3, MgAl 2 O 4, Al 2 O 3 -ZrO 2, Y 2 O 3- ZrO 2, boehmite and / or MgO and / or _ZrO 2 stabilized with CaO or the _{like, Al 2 O 3, Y 2} O 3, HfO 2, CeO 2, Al 2 O 3 -ZrO 2, Al 2 O 3, Y 2 O 3, Fe ₂ O ₃ and Si ₃ N ₄ stabilized with other rare earth oxides.

  The compound (C) causing the crosslinking reaction may be any compound as long as it causes a crosslinking reaction with the ceramic particles (B) modified with the reactive functional group.

  As the compound (C) that causes a crosslinking reaction, polythiol, polyamine, polyisocyanate, polyol and the like can be selected according to the ceramic particles (B) modified with the reactive functional group. There is no restriction | limiting in particular in the molecular weight of the compound (C) which raise | generates a crosslinking reaction, Any of a low molecular weight compound, an oligomer compound, and a polymer may be sufficient.

  The content of the ceramic particles (B) when the ink X liquid and the ink Y liquid are mixed is 5 vol% or more and 70 vol% or less, preferably 5 vol% or more and 60 vol% or less. If it is the said density | concentration range, since the distance between particle | grains is near and a network structure is fully formed, the hardened | cured material which included the solvent can be produced stably.

  In the ink X liquid and the ink Y liquid, a catalyst can be mixed and used as needed to promote the crosslinking reaction.

  In the present invention, a surfactant may be added to the ink X liquid and the ink Y liquid. The surfactant can be used mainly for preparation of surface tension and the like. Although the kind of surfactant is not specifically limited, For example, an anionic surfactant, a nonionic surfactant, a cationic surfactant, an amphoteric surfactant etc. can be used.

  Examples of the anionic surfactant include alkylbenzene sulfonate, alkylphenyl sulfonate, alkylnaphthalene sulfonate, higher fatty acid salt, sulfate of higher fatty acid ester, sulfonate of higher fatty acid ester, higher alcohol ether. Sulfate salts and sulfonates of the above, higher alkyl sulfosuccinates, polyoxyethylene alkyl ether carboxylates, polyoxyethylene alkyl ether sulfates, alkyl phosphates, polyoxyethylene alkyl ether phosphates, etc. Specific examples include dodecylbenzene sulfonate, isopropyl naphthalene sulfonate, monobutylphenylphenol monosulfonate, monobutylbiphenyl sulfonate, dibutylphenylphenol disulfate. It can be mentioned acid salts.

  Nonionic surfactants include, for example, polyoxyethylene nonyl phenyl ether, polyoxyethylene octyl phenyl ether, polyoxyethylene dodecyl phenyl ether, polyoxyethylene alkyl ether, polyoxyethylene alkyl phenyl ether, polyoxyethylene fatty acid ester, Sorbitan fatty acid ester, polyoxyethylene sorbitan fatty acid ester, polyoxyethylene sorbitol fatty acid ester, glycerin fatty acid ester, polyoxyethylene glycerin fatty acid ester, polyglycerin fatty acid ester, sucrose fatty acid ester, polyoxyethylene alkylamine, polyoxyethylene fatty acid amide , Fatty acid alkylolamide, alkyl alkanolamide, acetylene glycol, aceto Examples include oxyethylene adducts of lenglycol, polyethylene glycol polypropylene glycol block copolymers, etc. Among these, polyoxyethylene nonylphenyl ether, polyoxyethylene octylphenyl ether, polyoxyethylene dodecylphenyl ether, polyoxyethylene Preference is given to alkyl ethers, polyoxyethylene fatty acid esters, sorbitan fatty acid esters, polyoxyethylene sorbitan fatty acid esters, fatty acid alkylolamides, acetylene glycol, oxyethylene adducts of acetylene glycol, and polyethylene glycol polypropylene glycol block copolymers.

  Examples of the cationic surfactant include tetraalkyl ammonium halide surfactants, alkyl pyridinium halide surfactants, alkyl imidazoline halide surfactants, and the like.

  Examples of amphoteric surfactants include alkyl betaine surfactants, alkyl imidazolinium betaine surfactants, and lecithin surfactants.

  Other surfactants include silicone surfactants such as polysiloxane oxyethylene adducts; fluorine surfactants such as perfluoroalkyl carboxylates, perfluoroalkyl sulfonates, and oxyethylene perfluoroalkyl ethers. Biosurfactants such as spicrispolic acid, rhamnolipid, lysolecithin and the like can also be used.

  These surfactants can be used alone or in combination of two or more.

In the production of the three-dimensionally shaped ceramic body of the present invention, at least two types of modeling inks, ink X liquid and ink Y liquid, are simultaneously or separately supplied to the support for each layer or at once and cured. Then, the ceramic body is manufactured once or by laminating.
The support in the present invention may be any shape and material as long as it can hold the ink mixture before curing, for example, a flat support such as a graphite plate, a platinum plate, a metal plate, a ceramic plate, or a glass plate. And a three-dimensional support such as a container made of these materials.
The supply in the present invention is to make the ink come into contact with the support, and to make new ink come into contact with the cured ink. Although there is no restriction | limiting in the supply method, Application | coating, dripping, printing, dipping, etc. are mentioned.

  There is no particular limitation on the temperature at which the ink X liquid and the ink Y liquid are mixed and cured by a crosslinking reaction. Considering the viscosity and workability of the ink, room temperature or higher is preferable.

  For the purpose of increasing the curing rate, heating may be performed, or stimulation with energy rays may be given.

  The ink X liquid and the ink Y liquid may be divided into two or more liquids as necessary.

  When the ink X liquid and the ink Y liquid are simultaneously or separately supplied to the support layer by layer or once and mixed, the other ink liquids are added so as not to inhibit the curing reaction of the ink X liquid and the ink Y liquid. You may mix.

Hereinafter, although an example of the embodiment in the present invention is mentioned below, it is not necessarily limited to these.
Specific examples of a method for producing a ceramic body include a 3D-inkjet method in which ink is supplied to a support in small amounts separately, and the ink is mixed on the support to be cured and laminated, or a container is filled. A support is placed in the ink X liquid, ink Y liquid droplets are ejected and cured to the desired shape, and the support is moved up or down to create a three-dimensional shape step by step. And a material injection method.
As another example of the manufacturing method in the present invention, a method of supplying ink X liquid and ink Y liquid at a time into a mold having a prescribed size, mixing the ink, and curing the liquid is also possible. Examples of the mold having the prescribed dimensions include a container such as a petri dish, a mold manufactured with agar, a mold printed with a printer, and the like.

  In the production of the three-dimensionally shaped ceramic body of the present invention, since it is cured using the surface modification group of the ceramic particles, the type of ceramic is not limited as long as the particles can be provided with a desired surface modification group. Furthermore, by removing the organic portion by sintering or the like, a ceramic shaped article (ceramic sintered body) having a theoretically intended inorganic component purity of 100% can be produced. There are no particular restrictions on the types of objects that can be produced according to the present invention, models in the field of education and toys, models imitating animals and plants, various products in the industrial field, operation confirmation and fitting, texture, and size. Various models such as models in the prototype stage for confirmation, miniatures in the architectural field such as structural confirmation of the body, preparation of samples, etc., models of organs and bones in the medical field, prosthetic hands, crowns, artificial bones, etc. It is applicable to the production of a simple model.

  EXAMPLES Hereinafter, although this invention is demonstrated in more detail using an Example, this invention is not limited to the range of a following example.

Example 1
<Preparation of ink X liquid>
Epoxy group-modified silica MEK dispersion (Admanex Co., Ltd., Admanano YA010CMDV 20 wt%) was replaced with diethylene glycol ethyl methyl ether (DGME: vapor pressure 91 Pa / 20 ° C., molecular weight: 148) using an evaporator, and epoxy silica A DGEME dispersion of 39.7 wt% (22.8 vol%) was prepared to obtain ink X-1. The average dispersed particle size of silica particles in the obtained ink was 10 nm.
<Preparation of ink Y liquid>
As the ink Y-1 liquid, pentaerythritol tetrakis (Karenz MTPE1 Showa Denko KK), which is a tetrafunctional thiol, was used.
<Curing test>
2 g of ink X-1 solution was weighed in a petri dish (φ4 cm), 0.09 g of ink Y-1 solution was added and mixed, and then allowed to stand at 50 ° C. for 30 minutes. The volume concentration of the epoxy group-modified silica when mixed was 21.6 vol%. After standing, a plate-like cured product containing a solvent was obtained. The residual amount of solvent after curing with respect to the amount of solvent contained before curing was 99% or more.

The measuring method and the measuring apparatus used in the present invention are as follows.
<Analysis of average dispersed particle size>
Measuring device: Zeta potential / particle size measurement system ELS-Z manufactured by Otsuka Electronics Co., Ltd.
<Ultraviolet irradiation device>
Heraeus Corporation electrodeless UV lamp system F600V-10
<Ultrasonic homogenizer>
Heelscher UP-400S (400W) Tip H7φ7mm

Example 2
<Preparation of ink X liquid>
The ink X-1 liquid prepared in Example 1 was used.
<Preparation of ink Y liquid>
2,4,6-Trisdimethylaminomethylphenol (hereinafter referred to as TAP) was used as the ink Y-2 liquid.
<Curing test>
1.6 g of ink X-1 solution was weighed into a petri dish (φ4 cm), 0.44 g of ink Y-2 solution was added and mixed, and allowed to stand for 30 minutes. The volume concentration of the epoxy group-modified silica when mixed was 17.2 vol%. After standing, a plate-like cured product containing a solvent was obtained. The residual amount of solvent after curing with respect to the amount of solvent contained before curing was 99% or more.

Example 3
<Preparation of ink X liquid>
Amino group-modified silica (AEROSIL NA-50H particle size: 30 nm, manufactured by Nippon Aerosil Co., Ltd.) in N-methyl-2-pyrrolidone (NMP: vapor pressure 39 Pa / 20 ° C., molecular weight: 99.1) using an ultrasonic homogenizer Dispersed to prepare 21 wt% (11 vol%) ink X-2 liquid. The average dispersed particle size of silica particles in the obtained ink was 195.4 nm.
<Preparation of ink Y liquid>
Polyisocyanate (DN-980 manufactured by DIC Corporation) was used as the ink Y-3 liquid.
<Curing test>
Ink X-2 liquid 0.26 g was poured into a cylinder (inner diameter 0.5 cm, height 1.5 cm) prepared in advance with agar, and ink Y-3 liquid 0.016 g was added from above and allowed to stand for 12 hours. When mixed, the volume concentration of the amino group-modified silica was 10.3 vol%. After standing, a 1.5 cm cylindrical cured product enclosing a solvent was obtained. The residual amount of solvent after curing with respect to the amount of solvent contained before curing was 99% or more.

Example 4
<Preparation of ink X liquid>
The ink X-2 liquid prepared in Example 3 was used.
<Preparation of ink Y liquid>
Polyisocyanate (DN-902S manufactured by DIC Corporation) was used as the ink Y-4 liquid.
<Curing test>
2.9 g of the ink X-2 solution was weighed into a glass bottle, 0.06 g of the ink Y-4 solution was added and stirred, 1 g of this mixed solution was weighed into a petri dish (φ4 cm) and allowed to stand at room temperature for 12 hours. When mixed, the volume concentration of the amino group-modified silica was 10.8 vol%. After standing, a cured product containing the solvent was obtained. The residual amount of solvent after curing with respect to the amount of solvent contained before curing was 99% or more.

Comparative Example 1
<Preparation of ink X liquid>
Epoxy group-modified silica MEK dispersion liquid (containing 20% by weight of Admanano YA010CMDV manufactured by Admatechs Co., Ltd.) was concentrated by an evaporator to obtain 25.0 wt% (10.9 vol%) ink X-5 liquid.
<Preparation of ink Y liquid>
The ink Y-1 liquid prepared in Example 1 was used.
<Curing test>
2 g of ink X-5 solution was weighed into a petri dish (φ4 cm), 0.14 g of ink Y-1 solution was added, and after mixing, left at 50 ° C. for 30 minutes. When mixed, the volume concentration of the amino group-modified silica was 10.2 vol%. As a result, a thin film was formed, but the solvent was almost volatilized. The amount of residual solvent after curing relative to the amount of solvent contained before curing was 14.3%).
The above results are summarized in the table below.

Claims (13)

An ink X liquid containing a solvent (A) and ceramic particles (B) modified with reactive functional groups;
An ink Y liquid containing, as an essential component, a compound (C) that causes a crosslinking reaction with the ceramic particles (B) modified with the reactive functional group;
Simultaneously or separately,
Including the step (I) of curing by supplying and mixing the support layer by layer or at a time, and
The solvent (A) is a solvent having a vapor pressure at 20 ° C. of 1500 Pa or less and having no reactivity with either the ceramic particles (B) or the compound (C).
A method for producing a ceramic body. The method for producing a ceramic body according to claim 1, wherein in the step (I), the supplied method is a step of supplying the support to each layer. The method for producing a ceramic body according to claim 1, wherein the method supplied during the step (I) is coating. The method for producing a ceramic body according to claim 1, wherein the method supplied during the step (I) is printing. The method for producing a ceramic body according to claim 1, wherein the vapor pressure of the solvent (A) at 20 ° C is 1000 Pa or less. The solvent (A) is a compound represented by the following formula (1), a compound represented by the following formula (2), a compound represented by the following formula (3), N-methyl-2-pyrrolidone and dimethyl sulfoxide. The method for producing a ceramic body according to claim 1, wherein the ceramic body is one or more compounds selected from the group consisting of:

(In the formula (1), R ₁ is a hydrogen atom or a methyl group, R ₂ is a hydrogen atom or an alkyl group which may be branched having 1 to 12 carbon atoms, R ₃ is a hydrogen atom, a benzyl group, a phenyl group or carbon. (It is the alkyl group which may be branched of number 1-12. Moreover, n is an integer of 1-4.)

(In Formula (2), R ₄ is a hydrogen atom or a methyl group, R ₅ is a hydrogen atom, a benzyl group, or an alkyl group having 1 to 12 carbon atoms, and R ₆ is a methyl group or an ethyl group. Moreover, n is an integer of 1 to 4.)

(In formula (3), R ₇ is a methyl group or an ethyl group, R ₈ is a methyl group or an ethyl group, and n is an integer of 1 to 4.) 2. The ceramic body according to claim 1, wherein each layer of the ceramic body is cured by encapsulating a solvent as a dispersion medium by energy rays or heat without passing through a step of drying the solvent. A method for producing a ceramic body. The method for producing a ceramic body according to any one of claims 1 to 7, wherein the ink X liquid and the ink Y liquid substantially contain no binder resin. The manufacturing method of a ceramic sintered compact which has the process of drying or sintering the ceramic body obtained by Claims 1-8. A modeling ink set composed of two or more inks,
An ink X liquid containing a solvent (A) and ceramic particles (B) modified with reactive functional groups;
An ink Y liquid containing at least a ceramic particle (B) modified with the reactive functional group and a compound (C) that causes a crosslinking reaction as an essential component;
The solvent (A) is a solvent having a vapor pressure at 20 ° C. of 1500 Pa or less and not reactive with either the ceramic particles (B) or the compound (D).
Ink set for modeling. The modeling ink set according to claim 10, wherein a vapor pressure of the solvent (A) at 20 ° C. is 1000 Pa or less. The solvent (A) is a compound represented by the following formula (1), a compound represented by the following formula (2), a compound represented by the following formula (3), N-methyl-2-pyrrolidone and dimethyl sulfoxide. The ink set for modeling according to claim 10, wherein the ink set is one or more compounds selected from the group consisting of:

(In the formula (1), R ₁ is a hydrogen atom or a methyl group, R ₂ is a hydrogen atom or an alkyl group which may be branched having 1 to 12 carbon atoms, R ₃ is a hydrogen atom, a benzyl group, a phenyl group or carbon. (It is the alkyl group which may be branched of number 1-12. Moreover, n is an integer of 1-4.)

(In Formula (2), R ₄ is a hydrogen atom or a methyl group, R ₅ is a hydrogen atom, a benzyl group, or an alkyl group having 1 to 12 carbon atoms, and R ₆ is a methyl group or an ethyl group. Moreover, n is an integer of 1 to 4.)

(In formula (3), R ₇ is a methyl group or an ethyl group, R ₈ is a methyl group or an ethyl group, and n is an integer of 1 to 4.) The modeling ink set according to claim 10, wherein the ink X liquid and the ink Y liquid do not substantially contain a binder resin.