WO2017199323A1

WO2017199323A1 - Three-dimensional object precursor treatment composition

Info

Publication number: WO2017199323A1
Application number: PCT/JP2016/064560
Authority: WO
Inventors: 橋本　良一; 栄二樫原
Original assignee: 花王株式会社
Priority date: 2016-05-17
Filing date: 2016-05-17
Publication date: 2017-11-23
Also published as: TW201809205A

Abstract

This three-dimensional object precursor treatment composition is for removing a support material from a three-dimensional object precursor that includes a three-dimensional object and the support material including a (meth) acrylate copolymer having a hydrophylic monomer and a hydrophobic monomer as monomer units therefor. The three-dimensional object precursor treatment composition contains an alkaline agent (a) and a nonionic penetration agent (b). The present invention provides: a three-dimensional object precursor treatment composition capable of rapidly removing, using a small quantity thereof, the support material containing the (meth) acrylate copolymer and present in gaps in the three-dimensional object; and a production method for the three-dimensional object, using a fused deposition modeling method using said three-dimensional object precursor treatment composition.

Description

Three-dimensional object precursor treatment composition

The present invention relates to a three-dimensional object precursor treating agent composition.

The 3D printer is a type of rapid prototyping and is a three-dimensional printer that forms a three-dimensional object based on 3D data such as 3D CAD, 3D CG, and the like. As a 3D printer system, a hot melt lamination system (hereinafter also referred to as an FDM system), an inkjet ultraviolet curing system, an optical modeling system, a laser sintering system, and the like are known. Among these, the FDM method is a modeling method for obtaining a three-dimensional object by heating / melting and extruding and laminating polymer filaments, and unlike other methods, does not use a material reaction. For this reason, FDM 3D printers are small and inexpensive, and have become popular in recent years as devices with little post-processing. In order to model a three-dimensional object having a more complicated shape by the FDM method, a three-dimensional object is formed by stacking a modeling material constituting the three-dimensional object and a support material for supporting the three-dimensional structure of the modeling material. By obtaining the precursor and then removing the support material from the three-dimensional object precursor, the target three-dimensional object can be obtained.

As a method for removing the support material from the three-dimensional object precursor, when a (meth) acrylic acid copolymer is used as the support material, the carboxylic acid in the (meth) acrylic acid copolymer is neutralized by an alkali. It is used to dissolve and dissolve in an alkaline aqueous solution. The (meth) acrylic acid-based copolymer contained in the support material used in this method is dissolved in the hydrophobic group and the three-dimensional object precursor treating agent from the viewpoint of heating / melt extrusion by a 3D printer and lamination. From the viewpoint of safety, each has a hydrophilic group, so that treatment alone is not sufficient, and a method of removing the support material by further immersing in an organic solvent or heated water is mentioned (for example, No. 2014-83744 and JP-A-2016-2683).

The three-dimensional object precursor treating agent composition of the present invention comprises a three-dimensional object and a support material containing a (meth) acrylic acid-based copolymer having a hydrophilic monomer and a hydrophobic monomer as monomer units. A three-dimensional object precursor treatment agent composition for removing the support material from a precursor, wherein the three-dimensional object precursor treatment agent composition comprises (a) an alkaline agent, and (b) nonionic permeation. Contains agents.

The method for producing a three-dimensional object of the present invention includes a modeling step of obtaining a three-dimensional object precursor including a three-dimensional object and a support material, and bringing the three-dimensional object precursor into contact with the three-dimensional object precursor treatment composition. And a method of manufacturing a three-dimensional object by a hot melt lamination method having a support material removal step of removing the support material.

Schematic showing the shape of the evaluation sample used in the examples Schematic showing the cross-sectional shape of the evaluation sample used in the examples

Detailed Description of the Invention

A conventional three-dimensional object precursor treatment agent takes time to remove a support material containing a (meth) acrylic acid-based copolymer having a hydrophilic group and a hydrophobic group. In response to the problem, the reactivity can be increased by increasing the concentration of alkali in the three-dimensional object precursor treatment agent or increasing the temperature when the three-dimensional object precursor is immersed in the three-dimensional object precursor treatment agent. It is possible to raise.

However, increasing the concentration of alkali in the three-dimensional object precursor treating agent or increasing the temperature when the three-dimensional object precursor is immersed in the three-dimensional object precursor treating agent increases the reactivity. The support material swells. Therefore, it has been found that when the three-dimensional object has a narrow gap, the support material in the gap cannot be quickly removed.

In addition, in the conventional three-dimensional object precursor treatment agent, when the support material is dissolved / dispersed by the removal of the support material, the removal capability of the support material is significantly reduced. In general, a three-dimensional object precursor treatment agent is used repeatedly, but this not only consumes the active ingredient of the three-dimensional object precursor treatment agent for these dissolution and dispersion, but also dissolves and disperses the support material in three dimensions. If it is not uniformly dispersed in the object precursor treating agent, there is a high possibility that problems such as redeposition will occur.

The present invention provides a three-dimensional object precursor treating agent composition capable of quickly removing a support material containing a (meth) acrylic acid copolymer in a gap between three-dimensional objects, and the three-dimensional object. Provided is a method for producing a three-dimensional object by a hot melt lamination method using an object precursor treating agent composition.

The method for producing a three-dimensional object of the present invention includes a step of obtaining a three-dimensional object precursor including a three-dimensional object and a support material, and bringing the three-dimensional object precursor into contact with the three-dimensional object precursor treating agent composition. It is a manufacturing method of the three-dimensional object by the hot melt lamination system which has the support material removal process which removes the said support material.

According to the present invention, a three-dimensional object precursor treating agent composition capable of quickly removing a support material containing a (meth) acrylic acid copolymer in a gap between three-dimensional objects in a small amount, and the tertiary It is possible to provide a method for producing a three-dimensional object by a hot melt lamination method using the original object precursor treating agent composition.

Hereinafter, an embodiment of the present invention will be described.

<Three-dimensional object precursor treating agent composition>
The three-dimensional object precursor treating agent composition of the present embodiment includes a three-dimensional object and a three-dimensional object including a support material including a (meth) acrylic acid-based copolymer having a hydrophilic monomer and a hydrophobic monomer as monomer units. A three-dimensional object precursor treating agent composition for removing the support material from an object precursor, the three-dimensional object precursor treating agent composition comprising: (a) an alkaline agent; and (b) a nonionic system Contains penetrant.

As described above, the reactivity can be increased by increasing the concentration of alkali in the three-dimensional object precursor treating agent or by increasing the temperature when the three-dimensional object precursor is immersed in the three-dimensional object precursor treating agent. On the contrary, the support material swells, and the support material cannot be removed promptly. For removing the (meth) acrylic acid copolymer having a hydrophilic group and a hydrophobic group contained in the support material, the alkali metal salt contained in the conventional three-dimensional object precursor treating agent composition is the most. It was considered as an excellent active ingredient. However, it has been found that the alkali metal salt impedes water and swells instead, thereby inhibiting removal. In the three-dimensional object precursor treatment agent composition of the present embodiment, the swelling of the (meth) acrylic acid copolymer is suppressed by including (a) an alkaline agent and (b) a nonionic penetrant, Also, the support material containing the (meth) acrylic acid copolymer can be quickly removed.

[(A) Alkaline agent]
The alkali agent (a) may be either an inorganic alkali agent or an organic alkali agent. Examples of the inorganic alkali agent include alkali metal hydroxides and alkali metal carbonates. Examples of the organic alkali agent include organic amine compounds.

[Alkali metal hydroxide and alkali metal carbonate]
Examples of the alkali metal hydroxide include lithium hydroxide, sodium hydroxide, and potassium hydroxide.

Examples of the alkali metal carbonate include lithium carbonate, sodium carbonate, and potassium carbonate.

The total content of the alkali metal hydroxide and alkali metal carbonate in the three-dimensional object precursor treating agent composition is 2.5% by mass from the viewpoint of quickly removing the support material from the three-dimensional object precursor. Is less than 2.0% by mass, more preferably 1.0% by mass or less, still more preferably less than 0.5% by mass, preferably 0% by mass or more, and more preferably. Is 0.01% by mass or more, more preferably 0.25% by mass or more.

[Organic amine compounds]
Examples of the organic amine compounds include primary monoamine compounds, secondary monoamine compounds, tertiary monoamine compounds, primary diamine compounds, secondary diamine compounds, tertiary diamine compounds, primary triamine compounds, secondary triamine compounds, and tertiary. Examples thereof include at least one selected from the group consisting of triamine compounds.

Examples of the primary monoamine compound include methylamine, ethylamine, n-propylamine, isopropylamine, n-butylamine, isobutylamine, n-amylamine, isoamylamine, n-hexylamine, n-heptylamine, n-octylamine, Examples thereof include n-decylamine and n-octadecylamine.

Examples of the secondary monoamine compound include methylethanolamine, ethylethanolamine, diisopropanolamine, diisopropylamine, diethanolamine, butylethanolamine, dimethylamine, diethylamine, dipropylamine, dibutylamine, methylethylamine, methylpropylamine, and methylbutylamine. , Methylhexylamine, dipentylamine, piperidine, morpholine, 2,6-dimethylmorpholine, and the like. Among these, methylethanolamine, ethylethanolamine, diisopropanolamine, butylethanolamine, and diisopropylamine from the viewpoint of suppressing the swelling of the (meth) acrylic acid copolymer and expressing good removal of the support material At least one selected from the group consisting of

Examples of the tertiary monoamine compound include trimethylamine, triethylamine, dimethylethylamine, diethylmethylamine, tripropylamine, tributylamine, tripentylamine, triethanolamine, hydroxyethylpiperazine, dimethylaminoethanol, diethylaminoethanol, N-tert-butyl. Diethanolamine, dimethylaminoethoxyethanol (trade name KL-26; manufactured by Kao Corporation), ethyldiethanolamine, butyldiethanolamine, 6-dimethylamino-1-hexanol (trade name KL-25; manufactured by Kao Corporation), 5- (dimethyl Amino) -2-pentanol, 5- (dimethylamino) -1-pentanol, 3- (diethylamino) -1-propanol, n-methylmorpholine, n-e Rumoruhorin, and 4- (2-hydroxyethyl) morpholine and the like. Among these, dimethylaminoethanol, diethylaminoethanol, N-tert-butyldiethanolamine, dimethylaminoethoxyethanol are used from the viewpoint of suppressing the swelling of the (meth) acrylic acid copolymer and exhibiting good removal of the support material. At least one selected from the group consisting of ethyldiethanolamine and 6-dimethylamino-1-hexanol is preferred, and 6-dimethylamino-1-hexanol is more preferred.

Examples of the primary diamine compound include ethylenediamine, 1,4-diaminobutane, 1,6-diaminohexane, and the like.

Examples of the secondary diamine compound include piperazine and hydroxyethyl piperazine. Among these, hydroxyethylpiperazine is preferable from the viewpoint of suppressing swelling of the (meth) acrylic acid copolymer and expressing good removal of the support material.

Examples of the tertiary diamine compound include tetraethylhexanediamine, tetramethylhexanediamine (trade name KL-1; manufactured by Kao Corporation), tetramethylpropanediamine (trade name KL-2; manufactured by Kao Corporation), and (2-dimethyl). Examples include aminoethyl) methylethanolamine (trade name KL-28; manufactured by Kao Corporation), tetramethylethylenediamine, dipiperidinoethane, dipyrrolidinoethane, spartein, and trimethylaminopropylethanolamine. Among these, tetramethylhexanediamine, tetramethylpropanediamine, and (2-dimethylaminoethyl) are used from the viewpoint of suppressing the swelling of the (meth) acrylic acid copolymer and expressing good removal of the support material. At least one selected from the group consisting of methylethanolamine is preferred.

Examples of the primary triamine compound include 1,2,3-triaminopropane, triaminohexane, triaminononane, triaminododecane, and 1,3,6-triaminohexane.

Examples of the secondary triamine compound include N, N ″ -dimethyldiethylenetriamine, N, N ″ -diethyldiethylenetriamine, N, N ″ -dipropyldiethylenetriamine, and N, N ″ -dibutyldiethylenetriamine.

Examples of the tertiary triamine compound include N, N, N ′, N ″, N ″ -pentamethyldiethylenetriamine, N, N, N ′, N ″, N ″ -pentaethyldiethylenetriamine, N, N, N ′, N “, N” -pentapropyldiethylenetriamine, N, N, N ′, N ″, N ″ -pentabutyldiethylenetriamine and the like can be exemplified.

Among the organic amine compounds, a secondary diamine compound, a tertiary diamine compound, a secondary triamine compound, from the viewpoint of expressing good removal of the support material by suppressing swelling of the (meth) acrylic acid copolymer, And at least one selected from the group consisting of tertiary diamine compounds and at least one selected from the group consisting of secondary diamine compounds and tertiary diamine compounds are more preferable.

Among the organic amine compounds, from the viewpoint of suppressing swelling of the (meth) acrylic acid-based copolymer and imparting quick dispersion into the cleaning liquid to express good removal of the support material, an alcoholic hydroxyl group An amine compound having

The content of the organic amine compound in the three-dimensional object precursor treating agent composition is 0 from the viewpoint of suppressing the swelling of the (meth) acrylic acid copolymer and expressing good removal of the support material. 0.1 mass% or more is preferable, 0.5 mass% or more is more preferable, and 1.0 mass% or more is still more preferable. The content of the organic amine compound in the three-dimensional object precursor treating agent composition is 20 from the viewpoint of suppressing the swelling of the (meth) acrylic acid copolymer and expressing good removal of the support material. % By mass or less is preferable, 15% by mass or less is more preferable, 10% by mass or less is further preferable, and 8% by mass or less is even more preferable. Taking these viewpoints together, the content of the organic amine compound in the composition for treating a three-dimensional object precursor is preferably 0.1 to 20% by mass, more preferably 0.5 to 15% by mass, and 5 to 10% by mass is more preferable, and 1.0 to 8% by mass is even more preferable.

[(B) Nonionic penetrant]
The nonionic penetrant in the present embodiment is a nonionic compound having a hydrophilic part such as an oxyalkylene group and a hydrophobic part such as a hydrocarbon group. More specifically, an oxyalkylene adduct having at least one group selected from the group consisting of an alkyl group having 4 to 14 carbon atoms, an alkenyl group having 3 to 30 carbon atoms, and an aryl group having 6 to 30 carbon atoms. It is preferable that

The nonionic penetrant has a viewpoint of quickly removing the support material in the gap between the three-dimensional objects, and suppresses the swelling of the (meth) acrylic acid copolymer, thereby improving the support material's good removability. From the viewpoint of maintaining the time, a polyoxyalkylene alkyl ether represented by the following general formula (1) is used.

R ¹ —O— (AO) m—H (1)
(In the general formula (1), R ¹ is an alkyl group having 4 to 14 carbon atoms, an alkenyl group having 3 to 30 carbon atoms, or an aryl group having 6 to 30 carbon atoms, and AO is an oxyalkylene having 1 to 50 carbon atoms. And m is the average number of moles of AO added, and m is a number from 1 to 20.)

The number of carbon atoms of the alkyl group represented by R ¹ is a support material that suppresses the swelling of the (meth) acrylic acid copolymer from the viewpoint of quickly removing the support material in the gaps of the three-dimensional object. Is preferably 4 or more, more preferably 5 or more, and still more preferably 6 or more from the viewpoint of maintaining good removability for a long time. From the same viewpoint, the number of carbon atoms of the alkyl group represented by R ¹ is preferably 14 or less, more preferably 12 or less, and still more preferably 10 or less. Taking these viewpoints together, the number of carbon atoms of the alkyl group represented by R ¹ is preferably 4 to 14, more preferably 5 to 12, and still more preferably 6 to 10.

Examples of the alkyl group represented by R ¹ include hexyl, 2-ethylhexyl, isononyl, 2-hexyldecyl, and the like. Among these, a hexyl group is preferred from the viewpoint of achieving both gap cleaning properties and durability. And 2-ethylhexyl group is preferable, and 2-ethylhexyl group is more preferable.

The carbon number of the alkenyl group represented by R ¹ is a support material that suppresses the swelling of the (meth) acrylic acid-based copolymer from the viewpoint of quickly removing the support material in the gaps of the three-dimensional object. Is preferably 3 or more, more preferably 4 or more, and still more preferably 5 or more from the viewpoint of maintaining good removability for a long time. The carbon number of the alkenyl group represented by R ¹ is preferably 30 or less, more preferably 20 or less, and still more preferably 18 or less from the same viewpoint. Taking these viewpoints together, the carbon number of the alkenyl group represented by R ¹ is preferably 3 to 30, more preferably 4 to 20, and still more preferably 6 to 18.

The number of carbon atoms of the aryl group represented by R ¹ is a support material that suppresses the swelling of the (meth) acrylic acid copolymer and the viewpoint of quickly removing the support material in the gaps of the three-dimensional object. Is preferably 6 or more, more preferably 12 or more from the viewpoint of maintaining good removability for a long time. The number of carbon atoms of the aryl group represented by R ¹ is preferably 30 or less and more preferably 24 or less from the same viewpoint. Taking these viewpoints together, the aryl group represented by R ¹ preferably has 6 to 30 carbon atoms, and more preferably 12 to 24 carbon atoms.

Examples of the aryl group represented by R ¹ include a phenyl group, a styrenated phenyl group, a phenylethyl group, a distyrenated phenyl group, a tristyrenated phenyl group, a benzyl group, a benzylated phenyl group, a dibenzylated phenyl group, and a tribenzylated group. Phenyl groups and the like can be exemplified, but among these, the viewpoint of quickly removing the support material in the gap of the three-dimensional object, and the good support material by suppressing the swelling of the (meth) acrylic acid copolymer A benzylated phenyl group is preferable from the viewpoint of maintaining removability for a long time.

The benzylated phenyl group is a phenyl group substituted with one or more benzyl groups. In the benzyl group, the hydrogen atom of the benzene ring or the hydrogen atom of the methylene group may be substituted with a short chain hydrocarbon group such as a methyl group, for example, an alkyl group having 1 to 4 carbon atoms. For example, a styrene group is included in a benzyl group. Specific examples of the benzylated phenyl group include a monostyrenated phenyl group, a distyrenated phenyl group, a monobenzylated phenyl group, and a dibenzylated phenyl group, and among these, a support material in a gap between three-dimensional objects. Monostyrenated phenyl group and distyrenated phenyl group from the viewpoint of promptly removing water and from the viewpoint of suppressing the swelling of the (meth) acrylic acid copolymer and maintaining good removability of the support material for a long time 1 or more types selected from are preferable, and a distyrenated phenyl group is more preferable.

In the general formula (1), the number of carbon atoms of the oxyalkylene group represented by AO is the viewpoint of quickly removing the support material in the gaps of the three-dimensional object, and the swelling of the (meth) acrylic acid copolymer Is preferably 1 or more, more preferably 2 or more, more preferably 3 or more, and still more preferably 4 or more, from the viewpoint of suppressing the above-mentioned and maintaining good removability of the support material for a long time. In the general formula (1), the number of carbon atoms of the oxyalkylene group represented by AO is preferably 50 or less, more preferably 20 or less, and still more preferably 18 or less from the same viewpoint. Taking these viewpoints together, the number of carbon atoms of the oxyalkylene group represented by AO in the general formula (1) is preferably 1 to 50, more preferably 2 to 20, further preferably 3 to 20, and 4 to 18 Is even more preferable.

The m is a viewpoint of quickly removing the support material in the gap between the three-dimensional objects, and suppresses the swelling of the (meth) acrylic acid-based copolymer and maintains good removability of the support material for a long time. From the viewpoint, 1 or more is preferable, and 2 or more is more preferable. From the viewpoint of suppressing foaming, m is preferably 20 or less, more preferably 18 or less, and still more preferably 12 or less. Taking these viewpoints together, the m is preferably 1 to 20, more preferably 2 to 18, and still more preferably 2 to 12.

The content of the (b) nonionic penetrant is the viewpoint of quickly removing the support material in the gap between the three-dimensional objects, and the swelling of the (meth) acrylic acid copolymer is suppressed. From the viewpoint of maintaining good removability for a long time, the content is preferably 0.05% by mass or more, and more preferably 0.1% by mass or more in the three-dimensional object precursor treating agent composition. The content of the (b) nonionic penetrant is the viewpoint of quickly removing the support material in the gap between the three-dimensional objects, and the swelling of the (meth) acrylic acid copolymer is suppressed. From the viewpoint of maintaining good removability for a long time, 10% by mass or less is preferable and 5% by mass or less is more preferable in the three-dimensional object precursor treating agent composition. Summing up these viewpoints, the content of the nonionic penetrant (b) is preferably 0.05 to 10% by mass, more preferably 0.1 to 5% by mass in the three-dimensional object precursor treating agent composition. preferable.

[(C) Surfactant]
The three-dimensional object precursor treating agent composition may contain a surfactant. When the three-dimensional object precursor treating agent composition contains a surfactant, the support material in the gaps of the three-dimensional object can be quickly removed, and further, the (meth) acrylic acid copolymer is swollen. It is possible to maintain good removability of the support material for a long time. The (b) nonionic penetrant is not included in the (c) surfactant.

Examples of the surfactant include nonionic surfactants, amphoteric surfactants, and anionic surfactants.

Examples of the anionic surfactant include alkylbenzene sulfonate, alkyl or alkenyl ether sulfate, alkyl or alkenyl sulfate, olefin sulfonate, alkane sulfonate, saturated or unsaturated fatty acid salt, alkyl or alkenyl ether carboxylate , Α-sulfo fatty acid salts, N-acyl amino acid salts, phosphoric acid mono- or diesters, sulfosuccinic acid esters, and the like. Examples of the alkyl ether sulfate include polyoxyethylene alkyl ether sulfate. Of these, at least one selected from the group consisting of alkyl sulfates, alkyl ether sulfates, saturated fatty acid salts, and alkyl ether carboxylates is preferred. Counter ions of the anionic group of these anionic surfactants include alkali metal ions such as sodium ion and potassium ion; alkaline earth metal ions such as calcium ion and magnesium ion; ammonium ion; alkanol group having 2 or 3 carbon atoms And alkanolamine salts having 1 to 3 (for example, monoethanolamine salt, diethanolamine salt, triethanolamine salt, triisopropanolamine salt, etc.).

Examples of the amphoteric surfactant include imidazoline, carbobetaine, amide betaine, sulfobetaine, hydroxysulfobetaine, amide sulfobetaine and the like, and betaine surfactants such as alkyldimethylaminoacetic acid betaine and fatty acid amidopropyl betaine are more preferable. Fatty acid amidopropyl betaine is more preferable.

Examples of the nonionic surfactant include polyoxyalkylene alkyl ethers, polyoxyalkylene alkenyl ethers, polyoxyethylene distyrenated phenyl ethers, higher fatty acid sucrose esters, polyglycerin fatty acid esters, higher grades other than the nonionic penetrant (b). Examples include fatty acid mono- or diethanolamide, polyoxyethylene hydrogenated castor oil, polyoxyethylene sorbitan fatty acid ester, polyoxyethylene sorbite fatty acid ester, alkyl saccharide, alkyl amine oxide, alkyl amido amine oxide and the like. Of these, at least one selected from the group consisting of polyoxyalkylene alkyl ethers and polyoxyethylene distyrenated phenyl ethers is preferred.

The polyoxyalkylene alkyl ethers other than the (b) nonionic penetrant suppress the swelling of the (meth) acrylic acid-based copolymer from the viewpoint of quickly removing the support material in the gap between the three-dimensional objects. From the viewpoint of maintaining good removability of the support material for a long time, it is a polyoxyalkylene alkyl ether represented by the following general formula (2).

R ² —O— (EO) p (PO) q—H (2)
(In the general formula (2), R ² represents an alkyl group having 15 or more carbon atoms, EO represents an oxyethylene group, PO represents an oxypropylene group, and p and q are average added moles of EO and PO, respectively. , P is a number from 1 to 20, and q is a number from 0 to 20.)

When a large amount of the surfactant is contained, bubbles are likely to be generated. Therefore, the content of the surfactant is 0.05% by mass or less from the viewpoint of promptly removing the support material in the gap between the three-dimensional objects and maintaining good removability of the support material for a long time. Preferably, substantially 0% by mass is more preferable.

[Others]
The three-dimensional object precursor treatment agent composition is water, a water-soluble organic solvent, ethylenediaminetetraacetate, carboxymethylcellulose, polyvinylpyrrolidone, polyacrylate, as necessary, as long as the effects of the present invention are not impaired. Builder components such as alginates, thickeners, pH adjusters, preservatives, rust inhibitors, pigments, colorants and the like may be included. Depending on the type of the support material, the developer composition containing the colorant changes color when the support material dissolves. Therefore, the colorant is also expected to function as an indicator that indicates the degree of progress and completion of development. it can.

[water]
As the water, ultrapure water, pure water, ion-exchanged water, distilled water, normal tap water, or the like can be used. The water content may be the balance of the three-dimensional object precursor treating agent composition (a total amount of 100% by mass). The content of the water in the three-dimensional object precursor treating agent composition improves the stability and handling of the developer composition, and also improves the waste liquid treatability, etc. To 20% by mass or more, more preferably 40% by mass or more, and still more preferably 60% by mass or more. The content of the water in the three-dimensional object precursor treating agent composition improves the stability and handling of the developer composition, and also improves the waste liquid treatability, etc. To 99 mass% or less is preferable, 98 mass% or less is more preferable, and 97 mass% or less is still more preferable.

[Water-soluble organic solvent]
The water-soluble organic solvent exhibits the performance of disintegrating the support material and dissolving it in the developer composition.

The water-soluble organic solvent is preferably one that dissolves 1.5% by mass or more in 20 ° C. water. Examples of the water-soluble organic solvent include water-soluble organic solvents selected from monohydric alcohols, polyhydric alcohols, and glycol ethers.

Examples of the monohydric alcohol include monohydric alcohols having 1 to 5 carbon atoms. Specifically, a monohydric alcohol selected from methyl alcohol, ethyl alcohol, 1-propyl alcohol, isopropyl alcohol, allyl alcohol, n-butyl alcohol, isobutyl alcohol, sec-butyl alcohol, t-butyl alcohol, and amyl alcohol is used. Can be mentioned.

Examples of the polyhydric alcohol include alkylene glycols having a repeating unit having 2 to 3 carbon atoms (hereinafter referred to as C2-C3 alkylene glycol). C2-C3 alkylene glycols include ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, pentaethylene glycol, hexaethylene glycol, heptaethylene glycol, octaethylene glycol, nonaethylene glycol, decaethylene glycol, propylene glycol, dipropylene Examples include glycol and tripropylene glycol. The C2-C3 alkylene glycol preferably has 1 to 10 oxyethylene groups or oxypropylene groups which are repeating units.

In addition, examples of polyhydric alcohols other than C2 to C3 alkylene glycol include polyhydric alcohols having 2 to 8 carbon atoms. Specifically, trimethylene glycol, 1,3-octylene glycol, 1,2-propanediol, 1,3-propanediol, 2-methyl-1,3-propanediol, 1,2-butanediol, 1 , 3-butanediol, 1,4-butanediol, 1,4-butenediol, 1,4-pentanediol, 1,5-pentanediol, 1,5-hexanediol, 1,6-hexanediol, glycerin, Examples include trimethylolethane and trimethylolpropane.

The water-soluble organic solvents may be used alone or in combination of two or more. Among these, from the viewpoint of further enhancing disintegration of the support material and dissolution in the developer composition, methyl alcohol, ethyl alcohol, 1-propyl alcohol, isopropyl alcohol, t-butyl alcohol, ethylene glycol, diethylene glycol, triethylene glycol, A water-soluble organic solvent selected from propylene glycol, dipropylene glycol, and tripropylene glycol is preferable, and a water-soluble organic solvent selected from ethyl alcohol, ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, and dipropylene glycol is more preferable.

<Method of manufacturing a three-dimensional object>
The three-dimensional object manufacturing method of the present embodiment includes a three-dimensional object and a three-dimensional object precursor including a support material including a (meth) acrylic acid-based copolymer having a hydrophilic monomer and a hydrophobic monomer as monomer units. And a method for producing a three-dimensional object by a hot melt lamination method, which has a support material removing step of bringing the three-dimensional object precursor into contact with the three-dimensional object precursor treating agent composition and removing the support material. It is. According to the method for producing a three-dimensional object of this embodiment, the support material containing the methacrylic acid copolymer can be removed more quickly than in the past. The reason why such an effect is exhibited may be the same as the reason why the three-dimensional object precursor treating agent composition exhibits the effect.

[Modeling process]
A modeling process for obtaining a three-dimensional object precursor including a three-dimensional object and a support material including a (meth) acrylic acid-based copolymer having a hydrophilic monomer and a hydrophobic monomer as monomer units is a known hot-melt lamination method. The step of obtaining a three-dimensional object precursor including a three-dimensional object and a support material in the method for producing a three-dimensional object by the 3D printer can be used.

The modeling material that is the material of the three-dimensional object can be used without particular limitation as long as it is a resin that is used as a modeling material in a conventional FDM three-dimensional object manufacturing method. Examples of the modeling material include thermoplastic resins such as ABS resin, polylactic acid resin, polycarbonate resin, and polyphenylsulfone resin. Among these, ABS resin and / or polylactic acid resin are preferable from the viewpoint of modeling by a 3D printer. Is more preferable, and ABS resin is more preferable.

The three-dimensional modeling soluble material that is a material of the support material includes a (meth) acrylic acid-based copolymer having a hydrophilic monomer and a hydrophobic monomer as monomer units.

[(Meth) acrylic acid copolymer]
(Hydrophilic monomer)
Examples of the hydrophilic monomer include acrylic acid, methacrylic acid, diethylaminoethyl acrylate, 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, glycidyl acrylate, tetrahydrofurfuryl acrylate, diethylaminoethyl methacrylate, and methacrylic acid 2 -Hydroxyethyl, 2-hydroxypropyl methacrylate, glycidyl methacrylate, tetrahydrofurfuryl methacrylate, itaconic acid, maleic acid, fumaric acid, α-hydroxyacrylic acid and the like. Among these, at least one selected from the group consisting of acrylic acid and methacrylic acid is preferable from the viewpoint of the removability of the support material.

(Hydrophobic monomer)
Examples of the hydrophobic monomer include methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, isobutyl acrylate, tertiary butyl acrylate, 2-ethylhexyl acrylate, octyl acrylate, isodecyl acrylate, acrylic Lauryl acid, tridecyl acrylate, cetyl acrylate, stearyl acrylate, cyclohexyl acrylate, benzyl acrylate, methyl methacrylate, ethyl methacrylate, propyl methacrylate, butyl methacrylate, isobutyl methacrylate, tertiary butyl methacrylate, methacrylic acid 2-ethylhexyl acid, octyl methacrylate, isodecyl methacrylate, lauryl methacrylate, tridecyl methacrylate, cetyl methacrylate, stearyl methacrylate, methacrylate Le cyclohexyl, benzyl methacrylate, styrene, alpha-methylene -γ- valerolactone.

The (meth) acrylic acid copolymer may contain monomer units other than the hydrophilic monomer and the hydrophobic monomer.

[Support material removal process]
The support material removing step is a step of removing the support material by bringing the three-dimensional object precursor into contact with the three-dimensional object precursor treating agent composition. The method of bringing the three-dimensional object precursor into contact with the three-dimensional object precursor treating agent composition may be agitated after being immersed in the treatment liquid, exposed to a strong water stream, or moved. It is done. However, from the viewpoint of preventing loss of the precursor and from the viewpoint of ease of work, a method of immersing the three-dimensional object precursor in the three-dimensional object precursor treating agent composition is preferable. From the viewpoint of improving the removability of the support material, it is possible to promote the dissolution of the support material by irradiating ultrasonic waves during the immersion.

The pH of the three-dimensional object precursor treating agent composition is preferably 10 or more, more preferably 11 or more, from the viewpoint of solubility of the support material. The pH of the three-dimensional object precursor treating agent composition is preferably 14 or less, more preferably 13 or less, from the viewpoint of suppressing or reducing damage to the modeling material. Taking these viewpoints together, the pH of the three-dimensional object precursor treating agent composition is preferably 10 to 14, more preferably 10 to 13, and still more preferably 11 to 13.

The amount of the three-dimensional object precursor treating agent composition used is preferably 10 times by mass or more and more preferably 20 times by mass or more with respect to the support material from the viewpoint of solubility of the support material. The amount of the three-dimensional object precursor treating agent composition used is preferably 10,000 times by mass or less, more preferably 5000 times by mass or less, still more preferably 1000 times by mass or less, with respect to the support material from the viewpoint of workability. More preferably, it is less than mass times.

The temperature of the three-dimensional object precursor treating agent composition in the support material removing step is preferably 25 ° C. or higher, more preferably 40 ° C. or higher, from the viewpoint of solubility of the support material. From the same viewpoint, the temperature of the three-dimensional object precursor treating agent composition in the support material removing step is preferably 80 ° C. or less, and more preferably 70 ° C. or less. Taking these viewpoints together, the temperature of the three-dimensional object precursor treating agent composition in the support material removing step is preferably 25 to 80 ° C, more preferably 40 to 70 ° C.

The time for bringing the soluble material for 3D modeling into contact with the 3D object precursor treating agent composition is preferably 5 minutes or more from the viewpoint of the removability of the support material. In addition, the time for contacting the three-dimensional modeling soluble material with the three-dimensional object precursor treatment agent composition is preferably 180 minutes or less, more preferably 120 minutes or less from the viewpoint of reducing damage to the three-dimensional object, 90 minutes or less is more preferable, and 60 minutes or less is even more preferable. Taking these viewpoints together, the time for contacting the three-dimensional modeling soluble material with the three-dimensional object precursor treating agent composition is preferably 5 to 180 minutes, more preferably 5 to 120 minutes, and more preferably 5 to 90 minutes. Is more preferable, and 5 to 60 minutes is even more preferable.

The present specification further discloses the following invention with respect to the above-described embodiment.

<1> To remove the support material from a three-dimensional object precursor including a three-dimensional object and a support material containing a (meth) acrylic acid-based copolymer having a hydrophilic monomer and a hydrophobic monomer as monomer units. The three-dimensional object precursor treatment agent composition, wherein the three-dimensional object precursor treatment agent composition contains (a) an alkali agent and (b) a nonionic penetrant. Agent composition.
<2> The three-dimensional object precursor treatment agent composition according to <1>, wherein (a) the alkali agent is preferably at least one selected from the group consisting of an inorganic alkali agent and an organic alkali agent.
<3> The three-dimensional object precursor treatment composition according to <2>, wherein the inorganic alkali agent is preferably at least one selected from the group consisting of alkali metal hydroxides and alkali metal carbonates.
<4> The three-dimensional object precursor treatment composition according to <3>, wherein the alkali metal hydroxide is preferably at least one selected from the group consisting of lithium hydroxide, sodium hydroxide, and potassium hydroxide. object.
<5> The three-dimensional object precursor according to <3> or <4>, wherein the alkali metal carbonate is preferably at least one selected from the group consisting of lithium carbonate, sodium carbonate, and potassium carbonate. Treatment agent composition.
<6> The total content of the alkali metal hydroxide and alkali metal carbonate in the three-dimensional object precursor treatment agent composition is less than 2.5% by mass, preferably less than 2.0% by mass. More preferably, it is 1.0 mass% or less, More preferably, it is less than 0.5 mass%, Preferably it is 0 mass% or more, More preferably, it is 0.01 mass% or more, More preferably, it is 0.00. The three-dimensional object precursor treatment agent composition according to any one of <3> to <5>, which is 25% by mass or more.
<7> The three-dimensional object precursor treatment composition according to any one of <2> to <6>, wherein the organic alkali agent is preferably an organic amine compound.
<8> The organic amine compound is a primary monoamine compound, secondary monoamine compound, tertiary monoamine compound, primary diamine compound, secondary diamine compound, tertiary diamine compound, primary triamine compound, secondary triamine compound, and The three-dimensional object precursor treating agent composition according to <7>, wherein at least one selected from the group consisting of tertiary triamine compounds is preferred.
<9> The primary monoamine compound is methylamine, ethylamine, n-propylamine, isopropylamine, n-butylamine, isobutylamine, n-amylamine, isoamylamine, n-hexylamine, n-heptylamine, n-octyl. The three-dimensional object precursor treatment composition according to <8>, wherein at least one selected from the group consisting of amine, n-decylamine, and n-octadecylamine is preferable.
<10> The secondary monoamine compound is methylethanolamine, ethylethanolamine, diisopropanolamine, diisopropylamine, diethanolamine, butylethanolamine, dimethylamine, diethylamine, dipropylamine, dibutylamine, methylethylamine, methylpropylamine, Preferably, at least one selected from the group consisting of methylbutylamine, methylhexylamine, dipentylamine, piperidine, morpholine, and 2,6-dimethylmorpholine, methylethanolamine, ethylethanolamine, diisopropanolamine, butylethanolamine, And at least one selected from the group consisting of diisopropylamine is more preferable, and the three-dimensional object precursor according to <8> or <9> Treatment composition.
<11> The tertiary monoamine compound is trimethylamine, triethylamine, dimethylethylamine, diethylmethylamine, tripropylamine, tributylamine, tripentylamine, triethanolamine, hydroxyethylpiperazine, dimethylaminoethanol, diethylaminoethanol, N-tert. -Butyldiethanolamine, dimethylaminoethoxyethanol, ethyldiethanolamine, butyldiethanolamine, 6-dimethylamino-1-hexanol, 5- (dimethylamino) -2-pentanol, 5- (dimethylamino) -1-pentanol, 3- (Diethylamino) -1-propanol, n-methylmorpholine, n-ethylmorpholine, and 4- (2-hydroxyethyl) morpholine And at least one selected from the group consisting of dimethylaminoethanol, diethylaminoethanol, N-tert-butyldiethanolamine, dimethylaminoethoxyethanol, ethyldiethanolamine, and 6-dimethylamino-1-hexanol. The three-dimensional object precursor treating agent composition according to any one of <8> to <10>, more preferably 6-dimethylamino-1-hexanol.
<12> The primary diamine compound is preferably at least one selected from the group consisting of ethylenediamine, 1,4-diaminobutane, and 1,6-diaminohexane, <8> to <11> A three-dimensional object precursor treatment composition.
<13> The three-dimensional object according to any one of <8> to <12>, wherein the secondary diamine compound is preferably at least one selected from the group consisting of piperazine and hydroxyethylpiperazine, more preferably hydroxyethylpiperazine. Precursor treatment agent composition.
<14> The tertiary diamine compound is tetraethylhexanediamine, tetramethylhexanediamine, tetramethylpropanediamine, (2-dimethylaminoethyl) methylethanolamine, tetramethylethylenediamine, dipiperidinoethane, dipyrrolidinoethane, At least one selected from the group consisting of sparteine and trimethylaminopropylethanolamine is preferred, and at least selected from the group consisting of tetramethylhexanediamine, tetramethylpropanediamine, and (2-dimethylaminoethyl) methylethanolamine. The three-dimensional object precursor treating agent composition according to any one of <8> to <13>, wherein one or more are more preferable.
<15> The primary triamine compound is at least one selected from the group consisting of 1,2,3-triaminopropane, triaminohexane, triaminononane, triaminododecane, and 1,3,6-triaminohexane. The three-dimensional object precursor treating agent composition according to any one of <8> to <14>, wherein at least one species is preferred.
<16> The secondary triamine compound is at least selected from the group consisting of N, N ″ -dimethyldiethylenetriamine, N, N ″ -diethyldiethylenetriamine, N, N ″ -dipropyldiethylenetriamine, and N, N ″ -dibutyldiethylenetriamine. The three-dimensional object precursor treating agent composition according to any one of <8> to <15>, wherein one or more are preferable.
<17> The tertiary triamine compound is N, N, N ′, N ″, N ″ -pentamethyldiethylenetriamine, N, N, N ′, N ″, N ″ -pentaethyldiethylenetriamine, N, N, N ′ , N ″, N ″ -pentapropyldiethylenetriamine, and at least one selected from the group consisting of N, N, N ′, N ″, N ″ -pentabutyldiethylenetriamine is preferable, any one of <8> to <16> The three-dimensional object precursor treating agent composition described in 1.
<18> The organic amine compound is preferably at least one selected from the group consisting of secondary diamine compounds, tertiary diamine compounds, secondary triamine compounds, and tertiary triamine compounds, secondary diamine compounds, and tertiary. The three-dimensional object precursor treating agent composition according to any one of <8> to <17>, wherein at least one selected from the group consisting of diamine compounds is more preferred.
<19> The three-dimensional object precursor treating agent composition according to any one of <8> to <18>, wherein the organic amine compound is preferably an amine compound having an alcoholic hydroxyl group.
<20> The content of the organic amine compound in the three-dimensional object precursor treating agent composition is preferably 0.1% by mass or more, more preferably 0.5% by mass or more, and 1.0% by mass or more. More preferably, it is preferably 20% by mass or less, more preferably 15% by mass or less, further preferably 10% by mass or less, still more preferably 8% by mass or less, preferably 0.1 to 20% by mass, 0.5 to 15%. The composition for treating a three-dimensional object precursor according to any one of <8> to <19>, more preferably 0.5% by weight, further preferably 0.5 to 10% by weight, and still more preferably 1.0 to 8% by weight. .
<21> The nonionic penetrant is a nonionic compound having a hydrophilic part such as an oxyalkylene group and a hydrophobic part such as a hydrocarbon group. The nonionic penetrant includes an alkyl group having 4 to 14 carbon atoms and 3 to 3 carbon atoms. Preferably, it is an oxyalkylene adduct having at least one group selected from the group consisting of 30 alkenyl groups and aryl groups having 6 to 30 carbon atoms, <1> to <20> Three-dimensional object precursor treating agent composition.
<22> The three-dimensional object precursor treating agent composition according to any one of <1> to <21>, wherein the nonionic penetrant is preferably a polyoxyalkylene alkyl ether represented by the following general formula (1).
R ¹ —O— (AO) m—H (1)
(In the general formula (1), R ¹ is an alkyl group having 4 to 14 carbon atoms, an alkenyl group having 3 to 30 carbon atoms, or an aryl group having 6 to 30 carbon atoms, and AO is an oxyalkylene having 1 to 50 carbon atoms. And m is the average number of moles of AO added, and m is a number from 1 to 20.)
<23> The number of carbon atoms of the alkyl group represented by R ¹ is preferably 4 or more, more preferably 5 or more, still more preferably 6 or more, preferably 14 or less, more preferably 12 or less, and still more preferably 10 or less. The three-dimensional object precursor treatment composition according to <22>, preferably 4 to 14, more preferably 5 to 12, and still more preferably 6 to 10.
<24> The alkyl group represented by R ¹ is preferably at least one selected from the group consisting of hexyl, 2-ethylhexyl, isononyl, and 2-hexyldecyl, and is preferably a group consisting of a hexyl group and a 2-ethylhexyl group. The three-dimensional object precursor treating agent composition according to <22> or <23>, wherein at least one or more selected from the above is more preferable, and a 2-ethylhexyl group is still more preferable.
<25> The number of carbon atoms of the alkenyl group represented by R ¹ is preferably 3 or more, more preferably 4 or more, still more preferably 5 or more, preferably 30 or less, more preferably 20 or less, and still more preferably 18 or less. The three-dimensional object precursor treatment composition according to any one of <22> to <24>, preferably 3 to 30, more preferably 4 to 20, and still more preferably 6 to 18.
<26> The number of carbon atoms of the aryl group represented by R ¹ is preferably 6 or more, more preferably 12 or more, preferably 30 or less, more preferably 24 or less, preferably 6 to 30, and more preferably 12 to 24 The three-dimensional object precursor treating agent composition according to any one of <22> to <25>.
<27> The aryl group includes a phenyl group, a styrenated phenyl group, a phenylethyl group, a distyrenated phenyl group, a tristyrenated phenyl group, a benzyl group, a benzylated phenyl group, a dibenzylated phenyl group, and a tribenzylated phenyl group. The three-dimensional object precursor treatment composition according to any one of <22> to <26>, wherein at least one selected from the group is preferred, and a benzylated phenyl group is more preferred.
<28> The benzylated phenyl group is preferably at least one selected from the group consisting of a monostyrenated phenyl group, a distyrenated phenyl group, a monobenzylated phenyl group, and a dibenzylated phenyl group, a monostyrenated phenyl group, And at least one selected from the group consisting of distyrenated phenyl groups, more preferably distyrenated phenyl groups, and the three-dimensional object precursor treating agent composition according to <27>.
<29> The number of carbon atoms of the oxyalkylene group represented by AO in the general formula (1) is preferably 1 or more, more preferably 2 or more, more preferably 3 or more, still more preferably 4 or more, and 50 or less. Preferably, 20 or less is more preferable, 18 or less is more preferable, 1 to 50 is preferable, 2 to 20 is more preferable, 3 to 20 is still more preferable, and 4 to 18 is still more preferable, <22> to <28> The three-dimensional object precursor treating agent composition according to claim 1.
<30> The m is preferably 1 or more, more preferably 2 or more, preferably 20 or less, more preferably 18 or less, still more preferably 12 or less, preferably 1 to 20, more preferably 2 to 18, more preferably 2 to The three-dimensional object precursor treating agent composition according to any one of <22> to <29>, wherein 12 is more preferred.
<31> The content of the nonionic penetrant is preferably 0.05% by mass or more, more preferably 0.1% by mass or more, and preferably 10% by mass or less in the three-dimensional object precursor treatment agent composition. The composition for treating a three-dimensional object precursor according to any one of <22> to <30>, preferably 5% by mass or less, more preferably 0.05 to 10% by mass, and more preferably 0.1 to 5% by mass. .
<32> The three-dimensional object precursor treatment composition according to any one of <1> to <31>, further comprising (c) a surfactant.
<33> The three-dimensional object precursor treatment composition according to <32>, wherein the (b) nonionic penetrant is not included in the (c) surfactant.
<34> The content of the surfactant in the three-dimensional object precursor treating agent composition is preferably 0.05% by mass or less, and more preferably substantially 0% by mass, <32> or <33> The three-dimensional object precursor treating agent composition described in 1.
<35> A three-dimensional object, and a modeling process for obtaining a three-dimensional object precursor including a support material including a (meth) acrylic acid-based copolymer having a hydrophilic monomer and a hydrophobic monomer as monomer units, and the three-dimensional object A method for producing a three-dimensional object by a hot-melt laminating method, comprising a support material removing step of bringing an object precursor into contact with a three-dimensional object precursor treating agent composition and removing the support material, wherein the three-dimensional object precursor A method for producing a three-dimensional object, wherein the treatment composition is the three-dimensional object precursor treatment composition according to any one of <1> to <34>.
<36> The molding material is preferably at least one thermoplastic resin selected from the group consisting of ABS resin, polylactic acid resin, polycarbonate resin, and polyphenylsulfone resin, and ABS resin and / or polylactic acid resin is preferable. The method for producing a three-dimensional object according to <35>, more preferably an ABS resin.
<37> The three-dimensional modeling soluble material that is a material of the support material preferably includes a (meth) acrylic acid-based copolymer having a hydrophilic monomer and a hydrophobic monomer as monomer units, <35> or <35>36>. The method for producing a three-dimensional object according to 36>.
<38> The hydrophilic monomer is acrylic acid, methacrylic acid, diethylaminoethyl acrylate, 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, glycidyl acrylate, tetrahydrofurfuryl acrylate, diethylaminoethyl methacrylate, methacrylic acid. At least one selected from the group consisting of 2-hydroxyethyl acid, 2-hydroxypropyl methacrylate, glycidyl methacrylate, tetrahydrofurfuryl methacrylate, itaconic acid, maleic acid, fumaric acid, α-hydroxyacrylic acid is preferable, The method for producing a three-dimensional object according to any one of <35> to <37>, wherein at least one selected from the group consisting of acrylic acid and methacrylic acid is more preferable.
<39> The hydrophobic monomer is methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, isobutyl acrylate, tertiary butyl acrylate, 2-ethylhexyl acrylate, octyl acrylate, isodecyl acrylate , Lauryl acrylate, tridecyl acrylate, cetyl acrylate, stearyl acrylate, cyclohexyl acrylate, benzyl acrylate, methyl methacrylate, ethyl methacrylate, propyl methacrylate, butyl methacrylate, isobutyl methacrylate, tertiary butyl methacrylate , 2-ethylhexyl methacrylate, octyl methacrylate, isodecyl methacrylate, lauryl methacrylate, tridecyl methacrylate, cetyl methacrylate, stearyl methacrylate, meta Cyclohexyl acrylic acid, benzyl methacrylate, styrene, at least one or more preferably selected from the group consisting of α- methylene -γ- valerolactone, <35> - <38> three-dimensional object manufacturing method according to any one.
<40> The pH of the three-dimensional object precursor treating agent composition is preferably 10 or more, more preferably 11 or more, preferably 14 or less, more preferably 13 or less, more preferably 10 to 14, and more preferably 10 to 13 The method for producing a three-dimensional object according to any one of <35> to <39>, preferably 11 to 13.
<41> The temperature of the three-dimensional object precursor treating agent composition in the support material removing step is preferably 25 ° C or higher, more preferably 40 ° C or higher, preferably 80 ° C or lower, more preferably 70 ° C or lower, 25 The method for producing a three-dimensional object according to any one of <35> to <40>, preferably from 80 to 80 ° C, more preferably from 40 to 70 ° C.
<42> Use of the composition according to any one of <1> to <34> as a three-dimensional object precursor treatment agent.
Any one of <1> to <34> including a <43> three-dimensional object and a three-dimensional object precursor including a support material including a (meth) acrylic acid copolymer having a hydrophilic monomer and a hydrophobic monomer as monomer units A support material removing method for removing the support material by contacting the three-dimensional object precursor treating agent composition according to claim 1.

<Examples 1A to 8A, Comparative Example 1A and Comparative Example 2A>
[Production of evaluation samples]
In the FDM 3D printer Fortus250MC manufactured by Stratasys, ABS (Stratasys ABS resin) as a modeling material, SR-30 as a soluble material for three-dimensional modeling (methacrylic acid copolymer manufactured by Stratasys; monomer unit; methacrylic) An evaluation sample (three-dimensional object precursor) was prepared using 45% by mass of acid, 34% by mass of styrene, and 21% by mass of n-butyl acrylate). FIG. 1 is a schematic diagram showing the shape of the evaluation sample, and FIG. 2 is a schematic diagram showing the cross-sectional shape of the evaluation sample.

FIG. 1 is a schematic diagram showing the shape of the evaluation sample. In FIG. 1, the evaluation sample is a three-dimensional object having a trunk portion 1, a leg portion including a leg portion 21 and a leg portion 22, and a three-dimensional object precursor made of a support material. The leg part 21 and the leg part 22 are connected in the trunk | drum 1, and are one member. In order to assist understanding of the shape of the evaluation sample, only the outer edge portion of the support material is shown as the support material outer edge portion 3. FIG. 2 is a schematic view showing the cross-sectional shape of the evaluation sample. In FIG. 2, the body portion 1 has a shaft passing portion 11. The leg portion 21 and the leg portion 22 are connected by an axis (not shown) passing through the shaft-passing portion 11, and if there is no support material indicated by the support material outer edge portion 3, the leg portion 21 according to the evaluation sample and The leg portion composed of the leg portion 22 is movable with respect to the trunk portion 1. The distance between the shaft connecting the leg portion 21 and the leg portion 22 in the shaft passing portion 11 and the surface of the shaft passing portion 11 is 0.6 mm.

[Evaluation method: Initial operating time]
Aqueous solutions having the compositions shown in Table 1 were prepared and used as the three-dimensional object precursor treating agent compositions according to Examples 1A to 8A, Comparative Example 1A, and Comparative Example 2A. The evaluation sample is immersed in the three-dimensional object precursor treatment agent composition according to Examples 1A to 8A, Comparative Example 1A, and Comparative Example 2A at a liquid temperature of 60 ° C., and the leg 21 of FIG. The time until the leg part consisting of the leg part 22 becomes movable (initial movable time) was measured. The evaluation results are shown in Table 1. The composition of a 3% by weight aqueous solution of Water Works in Table 1 is shown in Table 2.

<Examples 1B to 5B, Comparative Example 1B and Comparative Example 2B>
[Evaluation method: endurance operation time]
An aqueous solution having the composition shown in Table 3 was prepared and used as a three-dimensional object precursor treating agent composition according to Examples 1B to 5B, Comparative Example 1B, and Comparative Example 2B. The evaluation sample is immersed in the three-dimensional object precursor treatment agent composition according to Examples 1B to 5B, Comparative Example 1B, and Comparative Example 2B at a liquid temperature of 60 ° C., and the leg 21 of FIG. The time (durability moving time) until the leg part which consists of the leg part 22 became movable was measured. Since the three-dimensional object precursor treating agent composition according to Examples 1B to 5B, Comparative Example 1B, and Comparative Example 2B contains a soluble material for three-dimensional modeling, the support material is brought into contact with the three-dimensional object precursor. It can be assumed that the state of the three-dimensional object precursor treating agent composition in the support material removing process for removing the substrate is close. Example 1B-5B and Comparative Example 1B and the results of evaluation of the three-dimensional object precursor treating agent composition according to Examples 1A-5A and Comparative Example 1A having the same composition other than the three-dimensional modeling soluble material (durability moving time) It can be determined that the smaller the difference between the evaluation results of Examples 1B to 5B and Comparative Example 1B, the longer the support material removability can be maintained. The evaluation results are shown in Table 3.

1: trunk part 11: shaft through part 21: leg part 22: leg part 3: support material outer edge part

Claims

Three-dimensional object for removing the support material from a three-dimensional object precursor comprising a three-dimensional object and a support material containing a (meth) acrylic acid-based copolymer having a hydrophilic monomer and a hydrophobic monomer as monomer units An object precursor treating agent composition comprising:
The three-dimensional object precursor treating agent composition, wherein the three-dimensional object precursor treating agent composition contains (a) an alkali agent and (b) a nonionic penetrant.
The nonionic penetrant (b) has at least one group selected from the group consisting of an alkyl group having 4 to 14 carbon atoms, an alkenyl group having 3 to 30 carbon atoms, and an aryl group having 6 to 30 carbon atoms. The three-dimensional object precursor treating agent composition according to claim 1, which is an oxyalkylene adduct.
The three-dimensional object precursor treating agent composition according to claim 1 or 2, wherein the nonionic penetrant (b) is a polyoxyalkylene alkyl ether represented by the following general formula (1).
R 1 —O— (AO) m—H (1)
(In the general formula (1), R 1 is an alkyl group having 4 to 14 carbon atoms, an alkenyl group having 3 to 30 carbon atoms, or an aryl group having 6 to 30 carbon atoms, and AO is an oxyalkylene having 1 to 50 carbon atoms. And m is the average number of moles of AO added, and m is a number from 1 to 20.)
The content of the (b) nonionic penetrant in the three-dimensional object precursor treating agent composition is 0.05% by mass or more and 10% by mass or less. Three-dimensional object precursor treating agent composition.
The three-dimensional object precursor treating agent composition according to any one of claims 1 to 4, wherein the (a) alkali agent contains an organic amine compound.
The three-dimensional object precursor according to claim 5, wherein the organic amine compound is at least one selected from the group consisting of a secondary diamine compound, a tertiary diamine compound, a secondary triamine compound, and a tertiary triamine compound. Treatment agent composition.
The three-dimensional object precursor treating agent according to any one of claims 1 to 6, wherein the content of the organic amine compound in the three-dimensional object precursor treating agent composition is 0.1 to 20% by mass. Composition.
The three-dimensional object precursor treatment composition according to any one of claims 1 to 7, further comprising (c) a surfactant.
The three-dimensional object precursor treating agent composition according to claim 8, wherein the content of the surfactant (c) in the three-dimensional object precursor treating agent composition is 0.05% by mass or less.
A modeling process for obtaining a three-dimensional object precursor including a three-dimensional object and a support material including a (meth) acrylic acid-based copolymer having a hydrophilic monomer and a hydrophobic monomer as monomer units, and the three-dimensional object precursor Is a method for producing a three-dimensional object by a hot melt laminating method having a support material removal step of contacting the three-dimensional object precursor treatment agent composition and removing the support material, the composition comprising the three-dimensional object precursor treatment agent composition A method for producing a three-dimensional object, wherein the object is the three-dimensional object precursor treating agent composition according to any one of claims 1 to 9.
The hydrophilic monomer is acrylic acid, methacrylic acid, diethylaminoethyl acrylate, 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, glycidyl acrylate, tetrahydrofurfuryl acrylate, diethylaminoethyl methacrylate, 2-methacrylic acid 2- 11. At least one selected from the group consisting of hydroxyethyl, 2-hydroxypropyl methacrylate, glycidyl methacrylate, tetrahydrofurfuryl methacrylate, itaconic acid, maleic acid, fumaric acid and α-hydroxyacrylic acid can be used. The manufacturing method of the three-dimensional object of description.
The hydrophobic monomer is methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, isobutyl acrylate, tertiary butyl acrylate, 2-ethylhexyl acrylate, octyl acrylate, isodecyl acrylate, acrylic acid Lauryl, tridecyl acrylate, cetyl acrylate, stearyl acrylate, cyclohexyl acrylate, benzyl acrylate, methyl methacrylate, ethyl methacrylate, propyl methacrylate, butyl methacrylate, isobutyl methacrylate, tertiary butyl methacrylate, methacrylic acid 2-ethylhexyl, octyl methacrylate, isodecyl methacrylate, lauryl methacrylate, tridecyl methacrylate, cetyl methacrylate, stearyl methacrylate, methacryl Cyclohexyl, benzyl methacrylate, styrene, can be at least one selected from the group consisting of α- methylene -γ- valerolactone, three-dimensional object manufacturing method according to claim 10 or 11.
The method for producing a three-dimensional object according to any one of claims 10 to 12, wherein the three-dimensional object precursor treating agent composition has a pH of 10 to 14.
Use of the composition according to any one of claims 1 to 9 as a three-dimensional object precursor treatment agent.
The three-dimensional object precursor according to any one of claims 1 to 9, wherein the three-dimensional object precursor includes a support material including a (meth) acrylic acid copolymer having a hydrophilic monomer and a hydrophobic monomer as monomer units. A support material removing method of contacting the treatment agent composition and removing the support material.