阅读说明：本技术 三维物体前体处理剂组合物 (Three-dimensional object precursor treatment agent composition ) 是由 久保田和男 于 2019-11-22 设计创作，主要内容包括：本发明的三维物体前体处理剂组合物用于从包含三维物体和支撑材料的三维物体前体中除去上述支撑材料,所述支撑材料包含具有亲水性单体和疏水性单体作为单体单元的(甲基)丙烯酸系共聚物,上述三维物体前体处理剂组合物含有下述式(I)所示的化合物(成分A)和水(成分B),pH为12以上。根据本发明的三维物体前体处理剂组合物,能够比以往更迅速地除去含有(甲基)丙烯酸共聚物的支撑材料。(式(I)中,R～1、R～2、R～3各自独立为选自碳原子数1以上且8以下的烷基和苯基中的至少1种,R～4表示碳原子数1以上且8以下的烷基、碳原子数1以上且8以下的羟基烷基、苯基或苄基。)(The three-dimensional object precursor treatment agent composition of the present invention is used for removing a support material from a three-dimensional object precursor comprising a three-dimensional object and the support material, the support material comprising a (meth) acrylic copolymer having a hydrophilic monomer and a hydrophobic monomer as monomer units, the three-dimensional object precursor treatment agent composition comprising a compound represented by the following formula (I) (component a) and water (component B), and having a pH of 12 or more. According to the three-dimensional object precursor treatment agent composition of the present invention, the support material containing the (meth) acrylic copolymer can be removed more rapidly than ever. (in the formula (I), R 1 、R 2 、R 3 Each independently selected from alkyl groups having 1 to 8 carbon atoms and phenyl groupsAt least 1 of (1), R 4 Represents an alkyl group having 1 to 8 carbon atoms, a hydroxyalkyl group having 1 to 8 carbon atoms, a phenyl group or a benzyl group. ))

1. A three-dimensional object precursor treating agent composition for removing a support material from a three-dimensional object precursor comprising a three-dimensional object and the support material, the support material comprising a (meth) acrylic copolymer having a hydrophilic monomer and a hydrophobic monomer as monomer units,

the three-dimensional object precursor treatment agent composition contains a compound represented by the following formula (I), namely a component A and a component B which is water, has a pH of 12 or more,

in the formula (I), R¹、R²、R³Each independently represents at least 1 selected from alkyl groups having 1 to 8 carbon atoms and phenyl groups, and R is⁴Represents an alkyl group having 1 to 8 carbon atoms, a hydroxyalkyl group having 1 to 8 carbon atoms, a phenyl group or a benzyl group.

2. The three-dimensional object precursor treating agent composition according to claim 1, wherein the component A is derived from a compound represented by the following formula (II) (component A',

in the formula (II), R¹、R²、R³Each independently represents at least 1 selected from alkyl groups having 1 to 8 carbon atoms and phenyl groups, and R is⁴Is an alkyl group having 1 to 8 carbon atoms, a hydroxyalkyl group having 1 to 8 carbon atoms, a phenyl group or a benzyl group, M^-Represents a hydroxide ion, a chloride ion or a bromide ion.

3. The three-dimensional object precursor treating agent composition according to claim 1 or 2, further comprising an inorganic base, component C.

4. A three-dimensional object precursor treating agent composition for removing a support material from a three-dimensional object precursor comprising a three-dimensional object and the support material, the support material comprising a (meth) acrylic copolymer having a hydrophilic monomer and a hydrophobic monomer as monomer units,

the three-dimensional object precursor treatment agent composition comprises a compound represented by the following formula (II), namely component A ', which is a source of a compound represented by the following formula (I), namely component A', water, namely component B, and an inorganic base, namely component C, and has a pH of 12 or more,

in the formula (I), R¹、R²、R³Each independently represents at least 1 selected from alkyl groups having 1 to 8 carbon atoms and phenyl groups, and R is⁴Represents an alkyl group having 1 to 8 carbon atoms, a hydroxyalkyl group having 1 to 8 carbon atoms, a phenyl group or a benzyl group,

in the formula (II), R¹、R²、R³Each independently represents at least 1 selected from alkyl groups having 1 to 8 carbon atoms and phenyl groups, and R is⁴Is a carbon atom number of 1 or more andan alkyl group of 8 or less, a hydroxyalkyl group of 1 to 8 carbon atoms, a phenyl group or a benzyl group, M^-Represents a hydroxide ion, a chloride ion or a bromide ion.

5. The three-dimensional object precursor treating agent composition according to any one of claims 1 to 4, further comprising a water-soluble solvent, component D.

6. The three-dimensional object precursor treating agent composition according to claim 5, wherein the component D is selected from the group consisting of monohydric alcohol, polyhydric alcohol, and glycol ether.

7. The three-dimensional object precursor treatment agent composition according to any one of claims 1 to 6, wherein a content of the component A in the three-dimensional object precursor treatment agent composition is 0.5% by mass or more and 5% by mass or less.

8. The three-dimensional object precursor treatment agent composition according to any one of claims 1 to 7, wherein a content of the component B of the treatment agent composition is 90% by mass or more.

9. The three-dimensional object precursor treatment agent composition according to any one of claims 1 to 8, wherein a shaping material as a material of the three-dimensional object is a resin other than a (meth) acrylic copolymer.

10. A method of manufacturing a three-dimensional object, comprising:

a shaping step of obtaining a three-dimensional object precursor including a three-dimensional object and a support material, the support material including a (meth) acrylic copolymer having a hydrophilic monomer and a hydrophobic monomer as monomer units; and

a support material removing step of removing the support material by bringing the three-dimensional object precursor into contact with a three-dimensional object precursor treatment agent composition,

the three-dimensional object precursor treatment agent composition according to any one of claims 1 to 9.

11. The method of manufacturing a three-dimensional object according to claim 10, wherein a modeling material as a material of the three-dimensional object is a resin other than a (meth) acrylic copolymer.

12. The method of manufacturing a three-dimensional object according to claim 10 or 11, wherein in the shaping step, an FDM method, an inkjet ultraviolet curing method, or a photo-shaping method is used.

13. The method of manufacturing a three-dimensional object according to any one of claims 10 to 12, wherein in the shaping step, the three-dimensional object and the support material are ejected from different nozzles, respectively.

14. A support material removing method of removing a support material by bringing a three-dimensional object precursor comprising a three-dimensional object and the support material into contact with the three-dimensional object precursor treating agent composition according to any one of claims 1 to 6, the support material comprising a (meth) acrylic copolymer having a hydrophilic monomer and a hydrophobic monomer as monomer units.

15. Use of the three-dimensional object precursor treatment agent composition according to any one of claims 1 to 9 for removing a support material from a three-dimensional object precursor comprising a three-dimensional object and the support material, the support material comprising a (meth) acrylic copolymer having a hydrophilic monomer and a hydrophobic monomer as monomer units.

Technical Field

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

Background

The 3D printer is one of Rapid Prototyping (Rapid Prototyping), and is a three-dimensional printer that shapes a three-dimensional object based on 3D data such as 3D CAD and 3D CG. As the 3D printer, a thermal fusion lamination method (hereinafter, also referred to as an FDM method), an inkjet ultraviolet curing method, a stereolithography method, a laser sintering method, and the like are known. The FDM method is a method of forming a three-dimensional object by heating/melt-extruding and laminating polymer filaments, and is different from other methods and does not use a material reaction. Therefore, the FDM type 3D printer is small and inexpensive, and has recently become popular as a device with less post-processing. In order to shape a three-dimensional object having a more complicated shape by the FDM method, a three-dimensional object precursor is obtained by laminating a shaping material constituting the three-dimensional object and a support material for supporting a three-dimensional structure of the shaping material, and then the support material is removed from the three-dimensional object precursor, whereby a target three-dimensional object can be obtained.

As a method for removing the support material from the three-dimensional object precursor, the following methods can be cited: the support material is removed by immersing a three-dimensional object precursor in a three-dimensional object precursor treatment agent containing a base using a (meth) acrylic copolymer (for example, japanese patent laid-open No. 2008-507619, japanese patent laid-open No. 2012-509777, international publication No. 2017/199323, international publication No. 2017/199324). The method utilizes the following means: the carboxylic acid in the (meth) acrylic acid-based copolymer is neutralized with a base and dissolved in an aqueous alkali solution. The (meth) acrylic copolymer contained in the support material used in this method has a hydrophobic group from the viewpoint of heating/melt extrusion and lamination properties by a 3D printer, and has a hydrophilic group from the viewpoint of solubility in the three-dimensional object precursor treatment agent.

Disclosure of Invention

The three-dimensional object precursor treatment agent composition of the present invention is a three-dimensional object precursor treatment agent composition for removing a support material from a three-dimensional object precursor including a three-dimensional object and the support material, the support material including a (meth) acrylic copolymer having a hydrophilic monomer and a hydrophobic monomer as monomer units, the three-dimensional object precursor treatment agent composition containing a compound represented by the following formula (I) (component a) and water (component B), and having a pH of 12 or more.

[ chemical formula 1]

(in the formula (I), R¹、R²、R³Each independently represents at least 1 selected from alkyl groups having 1 to 8 carbon atoms and phenyl groups, and R is⁴Represents an alkyl group having 1 to 8 carbon atoms, a hydroxyalkyl group having 1 to 8 carbon atoms, a phenyl group or a benzyl group. )

The method for manufacturing a three-dimensional object of the present invention includes: a shaping step of obtaining a three-dimensional object precursor including a three-dimensional object and a support material, the support material including a (meth) acrylic copolymer having a hydrophilic monomer and a hydrophobic monomer as monomer units; and a support material removing step of bringing the three-dimensional object precursor into contact with the three-dimensional object precursor treatment agent composition to remove the support material.

In the support material removing method of the present invention, a three-dimensional object precursor comprising a three-dimensional object and a support material comprising a (meth) acrylic copolymer having a hydrophilic monomer and a hydrophobic monomer as monomer units is brought into contact with the three-dimensional object precursor treating agent composition to remove the support material.

Drawings

Fig. 1 is a schematic diagram showing the shape of an evaluation sample used in the examples.

Detailed Description

The conventional three-dimensional object precursor treating agent takes time to remove the support material containing the (meth) acrylic copolymer having a hydrophilic group and a hydrophobic group. In order to solve this problem, it is conceivable to increase the reactivity by increasing the concentration of the base in the three-dimensional object precursor treatment agent or by increasing the temperature at the time of immersing the three-dimensional object precursor in the three-dimensional object precursor treatment agent.

However, it has been found that if the concentration of the base in the three-dimensional object precursor treatment agent is increased or the temperature at the time of immersing the three-dimensional object precursor in the three-dimensional object precursor treatment agent is increased to increase the reactivity, the support material is swollen instead, and the support material cannot be removed quickly.

The present invention provides a three-dimensional object precursor treatment agent composition capable of removing a support material containing a (meth) acrylic copolymer having a hydrophilic monomer and a hydrophobic monomer as monomer units more rapidly than ever from a three-dimensional object precursor containing the support material and a method for producing a three-dimensional object using the three-dimensional object precursor treatment agent composition.

The three-dimensional object precursor treatment agent composition of the present invention is used for removing a support material from a three-dimensional object precursor comprising a three-dimensional object and the support material, the support material comprising a (meth) acrylic copolymer having a hydrophilic monomer and a hydrophobic monomer as monomer units, the three-dimensional object precursor treatment agent composition comprising a compound represented by the following formula (I) (component a) and water (component B), and having a pH of 12 or more.

[ chemical formula 2]

(in the formula (I), R¹、R²、R³Each independently represents at least 1 selected from alkyl groups having 1 to 8 carbon atoms and phenyl groups, and R is⁴Represents an alkyl group having 1 to 8 carbon atoms, a hydroxyalkyl group having 1 to 8 carbon atoms, a phenyl group or a benzyl group. )

The method for manufacturing a three-dimensional object of the present invention includes: a shaping step of obtaining a three-dimensional object precursor including a three-dimensional object and a support material, the support material including a (meth) acrylic copolymer having a hydrophilic monomer and a hydrophobic monomer as monomer units; and a support material removing step of bringing the three-dimensional object precursor into contact with the three-dimensional object precursor treatment agent composition to remove the support material.

In the support material removing method of the present invention, a three-dimensional object precursor comprising a three-dimensional object and a support material comprising a (meth) acrylic copolymer having a hydrophilic monomer and a hydrophobic monomer as monomer units is brought into contact with the three-dimensional object precursor treating agent composition to remove the support material.

According to the present invention, it is possible to provide a three-dimensional object precursor treatment agent composition which can remove a support material containing a (meth) acrylic copolymer having a hydrophilic monomer and a hydrophobic monomer as monomer units more quickly than ever before from a three-dimensional object precursor containing the support material and a support material, and a method for producing a three-dimensional object using the three-dimensional object precursor treatment agent composition.

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

< three-dimensional object precursor treating agent composition >

The three-dimensional object precursor treatment agent composition of the present embodiment (hereinafter, also simply referred to as "treatment agent composition") is a treatment agent composition for removing a support material from a three-dimensional object precursor including a three-dimensional object and the support material, the support material including a (meth) acrylic copolymer having a hydrophilic monomer and a hydrophobic monomer as monomer units, the treatment agent composition containing a compound represented by the following formula (I) (component a) and water (component B), and having a pH of 12 or more.

[ chemical formula 3]

(in the formula (I), R¹、R²、R³Each independently selected from the group consisting of 1 to 8 carbon atomsAt least 1 of alkyl and phenyl of (A), R⁴Represents an alkyl group having 1 to 8 carbon atoms, a hydroxyalkyl group having 1 to 8 carbon atoms, a phenyl group or a benzyl group. )

According to the treatment agent composition of the present embodiment, the support material including the (meth) acrylic copolymer having the hydrophilic monomer and the hydrophobic monomer as monomer units can be removed more quickly than ever from the three-dimensional object precursor including the three-dimensional object and the support material. The mechanism of the effect of the present embodiment is not determined, but the following is considered.

The support material is considered to have a carboxylic acid group derived from (meth) acrylic acid and a modified carboxylic acid group because it contains a (meth) acrylic acid-based copolymer having a hydrophilic monomer and a hydrophobic monomer as monomer units, and it is presumed that the component a acts on the copolymer to permeate the copolymer, the component a forms a salt with the carboxylic acid, the solubility of the copolymer in water is improved, and thus disintegration of the copolymer is promoted, and the hydroxide ion also acts on the copolymer due to the basicity of pH12 or more, and hydrolysis or the like is promoted, and thus the support material is rapidly removed.

[ Compound (component A) represented by the formula (I) ]

In order to remove the support material quickly, any compound represented by the following formula (I) may be used as the component A.

[ chemical formula 4]

(in the formula (I), R¹、R²、R³Each independently represents at least 1 selected from alkyl groups having 1 to 8 carbon atoms and phenyl groups, and R is⁴Represents an alkyl group having 1 to 8 carbon atoms, a hydroxyalkyl group having 1 to 8 carbon atoms, a phenyl group or a benzyl group. )

In the above formula (I), R¹、R²、R³Each independently represents at least one member selected from the group consisting of an alkyl group having 1 to 8 carbon atoms and a phenyl groupThe number of the alkyl groups is 1 or less, and from the viewpoint of rapid removal of the support material, an alkyl group having 1 to 6 carbon atoms is preferable, an alkyl group having 1 to 4 carbon atoms is more preferable, and an alkyl group having 2 to 4 carbon atoms is even more preferable.

In the above formula (I), R⁴An alkyl group having 1 to 8 carbon atoms, a hydroxyalkyl group having 1 to 8 carbon atoms, a phenyl group or a benzyl group, and from the viewpoint of rapid removal of the support material, an alkyl group having 1 to 6 carbon atoms, a hydroxyalkyl group having 1 to 4 carbon atoms or a benzyl group is preferable, an alkyl group having 1 to 4 carbon atoms, a hydroxyethyl group or a benzyl group is more preferable, an alkyl group having 1 to 4 carbon atoms is further preferable, and an alkyl group having 2 to 4 carbon atoms is further more preferable.

Examples of the compound represented by the formula (I) include tetraethylammonium, tetrapropylammonium, tetrabutylammonium, tetrapentylammonium, tetrahexylammonium, tetraheptylammonium, tetraoctylammonium, ethyltrimethylammonium, propyltrimethylammonium, butyltrimethylammonium, pentyltrimethylammonium, hexyltrimethylammonium, octyltrimethylammonium, benzyltrimethylammonium, benzyltriethylammonium, hydroxyethyltrimethylammonium, and benzyldimethylphenylammonium, and from the viewpoint of rapid removal of the support material, tetraethylammonium, tetrapropylammonium, tetrabutylammonium, ethyltrimethylammonium, propyltrimethylammonium, butyltrimethylammonium, pentyltrimethylammonium, hexyltrimethylammonium, octyltrimethylammonium, benzyltrimethylammonium, benzyltriethylammonium, hydroxyethyltrimethylammonium, and benzyldimethylphenylammonium are preferred, and tetraethylammonium, tetrapropylammonium, tetrabutylammonium, ethyltrimethylammonium, and benzyldimethylphenylammonium are more preferred, Propyltrimethylammonium, butyltrimethylammonium, benzyltrimethylammonium, benzyltriethylammonium, or hydroxyethyltrimethylammonium, more preferably tetraethylammonium, tetrapropylammonium, tetrabutylammonium, benzyltrimethylammonium, benzyltriethylammonium, or hydroxyethyltrimethylammonium, and still more preferably tetraethylammonium, tetrabutylammonium, benzyltrimethylammonium, or benzyltriethylammonium. At least 1 kind of the above component A may be used, and 2 or more kinds may be used in combination.

The content of the component a in the treatment agent composition is preferably 0.5% by mass or more, more preferably 0.7% by mass or more, further preferably 0.8% by mass or more, and further preferably 1.0% by mass or more, from the viewpoint of rapid removal of the support material, and from the same viewpoint, is preferably 5% by mass or less, more preferably 4% by mass or less, further preferably 3.5% by mass or less, and further preferably 3% by mass or less. Further, it is preferably 0.5% by mass or more and 5% by mass or less, more preferably 0.7% by mass or more and 4% by mass or less, still more preferably 0.8% by mass or more and 3.5% by mass or less, and still more preferably 1.0% by mass or more and 3% by mass or less.

[ Compound (component A') of formula (II) ]

The source of the component a is preferably a compound represented by the following formula (II) (component a') which is a quaternary ammonium salt.

[ chemical formula 5]

(in the formula (II), R¹、R²、R³Each independently represents at least 1 selected from alkyl groups having 1 to 8 carbon atoms and phenyl groups, and R is⁴Is an alkyl group having 1 to 8 carbon atoms, a hydroxyalkyl group having 1 to 8 carbon atoms, a phenyl group or a benzyl group, M^-Represents a hydroxide ion, a chloride ion or a bromide ion. )

In the above formula (II), R¹、R²、R³、R⁴And R in the formula (I)¹、R²、R³、R⁴The same applies to each other, and therefore, the description thereof is omitted.

In the above formula (II), M^-The hydroxide ion, chloride ion or bromide ion is preferred from the viewpoint of rapid removal of the support material.

The compound represented by the formula (II) is specifically a hydroxide, chloride or bromide of the compound represented by the formula (I), and from the viewpoint of rapidly removing the support material, the hydroxide is preferable, tetraethylammonium hydroxide, tetrabutylammonium hydroxide, benzyltrimethylammonium hydroxide or benzyltriethylammonium hydroxide is more preferable, tetraethylammonium hydroxide, tetrabutylammonium hydroxide or benzyltrimethylammonium hydroxide is further preferable, and tetraethylammonium hydroxide or tetrabutylammonium hydroxide is further preferable. At least 1 kind of the above-mentioned component A' may be used, and 2 or more kinds may be used in combination.

The content of the component a' in the treatment agent composition may be within a range that satisfies the content of the component a, and is preferably 0.5% by mass or more, more preferably 0.7% by mass or more, further preferably 0.8% by mass or more, and further preferably 1.0% by mass or more, from the viewpoint of rapid removal of the support material, and is preferably 7% by mass or less, more preferably 6% by mass or less, further preferably 5% by mass or less, and further preferably 4% by mass or less from the same viewpoint. Further, it is preferably 0.5% by mass or more and 7% by mass or less, more preferably 0.7% by mass or more and 6% by mass or less, further preferably 0.8% by mass or more and 5% by mass or less, and further preferably 1.0% by mass or more and 4% by mass or less.

[ Water (component B) ])

As the component B, industrial water, tap water, ion-exchanged water, and the like can be used, and industrial water is preferable from the viewpoint of availability and cost, and ion-exchanged water is preferable from the viewpoint of rapid removal of the support material.

The content of the component B in the treatment agent composition is preferably 90% by mass or more, and preferably 99% by mass or less. In the case where the treatment agent composition does not contain a component other than the component a, the content of water in the treatment agent composition is the remainder other than the component a and the counter ion thereof.

[ others ]

The above-mentioned treating agent composition may contain an inorganic base, a water-soluble solvent, a surfactant, a builder component, a thickener, a pH adjuster, a preservative, a rust preventive, a pigment, a colorant, and the like as necessary within a range not impairing the effects of the present invention. Since the color of the treatment agent composition containing the colorant changes depending on the type of the support material due to the dissolution of the support material, the colorant can also be expected to function as an indicator showing the progress and termination of the treatment.

[ inorganic base (component C) ]

Any inorganic base may be used as the component C. Specific examples of the inorganic base include hydroxides of alkali metals such as sodium hydroxide and potassium hydroxide; alkali metal silicates such as sodium orthosilicate, sodium metasilicate, sodium sesquisilicate and the like; alkali metal phosphates such as trisodium phosphate; carbonates of alkali metals such as disodium carbonate, sodium bicarbonate, and dipotassium carbonate; and alkali metal borates such as sodium borate. Two or more kinds of inorganic bases may be combined. From the viewpoint of rapid removal of the support material, a hydroxide of an alkali metal is preferred, sodium hydroxide and potassium hydroxide are more preferred, and sodium hydroxide is further preferred. At least 1 kind of the component B may be used, and 2 or more kinds may be used in combination.

The content of the component C in the treatment agent composition is preferably 0.01% by mass or more, more preferably 0.02% by mass or more, even more preferably 0.05% by mass or more, even more preferably 0.1% by mass or more, and from the same viewpoint, is preferably 5% by mass or less, more preferably 3% by mass or less, even more preferably 2% by mass or less, even more preferably 1% by mass or less, from the viewpoint of rapidly removing the support material by setting the pH of the treatment agent composition for a three-dimensional object precursor to 12 or more. Further, it is preferably 0.01% by mass or more and 5% by mass or less, more preferably 0.02% by mass or more and 3% by mass or less, still more preferably 0.05% by mass or more and 2% by mass or less, and still more preferably 0.1% by mass or more and 1% by mass or less.

[ Water-soluble solvent (component D) ]

The above water-soluble solvent exhibits properties of disintegration of the support material and dissolution in the treatment agent composition.

The water-soluble solvent is preferably dissolved in water at 20 ℃ by 1.5 mass% or more. Examples of the water-soluble solvent include water-soluble solvents selected from monohydric alcohols, polyhydric alcohols, and glycol ethers.

The monohydric alcohol may be a monohydric alcohol having 1 to 5 carbon atoms. Specific examples thereof include monohydric alcohols selected from the group consisting of methanol, ethanol, 1-propanol, 2-propen-1-ol, 1-butanol, 2-methylpropanol, 2-butanol, 2-methyl-2-propanol and pentanol.

Examples of the polyhydric alcohol include alkylene glycols having a repeating unit with a carbon number of 2 to 3 [ hereinafter referred to as C2 to C3 alkylene glycols ]. Examples of the C2-C3 alkylene glycol include ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, pentaethylene glycol, hexaethylene glycol, heptaethylene glycol, octaethylene glycol, nonaethylene glycol, decaethylene glycol, propylene glycol, dipropylene glycol, tripropylene glycol, and the like. The C2 to C3 alkylene glycol preferably has an oxyethylene group or an oxypropylene group as a repeating unit of 1 to 10 inclusive.

Examples of the polyhydric alcohol other than the alkylene glycol having from C2 to C3 include polyhydric alcohols having from 2 to 8 carbon atoms. Specific examples thereof include trimethylene glycol, 1, 2-propanediol, 1, 3-propanediol, 2-methyl-1, 3-propanediol, 1, 2-butanediol, 1, 3-butanediol, 1, 4-butenediol, 1, 4-pentanediol, 1, 5-hexanediol, 1, 6-hexanediol, 1, 8-octanediol, glycerin, trimethylolethane, trimethylolpropane and the like.

Examples of the glycol ether include glycol ethers selected from polyoxyalkylene monoalkyl ethers and polyoxyalkylene dialkyl ethers. These oxyalkylene groups are preferably oxyethylene groups. The average molar number of addition of the oxyalkylene group is preferably 1 or more and 7 or less. The number of carbon atoms of the alkyl group (alkyl group of the terminal ether moiety) is preferably 1 to 4. Specifically, POE (1 or more and 7 or less) monomethyl ether, POE (1 or more and 7 or less) monoethyl ether, POE (1 or more and 7 or less) monopropyl ether, POE (1 or more and 7 or less) monobutyl ether, POE (1 or more and 7 or less) monoisobutyl ether, POE (1 or more and 7 or less) monoallyl ether, POE (1 or more and 7 or less) monohexyl ether, POE (1 or more and 7 or less) monophenyl ether, POE (1 or more and 7 or less) dimethyl ether, POE (1 or more and 7 or less) diethyl ether, POE (1 or more and 7 or less) dipropyl ether, POE (1 or more and 7 or less) dibutyl ether, and the like can be given. Here, POE is an abbreviation of polyoxyethylene, and the number in parentheses is an average molar number of ethylene oxide added (the same applies hereinafter).

The water-soluble solvents may be used alone or in combination of 2 or more. Among these, from the viewpoint of further improving the disintegration of the support material and the dissolution in the treatment agent composition, a water-soluble solvent selected from methanol, ethanol, 1-propanol, 2-methyl-2-propanol, ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, dipropylene glycol, tripropylene glycol, POE (1 or more and 5 or less) monomethyl ether, POE (1 or more and 5 or less) monoethyl ether, POE (1 or more and 5 or less) monopropyl ether, POE (1 or more and 5 or less) monobutyl ether, POE (1 or more and 5 or less) monoisobutyl ether, POE (2 or more and 5 or less) dimethyl ether, and POE (2 or more and 5 or less) diethyl ether is preferable, and a water-soluble solvent selected from ethanol, ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, dipropylene glycol, POE (1 or more and 3 or less) monomethyl ether, POE (1 or more and 3 or less) monoethyl ether, and, POE (1 or more and 3 or less) monopropyl ether, POE (1 or more and 3 or less) monobutyl ether, and POE (1 or more and 3 or less) monoisobutyl ether.

The content of the component D in the treatment agent composition is preferably 0.1% by mass or more, more preferably 0.5% by mass or more, further preferably 1% by mass or more, and even more preferably 2% by mass or more from the viewpoint of rapid removal of the support material, and is preferably 10% by mass or less, more preferably 8% by mass or less, even more preferably 6% by mass or less, and even more preferably 5% by mass or less from the viewpoint of reduction of the load of drainage treatment. Further, it is preferably 0.1% by mass or more and 10% by mass or less, more preferably 0.5% by mass or more and 8% by mass or less, still more preferably 1% by mass or more and 6% by mass or less, and still more preferably 2% by mass or more and 5% by mass or less.

[ surfactant ]

The above-mentioned treating agent composition may contain a surfactant. Examples of the surfactant include nonionic surfactants, anionic surfactants, cationic surfactants, and amphoteric surfactants, and from the viewpoint of rapid removal of the support material, nonionic surfactants are preferable, and nonionic surfactants represented by the following formula (III) are more preferable.

R⁵-O-{(EO)n/(PO)m}-H (III)

(in the formula (III), R⁵The alkyl group or alkenyl group having 8 to 18 carbon atoms, which is a linear or branched chain, EO is oxyethylene, PO is oxypropylene, n is the average molar number of EO added, m is the average molar number of PO added, n is a number satisfying 2 to 20, m is a number satisfying 0 to 20, and the addition form of PO and EO in { } may be either a random arrangement or a block arrangement. )

The pH of the treatment agent composition is 12 or more. From the viewpoint of rapid removal of the support material, the amount is 12 or more, preferably 12.5 or more, more preferably 12.8 or more, and still more preferably 13 or more.

The treating agent composition can be produced by blending the component A' and the component B, which are sources of the component A, and other optional components. When the component a ', the component B, the component C, and any other optional components are blended, the component a ' and the component C can be salt-exchanged, and the treating agent composition can be produced in which a plurality of salts different from the components a ' and C are in an equilibrium state.

< method for producing three-dimensional object >

The method for manufacturing a three-dimensional object of the present embodiment includes: a shaping step of obtaining a three-dimensional object precursor including a three-dimensional object and a support material, the support material including a (meth) acrylic copolymer having a hydrophilic monomer and a hydrophobic monomer as monomer units; and a support material removing step of bringing the three-dimensional object precursor into contact with the treatment agent composition to remove the support material. According to the method for producing a three-dimensional object of the present embodiment, the supporting material containing the (meth) acrylic copolymer can be removed more quickly than before. The reason why such an effect is exhibited is considered to be the same as the reason why the above-mentioned treating agent composition exhibits the above-mentioned effect.

[ Molding Process ]

As for the shaping step of obtaining the three-dimensional object precursor including the three-dimensional object and the support material including the (meth) acrylic copolymer having the hydrophilic monomer and the hydrophobic monomer as monomer units, a step of obtaining the three-dimensional object precursor including the three-dimensional object and the support material in a known method for producing a three-dimensional object by a 3D printer can be used. As a known method for manufacturing a three-dimensional object by using a 3D printer, there are FDM method, inkjet ultraviolet curing method, stereolithography method, laser sintering method, and the like, and among them, the FDM method, inkjet ultraviolet curing method, or stereolithography method is preferable, and the FDM method is more preferable.

The shaping material of the three-dimensional object is not particularly limited as long as it is a resin used as a shaping material in a conventional method for producing a three-dimensional object, and a resin other than a (meth) acrylic copolymer is preferable. Examples of the molding material include thermoplastic resins such as ABS resin, polylactic acid resin, polycarbonate resin, and polyphenylsulfone resin, and among them, ABS resin and/or polylactic acid resin are more preferable, and ABS resin is further preferable from the viewpoint of moldability by a 3D printer.

The soluble material for three-dimensional modeling as a material of the support material contains a (meth) acrylic copolymer having a hydrophilic monomer and a hydrophobic monomer as monomer units.

The shaping material and the three-dimensional shaping usable material are preferably ejected from different nozzles.

[ (meth) acrylic acid-based 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, 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, glycidyl methacrylate, tetrahydrofurfuryl methacrylate, itaconic acid, maleic acid, fumaric acid, and α -hydroxyacrylic acid. Among them, at least 1 or more selected from acrylic acid and methacrylic acid is preferable from the viewpoint of removability of the support material.

(hydrophobic monomer)

Examples of the hydrophobic monomer include methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, isobutyl acrylate, tert-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, tert-butyl methacrylate, 2-ethylhexyl methacrylate, octyl methacrylate, isodecyl methacrylate, lauryl methacrylate, tridecyl methacrylate, cetyl methacrylate, stearyl methacrylate, cyclohexyl methacrylate, benzyl methacrylate, styrene, and mixtures thereof, Alpha-methylene-gamma-valerolactone and the like.

The (meth) acrylic copolymer may contain a monomer unit 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 mixing the three-dimensional object precursor with the treatment agent composition. The method of bringing the three-dimensional object precursor into contact with the above-mentioned treatment agent composition may be a method of immersing the precursor in the treatment liquid and then stirring the precursor, or a method of exposing the precursor to a strong water flow, or a method of moving the precursor itself. However, from the viewpoint of preventing the precursor from being damaged and the viewpoint of ease of work, a method of immersing the three-dimensional object precursor in the treatment agent composition is preferred. From the viewpoint of improving the removability of the support material, the support material may be irradiated with ultrasonic waves during immersion to promote dissolution of the support material.

From the viewpoint of solubility of the support material, the amount of the treatment agent composition used is preferably 10 times by mass or more, and more preferably 20 times by mass or more, relative to the support material. From the viewpoint of workability, the amount of the treatment agent composition used is preferably 10000 times by mass or less, more preferably 5000 times by mass or less, further preferably 1000 times by mass or less, and further preferably 100 times by mass or less with respect to the support material.

The temperature of the treatment agent composition in the support material removing step is preferably 25 ℃ or higher, more preferably 40 ℃ or higher, from the viewpoint of solubility of the support material. The temperature of the treatment agent composition in the support material removing step is preferably 80 ℃ or lower, more preferably 70 ℃ or lower, from the viewpoint of suppressing swelling of the support material. From the above viewpoints, the temperature of the treating agent composition in the support material removing step is preferably 25 to 80 ℃, more preferably 40 to 70 ℃.

The time for bringing the support into contact with the treatment agent composition is preferably 2 minutes or longer, and more preferably 3 minutes or longer, from the viewpoint of removability of the support. In addition, from the viewpoint of reducing damage to the three-dimensional object, the time for bringing the support material into contact with the treatment agent composition is preferably 180 minutes or less, more preferably 120 minutes or less, still more preferably 90 minutes or less, and still more preferably 60 minutes or less. From the viewpoint of these points of view, the time for bringing the support material into contact with the treatment agent composition is preferably 2 to 180 minutes, more preferably 2 to 120 minutes, still more preferably 3 to 90 minutes, and still more preferably 3 to 60 minutes.

< method for removing support Material >

In the support material removing method of the present embodiment, a three-dimensional object precursor including a three-dimensional object and a support material including a (meth) acrylic copolymer having a hydrophilic monomer and a hydrophobic monomer as monomer units is brought into contact with the treatment agent composition to remove the support material. According to the support material removing method of the present embodiment, the support material containing the (meth) acrylic copolymer can be removed more quickly than before. The reason why such an effect is exhibited is considered to be the same as the reason why the above-mentioned treating agent composition exhibits the above-mentioned effect. The three-dimensional object precursor is the same as the three-dimensional object of the above-described method for producing a three-dimensional object, and therefore, the description thereof is omitted. The processing conditions in the supporting material removing method of the present embodiment are the same as those described in the supporting material removing step of the above-described method for manufacturing a three-dimensional object, and therefore, the description thereof is omitted.

Examples

The present invention will be described in more detail with reference to the following examples, but the present invention is not limited to these examples at all.

< preparation of three-dimensional object precursor treating agent composition >

[ examples 1 to 17 and comparative examples 1 to 5]

The three-dimensional object precursor treatment agent compositions of examples 1 to 17 and comparative examples 1 to 5 were prepared in 100mL screw vials each in an amount of 100g so as to be blended as shown in table 1 or table 2. The numerical values shown in table 1 or table 2 represent the amounts of the effective components in mass%.

[ Components ]

The following components were used for each component shown in table 1 or table 2.

Component A' (Compound represented by the formula (II))

Tetraethylammonium hydroxide: 10% aqueous solution manufactured by Tokyo chemical industry Co., Ltd

Tetrabutylammonium hydroxide: fuji film and Wako pure chemical industries, 40% aqueous solution

Benzyl trimethyl ammonium hydroxide: 10% aqueous solution manufactured by Tokyo chemical industry Co., Ltd

Benzyl triethyl ammonium hydroxide: 10% aqueous solution manufactured by Tokyo chemical industry Co., Ltd

Hydroxyethyl trimethyl ammonium hydroxide: fuji film and 50% Choline solution manufactured by Wako pure chemical industries, Ltd

Tetraethylammonium chloride: manufactured by Tokyo chemical industry Co Ltd

Tetraethylammonium bromide: fuji film and Wako pure chemical industries, Ltd

Tetrabutylammonium chloride: fuji film and Wako pure chemical industries, Ltd

Benzyl trimethyl ammonium chloride: fuji film and 60% aqueous solution manufactured by Wako pure chemical industries, Ltd

Benzyltriethylammonium chloride: fuji film and Wako pure chemical industries, Ltd

Benzyl dimethyl phenyl ammonium chloride: manufactured by Tokyo chemical industry Co Ltd

Hexyl trimethyl ammonium bromide: fuji film and Wako pure chemical industries, Ltd

Octyl trimethyl ammonium chloride: manufactured by Tokyo chemical industry Co Ltd

Non-component A'

Dodecyl trimethyl ammonium chloride: fuji film and Wako pure chemical industries, Ltd

Hexadecyl trimethyl ammonium hydroxide: 10% aqueous solution manufactured by Tokyo chemical industry Co., Ltd

Ingredient B (water)

Ion exchange water: purified water of 1 μ S/cm or less produced by water purifier G-10DSTSET manufactured by ORGANO K.K

Component C (inorganic base)

Sodium hydroxide: liquid caustic soda (concentration: 48% by mass), manufactured by Tokuyama, Ltd

Component D (Water-soluble solvent)

Diethylene glycol monobutyl ether: butyldiethylene glycol (BDG), a product of Japan emulsifier Co., Ltd

Ethanol: fuji film and Wako pure chemical industries, Ltd

[ Table 1]

[ Table 2]

[ comparative example 6 ]

As comparative example 6, a "support removing liquid (liquid type)" commercially available as a support material cleaning liquid for a shape forming system manufactured by Stratasys corporation (manufactured by Pimpinell Information systems Co., Ltd.) was used. The contents described in the safety data manual of "supporting removal liquid (liquid type)" are shown in table 3.

[ Table 3]

Content(s) therein	Content (%)
		Sodium carbonate	1.46
Sodium hydroxide	0.55
		Sodium sulfate	～0.13
Zeolite	～0.07
		+ dialkyl sodium sulfate (SDS)	～0.06
Film foamed polymer	～0.09

< evaluation method >

[ pH determination ]

The pH of the three-dimensional object precursor treatment agent composition was measured at 25 ℃ and the value obtained by immersing an electrode of a pH meter (DKK-TOA, HM-30G) in the three-dimensional object precursor treatment agent composition for 3 minutes was measured.

[ evaluation of removability of supporting Material I ]

[ preparation of evaluation sample I ]

As the evaluation sample I, a filamentous soluble material for three-dimensional modeling (methacrylic acid-based copolymer manufactured by Stratasys, Inc.; trade name SR-30 (monomer unit: 45 mass% of methacrylic acid, 34 mass% of styrene, 21 mass% of n-butyl acrylate) having a length of 60mm and a diameter of 1.8mm was used, and used for FDM).

[ evaluation procedure ]

100g of each of the three-dimensional object precursor treatment agent compositions of examples and comparative examples was added and heated to 60 ℃ in a 100mL screw-tube bottle to which a magnetic stirrer was added. Next, 1g of evaluation sample I was added thereto, and the mixture was stirred at 500rpm for 3 minutes. The evaluation sample I remaining after dissolution was taken out, separated by filtration, and dried at 60 ℃ under reduced pressure for 12 hours. From the mass difference before and after the test, the dissolution rate was calculated by the following formula. The results are shown in table 1 or table 2.

Dissolution rate (mg/min) ═ mass before test (mg) -mass after test (mg) ] ÷ 3 (min)

[ evaluation of removability of supporting Material II ]

[ preparation of evaluation sample II ]

An evaluation sample II (three-dimensional object precursor) was produced using ABS (ABS resin manufactured by Stratasys) as a molding material and SR-30 as a soluble material for three-dimensional molding by using an FDM type 3D printer Fortus250MC manufactured by Stratasys. Fig. 1 is a schematic diagram showing the shape of this evaluation sample II. The evaluation sample II shown in fig. 1 contains a three-dimensional object precursor including a three-dimensional object 1 and a support material 2. The supporting member 2 is not shown in order to help understand the shape of the three-dimensional object 1, but the supporting member 2 fills the void of the three-dimensional object 1.

[ evaluation procedure ]

Each 500g of the treating agent compositions of examples 2 and 3 and comparative examples 4 and 6 was prepared in a 500mL glass beaker. A magnetic stirrer was added, the mixture was heated to 60 ℃ and stirred at 500rpm, and the evaluation sample II added to the stainless steel basket was immersed in the three-dimensional object precursor treatment agent composition, and the time until the movable part moved was measured. The results are shown in table 1 or table 2.

It is found that the dissolution rates of examples 1 to 17 are higher than those of comparative examples 1 to 4 containing no component A, comparative example 5 having a pH of less than 12, and comparative example 6 which is a commercially available support material cleaning solution, and the support material can be removed quickly. Further, when examples 1 and 2 and comparative example 7, and example 4 and comparative example 8 were compared, respectively, it was found that the compound represented by the formula (II) obtained the same dissolution rate in a smaller amount than the amine compound. When example 2 and comparative example 8 were compared, it was found that the compound represented by formula (II) gave a greater dissolution rate at the same amount of addition as the amine compound.