WO2018021243A1

WO2018021243A1 - Fusible material for three-dimensional molding

Info

Publication number: WO2018021243A1
Application number: PCT/JP2017/026700
Authority: WO
Inventors: 丈士平井; 吉村　忠徳
Original assignee: 花王株式会社
Priority date: 2016-07-28
Filing date: 2017-07-24
Publication date: 2018-02-01

Abstract

This fusible material for three-dimensional molding is used as a support material for supporting a three-dimensional object when manufacturing the three-dimensional object using a fused deposition modeling (FDM) 3D printer. The fusible material for three-dimensional molding contains a polyamide resin having: a hydrophilic monomer unit A having a hydrophilic group; a hydrophobic dicarboxylic acid monomer unit B; and a hydrophobic diamine monomer unit C, wherein the proportion of the hydrophilic monomer unit A with respect to the sum of all of the monomer units in the polyamide resin is at least 2.5 mol% and less than 13.5 mol%. This fusible material for three-dimensional molding is used as a support material and suitable for manufacturing a three-dimensional object by the FDM method, has moisture absorption resistance, has a high dissolution rate in neutral water, and can be quickly removed from a three-dimensional object precursor without using a strong alkali aqueous solution.

Description

Soluble material for 3D modeling

The present invention relates to a soluble material for three-dimensional modeling used as a support material for supporting a three-dimensional object when a three-dimensional object is manufactured by a 3D printer, particularly a hot melt lamination type 3D printer.

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, there is a method for removing the support material by immersing the three-dimensional object precursor in a high-temperature strong alkaline aqueous solution using a methacrylic acid copolymer as the support material. (For example, JP-T-2012-509777). This method utilizes the fact that the carboxylic acid in the methacrylic acid copolymer is neutralized by an alkali and dissolved in a strong alkaline aqueous solution.

The three-dimensional modeling soluble material of the present invention is a three-dimensional modeling soluble material used as a support material for supporting the three-dimensional object when a three-dimensional object is manufactured by an FDM-type 3D printer, The three-dimensional modeling soluble material includes a polyamide resin, and the polyamide resin includes a hydrophilic monomer unit A having a hydrophilic group, a hydrophobic dicarboxylic acid monomer unit B, and a hydrophobic diamine monomer unit C, and the polyamide The ratio of the hydrophilic monomer unit A to the total of all monomer units in the resin is 2.5 mol% or more and less than 13.5 mol%.

The three-dimensional object manufacturing method of the present invention includes a step of obtaining a three-dimensional object precursor including a three-dimensional object and a support material, and a support material for removing the support material by bringing the three-dimensional object precursor into contact with neutral water. It is a manufacturing method of the three-dimensional object by the FDM system which has a removal process, Comprising: The material of the said support material is the said soluble material for three-dimensional modeling.

The support material of the present invention is a support material that supports a three-dimensional object when the three-dimensional object is manufactured by an FDM-type 3D printer. The support material includes a polyamide resin, and the polyamide resin is hydrophilic. The hydrophilic monomer unit A having a hydrophobic group, the hydrophobic dicarboxylic acid monomer unit B, and the hydrophobic diamine monomer unit C, and the ratio of the hydrophilic monomer unit A to the total of all monomer units in the polyamide resin is 2 0.5 mol% or more and less than 13.5 mol%.

Detailed Description of the Invention

In the case where the methacrylic acid copolymer disclosed in JP-T-2012-509777 is used as a support material, it is necessary to use a strong alkaline aqueous solution to remove the support material from the three-dimensional object precursor. Strong alkaline aqueous solutions have a great risk to people and environmental burden. Further, when the three-dimensional object precursor is immersed in a strong alkaline aqueous solution for a long time, the three-dimensional object in the three-dimensional object precursor tends to be eroded by alkali, and polyester such as polylactic acid (PLA) having low resistance to alkali. Resins have limited application as materials for three-dimensional objects. Therefore, there has been a demand for a support material that is not a strong alkaline aqueous solution and can be removed by neutral water having a pH of 6 to 8.

In response to the above-mentioned problem, Japanese Patent Publication No. 2002-516346 discloses a method for removing a support material by immersing a three-dimensional object precursor in water using polyvinyl alcohol or the like soluble in water as the support material. ing. According to the technique described in JP-T-2002-516346, the support material for the three-dimensional object precursor can be removed without using a strong alkaline aqueous solution, but polyvinyl alcohol or the like has a high affinity for moisture. Therefore, when a three-dimensional modeling soluble material containing polyvinyl alcohol is exposed to high humidity, it absorbs moisture in the air. When a 3D modeling soluble material containing water-containing polyvinyl alcohol, etc. is heated / melted / launched / laminated with an FDM 3D printer, the water will evaporate due to high temperature and foam, thereby improving the accuracy of the 3D object. There were times when it was seriously damaged.

The present invention is suitable for the production of a three-dimensional object by the FDM method, has moisture absorption resistance, has a high dissolution rate in neutral water, and can be rapidly produced from a three-dimensional object precursor without using a strong alkaline aqueous solution. A three-dimensional modeling soluble material for a support material that can be removed is provided.

The present invention can suppress foaming by suppressing the deterioration of accuracy of a three-dimensional object even if it is used for production of a three-dimensional object by a 3D printer after being exposed to high humidity, and can be dissolved in neutral water. Provided is a method for producing a three-dimensional object which has a high speed and can quickly remove a support material from a three-dimensional object precursor without using a strong alkaline aqueous solution.

The present invention can suppress foaming by suppressing the deterioration of accuracy of a three-dimensional object even if it is used for production of a three-dimensional object by a 3D printer after being exposed to high humidity, and can be dissolved in neutral water. Provided is a support material that has a high speed and can be quickly removed from a three-dimensional object precursor without using a strong alkaline aqueous solution.

According to the present invention, it is suitable for production of a three-dimensional object by the FDM method, has moisture absorption resistance, has a high dissolution rate in neutral water, and can be used from a three-dimensional object precursor without using a strong alkaline aqueous solution. It is possible to provide a three-dimensional modeling soluble material for a support material that can be quickly removed.

According to the present invention, even if it is used for manufacturing a three-dimensional object by a 3D printer after being exposed to high humidity, it is possible to suppress foaming and suppress a decrease in accuracy of the three-dimensional object, and to neutral water. Thus, it is possible to provide a method for producing a three-dimensional object capable of rapidly removing the support material from the three-dimensional object precursor without using a strong alkaline aqueous solution.

According to the present invention, even if it is used for manufacturing a three-dimensional object by a 3D printer after being exposed to high humidity, it is possible to suppress foaming and suppress a decrease in accuracy of the three-dimensional object, and to neutral water. Thus, it is possible to provide a support material that can be rapidly removed from the three-dimensional object precursor without using a strong alkaline aqueous solution.

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

<Soluble materials for 3D modeling>
The soluble material for 3D modeling according to the present embodiment is a soluble material for 3D modeling used as a support material for supporting the 3D object when a 3D object is manufactured by an FDM 3D printer. The three-dimensional modeling soluble material includes a polyamide resin, and the polyamide resin includes a hydrophilic monomer unit A having a hydrophilic group, a hydrophobic dicarboxylic acid monomer unit B, and a hydrophobic diamine monomer unit C, The ratio of the hydrophilic monomer unit A to the total of all monomer units in the polyamide resin is 2.5 mol% or more and less than 13.5 mol%.

The support material made of the soluble material for three-dimensional modeling has moisture absorption resistance and has a high dissolution rate in neutral water, so that it can be quickly developed from a three-dimensional object precursor without using a strong alkaline aqueous solution. Can be removed. The reason why the three-dimensional modeling soluble material has such an effect is not clear, but is considered as follows.

The three-dimensional modeling soluble material of the present embodiment has a polyamide resin having a specific amount of the hydrophilic monomer unit A, and thus has high solubility in neutral water. Moreover, since the said polyamide resin has the hydrophobic dicarboxylic acid monomer unit B, its hygroscopic property is low. Since the three-dimensional modeling soluble material of this embodiment has such a polyamide resin, the support material containing the three-dimensional modeling soluble material has moisture absorption resistance and is soluble in neutral water. It is considered that the speed is high and it can be quickly removed from the three-dimensional object precursor without using an alkaline aqueous solution.

[Polyamide resin]
[Hydrophilic monomer unit A]
The polyamide resin has a hydrophilic monomer unit A having a hydrophilic group. The hydrophilic monomer unit A is not particularly limited as long as it is a monomer unit having a hydrophilic group. A monomer for inducing the hydrophilic monomer unit A is also referred to as monomer A.

The hydrophilic group includes a primary amino group, a secondary amino group, a tertiary amino group, from the viewpoint of solubility in neutral water and the ease of the polymerization reaction during the production of the polyamide resin. Examples thereof include at least one selected from the group consisting of a quaternary ammonium base, an oxyethylene group, a hydroxyl group, a carboxyl group, a carboxyl base, a phosphate group, a phosphate group, a sulfonate group, and a sulfonate group.

The secondary amino group is —NHR ¹ group (where R ¹ is linear or branched, from the viewpoint of solubility in neutral water and ease of polymerization reaction during the production of polyamide resin. At least one selected from the group consisting of a secondary amino group represented by (II) and a secondary amino group represented by —NH— group.

The tertiary amino group is a —NR ² R ³ group (provided that R ² is linear or branched from the viewpoint of solubility in neutral water and ease of polymerization reaction during the production of polyamide resin. Jo having 1 to 4 carbon indicates an alkyl group, R ³ is a tertiary amino group represented by denotes a straight or branched carbon atoms 1 to 14 alkyl group.), and -NR ^At least one selected from the group consisting of tertiary amino groups represented by a ⁴ -group (wherein R ⁴ represents a linear or branched alkyl group having 1 to 4 carbon atoms) is preferred. .

The quaternary ammonium base is —N ⁺ {R ⁵ R ⁶ R ⁷ } · X ⁻ (where, from the viewpoint of solubility in neutral water and ease of polymerization reaction during the production of polyamide resin. R ⁵ , R ⁶ and R ⁷ each independently represent a hydrogen atom or an alkyl group having 1 to 14 carbon atoms, and X ⁻ represents a hydroxy ion, a halogen ion, CH ₃ SO ₄ ^— or CH ₃ CH ₂ SO. ₄ ^- at least one or more preferably selected from the group consisting of quaternary ammonium base represented by the illustrated)..

The oxyethylene group is — {CH ₂ CH ₂ O} _n — (where n represents an average number) from the viewpoint of solubility in neutral water and the ease of polymerization reaction during the production of polyamide resin. An oxyethylene group represented by a number of 1 to 2500, preferably 2 to 1000, more preferably 3 to 100, and still more preferably 4 to 50, and — {CH ₂ CH ₂ O } _m -R ⁸ (although, m represents the average number indicates the number of 1 or more 2500 or less, preferably 2 to 1,000, more preferably 3 or more and 100 or less, still more preferably .R ⁸ is 4 or more and 50 or less A hydrogen atom or a linear or branched alkyl group having 1 to 10 carbon atoms, more preferably 2 or more and 6 or less, and further preferably 3 or more and 5 or less. That at least one or more preferably selected from the group.

The carboxyl base is —COOM ¹ (where M ¹ represents a counter ion of the carboxyl group constituting the carboxyl base, from the viewpoint of solubility in neutral water and the ease of the polymerization reaction during the production of the polyamide resin. In view of solubility in neutral water, at least one selected from the group consisting of sodium ions, potassium ions, lithium ions, calcium ions, magnesium ions, ammonium ions, barium ions, and zinc ions is preferable, sodium More preferably, at least one selected from the group consisting of ions, potassium ions, lithium ions, magnesium ions, and ammonium ions, more preferably at least one selected from the group consisting of sodium ions and potassium ions, sodium ions Gayo Further preferred.) Carboxyl base is preferably represented by.

The phosphate group is —PO ₄ M ² ₂ , —PO ₄ HM ² , and —PO ₄ M ² from the viewpoint of solubility in neutral water and the ease of polymerization reaction during the production of polyamide resin. (However, M ² represents a counter ion of a phosphate group constituting a phosphate group, and from the viewpoint of solubility in neutral water, sodium ion, potassium ion, lithium ion, calcium ion, magnesium ion, ammonium ion, barium. Preferably at least one selected from the group consisting of ions and zinc ions, more preferably at least one selected from the group consisting of sodium ions, potassium ions, lithium ions, magnesium ions, and ammonium ions, sodium ions, And at least one selected from the group consisting of potassium ions is more preferred. Ku, at least one or more preferably sodium ion is selected from the group consisting of phosphoric acid base represented by even more preferred.).

From the viewpoint of solubility in neutral water and the ease of the polymerization reaction during the production of polyamide resin, the sulfonate group is —SO ₃ M ³ (where M ³ is a sulfonic acid constituting the sulfonate group). At least one selected from the group consisting of sodium ion, potassium ion, lithium ion, calcium ion, magnesium ion, ammonium ion, barium ion, and zinc ion from the viewpoint of solubility in neutral water Or more, preferably at least one selected from the group consisting of sodium ions, potassium ions, lithium ions, magnesium ions, and ammonium ions, and more preferably at least one selected from the group consisting of sodium ions and potassium ions. More preferably, sodium ions are more Preferred.) Sulfonate is preferably represented by.

The monomer A is a carboxylic acid from the viewpoint of solubility in neutral water, the viewpoint of moisture absorption resistance, the viewpoint of heat resistance required for modeling by a 3D printer, and the ease of polymerization reaction during the production of polyamide resin. , At least one selected from the group consisting of amines and amino acids is preferred, and carboxylic acids are more preferred. Among the carboxylic acids, aromatic carboxylic acids are preferable from the same viewpoint, and hydroxy group-containing aromatic dicarboxylic acid, primary amino group-containing aromatic dicarboxylic acid, sulfonic acid group-containing aromatic dicarboxylic acid, and sulfonate group-containing Aromatic dicarboxylic acids are more preferred. Among these, from the same viewpoint, 5-hydroxyisophthalic acid, 1,3,5-benzenetricarboxylic acid, 5-aminoisophthalic acid, 5-sulfoisophthalic acid, 2-sulfoterephthalic acid, and 4-sulfo-2,6- At least one selected from the group consisting of naphthalenedicarboxylic acid is preferable, at least one selected from the group consisting of 5-sulfoisophthalic acid and 2-sulfoterephthalic acid is more preferable, and 5-sulfoisophthalic acid is more preferable. .

From the viewpoint of solubility in neutral water, the content of the hydrophilic group in the polyamide resin is preferably 0.5 mmol / g or more, more preferably 0.6 mmol / g or more, and 0.7 mmol / g or more. Is more preferable, and from the viewpoint of moisture absorption resistance and from the viewpoint of heat resistance required for modeling by a 3D printer, it is preferably less than 1.0 mmol / g, preferably 0.8 mmol / g or less, and more preferably 0.75 mmol / g or less. preferable. In addition, in this specification, content of a hydrophilic group is measured by the method as described in an Example.

The ratio of the substance amount of the hydrophilic monomer unit A to the total substance amount of all the monomer units in the polyamide resin is 2.5 mol% or more from the viewpoint of solubility in neutral water, and 4 mol% or more. Is preferably 6 mol% or more, more preferably 8 mol% or more, still more preferably 10 mol% or more, and from the viewpoint of moisture absorption resistance and the heat resistance required for modeling by a 3D printer, less than 13.5 mol% 11.5 mol% or less is preferable, 10.0 mol% or less is more preferable, and 9.5 mol% or less is still more preferable. In the present specification, the composition of the monomer unit of the polyamide resin is measured by the method described in the examples.

[Hydrophobic dicarboxylic acid monomer unit B]
The polyamide resin has a hydrophobic dicarboxylic acid monomer unit B. The dicarboxylic acid monomer unit B does not have the hydrophilic group. In this specification, the dicarboxylic acid for deriving the hydrophobic dicarboxylic acid monomer unit B is also referred to as dicarboxylic acid B.

The dicarboxylic acid B is not particularly limited as long as it is a dicarboxylic acid, but from the viewpoint of solubility in neutral water, from the viewpoint of moisture absorption resistance, from the viewpoint of heat resistance required for modeling by a 3D printer, and during polyamide resin production From the viewpoint of ease of polymerization reaction, at least one selected from the group consisting of aromatic dicarboxylic acids, aliphatic dicarboxylic acids, and alicyclic dicarboxylic acids is preferred. Among these, from the same viewpoint, the group consisting of terephthalic acid, isophthalic acid, 2,5-furandicarboxylic acid, 2,6-naphthalenedicarboxylic acid, 1,4-cyclohexanedicarboxylic acid, and 1,3-adamantanedicarboxylic acid More preferably, at least one selected from the group consisting of terephthalic acid, 2,5-furandicarboxylic acid, and 2,6-naphthalenedicarboxylic acid is more preferable, and terephthalic acid is still more preferable. .

The ratio of the substance amount of the hydrophobic dicarboxylic acid monomer unit B in the polyamide resin to the total substance amount of all monomer units in the polyamide resin is preferably 10 mol% or more from the viewpoint of moisture absorption resistance, and is 20 mol%. The above is more preferable, 30 mol% or more is further preferable, 35 mol% or more is more preferable, 40 mol% or more is further more preferable, 42 mol% or more is further more preferable, and 47.5 mol from the viewpoint of solubility in neutral water. % Or less, more preferably 45 mol% or less, still more preferably 42 mol% or less, and even more preferably 40 mol% or less. Further, the ratio of the substance amount of the hydrophobic dicarboxylic acid monomer unit B in the polyamide resin to the total substance amount of all the monomer units in the polyamide resin is determined in terms of moisture absorption resistance and dissolved in neutral water. From the viewpoint of safety, 10 to 47.5 mol% is preferable, 20 to 45 mol% is more preferable, and 30 to 42 mol% is still more preferable.

The molar ratio of the hydrophilic monomer unit A to the hydrophobic dicarboxylic acid monomer unit B (the hydrophilic monomer unit A / the hydrophobic dicarboxylic acid monomer unit B) is determined by solubility in neutral water, moisture absorption resistance, and From the viewpoint of heat resistance required for modeling by a 3D printer, 10/90 or more is preferable, 15/85 or more is more preferable, 18/82 or more is further preferable, 20/80 or more is further more preferable, and the same viewpoint 27 / 73 is preferable, 25/75 or less is more preferable, and 21/79 or less is still more preferable.

[Hydrophobic diamine monomer unit C]
The polyamide resin has a hydrophobic diamine monomer unit C. The hydrophobic diamine monomer unit C does not have the hydrophilic group. The diamine for deriving the hydrophobic diamine monomer unit C is also referred to as diamine C.

The diamine C is not particularly limited, and at least one selected from the group consisting of aliphatic diamines, alicyclic diamines, and aromatic diamines can be used, and the ease of the polymerization reaction during polyamide resin production. In view of the above, an aliphatic diamine is preferable.

The number of carbon atoms of the diamine C is from the viewpoint of solubility in neutral water, from the viewpoint of moisture absorption resistance, from the viewpoint of heat resistance required for modeling by a 3D printer, and from the viewpoint of ease of polymerization reaction when producing a polyamide resin. 2 or more, preferably 3 or more, more preferably 4 or more, from the viewpoint of solubility in neutral water, the viewpoint of moisture absorption resistance, and the heat resistance required for modeling by a 3D printer, 20 or less Is preferably 15 or less, more preferably 10 or less.

Examples of the aliphatic diamine include ethylene diamine, trimethylene diamine, tetramethylene diamine, pentamethylene diamine, hexamethylene diamine, heptamethylene diamine, octamethylene diamine, nonane diamine, and decane diamine. Among these, hexamethylenediamine is preferable from the viewpoints of solubility in neutral water, moisture absorption resistance, and toughness (strength) required for modeling by a 3D printer.

Examples of the alicyclic diamine include 4,4'-diamino-3,3'-dimethyldicyclohexylmethane, diaminecyclohexane, and isophoronediamine. Among these, at least one selected from the group consisting of diamine cyclohexane and isophorone diamine is preferable from the viewpoint of solubility in neutral water, moisture absorption resistance, and toughness (strength) required for modeling by a 3D printer. More preferred is diamine cyclohexane.

Examples of the aromatic diamine include phenylenediamine, diethyltoluenediamine, and 4,4'-diaminodiphenylmethane. Among these, at least one or more selected from the group consisting of phenylenediamine and diethyltoluenediamine is preferable from the viewpoints of solubility in neutral water, moisture absorption resistance, and toughness (strength) required for modeling by a 3D printer. More preferred is phenylenediamine.

The diamine C is at least selected from the group consisting of hexamethylenediamine, diaminecyclohexane, and phenylenediamine from the viewpoint of solubility in neutral water, moisture absorption resistance, and toughness (strength) required for modeling by a 3D printer. One or more are preferable, at least one selected from the group consisting of hexamethylenediamine and phenylenediamine is more preferable, and hexamethylenediamine is still more preferable.

When the diamine C is at least one selected from the group consisting of hexamethylene diamine, diamine cyclohexane, and phenylene diamine, hexamethylene diamine, diamine cyclohexane, phenylene with respect to the total amount of all diamine monomer units in the polyamide resin. The total proportion of the diamine substances is preferably 50 mol% or more, more preferably 70 mol% or more, and 80 mol% from the viewpoints of solubility in neutral water, moisture absorption resistance, and heat resistance required for modeling by a 3D printer. % Or more is more preferable, 90 mol% or more is more preferable, substantially 100 mol% is still more preferable, and 100 mol% is still more preferable. In addition, substantially 100 mol% means the case where substances other than hexamethylene diamine, diamine cyclohexane, and phenylene diamine are inevitably mixed.

The polyamide resin can be exemplified by the following general formulas (1) to (6).

(In the general formula (1), p1 and q1 each represent the number of polymerization degrees. Each polymerization is a block bond and / or a random bond, and a random bond is more preferable from the viewpoint of solubility in neutral water. )

(In the general formula (2), p2 and q2 each represent the number of polymerization degrees. Each polymerization is a block bond and / or a random bond, and a random bond is more preferable from the viewpoint of solubility in neutral water. )

(In the general formula (3), p3 and q3 each represent the number of polymerization degrees. Each polymerization is a block bond and / or a random bond, and a random bond is more preferable from the viewpoint of solubility in neutral water. )

(In the general formula (4), p4 and q4 each represent the number of polymerization degrees. Each polymerization is a block bond and / or a random bond, and a random bond is more preferable from the viewpoint of solubility in neutral water. )

(In the general formula (5), p5 and q5 each represent the number of polymerization degrees. Each polymerization is a block bond and / or a random bond, and a random bond is more preferable from the viewpoint of solubility in neutral water. )

(In the general formula (6), p6 and q6 each represent the number of polymerization degrees. Each polymerization is a block bond and / or a random bond, and a random bond is more preferable from the viewpoint of solubility in neutral water. )

The weight average molecular weight of the polyamide resin is preferably 3000 or more, more preferably 3500 or more, still more preferably 4000 or more, and solubility in neutral water, from the viewpoint of improving toughness required for a three-dimensional modeling soluble material. And 70000 or less, more preferably 50000 or less, still more preferably 30000 or less, and even more preferably 20000 or less, from the viewpoint of formability by a 3D printer. In addition, in this specification, a weight average molecular weight is measured by the method as described in an Example.

The glass transition temperature of the polyamide resin is preferably 50 ° C. or higher, more preferably 60 ° C. or higher, still more preferably 70 ° C. or higher, still more preferably 80 ° C. or higher, from the same viewpoint, from the viewpoint of formability by a 3D printer. 250 ° C. or lower is preferable, and 220 ° C. or lower is more preferable. In addition, in this specification, a glass transition temperature is measured by the method as described in an Example.

The polyamide resin may have a monomer unit other than the monomer unit A, the dicarboxylic acid monomer unit B, and the diamine monomer unit C as long as the effects of the present embodiment are not impaired.

The method for producing the polyamide resin is not particularly limited, and a conventionally known method for producing a polyamide resin can be applied.

The content of the polyamide resin in the soluble material for three-dimensional modeling can be adjusted within a range that does not impair the effect of the present embodiment, but it is soluble in neutral water, moisture absorption resistance, and depending on the 3D printer. From the viewpoint of heat resistance required for modeling, it is preferably 30% by mass or more, more preferably 50% by mass or more, still more preferably 60% by mass or more, still more preferably 70% by mass or more, and even more preferably 80% by mass or more. 90 mass% or more is still more preferable, 95 mass% or more is further more preferable, substantially 100 mass% is still more preferable, and 100 mass% is still more preferable. In addition, substantially 100 mol% means that a substance other than the polyamide resin is inevitably mixed.

The glass transition temperature of the soluble material for three-dimensional modeling is preferably 50 ° C. or higher, more preferably 60 ° C. or higher, still more preferably 70 ° C. or higher, and still more preferably 80 ° C. or higher, from the viewpoint of formability by a 3D printer. From the same viewpoint, 250 ° C. or lower is preferable, and 220 ° C. or lower is more preferable.

The shape of the soluble material for three-dimensional modeling is not particularly limited, and examples thereof include a pellet shape, a powder shape, and a filament shape, but a filament shape is preferable from the viewpoint of modeling by a 3D printer.

The diameter of the filament is preferably 0.5 mm or more, more preferably 1.0 mm or more, and preferably 3.0 mm or less from the same viewpoint, from the viewpoints of formability by a 3D printer and improvement of accuracy of a three-dimensional object. 0 mm or less is more preferable, and 1.8 mm or less is still more preferable. Moreover, when producing a filament, it is preferable to perform an extending | stretching process from a viewpoint of improving toughness. The draw ratio in the drawing process is preferably 1.5 times or more, more preferably 2 times or more, more preferably 3 times or more, still more preferably 5 times or more, and the same viewpoint from the viewpoint of both toughness improvement and water solubility. To 200 times or less, more preferably 150 times or less, still more preferably 100 times or less, and even more preferably 50 times or less. Moreover, the extending | stretching temperature in the said extending | stretching process has the preferable inside of the range of the temperature 110 degreeC higher than the said glass transition temperature from the temperature 20 degreeC lower than the glass transition temperature of the said soluble material for three-dimensional modeling. The lower limit of the stretching temperature is preferably 10 ° C. lower than the glass transition temperature from the viewpoint of toughness improvement and thermal stability, and more preferably the same temperature as the glass transition temperature. From the same viewpoint, the upper limit of the stretching temperature is more preferably 110 ° C. higher than the glass transition temperature, more preferably 100 ° C. higher than the glass transition temperature, and still more preferably 90 ° C. higher than the glass transition temperature. The stretching may be performed while air cooling when the resin is discharged from the extruder, or may be heated by hot air or a laser. Moreover, the said extending | stretching may be extended | stretched to a predetermined draw ratio and a filament diameter in one step, and may be extended to a predetermined draw ratio and a filament diameter in multiple steps.

The three-dimensional modeling soluble material may contain a polymer other than the polyamide resin for the purpose of improving the physical properties of the three-dimensional modeling soluble material as long as the effects of the present embodiment are not impaired. Examples of such polymers include water-soluble polymers such as polyvinyl alcohol, polyethylene glycol, poly (ethylene glycol / propylene glycol), carboxymethylcellulose, and starch; hydrophobic polymers such as polymethyl methacrylate; hard segments and soft Segmented polyether ester, polyether ester amide, polyurethane and other elastomers, block copolymers of ionic monomers and water-soluble nonionic monomers and hydrophobic monomers, styrene-butadiene, alkyl methacrylates (1-18 carbon atoms) ) -A thermoplastic elastomer composed of alkyl acrylate (having 1 to 18 carbon atoms); a graft polymer obtained by grafting a polymer such as polyacrylic acid or N, N-dimethylacrylamide onto a hydrophobic rubber; Graft polymer such as graft polymer obtained by grafting polyoxazoline or N, N-dimethylacrylamide onto silicone; monomer having carboxyl group such as acrylic acid or methacrylic acid; monomer having epoxy group such as glycidyl methacrylate; N, N— Examples thereof include copolymers of ethylene and alkyl acrylates (having 1 to 18 carbon atoms) copolymerized with monomers having an amide group such as dimethylacrylamide; impact buffers such as acrylic rubber and natural rubber latex.

When the three-dimensional modeling soluble material contains a polymer other than the polyamide resin, the affinity and compatibility between the polymer and the polyamide resin are increased to improve the performance of the three-dimensional modeling soluble material and the three-dimensional modeling solubility. From the viewpoint of improving the toughness of the filament according to the material, the three-dimensional modeling soluble material can contain a compatibilizing agent. Examples of the compatibilizer include (i) a monomer having a glycidyl group, an isocyanate group, an epoxy group, an oxazoline group, and / or a monomer having an acid anhydride structure such as maleic anhydride, and acrylic acid or alkyl methacrylate. A copolymer with ethylene, propylene, vinyl acetate, etc., (ii) a block copolymer comprising two or more of the polymers shown below; polyester, polyamide, and acrylic acid, methacrylic acid, acrylic acid or alkyl methacrylate A polymer / copolymer comprising at least one monomer selected from acrylamide, N, N-dimethylacrylamide, ethylene, propylene, butadiene, isopropylene, vinyl acetate, ethylene glycol, or propylene glycol, and (iii) A group consisting of two or more of the indicated polymers Raft copolymer; polyester, polyamide, acrylic acid, methacrylic acid, acrylic acid or alkyl methacrylate, acrylamide, N, N-dimethylacrylamide, ethylene, propylene, butadiene, isopropylene, vinyl acetate, ethylene glycol, or propylene And a polymer / copolymer comprising at least one monomer selected from glycols, and (iv) a surfactant.

The soluble material for three-dimensional modeling may contain other components as long as the effects of the present embodiment are not impaired. Examples of the other components include polyamide resins other than the above polyamide resins, polymers other than polyamide resins, plasticizers such as polyalkylene glycol diesters of benzoic acid, calcium carbonate, magnesium carbonate, glass balls, graphite, carbon black, carbon Examples thereof include fillers such as fiber, glass fiber, talc, wollastonite, mica, alumina, silica, kaolin, whisker, and silicon carbide.

<Method of manufacturing a three-dimensional object>
The method for producing a three-dimensional object according to this embodiment includes a step of obtaining a three-dimensional object precursor including a three-dimensional object and a support material, and a support for removing the support material by bringing the three-dimensional object precursor into contact with neutral water. It is a manufacturing method of the three-dimensional object by the hot melt lamination system which has a material removal process, Comprising: The material of the said support material is the said soluble material for three-dimensional modeling. According to the method of manufacturing a three-dimensional object, foaming can be suppressed even when used for manufacturing a three-dimensional object by a 3D printer after being exposed to high humidity, and a decrease in accuracy of the three-dimensional object can be suppressed. The support material can be quickly removed from the three-dimensional object precursor without using a strong alkaline aqueous solution because of its high dissolution rate in neutral water. The reason why the manufacturing method of the three-dimensional object has such an effect is not clear, but the same reason as the reason why the soluble material for three-dimensional modeling has the effect can be considered.

[Step of obtaining a three-dimensional object precursor including a three-dimensional object and a support material]
The step of obtaining a three-dimensional object precursor including a three-dimensional object and a support material is performed in a three-dimensional manner using a known hot-melt lamination type 3D printer except that the material of the support material is the soluble material for three-dimensional modeling. A step of obtaining a three-dimensional object precursor including a three-dimensional object and a support material in the object manufacturing method 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. The molding material includes ABS resin, polylactic acid resin, polycarbonate resin, 12-nylon, 6,6-nylon, 6-nylon, polyphenylsulfone resin, polyetheretherketone, and polyetherimide. Among these, ABS resin and / or polylactic acid resin are more preferable, and ABS resin is more preferable from the viewpoint of the formability by a 3D printer.

[Support material removal process to remove the support material by bringing the three-dimensional object precursor into contact with neutral water]
In the support material removing step, the support material is removed by bringing the three-dimensional object precursor into contact with neutral water. The method of bringing the three-dimensional object precursor into contact with neutral water is preferably a method of immersing the three-dimensional object precursor in neutral water from the viewpoint of cost and ease of work. 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.

[Neutral water]
Examples of the neutral water include ion-exchanged water, pure water, tap water, and industrial water, but ion-exchanged water and tap water are preferable from the viewpoint of economy. Moreover, the neutral water may contain the water-soluble organic solvent in the range which does not damage the shaped three-dimensional object. Examples of water-soluble organic solvents include lower alcohols such as methanol, ethanol and 2-propanol, glycol ethers such as propylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monotertiary butyl ether and diethylene glycol monobutyl ether, acetone and methyl ethyl ketone. And ketones. When the neutral water contains the water-soluble organic solvent, the content of the water-soluble organic solvent in the neutral water is preferably 0.1% by mass or more from the viewpoint of solubility and damage to the shaped three-dimensional object, 0.5% by mass or more is more preferable, 1% by mass or more is further preferable, 3% by mass or more is further preferable, 50% by mass or less is preferable, 40% by mass or less is more preferable, and 30% by mass or less is more preferable. 20% by mass or less is even more preferable.

The amount of the neutral water used is preferably 10 times by mass or more, more preferably 20 times by mass or more with respect to the support material from the viewpoint of solubility of the support material, and 10,000 from the support material from the viewpoint of economy. The mass times or less are preferable, the 5000 mass times or less are more preferable, the 1000 mass times or less are more preferable, and the 100 mass times or less are more preferable.

The time for bringing the soluble material for 3D modeling into contact with neutral water is preferably 5 minutes or more from the viewpoint of the removability of the support material, and reducing damage to the 3D object by contacting with neutral water for a long time. From the viewpoint of viewpoint and economy, it is preferably 180 minutes or shorter, more preferably 120 minutes or shorter, and even more preferably 90 minutes or shorter. The cleaning temperature is preferably 15 ° C. or higher, more preferably 25 ° C. or higher, from the viewpoint of removal of the support material, reduction of damage to the three-dimensional object, and economy, although it depends on the type of model material. More preferably, the temperature is more preferably 40 ° C. or more, more preferably 40 ° C. or more, and from the same viewpoint, 85 ° C. or less is preferable, and 70 ° C. or less is more preferable.

<Support material>
The support material of the present embodiment is a support material that supports a three-dimensional object when the three-dimensional object is manufactured by a hot melt lamination type 3D printer, and includes the polyamide resin. The support material can suppress foaming and suppress deterioration in accuracy of a three-dimensional object even when used for manufacturing a three-dimensional object by a 3D printer after being exposed to high humidity. The dissolution rate is high, and the support material can be quickly removed from the three-dimensional object precursor without using a strong alkaline aqueous solution. The reason why the support material has such an effect is not certain, but the same reason as the reason why the soluble material for three-dimensional modeling has the effect can be considered.

Regarding the above-described embodiment, the present specification further discloses the following composition and production method.

<1> A three-dimensional modeling soluble material used as a material of a support material for supporting a three-dimensional object when a three-dimensional object is manufactured by a hot melt lamination type 3D printer, The material includes a polyamide resin, and the polyamide resin has a hydrophilic monomer unit A having a hydrophilic group, a hydrophobic dicarboxylic acid monomer unit B, and a hydrophobic diamine monomer unit C, and all the monomer units in the polyamide resin The three-dimensional modeling soluble material, wherein the ratio of the hydrophilic monomer unit A to the total is 2.5 mol% or more and less than 13.5 mol%.
<2> The hydrophilic group is a primary amino group, a secondary amino group, a tertiary amino group, a quaternary ammonium base, an oxyethylene group, a hydroxyl group, a carboxyl group, a carboxyl base, a phosphate group, The soluble material for three-dimensional modeling according to <1>, comprising at least one selected from the group consisting of a phosphate group, a sulfonate group, and a sulfonate group.
<3> A secondary amino group in which the secondary amino group is represented by —NHR ¹ group (wherein R ¹ represents a linear or branched alkyl group having 1 to 14 carbon atoms). And at least one selected from the group consisting of secondary amino groups represented by —NH— groups, is preferably the soluble material for three-dimensional modeling according to <2>.
<4> The tertiary amino group is a —NR ² R ³ group (wherein R ² represents a linear or branched alkyl group having 1 to 4 carbon atoms, and R ³ represents a linear or branched group. And a —NR ⁴ — group (wherein R ⁴ is a linear or branched carbon group having 1 to 4 carbon atoms). The soluble material for three-dimensional modeling according to <2> or <3>, wherein at least one selected from the group consisting of a tertiary amino group represented by:
<5> The quaternary ammonium base is —N ⁺ {R ⁵ R ⁶ R ⁷ } · X ⁻ (where R ⁵ , R ⁶ and R ⁷ are each independently a hydrogen atom or a carbon number of 1 or more and 14 X ⁻ represents a hydroxy ion, a halogen ion, CH ₃ SO ₄ ^— or CH ₃ CH ₂ SO ₄ ^— )), and at least selected from the group consisting of quaternary ammonium bases The soluble material for three-dimensional modeling according to any one of <2> to <4>, preferably one or more.
<6> The oxyethylene group is — {CH ₂ CH ₂ O} _n — (where n represents an average number, represents a number of 1 to 2500, preferably 2 to 1000, preferably 3 to 100 More preferably 4 or more and 50 or less), and — {CH ₂ CH ₂ O} _m —R ⁸ (where m represents an average number and 1 or more and 2500 or less). It is preferably 2 or more and 1000 or less, more preferably 3 or more and 100 or less, and still more preferably 4 or more and 50 or less, and R ⁸ represents a hydrogen atom or a linear or branched alkyl group having 1 to 10 carbon atoms. Or more, preferably 6 or less, more preferably 3 or more and 5 or less.) At least one selected from the group consisting of oxyethylene groups represented by the formula (2) to <5> is preferred. Three-dimensional modeling for the soluble material of the mounting.
<7> The carboxyl base is —COOM ¹ (where M ¹ represents a counter ion of the carboxyl group constituting the carboxyl base, and sodium ion, potassium ion, lithium ion, calcium from the viewpoint of solubility in neutral water) At least one selected from the group consisting of ions, magnesium ions, ammonium ions, barium ions, and zinc ions is preferred, and at least one selected from the group consisting of sodium ions, potassium ions, lithium ions, magnesium ions, and ammonium ions. More preferably, at least one selected from the group consisting of sodium ions and potassium ions is more preferable, and sodium ions are more preferable. <2> to <6> No Three-dimensional modeling for the soluble material according to any Re.
<8> The phosphate group is —PO ₄ M ² ₂ , —PO ₄ HM ² , or —PO ₄ M ² (where M ² represents a counter ion of a phosphate group constituting the phosphate group, From the viewpoint of solubility in basic water, at least one selected from the group consisting of sodium ion, potassium ion, lithium ion, calcium ion, magnesium ion, ammonium ion, barium ion, and zinc ion is preferable. Sodium ion, potassium At least one selected from the group consisting of ions, lithium ions, magnesium ions, and ammonium ions is more preferable, at least one selected from the group consisting of sodium ions and potassium ions is more preferable, and sodium ions are even more preferable. Preferably). More least one preferably selected, <2> to <7> 3D modeling for soluble material as claimed in any one.
<9> The sulfonate group is —SO ₃ M ³ (wherein M ³ represents a counter ion of a sulfonate group constituting the sulfonate group, and from the viewpoint of solubility in neutral water, sodium ion and potassium ion) And preferably at least one selected from the group consisting of lithium ions, calcium ions, magnesium ions, ammonium ions, barium ions, and zinc ions, and a group consisting of sodium ions, potassium ions, lithium ions, magnesium ions, and ammonium ions At least one selected from the group consisting of sodium ions and potassium ions is more preferable, and sodium ions are more preferable. Any of 2> to <8> Three-dimensional modeling for the soluble material described.
<10> The monomer A for deriving the hydrophilic monomer unit A is preferably at least one selected from the group consisting of carboxylic acid, amine and amino acid, more preferably carboxylic acid, <1> to <9> The soluble material for three-dimensional modeling according to any one of the above.
<11> The carboxylic acid is preferably an aromatic carboxylic acid, a hydroxy group-containing aromatic dicarboxylic acid, a primary amino group-containing aromatic dicarboxylic acid, a sulfonic acid group-containing aromatic dicarboxylic acid, and a sulfonate group-containing aromatic. More preferred are dicarboxylic acids, such as 5-hydroxyisophthalic acid, 1,3,5-benzenetricarboxylic acid, 5-aminoisophthalic acid, 5-sulfoisophthalic acid, 2-sulfoterephthalic acid, and 4-sulfo-2,6-naphthalene. At least one selected from the group consisting of dicarboxylic acids is more preferable, at least one selected from the group consisting of 5-sulfoisophthalic acid and 2-sulfoterephthalic acid is still more preferable, and 5-sulfoisophthalic acid is more preferable. More preferably, the soluble material for three-dimensional modeling according to <10>.
<12> The hydrophilic group content in the polyamide resin is preferably 0.5 mmol / g or more, more preferably 0.6 mmol / g or more, still more preferably 0.7 mmol / g or more, and 1.0 mmol / The soluble material for three-dimensional modeling according to any one of <1> to <11>, preferably less than g, more preferably 0.8 mmol / g or less, and still more preferably 0.75 mmol / g or less.
<13> The ratio of the substance amount of the hydrophilic monomer unit A to the total substance amount of all monomer units in the polyamide resin is 2.5 mol% or more, preferably 4 mol% or more, more preferably 6 mol% or more. Preferably, 8 mol% or more is more preferable, 10 mol% or more is more preferable, less than 13.5 mol%, 11.5 mol% or less is preferable, 10.0 mol% or less is more preferable, and 9.5 mol% or less is more preferable. <3> The soluble material for three-dimensional modeling according to any one of <1> to <12>.
<14> The dicarboxylic acid B for deriving the hydrophobic dicarboxylic acid monomer unit B is preferably at least one selected from the group consisting of aromatic dicarboxylic acids, aliphatic dicarboxylic acids, and alicyclic dicarboxylic acids, At least one selected from the group consisting of terephthalic acid, isophthalic acid, 2,5-furandicarboxylic acid, 2,6-naphthalenedicarboxylic acid, 1,4-cyclohexanedicarboxylic acid, and 1,3-adamantanedicarboxylic acid is more Preferably, at least one selected from the group consisting of terephthalic acid, 2,5-furandicarboxylic acid, and 2,6-naphthalenedicarboxylic acid is more preferable, and terephthalic acid is still more preferable. Any of <1> to <13> The soluble material for three-dimensional modeling described in Crab.
<15> The ratio of the substance amount of the hydrophobic dicarboxylic acid monomer unit B in the polyamide resin to the total substance amount of all monomer units in the polyamide resin is preferably 10 mol% or more, more preferably 20 mol% or more. 30 mol% or more, more preferably 35 mol% or more, still more preferably 40 mol% or more, still more preferably 42 mol% or more, further preferably 47.5 mol% or less, more preferably 45 mol% or less, and 42 mol% or less. Is more preferably 40 mol% or less, more preferably 10 to 47.5 mol%, more preferably 20 to 45 mol%, still more preferably 30 to 42 mol%, <3> according to any one of <1> to <14> Soluble material for original modeling.
<16> The molar ratio of the hydrophilic monomer unit A to the hydrophobic dicarboxylic acid monomer unit B (the hydrophilic monomer unit A / the hydrophobic dicarboxylic acid monomer unit B) is preferably 10/90 or more, and 15/85 The above is more preferable, 18/82 or more is further preferable, 20/80 or more is more preferable, less than 27/73 is preferable, 25/75 or less is more preferable, and 21/79 or less is more preferable, <1> to <15> The soluble material for three-dimensional modeling according to any one of the above.
<17> The diamine C for deriving the hydrophobic diamine monomer unit C is preferably at least one selected from the group consisting of an aliphatic diamine, an alicyclic diamine, and an aromatic diamine, and more preferably an aliphatic diamine. The three-dimensional modeling soluble material according to any one of <1> to <16>.
<18> The carbon number of the diamine C for deriving the hydrophobic diamine monomer unit C is preferably 2 or more, more preferably 3 or more, still more preferably 4 or more, preferably 20 or less, more preferably 15 or less, The soluble material for three-dimensional modeling according to any one of <1> to <17>, further preferably 10 or less.
<19> The aliphatic diamine is at least one selected from the group consisting of ethylenediamine, trimethylenediamine, tetramethylenediamine, pentamethylenediamine, hexamethylenediamine, heptamethylenediamine, octamethylenediamine, nonanediamine, and decanediamine. The soluble material for three-dimensional modeling according to <17> or <18>, wherein hexamethylenediamine is more preferable.
<20> The alicyclic diamine is preferably at least one selected from the group consisting of 4,4′-diamino-3,3′-dimethyldicyclohexylmethane, diaminecyclohexane and isophoronediamine, and diaminecyclohexane and isophorone. The soluble material for three-dimensional modeling according to any one of <17> to <19>, wherein at least one selected from the group consisting of diamines is more preferable, and diaminecyclohexane is more preferable.
<21> The aromatic diamine is preferably at least one selected from the group consisting of phenylenediamine, diethyltoluenediamine, and 4,4′-diaminodiphenylmethane, and at least selected from the group consisting of phenylenediamine and diethyltoluenediamine. The soluble material for three-dimensional modeling according to any one of <17> to <20>, wherein one or more are more preferable, and phenylenediamine is more preferable.
<22> The diamine C for deriving the hydrophobic diamine monomer unit C is preferably at least one selected from the group consisting of hexamethylene diamine, diamine cyclohexane and phenylene diamine, and a group consisting of hexamethylene diamine and phenylene diamine. The soluble material for three-dimensional modeling according to any one of <1> to <21>, wherein at least one selected from the above is more preferable, and hexamethylenediamine is further preferable.
<23> When the diamine C for deriving the hydrophobic diamine monomer unit C is at least one selected from the group consisting of hexamethylene diamine, diamine cyclohexane and phenylene diamine, all diamine monomer units in the polyamide resin The ratio of the total amount of hexamethylenediamine, diaminecyclohexane, and phenylenediamine to the total amount of these is preferably 50 mol% or more, more preferably 70 mol% or more, still more preferably 80 mol% or more, and more preferably 90 mol% or more. More preferably, the soluble material for three-dimensional modeling according to any one of <1> to <22>, which is substantially more preferably 100 mol%, still more preferably 100 mol%.
<24> The three-dimensional modeling soluble material according to any one of <1> to <23>, wherein the polyamide resin is preferably at least one selected from the group consisting of the following general formulas (1) to (6).

(In the general formula (6), p6 and q6 each represent the number of polymerization degrees. Each polymerization is a block bond and / or a random bond, and a random bond is more preferable from the viewpoint of solubility in neutral water. )
<25> The weight average molecular weight of the polyamide resin is preferably 3000 or more, more preferably 3500 or more, further preferably 4000 or more, preferably 70000 or less, more preferably 50000 or less, still more preferably 30000 or less, and more preferably 20000 or less. More preferably, the soluble material for three-dimensional modeling according to any one of <1> to <24>.
<26> The glass transition temperature of the polyamide resin is preferably 50 ° C. or higher, more preferably 60 ° C. or higher, still more preferably 70 ° C. or higher, still more preferably 80 ° C. or higher, preferably 250 ° C. or lower, and 220 ° C. or lower. More preferably, the soluble material for three-dimensional modeling according to any one of <1> to <25>.
<27> The content of the polyamide resin in the three-dimensional modeling soluble material is preferably 30% by mass or more, more preferably 50% by mass or more, still more preferably 60% by mass or more, and even more preferably 70% by mass or more. Preferably, 80% by mass or more is more preferable, 90% by mass or more is further preferable, 95% by mass or more is further preferable, substantially 100% by mass is further more preferable, and 100% by mass is further more preferable, <1 The soluble material for three-dimensional modeling according to any one of> to <26>.
<28> The glass transition temperature of the three-dimensional modeling soluble material is preferably 50 ° C or higher, more preferably 60 ° C or higher, still more preferably 70 ° C or higher, still more preferably 80 ° C or higher, and preferably 250 ° C or lower, The soluble material for three-dimensional modeling according to any one of <1> to <27>, wherein 220 ° C. or lower is more preferable.
<29> The shape of the three-dimensional modeling soluble material is preferably at least one selected from the group consisting of pellets, powders, and filaments, more preferably filaments, <1> to <28> The soluble material for 3D modeling described.
<30> When the shape of the three-dimensional modeling soluble material is a filament, the filament has a diameter of preferably 0.5 mm or more, more preferably 1.0 mm or more, preferably 3.0 mm or less, 2.0 mm The soluble material for three-dimensional modeling according to any one of <1> to <29>, wherein the following is more preferable and 1.8 mm or less is further preferable.
<31> A hot melt lamination method having a step of obtaining a three-dimensional object precursor including a three-dimensional object and a support material, and a support material removing step of bringing the three-dimensional object precursor into contact with neutral water and removing the support material The method for manufacturing a three-dimensional object according to claim 1, wherein the material of the support material is any one of the soluble materials for three-dimensional modeling <1> to <30>.
<32> A modeling material which is a material of a three-dimensional object is ABS resin, polylactic acid resin, polycarbonate resin, 12-nylon, 6,6-nylon, 6-nylon, polyphenylsulfone resin, polyetheretherketone, and The method for producing a three-dimensional object according to <31>, wherein at least one selected from the group consisting of polyetherimide is preferable, ABS resin and / or polylactic acid resin is more preferable, and ABS resin is more preferable.
<33> The method for producing a three-dimensional object according to <31> or <32>, comprising a support material removing step of immersing the three-dimensional object precursor in neutral water and dissolving and removing the support material.
<34> The method for producing a three-dimensional object according to <33>, wherein the neutral water contains a water-soluble organic solvent.
<35> The water-soluble organic solvent is a lower alcohol such as methanol, ethanol, 2-propanol, glycol ethers such as propylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monotertiary butyl ether, diethylene glycol monobutyl ether, The method for producing a three-dimensional object according to <34>, wherein at least one selected from the group consisting of ketones such as acetone and methyl ethyl ketone is preferred.
<36> The content of the water-soluble organic solvent in the neutral water is preferably 0.1% by mass or more, more preferably 0.5% by mass or more, further preferably 1% by mass or more, and further preferably 3% by mass or more. The method for producing a three-dimensional object according to <34> or <35>, wherein 50% by mass or less is preferable, 40% by mass or less is more preferable, 30% by mass or less is more preferable, and 20% by mass or less is even more preferable.
<37> The amount of the neutral water used is preferably 10 times by mass or more, more preferably 20 times by mass or more, more preferably 10,000 times by mass or less, and preferably 5000 times by mass or less with respect to the support material. The method for producing a three-dimensional object according to any one of <34> to <36>, wherein is more preferably 1000 times by mass or less, and still more preferably 100 times by mass or less.
<38> A support material that supports a three-dimensional object when a three-dimensional object is manufactured by a hot melt lamination type 3D printer, the support material including a polyamide resin, and the polyamide resin is a hydrophilic group The hydrophilic monomer unit A, the hydrophobic dicarboxylic acid monomer unit B, and the hydrophobic diamine monomer unit C are included, and the ratio of the hydrophilic monomer unit A to the total of all monomer units in the polyamide resin is 2. The support material which is 5 mol% or more and less than 13.5 mol%.
<39> The support material according to <38>, wherein the polyamide resin is a polyamide resin used for the three-dimensional modeling soluble material according to any one of <1> to <30>.
<40> Use of the soluble material for three-dimensional modeling according to any one of <1> to <30> as a support material.

<Analysis method>
[Polyamide resin hydrophilic monomer composition, hydrophobic dicarboxylic acid composition, hydrophobic diamine composition]
The composition of the hydrophilic monomer unit, the hydrophobic dicarboxylic acid monomer unit, and the composition of the hydrophobic diamine monomer unit were determined by proton NMR measurement using NMR and MR400 manufactured by Agilent.

[Amount of hydrophilic monomer of polyamide resin]
The hydrophilic monomer amount (mmol / g) in the polyamide was calculated from the composition of the hydrophilic monomer unit determined by the analysis method according to the following formula. However, the number of moles of all dicarboxylic acid monomer units and the number of moles of all amine monomer units were assumed to be equal.
Hydrophilic monomer amount (mmol / g) = A × 1000 / (A × Ms + B × Mc + C × Ma−2 × 18.0 × 50)
A: Ratio of hydrophilic monomer (mol%)
B: Ratio of hydrophobic dicarboxylic acid monomer (mol%)
C: Ratio of hydrophobic diamine monomer (mol%)
Ms: molecular weight of hydrophilic monomer Mc: molecular weight of hydrophobic dicarboxylic acid other than hydrophilic monomer (however, when there are a plurality of dicarboxylic acid species, number average molecular weight)
Ma: Molecular weight of a hydrophobic diamine other than a hydrophilic monomer (however, when there are a plurality of diamine species, the number average molecular weight)

[Amount of hydrophilic group in polyamide resin]
The amount (unit: mmol / g) of hydrophilic groups in the polyamide resin was determined from the composition of the polyamide resin determined by the above method.

[Weight average molecular weight and molecular weight distribution of polyamide resin]
10 mg of polyamide resin was dissolved in 3 g of HFIP (1,1,1,3,3,3-Hexafluoro-2-propanol manufactured by Wako Pure Chemical Industries, Ltd.) for 8 hours and measured by gel permeation chromatography (GPC) according to the following conditions.
・ Measurement device: HLC-8320GPC (manufactured by TOSOH)
Eluent: HFIP / 0.5 mM sodium trifluoroacetate Flow rate: 0.2 mL / min
・ Measurement temperature: 40 ℃
・ Analytical column: TSK-Gel Super AWM-H (manufactured by TOSOH)
-Calibration curve: ShodexSTANDARD M-75
・ Standard material: Polymethylmethacrylate (PMMA)

[Glass transition temperature of polyamide resin]
A sample of 5 to 10 mg is precisely weighed and sealed in an aluminum pan, and the temperature is increased from 30 ° C. to 350 ° C. at 10 ° C./min using a differential scanning calorimeter “DSC device (DSC7020 manufactured by Seiko Instruments Inc.). And then rapidly cooled to 30 ° C. From the DSC curve obtained by raising the temperature again to 350 ° C. at 10 ° C./min, the glass transition temperature (° C.), melting point (° C.), crystallization temperature (° C.) Asked.

<Synthesis of polyamide resin>
[Synthesis Example 1] (Compound 1)
A glass reactor equipped with a thermometer and stirring blades and having an internal volume of 100 ml was charged with 1.66 g of terephthalic acid, 4.36 g of monosodium 5-sulfoisophthalate, 3.05 g of hexamethylenediamine, 5.31 g of 4-methylmorpholine, N-methylpyrrolidone (50 g) was charged, and the temperature was lowered to 0 ° C. Next, 16.7 g of 4- (4,6-dimethoxy-1,3,5-triazin-2-yl) -4-methylmorpholinium chloride was added and maintained at 0 ° C., and stirring was continued for 6 hours in the atmosphere. did. After stirring, the mixture was poured into a DMF / methanol mixed solution to precipitate the polymer. The polymer was filtered off and dried under reduced pressure at 60 ° C. to obtain a white solid (Compound 1).

[Synthesis Example 2] (Compound 2)
In Synthesis Example 1, 2.49 g of terephthalic acid, 3.11 g of monosodium 5-sulfoisophthalate, 3.09 g of hexamethylenediamine, 5.38 g of 4-methylmorpholine, 4- (4,6-dimethoxy-1,3 , 5-Triazin-2-yl) -4-methylmorpholinium chloride was obtained in the same manner as in Synthesis Example 1 except that the amount was changed to 16.9 g.

[Synthesis Example 3] (Compound 3)
In Synthesis Example 1, 3.32 g of terephthalic acid, 2.03 g of monosodium 5-sulfoisophthalate, 3.20 g of hexamethylenediamine, 5.58 g of 4-methylmorpholine, 4- (4,6-dimethoxy-1,3 , 5-Triazin-2-yl) -4-methylmorpholinium chloride was obtained in the same manner as in Synthesis Example 1 except that the amount was changed to 17.5 g.

[Synthesis Example 4] (Compound 4)
In Synthesis Example 1, 2.41 g of terephthalic acid, 1.46 g of monosodium 5-sulfoisophthalate, 2.32 g of hexamethylenediamine, 4.04 g of 4-methylmorpholine, 4- (4,6-dimethoxy-1,3 , 5-Triazin-2-yl) -4-methylmorpholinium chloride was obtained in the same manner as in Synthesis Example 1 except that the amount was changed to 13.8 g.

[Synthesis Example 5] (Compound 5)
In Synthesis Example 1, 1.16 g of terephthalic acid, 1.16 g of isophthalic acid, 1.61 g of monosodium 5-sulfoisophthalate, 2.32 g of hexamethylenediamine, 4.04 g of 4-methylmorpholine, 4- (4, Compound 5 was obtained in the same manner as in Synthesis Example 1 except that the amount of 6-dimethoxy-1,3,5-triazin-2-yl) -4-methylmorpholinium chloride was changed to 13.8 g.

For the polyamide compounds 1 to 5 obtained in Synthesis Examples 1 to 5, the dicarboxylic acid composition, the diol composition, the amount of sulfonate group, the weight average molecular weight (Mw), the glass transition temperature (° C.), the melting point (° C.), the crystallization temperature (° C.) was determined by the analysis method. The measurement results are shown in Table 1. In Table 1, SIP (mol%) is the ratio (mol%) of 5-sulfoisophthalic acid monomer units in all dicarboxylic acid monomer units, and TPA (mol%) is terephthalic acid monomer units in all dicarboxylic acid monomer units. Ratio (mol%), IPA (mol%) is the ratio (mol%) of isophthalic acid monomer units in all dicarboxylic acid monomer units, and HMDA (mol%) is the ratio of hexamethylenediamine monomer units in all diamine monomer units. (Mol%) and the amount of sulfonic acid group (mmol / g) indicate the amount of sulfonic acid group (mmol / g) in the polyamide. In Table 1, Tg means glass transition temperature and Tc means crystallization temperature.

<Examples and Comparative Examples>
[Performance evaluation method]
[Solubility in neutral water]
0.25 g of polymer powder pulverized with a coffee mill (Mini Blender manufactured by Osaka Chemical Co., Ltd.) (pulverization time was 120 seconds) was dispersed in 5 g of ion-exchanged water (pH 7) at 70 ° C. and allowed to stand for 10 minutes. The undissolved polymer was filtered off under reduced pressure (advantech, filter paper No. 2/70 mm), washed with a small amount of ion-exchanged water, and dried. The dry mass of the undissolved polymer was measured, and the dissolution rate was calculated by the following formula.
Dissolution rate (%) = (polymer mass before dissolution−polymer mass remaining undissolved) / polymer mass before dissolution × 100

[Hygroscopicity]
About 2 g of the polymer powder pulverized by the same method as above was vacuum-dried at 80 ° C. for 3 hours, precisely weighed in a petri dish, and left in a constant humidity chamber at 25 ° C. and 98% RH. After 24 hours, mass measurement was performed, and the moisture absorption rate was calculated by the following formula.
Moisture absorption (%) = (polymer weight after standing-polymer weight before standing) / polymer weight before standing × 100

[Foaming by heat]
About 2 g of the polymer powder pulverized by the same method as above was vacuum-dried at 80 ° C. for 3 hours, precisely weighed in a petri dish, and left in a constant humidity chamber at 25 ° C. and 98% RH. After 24 hours, the sample was placed on a hot plate at 280 ° C. (ND-1 manufactured by ASONE), and the presence or absence of foaming was observed.

[Examples 1 to 3 and Comparative Examples 1 to 5]
With respect to the polyamide compounds 1 to 5 obtained in the synthesis examples described above and the following commercially available support materials 1 to 3, the solubility in neutral water and the hygroscopicity were evaluated by the analysis method. The analysis results are shown in Table 1. The commercial products 1 to 3 in Table 1 are as follows.
Commercial product 1: Soluble Support Material SR-30 (registered trademark), methacrylic acid / styrene / butyl methacrylate: 45/34/21% by weight copolymer (manufactured by Stratasys, composition is proton NMR (DMSO-d6)) Analysis, weight average molecular weight: 130000, glass transition temperature: 113 ° C., additive: epoxy group-containing polymer)
-Commercial product 2: Natural PVA / 1.75 mm polyvinyl alcohol (manufactured by Kenville, number average molecular weight 30000, glass transition temperature: 80 ° C.)
-Commercial product 3: Soluble Support Material P400SR (registered trademark), methacrylic acid / methyl methacrylate: 55/45% by weight copolymer (manufactured by Stratasys, composition is analyzed by proton NMR (DMSO-d6), weight average molecular weight : 130000, glass transition temperature: 100 ° C., plasticizer: containing triphenyl phosphate, etc.)

Claims

When manufacturing a three-dimensional object by a hot melt lamination type 3D printer, a soluble material for three-dimensional modeling used as a material of a support material for supporting the three-dimensional object,
The three-dimensional modeling soluble material includes a polyamide resin,
The polyamide resin has a hydrophilic monomer unit A having a hydrophilic group, a hydrophobic dicarboxylic acid monomer unit B, and a hydrophobic diamine monomer unit C;
The soluble material for three-dimensional modeling, wherein the ratio of the hydrophilic monomer unit A to the total of all monomer units in the polyamide resin is 2.5 mol% or more and less than 13.5 mol%.
The hydrophilic group is a primary amino group, a secondary amino group, a tertiary amino group, a quaternary ammonium base, an oxyethylene group, a hydroxyl group, a carboxyl group, a carboxyl group, a phosphate group, or a phosphate group. The soluble material for three-dimensional modeling according to claim 1, comprising at least one selected from the group consisting of sulfonic acid groups and sulfonic acid groups.
The sulfonate group counter ion constituting the sulfonate group is at least one selected from the group consisting of sodium ion, potassium ion, lithium ion, magnesium ion, calcium ion, barium ion, zinc ion and ammonium ion. The three-dimensional modeling soluble material according to claim 2.
The monomer A for deriving the hydrophilic monomer unit A is at least one selected from the group consisting of 5-sulfoisophthalic acid and 2-sulfoterephthalic acid. The soluble material for 3D modeling described.
The dicarboxylic acid B for deriving the hydrophobic dicarboxylic acid monomer unit B includes at least one selected from the group consisting of an aromatic dicarboxylic acid and an alicyclic dicarboxylic acid. The soluble material for three-dimensional modeling described in the item.
The three-dimensional modeling soluble material according to any one of claims 1 to 5, wherein the content of the hydrophilic group in the polyamide resin is 0.5 mmol / g or more and less than 1.0 mmol / g.
The soluble material for three-dimensional modeling according to any one of claims 1 to 6, wherein the diamine C for inducing the hydrophobic diamine monomer unit C has 2 to 20 carbon atoms.
The soluble material for three-dimensional modeling according to any one of claims 1 to 7, wherein the polyamide resin has a weight average molecular weight of 3000 to 70000.
The soluble material for three-dimensional modeling according to any one of claims 1 to 8, wherein the shape is a filament.
The soluble material for three-dimensional modeling according to claim 9, wherein the filament has a diameter of 0.5 to 3.0 mm.
Three-dimensional by a hot melt laminating method having a step of obtaining a three-dimensional object precursor including a three-dimensional object and a support material, and a support material removing step of bringing the three-dimensional object precursor into contact with neutral water and removing the support material An object manufacturing method comprising:
A method for producing a three-dimensional object, wherein the material of the support material is the soluble material for three-dimensional modeling according to any one of claims 1 to 10.
The method for producing a three-dimensional object according to claim 11, further comprising a support material removing step of immersing the three-dimensional object precursor in neutral water to dissolve and remove the support material.
A support material for supporting a three-dimensional object when the three-dimensional object is manufactured by a hot melt lamination type 3D printer,
The support material includes a polyamide resin, and the polyamide resin includes a hydrophilic monomer unit A having a hydrophilic group, a hydrophobic dicarboxylic acid monomer unit B, and a hydrophobic diamine monomer unit C. The support material whose ratio of the said hydrophilic monomer unit A with respect to the sum total of all the monomer units is 2.5 mol% or more and less than 13.5 mol%.