WO2018025703A1 - Method for producing fusible material for three-dimensional molding - Google Patents

Abstract

The present invention is a method for producing a fusible material for three-dimensional molding to be used, when producing a three-dimensional object with a fused deposition-mode 3-D printer, as a material for a support member that supports said three-dimensional object. The method for producing a fusible material for three-dimensional molding has a kneading step for kneading with a screw configuration such that the ratio of the total length K of the kneading discs with respect to the total effective screw length L of a twin screw extruder, which kneads a starting material for the fusible material for three-dimensional molding, is 0.20<K/L<0.70. The temperature Tmix of the starting material for the fusible material for three-dimensional molding in the kneading step with respect to the glass transition temperature Tg of a base polymer contained in the starting material for said fusible material for three-dimensional molding is Tg+80(°C)<Tmix<Tg+200(°C). The present invention is capable of providing a method for producing a fusible material for three-dimensional molding that has excellent mechanical properties and even when made into filaments, is not susceptible to breakage.

Description

Method for producing soluble material for three-dimensional modeling

The present invention relates to a method for producing a soluble material for three-dimensional modeling that is used as a support material for supporting a three-dimensional object when the three-dimensional object is produced by a 3D printer, in particular, 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, a target three-dimensional object can be obtained (for example, JP-T-2008-507619).

The manufacturing method of the three-dimensional modeling soluble material of the present invention is a three-dimensional modeling soluble material used as a material for a support material that supports the three-dimensional object when the three-dimensional object is manufactured by a hot melt lamination type 3D printer. A method for producing a material, wherein the ratio of the length K of the kneading disk to the total length L of the effective screw of the twin screw extruder for kneading the raw material of the three-dimensional modeling soluble material is 0.20 <K / L < A glass of a base polymer that has a kneading step of kneading with a screw configuration of 0.70, and the temperature Tmix of the raw material of the three-dimensional modeling soluble material in the kneading step is included in the raw material of the three-dimensional modeling soluble material Tg + 80 (° C.) <Tmix <Tg + 200 (° C.) with respect to the transition temperature Tg.

Detailed Description of the Invention

The three-dimensional modeling soluble material used as a support material for supporting the three-dimensional object is provided in the form of a filament wound around a supply reel, and is supplied from the supply reel to a hot melt lamination type 3D printer. However, the filamentous three-dimensional modeling soluble material has a problem that it is easily broken when it is wound around the supply reel or when it is supplied to a 3D printer.

The present invention provides a method for producing a soluble material for three-dimensional modeling that has excellent mechanical properties and is difficult to break even when a filament is used.

The manufacturing method of the three-dimensional modeling soluble material of the present invention is a three-dimensional modeling soluble material used as a material for a support material that supports the three-dimensional object when the three-dimensional object is manufactured by a hot melt lamination type 3D printer. A method for producing a material, wherein the ratio of the length K of the kneading disk to the total length L of the effective screw of the twin screw extruder for kneading the raw material of the three-dimensional modeling soluble material is 0.20 <K / L < A glass of a base polymer that has a kneading step of kneading with a screw configuration of 0.70, and the temperature Tmix of the raw material of the three-dimensional modeling soluble material in the kneading step is included in the raw material of the three-dimensional modeling soluble material Tg + 80 (° C.) <Tmix <Tg + 200 (° C.) with respect to the transition temperature Tg.

According to the present invention, it is possible to provide a method for producing a soluble material for three-dimensional modeling that has excellent mechanical properties and is difficult to break even when a filament is used.

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

<Method for producing soluble material for three-dimensional modeling>
The manufacturing method of the soluble material for 3D modeling of the present embodiment is for 3D modeling used as a material for a support material that supports the 3D object when the 3D object is manufactured by a hot melt lamination type 3D printer. A method for producing a soluble material, wherein the ratio of the total length K of the kneading disk to the total length L of the effective screw of the twin-screw extruder for kneading the raw material for the three-dimensional modeling soluble material is 0.20 <K / A base polymer having a kneading step of kneading with a screw configuration satisfying L <0.70, wherein the temperature Tmix of the raw material of the three-dimensional modeling soluble material in the kneading step is included in the raw material of the three-dimensional modeling soluble material Tg + 80 (° C.) <Tmix <Tg + 200 (° C.) with respect to the glass transition temperature Tg.

According to the manufacturing method of the soluble material for three-dimensional modeling of the present embodiment, it is possible to provide a soluble material for three-dimensional modeling that is excellent in mechanical properties and is not easily broken even by a filament. The reason why the manufacturing method of the soluble material for three-dimensional modeling of the present embodiment has such an effect is not clear, but is considered as follows.

In order to impart toughness and make the filament difficult to break, an elastomer may be used as a raw material for the three-dimensional modeling soluble material. Even if the elastomer is included in the three-dimensional modeling soluble material, The effect of is difficult to obtain. This is because the elastomer is poorly compatible with the base polymer that is the base material of the three-dimensional modeling soluble material, so that even if a compatibilizer is used, the elastomer is sufficiently dispersed in the three-dimensional modeling soluble material. It is speculated that not. In the manufacturing method of the three-dimensional modeling soluble material of the present embodiment, the elastomer is sufficiently dispersed in the three-dimensional modeling soluble material, so that the design effect by the elastomer is obtained and the toughness is improved. It is considered that it is possible to provide a soluble material for three-dimensional modeling that is excellent in mechanical properties and is not easily broken even by a filament.

[Raw materials for soluble materials for 3D modeling]
The raw material of the three-dimensional modeling soluble material includes a base polymer of the three-dimensional modeling soluble material, a compatibilizing agent, and an elastomer.

[Base polymer of soluble material for 3D modeling]
The base polymer of the three-dimensional modeling soluble material can be used without particular limitation as long as it is used as the base polymer of the three-dimensional modeling soluble material in the conventional FDM type three-dimensional object manufacturing method. Examples of the base polymer include polyvinyl alcohol, polyoxazoline, polyacrylamide, acrylate (co) polymer, methacrylate (co) polymer, polyester resin, polyamide resin, and methacrylic resin.

However, if a resin with low solubility in neutral water such as methacrylic resin is used as the base polymer of the soluble material for 3D modeling, it is necessary to use a strong alkaline aqueous solution to remove the support material from the 3D object precursor. However, the strong alkaline aqueous solution has a great danger to humans and a large burden on the environment. 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 are limited in application as materials for three-dimensional objects. Therefore, the base polymer of the three-dimensional modeling soluble material is preferably a resin having a hydrophilic group that can be removed by neutral water having a pH of 6 to 8, which is not a strong alkaline aqueous solution.

Furthermore, in general, a modeling material having high heat resistance has a high melting point, but the temperature when the modeling material is heated / melted and extruded and laminated by a 3D printer is significantly different from the temperature of the support material in contact with the modeling material. The accuracy of 3D objects may be impaired. Therefore, when a modeling material having a high melting point is heated / melted and extruded and laminated by a 3D printer, the three-dimensional modeling soluble material, which is a material of the support material, is also heated / melted and extruded to a temperature close to the temperature of the modeling material for lamination. To do. In such a case, a three-dimensional modeling soluble material that is a support material that can be removed by neutral water having a pH of 6 to 8 that is not a strong alkaline aqueous solution also preferably has a high melting point.

Examples of the resin having a high melting point that can be removed by neutral water whose pH is not strong alkaline aqueous solution is 6 to 8, and polyester resins having hydrophilic groups and polyamide resins having hydrophilic groups.

(Polyester resin having a hydrophilic group)
The polyester resin, a hydrophilic monomer unit A ₁ having a hydrophilic _group, a hydrophobic dicarboxylic acid monomer units B _1, and has a diol monomer units, hydrophilic monomeric units A ₁ and hydrophobic dicarboxylic of the polyester resin A polyester resin in which the ratio of the hydrophilic monomer unit A ₁ to the total of the acid monomer units B ₁ is 10 to 70 mol% can be exemplified.

"Hydrophilic monomer units _A 1"
The polyester resin has a hydrophilic monomer unit A ₁ having a hydrophilic group. The hydrophilic monomer unit A ₁ is not particularly limited as long as the monomer unit having a hydrophilic group. Also, the monomer to induce the hydrophilic monomer unit A ₁ is also referred to as a monomer A _1.

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 polymerization reaction during the production of the polyester 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 the ease of polymerization reaction during the production of the polyester 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 the polyester resin. Jo of represents a number 1 to 14 alkyl group carbon, 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 14 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 the polyester 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} _n1 — (where n1 represents an average number) from the viewpoint of solubility in neutral water and ease of polymerization reaction during the production of the polyester 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 } _m1 -R ⁸ (although, m1 represents an average number, the number of 1 or more 2500 or less, preferably 2 to 1,000, more preferably 3 or more and 100 or less, 4 or more and 50 or less is more preferred .R ⁸ is Represents 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. At least one selected from the group consisting of down group.

From the viewpoint of solubility in neutral water and the ease of the polymerization reaction during the production of the polyester resin, the carboxyl base is —COOM ¹ (where M ¹ represents a counter ion of the carboxyl group constituting the carboxyl base. 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 But Further preferred.) Carboxyl base is preferably represented by Ri.

From the viewpoint of solubility in neutral water and the ease of polymerization reaction during the production of the polyester resin, the phosphate group is —PO ₄ M ² ₂ , —PO ₄ HM ² , and —PO ₄ M ^2. (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. Properly, the sodium ion is more preferable and more.) At least one or more preferably selected from the group consisting of phosphoric acid base represented by.

From the viewpoint of solubility in neutral water and the ease of the polymerization reaction during the production of the polyester 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, more sodium ions Sulfonate group is preferably represented by the preferred.) To.

From the viewpoint of solubility in neutral water, moisture absorption resistance, heat resistance required for modeling by 3D printer, and ease of polymerization reaction during polyester resin production, the monomer A ₁ At least one selected from the group consisting of acids, 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 At least one selected from the group consisting of aromatic dicarboxylic acids is more preferable. 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 polyester 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, 3.0 mmol / g or less is preferable, 2.0 mmol / g or less is more preferable, and 1.5 mmol / g or less is still more preferable. In addition, the content of the hydrophilic group in the polyester resin is preferably 0.5 to 3.0 mmol / g from the viewpoint of solubility in neutral water and moisture absorption resistance, and is preferably 0.6 to 2.0 mmol / g is more preferable, and 0.7 to 1.5 mmol / g is more preferable.

To the total of the substance amount of the total monomer units of the polyester resin, the proportion of a substance amount of the hydrophilic monomer unit A ₁ is from the standpoint of solubility in neutral water, not less than 5 mol%, more than 7 mol% Preferably, 10 mol% or more is more preferable, 12 mol% or more is more preferable, and from the viewpoint of moisture absorption resistance, it is 35 mol% or less, preferably 33 mol% or less, more preferably 32 mol% or less, and further preferably 30 mol% or less. Further, to the total amount of substance of the total monomer units of the polyester resin, the proportion of a substance amount of the hydrophilic monomer unit A ₁ is preferably 5 - 35 mol% from the viewpoint of solubility in neutral water, 7 ~ 33 mol% is more preferable, 10 to 32 mol% is still more preferable, 12 to 30 mol% is still more preferable, and 8 to 13 mol% is still more preferable from the viewpoint of solubility in neutral water and moisture absorption resistance.

"Hydrophobic dicarboxylic acid monomer units _B 1"
The polyester resin has a hydrophobic dicarboxylic acid monomer units B _1. The dicarboxylic acid monomer units B ₁ represents no said hydrophilic groups. In this specification, the dicarboxylic acid to induce the hydrophobic dicarboxylic acid monomer units B ₁ is also referred to as a dicarboxylic acid B _1.

The dicarboxylic acid B ₁ 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 when producing a polyester resin From the viewpoint of the ease of the 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 At least one selected from the group consisting of terephthalic acid, 2,5-furandicarboxylic acid, and 2,6-naphthalenedicarboxylic acid is more preferable.

To the total of the substance amount of the total monomer units of the polyester resin, the proportion of the hydrophobic substance amount of the dicarboxylic acid monomer units B ₁ of the polyester resin, from the viewpoint of moisture resistance, or 15 mol% are preferred, 18 mol % Or more is more preferable, 20 mol% or more is more preferable, and from the viewpoint of solubility in neutral water, 45 mol% or less is preferable, 42 mol% or less is more preferable, and 40 mol% or less is more preferable. Further, to the total amount of substance of the total monomer units of the polyester resin, the proportion of the hydrophobic substance amount of the dicarboxylic acid monomer units B ₁ of the polyester resin is, the moisture absorption resistance viewpoint, and to neutral water From the viewpoint of solubility, it is preferably 15 to 45 mol%, more preferably 20 to 42 mol%, still more preferably 30 to 40 mol%.

The molar ratio of the hydrophilic monomer unit A ₁ to the hydrophobic dicarboxylic acid monomer unit B ₁ (the hydrophilic monomer unit A ₁ / the hydrophobic dicarboxylic acid monomer unit B ₁ ) is determined based on solubility in water and resistance to neutral water. From the viewpoint of hygroscopicity and 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 more preferable, 20/80 or more is more preferable, and the same In view of the above, 70/30 or less is preferable, 65/35 or less is more preferable, 60/40 or less is more preferable, 40/60 or less is still more preferable, and 26/74 or less is even more preferable.

<Diol monomer unit>
The polyester resin has a diol monomer unit. The diol for deriving the diol monomer unit is also referred to as diol C.

The diol C is not particularly limited, and aliphatic diols, aromatic diols, and the like can be used, but aliphatic diols are preferable from the viewpoint of the production cost of the polyester resin.

The number of carbon atoms of the diol C is preferably 2 or more from the viewpoint of solubility in neutral water, moisture absorption resistance, and heat resistance required for modeling by a 3D printer, and from the same viewpoint, 31 or less is preferable, 25 The following is more preferable, 20 or less is further preferable, and 15 or less is more preferable.

Examples of the aliphatic diol include at least one selected from the group consisting of a chain diol and a cyclic diol, and are required for solubility in neutral water, moisture absorption resistance, and modeling by a 3D printer. From the viewpoint of toughness (strength), a chain diol is preferred.

The number of carbon atoms of the chain diol is preferably 2 or more from the viewpoint of solubility in neutral water, moisture absorption resistance, and heat resistance required for modeling by a 3D printer, and from the same viewpoint, 6 or less is preferable. 4 or less is more preferable, and 3 or less is more preferable.

The number of carbon atoms of the cyclic diol is preferably 6 or more from the viewpoint of solubility in neutral water, moisture absorption resistance, and heat resistance required for modeling by a 3D printer, and from the same viewpoint, 31 or less is preferable. 30 or less is more preferable, and 27 or less is more preferable.

The diol C may have ether oxygen. However, when the diol C is a chain aliphatic diol, it is required for solubility in neutral water, moisture absorption resistance, and modeling by a 3D printer. From the viewpoint of heat resistance, the number of ether oxygens is preferably 1 or less, and when the diol C is a cycloaliphatic diol, the number of ether oxygens is preferably 2 or less from the same viewpoint.

The chain diol is ethylene glycol, 1,2-propanediol, 1,3-propanediol, diethylene glycol from the viewpoints of solubility in neutral water, moisture absorption resistance, and heat resistance required for modeling by a 3D printer. And preferably at least one selected from the group consisting of dipropylene glycol, more preferably at least one selected from the group consisting of ethylene glycol, 1,2-propanediol, and 1,3-propanediol. Among these, diethylene glycol and dipropylene glycol may be charged as a raw material for the polymerization reaction, or may be by-produced during the polymerization reaction.

When the diol C contains diethylene glycol, the ratio of the diethylene glycol unit to the total of all diol monomer units in the polyester resin is the solubility in neutral water, moisture absorption resistance, and the heat resistance required for modeling by a 3D printer. From the viewpoint, 5 mol% or more is preferable, 10 mol% or more is more preferable, 15 mol% or more is further preferable, 20 mol% or more is further preferable, 25 mol% or more is further more preferable, 30 mol% or more is more preferable, and 60 mol%. The following is preferable, 55 mol% or less is more preferable, 50 mol% or less is more preferable, and 45 mol% or less is still more preferable.

The cyclic diol is composed of 1,4-cyclohexanedimethanol, hydrogenated bisphenol A, isosorbide, bisphenoxyethanol fluorene from the viewpoints of solubility in neutral water, moisture absorption resistance, and heat resistance required for modeling by a 3D printer. At least one selected from the group consisting of bisphenol fluorene, biscrezoxyethanol fluorene, and biscresol fluorene is preferred.

Diol C is ethylene glycol, 1,2-propanediol, 1,3-propanediol, diethylene glycol, dipropylene glycol, 1,4-cyclohexanedimethanol, hydrogenated bisphenol A, isosorbide, bisphenoxyethanol fluorene, bisphenol fluorene, bisque In the case of at least one selected from the group consisting of resoxyethanol fluorene and biscresol fluorene, ethylene glycol, 1,2-propanediol, 1,3-propane with respect to the total of all diol monomer units in the polyester resin Diol, diethylene glycol, dipropylene glycol, 1,4-cyclohexanedimethanol, hydrogenated bisphenol A, isosorbide, bisphenoxyethanol The total proportion of loulene, bisphenol fluorene, biscrezoxyethanol fluorene, and biscresol fluorene is 80 mol% or more from the viewpoints of solubility in neutral water, moisture absorption resistance, and heat resistance required for modeling with a 3D printer. Is preferable, 90 mol% or more is more preferable, 95 mol% or more is further preferable, 98 mol% or more is further preferable, substantially 100 mol% is still more preferable, and 100 mol% is still more preferable.

The polyester resin is solubility in neutral water, moisture absorption resistance, and a heat-resistant viewpoint required for shaping by 3D printers, to the total of all the dicarboxylic acid monomer units containing the hydrophilic monomer unit A _1, wherein the proportion of hydrophilic monomer units _{a 1,} and the ratio of the dicarboxylic acid monomer units _{B 1} is, 10 ~ 70 mol%, respectively, and a 30 ~ 90 mol%, dicarboxylic acids for obtaining the dicarboxylic acid monomer units _{B 1 B 1} Polyester resin α in which is 2,6-naphthalenedicarboxylic acid is preferred.

<Polyester resin α>
Wherein in the polyester resin alpha, to the total of all the dicarboxylic acid monomer units containing the hydrophilic monomer unit A _1, the ratio of the hydrophilic monomer unit A ₁ is solubility in neutral water, moisture absorption resistance, and 3D printer From the viewpoint of the heat resistance required for modeling according to the above, 10 mol% or more is preferable, 20 mol% or more is more preferable, and from the same viewpoint, 70 mol% or less is preferable, 65 mol% or less is more preferable, 60 mol% or less is more preferable, 40 mol % Or less is still more preferable, and 27 mol% or less is still more preferable.

The ratio of the dicarboxylic acid monomer unit B _{1 to} the total of all dicarboxylic acid monomer units including the hydrophilic monomer unit A ₁ in the polyester resin α is determined by solubility in neutral water, moisture absorption resistance, and 3D printer. From the viewpoint of the heat resistance required for modeling by, preferably 30 mol% or more, more preferably 35 mol% or more, still more preferably 40 mol% or more, still more preferably 65 mol% or more, still more preferably 73 mol% or more, the same viewpoint Therefore, 90 mol% or less is preferable, and 80 mol% or less is more preferable.

In the polyester resin α, the monomer A ₁ contains 5-sulfoisophthalic acid and 2-sulfoisophthalic acid from the viewpoints of solubility in neutral water, moisture absorption resistance, and heat resistance required for modeling by a 3D printer. Preferably, at least one selected from the group consisting of: 5-sulfoisophthalic acid is more preferable.

The diol C in the polyester resin α is ethylene glycol, 1,2-propanediol, diethylene glycol, 1 from the viewpoints of solubility in neutral water, moisture absorption resistance, and heat resistance required for modeling by a 3D printer. At least one selected from the group consisting of 1,3-propanediol, dipropylene glycol, 1,4-cyclohexanedimethanol, hydrogenated bisphenol A, isosorbide, bisphenoxyethanol fluorene, bisphenol fluorene, biscrezoxyethanol fluorene, and biscresol fluorene. More than one species, preferably a group consisting of ethylene glycol, diethylene glycol, 1,4-cyclohexanedimethanol, hydrogenated bisphenol A, isosorbide, bisphenoxyethanol fluorene Ri least one and more preferably be selected.

The polyester resin α can be exemplified by the following general formulas (1) and (2).

 
（前記化学式（１）中、ｐ１はエチレン２，６－ナフタレンジカルボキシレートの重合度、ｑ１はエチレン５－スルホイソフタレートの重合度の数を表す。ただし、エチレン２，６－ナフタレンジカルボキシレートとエチレン５－スルホイソフタレートはブロック結合及び／又はランダム結合であり、中性水への溶解性の観点からランダム結合がより好ましい。）

(In the chemical formula (1), p1 represents the polymerization degree of ethylene 2,6-naphthalene dicarboxylate, and q1 represents the number of polymerization degrees of ethylene 5-sulfoisophthalate, where ethylene 2,6-naphthalene dicarboxylate And ethylene 5-sulfoisophthalate are block bonds and / or random bonds, and a random bond is more preferable from the viewpoint of solubility in neutral water.)

 
（前記化学式（２）中、ｐ２はエチレン２，６－ナフタレンジカルボキシレートの重合度、ｑ２はエチレン５－スルホイソフタレートの重合度、ｒ２はビスフェノキシエタノールフルオレンと２，６－ナフタレンジカルボン酸との縮合物の重合度、ｓ２はビスフェノキシエタノールフルオレンと５-スルホイソフタル酸との縮合物の重合度の数を表す。ただし、エチレン２，６－ナフタレンジカルボキシレート、エチレン５－スルホイソフタレート、ビスフェノキシエタノールフルオレンと２，６－ナフタレンジカルボン酸との縮合物、ビスフェノキシエタノールフルオレンと５-スルホイソフタル酸との縮合物はブロック結合及び／又はランダム結合であり、中性水への溶解性の観点からランダム結合がより好ましい。）

(In the chemical formula (2), p2 is the degree of polymerization of ethylene 2,6-naphthalenedicarboxylate, q2 is the degree of polymerization of ethylene 5-sulfoisophthalate, and r2 is the amount of bisphenoxyethanol fluorene and 2,6-naphthalenedicarboxylic acid. The degree of polymerization of the condensate, s2 represents the number of degrees of polymerization of the condensate of bisphenoxyethanol fluorene and 5-sulfoisophthalic acid, provided that ethylene 2,6-naphthalenedicarboxylate, ethylene 5-sulfoisophthalate, bisphenoxyethanol The condensate of fluorene and 2,6-naphthalenedicarboxylic acid, the condensate of bisphenoxyethanol fluorene and 5-sulfoisophthalic acid are block bonds and / or random bonds, and are randomly bonded from the viewpoint of solubility in neutral water. Is more preferred.)

The polyester resin may have a monomer unit other than the hydrophilic monomer unit A ₁ , the dicarboxylic acid monomer unit B ₁ , and the diol monomer unit as long as the effects of the present embodiment are not impaired.

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

(Polyamide resin having hydrophilic group)
The polyamide resin has a hydrophilic monomer unit A ₂ having a hydrophilic group, a hydrophobic dicarboxylic acid monomer unit B ₂ , and a hydrophobic diamine monomer unit, and the hydrophilicity relative to the total of all monomer units in the polyamide resin. polyamide resin proportion of sexual monomer unit _{a 2} is 2.5 ~ 40 mol% can be exemplified.

"Hydrophilic monomer unit _A 2"
The polyamide resin has a hydrophilic monomer unit A ₂ having a hydrophilic group. The hydrophilic monomer unit A ₂ is not particularly limited as long as the monomer unit having a hydrophilic group. Also, the monomer to induce the hydrophilic monomer unit A ₂ is also referred to as monomer A _2.

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.

From the viewpoint of solubility in neutral water and the ease of the polymerization reaction during the production of the polyamide resin, the secondary amino group is a —NHR ⁹ group (where R ⁹ is a linear or branched group). 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 ¹⁰ R ¹¹ group (provided that R ¹⁰ is linear or branched from the viewpoint of solubility in neutral water and ease of polymerization reaction during the production of polyamide resin. A tertiary amino group having a carbon number of 1 to 14 and R ¹¹ represents a linear or branched alkyl group having a carbon number of 1 to 14), and —NR ^At least one selected from the group consisting of a tertiary amino group represented by a ¹² -group (wherein R ¹² represents a linear or branched alkyl group having 1 to 14 carbon atoms) is preferred. .

The quaternary ammonium base is —N ⁺ {R ¹³ R ¹⁴ R ¹⁵ } · X ⁻ (where, from the viewpoint of solubility in neutral water and ease of polymerization reaction during the production of polyamide resin. R ¹³ , R ¹⁴ and R ¹⁵ 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} _n2 — (where n2 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 @ 2} -R ¹⁶ (although, m2 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 16} is 4 or more and 50 or less A hydrogen atom or a linear or branched alkyl group having 1 to 10 carbon atoms, preferably 2 or more and 6 or less, more preferably 3 or more and 5 or less. At least one selected from the group consisting of alkylene groups are preferred.

The carboxyl base is —COOM ⁴ (where M ⁴ 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, in view of the solubility in neutral water, and from the viewpoint of easiness of the polyamide resin during manufacture of the polymerization ^{_{reaction, -PO 4 M 5 2, -PO}} 4 HM 5, and _-PO 4 ^{M 5} (However, M ⁵ represents a counter ion of the phosphate groups constituting the phosphoric acid salt, sodium from the viewpoint of solubility in neutral water ions, potassium ions, lithium ions, calcium ions, magnesium ions, ammonium ions, 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 ⁶ (where M ⁶ 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.

From the viewpoints of solubility in neutral water, moisture absorption resistance, heat resistance required for modeling by 3D printer, and ease of polymerization reaction during polyamide resin production, the monomer A ₂ is a carboxylic acid. At least one selected from the group consisting of acids, 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, 3.0 mmol / g or less is preferable, 2.0 mmol / g or less is more preferable, and 1.5 mmol / g or less is still more preferable. Further, the content of the hydrophilic group in the polyamide resin is preferably 0.5 to 3.0 mmol / g from the viewpoint of solubility in neutral water and moisture absorption resistance, and preferably 0.6 to 2.0 mmol / g is more preferable, and 0.7 to 1.5 mmol / g is more preferable.

To the total of the substance amount of the total monomer units of the polyamide resin, the proportion of a substance amount of the hydrophilic monomer unit A _2, from the viewpoint of solubility in neutral water, not less than 2.5 mol%, 4 mol% The above is preferable, 6 mol% or more is more preferable, 8 mol% or more is further preferable, 10 mol% or more is more preferable, and from the viewpoint of moisture absorption resistance, it is 40 mol% or less, preferably 35 mol% or less, and more preferably 31 mol% or less. Preferably, it is further preferably 25 mol% or less, more preferably 20 mol% or less, still more preferably 15 mol% or less, still more preferably 10 mol% or less, and even more preferably 8 mol% or less. The ratio of the total for the substance amount of the hydrophilic monomer unit A ₂ substance of the total monomer units of the polyamide resin is 2 in view of the solubility in neutral water, and in view of moisture absorption resistance. It is preferably 5 to 40 mol%, more preferably 4 to 35 mol%, still more preferably 6 to 31 mol%, still more preferably 8 to 20 mol%, still more preferably 8 to 15 mol%, and still more preferably 8 to 12 mol%.

"Hydrophobic dicarboxylic acid monomer units _B 2"
The polyamide resin has a hydrophobic dicarboxylic acid monomer unit B _2. The dicarboxylic acid monomer units B ₂ has no the hydrophilic group. In this specification, the dicarboxylic acid to induce the hydrophobic dicarboxylic acid monomer units B ₂ is also referred to as a dicarboxylic acid B _2.

The dicarboxylic acid B ₂ 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 at the time of producing a polyamide resin From the viewpoint of the ease of the 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. .

To the total of the substance amount of the total monomer units of the polyamide resin, the proportion of the hydrophobic substance amount of the dicarboxylic acid monomer units B ₂ of the polyamide resin, from the viewpoint of moisture resistance, preferably at least 10 mol%, 20 mol % Or more, more preferably 30 mol% or more, still more preferably 35 mol% or more, still more preferably 40 mol% or more, still more preferably 42 mol% or more, and from the viewpoint of solubility in neutral water, 47. 5 mol% or less is preferable, 45 mol% or less is more preferable, 42 mol% or less is more preferable, and 40 mol% or less is still more preferable. Further, to the total amount of substance of the total monomer units of the polyamide resin, the proportion of the hydrophobic substance amount of the dicarboxylic acid monomer units B ₂ of the polyamide resin is, the moisture absorption resistance viewpoint, and to neutral water From the viewpoint of solubility, it is preferably 10 to 47.5 mol%, more preferably 20 to 45 mol%, still more preferably 30 to 42 mol%.

The molar ratio of the hydrophilic monomer unit A ₂ to the hydrophobic dicarboxylic acid monomer unit B ₂ (the hydrophilic monomer unit A ₂ / the hydrophobic dicarboxylic acid monomer unit B ₂ ) is determined based on solubility in neutral water and resistance to water. From the viewpoint of hygroscopicity and 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 more preferable, 20/80 or more is more preferable, and the same In view of the above, 50/50 or less is preferable, 40/60 or less is more preferable, 30/70 or less is more preferable, and 25/75 or less is even more preferable.

<< Hydrophobic diamine monomer unit >>
The polyamide resin has a hydrophobic diamine monomer unit. The hydrophobic diamine monomer unit does not have the hydrophilic group. The diamine for deriving the hydrophobic diamine monomer unit 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 at least one selected from the group consisting of diamine and 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. And at least one selected from the group consisting of phenylenediamine is more preferable.

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 (3) to (8).

 
（前記一般式（３）中、ｐ３及びｑ３はそれぞれ重合度の数を表す。各重合はブロック結合及び／又はランダム結合であり、中性水への溶解性の観点からランダム結合がより好ましい。）

(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. )

 
（前記一般式（４）中、ｐ４及びｑ４はそれぞれ重合度の数を表す。各重合はブロック結合及び／又はランダム結合であり、中性水への溶解性の観点からランダム結合がより好ましい。）

(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. )

 
（前記一般式（５）中、ｐ５及びｑ５はそれぞれ重合度の数を表す。各重合はブロック結合及び／又はランダム結合であり、中性水への溶解性の観点からランダム結合がより好ましい。）

(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. )

 
（前記一般式（６）中、ｐ６及びｑ６はそれぞれ重合度の数を表す。各重合はブロック結合及び／又はランダム結合であり、中性水への溶解性の観点からランダム結合がより好ましい。）

(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. )

 
（前記一般式（７）中、ｐ７及びｑ７はそれぞれ重合度の数を表す。各重合はブロック結合及び／又はランダム結合であり、中性水への溶解性の観点からランダム結合がより好ましい。）

(In the general formula (7), p7 and q7 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. )

 
（前記一般式（８）中、ｐ８及びｑ８はそれぞれ重合度の数を表す。各重合はブロック結合及び／又はランダム結合であり、中性水への溶解性の観点からランダム結合がより好ましい。）

(In the general formula (8), p8 and q8 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 polyamide resin may have a monomer unit other than the monomer unit A ₂ , the dicarboxylic acid monomer unit B ₂ , and the hydrophobic diamine monomer unit 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 polyester resin and the polyamide resin can be removed by neutral water having a pH of 6 to 8 which is not a strong alkaline aqueous solution and have a high melting point, but have a hydrophilic group, so that they are used as a base polymer for a soluble material for three-dimensional modeling. There is a tendency that the compatibility with the elastomer is worse than that of a general resin used. However, according to the manufacturing method of the soluble material for three-dimensional modeling of this embodiment, the polyester resin having the hydrophilic group and / or the polyamide resin having the hydrophilic group is used as a raw material for the soluble material for three-dimensional modeling. Even when the elastomer is sufficiently dispersed in the three-dimensional modeling soluble material, the design effect of the elastomer is obtained and the toughness is improved, so that the mechanical properties are excellent and the filament is not easily broken. A soluble material for three-dimensional modeling can be provided.

The weight average molecular weight of the base polymer 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 soluble material for three-dimensional modeling. 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 (Tg) of the base polymer is 50 ° C. or higher, preferably 60 ° C. or higher, more preferably 70 ° C. or higher, still more preferably 80 ° C. or higher, from the viewpoint of formability by a 3D printer. Therefore, it is 250 ° C. or lower, preferably 220 ° C. or lower, more preferably 180 ° C. or lower, still more preferably 160 ° C. or lower, still more preferably 140 ° C. or lower, and still more preferably 120 ° C. or lower. In addition, in this specification, a glass transition temperature is measured by the method as described in an Example.

From the viewpoint of resin fluidity, the melt flow rate of the base polymer is preferably 1.0 g / 10 min or more, more preferably 1.5 g / 10 min or more, further preferably 2.0 g / 10 min or more, and 2.5 g / min. 10 g or more is more preferable, and from the viewpoint of resin toughness, 10 g / 10 min or less is preferable, 7 g / 10 min or less is more preferable, 6 g / 10 min or less is further preferable, and 5 g / 10 min or less is even more preferable. In this specification, the melt flow rate is measured by the method described in the examples.

The blending ratio of the base polymer is preferably 70% by mass or more and more preferably 80% by mass or more in the soluble material for three-dimensional modeling from the viewpoint of modeling by a 3D printer. The blending ratio of the base polymer is preferably 95% by mass or less, more preferably 90% by mass or less, in the soluble material for three-dimensional modeling.

[Compatibilizer]
The compatibilizer can be used without particular limitation as long as it is a compatibilizer used for the three-dimensional modeling soluble material according to the FDM method. From the viewpoint of improving toughness, a compatibilizing agent containing at least one reactive group selected from the group consisting of an epoxy group, an acid anhydride group, an isocyanate group, an amino group, a carboxyl group, and an oxazoline group is preferable. A reactive compatibilizing agent having is more preferred. Examples of reactive compatibilizers having an epoxy group include Bondfast (registered trademark) 7B, Bondfast 7M (manufactured by Sumitomo Chemical Co., Ltd.), Rotada (registered trademark) AX8840 (manufactured by Akema), JONCRYL (registered trademark) ADR4370S, JONCRYL Examples include ADR4368CS, JONCRYL ADR4368F, JONCRYL ADR4300S (above, manufactured by BASF), ARUFON (registered trademark) UG4035, ARUFON UG4040, ARUFON UG4070 (above, manufactured by Toagosei Co., Ltd.). As a reactive compatibilizing agent having an acid anhydride group, Yumex (registered trademark) 1010 (manufactured by Sanyo Chemical Co., Ltd.), Admer (registered trademark) (manufactured by Mitsui Chemicals), Modiper (registered trademark) A8200 (manufactured by NOF Corporation) ), OREVAC (registered trademark) (manufactured by Arkema), FG1901, FG1924 (above, Kraton Polymer), Tuftec (registered trademark) M1911, Tuftec M1913, and Tuftec M1943 (above, manufactured by Asahi Kasei Chemicals). Examples of the reactive compatibilizer having an isocyanate group include “Carbodilite LA-1 (registered trademark)” manufactured by Nisshinbo.

The blending ratio of the compatibilizing agent is preferably 2 parts by mass or more and more preferably 3 parts by mass or more with respect to 100 parts by mass of the base polymer from the viewpoint of the formability by a 3D printer. The blending ratio of the compatibilizer is preferably 20 parts by mass or less and more preferably 10 parts by mass or less with respect to 100 parts by mass of the base polymer.

[Elastomer]
The elastomer can be used without particular limitation as long as it is an elastomer used for a three-dimensional modeling soluble material according to the FDM method, but a viewpoint of modeling by a 3D printer and a viewpoint of improving toughness of the three-dimensional modeling soluble material. Therefore, at least one selected from the group consisting of acrylic elastomers, olefin elastomers, styrene elastomers, polyester elastomers, urethane elastomers, polyamide elastomers, and silicone elastomers is preferred, and acrylic elastomers are more preferred. Examples of the acrylic elastomer include Clarity (registered trademark) LA2250, Clarity LA2140, and Clarity LA4285 (above, manufactured by Kuraray Co., Ltd.). Examples of the olefin elastomer include Kraton (registered trademark) ERS polymer (manufactured by Kraton Polymer Co., Ltd.). Examples of the styrenic elastomer include Kraton A polymer, Kraton G polymer (manufactured by Kraton Polymer Co., Ltd.), “Tuftec H” series, “Tuftec P” series (produced by Asahi Kasei Chemicals), Septon (registered trademark), and Hibler (registered). Trademark) (Kuraray Plastics, Inc.).

The blending ratio of the elastomer is preferably 5 parts by mass or more and more preferably 10 parts by mass or more with respect to 100 parts by mass of the base polymer from the viewpoint of the formability by a 3D printer. The blending ratio of the elastomer is preferably 40 parts by mass or less and more preferably 30 parts by mass or less with respect to 100 parts by mass of the base polymer.

The raw material of the three-dimensional object precursor treating agent composition is water, a water-soluble organic solvent, a filler, a thickener, a pH adjuster, a preservative, as necessary, as long as the effects of the present embodiment are not impaired. Rust preventives, pigments, colorants and the like may be included.

[Kneading process]
In the manufacturing method of the soluble material for three-dimensional modeling of this embodiment, the ratio of the total length K of the kneading disk to the total length L of the effective screw of the twin screw extruder for kneading the raw material of the three-dimensional modeling soluble material is A kneading step of kneading with a screw configuration satisfying 0.20 <K / L <0.70. In this specification, the effective screw means a screw having functions such as conveying, shearing, and compressing powder, and includes a kneading disk. Further, in this specification, the total length L of the effective screw means the total length of the screw having functions such as conveying, shearing, and compressing powder, and specifically, the length from the hopper to the tip of the screw. Say. Furthermore, the total length of the kneading disc refers to the total length of the kneading disc in the axial direction.

The method of supplying the raw material of the three-dimensional modeling soluble material to the twin-screw extruder is not particularly limited, and a method of supplying the raw material mixed in advance to the twin-screw extruder by a feeder, The method of supplying to a screw extruder is mentioned.

The shape of the raw material of the three-dimensional modeling soluble material supplied to the twin-screw extruder may be any of powder, fine particles, flakes, and pellets.

The screw constitutes a kneading element by combining a screw-like full flight screw portion and a kneading disc portion which are feed portions. Examples of the shape of the kneading disk include a forward twist type, a reverse twist type, an orthogonal type, and a neutral type. Other parts including the full flight screw include a forward lead, a reverse lead, a seal ring, a pineapple screw, and the like. There are two and three types of screw depending on how the screw is cut, and the kneading disk may be a two or three type. The arrangement of the full flight screw and the kneading disk is not particularly limited.

From the viewpoint of the dispersibility of the elastomer, the ratio (K / L) of the total length K of the kneading disk to the total length L of the effective screw of the twin screw extruder for kneading the raw material for the three-dimensional modeling soluble material is 0. Greater than .20, preferably greater than 0.25, more preferably greater than 0.30. From the viewpoint of production efficiency, the ratio (K / L) of the total length K of the kneading disk to the total length L of the effective screw of the twin screw extruder for kneading the three-dimensional modeling soluble material is 0.70. Less than, preferably less than 0.60, more preferably less than 0.50, and even more preferably less than 0.40. Further, the ratio (K / L) of the total length K of the kneading disk to the total length L of the effective screw of the twin screw extruder for kneading the raw material of the three-dimensional modeling soluble material is the viewpoint of the dispersibility of the elastomer, From the viewpoint of production efficiency, 0.20 <(K / L) <0.70, preferably 0.25 <(K / L) <0.60, and more preferably 0.30 <(K /L)<0.5, and more preferably 0.30 <(K / L) <0.4.

The ratio (L / D) of the effective screw overall length L to the screw diameter D of the twin screw extruder for kneading the three-dimensional modeling soluble material is larger than 25, preferably from the viewpoint of improving the dispersibility of the elastomer. Greater than 27, more preferably greater than 30. The ratio (L / D) of the effective screw overall length L to the screw diameter D of the twin screw extruder for kneading the raw material for the three-dimensional modeling soluble material suppresses the decomposition and deterioration of the raw material for the three-dimensional modeling soluble material. From this viewpoint, it is preferably smaller than 120, more preferably smaller than 100, and still more preferably smaller than 80. Further, the ratio (L / D) of the effective screw total length L to the screw diameter D of the twin-screw extruder for kneading the raw material of the soluble material for three-dimensional modeling is the viewpoint of improving the dispersibility of the elastomer, and the three-dimensional modeling. 25 <(L / D), 25 <(L / D) <120 is preferable, and 27 <(L / D) <100 is more preferable, from the viewpoint of suppressing decomposition and deterioration of the raw material of the soluble material More preferably, 30 <(L / D) <80.

From the viewpoint of improving the dispersibility of the elastomer, the temperature Tmix of the three-dimensional modeling soluble material in the kneading step is based on the glass transition temperature Tg of the base polymer contained in the three-dimensional modeling soluble material. Greater than Tg + 80 (° C.), preferably greater than Tg + 90 (° C.), more preferably greater than Tg + 100 (° C.), even more preferably greater than Tg + 110 (° C.), even more preferably greater than Tg + 120 (° C.), even more preferably Is greater than Tg + 130 (° C.). The temperature Tmix of the raw material of the three-dimensional modeling soluble material in the kneading step is a base included in the raw material of the three-dimensional modeling soluble material from the viewpoint of suppressing decomposition and deterioration of the raw material of the three-dimensional modeling soluble material. It is smaller than Tg + 200 (° C.), preferably smaller than Tg + 190 (° C.), more preferably smaller than Tg + 180 (° C.), and still more preferably smaller than Tg + 170 (° C.) with respect to the glass transition temperature Tg of the polymer. Further, the temperature Tmix of the raw material of the soluble material for three-dimensional modeling in the kneading step is the third order from the viewpoint of improving the dispersibility of the elastomer and suppressing the decomposition and deterioration of the raw material of the soluble material for three-dimensional modeling. Tg + 80 (° C.) <Tmix <200 (° C.), preferably Tg + 90 (° C.) <Tmix <Tg + 190 (° C.) with respect to the glass transition temperature Tg of the base polymer contained in the raw material of the original modeling soluble material, and Tg + 100 (° C.) <Tmix <Tg + 180 (° C.) is more preferable, Tg + 110 (° C.) <Tmix <Tg + 170 (° C.) is further preferable, Tg + 120 (° C.) <Tmix <Tg + 170 (° C.) is further preferable, and Tg + 130 (° C.) <Tmix <Tg + 170 (° C.) is more preferable.

<Soluble materials for 3D modeling>
The glass transition temperature (Tg) 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, and more preferably 80 ° C. or higher, from the viewpoint of formability by a 3D printer. More preferably, from the same viewpoint, 250 ° C or lower is preferable, 220 ° C or lower is more preferable, 180 ° C or lower is further preferable, 160 ° C or lower is further preferable, 140 ° C or lower is further preferable, and 120 ° C or lower is still higher. preferable.

From the viewpoint of resin fluidity, the melt flow rate of the three-dimensional modeling soluble material is preferably 1.0 g / 10 min or more, more preferably 1.5 g / 10 min or more, further preferably 2.0 g / 10 min or more, 2.5 g / 10 min or more is more preferable, and from the viewpoint of resin toughness, 10 g / 10 min or less is preferable, 7 g / 10 min or less is more preferable, 6 g / 10 min or less is further preferable, and 5 g / 10 min or less is even more preferable.

From the viewpoint of improving the toughness of the three-dimensional modeling soluble material, the average particle size of the elastomer in the three-dimensional modeling soluble material is preferably 2.5 μm or less, more preferably 2.0 μm or less, and further preferably 1.7 μm or less. Preferably, 1.4 μm or less is even more preferable. In the present specification, the average particle diameter of the elastomer in the soluble material for three-dimensional modeling is measured by the method described in the examples.

〔filament〕
The three-dimensional modeling soluble material manufactured by the three-dimensional modeling soluble material manufacturing method is formed into a filament shape and used for manufacturing a three-dimensional object.

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.

<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. A method of manufacturing a three-dimensional object by a hot melt lamination method having a material removing step, wherein the material of the support material is a soluble material for three-dimensional modeling manufactured by the method of manufacturing a soluble material for three-dimensional modeling.

[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, except that the material of the support material is a three-dimensional modeling soluble material manufactured by the three-dimensional modeling soluble material manufacturing method. A method of obtaining a three-dimensional object precursor including a three-dimensional object and a support material in a known method for producing a three-dimensional object by a hot-melt lamination type 3D printer can be used. The three-dimensional modeling soluble material manufactured by the method of manufacturing the three-dimensional modeling soluble material, which is the material of the support material, is formed into the filament shape and supplied to the 3D printer.

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 preferable, and 30% by mass or less is preferable. % Mass or less is preferred.

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, and further preferably 40 ° C. or more.

<Support material>
The support material of the present embodiment is a support material that supports the three-dimensional object when the three-dimensional object is manufactured by a hot melt lamination type 3D printer, and the raw material of the support material is used for the three-dimensional modeling. It is the soluble material for three-dimensional modeling manufactured by the manufacturing method of a soluble material.

Regarding the above-described embodiment, the present specification further discloses the following manufacturing method.

<1> A method for manufacturing a soluble material for three-dimensional modeling used as a material for a support material for supporting a three-dimensional object when a three-dimensional object is manufactured by a 3D printer using a hot melt lamination method, Kneading with a screw configuration in which the ratio of the total length K of the kneading disk to the total length L of the effective screw of the twin screw extruder for kneading the raw material of the modeling soluble material is 0.20 <K / L <0.70. A temperature Tmix of the raw material for the three-dimensional modeling soluble material in the kneading step is Tg + 80 (° C.) with respect to the glass transition temperature Tg of the base polymer contained in the raw material for the three-dimensional modeling soluble material. ) <Tmix <Tg + 200 (° C.) A method for producing a soluble material for three-dimensional modeling.
<2> The method for producing a soluble material for three-dimensional modeling according to <1>, wherein the raw material of the soluble material for three-dimensional modeling includes a base polymer, a compatibilizing agent, and an elastomer of the soluble material for three-dimensional modeling.
<3> The base polymer is selected from the group consisting of polyvinyl alcohol, polyoxazoline, polyacrylamide, acrylate (co) polymer, methacrylate (co) polymer, polyester resin, polyamide resin, and methacrylic resin. One or more types are preferable, The manufacturing method of the soluble material for three-dimensional modeling as described in <1> or <2>.
<4> The resin according to any one of <1> to <3>, wherein the base polymer is preferably a resin having a hydrophilic group, more preferably a polyester resin having a hydrophilic group and / or a polyamide resin having a hydrophilic group. Manufacturing method of soluble material for three-dimensional modeling.
<5> Hydrophilic monomer unit A in which the polyester resin having a hydrophilic group has a hydrophilic group ₁ Hydrophobic dicarboxylic acid monomer unit B ₁ And a diol monomer unit, the hydrophilic monomer unit A in the polyester resin ₁ And hydrophobic dicarboxylic acid monomer unit B ₁ The hydrophilic monomer unit A with respect to the sum of ₁ The method for producing a soluble material for three-dimensional modeling according to any one of <1> to <4>, wherein the ratio is from 10 to 70 mol%.
<6> The hydrophilic monomer unit A ₁ Monomer A for deriving ₁ Is at least one selected from the group consisting of hydroxy group-containing aromatic dicarboxylic acids, primary amino group-containing aromatic dicarboxylic acids, sulfonic acid group-containing aromatic dicarboxylic acids, and sulfonate group-containing aromatic dicarboxylic acids. Preferably, it consists of 5-hydroxyisophthalic acid, 1,3,5-benzenetricarboxylic acid, 5-aminoisophthalic acid, 5-sulfoisophthalic acid, 2-sulfoterephthalic acid, and 4-sulfo-2,6-naphthalenedicarboxylic acid. At least one selected from the group is more 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 still more preferable, <1 The method for producing a soluble material for three-dimensional modeling according to any one of> to <5>.
<7> The content of the hydrophilic group in the polyester resin is preferably 0.5 mmol / g or more, more preferably 0.6 mmol / g or more, further preferably 0.7 mmol / g or more, 3.0 mmol / g g or less, preferably 2.0 mmol / g or less, more preferably 1.5 mmol / g or less, preferably 0.5 to 3.0 mmol / g, more preferably 0.6 to 2.0 mmol / g. 0.7 to 1.5 mmol / g is more preferable, The method for producing a soluble material for three-dimensional modeling according to any one of <1> to <6>.
<8> The hydrophilic monomer unit A relative to the total amount of all monomer units in the polyester resin ₁ The ratio of the amount of the substance is 5 mol% or more, preferably 7 mol% or more, more preferably 10 mol% or more, still more preferably 12 mol% or more, 35 mol% or less, preferably 33 mol% or less, more preferably 32 mol% or less. Preferably, 30 mol% or less is more preferable, 5 to 35 mol% is preferable, 7 to 33 mol% is more preferable, 10 to 32 mol% is further preferable, 12 to 30 mol% is still more preferable, and 8 to 13 mol% is still more preferable. <1>-<7> The manufacturing method of the soluble material for three-dimensional modeling as described in any one of <7>.
<9> The hydrophobic dicarboxylic acid monomer unit B ₁ Dicarboxylic acid B to induce ₁ Are preferably at least one selected from the group consisting of aromatic dicarboxylic acids, aliphatic dicarboxylic acids, and alicyclic dicarboxylic acids, and include terephthalic acid, isophthalic acid, 2,5-furandicarboxylic acid, and 2,6-naphthalene. More preferably, at least one selected from the group consisting of dicarboxylic acid, 1,4-cyclohexanedicarboxylic acid, and 1,3-adamantanedicarboxylic acid, terephthalic acid, 2,5-furandicarboxylic acid, and 2,6-naphthalene The method for producing a soluble material for three-dimensional modeling according to any one of <1> to <8>, wherein at least one selected from the group consisting of dicarboxylic acids is further preferred.
<10> The hydrophobic dicarboxylic acid monomer unit B in the polyester resin relative to the total amount of all monomer units in the polyester resin ₁ The ratio of the amount of the substance is preferably 15 mol% or more, more preferably 18 mol% or more, further preferably 20 mol% or more, preferably 45 mol% or less, more preferably 42 mol% or less, still more preferably 40 mol% or less, and 15 to 45 mol %, Preferably 20 to 42 mol%, more preferably 30 to 40 mol%, and the method for producing a soluble material for three-dimensional modeling according to any one of <1> to <9>.
<11> The hydrophilic monomer unit A ₁ And the hydrophobic dicarboxylic acid monomer unit B ₁ Mol ratio (the hydrophilic monomer unit A ₁ / The hydrophobic dicarboxylic acid monomer unit B ₁ ) Is preferably 10/90 or more, more preferably 15/85 or more, further preferably 18/82 or more, still more preferably 20/80 or more, preferably 70/30 or less, more preferably 65/35 or less, The method for producing a soluble material for three-dimensional modeling according to any one of <1> to <10>, further preferably 60/40 or less, further preferably 40/60 or less, and still more preferably 26/74 or less.
<12> The ratio of diethylene glycol units to the total of all diol monomer units in the polyester resin is preferably 5 mol% or more, more preferably 10 mol% or more, further preferably 15 mol% or more, further preferably 20 mol% or more, and 25 mol%. The above is more preferable, 30 mol% or more is more preferable, 60 mol% or less is preferable, 55 mol% or less is more preferable, 50 mol% or less is further preferable, and 45 mol% or less is more preferable, <1> to <11 The manufacturing method of the soluble material for three-dimensional modeling in any one of>.
<13> Ethylene glycol, 1,2-propanediol, 1,3-propanediol, diethylene glycol, dipropylene glycol, 1,4-cyclohexanedimethanol, hydrogenated bisphenol with respect to the total of all diol monomer units in the polyester resin The total ratio of A, isosorbide, bisphenoxyethanol fluorene, bisphenol fluorene, biscrezoxyethanol fluorene, and biscresol fluorene is preferably 80 mol% or more, more preferably 90 mol% or more, still more preferably 95 mol% or more, and 98 mol% or more. The soluble material for three-dimensional modeling according to any one of <1> to <12>, further preferably 100 mol%, further preferably 100 mol%, and still more preferably 100 mol%. The method of production.
<14> The polyester resin is the hydrophilic monomer unit A. ₁ The hydrophilic monomer unit A with respect to the total of all dicarboxylic acid monomer units containing ₁ And the dicarboxylic acid monomer unit B ₁ Of the dicarboxylic acid monomer unit B are 10 to 70 mol% and 30 to 90 mol%, respectively. ₁ Dicarboxylic acid B for obtaining ₁ The method for producing a soluble material for three-dimensional modeling according to any one of <1> to <13>, in which is a polyester resin α wherein 2,6 is naphthalenedicarboxylic acid.
<15> Hydrophilic monomer unit A in which the polyamide resin having a hydrophilic group has a hydrophilic group ₂ Hydrophobic dicarboxylic acid monomer unit B ₂ And the hydrophilic monomer unit A with respect to the total of all monomer units in the polyamide resin. ₂ The method for producing a soluble material for three-dimensional modeling according to any one of <1> to <14>, wherein the ratio is from 2.5 to 40 mol%.
<16> The hydrophilic monomer unit A ₂ Monomer A for deriving ₂ Is preferably 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 dicarboxylic acid, such as 5-hydroxyisophthalic acid, 1, At least one selected from the group consisting of 3,5-benzenetricarboxylic acid, 5-aminoisophthalic acid, 5-sulfoisophthalic acid, 2-sulfoterephthalic acid, and 4-sulfo-2,6-naphthalenedicarboxylic acid is more Preferably, at least one selected from the group consisting of 5-sulfoisophthalic acid and 2-sulfoterephthalic acid is more preferable, and 5-sulfoisophthalic acid is still more preferable. Any one of <1> to <15> Manufacturing method of soluble material for three-dimensional modeling.
<17> 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, still more preferably 0.7 mmol / g or more, 3.0 mmol / g g or less is preferred, 2.0 mmol / g or less is more preferred, 1.5 mmol / g or less is more preferred, 0.5 to 3.0 mmol / g is preferred, 0.6 to 2.0 mmol / g is more preferred, The method for producing a soluble material for three-dimensional modeling according to any one of <1> to <16>, wherein 0.7 to 1.5 mmol / g is more preferable.
<18> The hydrophilic monomer unit A relative to the total amount of all monomer units in the polyamide resin ₂ The ratio of the amount of the substance is 2.5 mol% or more, preferably 4 mol% or more, more preferably 6 mol% or more, still more preferably 8 mol% or more, still more preferably 10 mol% or more, and 40 mol% or less, 35 mol % Or less, more preferably 31 mol% or less, still more preferably 25 mol% or less, still more preferably 20 mol% or less, still more preferably 15 mol% or less, still more preferably 10 mol% or less, and even more preferably 8 mol% or less. 2.5 to 40 mol%, preferably 4 to 35 mol%, more preferably 6 to 31 mol%, still more preferably 8 to 20 mol%, still more preferably 8 to 15 mol%, and more preferably 8 to 12 mol%. More preferably, the tertiary according to any one of <1> to <17> The method of manufacturing the shaped for the soluble material.
<19> The hydrophobic dicarboxylic acid monomer unit B ₂ Dicarboxylic acid B to induce ₂ Are preferably at least one selected from the group consisting of aromatic dicarboxylic acids, aliphatic dicarboxylic acids, and alicyclic dicarboxylic acids, and include terephthalic acid, isophthalic acid, 2,5-furandicarboxylic acid, and 2,6-naphthalene. More preferably, at least one selected from the group consisting of dicarboxylic acid, 1,4-cyclohexanedicarboxylic acid, and 1,3-adamantanedicarboxylic acid, terephthalic acid, 2,5-furandicarboxylic acid, and 2,6-naphthalene The method for producing a soluble material for three-dimensional modeling according to any one of <1> to <18>, wherein at least one selected from the group consisting of dicarboxylic acids is more preferable, and terephthalic acid is still more preferable.
<20> The hydrophobic dicarboxylic acid monomer unit B in the polyamide resin relative to the total amount of all monomer units in the polyamide resin ₂ The ratio of the amount of the substance is preferably 10 mol% or more, more preferably 20 mol% or more, still more preferably 30 mol% or more, still more preferably 35 mol% or more, still more preferably 40 mol% or more, still more preferably 42 mol% or more. 47.5 mol% or less is preferred, 45 mol% or less is more preferred, 42 mol% or less is more preferred, 40 mol% or less is even more preferred, 10 to 47.5 mol% is preferred, 20 to 45 mol% is more preferred, 30 to The method for producing a soluble material for three-dimensional modeling according to any one of <1> to <19>, further preferably 42 mol%.
<21> The hydrophilic monomer unit A ₂ And the hydrophobic dicarboxylic acid monomer unit B ₂ Mol ratio (the hydrophilic monomer unit A ₂ / The hydrophobic dicarboxylic acid monomer unit B ₂ ) Is preferably 10/90 or more, more preferably 15/85 or more, further preferably 18/82 or more, still more preferably 20/80 or more, preferably 50/50 or less, more preferably 40/60 or less, The method for producing a soluble material for three-dimensional modeling according to any one of <1> to <20>, further preferably 30/70 or less, and further preferably 25/75 or less.
<22> The weight average molecular weight of the base polymer 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 method for producing a soluble material for three-dimensional modeling according to any one of <1> to <21>.
<23> The glass transition temperature (Tg) of the base polymer is 50 ° C. or higher, preferably 60 ° C. or higher, more preferably 70 ° C. or higher, further preferably 80 ° C. or higher, 250 ° C. or lower, and 220 ° C. or lower. Is preferably 180 ° C. or lower, more preferably 160 ° C. or lower, still more preferably 140 ° C. or lower, and still more preferably 120 ° C. or lower, for three-dimensional modeling according to any one of <1> to <22> A method for producing a soluble material.
<24> The melt flow rate of the base polymer is preferably 1.0 g / 10 min or more, more preferably 1.5 g / 10 min or more, further preferably 2.0 g / 10 min or more, and further more preferably 2.5 g / 10 min or more. Preferably, 10 g / 10 min or less, more preferably 7 g / 10 min or less, more preferably 6 g / 10 min or less, still more preferably 5 g / 10 min or less, 3D modeling according to any one of <1> to <23> Of a soluble material for use.
<25> The blending ratio of the base polymer is preferably 70% by mass or more, more preferably 80% by mass or more, preferably 95% by mass or less, more preferably 90% by mass or less, and any one of <1> to <24> A method for producing a soluble material for three-dimensional modeling according to claim 1.
<26> The mixing ratio of the compatibilizer is preferably 2 parts by mass or more, more preferably 3 parts by mass or more, preferably 20 parts by mass or less, more preferably 10 parts by mass or less, relative to 100 parts by mass of the base polymer. A preferable method for producing a soluble material for three-dimensional modeling according to any one of <1> to <25>.
<27> Preferably, the compatibilizer includes at least one reactive group selected from the group consisting of an epoxy group, an acid anhydride group, an isocyanate group, an amino group, a carboxyl group, and an oxazoline group. The method for producing a soluble material for three-dimensional modeling according to any one of <1> to <25>, wherein a reactive compatibilizing agent having an epoxy group is more preferred.
<28> The elastomer is preferably at least one selected from the group consisting of acrylic elastomers, olefin elastomers, styrene elastomers, polyester elastomers, urethane elastomers, polyamide elastomers, and silicone elastomers. The method for producing a soluble material for three-dimensional modeling according to any one of <1> to <27>, wherein an elastomer is more preferable.
<29> The blending ratio of the elastomer is preferably 5 parts by mass or more, more preferably 10 parts by mass or more, preferably 40 parts by mass or less, more preferably 30 parts by mass or less, with respect to 100 parts by mass of the base polymer. The method for producing a soluble material for three-dimensional modeling according to any one of <1> to <28>.
<30> The ratio (K / L) of the total length K of the kneading disk to the total length L of the effective screw of the twin-screw extruder for kneading the raw material for the three-dimensional modeling soluble material is greater than 0.20, Preferably greater than 0.25, more preferably greater than 0.30, less than 0.70, preferably less than 0.60, more preferably less than 0.50, even more preferably less than 0.40, 0.20 <(K / L) <0.70, preferably 0.25 <(K / L) <0.60, more preferably 0.30 <(K / L) <0.5. More preferably, 0.30 <(K / L) <0.4, The method for producing a soluble material for three-dimensional modeling according to any one of <1> to <29>.
<31> The ratio (L / D) of the effective screw full length L to the screw diameter D of the twin-screw extruder for kneading the raw material for the three-dimensional modeling soluble material is larger than 25, preferably larger than 27, more preferably. Is greater than 30, preferably less than 120, more preferably less than 100, even more preferably less than 80, 25 <(L / D), 25 <(L / D) <120 is preferred, and 27 <( L / D) <100 is more preferable, and 30 <(L / D) <80 is more preferable. The method for producing a soluble material for three-dimensional modeling according to any one of <1> to <30>.
<32> The temperature Tmix of the raw material for the three-dimensional modeling soluble material in the kneading step is greater than Tg + 80 (° C.) with respect to the glass transition temperature Tg of the base polymer contained in the raw material for the three-dimensional modeling soluble material. , Preferably greater than Tg + 90 (° C.), more preferably greater than Tg + 100 (° C.), even more preferably greater than Tg + 110 (° C.), even more preferably greater than Tg + 120 (° C.), even more preferably greater than Tg + 130 (° C.). Large, smaller than Tg + 200 (° C.), preferably smaller than Tg + 190 (° C.), more preferably smaller than Tg + 180 (° C.), still more preferably smaller than Tg + 170 (° C.), and Tg + 80 (° C.) <Tmix <200 (° C.) Yes, Tg + 90 (° C) <Tmix <Tg + 190 (° C) Preferably, Tg + 100 (° C.) <Tmix <Tg + 180 (° C.), more preferably Tg + 110 (° C.) <Tmix <Tg + 170 (° C.), more preferably Tg + 120 (° C.) <Tmix <Tg + 170 (° C.), Tg + 130 (° C.) ) <Tmix <Tg + 170 (° C.) is more preferable. The method for producing a soluble material for three-dimensional modeling according to any one of <1> to <31>.
<33> A soluble material for three-dimensional modeling manufactured by the method for manufacturing a soluble material for three-dimensional modeling according to any one of <1> to <32>.
<34> The glass transition temperature (Tg) 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 250 ° C. or lower. 3D modeling according to <33>, preferably 220 ° C. or lower, more preferably 180 ° C. or lower, still more preferably 160 ° C. or lower, still more preferably 140 ° C. or lower, and still more preferably 120 ° C. or lower. Soluble material.
<35> The melt flow rate of the three-dimensional modeling soluble material is preferably 1.0 g / 10 min or more, more preferably 1.5 g / 10 min or more, further preferably 2.0 g / 10 min or more, and 2.5 g / 10 min. The above is more preferable, 10 g / 10 min or less is preferable, 7 g / 10 min or less is more preferable, 6 g / 10 min or less is more preferable, and 5 g / 10 min or less is more preferable, 3D according to <33> or <34> Soluble material for modeling.
<36> The average particle size of the elastomer in the three-dimensional modeling soluble material is preferably 2.5 μm or less, more preferably 2.0 μm or less, still more preferably 1.7 μm or less, and even more preferably 1.4 μm or less. <33>-<35> The soluble material for three-dimensional modeling according to any one of the above.
<37> The soluble material for 3D modeling according to any one of <33> to <36>, wherein the soluble material for 3D modeling is a filament.
<38> 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, more preferably 2.0 mm or less, still more preferably 1.8 mm or less, <33> The soluble material for three-dimensional modeling according to any one of to <36>.
<39> The soluble material for three-dimensional modeling according to any one of <33> to <38>, wherein the filament is drawn.
<40> The draw ratio in the drawing process is preferably 1.5 times or more, more preferably 2 times or more, further preferably 3 times or more, still more preferably 5 times or more, preferably 200 times or less, and 150 times or less. The soluble material for three-dimensional modeling according to any one of <33> to <39>, more preferably 100 times or less, and still more preferably 50 times or less.
<41> The stretching temperature in the stretching process is preferably in the range of a temperature that is 20 ° C. lower than the glass transition temperature of the soluble material for three-dimensional modeling to a temperature that is 110 ° C. higher than the glass transition temperature. More preferably, the temperature is 10 ° C. lower than the glass transition temperature, more preferably the same temperature as the glass transition temperature, the upper limit of the stretching temperature is more preferably 110 ° C. higher than the glass transition temperature, and 100 ° C. higher than the glass transition temperature. The soluble material for three-dimensional structure fabrication according to any one of <33> to <40>, wherein the temperature is more preferable, and a temperature higher by 90 ° C. than the glass transition temperature is further preferable.
<42> 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 3D object manufacturing method according to claim 1, wherein the material of the support material is manufactured by the method of manufacturing a 3D modeling soluble material according to any one of <1> to <32>. A method for manufacturing a three-dimensional object.
<43> The modeling material that is the material of the three-dimensional object is ABS resin, polylactic acid resin, polycarbonate resin, 12-nylon, 6,6-nylon, 6-nylon, polyphenylsulfone resin, polyetheretherketone, And a thermoplastic resin such as polyetherimide is preferable, an ABS resin and / or a polylactic acid resin is more preferable, and an ABS resin is still more preferable.
<44> The method for producing a three-dimensional object according to <42> or <43>, wherein the neutral water includes a water-soluble organic solvent.
<45> The water-soluble organic solvent is a lower alcohol such as methanol, ethanol or 2-propanol, a glycol ether such as propylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monotertiary butyl ether or diethylene glycol monobutyl ether, The method for producing a three-dimensional object according to any one of <42> to <44>, wherein ketones such as acetone and methyl ethyl ketone are preferred.
<46> 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 more preferably 3% by mass or more. Further preferably, 50% or less is preferable, 40% or less is preferable, 30% or less is preferable, and 20% or less is preferable, the three-dimensional object according to any one of <42> to <45> Production method.
<47> The amount of the neutral water used is preferably 10 times by mass or more, more preferably 20 times by mass or more, preferably 10,000 times by mass or less, more preferably 5000 times by mass or less, more preferably 1000 masses with respect to the support material. The method for producing a three-dimensional object according to any one of <42> to <46>, wherein the ratio is more preferably double or less and even more preferably 100 mass times or less.
<48> Time for contacting the three-dimensional modeling soluble material with neutral water is preferably 5 minutes or more, preferably 180 minutes or less, more preferably 120 minutes or less, and even more preferably 90 minutes or less, <42> to The method for producing a three-dimensional object according to any one of <47>.
<49> The temperature of the neutral water to be brought into contact with the three-dimensional modeling soluble material is preferably 15 ° C or higher, more preferably 25 ° C or higher, further preferably 30 ° C or higher, still more preferably 40 ° C or higher, 85 ° C. The method for producing a three-dimensional object according to any one of <42> to <48>, wherein the following is preferable, 70 ° C. or lower is more preferable, and 60 ° C. or lower is further preferable.
<50> 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 the raw material of the support material is any one of <1> to <32> The support material which is the soluble material for three-dimensional modeling manufactured by the manufacturing method of the soluble material for three-dimensional modeling described in 1.

<Synthesis of base polymer>
[Synthesis Example 1]
To a 100 L stainless steel reactor (stirrer with nitrogen inlet tube), dimethyl 2,6-naphthalenedicarboxylate (manufactured by BP), 4.09 kg, ethylene glycol (manufactured by Wako Pure Chemical Industries, Ltd., special grade) 3.06 kg, 5 -1.69 kg of dimethyl sodium sulfoisophthalate (manufactured by Takemoto Yushi Co., Ltd.), 1.71 g of titanium tetrabutoxide (manufactured by Tokyo Chemical Industry Co., Ltd., first grade), sodium acetate trihydrate (manufactured by Wako Pure Chemical Industries, Ltd., special grade) 42 0.0 g was charged, the temperature was raised to 230 ° C. over 1.5 hours under normal pressure and nitrogen atmosphere, and transesterification was performed by heating at 230 ° C. for 360 minutes. 637 mg of 85% phosphoric acid (Sigma Aldrich Japan Co., Ltd., special grade) was added and stirred for 10 minutes, then heated to 260 ° C. over 90 minutes, and simultaneously polycondensed by stirring while reducing the pressure to 30 mmHg. A white solid (room temperature) polyester compound 1 was obtained.

[Synthesis Example 2]
Ethylene glycol was changed to 3.20 kg, the temperature raising time up to 260 ° C. was changed from 90 minutes to 130 minutes, and polyester resin 2 was obtained.

[Synthesis Example 3]
Ethylene glycol was changed to 3.20 kg, the temperature raising time up to 260 ° C. was changed from 90 minutes to 150 minutes, and polyester resin 3 was obtained.

[Analysis of base polymer]
[Composition of polyester resin]
The compositions of the polyester resins 1 to 3 were determined by proton NMR measurement using Agilent NMR and MR400.

[Amount of hydrophilic group in polyester resin]
The amount (unit: mmol / g) of the hydrophilic group (SO ₃ ) in the polyester resin was determined from the compositions of the polyester resins 1 to 3 determined by the above method.

[Melt flow rate]
Resin that flows per 10 minutes at 240 ° C./5.0 kg of the polyester resins 1 to 3 using a melt flow rate measuring device “Semi-automatic melt flow index tester No. 120-SAS-2000” manufactured by Yasuda Seiki Seisakusho Co., Ltd. The mass of was measured.

[Weight average molecular weight]
10 mg of each of the polyester resins 1 to 3 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 gel permeation chromatography (GPC) was performed according to the following conditions. ).
Measuring device: HLC-8320GPC (manufactured by TOSOH)
Eluent: HFIP / 0.5 mM sodium trifluoroacetate Flow rate: 0.2 mL / min
Measurement temperature: 40 ° C
Analytical column: TSK-Gel Super AWM-H (manufactured by TOSOH)
Calibration curve: ShodexSTANDARD M-75
Reference material: Polymethylmethacrylate (PMMA)

[Glass-transition temperature]
Using a press machine (Lab Press P2-30T manufactured by Toyo Seiki Seisakusho Co., Ltd.), the polyester resins 1 to 3 were respectively pressed at 230 ° C. and 0.5 MPa for 2 minutes, and subsequently at 230 ° C. and 20 MPa for 2 minutes. Thereafter, a sheet having a thickness of 0.4 mm was prepared by rapid cooling. A 5 to 10 mg sample is cut out from this sheet with scissors, precisely weighed in an aluminum pan, sealed, and heated at a rate of 10 ° C./min from 30 ° C. to 250 ° C. using a DSC device (DSC7020 manufactured by Seiko Instruments Inc.). And then cooled rapidly to 30 ° C. The glass transition temperature (° C.) was determined from the DSC curve obtained by raising the temperature again to 250 ° C. at 10 ° C./min.

The results of the analysis are shown in Table 1. In Table 1, SIP (mol%) is the ratio (mol%) of 5-sulfoisophthalic acid monomer unit in all dicarboxylic acid monomer units, and NPDCA (mol%) is 2,6- Ratio of naphthalenedicarboxylic acid monomer units (mol%), EG (mol%) is the ratio of ethylene glycol monomer units in all diol monomer units (mol%), and DEG (mol%) is diethylene glycol monomer units in all diol monomer units. The ratio (mol%) is shown.

 

 

<Example>
[Example 1]
80.0 kg of the polyester compound 3 and Clarity (registered trademark) LA2250 (manufactured by Kuraray Co., Ltd .: thermoplastic elastomer: polymethyl methacrylate-polybutyl acrylate-polymethyl methacrylate triblock copolymer) 10.0 kg, compatibilized Bondfast (registered trademark) 7B (manufactured by Sumitomo Chemical Co., Ltd .: ethylene-vinyl acetate-glycidyl methacrylate copolymer) 4.0 kg as an agent was dried at 60 ° C. under reduced pressure, and then a twin screw extruder ( TOSHIBA MACHINE CO., LTD .: TEM-41SS, screw diameter 41 mm, two-row type) was melt kneaded at a cylinder temperature of 220 ° C., a screw rotation speed of 250 rpm, and a discharge speed of 70 kg / h to obtain a white mixture composition. . The configuration of the screw of the twin screw extruder in Example 1 was as follows.
7 kneading discs (forward twisted type) 776 mm to 1050 mm from the starting point 2 kneading discs (forward twisted type) 1302 mm to 1650 mm from the starting point 2 kneading discs (orthogonal) 1 kneading disc (forward twist type), 2 kneading discs (orthogonal), 2 kneading discs (reverse twist type) 1 kneading disc (forward twist type) 1934 mm to 2176 mm from the starting point Sheets, 1 kneading disc (orthogonal), 1 kneading disc (forward twisted), 1 kneading disc (orthogonal), 1 kneading disc (forward twisted), kneading disc ( 1 orthogonal) Note that the total screw length is 2551mm, kneading disc The total was 864 mm.

[Example 2]
8.0 kg of the above-mentioned polyester compound 2 and 1.0 kg of Clarity (registered trademark) LA2250 and 0.4 kg of Bondfast (registered trademark) 7B as a compatibilizer were dried at 60 ° C. under reduced pressure, and these were premixed in a Henschel mixer. Thereafter, the mixture was melt kneaded at a cylinder temperature of 210 ° C., a screw rotation speed of 200 rpm, and a discharge speed of 3 kg / h using a twin-screw extruder (manufactured by Ikegai Co., Ltd .: PCM30, screw diameter 29 mm, Sanjo type), and was a white mixture composition I got a thing. The configuration of the screw of the twin screw extruder in Example 2 was as follows.
Four kneading discs (neutral type), two kneading discs (forward twist type), and one kneading disc (reverse twist type) at a distance of 250 mm to 365.5 mm from the starting point 410.5 mm to the starting point One kneading disc (forward twist type) at 443.5 mm and one kneading disc (reverse twist type) A kneading disc (forward twist type) 488.5 mm to 521.5 mm from the starting point 1 piece, 1 kneading disc (reverse twist type) 1 kneading disc (forward twist type), 1 kneading disc (reverse twist type) from the start point 566.5 mm to 599.5 mm Start point From 614.5 mm to 649.5 mm from the seal ring From the starting point to 749.5 mm to 799.5 mm Lee Nappuru screw It should be noted that the total length of the screw is 799.5mm, the sum of the kneading disk was 214.5mm.

Example 3
Except for changing the cylinder temperature to 230 ° C., the same operation as in Example 2 was performed to obtain a composition which was a white mixture.

Example 4
Except for changing the cylinder temperature to 190 ° C., the same operation as in Example 2 was performed to obtain a composition which was a white mixture.

Example 5
40.0 kg of the polyester compound 3 and 5.0 kg of Tuftec (registered trademark) M1913 (manufactured by Asahi Kasei Chemicals Corporation: thermoplastic elastomer having acid anhydride group: maleic anhydride-modified SEBS) were dried at 60 ° C. under reduced pressure, and weight Using a feeder, melt kneading using a twin screw extruder (Toshiba Machine Co., Ltd .: TEM-41SS, screw diameter 41 mm, double thread type) at a cylinder temperature of 230 ° C., a screw rotation speed of 250 rpm, and a discharge speed of 70 kg / h. The composition which is a white mixture was obtained. The screw configuration, total screw length, and total kneading disc length of the twin screw extruder in Example 5 were the same as in Example 1.

Example 6
40.0 kg of the above-mentioned polyester compound 3 and 7.0 kg of Tuftec (registered trademark) M1913 (manufactured by Asahi Kasei Chemicals: thermoplastic elastomer having an acid anhydride group: maleic anhydride-modified SEBS) were dried at 60 ° C. under reduced pressure, and weight Using a feeder, melt kneading using a twin screw extruder (Toshiba Machine Co., Ltd .: TEM-41SS, screw diameter 41 mm, double thread type) at a cylinder temperature of 230 ° C., a screw rotation speed of 250 rpm, and a discharge speed of 70 kg / h. The composition which is a white mixture was obtained. The screw configuration, total screw length, and total kneading disc length of the twin screw extruder in Example 6 were the same as in Example 1.

[Comparative Example 1]
Except having changed the structure of the screw as follows, operation similar to Example 2 was performed and the composition which is a white mixture was obtained.
Four kneading discs (neutral type) 330 mm to 396 mm from the start point Four kneading discs (forward twist type) 496 mm to 562 mm from the start point Seal ring from the start point 562 mm to 597 mm 747 mm from the start point Pineapple screw at ˜797 mm The total screw length was 797 mm and the total kneading disk was 132 mm.

[Reference Example 1] (Preparation of drawn filament (monofilament manufacturing apparatus) 1)
In order to produce a drawn filament of the composition obtained in Example 1, a monofilament production apparatus (manufactured by Chubu Machine Co., Ltd .: monofilament production apparatus) equipped with an extruder, a winding device, and a hot air tank was used. The composition obtained in Example 1 was charged into a hopper of an extruder having a nozzle diameter of 5 mm (gear pump = 2.4 cc / rotation, gear pump rotation speed 29.4 rpm, screw diameter 35 mm, L / D = 28), and cylinder Extrusion was performed at a temperature of 230 ° C. and a rotation speed of 23 rpm (resin temperature at discharge 210 ° C.). The extruded composition is wound with air in a first roll while winding the filament at a speed of 12.0 m / min (resin temperature 80 ° C. behind the first roll), and further heated with hot air of 90 ° C., Stretching was performed while winding with a second roll at a speed of 37.0 m / min to obtain a filament having a diameter of about 1.4 to 1.6 mm (total stretching ratio: 10 to 13 times). The elongation at break of this stretched filament was 12%, and the toughness was higher than that of a filament having the same composition prepared from a capillograph and having a low stretch ratio (stretch ratio of 1.8). It is considered that as the draw ratio increases, the orientation of the polyester molecules progresses, and the elastomer is stretched to reduce the particle size, thereby increasing the toughness of the filament. Thereafter, the filament was supplied to the makerbot 3D printer Replicator 2X and extruded from a heat nozzle having a temperature of 230 ° C. As a result, the nozzle could be discharged without clogging, and it was confirmed that the melt also solidified immediately. .

[Reference Example 2] (Preparation of drawn filament (monofilament manufacturing apparatus) 2)
A filament was produced in the same manner as in Reference Example 1 except that the winding speed of the first roll was changed to 18.2 m / min, and a filament having a diameter of about 1.4 to 1.6 mm was obtained (total draw ratio of 10 to 13 times). The elongation at break of this drawn filament was 17%.

[Reference Example 3] (Preparation of drawn filament (monofilament manufacturing apparatus) 3)
A filament was produced in the same manner as above except that the winding speed of the first roll was changed to 21.5 m / min, and a filament having a diameter of about 1.4 to 1.6 mm was obtained (total draw ratio: 10 to 13 times) ). The elongation at break of this drawn filament was 19%.

The higher the winding speed on the first roll, the more the polyester molecules are stretched between the extruder nozzle and the first roll, the molecular orientation proceeds, and the elastomer is stretched to reduce the particle size, so that the toughness of the filaments It is thought that will increase.

〔Evaluation methods〕
[Temperature of soluble materials for 3D modeling]
The temperature of the discharged soluble material for 3D modeling was measured using a thermocouple near the die of the twin screw extruder.

[Glass transition temperature of soluble materials for 3D modeling]
The analysis was performed in the same manner as the method for analyzing the glass transition temperature of the base polymer.

[Filament elongation at break]
Using a tensile compression tester (manufactured by SHIMADZU, trade name “Autograph AGS-X”), it was measured by a tensile elongation test at break of the molded body. A 90 mm filament was set at a fulcrum distance of 50 mm, measured at a crosshead speed of 1 mm / min, and the elongation at break (%) was examined. High fracture elongation and high toughness. A 10-point test was performed per sample, and the average value was taken as the measured value.
(Preparation of drawn filament)
A finely crushed sample piece is extruded from a capillary having a diameter of 2.0 mm and a length of 10 mm at a melting temperature of 210 ° C. and an extrusion speed of 10 mm / min using a capillograph (Capigraph 1D manufactured by Toyo Seiki Seisakusho), and the tip is pinched with tweezers. While being pulled lightly by hand, it was processed into a filament having a diameter of 1.5 mm (stretching ratio 1.8 times).

[Toughness]
The toughness of the drawn filaments obtained by the above method was evaluated. As a simple evaluation of toughness, the prepared filament was evaluated by bending it by hand. The evaluation criteria are as follows.
A: 180 ° bendable B: 90 ° bendable C: 90 ° bendable

[Average particle diameter of elastomer]
[Average Particle Size of Elastomer Used in Examples 1 to 4 and Comparative Example 1]
Using a press machine (Lab Press P2-30T manufactured by Toyo Seiki Seisakusho Co., Ltd.), the sample was pressed at 230 ° C. and 0.5 MPa for 2 minutes, and subsequently at 230 ° C. and 20 MPa for 2 minutes. Thereafter, a sheet having a thickness of 0.4 mm was prepared by rapid cooling. The sheet was folded and broken in liquid nitrogen. The sheet was immersed in ethyl acetate for 1 hour to elute elastomer Clarity (registered trademark) LA2250. Then, the sample was taken out from ethyl acetate and dried under reduced pressure at 60 ° C. for 1 hour. After vacuum drying, the fracture surface of the sample was observed with an SEM (VE-8800 manufactured by Keyence), and the equivalent circle diameter of the voids found in the cross section of the sample was determined using image analysis software WINROOF. The voids were counted in a 61 μm × 46 μm photograph, the average value was calculated, and the average particle size was obtained.

[Average Particle Size of Elastomer Used in Examples 5 and 6]
Using a press machine (Lab Press P2-30T manufactured by Toyo Seiki Seisakusho Co., Ltd.), the sample was pressed at 230 ° C. and 0.5 MPa for 2 minutes, and then at 230 ° C. and 20 MPa for 2 minutes. Thereafter, a sheet having a thickness of 0.4 mm was prepared by rapid cooling. The sheet was folded and broken in liquid nitrogen. The sheet was immersed in cyclohexane for 1 hour to elute the elastomer TUFTEC (registered trademark) M1913. Then, the sample was taken out from cyclohexane and dried under reduced pressure at 60 ° C. for 1 hour. After vacuum drying, the fracture surface of the sample was observed with an SEM (VE-8800 manufactured by Keyence), and the equivalent circle diameter of the voids found in the cross section of the sample was determined using image analysis software WINROOF. The voids were counted in a 61 μm × 46 μm photograph, the average value was calculated, and the average particle size was obtained.

[Melt flow rate of soluble materials for 3D modeling]
The analysis was performed in the same manner as the analysis method of the melt flow rate of the base polymer.

[Filament dissolution time]
1 L of water was put into a beaker with a capacity of 1 L, and heated to 70 ° C. with a heater while stirring at 300 rpm with a magnetic stirrer. A resin filament (diameter: about 1.5 mm, length: 13 cm) molded by a capillograph was hung and immersed from above, and the time until the filament was dissolved and cut was measured with a stopwatch.

The results of the analysis are shown in Table 2. “Ratio of melt flow rate (N / M)” in Table 2 is the ratio between the melt flow rate (M) of the base polymer and the melt flow rate (N) of the soluble material for three-dimensional modeling, and the numerical value is low. This means that the elastomer is dispersed.

 

 

Claims (10)

When producing a three-dimensional object by a hot melt lamination type 3D printer, a method for producing a soluble material for three-dimensional modeling used as a material for a support material for supporting the three-dimensional object,
Screw structure in which the ratio of the total length K of the kneading disk to the total length L of the effective screw of the twin-screw extruder for kneading the three-dimensional modeling soluble material is 0.20 <K / L <0.70 The temperature Tmix of the raw material of the soluble material for three-dimensional modeling in the kneading step is relative to the glass transition temperature Tg of the base polymer contained in the raw material of the soluble material for three-dimensional modeling, The manufacturing method of the soluble material for three-dimensional modeling which is Tg + 80 (degreeC) <Tmix <Tg + 200 (degreeC). 2. The method for producing a soluble material for three-dimensional modeling according to claim 1, wherein in the kneading step, a ratio L / D of the screw diameter D of the twin-screw extruder and the effective screw full length L is L / D> 25. . The method for producing a soluble material for three-dimensional modeling according to claim 1 or 2, wherein the glass transition temperature Tg of the base polymer is 50 ° C or higher and 250 ° C or lower. The method for producing a soluble material for three-dimensional modeling according to any one of claims 1 to 3, wherein the base polymer includes a resin having a hydrophilic group. The method for producing a soluble material for three-dimensional modeling according to any one of claims 1 to 4, wherein the base polymer has a polyester resin having a hydrophilic group and / or a polyamide resin having a hydrophilic group. The polyester resin is a hydrophilic monomer unit A ₁ having a hydrophilic _group, a hydrophobic dicarboxylic acid monomer units B _1, and the diol monomer units, wherein the hydrophilic monomer units to the sum of the total monomer units of the polyester resin the proportion of a ₁ is 10 ~ 70 mol%, the production method of the three-dimensional shaping soluble material according to claim 5. The polyamide resin has a hydrophilic monomer unit A ₂ having a hydrophilic group, a hydrophobic dicarboxylic acid monomer unit B ₂ , and a hydrophobic diamine monomer unit, and the hydrophilicity with respect to the total of all monomer units in the polyamide resin the proportion of the monomer unit _{a 2} is 2.5 ~ 40 mol%, the production method of the three-dimensional shaping soluble material according to claim 5 or 6. The method for producing a soluble material for three-dimensional modeling according to any one of claims 1 to 7, wherein the raw material of the soluble material for three-dimensional modeling contains a base polymer, an elastomer, and a compatibilizing agent. The method for producing a soluble material for three-dimensional modeling according to claim 8, wherein the elastomer is an acrylic elastomer resin. The method for producing a soluble material for three-dimensional modeling according to claim 8 or 9, wherein the compatibilizing agent has a reactive functional group, and the reactive functional group is an epoxy group.