WO2024237059A1 - Resin composition - Google Patents

Abstract

The present invention is a resin composition containing the following components A and B, wherein the content mass ratio of component B to component A is 0.32 or less. According to the present invention, it is possible to provide a resin composition that serves as a material for a soluble material for three-dimensional molding, the material being removable with neutral water while being highly adhesive to many types of molding materials and being flexible and hard to break. Component A: a water-soluble polyester resin α having aromatic dicarboxylic acid monomer units A that have a hydrophilic group, dicarboxylic acid monomer units B that do not have hydrophilic groups, and diol monomer units Component B: a non-water-soluble resin β having a SP value in the range of 15 (J/cm³)^1/2 to 25 (J/cm³)^1/2, and a glass transition temperature in the range of 80°C to 160°C

Description

Resin composition

The present invention relates to a resin composition.

A 3D printer is a type of rapid prototyping, a three-dimensional printer that creates three-dimensional objects based on 3D data such as 3D CAD and 3D CG. Known 3D printer methods include fused deposition modeling (FDM), inkjet ultraviolet curing, photolithography, and laser sintering. Of these, the FDM method is a modeling method in which a modeling material is heated/melted, extruded, and laminated to obtain a three-dimensional object. Polymer filaments and powder materials for toner are mainly used as modeling materials, but unlike other methods, no chemical reaction of the modeling material is used. Therefore, FDM 3D printers, especially those using polymer filaments as modeling materials, are small and low-cost, and have become increasingly popular in recent years as devices that require little post-processing. To create three-dimensional objects with more complex shapes using the FDM method, the modeling material that constitutes the three-dimensional object and the support material that supports the three-dimensional structure of the modeling material are layered to obtain a three-dimensional object precursor, and then the support material is removed from the three-dimensional object precursor to obtain the desired three-dimensional object.

One method for removing support material from a three-dimensional object precursor is to use a methacrylic acid copolymer as the support material and remove the support material by immersing the three-dimensional object precursor in a high-temperature strong alkaline aqueous solution (for example, JP2012-509777A). This method utilizes the fact that the carboxylic acid in the methacrylic acid copolymer is neutralized by the alkali and dissolves in the strong alkaline aqueous solution.

However, when the methacrylic acid copolymer disclosed in JP2012-509777 is used as a support material, it is necessary to use a strong alkaline aqueous solution to remove the support material from the three-dimensional object precursor, but this strong alkaline aqueous solution is dangerous to people and places a large burden on the environment.

In response to the above-mentioned problem, JP 2017-030346 A discloses a soluble material for three-dimensional modeling that contains a specific water-soluble polyester resin. The soluble material for three-dimensional modeling disclosed in JP 2017-030346 A is suitable for the manufacture of three-dimensional objects using the FDM method, and is resistant to moisture absorption, has a high dissolution rate in neutral water, and can provide a support material that can be quickly removed from a three-dimensional object precursor without using a strong alkaline aqueous solution.

The present invention relates to a resin composition comprising the following components A and B, in which the mass ratio of the content of the component B to the content of the component A is 0.32 or less.
Component A: a water-soluble polyester resin α having an aromatic dicarboxylic acid monomer unit A having a hydrophilic group, a dicarboxylic acid monomer unit B not having a hydrophilic group, and a diol monomer unit
Component B: a water-insoluble resin β having an SP value in the range of 15 (J/cm ³ ) ^1/2 or more and 25 (J/cm ³ ) ^1/2 or less and a glass transition temperature in the range of 80° C. or more and 160° C. or less.

The present invention is a soluble material for three-dimensional modeling that contains the resin composition.

The present invention provides a method for producing a three-dimensional object by a fused deposition modeling method, the method including a step of obtaining a three-dimensional object precursor including a three-dimensional object and a supporting material, and a supporting material removal step of contacting the three-dimensional object precursor with neutral water to remove the supporting material,
The material of the support material is the soluble material for three-dimensional modeling.

Schematic diagram showing the shape of a three-dimensional object precursor produced in the examples.

Detailed Description of the Invention

If the adhesion between the modeling material and support material that make up the three-dimensional object is poor, the support material may easily peel off from the modeling material during modeling of the three-dimensional object using the FDM method, which may reduce the modeling accuracy of the three-dimensional object. In order to improve adhesion to the modeling material, it is possible to develop a support material that is tailored to the modeling material, but since there are many types of modeling materials, there is a demand for a versatile support material that has high adhesion to many types of modeling materials.

In the FDM method, which uses polymer filaments as the modeling material, a filament-shaped modeling material and a soluble material for three-dimensional modeling, which serves as the support material, are supplied to a 3D printer and then stacked to form a three-dimensional object. However, if the supplied filament breaks during modeling, the supply of material stops, resulting in a decrease in productivity and modeling accuracy. For this reason, there is a demand for filaments that are flexible and difficult to break.

The present invention provides a resin composition that can be used as a soluble material for three-dimensional modeling that is removable with neutral water, has high adhesiveness to many types of modeling materials, and is flexible and resistant to breaking; a soluble material for three-dimensional modeling that contains the resin composition; and a method for manufacturing a three-dimensional object using the soluble material for three-dimensional modeling.

The present invention relates to a resin composition comprising the following components A and B, in which the mass ratio of the content of the component B to the content of the component A is 0.32 or less.
Component A: a water-soluble polyester resin α having an aromatic dicarboxylic acid monomer unit A having a hydrophilic group, a dicarboxylic acid monomer unit B not having a hydrophilic group, and a diol monomer unit
Component B: a water-insoluble resin β having an SP value in the range of 15 (J/cm ³ ) ^1/2 or more and 25 (J/cm ³ ) ^1/2 or less and a glass transition temperature in the range of 80° C. or more and 160° C. or less.

The present invention is a soluble material for three-dimensional modeling that contains the resin composition.

The present invention provides a method for producing a three-dimensional object by a fused deposition modeling method, the method including a step of obtaining a three-dimensional object precursor including a three-dimensional object and a supporting material, and a supporting material removal step of contacting the three-dimensional object precursor with neutral water to remove the supporting material,
The material of the support material is the soluble material for three-dimensional modeling.

The present invention provides a resin composition that can be used as a soluble material for three-dimensional modeling that is removable with neutral water, has high adhesion to many types of modeling materials, and is flexible and resistant to breaking; a soluble material for three-dimensional modeling that contains the resin composition; and a method for manufacturing a three-dimensional object using the soluble material for three-dimensional modeling.

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

<Resin Composition>
The resin composition of the present embodiment contains the following component A and component B, and the content mass ratio of component B to component A is 0.32 or less.
Component A: a water-soluble polyester resin α having an aromatic dicarboxylic acid monomer unit A having a hydrophilic group, a dicarboxylic acid monomer unit B not having a hydrophilic group, and a diol monomer unit
Component B:
A water-insoluble resin β having an SP value in the range of 15 (J/cm ³ ) ^1/2 or more and 25 (J/cm ³ ) ^1/2 or less and a glass transition temperature in the range of 80° C. or more and 160° C. or less.

The resin composition of this embodiment can provide a resin composition that can be used as a soluble material for three-dimensional modeling, which is removable with neutral water, has high adhesion to many types of modeling materials, and is flexible and resistant to breaking.

[Component A]
The component A is a water-soluble polyester resin α having an aromatic dicarboxylic acid monomer unit A having a hydrophilic group other than the hydrophilic group constituting the polymerization for producing the water-soluble polyester resin α (hereinafter, also simply referred to as a hydrophilic group), a dicarboxylic acid monomer unit B having no hydrophilic group, and a diol monomer unit. In this specification, water-soluble means that 1 g of the component is dissolved in 100 g of neutral water and does not precipitate even when the water temperature is kept at 20 ° C. Thereafter, water-insoluble means that the component does not dissolve when 1 g is added to 100 g of neutral water, or that the component dissolves but precipitates when the temperature is returned to 20 ° C.

The neutral water may be water or an aqueous solution having a pH of 6 to 8. Specific examples of the neutral water include deionized water, pure water, tap water, and industrial water. Deionized water or tap water is preferred from the viewpoint of availability. The neutral water may also contain other components such as a water-soluble organic solvent and a surfactant. Examples of the water-soluble organic solvent 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; and ketones such as acetone and methyl ethyl ketone. Examples of the surfactant include anionic surfactants such as alkyl sulfate salts, alkyl ether sulfate salts, olefin sulfonates, and alkyl ether carboxylate salts; cationic surfactants such as alkyl trimethyl ammonium salts; and nonionic surfactants such as polyoxyethylene alkyl ethers and alkyl glycosides.

[Aromatic dicarboxylic acid monomer unit A]
The hydrophilic group may be one or more selected from the group consisting of a primary amino group, a secondary amino group, a tertiary amino group, a quaternary ammonium base, an oxyalkylene group, a hydroxyl group, a carboxyl group, a carboxyl group, a phosphoric acid group, a phosphoric acid group, a sulfonic acid group, and a sulfonate group, from the viewpoint of imparting removability with neutral water. Among these, from the same viewpoint, one or more selected from the group consisting of a quaternary ammonium base, an oxyalkylene group, a carboxyl group, a phosphoric acid group, and a sulfonate group are preferred, one or more selected from the group consisting of a quaternary ammonium base, an oxyalkylene group, and a sulfonate group are more preferred, and a sulfonate group is even more preferred.

From the viewpoint of imparting removability with neutral water and from the viewpoint of ease of polymerization reaction during production of the water-soluble polyester resin α, the sulfonate group is preferably a sulfonate group represented by —SO ₃ M ³ (wherein M ³ represents a counter ion of the sulfonic acid group constituting the sulfonate group, and from the viewpoint of imparting removability with neutral water, at least one selected from the group consisting of sodium ion, potassium ion, lithium ion, calcium ion, magnesium ion, ammonium ion, barium ion, and zinc ion is preferred, at least one selected from the group consisting of sodium ion, potassium ion, lithium ion, magnesium ion, and ammonium ion is more preferred, at least one selected from the group consisting of sodium ion and potassium ion is even more preferred, and sodium ion is even more preferred).

The content of the hydrophilic groups in the water-soluble polyester resin α is preferably 0.2 mmol/g or more, more preferably 0.5 mmol/g or more, and even more preferably 0.7 mmol/g or more, from the viewpoint of imparting removability with neutral water, and is preferably 3.0 mmol/g or less, more preferably 2.0 mmol/g or less, and even more preferably 1.5 mmol/g or less, from the viewpoint of moisture resistance required for modeling with a 3D printer. Note that the content of hydrophilic groups in this specification can be determined by the method described in the Examples.

The aromatic dicarboxylic acid for deriving the aromatic dicarboxylic acid monomer unit A is preferably one or more selected from the group consisting of sulfonate group-containing aromatic dicarboxylic acids and their salts, from the viewpoint of imparting removability with neutral water and the viewpoint of moisture resistance required for modeling with a 3D printer. Among these, from the same viewpoint, one or more selected from the group consisting of sulfophthalic acid, sulfonaphthalenedicarboxylic acid, and their salts are preferred, one or more selected from the group consisting of sulfophthalic acid and their salts are even more preferred, one or more selected from the group consisting of sulfoisophthalic acid, sulfoterephthalic acid, and their salts are even more preferred, and 5-sulfoisophthalic acid or its salt is even more preferred.

The ratio of the amount of the aromatic dicarboxylic acid monomer unit A to the total amount of all monomer units in the water-soluble polyester resin α is preferably 1 mol% or more, more preferably 5 mol% or more, and even more preferably 10 mol% or more, from the viewpoint of imparting removability with neutral water, and is preferably 35 mol% or less, more preferably 25 mol% or less, and even more preferably 15 mol% or less, from the viewpoint of moisture resistance required for modeling with a 3D printer. Note that in this specification, the ratio of each monomer unit in the resin is calculated by the method described in the Examples.

The ratio of the aromatic dicarboxylic acid monomer unit A to the total of all dicarboxylic acid monomer units in the water-soluble polyester resin α is preferably 2 mol% or more, more preferably 10 mol% or more, and even more preferably 20 mol% or more, from the viewpoint of imparting removability with neutral water, and is preferably 75 mol% or less, more preferably 50 mol% or less, and even more preferably 30 mol% or less, from the viewpoint of moisture resistance required for modeling with a 3D printer.

[Dicarboxylic acid monomer unit B]
From the viewpoint of moisture resistance required for modeling using a 3D printer, the dicarboxylic acid for deriving the dicarboxylic acid monomer unit B is preferably one or more selected from the group consisting of aromatic dicarboxylic acids having no hydrophilic groups and aliphatic dicarboxylic acids having no hydrophilic groups, and more preferably one or more selected from the group consisting of aromatic dicarboxylic acids having no hydrophilic groups.

Examples of the aromatic dicarboxylic acid having no hydrophilic group include one or more selected from the group consisting of benzenedicarboxylic acid, furandicarboxylic acid, and naphthalenedicarboxylic acid. Among these, from the viewpoint of moisture resistance required for modeling using a 3D printer, one or more selected from the group consisting of terephthalic acid, isophthalic acid, and 2,6-naphthalenedicarboxylic acid are preferred.

The aliphatic dicarboxylic acid having no hydrophilic group may be one or more selected from the group consisting of malonic acid, succinic acid, glutaric acid, adipic acid, 1,4-cyclohexanedicarboxylic acid, and 1,3-adamantanedicarboxylic acid. Among these, adipic acid is preferred from the viewpoint of moisture resistance required for modeling using a 3D printer.

The ratio of the amount of substance of the dicarboxylic acid monomer unit B to the total amount of substance of all monomer units in the water-soluble polyester resin α is preferably 15 mol% or more, more preferably 25 mol% or more, and even more preferably 35 mol% or more, from the viewpoint of moisture resistance required for modeling with a 3D printer, and is preferably 49 mol% or less, more preferably 45 mol% or less, and even more preferably 40 mol% or less, from the viewpoint of imparting removability with neutral water.

The ratio of the amount of dicarboxylic acid monomer unit B to the total amount of all dicarboxylic acid monomer units in the water-soluble polyester resin α is preferably 30 mol% or more, more preferably 50 mol% or more, and even more preferably 70 mol% or more, from the viewpoint of moisture resistance required for modeling with a 3D printer, and is preferably 98 mol% or less, more preferably 90 mol% or less, and even more preferably 80 mol% or less, from the viewpoint of imparting removability with neutral water.

[Diol monomer unit]
As the diol for deriving the diol monomer unit, an aliphatic diol, an aromatic diol, or the like can be used. From the viewpoint of easy availability of raw materials for the water-soluble polyester resin, an aliphatic diol is preferred.

The carbon number of the diol is preferably 2 or more from the viewpoint of imparting removability with neutral water, and is preferably 31 or less from the viewpoint of moisture resistance required for modeling with a 3D printer, more preferably 25 or less, even more preferably 20 or less, and even more preferably 15 or less.

The aliphatic diol may be one or more selected from the group consisting of chain diols and cyclic diols, with chain diols being preferred from the viewpoint of easy availability of raw materials.

From the viewpoint of imparting removability with neutral water and the viewpoint of moisture resistance required for modeling with a 3D printer, the chain diol is preferably one or more selected from the group consisting of ethylene glycol, propanediol, butanediol, neopentyl glycol, pentanediol, hexanediol, diethylene glycol, triethylene glycol, polyethylene glycol, dipropylene glycol, and polypropylene glycol, and more preferably one or more selected from the group consisting of ethylene glycol, 1,3-propanediol, and 1,6-hexanediol.

The water-soluble polyester resin α may contain monomer units other than the aromatic dicarboxylic acid monomer unit A, the dicarboxylic acid monomer unit B, and the diol monomer unit, as long as the effect of this embodiment is not impaired.

There are no particular limitations on the method for producing the water-soluble polyester resin α, and any method for producing a polyester resin that is publicly known in the art can be used.

The weight average molecular weight of the water-soluble polyester resin α is preferably 1000 or more, more preferably 3000 or more, and even more preferably 4000 or more, from the viewpoint of moisture resistance required for modeling with a 3D printer, and is preferably 100,000 or less, more preferably 80,000 or less, and even more preferably 30,000 or less, from the viewpoint of imparting removability with neutral water. Note that in this specification, the weight average molecular weight is measured by the method described in the Examples.

The glass transition temperature of the water-soluble polyester resin α is preferably 0°C or higher, more preferably 5°C or higher, and even more preferably 10°C or higher, from the viewpoint of moisture resistance required for modeling using a 3D printer, and is preferably 200°C or lower, more preferably 160°C or lower, and even more preferably 120°C or lower, from the viewpoint of imparting removability with neutral water. In this specification, the glass transition temperature is measured by the method described in the examples.

The content of the water-soluble polyester resin α in the resin composition is preferably 40% by mass or more, more preferably 50% by mass or more, and even more preferably 60% by mass or more, from the viewpoint of imparting removability with neutral water, and is preferably 95% by mass or less, more preferably 90% by mass or less, and even more preferably 85% by mass or less, from the viewpoint of moisture resistance required for modeling with a 3D printer.

[Component B]
Component B is a water-insoluble resin β having an SP value in the range of 15 (J/cm ³ ) ^1/2 to 25 (J/cm ³ ) ^1/2 and a glass transition temperature in the range of 80° C. to 160° C.

The SP value of the water-insoluble resin β is 15 (J/cm ³ ) ^1/2 or more, preferably 17 (J/cm ³ ) ^1/2 or more, more preferably 18 (J/cm ³ ) ^1/2 or more, and even more preferably 19 (J/cm ³ ) ^1/2 or more, from the viewpoint of improving the adhesiveness to the molding material, and from the same viewpoint, is 25 (J/cm ³ ) ^1/2 or less, preferably 24 (J/cm ³ ) ^1/2 or less, more preferably 23 (J/cm ³ ) ^1/2 or less, and even more preferably 22.5 (J/cm ³ ) ^1/2 or less. In this specification, the SP value is the Hansen solubility parameter. The Hansen solubility parameter can be calculated based on the chemical structure by dividing the types of interaction energy acting between the molecules of a substance into three. Specifically, the following formula can be used.
δ=(δ _d ² + δ _p ² + δ _h ² ) ^1/2
Here, δ _d is the London dispersion force term, δ _p is the molecular polarization term, and δ _h is the hydrogen bond term. A more detailed definition and calculation of the Hansen solubility parameters is described in Charles M. Hansen, Hansen Solubility Parameters: A Users Handbook, 2nd Ed., CM Hansen, CRC Press, Boca Raton, FL, 2007. In addition, by using computer software Hansen Solubility Parameters in Practice (HSPiP), the Hansen solubility parameters of compounds for which literature values are not known can be easily estimated from their chemical structures.

The glass transition temperature of the water-insoluble resin β is 80°C or higher, preferably 85°C or higher, and more preferably 90°C or higher, from the viewpoint of heat resistance required for modeling with a 3D printer, and is 160°C or lower, preferably 155°C or lower, and more preferably 150°C or lower, from the viewpoint of low melt viscosity required to facilitate ejection during modeling with a 3D printer. Note that in this specification, the glass transition temperature is measured by the method described in the Examples.

The water-insoluble resin β can be any water-insoluble resin having an SP value in the range of 15 (J/cm ³ ) ^1/2 or more and 25 (J/cm ³ ) ^1/2 or less and a glass transition temperature in the range of 80°C or more and 160°C or less, without any particular limitation. Examples of the non-water-soluble resin β include one or more types selected from the group consisting of polyethylene resin, polybutylene resin, polystyrene resin, polycarbonate resin, ABS resin, polyethylene terephthalate resin, polybutylene terephthalate resin, polyamide resin, and PPS resin. More specifically, from the viewpoint of improving adhesion to the molding material, it is preferable to include one or more types selected from acrylonitrile copolymer, styrene copolymer, polyolefin resin, polyester resin, polyacrylic resin, polyamide resin, polycarbonate resin, polyphenylsulfone resin, polyether ether ketone, polyetherimide, and copolymers thereof, more preferably to include one or more types selected from the group consisting of polycarbonate resin, acrylonitrile copolymer, styrene copolymer, polyolefin resin, and copolymers thereof, and even more preferably to include one or more types selected from the group consisting of polycarbonate resin and ABS resin.

The content of the water-insoluble resin β in the resin composition is preferably 20% by mass or less, more preferably 10% by mass or less, even more preferably 5% by mass or less, and even more preferably 3% by mass or less, from the viewpoint of not impairing removability with neutral water, and is preferably 0.5% by mass or more, more preferably 0.7% by mass or more, and even more preferably 1.0% by mass or more, from the viewpoint of improving toughness and improving adhesion to the molding material.

The mass ratio (content mass ratio) of the water-insoluble resin β to the water-soluble polyester resin α in the resin composition is 0.32 or less, preferably 0.20 or less, and more preferably 0.15 or less, from the viewpoint of not impairing removability with neutral water, and is preferably 0.015 or more, more preferably 0.02 or more, and even more preferably 0.03 or more, from the viewpoint of improving toughness and improving adhesion to molding materials.

The resin composition may contain other components to the extent that the effect of this embodiment is not impaired. Examples of such other components include polymers other than the water-soluble polyester resin α and the water-insoluble resin β fat, plasticizers such as benzoic acid polyalkylene glycol diester, fillers such as calcium carbonate, magnesium carbonate, glass spheres, graphite, carbon black, carbon fiber, glass fiber, talc, wollastonite, mica, alumina, silica, kaolin, whiskers, and silicon carbide, viscosity reducers, compatibilizers, elastomers, etc.

[Thinner]
The resin composition may contain a viscosity reducer from the viewpoint of controlling the molecular weight during the production of the water-soluble polyester resin α and from the viewpoint of improving removability with neutral water. Examples of the viscosity reducer include an organic salt compound represented by the following general formula (1).
(R-SO ^3- ) _n X ⁿ⁺ (1)
(In the general formula (1), R represents a hydrocarbon group having 1 to 30 carbon atoms which may have a substituent, n represents the number 1 or 2, and X ⁿ⁺ represents a cation, and when n is 1, X ⁿ⁺ represents a sodium ion, a potassium ion, a lithium ion, an ammonium ion, or a phosphonium ion, and when n is 2, X ⁿ⁺ represents a magnesium ion, a calcium ion, a barium ion, or a zinc ion.)

In the general formula (1), R represents a hydrocarbon group having 1 to 30 carbon atoms, which may have a substituent, from the viewpoint of molecular weight control during the production of the water-soluble polyester resin α and from the viewpoint of improving removability with neutral water. The hydrocarbon group may be any of an aliphatic hydrocarbon group, an alicyclic hydrocarbon group, and an aromatic hydrocarbon group. When the hydrocarbon group is an aliphatic hydrocarbon group, the number of carbon atoms of the hydrocarbon group is preferably 1 or more, more preferably 4 or more, and even more preferably 8 or more, and is preferably 30 or less, more preferably 25 or less, and even more preferably 20 or less, from the viewpoint of molecular weight control during the production of the water-soluble polyester resin α, from the viewpoint of improving removability with neutral water, and from the viewpoint of imparting heat resistance and moisture resistance to the resin composition. When the hydrocarbon group is an alicyclic hydrocarbon group, the number of carbon atoms of the hydrocarbon group is preferably 3 or more, more preferably 5 or more, even more preferably 6 or more, even more preferably 10 or more, preferably 30 or less, more preferably 25 or less, and even more preferably 20 or less, from the viewpoint of molecular weight control during the production of the water-soluble polyester resin α, from the viewpoint of improving removability with neutral water, and from the viewpoint of imparting heat resistance and moisture resistance to the resin composition. When the hydrocarbon group is an aromatic hydrocarbon group, the number of carbon atoms of the hydrocarbon group is preferably 6 or more, more preferably 8 or more, even more preferably 10 or more, from the viewpoint of molecular weight control during the production of the water-soluble polyester resin α, from the viewpoint of improving removability with neutral water, and from the viewpoint of imparting heat resistance and moisture resistance to the resin composition., preferably 30 or less, more preferably 25 or less.

In addition, from the viewpoint of improving removability with neutral water and imparting heat resistance and moisture resistance to the resin composition, the substituent preferably contains one or more selected from the group consisting of hydrogen atoms, carbon atoms, oxygen atoms, nitrogen atoms, sulfur atoms, phosphorus atoms, silicon atoms, and halogen atoms, and among these, a hydrocarbon group or halogenated alkyl group having 1 to 22 carbon atoms is preferred, a hydrocarbon group or halogenated alkyl group having 1 to 16 carbon atoms is more preferred, a hydrocarbon group or halogenated alkyl group having 1 to 12 carbon atoms is even more preferred, and a hydrocarbon group having 1 to 12 carbon atoms is even more preferred.

In the general formula (1), Xn ⁺ represents sodium ion, potassium ion, lithium ion, ammonium ion, phosphonium ion, magnesium ion, calcium ion, barium ion, zinc ion, or phosphonium ion from the viewpoint of molecular weight control during the production of the water-soluble polyester resin α, from the viewpoint of improving removability with neutral water, and from the viewpoint of imparting heat resistance and moisture resistance to the resin composition, and sodium ion, potassium ion, lithium ion, magnesium ion, ammonium ion, or phosphonium ion is preferred, sodium ion, lithium ion, ammonium ion, or phosphonium ion is more preferred, lithium ion or phosphonium ion is even more preferred, and phosphonium ion is even more preferred. Among the phosphonium ions, tetraalkylphosphonium ion is preferred, and tetrabutylphosphonium ion is more preferred from the viewpoint of ensuring heat resistance required during the production of the water-soluble polyester resin α.

In the general formula (1), n is preferably 1 from the viewpoints of controlling the molecular weight during the production of the water-soluble polyester resin α, improving removability with neutral water, and imparting heat resistance and moisture resistance to the resin composition.

The content of the organic salt compound in the resin composition is preferably 0.1% by mass or more, more preferably 1% by mass or more, and even more preferably 3% by mass or more, from the viewpoint of improving removability with neutral water, and is preferably 20% by mass or less, more preferably 15% by mass or less, and even more preferably 10% by mass or less, from the viewpoint of imparting heat resistance and moisture resistance to the resin composition.

[Compatibilizer]
The resin composition may contain a compatibilizer from the viewpoint of improving the compatibility between the water-soluble polyester resin α and the water-insoluble resin β. Examples of the compatibilizer include the LOTRYL (registered trademark) series (manufactured by SK Functional Polymers) which is a polymer obtained by copolymerizing ethylene with butyl acrylate or methyl acrylate, respectively; Bondfast (registered trademark) 7B, Bondfast 7M, and Bondfast CG-5001 (all manufactured by Sumitomo Chemical Co., Ltd.); Lotader (registered trademark) AX8840 (manufactured by Arkema), JONCRYL (registered trademark) ADR4370S, JONCRYL ADR4368CS, JONCRYL ADR4368F, JONCRYL ADR4300S, and JONCRYL ADR4468 (all manufactured by BASF Corporation); ARUFON (registered trademark) UG4035, ARUFON Examples of such a reactive compatibilizer include reactive compatibilizers having an epoxy group, such as UG4040 and ARUFON UG4070 (manufactured by Toagosei Co., Ltd.); reactive compatibilizers having an acid anhydride group, such as UMEX (registered trademark) 1010 (manufactured by Sanyo Chemical Co., Ltd.), ADMER (registered trademark) (manufactured by Mitsui Chemicals, Inc.), MODIPER (registered trademark) A8200 (manufactured by NOF Corporation), OREVAC (registered trademark) (manufactured by Arkema), FG1901, FG1924 (all manufactured by Kraton Polymers), TUFTEC (registered trademark) M1911, TUFTEC M1913, TUFTEC M1943 (all manufactured by Asahi Kasei Chemicals Corporation); and reactive compatibilizers having an isocyanate group, such as Carbodilite LA-1 (registered trademark) (manufactured by Nisshinbo Co., Ltd.).

From the viewpoint of imparting high toughness to the resin composition, the compatibilizer preferably has a glass transition temperature of 0°C or lower, more preferably has a glass transition temperature of -10°C or lower, and even more preferably has a glass transition temperature of -20°C or lower, and from the viewpoint of maintaining the heat resistance of the resin composition, the compatibilizer preferably has a glass transition temperature of -80°C or higher, more preferably has a glass transition temperature of -60°C or higher, and even more preferably has a glass transition temperature of -40°C or higher.

The content of the compatibilizer in the resin composition is preferably 0.1% by mass or more, more preferably 0.4% by mass or more, even more preferably 0.5% by mass or more, even more preferably 0.9% by mass or more, and even more preferably 1.0% by mass or more, from the viewpoint of improving the compatibility between the water-soluble polyester resin α and the water-insoluble resin β, and is preferably 25% by mass or less, more preferably 20% by mass or less, even more preferably 18% by mass or less, and even more preferably 15% by mass or less, from the viewpoint of maintaining the heat resistance of the resin composition.

[Elastomer]
The resin composition may contain an elastomer from the viewpoint of moldability when molded into a filament. From the viewpoint of moldability when molded into a filament, 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, and more preferably an acrylic elastomer. Examples of the acrylic elastomer include Clarity (registered trademark) LA2250, Clarity LA2140, and Clarity LA4285 (all manufactured by Kuraray Co., Ltd.). Examples of the olefin elastomer include Kraton (registered trademark) ERS polymer (manufactured by Kraton Polymers Co., Ltd.). Examples of the styrene-based elastomer include Kraton A polymer, Kraton G polymer (both manufactured by Kraton Polymers), "Tuftec H" series, "Tuftec P" series (manufactured by Asahi Kasei Chemicals Corporation), Septon (registered trademark), and Hybler (registered trademark) (both manufactured by Kuraray Plastics Co., Ltd.).

From the viewpoint of imparting high toughness to the resin composition, the elastomer preferably has a glass transition temperature of 0°C or lower, more preferably has a glass transition temperature of -20°C or lower, and even more preferably has a glass transition temperature of -40°C or lower; from the viewpoint of maintaining the heat resistance of the resin composition, the elastomer preferably has a glass transition temperature of -80°C or higher, more preferably has a glass transition temperature of -70°C or higher, and even more preferably has a glass transition temperature of -60°C or higher.

The content of the elastomer in the resin composition is preferably 0.1% by mass or more, more preferably 0.4% by mass or more, even more preferably 0.5% by mass or more, even more preferably 0.9% by mass or more, and even more preferably 1.0% by mass or more, from the viewpoint of moldability when molded into filaments, and is preferably 20% by mass or less, more preferably 10% by mass or less, and even more preferably 5% by mass or less, from the viewpoint of maintaining the heat resistance of the resin composition.

The method for producing the resin composition is not particularly limited, and the resin composition can be produced by a known method. When producing a resin composition containing the water-soluble polyester resin α, the water-insoluble resin β, and the other components, the method for producing the resin composition may be a method for producing the resin composition by kneading the other components. The kneading can be performed with a kneader such as a batch kneader or a twin-screw extruder. The kneading is preferably melt kneading.

<Soluble materials for three-dimensional modeling>
The resin composition may be used as a soluble material for three-dimensional modeling, which is used as a material of a support material for supporting a three-dimensional object when manufacturing the three-dimensional object by an FDM type 3D printer. That is, The soluble material for three-dimensional printing of the present embodiment may be a soluble material for three-dimensional printing that contains the resin composition.

The shape of the soluble material for three-dimensional modeling is not particularly limited, and examples include pellets, powder, filaments, etc., but filaments are preferred from the viewpoint of modeling properties using a 3D printer.

The diameter of the filament is preferably 0.5 mm or more, more preferably 1.0 mm or more, from the viewpoint of modeling with a 3D printer and improving the precision of three-dimensional objects, and from the same viewpoint, is preferably 3.0 mm or less.

When preparing filaments, it is preferable to perform a stretching process from the viewpoint of improving toughness. The stretching ratio in the stretching process is preferably 1.5 times or more from the viewpoint of improving toughness and achieving water solubility, more preferably 2 times or more, even more preferably 3 times or more, and even more preferably 5 times or more. From the same viewpoint, it is preferable to have 200 times or less, more preferably 150 times or less, even more preferably 100 times or less, and even more preferably 50 times or less. In addition, the stretching temperature in the stretching process is preferably within a range from a temperature 20°C lower than the glass transition temperature of the soluble material for three-dimensional modeling to a temperature 110°C higher than the glass transition temperature. From the viewpoint of improving toughness and thermal stability, the lower limit of the stretching temperature is more preferably a temperature 10°C lower than the glass transition temperature, and even more preferably the same temperature as the glass transition temperature. From the same viewpoint, the upper limit of the stretching temperature is more preferably a temperature 110°C higher than the glass transition temperature, more preferably a temperature 100°C higher than the glass transition temperature, and even more preferably a temperature 90°C higher than the glass transition temperature. The stretching may be performed while air-cooling the resin when it is discharged from the extruder, or it may be performed by heating with hot air or a laser. The stretching may be performed in one step to a predetermined stretch ratio and filament diameter, or in multiple steps to a predetermined stretch ratio and filament diameter.

<Method of manufacturing three-dimensional object>
The method for producing a three-dimensional object according to the present embodiment is a method for producing a three-dimensional object by FDM, which includes a step of obtaining a three-dimensional object precursor including a three-dimensional object and a supporting material, and a step of removing the supporting material by contacting the three-dimensional object precursor with neutral water, the supporting material being the soluble material for three-dimensional modeling. According to the method for producing a three-dimensional object, a three-dimensional object with high modeling accuracy can be produced.

[Step of obtaining a three-dimensional object precursor including a three-dimensional object and a support material]
The process for obtaining a three-dimensional object precursor including a three-dimensional object and a supporting material can utilize the process for obtaining a three-dimensional object precursor including a three-dimensional object and a supporting material in a known method for manufacturing a three-dimensional object using a 3D printer of the FDM type, except that the material of the supporting material is the soluble material for three-dimensional modeling.

The modeling material, which is the material for the three-dimensional object, can be any resin that is used as a modeling material in conventional FDM-type manufacturing methods for three-dimensional objects, without any particular limitations. Examples of the modeling material include thermoplastic resins such as ABS resin, polylactic acid resin, polycarbonate resin, 12-nylon, 6,6-nylon, 6-nylon, polyphenylsulfone resin, polyetheretherketone, and polyetherimide, and among these, polycarbonate resin, 12-nylon, 6,6-nylon, 6-nylon, polyphenylsulfone resin, polyetheretherketone, and polyetherimide are more preferable. In addition, it is preferable that the modeling material contains the non-water-soluble resin β.

[Support material removal step of contacting the three-dimensional object precursor with neutral water to remove the support material]
In the support material removal step, the support material is removed by contacting the three-dimensional object precursor with neutral water. From the viewpoints of cost and ease of operation, the method of contacting the three-dimensional object precursor with neutral water is preferably a method of immersing the three-dimensional object precursor in neutral water. From the viewpoint of improving the removability of the support material, ultrasonic waves can be irradiated during immersion to promote dissolution of the support material.

The amount of neutral water used is preferably 10 times by mass or more, more preferably 20 times by mass or more, relative to the support material in terms of the solubility of the support material, and from the standpoint of economic efficiency, is preferably 10,000 times by mass or less, more preferably 5,000 times by mass or less, even more preferably 1,000 times by mass or less, and even more preferably 100 times by mass or less.

The time for which the soluble material for three-dimensional modeling is in contact with neutral water is preferably 5 minutes or more from the viewpoint of removability of the support material, and is preferably 180 minutes or less, more preferably 120 minutes or less, and even more preferably 90 minutes or less, from the viewpoint of reducing damage to the three-dimensional object caused by prolonged contact with neutral water and from the viewpoint of economy. The cleaning temperature, which depends on the type of model material, is preferably 15°C or more, more preferably 25°C or more, even more preferably 30°C or more, and even more preferably 40°C or more, and from the same viewpoint, is preferably 85°C or less, and more preferably 70°C or less.

[Other uses]
Since the resin composition has good adhesion to various resins, it can also be used as a base layer for a de-printing layer of a printed matter, an intermediate layer of a laminated film, a coating agent, a water-soluble temporary fixing agent, etc. Since the water-soluble polyester resin α is water-soluble, a printed matter printed using the resin composition as a base layer for a de-printing layer, or a laminated film using the resin composition as an intermediate layer can be easily peeled off by immersing it in warm water, thereby increasing the recycling rate and its efficiency.

　With respect to the above-mentioned embodiment, the present invention further discloses the following compositions, etc.

＜1＞
A resin composition comprising the following component A and component B, wherein the content mass ratio of component B to component A is 0.32 or less:
Component A: a water-soluble polyester resin α having an aromatic dicarboxylic acid monomer unit A having a hydrophilic group, a dicarboxylic acid monomer unit B not having a hydrophilic group, and a diol monomer unit
Component B: a water-insoluble resin β having an SP value in the range of 15 (J/cm ³ ) ^1/2 or more and 25 (J/cm ³ ) ^1/2 or less and a glass transition temperature in the range of 80° C. or more and 160° C. or less.
＜2＞
The resin composition according to <1>, wherein the SP value of the water-insoluble resin β is 15 (J/ ^cm3 ) ^1/2 or more, preferably 17 (J/ ^cm3 ) ^1/2 or more, more preferably 18 (J/ ^cm3 ) ^1/2 or more, even more preferably 19 (J/ ^cm3 ) ^1/2 or more, and is 25 (J/ ^cm3 ) ^1/2 or less, preferably 24 (J/ ^cm3 ) ^1/2 or less, more preferably 23 (J/ ^cm3 ) ^1/2 or less, and even more preferably 22.5 (J/ ^cm3 ) ^1/2 or less.
＜3＞
The water-insoluble resin β has a glass transition temperature of 80° C. or more, preferably 85° C. or more, more preferably 90° C. or more, and is 160° C. or less, preferably 155° C. or less, more preferably 150° C. or less. The resin composition according to <1> or <2>.
＜4＞
The water-insoluble resin β is preferably one or more selected from the group consisting of polyethylene resin, polybutylene resin, polystyrene resin, polycarbonate resin, ABS resin, polyethylene terephthalate resin, polybutylene terephthalate resin, polyamide resin, and PPS resin, more preferably one or more selected from acrylonitrile copolymer, styrene copolymer, polyolefin resin, polyester resin, polyacrylic resin, polyamide resin, polycarbonate resin, polyphenylsulfone resin, polyether ether ketone, polyetherimide, and copolymers thereof, more preferably one or more selected from the group consisting of polycarbonate resin, acrylonitrile copolymer, styrene copolymer, polyolefin resin, and copolymers thereof, more preferably one or more selected from the group consisting of ABS resin, and polycarbonate resin, the resin composition according to any of <1> to <3>.
＜5＞
The content of the water-insoluble resin β in the resin composition is preferably 20 mass% or less, more preferably 10 mass% or less, even more preferably 5 mass% or less, even more preferably 3 mass% or less, preferably 0.5 mass% or more, more preferably 0.7 mass% or more, and even more preferably 1.0 mass% or more. The resin composition according to any one of <1> to <4>.
＜6＞
The content of the water-soluble polyester resin α in the resin composition is preferably 40% by mass or more, more preferably 50% by mass or more, and even more preferably 60% by mass or more, and is preferably 95% by mass or less, more preferably 90% by mass or less, and even more preferably 85% by mass or less. The resin composition according to any one of <1> to <5>.
＜７＞
The resin composition according to any one of <1> to <6>, wherein a mass ratio (content mass ratio) of the water-insoluble resin β to the water-soluble polyester resin α in the resin composition is 0.32 or less, preferably 0.20 or less, more preferably 0.15 or less, preferably 0.015 or more, more preferably 0.02 or more, and even more preferably 0.03 or more.
＜8＞
A soluble material for three-dimensional modeling, comprising the resin composition according to any one of <1> to <7>.
＜9＞
The soluble material for three-dimensional modeling according to <8>, which has a filament shape.
＜10＞
The soluble material for three-dimensional printing according to <9>, wherein the filament has a diameter of 0.5 to 3.0 mm.
<11>
A method for producing a three-dimensional object, comprising: a step of obtaining a three-dimensional object precursor including a three-dimensional object and a supporting material; and a supporting material removal step of contacting the three-dimensional object precursor with neutral water to remove the supporting material,
A method for manufacturing a three-dimensional object, wherein the material of the supporting material is the soluble material for three-dimensional modeling according to any one of <8> to <10>.
＜12＞
The method for producing a three-dimensional object according to <11>, wherein a modeling material that is a material of the three-dimensional object contains the water-insoluble resin β.
＜13＞
The water-insoluble resin β is preferably one or more selected from the group consisting of polyethylene resin, polybutylene resin, polystyrene resin, polycarbonate resin, ABS resin, polyethylene terephthalate resin, polybutylene terephthalate resin, polyamide resin, and PPS resin, more preferably one or more selected from acrylonitrile copolymer, styrene copolymer, polyolefin resin, polyester resin, polyacrylic resin, polyamide resin, polycarbonate resin, polyphenylsulfone resin, polyether ether ketone, polyetherimide, and copolymers thereof, more preferably one or more selected from the group consisting of polycarbonate resin, acrylonitrile copolymer, styrene copolymer, polyolefin resin, and copolymers thereof, more preferably one or more selected from the group consisting of ABS resin, and polycarbonate resin. The method for producing a three-dimensional object according to claim <12>.

<Method for preparing water-soluble polyester resin composition>
A 2L stainless steel separable flask (with K-shaped tube, stirrer, and nitrogen inlet tube) was charged with 2,6-dimethyl naphthalene dicarboxylate (Tokyo Chemical Industry Co., Ltd., first grade) 97.7 g, 5-dimethyl sodium sulfoisophthalate (Fujifilm Wako Pure Chemical Industries, Ltd., special grade) 40.6 g, ethylene glycol (Fujifilm Wako Pure Chemical Industries, Ltd., special grade) 76.7 g, titanium tetrabutoxide (Tokyo Chemical Industry Co., Ltd., first grade) 82 mg, and sodium acetate (Fujifilm Wako Pure Chemical Industries, special grade) 506 mg. The mixture was heated to 260 ° C. from the surface of the heater over 1 hour under normal pressure and nitrogen atmosphere with a mantle heater while stirring, and the mixture was stirred at that temperature for 6 hours and 30 minutes to carry out an ester exchange reaction. Then, 6.89 g of dodecylbenzenesulfonic acid tetrabutylphosphonium salt (Takemoto Oil Co., Ltd.: Elecut S-418) was added and stirred for 15 minutes. Thereafter, the surface temperature of the heater was raised from 260 to 290°C over 30 minutes to carry out the reaction, and the reaction was carried out by stirring while gradually increasing the degree of vacuum to 100 Pa, to obtain a water-soluble polyester resin composition containing a water-soluble polyester resin α. At this time, it was assumed that the excess amount of ethylene glycol was distilled out of the reaction system, and that the diol unit and the dicarboxylic acid unit reacted in equal amounts. The contents of the water-soluble polyester resin α and the dodecylbenzenesulfonic acid tetrabutylphosphonium salt contained in the water-soluble polyester resin composition calculated from the amount of raw materials added are shown in Table 1. The ratio of the aromatic dicarboxylic acid monomer unit A and the ratio of the dicarboxylic acid monomer unit B to the total of all dicarboxylic acid monomer units of the water-soluble polyester resin α contained in the water-soluble polyester resin composition, as well as the weight average molecular weight and the content of the hydrophilic group are shown in Table 2. At this time, the ratio of the aromatic dicarboxylic acid monomer unit A and the ratio of the dicarboxylic acid monomer unit B were calculated from the amount of the feed.

[Weight average molecular weight (Mw)]
A calibration curve was prepared from standard polystyrene using gel permeation chromatography (GPC) under the following conditions, and the weight average molecular weight (Mw) was determined.
Apparatus: HLC-8320 GPC (Tosoh Corporation, detector integrated type)
Column: α-M × 2 (Tosoh Corporation, 7.8 mm I.D. × 30 cm)
Eluent: 60 mmol/L phosphoric acid + 50 mmol/L lithium bromide dimethylformamide solution Flow rate: 1.0 mL/min
Column temperature: 40°C Detector: RI detector Standard material: polystyrene

<Preparation of Resin Composition (Support Material)>
Using a Labo Plastomill (Labo Plastmill 4C150 manufactured by Toyo Seiki Seisakusho, Ltd.), the raw materials were melt-kneaded under conditions of 230° C./90 rpm/10 min so as to obtain resin compositions 1 to 5, so as to obtain the compositions shown in Table 3.

<Preparation of filament>
Each of the resin compositions 1 to 5 was melted at a barrel temperature of 200° C. using a Capillograph (Capillograph 1D manufactured by Toyo Seiki Seisakusho Co., Ltd.), extruded from a capillary having a diameter of 2.0 mm and a length of 10 mm at an extrusion speed of 15 mm/min, and wound up to a diameter of 1.7 mm.

<Evaluation method>
[SP value]
The SP value was calculated using the Hansen solubility parameter. The Hansen solubility parameter was calculated by dividing the types of interaction energy acting between the molecules of a substance into three types and calculating it based on the chemical structure. Specifically, the following formula was used.
δ=(δ _d ² + δ _p ² + δ _h ² ) ^1/2
Here, δ _d is the London dispersion force term, δ _p is the molecular polarization term, and δ _h is the hydrogen bond term. The detailed definition and calculation of the Hansen solubility parameters were based on the description in Charles M. Hansen, Hansen Solubility Parameters: A Users Handbook, 2nd Ed., CM Hansen, CRC Press, Boca Raton, FL, 2007.

[Glass transition temperature]
25 to 10 mg of sample was precisely weighed and sealed in an aluminum pan, and the sample was heated from 30° C. to 230° C. at 10° C./min using a DSC device (DSC7020 manufactured by Seiko Instruments Inc.), and then cooled to 30° C. at a cooling rate of 150° C./min. The sample was again heated to 230° C. at 10° C./min, and the glass transition temperature (° C.) was determined from the resulting DSC curve. The results are shown in Table 3.

[Evaluation of toughness]
The breaking elongation was measured by a tensile test using a tension and compression tester (manufactured by Shimadzu Corporation, product name "Autograph AGS-X"). A 10 cm filament was set with a support distance of 50 mm, and the measurement was performed at a crosshead speed of 10 mm/min to examine the breaking elongation (%). A high breaking elongation value indicates high toughness. Five points were tested per sample, and the average value was taken as the measured value. The evaluation results are shown in Table 3.

[Adhesion to molding materials]
Each filament of the resin compositions 1 to 5 was supplied to an FDM 3D printer (FUNMAT PRO 410 manufactured by INTAMSYS) and discharged from a heat nozzle having a temperature of 250 ° C. to form a three-dimensional object precursor 1 having the shape shown in FIG. 1 containing the molding material described in Table 3. The three-dimensional object precursor 1 has a box-shaped three-dimensional object 11 with outer dimensions of 24.0 mm in length, 25.0 mm in width, and 14.0 mm in height, and a rectangular parallelepiped support material 12 with outer dimensions of 20 mm in length, 21 mm in width, and 10 mm in height. The three-dimensional object 11 is made of a molding material, and the support material 12 is made of a resin composition. The three-dimensional object precursor 1 was modeled twice using a combination of each of the resin compositions 1 to 5 and the molding material described in Table 3, and the case where it was properly modeled both times was evaluated as ○, the case where it was possible to model once and was not properly modeled once due to insufficient adhesion was evaluated as △, and the case where it was not possible to model both times was evaluated as ×. The evaluation results are shown in Table 3.

Claims (9)

A resin composition comprising the following component A and component B, wherein the content mass ratio of component B to component A is 0.32 or less:
Component A: a water-soluble polyester resin α having an aromatic dicarboxylic acid monomer unit A having a hydrophilic group, a dicarboxylic acid monomer unit B not having a hydrophilic group, and a diol monomer unit
Component B: a water-insoluble resin β having an SP value in the range of 15 (J/cm ³ ) ^1/2 or more and 25 (J/cm ³ ) ^1/2 or less and a glass transition temperature in the range of 80° C. or more and 160° C. or less. The resin composition according to claim 1, wherein the water-insoluble resin β comprises at least one selected from the group consisting of ABS resin and polycarbonate resin. The resin composition according to claim 1 or 2, wherein the content of the water-insoluble resin β is 20 mass% or less. A soluble material for three-dimensional modeling, comprising the resin composition according to any one of claims 1 to 3. The soluble material for three-dimensional modeling according to claim 4, which has a filament-like shape. The soluble material for three-dimensional modeling according to claim 5, wherein the filament has a diameter of 0.5 to 3.0 mm. A method for producing a three-dimensional object, comprising: a step of obtaining a three-dimensional object precursor including a three-dimensional object and a supporting material; and a supporting material removal step of contacting the three-dimensional object precursor with neutral water to remove the supporting material,
A method for manufacturing a three-dimensional object, wherein the material of the support material is the soluble material for three-dimensional modeling according to any one of claims 4 to 6. The method for manufacturing a three-dimensional object according to claim 7, wherein the molding material that is the material of the three-dimensional object contains the water-insoluble resin β. The method for manufacturing a three-dimensional object according to claim 8, wherein the water-insoluble resin β includes at least one resin selected from the group consisting of ABS resin and polycarbonate resin.

Images