Resin composition for forming water-disintegrable member, water-disintegrable member, and method for producing three-dimensional shaped object

Abstract

To provide a resin composition that enables acquisition of a molded member having excellent heat resistance and water-disintegration property.SOLUTION: A resin composition for forming water-disintegrating member is provided, including at least one kind of resin (A) selected from the group consisting of a polyether-ester-amide resin (A1) having a polyoxyethylene group, a polyether-amide resin (A2) having a polyoxyethylene group, and a polyether-amide-imide resin (A3) having a polyoxyethylene group, wherein the percentage content of oxyethylene groups included in the resin (A) is 20 to 85 wt.% based on the weight of the resin (A).SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to a resin composition for forming a water-disintegrable member, and a method for producing a water-disintegrable member and a three-dimensional shaped object using the same. [Background technology]

[0002] Water-disintegrating materials, which disintegrate when exposed to large amounts of water, can be easily removed by using water, so fixing part of the structure of an article with a water-disintegrating material makes it easy to disassemble the article. Furthermore, using a water-disintegrating material in packaging materials for agricultural chemicals makes it possible to release the chemicals by irrigation. As a water-disintegrable composition that can be used to form fixing members, packaging materials, and the like having water-disintegrability, a water-disintegrable composition containing a block copolymer including, as constituent units, a unit containing an aliphatic polyoxyalkylene portion and an aliphatic polyester unit is known (Patent Document 1).

[0003] However, there is a problem in that the molded article made from the water-disintegrable composition described in Patent Document 1 does not have sufficient heat resistance, and is unable to maintain its shape in a high-temperature environment, making it unusable. [Prior art documents] [Patent documents]

[0004] [Patent Document 1] Japanese Patent Application Laid-Open No. 2008-69324 Summary of the Invention [Problem to be solved by the invention]

[0005] An object of the present invention is to provide a resin composition that can give a molded part having excellent heat resistance and water-degradability. [Means for solving the problem]

[0006] The present inventors have conducted research to achieve the above object and have arrived at the present invention. Specifically, the present invention provides a resin composition for forming a water-disintegrable member, which comprises at least one resin (A) selected from the group consisting of polyetheresteramide resin (A1) having polyoxyethylene groups, polyetheramide resin (A2) having polyoxyethylene groups, and polyetheramideimide resin (A3) having polyoxyethylene groups, wherein the total weight proportion of the oxyethylene groups contained in the resin (A) is 20 to 85 wt % based on the weight of the resin (A); a water-disintegrable member made from the resin composition for forming a water-disintegrable member; a resin filament for a fused deposition modeling three-dimensional modeling machine made from the resin composition for forming a water-disintegrable member; and a method for producing a three-dimensional object using the resin filament for a fused deposition modeling three-dimensional modeling machine. [Effects of the Invention]

[0007] The resin composition for forming a water-disintegrable member of the present invention has high heat resistance, and molded articles thereof can maintain their shape even in a temperature environment higher than conventional ones. DETAILED DESCRIPTION OF THE INVENTION

[0008] <Resin composition for forming water-disintegrable member> The resin composition for forming a water-disintegrable member according to the first invention contains at least one resin (A) selected from the group consisting of polyetheresteramide resins (A1) having polyoxyethylene groups, polyetheramide resins (A2) having polyoxyethylene groups, and polyetheramideimide resins (A3) having polyoxyethylene groups, and the total weight proportion of oxyethylene groups contained in the resin (A) is 20 to 85% by weight based on the weight of the resin (A).

[0009] Water disintegrability refers to the property of an article that, upon contact with water or a liquid containing water, the initial shape of the article changes as a result of the article being partially or completely dissolved in water, swollen in water, or decomposed by water, and the presence or absence of this property can be confirmed by immersing the article to be measured in water and visually observing the change in shape. The degree of water disintegrability in the present invention is determined by immersing a test piece of 5 mm width x 5 mm length x 2 mm thickness in water at a temperature of 39 to 41°C and visually observing the state of dissolution or change in shape of the test piece.

[0010] There are no limitations on the water-disintegrating member as long as it is a member that has the above-mentioned water-disintegrating properties, and examples thereof include a fixing member that fixes two or more members that make up an article, a container (capsule, etc.) that encapsulates a drug or the like, a protective layer that covers part or all of the surface of an article, and a support member for a three-dimensional molded object structure.

[0011] The resin composition for forming a water-disintegrable member of the present invention contains at least one resin (A) selected from the group consisting of a polyetheresteramide resin (A1) having a polyoxyethylene group, a polyetheramide resin (A2) having a polyoxyethylene group, and a polyetheramideimide resin (A3) having a polyoxyethylene group.

[0012] <Polyetheresteramide resin (A1) having polyoxyethylene groups> The polyether ester amide resin (A1) having a polyoxyethylene group is a compound having a structure in which a residue obtained by removing a carboxyl group from a polyamide (a11) having a carboxyl group at the end of the main chain and a residue obtained by removing a hydroxyl group from a polyether diol (a21) having a polyoxyethylene group are bonded via an ester group. The main chain refers to the atomic group that constitutes the longest molecular chain in the molecular structure.

[0013] Examples of the polyamide (a11) include ring-opening polymers of lactams, self-polycondensation polymers of aminocarboxylic acids, polycondensation polymers of diamines and dicarboxylic acids, and mixtures thereof.

[0014] As the lactam whose ring-opening polymer constitutes the polyamide (a11), from the viewpoint of the heat resistance of the molded article, preferred are 6- to 8-membered ring lactams (2-oxopentamethyleneimine, 2-oxohexamethyleneimine, 2-oxooctamethyleneimine, etc.), and among the polyamides (a11), preferred lactam ring-opening polymers include nylon 5, nylon 6, nylon 8, etc. These ring-opening polymers are obtained by a known method of ring-opening polymerization of the lactam in the presence of a dicarboxylic acid, which will be described later, to form polyamides having terminal carboxyl groups.

[0015] As the aminocarboxylic acid whose self-polycondensation polymer constitutes the polyamide (a11), from the viewpoint of the heat resistance of the molded article, preferred ones include aminocarboxylic acids having 6 to 12 carbon atoms (5-aminopentanoic acid, 7-aminoheptanoic acid, 11-aminoundecanoic acid, and 12-aminododecanoic acid), and the like. Among the polyamides (a11), preferred self-polycondensation polymers of aminocarboxylic acids include nylon 7 obtained by polycondensation of 7-aminoheptanoic acid, nylon 11 obtained by polycondensation of 11-aminoundecanoic acid, and nylon 12 obtained by polycondensation of 12-aminododecanoic acid. The self-polycondensation products of these aminocarboxylic acids have an amino group at one end and a carboxyl group at the other, and become polyamides having a carboxyl group at one end.

[0016] Of the diamines and dicarboxylic acids whose polycondensates constitute the polyamide (a11), from the viewpoint of heat resistance of the molded article, preferred diamines include aliphatic diamines having 2 to 11 carbon atoms, aromatic diamines having 6 to 20 carbon atoms, and mixtures thereof.

[0017] Examples of aliphatic diamines having 2 to 11 carbon atoms include ethylenediamine, propylenediamine, 1,4-butylenediamine, 1,6-hexamethylenediamine, and 1,11-undecanediamine. From the viewpoint of the heat resistance of the molded body, aliphatic diamines having 4 to 11 carbon atoms (1,4-butylenediamine, 1,6-hexamethylenediamine, and 1,11-undecanediamine) are particularly preferred.

[0018] Examples of aromatic diamines having 6 to 20 carbon atoms include p-phenylenediamine, 2,4- or 2,6-toluylenediamine, 2,2-bis(4,4'-diaminophenyl)propane, 4-aminobenzylamine, xylylenediamine, bis(aminoethyl)benzene, bis(aminopropyl)benzene, and bis(aminobutyl)benzene, and among these, p-phenylenediamine is preferred.

[0019] From the viewpoint of heat resistance of the molded article, preferred dicarboxylic acids include aliphatic dicarboxylic acids having 6 to 13 carbon atoms, aromatic ring-containing dicarboxylic acids having 6 to 14 carbon atoms, acid anhydrides thereof, alkyl (having 1 to 4 carbon atoms) esters thereof, and mixtures of two or more of these.

[0020] Examples of the aliphatic dicarboxylic acid having 6 to 13 carbon atoms include adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, undecanedioic acid, dodecanedioic acid, and tridecanedioic acid.

[0021] Examples of aromatic ring-containing dicarboxylic acids having 6 to 14 carbon atoms include ortho-, iso-, or terephthalic acid, naphthalene-2,6- or -2,7-dicarboxylic acid, diphenyl-4,4'-dicarboxylic acid, diphenoxyethanedicarboxylic acid, tolylenedicarboxylic acid, and xylylenedicarboxylic acid.

[0022] The dicarboxylic acid may have a sulfo group, and preferred examples of the dicarboxylic acid having a sulfo group include 5-sulfoisophthalic acid and salts thereof.

[0023] Preferred examples of the polycondensation product of a diamine and a dicarboxylic acid include a polycondensation product of adipic acid, sebacic acid, azelaic acid, or dodecanedioic acid with hexamethylenediamine (nylon 66, nylon 610, nylon 69, or nylon 612), and a polycondensation product of tetramethylenediamine and adipic acid (nylon 46).

[0024] The polycondensate of diamine and dicarboxylic acid may be a copolymer nylon using different monomers in combination, and examples of the copolymer nylon include nylon 6 / 66 {a copolymer of nylon 6 and nylon 66 [copolymerization ratio (weight ratio) = 5 / 95 to 95 / 5]} and nylon 6 / 12 {a copolymer of nylon 6 and nylon 12 [copolymerization ratio (weight ratio) = 5 / 95 to 95 / 5]}.

[0025] The polyamide (a11) preferably has a structure in which amide groups are linked together by a divalent saturated aliphatic hydrocarbon group having 4 to 11 carbon atoms or a divalent hydrocarbon group having 6 to 14 carbon atoms and an aromatic ring.

[0026] Among the polyamides (a11), from the viewpoint of heat resistance and the like, preferred polyamides are ring-opening polymers of caprolactam and polycondensates of adipic acid and hexamethylenediamine, and more preferred polyamides are ring-opening polymers of caprolactam. The polyamide (a11) can be obtained by a known method described in JP-A-2016-166332, for example.

[0027] The number average molecular weight (hereinafter referred to as Mn) of the polyamide (a11) is preferably from 500 to 5,000, more preferably from 700 to 3,000, from the viewpoint of the heat resistance of the polyetheramide (A1). The Mn of the polyamide (a11) is a calculated value calculated using the acid value of the polyamide.

[0028] Examples of the polyether diol (a21) having a polyoxyethylene group include an aliphatic polyether diol having a polyoxyethylene group and an aromatic polyether diol having a polyoxyethylene group.

[0029] Examples of aliphatic polyether diols having a polyoxyethylene group include alkylene oxide adducts obtained by adding an alkylene oxide (hereinafter sometimes abbreviated as AO) that requires ethylene oxide (hereinafter abbreviated as EO) to a linear or branched aliphatic dihydric alcohol having 2 to 8 carbon atoms, and alkylene oxide adducts obtained by adding an alkylene oxide that requires EO to an alicyclic dihydric alcohol having 6 to 10 carbon atoms. Examples of alkylene oxides that can be used in combination with ethylene oxide (hereinafter sometimes abbreviated as EO) include alkylene oxides having 3 or 4 carbon atoms [1,2-propylene oxide (hereinafter sometimes abbreviated as PO), 1,3-propylene oxide, 1,2-, 2,3- or 1,3-butylene oxide, tetrahydrofuran, etc.].

[0030] In an aliphatic polyether diol having a polyoxyethylene group, when ethylene oxide and another alkylene oxide are used in combination, the poly(oxyalkylene) group of the polyether diol may have a structural unit formed by two or more of the same type of alkylene oxide linked together, or may have a structure in which ethylene oxide and another alkylene oxide are alternately bonded, or may have both of these two types of structures.

[0031] Aliphatic polyether diols having polyoxyethylene groups can be obtained by known methods, such as a method of ring-opening addition polymerization of a linear or branched aliphatic dihydric alcohol having 2 to 8 carbon atoms or an alicyclic dihydric alcohol having 6 to 10 carbon atoms with an alkylene oxide essentially containing ethylene oxide, in the presence of an alkali catalyst at a temperature of 100 to 200°C.

[0032] Examples of the linear or branched aliphatic dihydric alcohol having 2 to 8 carbon atoms include ethylene glycol, diethylene glycol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,2-propanediol, neopentyl glycol, 3-methyl-1,5-pentanediol, 2,2-diethyl-1,3-propanediol, and 1,2-, 1,3-, or 2,3-butanediol.

[0033] Examples of the alicyclic dihydric alcohol having 6 to 10 carbon atoms include 1,4-bis(hydroxymethyl)cyclohexane and 2,2-bis(4-hydroxycyclohexyl)propane.

[0034] Preferred examples of the aliphatic polyether diol having a polyoxyethylene group include polyoxyethylene polyols [polyethylene glycol (hereinafter abbreviated as PEG), etc.] and copolymers of polyoxyethylene and propylene polyol.

[0035] Examples of aromatic polyether diols having polyoxyethylene groups include alkylene oxide adducts of aromatic diols, which essentially contain ethylene oxide. Examples of alkylene oxides used in combination with ethylene oxide (hereinafter abbreviated as EO) include alkylene oxides having 3 or 4 carbon atoms [1,2-propylene oxide (hereinafter abbreviated as PO), 1,3-propylene oxide, 1,2-, 2,3-, or 1,3-butylene oxide, tetrahydrofuran, etc.].

[0036] In an aromatic polyether diol having a polyoxyethylene group, when ethylene oxide and another alkylene oxide are used in combination, the poly(oxyalkylene) group of the polyether diol may have a structural unit formed by two or more of the same type of alkylene oxide linked together, or may have a structure in which ethylene oxide and another alkylene oxide are alternately bonded, or may have both of these two types of structures.

[0037] Aromatic polyether diols having polyoxyethylene groups can be obtained by known methods, such as a method of subjecting an aromatic diol to ring-opening addition polymerization of an alkylene oxide, essentially containing ethylene oxide, in the presence of an alkali catalyst at a temperature of 100 to 200°C.

[0038] Examples of aromatic diols include hydroquinone, benzyloxy-1,3-propanediol, and bisphenol A.

[0039] Preferred examples of aromatic polyether diols having a polyoxyethylene group include EO adducts of bisphenol A (such as an adduct of bisphenol A with 2 moles of EO, an adduct of bisphenol A with 4 moles of EO, an adduct of bisphenol A with 6 moles of EO, an adduct of bisphenol A with 8 moles of EO, an adduct of bisphenol A with 10 moles of EO, and an adduct of bisphenol A with 20 moles of EO), and adducts of dihydroxybenzene.

[0040] The total weight proportion of polyoxyethylene groups in the polyether diol (a21) having polyoxyethylene groups is preferably 60% by weight or more, more preferably 80 to 95% by weight, based on the weight of the polyether diol (a21), from the viewpoint of water decomposability.

[0041] The Mn of the polyether diol (a21) is preferably from 500 to 5,000, more preferably from 1,000 to 3,000, from the viewpoints of water disintegrability and strength during molding.

[0042] The Mn of the polyether diol (a21) is measured by gel permeation chromatography (hereinafter abbreviated as GPC) under the following conditions. Apparatus: "Waters Alliance 2695" [Waters] Column: "Guardcolumn Super HL" (1 column), "TSKgel SuperH2000, TSKgel SuperH3000, TSKgel SuperH4000 connected together" [all manufactured by Tosoh Corporation] Sample solution: 0.25% by weight tetrahydrofuran solution ·Solution injection volume: 10μl ·Flow rate: 0.6ml / min ·Measurement temperature: 40℃ Detector: Refractive index detector Reference material: Standard polyethylene glycol

[0043] The total weight proportion of all residues obtained by removing two hydroxyl groups from the polyether diol (a21) constituting the polyether ester amide resin (A1) is preferably 50% by weight to 85% by weight, more preferably 55% by weight to 85% by weight, based on the weight of the polyether ester amide resin (A1), from the viewpoint of achieving both water-disintegrability and strength of the component.

[0044] The polyether ester amide resin (A1) preferably has a structure in which amide groups are linked together via a divalent saturated aliphatic hydrocarbon group having 4 to 11 carbon atoms or a divalent hydrocarbon group having 6 to 14 carbon atoms and an aromatic ring. By using the above-mentioned preferred lactams, aminocarboxylic acids, diamines and dicarboxylic acids constituting the polyamide (a11), the polyetheresteramide (A1) can have a structure in which amide groups are linked together by a divalent saturated aliphatic hydrocarbon group having 4 to 11 carbon atoms or a divalent hydrocarbon group having 6 to 14 carbon atoms and an aromatic ring. When the polyether ester amide resin (A1) has a structure in which amide groups are linked together by a divalent saturated aliphatic hydrocarbon group having 4 to 11 carbon atoms or a divalent hydrocarbon group having 6 to 14 carbon atoms and an aromatic ring, the resin composition for forming a water-disintegrable member has better heat resistance and water-disintegrability, which is preferable.

[0045] As the polyether ester amide resin (A1) having a polyoxyethylene group, those described in JP-A-6-287547 and JP-B-4-5691 can be used. Among the polyether ester amides (A1), preferred is the polyether ester amide described in JP-A-6-287547, which is composed of a polyamide having an Mn of 200 to 5,000 and an AO adduct of a bisphenol having an Mn of 300 to 5,000 or a polyoxyalkylene.

[0046] The polyetheresteramide resin (A1) can be produced by known methods such as those described in JP 2016-166332 A, including a method of esterifying a polyetherdiol (a21) to a polyamide (a11) having a carboxyl group at its end, which is obtained by ring-opening or polycondensation polymerization of a dicarboxylic acid with the lactam or the aminocarboxylic acid (hereinafter, these two will be referred to as polyamide-forming monomers), and a method of esterifying a polyetherdiol (a21) to a polyamide (a11) that is a polycondensation product of a diamine and a dicarboxylic acid using an excess of dicarboxylic acid. The polyetheresteramide resin (A1) may contain an ester of the polyetherdiol (a21) and a dicarboxylic acid in its structure. The ring-opening or polycondensation polymerization of polyamide-forming monomers and the polycondensation of diamines and dicarboxylic acids can be carried out by known methods such as those described in JP-A-2016-166332.

[0047] The esterification reaction of the polyether diol with the polyamide having a carboxyl group at its terminal can be carried out by a known method, and a known esterification catalyst may be used. Preferred esterification catalysts include antimony catalysts (antimony trioxide, etc.), tin catalysts (monobutyltin oxide, etc.), titanium catalysts (tetrabutyl titanate, etc.), zirconium catalysts (tetrabutyl zirconate, etc.), and metal acetate catalysts (zinc acetate, zirconyl acetate, etc.).

[0048] From the viewpoint of water decomposability, the total weight proportion of polyoxyethylene groups contained in the polyether ester amide resin (A1) is preferably 20% by weight to 85% by weight, and more preferably 50% by weight to 80% by weight, based on the weight of the polyether ester amide resin (A1).

[0049] The Mn of the polyether ester amide resin (A1) is preferably 10,000 to 100,000, and more preferably 10,000 to 50,000, from the viewpoints of the mechanical properties and heat resistance of the water-disintegrable member.

[0050] The Mn of the polyether ester amide resin (A1) is measured by GPC under the following conditions. Equipment: "HLC-8120" [Tosoh Corporation] Columns: "TSKgelGMHXL" [manufactured by Tosoh Corporation] (2 tubes), "TSKgelMultiporeHXL-M" [manufactured by Tosoh Corporation] (1 tube) Sample solution: 0.3% by weight orthodichlorobenzene solution ·Solution injection volume: 100μl ·Flow rate: 1ml / min ·Measurement temperature: 135℃ Detector: Refractive index detector Reference material: Standard polystyrene

[0051] <Polyetheramide resin (A2) having polyoxyethylene groups> The polyetheramide resin (A2) having a polyoxyethylene group is a compound having a structure in which a residue obtained by removing a carboxyl group from a polyamide (a12) having a carboxyl group at the end of the main chain and a residue obtained by removing an amino group from a polyetherdiamine (a22) having a polyoxyethylene group are bonded via an amide group.

[0052] Examples of the polyamide (a12) having a carboxyl group at the end of the main chain include the same as those exemplified as the polyamide (a11) constituting the polyetheresteramide resin (A1), such as ring-opening polymers of lactams, self-polycondensates of aminocarboxylic acids, and polycondensates of diamines and dicarboxylic acids, and the preferred examples are also the same.

[0053] The polyetherdiamine (a22) having a polyoxyethylene group may be obtained by converting the terminal hydroxyl groups of the above polyetherdiol (a21) to amino groups, and can be obtained by a known method, for example, by cyanoalkylating the hydroxyl groups of the polyetherdiol and reducing the resulting terminal to form an amino group.

[0054] The total weight proportion of polyoxyethylene groups in the polyetherdiamine (a22) having polyoxyethylene groups is preferably 60% by weight or more, more preferably 80 to 95% by weight, based on the weight of the polyetherdiol (a22), from the viewpoint of water decomposability.

[0055] The Mn of the polyetherdiamine (a22) is preferably from 500 to 5,000, more preferably from 1,000 to 3,000, from the viewpoints of water disintegrability and strength during molding.

[0056] The Mn of the polyetherdiamine (a22) is measured under the same conditions as those for the polyetherdiol (a11).

[0057] The total weight proportion of residues obtained by removing amino groups from polyetherdiamine (a22) constituting the polyetheramide resin (A2) is preferably 50% by weight to 85% by weight, more preferably 55% by weight to 85% by weight, based on the weight of the polyetheresteramide resin (A2), from the viewpoint of achieving both water-disintegrability and strength of the component.

[0058] The polyetheramide resin (A2) preferably has a structure in which amide groups are linked together by a divalent saturated aliphatic hydrocarbon group having 4 to 11 carbon atoms or a divalent hydrocarbon group having 6 to 14 carbon atoms and an aromatic ring. By using the above-mentioned preferred lactams, aminocarboxylic acids, diamines, and dicarboxylic acids that constitute the polyamide (a12), the polyetheramide resin (A2) can have a structure in which amide groups are linked together by a divalent saturated aliphatic hydrocarbon group having 4 to 11 carbon atoms or a divalent hydrocarbon group having 6 to 14 carbon atoms and an aromatic ring. When the polyetheramide resin (A2) has a structure in which amide groups are linked together via a divalent saturated aliphatic hydrocarbon group having 4 to 11 carbon atoms or a divalent hydrocarbon group having 6 to 14 carbon atoms and an aromatic ring, the resin composition for forming a water-disintegrable member has better heat resistance and water-disintegrability, which is preferable.

[0059] Examples of methods for producing the polyetheramide resin (A2) include a method in which a polyamide (a12) having a carboxyl group at its terminal is obtained by ring-opening or polycondensation polymerization of a dicarboxylic acid with the lactam or the aminocarboxylic acid (hereinafter, these two will be referred to as polyamide-forming monomers), and then bonding the polyetherdiamine (a22) to the polyamide (a12) by an amidation reaction; and a method in which a polyamide (a12), which is a polycondensate of a diamine and a dicarboxylic acid using an excess of dicarboxylic acid, is bonded to the polyetherdiamine (a22) by an amidation reaction.

[0060] From the viewpoint of water disintegrability, the total weight proportion of polyoxyethylene groups contained in the polyetheramide resin (A2) is preferably 20% by weight to 85% by weight, and more preferably 50% by weight to 80% by weight, based on the weight of the polyetheramide resin (A2).

[0061] The Mn of the polyetheramide resin (A2) is preferably 10,000 to 100,000, and more preferably 10,000 to 50,000, from the viewpoints of the mechanical properties and heat resistance of the water-disintegrable member.

[0062] The Mn of the polyetheramide resin (A2) is measured by GPC under the same conditions as those for the polyetheresteramide resin (A1).

[0063] <Polyetheramideimide resin (A3) having polyoxyethylene groups> The polyetheramideimide resin (A3) having a polyoxyethylene group is a compound obtained by bonding, via an amide group, a residue obtained by removing a carboxyl group from a polyamideimide (a13) having a carboxyl group bonded to the end of the main chain and at least one imide ring, and a residue obtained by removing a hydroxyl group from a polyetherdiol (a23) having a polyoxyethylene group.

[0064] Examples of the polyamideimide (a13) having a carboxyl group bonded to the end of the main chain and at least one imide ring include polymers of an aromatic tricarboxylic acid or aromatic tetrapolycarboxylic acid capable of forming at least one imide ring and a lactam exemplified in the polyamide (a11) constituting the polyetheresteramide resin (A1); polymers of an aromatic tricarboxylic acid or aromatic tetrapolycarboxylic acid capable of forming at least one imide ring and an aminocarboxylic acid exemplified in the polyamide (a11) constituting the polyetheresteramide resin (A1); and polymers of an aromatic tricarboxylic acid or aromatic tetrapolycarboxylic acid capable of forming at least one imide ring and a diamine and dicarboxylic acid exemplified in the polyamide (a11) constituting the polyetheresteramide resin (A1).

[0065] Preferred aromatic tricarboxylic acids and aromatic tetrapolycarboxylic acids capable of forming at least one imide ring include trimellitic acid, 1,2,5- or 2,6,7-naphthalenetricarboxylic acid, 3,3,'4-biphenyltricarboxylic acid, benzophenone-3,3',4-tricarboxylic acid, diphenylsulfone-3,3',4-tricarboxylic acid, diphenylether-3,3',4-tricarboxylic acid, pimellitic acid, phenyl-2,2',3,3'-tetracarboxylic acid, benzophenone-2,2',3,3'-tetracarboxylic acid, diphenylsulfone-2,2',3,3'-tetracarboxylic acid, diphenylether-2,2',3,3'-tetracarboxylic acid, and anhydrides thereof.

[0066] The polyamideimide (a13) preferably has a structure in which amide groups and amide groups are bonded to each other and amide groups and imide groups are bonded to each other by a divalent saturated aliphatic hydrocarbon group having 4 to 11 carbon atoms or a divalent hydrocarbon group having 6 to 14 carbon atoms and an aromatic ring.

[0067] The Mn of the polyamideimide (a13) is preferably from 500 to 50,000, more preferably from 700 to 30,000, from the viewpoint of the heat resistance of the polyetheramideimide (A2). The Mn of the polyamideimide (a13) is calculated using the acid value of the polyamide.

[0068] Examples of the polyether diol (a23) having a polyoxyethylene group include the same as the polyether diol (a21) constituting the polyether ester amide (A1), and the preferred examples are also the same.

[0069] The total weight proportion of polyoxyethylene groups in the polyether diol (a23) having polyoxyethylene groups is preferably 60% by weight or more, more preferably 80 to 95% by weight, based on the weight of the polyether diol (a23), from the viewpoint of water decomposability.

[0070] The Mn of the polyether diol (a23) is preferably from 500 to 5,000, more preferably from 1,000 to 3,000, from the viewpoints of water disintegrability and strength during molding.

[0071] The Mn of the polyetherdiamine (a23) is measured under the same conditions as those for the polyetherdiol (a11).

[0072] The content of the residue obtained by removing two hydroxyl groups from the polyetherdiol (a23) constituting the polyetheramideimide resin (A3) is preferably 50% by weight to 85% by weight, more preferably 55% by weight to 85% by weight, based on the weight of the polyetheramideimide resin (A3), from the viewpoint of achieving both water-disintegrability and strength of the component.

[0073] The polyetheramideimide resin (A3) preferably has a structure in which amide groups and imide groups are linked together by a divalent saturated aliphatic hydrocarbon group having 4 to 11 carbon atoms or a divalent hydrocarbon group having 6 to 14 carbon atoms and an aromatic ring. By using the above-mentioned preferred lactams, aminocarboxylic acids, diamines and dicarboxylic acids, as well as aromatic tricarboxylic acids and aromatic tetrapolycarboxylic acids that constitute the polyamideimide (a13), the polyetheramideimide resin (A3) can have a structure in which amide groups and imide groups are linked together via a divalent saturated aliphatic hydrocarbon group having 4 to 11 carbon atoms or a divalent hydrocarbon group having an aromatic ring and 6 to 14 carbon atoms. When the polyetheramideimide resin (A3) has a structure in which an amide group and an imide group are linked together via a divalent saturated aliphatic hydrocarbon group having 4 to 11 carbon atoms or a divalent hydrocarbon group having 6 to 14 carbon atoms and an aromatic ring, the resin composition for forming a water-disintegrable member has better heat resistance and water-disintegrability, which is preferable.

[0074] The polyetheramideimide resin (A3) can be produced, for example, by bonding the polyamideimide (a13) and polyetherdiamine (a23) by amidation reaction using a known method.

[0075] From the viewpoint of water decomposability, the weight proportion of polyoxyethylene groups contained in the polyetheramideimide resin (A3) is preferably 20% by weight to 85% by weight, and more preferably 50% by weight to 80% by weight, based on the weight of the polyetheramideimide resin (A3).

[0076] The Mn of the polyetheramideimide resin (A3) is preferably 10,000 to 100,000, and more preferably 10,000 to 50,000, from the viewpoints of the mechanical properties and heat resistance of the water-disintegrable member.

[0077] The Mn of the polyetheramideimide resin (A3) is measured by GPC under the same conditions as those for the polyetheresteramide resin (A1).

[0078] The resin composition for forming a water-disintegrable member of the present invention may contain at least one resin selected from the group consisting of polyetheresteramide resins (A1), polyetheramide resins (A2) and polyetheramideimide resins (A3). When two or more types of resin (A) are contained, the total weight proportion of oxyethylene groups contained in resin (A) is 20 to 85% by weight, and preferably 50 to 80% by weight, based on the weight of resin (A). When two or more types of resin (A) are contained, the total weight proportion of oxyethylene groups contained in resin (A) is calculated based on the total weight of oxyethylene groups contained in each of the polyetheresteramide resin (A1), the polyetheramide resin (A2), and the polyetheramideimide resin (A3). Of the above (A1) to (A3), (A1) is preferred.

[0079] The resin composition for forming a water-disintegrable member of the present invention may contain, in addition to the polyether-containing polyamide resin (A), a polyurethane (B1) having a polyoxyalkylene chain and / or a polyoxyalkylene glycol (B2). Furthermore, by including a polyurethane (B1) having a polyoxyalkylene chain and / or a polyoxyalkylene glycol (B2), the degree of water-disintegrability of the resin composition for forming a water-disintegrable member can be adjusted. Of the above (B1) and (B2), (B1) is preferred.

[0080] <Polyurethane having polyoxyalkylene chain (B1)> The polyurethane (B1) having a polyoxyalkylene chain is a polyurethane having a polyoxyalkylene glycol (b11) and a polyisocyanate (b21) as essential constituent units.

[0081] The polyoxyalkylene glycol (b11) is preferably a polyoxyalkylene glycol having a polyoxyethylene group, such as polyoxyethylene glycol and copolymerized diols of ethylene oxide and other alkylene oxides, among which polyoxyethylene glycol is preferred. The copolymerized diols of ethylene oxide and other alkylene oxides can be obtained by the same method as the polyether diol (a11).

[0082] The Mn of the polyoxyalkylene glycol (b11) is preferably from 5,000 to 200,000, more preferably from 10,000 to 100,000, from the viewpoints of water disintegrability and shape retention, etc. The Mn of the polyoxyalkylene glycol (b11) is measured under the same conditions as those for the polyether diol (a11).

[0083] Examples of the diisocyanate (b21) include aromatic diisocyanates having 6 to 20 carbon atoms (excluding carbon atoms in NCO groups; the same applies below), aliphatic diisocyanates having 2 to 18 carbon atoms, modified products of these diisocyanates (modified products containing a urethane group, a carbodiimide group, an allophanate group, a urea group, a biuret group, a uretdione group, a uretoimine group, an isocyanurate group, or an oxazolidone group, etc.), and mixtures of two or more of these.

[0084] Examples of aromatic diisocyanates having 6 to 20 carbon atoms include 1,3- or 1,4-phenylene diisocyanate, 2,4- or 2,6-tolylene diisocyanate (TDI), crude TDI, m- or p-xylylene diisocyanate (XDI), α,α,α',α'-tetramethylxylylene diisocyanate (TMXDI), 2,4'- or 4,4'-diphenylmethane diisocyanate (MDI), and crude diaminophenylmethane diisocyanate (crude MDI).

[0085] Examples of the aliphatic diisocyanate having 2 to 18 carbon atoms include chain aliphatic diisocyanates having 2 to 18 carbon atoms and cyclic aliphatic diisocyanates having 3 to 18 carbon atoms.

[0086] Examples of the chain aliphatic diisocyanate having 2 to 18 carbon atoms include ethylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate (HDI), dodecamethylene diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, lysine diisocyanate, 2,6-diisocyanatomethyl caproate, bis(2-isocyanatoethyl) fumarate, bis(2-isocyanatoethyl) carbonate, 2-isocyanatoethyl-2,6-diisocyanatohexanoate, and mixtures thereof.

[0087] Examples of the cycloaliphatic diisocyanate having 3 to 18 carbon atoms include isophorone diisocyanate (IPDI), dicyclohexylmethane-4,4'-diisocyanate (hydrogenated MDI), cyclohexylene diisocyanate, methylcyclohexylene diisocyanate (hydrogenated TDI), bis(2-isocyanatoethyl)-4-cyclohexene-1,2-dicarboxylate, 2,5- or 2,6-norbornane diisocyanate, and mixtures thereof.

[0088] The diisocyanate modification product may be one containing at least one group selected from the group consisting of a urethane group, a carbodiimide group, an allophanate group, a urea group, a biuret group, a uretdione group, a uretoimine group, an isocyanurate group, and an oxazolidone group, and examples thereof include modified MDI (urethane-modified MDI, carbodiimide-modified MDI, trihydrocarbyl phosphate-modified MDI, etc.), urethane-modified TDI, and mixtures thereof [for example, a mixture of modified MDI and urethane-modified TDI (isocyanate-containing prepolymer)].

[0089] Of these diisocyanates, aromatic diisocyanates having 6 to 15 carbon atoms and aliphatic diisocyanates having 4 to 15 carbon atoms are preferred in terms of durability, and TDI, MDI, HDI, hydrogenated MDI and IPDI are more preferred.

[0090] The polyurethane (B1) may contain a divalent active hydrogen-containing compound other than the polyoxyalkylene glycol (b11) (such as the divalent active hydrogen-containing compound described in JP 2017-57166 A).

[0091] The weight proportion of units derived from polyoxyalkylene glycol (b11) (residues obtained by removing hydrogen atoms from hydroxyl groups of polyoxyalkylene glycol) contained in polyurethane (B1) is preferably 60 to 99 wt %, and more preferably 75 to 99 wt %, based on the weight of polyurethane (B1), from the viewpoints of water-disintegrability, shape-retaining property, etc.

[0092] The polyurethane (B1) can be obtained by urethanizing a polyoxyalkylene glycol (b11) with a diisocyanate (b21) by a known method.

[0093] From the viewpoints of water disintegrability, shape retention, etc., the Mn of the polyurethane (B1) is preferably from 10,000 to 200,000, more preferably from 40,000 to 150,000. The Mn of the polyurethane (B1) is measured under the same conditions as for the polyether diol (a11).

[0094] <Polyoxyalkylene glycol (B2)> As the polyoxyalkylene glycol (B2), the same polyoxyalkylene glycols as those (b11) constituting the polyurethane (B1) can be used, and the preferred ones are also the same.

[0095] The Mn of the polyoxyalkylene glycol (B2) is preferably 10,000 to 10,000,000, and more preferably 50,000 to 5,000,000, from the viewpoints of water disintegrability, shape retention, etc. The Mn of the polyoxyalkylene glycol (B2) is measured under the same conditions as those for the polyether diol (a11).

[0096] When the resin composition for forming a water-disintegrable member of the present invention further contains a polyurethane (B1) and / or a polyoxyalkylene glycol (B2) having a polyoxyalkylene chain, the total weight proportion of the polyurethane (B1) and the polyoxyalkylene glycol (B2) is preferably 20% by weight to 80% by weight, and more preferably 50% by weight to 80% by weight, based on the total weight of the resin (A), the polyurethane (B1), and the polyoxyalkylene glycol (B2), from the viewpoints of water-disintegrability, shape retention, etc.

[0097] The resin composition for forming a water-disintegrable member of the present invention may contain, in addition to the resin (A), polyurethane (B1), and polyoxyalkylene glycol (B2), a known thermoplastic resin (excluding the resin (A)) and a resin additive.

[0098] The thermoplastic resin that may be contained in the resin composition for forming a water-disintegrable member of the present invention is not particularly limited, and can be selected depending on the intended use of the water-disintegrable member. In particular, when the resin composition for forming water-disintegrable parts is used as a filament resin composition for a fused deposition modeling three-dimensional modeling machine, the resin composition for forming water-disintegrable parts of the present invention preferably contains, as a thermoplastic resin, polyvinyl alcohol, an ethylene-vinyl alcohol copolymer, a butylene-vinyl alcohol copolymer, a polyamide resin having an ionic group (such as a sulfo group) (such as polyamide 66 containing sodium sulfoisophthalate as a constituent monomer), or a polyester resin having an ionic group (such as a sulfo group) (such as a polyester resin containing sodium sulfoisophthalate as a constituent monomer).

[0099] Examples of resin additives that can be contained in the resin composition for forming a water-disintegrable member of the present invention include known fillers, dyes, pigments, stabilizers, lubricants, crystal nucleating agents, antistatic agents, etc. The content of the resin additives is not limited as long as it is an amount that does not inhibit the water-disintegrability and shape-retaining properties of the resin composition for forming a water-disintegrable member of the present invention, and can be adjusted depending on the application of the resin composition for forming a water-disintegrable member.

[0100] When the resin composition for forming a water-disintegrable member of the present invention further contains a thermoplastic resin, the water-disintegrability, heat resistance, and shape retention of the resin composition for forming a water-disintegrable member can be adjusted by the total weight proportion of the resin (A), polyurethane (B1), and polyoxyalkylene glycol (B2) contained in the resin composition for forming a water-disintegrable member. The water-disintegrability, heat resistance, and shape retention required for the resin composition for forming a water-disintegrable member of the present invention vary depending on the application for which the resin composition for forming a water-disintegrable member of the present invention is used, and it is preferable to adjust the total weight ratio of the resin (A), polyurethane (B1), and polyoxyalkylene glycol (B2) depending on the application.

[0101] The total weight proportion of the polyurethane (B1) and the polyoxyalkylene glycol (B2) contained in the resin composition for forming a water-disintegrable member of the present invention is preferably 30% by weight to 80% by weight, and more preferably 45% by weight to 75% by weight, based on the total weight of the resin composition for forming a water-disintegrable member, from the viewpoints of water-disintegrability, shape retention, etc.

[0102] The resin composition for forming a water-disintegrable member of the present invention can be obtained by melt-mixing the resin (A), polyurethane (B1), polyoxyalkylene glycol (B2), and optionally other thermoplastic resins and resin additives by a known method. The melt-kneading temperature is not limited as long as it is a temperature at which the resin (A), polyurethane (B1), polyoxyalkylene glycol (B2), and other thermoplastic resins and resin additives used as needed are melted. However, for reasons such as reducing coloration of the resin composition for forming a water-disintegrable member, the melt-kneading temperature is preferably in the range from the same temperature as the melting point of the polyether-containing polyamide-based resin (A) to a temperature 40°C higher than the melting point.

[0103] The resin composition for forming a water-disintegrable member of the present invention can be preferably used for water-disintegrable pressure-sensitive adhesives and water-disintegrable molded articles, etc. Examples of water-disintegrable molded articles include packaging materials, agricultural and horticultural materials, and supports for three-dimensional shaped structures produced by a molten resin lamination method.

[0104] <Water-disintegrating materials> The water-disintegrable member of the second invention is a member made from the resin composition for forming a water-disintegrable member. Note that the member refers to a material that constitutes a part of a certain article, and there are no restrictions on its shape.

[0105] Preferred examples of the water-disintegrable member of the present invention include water-disintegrable pressure-sensitive adhesives and water-disintegrable molded articles, and examples of the water-disintegrable molded articles include fibers, nonwoven fabrics thereof, films, and members molded into any shape.

[0106] The water-disintegrable pressure-sensitive adhesive comprising the water-disintegrable member of the present invention can be used for various purposes such as sanitary materials, packaging, heat insulating materials and woodworking, and the parts fixed with the pressure-sensitive adhesive can be easily separated by washing with water.

[0107] When the water-disintegrable molded article made of the water-disintegrable member of the present invention is a fiber or a nonwoven fabric using the same, it can be preferably used in draining bags, medical clothing, medical sheets, and the like.

[0108] When the water-disintegrable molded article made of the water-disintegrable member of the present invention is a film, it can be used as a packaging film, a packaging bag, a compost bag, a shopping bag, a garbage bag, etc. In particular, when used as a garbage bag for disposing of food waste, it can be preferably used because the bag can be disintegrated by water, allowing the food waste to be recycled together with the food waste.

[0109] The water-disintegrable molded article made of the water-disintegrable member of the present invention can also be preferably used for agricultural and horticultural materials (mulch films, seedling raising pots, agricultural and horticultural tapes, fruit cultivation bags, stakes, fumigation sheets, greenhouse films, etc.), pesticide packaging materials, etc. For example, when used as a seedling pot, it can maintain sufficient strength during the seedling growth and distribution stages, and can be decomposed by water after being buried in soil, eliminating the need to remove the seedling pot. Also, when used as a packaging material for enclosing an agricultural chemical active ingredient or formulation, the packaging material can be decomposed by contact with sprayed water, releasing the active ingredient.

[0110] In addition, molded articles made from the water-disintegratable material of the present invention can also be used as structural support members for three-dimensional molding machines using the fused (resin) deposition modeling method, binding components for chemicals (medicines, pesticides, veterinary drugs, and fertilizers), housings for electrical equipment, and pet waste disposal materials, etc.

[0111] <Resin filament for fused deposition modeling 3D modeling machines> The third invention is a resin filament for a fused deposition modeling three-dimensional modeling machine, which is a resin filament made of the resin composition for forming a water-disintegrable member. A fused deposition modeling 3D printer is a printing machine that heats and melts a material called a resin filament (a thermoplastic resin molded into thread form) and expels it from a nozzle. The resin that comes out of the nozzle is then layered based on data from 3D-CAD or other sources to create a three-dimensional object (a three-dimensional model). When creating a three-dimensional object, support members (also known as support materials) are also required to maintain its shape and reinforce it, and these support members are formed at the same time as the three-dimensional object is being formed by the fused deposition modeling 3D printer.

[0112] The support member needs to be heat-resistant and easily removable so that it can maintain its support structure even while the three-dimensional object is being formed. The resin filament for a fused deposition modeling three-dimensional modeling machine of the present invention is made of the resin composition for forming a water-disintegrable member, which has excellent heat resistance and water-disintegrability, and therefore it is possible to obtain a support member that has heat resistance and is easily removable so that it can maintain its support structure even while the three-dimensional object is being formed.

[0113] The resin filament for a fused deposition modeling three-dimensional modeling machine of the present invention can be obtained by molding the resin composition for forming a water-disintegrable member into a filament shape (preferably a filament with a diameter of 1.75 mm to 3 mm, etc.) using a known method.

[0114] <Method of manufacturing three-dimensional objects> The fourth invention is a method for manufacturing a three-dimensional object using the resin filament for a fused deposition modeling three-dimensional modeling machine, and includes a step of forming a support member made of the resin filament for a fused deposition modeling three-dimensional modeling machine.

[0115] In the manufacturing method of the present invention, a known method for manufacturing a three-dimensional object by fused deposition modeling can be used, except that the resin filament for a fused deposition modeling three-dimensional modeling machine made of the resin composition for forming a water-disintegrable member is used to form the support member.

[0116] In the manufacturing method of the present invention, the step of forming a support member for a three-dimensional object using the resin filament for a fused deposition modeling three-dimensional modeling machine is carried out by heating the resin filament (preferably to 170 to 240°C, more preferably 190 to 230°C) and melting it, and then ejecting the molten resin from an ejection nozzle at a predetermined position based on three-dimensional data such as 3D-CAD input into the three-dimensional modeling machine to form a structural support member.

[0117] The manufacturing method of the present invention preferably further comprises a step of removing the support member made of the resin filament for a fused deposition modeling three-dimensional modeling machine.

[0118] The support member of the three-dimensional object can be removed by bringing the support member into contact with a dissolving liquid. Methods that can be used include bringing part or all of the support member into contact with the dissolving liquid, and immersing the entire support member in the dissolving liquid. The dissolving liquid is preferably water, and a water-soluble compound may be dissolved in water for use. Examples of compounds that can be dissolved in water for use include organic acids, inorganic acids, alkali metal hydroxides, and alkali metal carbonates. [Example]

[0119] The present invention will be further explained below with reference to examples, but the present invention is not limited thereto. In the examples, parts are by weight.

[0120] [Production Example 1: Polyether Urethane (B-1)] A stainless steel autoclave (a simple pressure reactor equipped with a heater and stirrer) was charged with 100 parts of polyethylene glycol (Mn 20,000) (a21-6). The autoclave was then purged with nitrogen, and the pressure was reduced to 1.0-2.0 kPa while heating to 110°C. Stirring was continued for 1 hour to dehydrate the mixture. The pressure was then returned to normal, and 0.8 parts of toluene diisocyanate was added. The mixture was heated to 150°C with stirring, and reacted for 2 hours to obtain polyether urethane (B-1). The Mn of the polyether urethane (B-1) was 80,000.

[0121] [Production Example 2: Polyetheresteramide Resin (A-1)] A stainless steel autoclave similar to that used in Production Example 1 was charged with 170 parts of ε-caprolactam, 20.0 parts of terephthalic acid, 5.0 parts of isophthalic acid, 0.4 parts of an antioxidant, and 10 parts of water. The autoclave was then purged with nitrogen and heated and stirred for 4 hours at 220°C under pressure (0.3 to 0.4 MPa, the same applies hereinafter) while sealed, to obtain polyamide (a11-1) having carboxyl groups at both ends and an acid value of 111. The Mn of polyamide (a11-1) was 1,000. The Mn of polyamide (a11-1) was calculated using the formula [{mg of potassium hydroxide per mole (56,100) / acid value (111)} × number of functional groups (2)], assuming that polyamide (a11-1) was bifunctional and had carboxyl groups at both ends. Next, 300 parts of polyamide (a11-1), 300 parts of polyethylene glycol (Mn 2,000) (a21-1), 600 parts of EO adduct of bisphenol A (Mn 4,000) (a21-2), and 0.6 parts of zirconyl acetate were heated to 240°C with stirring in a stainless steel autoclave, and polymerized for 6 hours while reducing the pressure to 0.13 kPa or less to obtain a viscous polyetheresteramide resin (A-1). The Mn of the polyetheresteramide resin (A-1) was 28,000, and the content of oxyethylene groups contained in (A-1) was 75 wt% based on the weight of the resin (A-1).

[0122] [Production Example 3: Polyetheresteramide Resin (A-2)] A stainless steel autoclave similar to that used in Production Example 1 was charged with 190 parts of ε-caprolactam, 23.7 parts of the sodium salt of 5-sulfoisophthalic acid, 0.4 parts of an antioxidant, and 10 parts of water. After purging the autoclave with nitrogen, the contents were heated and stirred at 220°C under pressure (0.3 to 0.4 MPa, the same applies below) for 4 hours while sealed, to obtain polyamide (a11-2) having carboxyl groups at both ends and an acid value of 55. The Mn of polyamide (a11-2) was 2,000. The Mn of polyamide (a11-2) was calculated using the formula [{mg of potassium hydroxide per mole (56100) / acid value (55)} × number of functional groups (2)], assuming that polyamide (a11-2) was bifunctional and had carboxyl groups at both ends. A stainless steel autoclave similar to that used in Production Example 1 was charged with 190 parts of polyethylene glycol (Mn600) (a21-3), 76 parts of the sodium salt of 5-sulfoisophthalic acid dimethyl ester, and 0.2 parts of dibutyltin oxide, and the temperature was raised to 190°C. A transesterification reaction was carried out for 6 hours while distilling off methanol, to obtain polyether (a21-4). Next, 300 parts of polyamide (a11-2), 750 parts of polyether ester (a21-4), and 0.6 parts of zirconyl acetate were heated to 240°C with stirring in a stainless steel autoclave, and thermal polymerization was carried out for 6 hours while reducing the pressure to 0.13 kPa or less, to obtain a viscous polyether ester amide resin (A-2). The Mn of the polyether ester amide resin (A-2) was 41,000, and the content of oxyethylene groups contained in the resin (A-2) was 51 wt% based on the weight of the resin (A-2).

[0123] [Examples 1 and 2] The polyether ester amide resin (A-1) and the polyether ester amide resin (A-2) obtained in Production Examples 2 and 3 were designated as resin compositions (Y-1) and (Y-2) for forming water-disintegrable members, respectively.

[0124] [Examples 3-4: Mixture of polyetheresteramide resin and polyetherurethane] 50 parts of the polyether ester amide resins (A-1) and (A-2) obtained in Production Examples 2 and 3 and 50 parts of the polyether urethane (B-1) obtained in Production Example 1 were melt-kneaded for 5 minutes using a Laboplastomill (manufactured by Toyo Seiki Seisakusho, Ltd.) at 220°C and 50 rpm to obtain resin compositions (Y-3) and (Y-4) for forming water-disintegratable members each consisting of a mixture of the polyether ester amide resins (A-1) and (A-2) and the polyurethane (B-1).

[0125] [Examples 5-6: Mixture of polyetheresteramide resin and polyoxyalkylene glycol] 40 parts of the polyether ester amide resins (A-1) to (A-2) obtained in Production Examples 2 and 3 and 60 parts of the polyoxyalkylene glycol (B-2) [polyethylene glycol (Mn 20,000)] obtained in Production Example 1 were melt-kneaded for 5 minutes at 220°C and 50 rpm using a Laboplastomill (manufactured by Toyo Seiki Seisakusho, Ltd.) to obtain resin compositions (Y-5) to (Y-6) for forming water-disintegratable members each consisting of a mixture of the polyether ester amide resins (A-1) to (A-2) and the polyoxyalkylene glycol (B-2).

[0126] [Examples 7 to 10] Polyether ester amide resin (A-1), polyether ester amide resin (A-2), polyether urethane (B-1), and polyoxyalkylene glycol (B-2) were melt-kneaded for 5 minutes at 220°C and 50 rpm using a Laboplastomill (manufactured by Toyo Seiki Seisakusho) according to the compositions (parts by weight) in Table 1 to obtain resin compositions (Y-7) to (Y-10) for forming water-disintegrable members.

[0127] [Comparative Example 1] 50 parts of the polyamide (a11-1), 1,000 parts of polyethylene glycol (Mn 20,000) (a21-6), and 0.6 parts of zirconyl acetate used in Production Example 2 were heated to 240°C with stirring in a stainless steel autoclave, and polymerization reaction was carried out for 6 hours while reducing the pressure to 0.13 kPa or less to obtain a comparative resin composition (Z-1) containing a polyetheresteramide resin (Comparative A-1). The Mn of the polyetheresteramide resin (Comparative A-1) was 31,000, and the content of oxyethylene groups in the resin composition (Comparative A-1) was 95 wt% based on the weight of the resin composition (Comparative A-1).

[0128] Comparative Example 2 850 parts of the polyamide (a11-1) used in Production Example 2, 170 parts of polyethylene glycol (Mn 600) (a21-7), and 0.6 parts of zirconyl acetate were heated to 240°C with stirring in a stainless steel autoclave, and polymerization reaction was carried out for 6 hours while reducing the pressure to 0.13 kPa or less to obtain a comparative resin composition (Z-2) containing a viscous polyetheresteramide (Comparative A-2). The Mn of the resin composition (Comparative A-2) was 30,000, and the content of oxyethylene groups contained in (Comparative A-2) was 17 wt% based on the weight of the resin composition (Comparative A-2).

[0129] Comparative Example 3 A stainless steel autoclave was charged with 90.40 g of succinic anhydride, 990.10 g of polyethylene glycol (Mn1000) (a21-8), 1.63 g of titanium isopropoxide, and 800 ml of diethylbenzene, and the mixture was heated to reflux for 8 hours. The diethylbenzene was then distilled off under reduced pressure, and the mixture was stirred at 200°C for 5 hours under a reduced pressure of 5 mmHg to carry out a polyesterification reaction, yielding a polyester with an Mn of 12,000, a terminal hydroxyl value of 9.55 KOHmg / g, and an acid value of 1.27 KOHmg / g. 27.30 g of the above polyester, 3.30 g of poly(butylene adipate) (PBA) diol (Mitsui Chemicals Polyurethanes, Inc.; average molecular weight 2000), and 30 ml of toluene were added to a stainless steel autoclave similar to that used in Production Example 1 and mixed at 90°C. 0.63 g of hexamethylene diisocyanate and 50 mg of dibutyltin dilaurate were then added and stirred at 90°C for 4 hours. Next, 0.30 g of 2,6-di-tert-butyl-4-methylphenol was added and mixed, and the toluene was removed by distillation under reduced pressure to obtain a comparative resin composition (Z-3) consisting of a block copolymer (Comparative A-3) containing aliphatic polyoxyalkylene units and aliphatic polyester units as structural units. The Mn of the resulting resin composition (Comparative A-3) was 52,000.

[0130] The melting points of the resin compositions for forming water-disintegrable members (Y-1) to (Y-10) obtained in Examples 1 to 10 and the comparative resin compositions (Z-1) to (Z-3) obtained in Comparative Examples 1 to 3 were measured by the following method, and the results are shown in Table 1. Furthermore, the shape retention and water disintegration properties of the formed film at high temperatures (180°C) were evaluated by the following method. The results are shown in Table 1.

[0131] [Melt point measurement] Each of the resin compositions for forming water-disintegrable members (Y-1) to (Y-10) obtained in Examples 1 to 10 and the comparative resin compositions (Z-1) to (Z-3) obtained in Comparative Examples 1 to 3 was placed in a standard temperature condition class 2 environment as specified in JIS K 7100 for 24 hours, weighed out approximately 5 mg, and measured using a differential scanning calorimeter (DSC) [trade name: DSC2910, manufactured by TA Instruments Co., Ltd.]. The sample was heated to 240°C at a heating rate of 10°C per minute, held for 10 minutes, and then cooled to -50°C at a cooling rate of 10°C per minute. After further holding at -50°C for 10 minutes, the sample was heated to 240°C at a heating rate of 10°C per minute. The transition temperature (the apex of the melting peak) due to heating was read from the DSC curve and recorded as the melting point. The higher the melting point, the more likely it is that the shape can be maintained even at a higher temperature.

[0132] [Formed film maintains shape at high temperatures] Each of the resin compositions for forming water-disintegrable members (Y-1) to (Y-10) obtained in Examples 1 to 10 and the comparative resin compositions (Z-1) to (Z-3) obtained in Comparative Examples 1 to 3 was molded into a film having a thickness of 2 mm using a heat press. The molded films were cut into a size of 5 mm wide x 5 mm long x 2 mm thick and left to stand in a circulating air dryer at 180°C for 2 hours. After cooling to room temperature, the thickness of the film was measured and the results are shown in Table 1. In Table 1, the case where there was no change in thickness is marked as "GOOD", and the case where the thickness was 1 mm or less is marked as "BAD".

[0133] [Water disintegration] For the resin compositions (Y-1) to (Y-10) for forming water-disintegrable members obtained in Examples 1 to 10 and the comparative resin compositions (Z-1) to (Z-3) obtained in Comparative Examples 1 to 3, samples were cut into 5 mm x 5 mm pieces from films molded to a thickness of 2 mm, as with the samples used in the "Heat Resistance" section above. The samples were placed in a beaker containing 100 g of ion-exchanged water adjusted to 39 to 41°C and a cylindrical magnetic stirrer (5 mm diameter, 30 mm length) and immediately stirred at 400 rpm. Stirring was stopped 10 minutes after the start of stirring, and the film was allowed to stand for 20 minutes. The state of the film in the ion-exchanged water after 30 minutes of stirring was visually observed to evaluate the water-disintegrability of the molded film. The results are shown in Table 1. Table 1 shows that the formed film is completely dissolved or remains undissolved up to 0.5 mm in size. 3 If the dissolution rate is less than 0.5 mm, it is classified as "Water disintegration A" and there is residual dissolution. 3 Cases where the result was above this were described as "water-disintegrability B." In the present invention, a resin composition that leaves less residual dissolution when immersed in water is more preferably usable for a water-disintegrable member, and a water-disintegrability evaluation result of "water-disintegrability A" is more preferable.

[0134] [Table 1]

[0135] [Examples 11 to 20 and Comparative Examples 4 to 6: Resin filaments for fused deposition modeling three-dimensional modeling machines and modeling using the same with a fused deposition modeling three-dimensional modeling machine] A long die with a diameter of 1.75 mm and a flow path length of 5 mm was attached to a capillary rheometer (IMATEC R6000). Each of the resin compositions for forming water-disintegrable components (Y-1) to (Y-10) obtained in Examples 1 to 10 and the comparative resin compositions (Z-1) to (Z-3) obtained in Comparative Examples 1 to 3 was extruded at a melting temperature of 220°C and an extrusion speed of 75 mm / min to be processed into filaments with a diameter of 1.75±0.15 mm, yielding resin filaments (F-1) to (F-10) for fused deposition modeling three-dimensional modeling machines and comparative resin filaments (Z-4) to (Z-6). The obtained resin filaments (F-1) to (F-10) and the comparative resin filaments (Z-4) to (Z-6) were evaluated for their moldability using a 3D printer, the water disintegration properties of the molded objects, and the shape retention of the molded objects at high temperatures using the following methods.

[0136] [Formability using 3D printers] Each of the resin filaments (F-1) to (F-10) and the comparative resin filaments (Z-4) to (Z-6) was fed into a MakerBot Replicator X2, into which data for the shape of the object (a 5 mm x 5 mm x 2 mm rectangular parallelepiped) had been input, and extruded from a heat nozzle at a temperature of 250 ° C. Visual observation was performed to determine whether the desired shape had been formed, and the results are shown in Table 2. In Table 2, when the moldability is marked as ◯, it means that the material could be molded into the desired shape.

[0137] [Water disintegration of objects] A 3D printed object (shape: 5mm x 5mm x 2mm) was placed in a beaker containing ion-exchanged water (100g) adjusted to 39-41°C and a cylindrical magnetic stirrer (diameter 5mm, length 30mm), and immediately stirred at 400 rpm. Stirring was stopped 10 minutes after the start of stirring, and the object was allowed to stand for 20 minutes. The state of the object in the ion-exchanged water was visually observed to evaluate its water disintegration properties, and the results are shown in Table 2. Table 2 shows that the size of the printed object is 0.5 mm even if it is completely dissolved or there is a residual dissolution. 3 If the dissolution rate is less than 0.5 mm, it is classified as "Water disintegration A" and there is residual dissolution. 3 Cases where the result was above this were described as "water-disintegrability B." In the present invention, a shaped article that leaves less residual dissolution when immersed in water is preferable as a water-disintegrable member, and an evaluation result of water-disintegrability of "water-disintegrability A" is preferable.

[0138] [Maintaining the shape of the object under high temperatures] The object (shape: 5mm x 5mm x 2mm) created by the 3D printer was left in a circulating air dryer at 180°C for 2 hours, and the thickness of the film was measured after it was cooled to room temperature. The results are shown in Table 2. In Table 2, the case where there was no change in thickness is marked as "GOOD", and the case where the thickness was 1 mm or less is marked as "BAD".

[0139] [Table 2]

[0140] As shown in Tables 1 and 2, the resin composition for forming a water-disintegrable member of the present invention and a shaped article using the same can achieve both water-disintegrability and heat resistance, which cannot be achieved with the resin compositions of the comparative examples. [Industrial Applicability]

[0141] The resin composition for water-disintegrable members of the present invention has heat resistance and can be easily removed by immersion in water, and therefore can be preferably used for molded articles that require water-disintegrability, adhesives used for temporary fixing of members, and filaments for fused deposition modeling three-dimensional modeling machines.

Claims

1. A resin composition for forming a water-disintegrable member, comprising at least one resin (A) selected from the group consisting of a polyetheresteramide resin (A1) having a polyoxyethylene group, a polyetheramide resin (A2) having a polyoxyethylene group, and a polyetheramideimide resin (A3) having a polyoxyethylene group, wherein the total weight proportion of the oxyethylene groups contained in the resin (A) is 20 to 85 wt % based on the weight of the resin (A), and further comprising a polyurethane (B1) having a polyoxyalkylene chain and / or a polyoxyalkylene glycol (B2), wherein the total weight of the polyurethane (B1) having a polyoxyalkylene chain and the polyoxyalkylene glycol (B2) is 20 to 80 wt % based on the total weight of the resin composition for forming a water-disintegrable member.

2. 2. The resin composition for forming a water-disintegrable member according to claim 1, wherein the resin (A) has a number average molecular weight of 10,000 to 100,000.

3. A water-disintegrable member comprising the resin composition for forming a water-disintegrable member according to claim 1 or 2.

4. A resin filament for a fused deposition modeling three-dimensional modeling machine, comprising the resin composition for forming a water-disintegrable member according to claim 1 or 2.

5. A method for manufacturing a three-dimensional object using the resin filament for a fused deposition modeling three-dimensional modeling machine according to claim 4.

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