WO2021246432A1 - 水分散性樹脂組成物 - Google Patents

水分散性樹脂組成物 Download PDF

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Publication number
WO2021246432A1
WO2021246432A1 PCT/JP2021/020942 JP2021020942W WO2021246432A1 WO 2021246432 A1 WO2021246432 A1 WO 2021246432A1 JP 2021020942 W JP2021020942 W JP 2021020942W WO 2021246432 A1 WO2021246432 A1 WO 2021246432A1
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Prior art keywords
water
resin composition
group
resin
dispersible resin
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Ceased
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PCT/JP2021/020942
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English (en)
French (fr)
Japanese (ja)
Inventor
昭弘 尾之上
忠徳 吉村
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Kao Corp
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Kao Corp
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Application filed by Kao Corp filed Critical Kao Corp
Priority to US17/925,074 priority Critical patent/US20230183482A1/en
Priority to CN202180016922.XA priority patent/CN115151612A/zh
Priority to JP2022528858A priority patent/JPWO2021246432A1/ja
Priority to EP21818181.6A priority patent/EP4163329A4/en
Publication of WO2021246432A1 publication Critical patent/WO2021246432A1/ja
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L81/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing sulfur with or without nitrogen, oxygen or carbon only; Compositions of polysulfones; Compositions of derivatives of such polymers
    • C08L81/06—Polysulfones; Polyethersulfones
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G69/00—Macromolecular compounds obtained by reactions forming a carboxylic amide link in the main chain of the macromolecule
    • C08G69/02—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids
    • C08G69/26—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids derived from polyamines and polycarboxylic acids
    • C08G69/265—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids derived from polyamines and polycarboxylic acids from at least two different diamines or at least two different dicarboxylic acids
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
    • C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
    • C08G63/12—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from polycarboxylic acids and polyhydroxy compounds
    • C08G63/16—Dicarboxylic acids and dihydroxy compounds
    • C08G63/18—Dicarboxylic acids and dihydroxy compounds the acids or hydroxy compounds containing carbocyclic rings
    • C08G63/181—Acids containing aromatic rings
    • C08G63/185—Acids containing aromatic rings containing two or more aromatic rings
    • C08G63/187—Acids containing aromatic rings containing two or more aromatic rings containing condensed aromatic rings
    • C08G63/189—Acids containing aromatic rings containing two or more aromatic rings containing condensed aromatic rings containing a naphthalene ring
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
    • C08G63/68—Polyesters containing atoms other than carbon, hydrogen and oxygen
    • C08G63/688—Polyesters containing atoms other than carbon, hydrogen and oxygen containing sulfur
    • C08G63/6884—Polyesters containing atoms other than carbon, hydrogen and oxygen containing sulfur derived from polycarboxylic acids and polyhydroxy compounds
    • C08G63/6886—Dicarboxylic acids and dihydroxy compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G69/00—Macromolecular compounds obtained by reactions forming a carboxylic amide link in the main chain of the macromolecule
    • C08G69/42—Polyamides containing atoms other than carbon, hydrogen, oxygen, and nitrogen
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
    • C08L67/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L71/00—Compositions of polyethers obtained by reactions forming an ether link in the main chain; Compositions of derivatives of such polymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L77/00—Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers
    • C08L77/06—Polyamides derived from polyamines and polycarboxylic acids
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L79/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen or carbon only, not provided for in groups C08L61/00 - C08L77/00
    • C08L79/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
    • C08L79/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C64/00—Additive manufacturing, i.e. manufacturing of three-dimensional [3D] objects by additive deposition, additive agglomeration or additive layering, e.g. by 3D printing, stereolithography or selective laser sintering
    • B29C64/10—Processes of additive manufacturing
    • B29C64/106—Processes of additive manufacturing using only liquids or viscous materials, e.g. depositing a continuous bead of viscous material
    • B29C64/118—Processes of additive manufacturing using only liquids or viscous materials, e.g. depositing a continuous bead of viscous material using filamentary material being melted, e.g. fused deposition modelling [FDM]
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C64/00—Additive manufacturing, i.e. manufacturing of three-dimensional [3D] objects by additive deposition, additive agglomeration or additive layering, e.g. by 3D printing, stereolithography or selective laser sintering
    • B29C64/40—Structures for supporting 3D objects during manufacture and intended to be sacrificed after completion thereof
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B33—ADDITIVE MANUFACTURING TECHNOLOGY
    • B33Y—ADDITIVE MANUFACTURING, i.e. MANUFACTURING OF THREE-DIMENSIONAL [3D] OBJECTS BY ADDITIVE DEPOSITION, ADDITIVE AGGLOMERATION OR ADDITIVE LAYERING, e.g. BY 3D PRINTING, STEREOLITHOGRAPHY OR SELECTIVE LASER SINTERING
    • B33Y10/00—Processes of additive manufacturing
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B33—ADDITIVE MANUFACTURING TECHNOLOGY
    • B33Y—ADDITIVE MANUFACTURING, i.e. MANUFACTURING OF THREE-DIMENSIONAL [3D] OBJECTS BY ADDITIVE DEPOSITION, ADDITIVE AGGLOMERATION OR ADDITIVE LAYERING, e.g. BY 3D PRINTING, STEREOLITHOGRAPHY OR SELECTIVE LASER SINTERING
    • B33Y70/00—Materials specially adapted for additive manufacturing
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B33—ADDITIVE MANUFACTURING TECHNOLOGY
    • B33Y—ADDITIVE MANUFACTURING, i.e. MANUFACTURING OF THREE-DIMENSIONAL [3D] OBJECTS BY ADDITIVE DEPOSITION, ADDITIVE AGGLOMERATION OR ADDITIVE LAYERING, e.g. BY 3D PRINTING, STEREOLITHOGRAPHY OR SELECTIVE LASER SINTERING
    • B33Y80/00—Products made by additive manufacturing
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2201/00—Properties
    • C08L2201/08—Stabilised against heat, light or radiation or oxydation
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2201/00—Properties
    • C08L2201/54—Aqueous solutions or dispersions

Definitions

  • the present invention relates to a water-dispersible resin composition.
  • the present invention contains a resin ⁇ having a structure M in which two aromatic rings are linked by a sulfide group, a sulfonyl group, an imide group or a keto group in the main chain, and a resin ⁇ having a hydrophilic group.
  • the resin ⁇ and the resin ⁇ are both water-dispersible resin compositions that form a co-continuous structure forming a three-dimensional continuous phase.
  • Engineering plastics such as polyamide resin, acrylonitrile, butadiene, and styrene copolymer resin, and super engineering plastics such as polysulfone resin and polyamide-imide resin have excellent heat resistance and chemical resistance. Therefore, it is difficult to remove by the above-mentioned removal method by adding a solvent other than water or a component other than water to water.
  • the present invention provides a water-dispersible resin composition that can be easily removed only with water while maintaining heat resistance.
  • the present invention contains a resin ⁇ having a structure M in which two aromatic rings are linked by a sulfide group, a sulfonyl group, an imide group or a keto group in the main chain, and a resin ⁇ having a hydrophilic group.
  • the resin ⁇ and the resin ⁇ are both water-dispersible resin compositions that form a co-continuous structure forming a three-dimensional continuous phase.
  • the water-dispersible resin composition of the present embodiment has a resin ⁇ having a structure M in which two aromatic rings are linked by a sulfide group, a sulfonyl group, an imide group or a keto group in the main chain, and a hydrophilic group. It contains the resin ⁇ , and the resin ⁇ and the resin ⁇ both form a co-continuous structure forming a three-dimensional continuous phase. According to the water-dispersible resin composition of the present embodiment, it is possible to provide a water-dispersible resin composition that can be removed only with water while maintaining heat resistance. The reason why the water-dispersible resin composition of the present embodiment can achieve both heat resistance and water dispersibility can be considered as follows.
  • the aromatic ring in the resin ⁇ is mainly effective for imparting heat resistance. Further, the sulfide group, the sulfonyl group, the imide group, and the keto group connecting the aromatic rings in the resin ⁇ have high polarities, and easily interact with the hydrophilic group in the resin ⁇ between molecules. This makes it possible to enhance the electrostatic interaction with the hydrophilic group in the resin ⁇ . By increasing the interaction between the resin ⁇ and the resin ⁇ , the resin ⁇ and the resin ⁇ both form a co-continuous structure forming a three-dimensional continuous phase in the water-dispersible resin composition. Therefore, it is considered that the functions of heat resistance and water dispersibility can be compatible without separation.
  • the resin ⁇ is The main chain has a structure M in which two aromatic rings are linked by a sulfide group, a sulfonyl group, an imide group or a keto group.
  • the structure M is preferably a structure in which two aromatic rings are linked by an imide group from the viewpoint of ensuring the water dispersibility of the water-dispersible resin composition. Further, the structure M is preferably a structure in which two aromatic rings are linked by a sulfonyl group from the viewpoint of ensuring the heat resistance of the water-dispersible resin composition.
  • the structure M is preferably represented by the following general formula (1) or the following general formula (2) from the viewpoint of achieving both heat resistance and water dispersibility of the water-dispersible resin composition.
  • the resin ⁇ may have one kind or two or more kinds of structures M from the viewpoint of achieving both heat resistance and water dispersibility of the water-dispersible resin composition.
  • the content of the structure M in the resin ⁇ is preferably 1 mmol / g or more, more preferably 2 mmol / g or more, still more preferably 2 mmol / g or more, from the viewpoint of achieving both heat resistance and water dispersibility of the water-dispersible resin composition. It is 3 mmol / g or more, and from the same viewpoint, it is preferably 10 mmol / g or less, more preferably 6 mmol / g or less, and further preferably 5 mmol / g or less.
  • the content of the structure M in the resin ⁇ is preferably 1 to 10 mmol / g, more preferably 2 to 6 mmol / g, from the viewpoint of achieving both heat resistance and water dispersibility of the water-dispersible resin composition. , More preferably 3-5 mmol / g.
  • the resin ⁇ preferably has a structure L in which two aromatic rings are connected, which is different from the structure M, in the main chain. Further have.
  • the structure L has two aromatic rings, preferably a single bond, an ether group or an alkylmethylene group, and more preferably a single bond or ether, from the viewpoint of achieving both heat resistance and water dispersibility of the water-dispersible resin composition. It is a structure linked by a group, more preferably an ether group.
  • the resin ⁇ may have one or more types of structures L from the viewpoint of achieving both heat resistance and water dispersibility of the water-dispersible resin composition.
  • the glass transition temperature of the resin ⁇ is preferably 150 ° C. or higher, more preferably 200 ° C. or higher, still more preferably 210 ° C. or higher, and the water-dispersible resin, from the viewpoint of ensuring the heat resistance of the water-dispersible resin composition. From the viewpoint of ensuring the moldability of the composition, it is preferably 280 ° C. or lower, more preferably 250 ° C. or lower, and further preferably 230 ° C. or lower.
  • the glass transition temperature of the resin ⁇ is preferably 150 to 280 ° C, more preferably 200 to 250 ° C, still more preferably 210 to 230, from the viewpoint of ensuring the heat resistance and moldability of the water-dispersible resin composition. °C.
  • the resin ⁇ contains polyphenylsulfone, polysulfone, polyetherimide, polyetheretherketone, polyphenylenesulfide, polyethersulfone, and polyamideimide from the viewpoint of achieving both heat resistance and water dispersibility of the water-dispersible resin composition.
  • One or more selected from the group consisting of, is preferable, and one or more selected from the group consisting of polyphenylsulfone, polysulfone, polyetherimide, and polyethersulfone is more preferable.
  • the resin ⁇ is more preferably a polyether sulfone from the viewpoint of ensuring the heat resistance of the water-dispersible resin composition, and the polyetherimide from the viewpoint of ensuring the water dispersibility of the water-dispersible resin composition. Is more preferable.
  • the content of the resin ⁇ in the water-dispersible resin composition is preferably 10% by mass or more, more preferably 15% by mass or more, and more preferably 20% by mass or more from the viewpoint of heat resistance of the water-dispersible resin composition. Is more preferable, and from the viewpoint of water dispersibility of the water-dispersible resin composition, 80% by mass or less is preferable, 75% by mass or less is more preferable, 70% by mass or less is further preferable, and 65% by mass or less is further preferable.
  • the content of the resin ⁇ in the water-dispersible resin composition is preferably 10 to 80% by mass, preferably 15 to 75% by mass, from the viewpoint of achieving both heat resistance and water dispersibility of the water-dispersible resin composition. The mass% is more preferable, 20 to 70% by mass is further preferable, and 20 to 65% by mass is further preferable.
  • the method for producing the resin ⁇ is not particularly limited, and a conventionally known method can be applied.
  • the resin ⁇ has a hydrophilic group (also simply referred to as a hydrophilic group in the present specification) other than the hydrophilic group constituting the polymerization related to the formation of the resin ⁇ .
  • the resin ⁇ is preferably an aromatic dicarboxylic acid monomer unit A having a hydrophilic group and a dicarboxylic acid having no hydrophilic group from the viewpoint of achieving both heat resistance and water dispersibility of the water-dispersible resin composition. It has a monomer unit B.
  • aromatic dicarboxylic acid monomer unit A the aromatic dicarboxylic acid monomer unit having a hydrophilic group of the resin ⁇ is referred to as an aromatic dicarboxylic acid monomer unit A. Further, the aromatic dicarboxylic acid for inducing the aromatic dicarboxylic acid monomer unit A is referred to as an aromatic dicarboxylic acid A.
  • the hydrophilic group is one or two selected from the group consisting of an anionic group, a cationic group, and a neutral group from the viewpoint of achieving both heat resistance and water dispersibility of the water-dispersible resin composition.
  • the above can be mentioned.
  • one or more selected from the group consisting of anionic groups is preferable, and a sulfonic acid base is more preferable.
  • the sulfonic acid base represents ⁇ SO 3 M (where M represents a counter ion of the sulfonic acid group constituting the sulfonic acid base, from the viewpoint of achieving both heat resistance and water dispersibility of the water-dispersible resin composition.
  • M represents a counter ion of the sulfonic acid group constituting the sulfonic acid base
  • M represents a counter ion of the sulfonic acid group constituting the sulfonic acid base
  • the content of the hydrophilic group in the resin ⁇ is preferably 0.5 mmol / g or more, more preferably 0.6 mmol / g or more, and 0. 7 mmol / g or more is further preferable, and from the viewpoint of heat resistance of the water-dispersible resin composition, 3 mmol / g or less is preferable, 2 mmol / g or less is more preferable, and 1.5 mmol / g or less is further preferable.
  • the glass transition temperature of the resin ⁇ is preferably 30 ° C. or higher, more preferably 70 ° C. or higher, still more preferably 90 ° C. or higher, still more preferably 100 ° C., from the viewpoint of improving the heat resistance of the water-dispersible resin composition. From the viewpoint of ensuring the moldability of the water-dispersible resin composition, the temperature is preferably 280 ° C. or lower, more preferably 200 ° C. or lower, still more preferably 170 ° C. or lower.
  • the aromatic dicarboxylic acid A is one or more selected from the group consisting of the aromatic dicarboxylic acid having a hydrophilic group from the viewpoint of achieving both heat resistance and water dispersibility of the water-dispersible resin composition. Is preferable, and one or more selected from the group consisting of anionic group-containing aromatic dicarboxylic acid, cationic group-containing aromatic dicarboxylic acid, and neutral group-containing aromatic dicarboxylic acid is more preferable, and sulfonic acid base-containing. One or more selected from the group consisting of aromatic dicarboxylic acids is more preferable.
  • one or more selected from the group consisting of sulfophthalic acid and sulfonaphthalenedicarboxylic acid is preferable, one or more selected from the group consisting of sulfophthalic acid is more preferable, and sulfoisophthalic acid is more preferable.
  • One or more selected from the group consisting of acid and sulfoterephthalic acid is more preferable, and 5-sulfoisophthalic acid is further preferable.
  • the ratio of the aromatic dicarboxylic acid monomer unit A to the total of all the monomer units of the resin ⁇ is preferably 5 mol% or more, more preferably 7 mol% or more, from the viewpoint of water dispersibility of the water-dispersible resin composition. 10 mol% or more is further preferable, and from the viewpoint of heat resistance of the water-dispersible resin composition, 30 mol% or less is more preferable, 25 mol% or less is more preferable, and 20 mol% or less is further preferable.
  • the ratio of the aromatic dicarboxylic acid monomer unit A to the total of all the dicarboxylic acid monomer units in the resin ⁇ is preferably 10 mol% or more, preferably 15 mol% or more, from the viewpoint of water dispersibility of the water-dispersible resin composition. Is more preferable, 20 mol% or more is further preferable, and from the viewpoint of heat resistance of the water-dispersible resin composition, 50 mol% or less is more preferable, 40 mol% or less is more preferable, and 35 mol% or less is further preferable.
  • the resin ⁇ has a dicarboxylic acid monomer unit having no hydrophilic group.
  • the dicarboxylic acid monomer unit having no hydrophilic group of the resin ⁇ is referred to as a dicarboxylic acid monomer unit B.
  • the dicarboxylic acid for inducing the dicarboxylic acid monomer unit B is referred to as a dicarboxylic acid B.
  • the dicarboxylic acid B is selected from the group consisting of the aromatic dicarboxylic acid having no hydrophilic group and the aliphatic dicarboxylic acid having no hydrophilic group from the viewpoint of heat resistance of the water-dispersible resin composition.
  • One kind or two or more kinds are more preferable.
  • one or more selected from the group consisting of phthalic acid, frangylcarboxylic acid, naphthalenedicarboxylic acid, cyclohexanedicarboxylic acid, and adamantandicarboxylic acid is more preferable, and terephthalic acid, isophthalic acid, and the like.
  • One or more selected from the group consisting of 2,5-furandicarboxylic acid, 2,6-naphthalenedicarboxylic acid, 1,4-cyclohexanedicarboxylic acid, and 1,3-adamantandicarboxylic acid is more preferable, and terephthalic acid is more preferable.
  • terephthalic acid is more preferable.
  • 2,6-naphthalenedicarboxylic acids are more preferred.
  • the ratio of the amount of substance of the dicarboxylic acid monomer unit B to the total amount of substances of all the monomer units in the resin ⁇ is preferably 15 mol% or more, preferably 25 mol%, from the viewpoint of heat resistance of the water-dispersible resin composition.
  • the above is more preferable, 30 mol% or more is further preferable, and from the viewpoint of water dispersibility of the water-dispersible resin composition, 45 mol% or less is more preferable, 42 mol% or less is more preferable, and 40 mol% or less is further preferable.
  • the ratio of the dicarboxylic acid monomer unit B to the total of all the dicarboxylic acid monomer units in the resin ⁇ is preferably 30 mol% or more, more preferably 50 mol% or more, from the viewpoint of heat resistance of the water-dispersible resin composition. , 70 mol% or more is further preferable, and from the viewpoint of water dispersibility of the water-dispersible resin composition, 90 mol% or less is preferable, 85 mol% or less is more preferable, and 80 mol% or less is further preferable.
  • the mol ratio of the aromatic dicarboxylic acid monomer unit A and the dicarboxylic acid monomer unit B in the resin ⁇ is the water-dispersible resin composition. From the viewpoint of heat resistance, 10/90 or more is preferable, 15/85 or more is more preferable, 20/80 or more is further preferable, and 60/40 or less is preferable from the viewpoint of water dispersibility of the water-dispersible resin composition. , 40/60 or less is more preferable, and 30/70 or less is further preferable.
  • the resin ⁇ preferably has a monomer unit derived from a monomer having two functional groups that react with a carboxy group.
  • a monomer having two functional groups that react with a carboxy group is referred to as a monomer C
  • a monomer unit derived from the monomer C is referred to as a monomer unit C.
  • Examples of the monomer unit C include a monomer unit derived from one or more selected from the group consisting of diols, diamines and alkanolamines, and an aliphatic diol monomer unit derived from an aliphatic diol and an aromatic.
  • Aromatic diol monomer units derived from diols, aliphatic diamine monomer units derived from aliphatic diamines, and the like are preferable, and among these, the aliphatic diol monomer unit is preferable.
  • the carbon number of the aliphatic diol is preferably 2 or more from the viewpoint of imparting dispersibility in water to the resin composition and from the viewpoint of maintaining the heat resistance of the resin composition, and 31 or less from the same viewpoint. Is preferable, 25 or less is more preferable, 20 or less is further preferable, and 15 or less is further preferable.
  • Examples of the aliphatic diol include one or more selected from the group consisting of chain diols and cyclic diols, from the viewpoint of imparting dispersibility in water to the resin composition, and the resin. From the viewpoint of maintaining the heat resistance of the composition, a chain diol is preferable.
  • the number of carbon atoms of the chain diol is preferably 2 or more from the viewpoint of imparting dispersibility in water to the resin composition and from the viewpoint of maintaining the heat resistance of the resin composition, and 6 or less from the same viewpoint. Is preferable, 4 or less is more preferable, 3 or less is further preferable, and 2 is further preferable.
  • the aliphatic diol may have ether oxygen, but when the aliphatic diol is a chain diol, the viewpoint of imparting dispersibility in water to the resin composition and the resin composition From the viewpoint of maintaining heat resistance, the number of ether oxygen is preferably 1 or less, and when the aliphatic diol C is a cyclic diol, the number of ether oxygen is preferably 2 or less from the same viewpoint.
  • the chain diols are ethylene glycol, 1,2-propanediol, and 1,3-propane from the viewpoint of imparting dispersibility in water to the resin composition and maintaining the heat resistance of the resin composition.
  • One or more selected from the group consisting of diol, diethylene glycol and dipropylene glycol is preferable, and one or two selected from the group consisting of ethylene glycol, 1,2-propanediol and 1,3-propanediol.
  • the above is more preferable, and ethylene glycol is further preferable.
  • a chain diamine is used from the viewpoint of imparting dispersibility in water to the resin composition and maintaining the heat resistance of the resin composition. preferable.
  • the number of carbon atoms of the chain diamine is preferably 2 or more, more preferably 3 or more, from the viewpoint of imparting dispersibility in water to the resin composition and maintaining the heat resistance of the resin composition.
  • the above is more preferable. From the same viewpoint, 12 or less is preferable, 10 or less is more preferable, and 8 or less is further preferable.
  • the chain diamine may be one or more selected from the group consisting of alkyldiamine from the viewpoint of imparting dispersibility in water to the resin composition and from the viewpoint of maintaining the heat resistance of the resin composition. Hexamethylenediamine is preferable, and hexamethylenediamine is more preferable.
  • the resin ⁇ may have a monomer unit other than the aromatic dicarboxylic acid monomer unit A, the dicarboxylic acid monomer unit B, and the monomer unit C as long as the effects of the present embodiment are not impaired. ..
  • the resin ⁇ is preferably polyester, polyamide or polyesteramide, and more preferably polyester or polyamide.
  • a resin having a unit represented by the following general formula (3) and a unit represented by the following general formula (4) can be exemplified.
  • m 1 and m 2 indicate the average number of moles of ethylene glycol monomer units added, which are 1 to 3, preferably 1, respectively, and the general formula (3) and m 2 are shown.
  • (4) is a block bond or a random bond, and a random bond is preferable.
  • the weight average molecular weight of the resin ⁇ is preferably 5000 or more, more preferably 10000 or more, further preferably 13000 or more, and water dispersion of the water-dispersible resin composition from the viewpoint of heat resistance of the water-dispersible resin composition. From the viewpoint of properties, 50,000 or less is preferable, 40,000 or less is more preferable, 30,000 or less is further preferable, and 20,000 or less is further preferable. In this specification, the weight average molecular weight is measured by the method described in Examples.
  • the content of the resin ⁇ in the water-dispersible resin composition is preferably 25% by mass or more, more preferably 35% by mass or more, and more preferably 40% by mass from the viewpoint of water dispersibility of the water-dispersible resin composition.
  • the above is more preferable, and from the viewpoint of heat resistance of the water-dispersible resin composition, 90% by mass or less is preferable, 80% by mass or less is more preferable, and 70% by mass or less is further preferable.
  • the method for producing the resin ⁇ is not particularly limited, and a conventionally known method can be applied.
  • the mass ratio of the content of the resin ⁇ to the content of the resin ⁇ contained in the water-dispersible resin composition is the water-dispersible resin composition. From the viewpoint of water dispersibility of the substance, 25/75 or more is preferable, 35/65 or more is more preferable, and 40/60 or more is further preferable. Further, from the viewpoint of heat resistance of the water-dispersible resin composition, 90/10 or less is preferable, 80/20 or less is more preferable, and 75/25 or less is further preferable.
  • the mass ratio of the content of the resin ⁇ to the content of the resin ⁇ contained in the water-dispersible resin composition is from the viewpoint of achieving both heat resistance and water dispersibility of the water-dispersible resin composition. , 25/75 to 90/10, more preferably 35/65 to 80/20, and even more preferably 40/60 to 75/25.
  • the mol ratio of the content of the hydrophilic group of the resin ⁇ (the content of the structure M / the content of the hydrophilic group) to the content of the structure M of the resin ⁇ contained in the water-dispersible resin composition is. From the viewpoint of achieving both heat resistance and water dispersibility of the water-dispersible resin composition, 40/60 or more is preferable, 45/55 or more is more preferable, 50/50 or more is further preferable, and the water-dispersible resin composition is more preferable. From the viewpoint of water dispersibility, 99/1 or less is preferable, 90/10 or less is more preferable, and 85/15 or less is further preferable.
  • the mol ratio of the content of the hydrophilic group of the resin ⁇ to the content of the structure M of the resin ⁇ contained in the water-dispersible resin composition (content of structure M / content of hydrophilic group). Is preferably 40/60 to 99/1, more preferably 45/55 to 90/10, and 50/50 to 85/15, from the viewpoint of achieving both heat resistance and water dispersibility of the water-dispersible resin composition. Is more preferable.
  • the water-dispersible resin composition may contain other components as long as the effects of the present embodiment are not impaired.
  • the other components include polymers other than the resin ⁇ and the resin ⁇ , plasticizers such as benzoic acid polyalkylene glycol diester, calcium carbonate, magnesium carbonate, glass spheres, graphite, carbon black, carbon fiber, and glass.
  • plasticizers such as benzoic acid polyalkylene glycol diester, calcium carbonate, magnesium carbonate, glass spheres, graphite, carbon black, carbon fiber, and glass.
  • fillers such as fiber, talc, wollastonite, mica, alumina, silica, kaolin, whiskers, and silicon carbide, compatibilizers, and elastomers.
  • the polymer other than the resin ⁇ and the resin ⁇ include the following water-insoluble resin ⁇ .
  • the compatibilizer include the following organic salt compound ⁇ .
  • the water-dispersible resin composition contains a water-insoluble resin ⁇ having an epoxy group, a carbodiimide group, or an acid anhydride group from the viewpoint of achieving both heat resistance and water dispersibility of the water-dispersible resin composition. You may. From the same viewpoint, the water-insoluble resin ⁇ preferably has an epoxy group from the same viewpoint.
  • water-insoluble resin ⁇ having an epoxy group examples include Bondfast (registered trademark) 7B, Bondfast 2E, Bondfast 2C, Bondfast 7M, Bondfast CG5001 (all manufactured by Sumitomo Chemical Co., Ltd.), Rotada (registered trademark) AX8840 (manufactured by Archema).
  • JONCRYL (registered trademark) ADR4370S, JONCRYL ADR4368CS, JONCRYL ADR4368F, JONCRYL ADR4300S, JONCRYL ADR4468 (above, BASF), ARUFON (registered trademark) UG4035, ARUFON (registered trademark) UG4035, ARUFON UG4040, ARUFON
  • water-insoluble resin ⁇ having a carbodiimide group include carbodilite (registered trademark) LA-1 (manufactured by Nisshinbo Chemical Co., Ltd.) and StabaXol (registered trademark) P (manufactured by Rheinchemy).
  • Examples of the water-insoluble resin ⁇ having an acid anhydride group include Yumex (registered trademark) 1010 (manufactured by Sanyo Kasei Co., Ltd.), Admer (registered trademark) (manufactured by Mitsui Kagaku Co., Ltd.), and Modiper (registered trademark) A8200 (manufactured by Nippon Oil & Fats Co., Ltd.).
  • OREVAC registered trademark
  • FG1901, FG1924 above, Kraton Polymer
  • Toughtech registered trademark M1911, Toughtech M1913, Toughtech M1943 (above, manufactured by Asahi Kasei Chemicals)
  • the content of the water-insoluble resin ⁇ in the water-dispersible resin composition is preferably 1% by mass or more, more preferably 3% by mass or more, from the viewpoint of water dispersibility of the water-dispersible resin composition.
  • the mass% or more is more preferable, and from the viewpoint of maintaining the heat resistance of the water-dispersible resin composition, 40% by mass or less is more preferable, 30% by mass or less is more preferable, and 20% by mass or less is further preferable.
  • the mass ratio of the resin ⁇ to the water-insoluble resin ⁇ (mass of the resin ⁇ / mass of the water-insoluble resin ⁇ ) in the water-dispersible resin composition is the heat resistance and water dispersibility of the water-dispersible resin composition. From the viewpoint of achieving both, it is preferably 50/50 or more, more preferably 60/40 or more, still more preferably 70/30 or more, and from the same viewpoint, preferably 95/5 or less, more preferably 93/7 or less. , More preferably 90/10 or less.
  • the water-dispersible resin composition may contain an organic salt compound represented by the following general formula (5) from the viewpoint of compatibility between the resin ⁇ and the resin ⁇ .
  • the organic salt compound represented by the following general formula (5) is referred to as an organic salt compound ⁇ .
  • R indicates a hydrocarbon group having 1 to 30 carbon atoms which may have a substituent
  • n indicates a number of 1 or 2
  • Q n + Indicates a monovalent cation, preferably an alkali metal ion, an ammonium ion, or a phosphonium ion, and when n is 2, Q n + indicates a divalent cation, and an alkaline earth metal ion or a transition metal ion is preferable.
  • R has a substituent from the viewpoint of controlling the molecular weight at the time of producing the water-dispersible resin composition, and from the viewpoint of ensuring solubility in neutral water and hygroscopicity.
  • the hydrocarbon group which may have 1 to 30 carbon atoms is shown.
  • the hydrocarbon group may be any of an aliphatic hydrocarbon group, an alicyclic hydrocarbon group, and an aromatic hydrocarbon group.
  • the number of carbon atoms of the hydrocarbon group is preferably 6 or more, preferably 10 or more, from the viewpoint of controlling the molecular weight at the time of producing the water-dispersible resin composition, and from the viewpoint of ensuring solubility in neutral water and hygroscopicity.
  • the aromatic hydrocarbon group is preferably one or more substituents from the viewpoint of controlling the molecular weight at the time of producing the water-dispersible resin composition, and from the viewpoint of ensuring solubility in neutral water and moisture absorption resistance. It is a phenyl group having a branched chain or a linear alkyl group or a phenyl group having an alkenyl, and more preferably a phenyl group having a branched chain or a straight chain alkyl group.
  • Q n + is a monovalent cation from the viewpoint of controlling the molecular weight at the time of producing the water-dispersible resin composition, and from the viewpoint of ensuring solubility in neutral water and moisture absorption resistance.
  • Alkali metal ions, ammonium ions, or phosphonium ions are more preferable, lithium ions or phosphonium ions are more preferable, and phosphonium ions are even more preferable.
  • phosphonium ions tetraalkylphosphonium ions are preferable, and tetrabutylphosphonium ions are more preferable, from the viewpoint of ensuring the heat resistance required at the time of producing the water-dispersible resin composition.
  • n is preferably 1 from the viewpoint of controlling the molecular weight at the time of producing the water-dispersible resin composition, the viewpoint of solubility in neutral water, and the viewpoint of ensuring hygroscopicity.
  • the content of the organic salt compound ⁇ in the water-dispersible resin composition is preferably 0.1% by mass or more, more preferably 1% by mass or more, from the viewpoint of compatibility between the resin ⁇ and the resin ⁇ .
  • the mass% or more is further preferable, and from the viewpoint of maintaining the heat resistance of the water-dispersible resin composition, 15% by mass or less is preferable, 10% by mass or less is more preferable, and 5% by mass or less is further preferable.
  • 0.005 or more is preferable, 0.01 or more is more preferable, 0.02 or more is further preferable, and from the viewpoint of maintaining the heat resistance of the water-dispersible resin composition and suppressing the bleed-out of the organic salt compound, 0. 35 or less is preferable, 0.25 or less is more preferable, and 0.2 or less is further preferable.
  • the water-dispersible resin composition preferably has a glass transition temperature of 150 ° C. or higher, more preferably 170 ° C. or higher, and further preferably 170 ° C. or higher, from the viewpoint of ensuring heat resistance during use. It has a glass transition temperature of 180 ° C or higher. Further, the water-dispersible resin composition is preferably 280 ° C. or lower, more preferably 250 ° C. or lower, still more preferably 235 ° C. or lower, from the viewpoint of ensuring moldability. In this specification, the glass transition temperature is measured by the method described in Examples.
  • the method for producing the water-dispersible resin composition is not particularly limited, and the water-dispersible resin composition can be produced by a known method.
  • Examples of the method for producing the water-dispersible resin composition include a method of kneading raw materials with a kneader such as a batch type kneader or a twin-screw extruder.
  • the water-dispersible resin composition has a step of obtaining a three-dimensional object precursor containing a three-dimensional object and a support material, and a support material removing step of bringing the three-dimensional object precursor into contact with neutral water to remove the support material. It can be used as a material for a support material in a method for manufacturing a three-dimensional object by a heat-melt lamination method having the above. Further, the water-dispersible resin composition can be used as a material for a water-soluble printing layer and a printing primer layer. Further, the water-dispersible resin composition can be used as a material for the water-soluble coating layer. Further, the water-dispersible resin composition can be used as a material for a water-soluble adhesive and a water-soluble pressure-sensitive adhesive.
  • the present invention further discloses the following compositions and the like.
  • ⁇ 2> The water-dispersible resin composition according to ⁇ 1>, wherein the structure M is a structure in which two aromatic rings are preferably linked by an imide group, preferably a structure in which two aromatic rings are linked by a sulfonyl group.
  • the structure M is represented by the following general formula (1) or the following general formula (2). (However, in the general formula (1), X indicates SO 2 , S or CO).
  • ⁇ 4> The water-dispersible resin composition according to any one of ⁇ 1> to ⁇ 3>, wherein the resin ⁇ has one kind or two or more kinds of structures M.
  • the content of the structure M in the resin ⁇ is preferably 10 mmol / g or less, more preferably 6 mmol / g or less, still more preferably 5 mmol / g or less, according to any one of ⁇ 1> to ⁇ 5>.
  • the content of the structure M in the resin ⁇ is preferably 1 to 10 mmol / g, more preferably 2 to 6 mmol / g, still more preferably 3 to 5 mmol / g, as described in ⁇ 1> to ⁇ 6>.
  • the water-dispersible resin composition according to any one. ⁇ 8> The water-dispersible resin according to any one of ⁇ 1> to ⁇ 7>, wherein the resin ⁇ further has a structure L in the main chain in which two aromatic rings different from the structure M are connected. Composition.
  • the structure L is a structure in which two aromatic rings are preferably linked by a single bond, an ether group or an alkylmethylene group, more preferably a single bond or an ether group, and further preferably an ether group.
  • the water-dispersible resin composition according to. ⁇ 10> The water-dispersible resin composition according to ⁇ 8> or ⁇ 9>, wherein the resin ⁇ has one kind or two or more kinds of structures L.
  • ⁇ 11> The water-dispersible resin composition according to any one of ⁇ 1> to ⁇ 10>, wherein the glass transition temperature of the resin ⁇ is preferably 150 ° C. or higher, more preferably 200 ° C. or higher, still more preferably 210 ° C. or higher. thing.
  • ⁇ 12> The water-dispersible resin composition according to any one of ⁇ 1> to ⁇ 11>, wherein the glass transition temperature of the resin ⁇ is preferably 280 ° C. or lower, more preferably 250 ° C. or lower, still more preferably 230 ° C. or lower. thing. ⁇ 13>
  • the resin ⁇ is preferably one or more, more preferably polyphenyl, selected from the group consisting of polyphenylsulfone, polysulfone, polyetherimide, polyetheretherketone, polyphenylene sulfide, polyethersulfone, and polyamideimide.
  • the water-dispersible resin composition described in Crab The water-dispersible resin composition described in Crab.
  • the content of the resin ⁇ in the water-dispersible resin composition is preferably 10% by mass or more, more preferably 15% by mass or more, still more preferably 20% by mass or more, said ⁇ 1> to ⁇ 14>.
  • the water-dispersible resin composition according to any one of. ⁇ 16> The content of the resin ⁇ in the water-dispersible resin composition is preferably 80% by mass or less, more preferably 75% by mass or less, still more preferably 70% by mass or less, still more preferably 65% by mass or less.
  • the content of the resin ⁇ in the water-dispersible resin composition is preferably 10 to 80% by mass, more preferably 15 to 75% by mass, further preferably 20 to 70% by mass, and 20 to 65% by mass.
  • Examples of the hydrophilic group include one or more selected from the group consisting of an anionic group, a cationic group, and a neutral group. Among these, from the same viewpoint, one or more selected from the group consisting of anionic groups is preferable, and the water-dispersible resin according to any one of ⁇ 1> to ⁇ 17> above, which is a sulfonic acid base. Composition.
  • the sulfonic acid base represents -SO 3 M (where M represents a counter ion of the sulfonic acid group constituting the sulfonic acid base, and the heat resistance and the water dispersibility of the water-dispersible resin composition are compatible with each other.
  • M represents a counter ion of the sulfonic acid group constituting the sulfonic acid base
  • the heat resistance and the water dispersibility of the water-dispersible resin composition are compatible with each other.
  • One or two or more selected from the group consisting of metal ions and ammonium ions is preferable, one or two or more selected from the group consisting of metal ions is more preferable, and a group consisting of alkali metal ions and alkaline earth metal ions.
  • the water-dispersible resin composition according to ⁇ 18> which is more preferably represented by (more preferably, sodium ion).
  • the content of the hydrophilic group in the resin ⁇ is preferably 0.5 mmol / g or more, more preferably 0.6 mmol / g or more, still more preferably 0.7 mmol / g or more.
  • the content of the hydrophilic group in the resin ⁇ is preferably 3 mmol / g or less, more preferably 2 mmol / g or less, still more preferably 1.5 mmol / g or less, as described in ⁇ 1> to ⁇ 20>.
  • the water-dispersible resin composition according to any one. ⁇ 22> The water-dispersible resin composition according to any one of ⁇ 1> to ⁇ 21>, wherein the glass transition temperature of the resin ⁇ is preferably 30 ° C. or higher, more preferably 70 ° C. or higher.
  • the aromatic dicarboxylic acid A for inducing the aromatic dicarboxylic acid monomer unit A is preferably one or more, more preferably anionic, selected from the group consisting of the aromatic dicarboxylic acids having a hydrophilic group.
  • sulfophthalic acid more preferably one or more selected from the group consisting of sulfophthalic acid and sulfonaphthalenedicarboxylic acid, still more preferably one selected from the group consisting of sulfophthalic acid.
  • the water-dispersible resin composition according to ⁇ 24> above which is one or more selected from the group consisting of two or more, more preferably sulfoisophthalic acid and sulfoterephthalic acid, and more preferably 5-sulfoisophthalic acid. thing.
  • the ratio of the aromatic dicarboxylic acid monomer unit A to the total of all the monomer units of the resin ⁇ is preferably 5 mol% or more, more preferably 7 mol% or more, still more preferably 10 mol% or more, the above ⁇ 24> or ⁇ .
  • the ratio of the aromatic dicarboxylic acid monomer unit A to the total of all the monomer units of the resin ⁇ is preferably 30 mol% or less, more preferably 25 mol% or less, still more preferably 20 mol% or less, the above ⁇ 24> to ⁇ . 26>
  • the water-dispersible resin composition according to any one of.
  • the ratio of the aromatic dicarboxylic acid monomer unit A to the total of all the dicarboxylic acid monomer units in the resin ⁇ is preferably 10 mol% or more, more preferably 15 mol% or more, still more preferably 20 mol% or more.
  • ⁇ 29> The ratio of the aromatic dicarboxylic acid monomer unit A to the total of all the dicarboxylic acid monomer units in the resin ⁇ is preferably 50 mol% or less, more preferably 40 mol% or less, still more preferably 35 mol% or less.
  • the dicarboxylic acid B for inducing the dicarboxylic acid monomer unit B is preferably selected from the group consisting of the aromatic dicarboxylic acid having no hydrophilic group and the aliphatic dicarboxylic acid having no hydrophilic group1.
  • the water-dispersible resin composition according to any one of. ⁇ 31> The ratio of the amount of substance of the dicarboxylic acid monomer unit B to the total amount of substance of all the monomer units in the resin ⁇ is preferably 15 mol% or more, more preferably 25 mol% or more, still more preferably 30 mol%.
  • the ratio of the amount of substance of the dicarboxylic acid monomer unit B to the total amount of substance of all the monomer units in the resin ⁇ is preferably 45 mol% or less, more preferably 42 mol% or less, still more preferably 40 mol% or less.
  • the ratio of the dicarboxylic acid monomer unit B to the total of all the dicarboxylic acid monomer units in the resin ⁇ is preferably 30 mol% or more, more preferably 50 mol% or more, still more preferably 70 mol% or more, said ⁇ 24>.
  • the ratio of the dicarboxylic acid monomer unit B to the total of all the dicarboxylic acid monomer units in the resin ⁇ is preferably 90 mol% or less, more preferably 85 mol% or less, still more preferably 80 mol% or less, said ⁇ 24>.
  • the mol ratio of the aromatic dicarboxylic acid monomer unit A and the dicarboxylic acid monomer unit B in the resin ⁇ is preferably 10/90 or more.
  • the mol ratio of the aromatic dicarboxylic acid monomer unit A to the dicarboxylic acid monomer unit B in the resin ⁇ is preferably 60/40 or less.
  • the water-dispersible resin composition according to any one of ⁇ 1> to ⁇ 36>, wherein the resin ⁇ has a monomer unit C derived from a monomer having two functional groups that react with a carboxy group.
  • the monomer unit C is preferably a monomer unit derived from one or more selected from the group consisting of diols, diamines and alkanolamines, more preferably an aliphatic diol monomer unit derived from an aliphatic diol, and an aroma.
  • the water-dispersible resin composition according to ⁇ 37> above which is an aromatic diol monomer unit derived from a group diol, an aliphatic diamine monomer unit derived from an aliphatic diamine, and more preferably an aliphatic diol monomer unit. .. ⁇ 39>
  • the water-dispersible resin composition according to ⁇ 38> wherein the aliphatic diol has preferably 2 or more carbon atoms for inducing the aliphatic diol monomer unit.
  • the ⁇ 38> or ⁇ 39>. The water-dispersible resin composition.
  • ⁇ 41> The water-dispersible resin composition according to ⁇ 39> or ⁇ 40>, wherein the aliphatic diol has ether oxygen.
  • the aliphatic diol is preferably one or more selected from the group consisting of chain diols and cyclic diols, and more preferably chain diols, any of the above ⁇ 39> to ⁇ 41>.
  • the water-dispersible resin composition according to the above. ⁇ 43> The water-dispersible resin composition according to ⁇ 42>, wherein the chain diol has 2 or more carbon atoms.
  • the chain diol is one or more selected from the group consisting of ethylene glycol, 1,2-propanediol, 1,3-propanediol, diethylene glycol, and dipropylene glycol, more preferably ethylene glycol, 1,.
  • Sex resin composition ⁇ 48> The water-dispersible resin composition according to any one of ⁇ 38> to ⁇ 47>, wherein the aliphatic diamine is a chain diamine.
  • the resin ⁇ is preferably a resin having a polyester, a polyamide or a polyester amide, more preferably a polyester or a polyamide, and more preferably a unit represented by the following general formula (3) and a unit represented by the following general formula (4).
  • the water-dispersible resin composition according to any one of ⁇ 1> to ⁇ 51>.
  • m 1 and m 2 indicate the average number of moles of ethylene glycol monomer units added, which are 1 to 3, preferably 1, respectively, and the general formula (3) and m 2 are shown.
  • (4) is a block bond or a random bond, and a random bond is preferable.
  • ⁇ 53> The water-dispersible resin composition according to any one of ⁇ 1> to ⁇ 52>, wherein the weight average molecular weight of the resin ⁇ is preferably 5000 or more, more preferably 10000 or more, and further preferably 13000 or more.
  • ⁇ 54> The water dispersion according to any one of ⁇ 1> to ⁇ 53>, wherein the weight average molecular weight of the resin ⁇ is preferably 50,000 or less, more preferably 40,000 or less, still more preferably 30,000 or less, still more preferably 20,000 or less. Sex resin composition.
  • the content of the resin ⁇ in the water-dispersible resin composition is preferably 25% by mass or more, more preferably 35% by mass or more, still more preferably 40% by mass or more, said ⁇ 1> to ⁇ 54>.
  • the water-dispersible resin composition according to any one of. ⁇ 56> The content of the resin ⁇ in the water-dispersible resin composition is preferably 90% by mass or less, more preferably 80% by mass or less, still more preferably 70% by mass or less, said ⁇ 1> to ⁇ 55>.
  • the mass ratio of the content of the resin ⁇ to the content of the resin ⁇ contained in the water-dispersible resin composition is preferably 25/75 or more.
  • the mass ratio of the content of the resin ⁇ to the content of the resin ⁇ contained in the water-dispersible resin composition (content of the resin ⁇ / content of the resin ⁇ ) is preferably 90/10 or less.
  • the mass ratio of the content of the resin ⁇ to the content of the resin ⁇ contained in the water-dispersible resin composition is 25/75 to 90 /. 10.
  • the mol ratio (content of structure M / content of hydrophilic group) of the content of the hydrophilic group of the resin ⁇ to the content of the structure M of the resin ⁇ contained in the water-dispersible resin composition is The water-dispersible resin composition according to any one of ⁇ 1> to ⁇ 59>, preferably 40/60 or more, more preferably 45/55 or more, still more preferably 50/50 or more.
  • the mol ratio (content of structure M / content of hydrophilic group) of the content of the hydrophilic group of the resin ⁇ to the content of the structure M of the resin ⁇ contained in the water-dispersible resin composition is The water-dispersible resin composition according to any one of ⁇ 1> to ⁇ 60>, preferably 99/1 or less, more preferably 90/10 or less, still more preferably 85/15 or less.
  • the mol ratio (content of structure M / content of hydrophilic group) of the content of the hydrophilic group of the resin ⁇ to the content of the structure M of the resin ⁇ contained in the water-dispersible resin composition is The aqueous dispersion according to any one of ⁇ 1> to ⁇ 61>, preferably 40/60 to 99/1, more preferably 45/55 to 90/10, and even more preferably 50/50 to 85/15. Sex resin composition.
  • the water-dispersible resin composition preferably contains a water-insoluble resin ⁇ having an epoxy group, a carbodiimide group, or an acid anhydride group, and more preferably an epoxy group.
  • the water-dispersible resin composition according to the above. ⁇ 64>
  • the content of the water-insoluble resin ⁇ in the water-dispersible resin composition is preferably 1% by mass or more, more preferably 3% by mass or more, still more preferably 5% by mass or more, according to the above ⁇ 63>.
  • the content of the water-insoluble resin ⁇ in the water-dispersible resin composition is preferably 40% by mass or less, more preferably 30% by mass or less, still more preferably 20% by mass or less, said ⁇ 63> or ⁇ . 64> The water-dispersible resin composition.
  • the mass ratio of the resin ⁇ to the water-insoluble resin ⁇ (mass of resin ⁇ / mass of water-insoluble resin ⁇ ) in the water-dispersible resin composition is preferably 50/50 or more, more preferably 60/40 or more.
  • the mass ratio of the resin ⁇ to the water-insoluble resin ⁇ (mass of the resin ⁇ / mass of the water-insoluble resin ⁇ ) in the water-dispersible resin composition is preferably 95/5 or less, more preferably 93/7 or less.
  • ⁇ 68> The water-dispersible resin composition according to any one of ⁇ 1> to ⁇ 67>, wherein the water-dispersible resin composition contains the organic salt compound ⁇ represented by the following general formula (5).
  • R indicates a hydrocarbon group having 1 to 30 carbon atoms which may have a substituent, n indicates a number of 1 or 2, and when n is 1, Q n + Indicates a monovalent cation, preferably an alkali metal ion, an ammonium ion, or a phosphonium ion, and when n is 2, Q n + indicates a divalent cation, and an alkaline earth metal ion or a transition metal ion is preferable.
  • R is an aliphatic hydrocarbon group, an alicyclic hydrocarbon group, or an aromatic hydrocarbon group.
  • ⁇ 70> The water according to ⁇ 68> or ⁇ 69>, wherein the hydrocarbon group having R in the general formula (5) has a carbon number of preferably 6 or more, more preferably 10 or more, still more preferably 12 or more. Dispersible resin composition. ⁇ 71> Any of the above ⁇ 68> to ⁇ 70>, wherein the hydrocarbon group of R in the general formula (5) has a carbon number of preferably 30 or less, more preferably 25 or less, still more preferably 20 or less.
  • the water-dispersible resin composition according to the above.
  • the aromatic hydrocarbon group which is R in the general formula (5), is preferably a phenyl group having one or more substituents, and more preferably a branched chain or linear alkyl group or alkenyl.
  • Q n + is preferably a monovalent cation, more preferably an alkali metal ion, an ammonium ion, or a phosphonium ion, still more preferably a tetraalkylphosphonium ion, and still more preferably a tetrabutylphosphonium ion.
  • ⁇ 74> The water-dispersible resin composition according to any one of ⁇ 68> to ⁇ 73>, wherein n is 1 in the general formula (5).
  • the content of the organic salt compound ⁇ in the water-dispersible resin composition is preferably 0.1% by mass or more, more preferably 1% by mass or more, still more preferably 2% by mass or more, said ⁇ 68>.
  • the content of the organic salt compound ⁇ in the water-dispersible resin composition is preferably 15% by mass or less, more preferably 10% by mass or less, still more preferably 5% by mass or less, said ⁇ 68> to ⁇ .
  • the water-dispersible resin composition according to any one of ⁇ 68> to ⁇ 76>, which is more preferably 0.02 or more.
  • a soluble material for three-dimensional modeling which comprises the water-dispersible resin composition according to any one of ⁇ 1> to ⁇ 78>.
  • the water-dispersible resin composition according to any one of ⁇ 1> to ⁇ 79> which is a support material for supporting the three-dimensional object when the three-dimensional object is manufactured by a fused deposition modeling type 3D printer. Including support material.
  • ⁇ 81> Use as a support material for the soluble material for 3D modeling according to ⁇ 79> when manufacturing a 3D object by a 3D printer of the hot melt lamination method.
  • Pressure is expressed as absolute pressure. "Normal pressure" indicates 101.3 kPa.
  • the reaction was carried out with stirring at 400 Pa for 2 hours, and then the reaction was carried out with stirring while gradually increasing the degree of reduced pressure to 100 Pa to obtain a resin composition 1 containing resin ⁇ 1.
  • Table 1 shows the contents of the resin ⁇ 1 and the organic salt compound ⁇ contained in the resin composition 1 and the glass transition temperature of the resin composition 1 calculated from the amount of the raw material added. At this time, it was assumed that the excess amount of ethylene glycol was distilled off from the reaction system and the diol unit and the dicarboxylic acid unit reacted in equal amounts.
  • Table 2 shows the ratio of the monomer unit A and the ratio of the monomer unit B to the total of all the dicarboxylic acid monomer units of the resin ⁇ 1 contained in the resin composition 1, the weight average molecular weight, and the content of the hydrophilic group.
  • the ratio of the monomer unit A was calculated by the analysis by NMR described later, and the ratio of the monomer unit B was calculated from the charged amount.
  • a resin composition 8 containing ⁇ 2 was obtained. At this time, it was assumed that the excess amount of ethylene glycol was distilled off from the reaction system and the diol unit and the dicarboxylic acid unit reacted in equal amounts.
  • the glass transition temperature of the resin composition 8 is shown in Table 1.
  • Table 2 shows the ratio of the monomer unit A and the ratio of the monomer unit B to the total of all the dicarboxylic acid monomer units of the resin ⁇ 2 contained in the resin composition 8, the weight average molecular weight, and the content of the hydrophilic group. At this time, the ratio of the monomer unit A was calculated by the analysis by NMR described later, and the ratio of the monomer unit B was calculated from the charged amount.
  • Resin Composition 11 100 g of N-methylpyrrolidone (manufactured by Tokyo Chemical Industry Co., Ltd.) was placed in a glass reactor having a content of 500 mL and equipped with stirring blades. Subsequently, in the reactor, terephthalic acid (manufactured by Tokyo Chemical Industry Co., Ltd.) 3.62 g, monosophthalic 5-sulfoisophthalate (manufactured by Tokyo Chemical Industry Co., Ltd.) 2.19 g, hexamethylenediamine (manufactured by Tokyo Chemical Industry Co., Ltd.) 3.
  • the resin was separated by filtration and dried at 150 ° C. under reduced pressure (1 kPa or less) for 12 hours or more to obtain a resin composition 11 containing the resin ⁇ 3.
  • the glass transition temperature of the resin composition 11 is shown in Table 1.
  • Table 2 shows the ratio of the monomer unit A and the ratio of the monomer unit B to the total of all the dicarboxylic acid monomer units of the resin ⁇ 2 contained in the resin composition 11, the weight average molecular weight, and the content of the hydrophilic group.
  • the resin ⁇ and the water-insoluble resin ⁇ in Tables 3 and 4 are as follows.
  • Polyether sulfone Stratasys, support material for ULTEM1010
  • Polyphenylsulfone Stratasys
  • PPSF Polyetherimide
  • Stratasys ULTEM1010 model material
  • Ethylene-vinyl acetate-glycidyl methacrylate copolymer Sumitomo Chemical, Bondfast 7B
  • Resin Composition 12 Prepare a solution of 1,1,1,3,3,3-hexafluoro-2-propanol (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) in an amount of 5% by mass of the raw materials shown in Table 5, and mix them in parts by mass shown in Table 5. Then, a 1,1,1,3,3,3-hexafluoro-2-propanol solution containing resin ⁇ and resin ⁇ 3 was obtained. These solutions were poured into an aluminum cup and dried under reduced pressure at 50 ° C. and 1 kPa or less for 12 hours or more to obtain a resin composition 12.
  • the resin ⁇ in Table 5 is as follows. Polyester sulfone: Solvay, Veradel 3300 PREM
  • ⁇ Analysis method> [Ratio of the amount of substance of the monomer unit (hereinafter referred to as monomer unit A) derived from dimethyl sodium 5-sulfoisophthalate to the total amount of substance of all the monomer units in the resin] Benzene in a monomer unit (monomer unit A) derived from dimethyl sodium 5-sulfoisophthalate by dissolving a sample in a mixed solvent of dichlorochloro and trifluoroacetic acid and measuring proton NMR using NMR and MR400 manufactured by Agent.
  • the amount of substance A obtained by dividing the integrated value A of the ring-derived peak by the number of protons corresponding to the benzene ring in the monomer unit A, and the monomer unit derived from dimethyl 2,6-naphthalenedicarboxylate (hereinafter referred to as monomer unit B).
  • the amount of substance B obtained by dividing the integrated value B of the peak derived from the naphthalene ring in (referred to as) by the number of protons corresponding to the naphthalene ring in the monomer unit B was calculated.
  • ⁇ Glass-transition temperature A sample of 5 to 10 mg is precisely weighed and sealed in an aluminum pan, and the temperature is raised from 30 ° C. to 300 ° C. at 10 ° C./min using a DSC device (DSC7020 manufactured by Seiko Instruments Inc.), and then the cooling rate is adjusted. It was set to 150 ° C./min and cooled to 30 ° C.
  • the glass transition temperature (° C.) was determined from the DSC curve obtained by raising the temperature to 300 ° C. at 10 ° C./min again. At the time of temperature rise, a baseline in which the calorific value is constant appears, and then an inflection point appears due to the glass transition. The temperature at the intersection of the straight line extending the baseline to the high temperature side and the tangent line at the inflection point was defined as the glass transition temperature. The results are shown in Tables 4-6.
  • the filaments of the resin compositions 2 to 7, 9 and 10 were cut out in an amount of 5 to 10 cm, and the cut out filaments were put into 500 g of deionized water at 80 ° C. in a 500 mL beaker and stirred at 300 rpm using a magnetic stirrer.
  • the time required for the filament to break was measured as the resin composition was dispersed in water.
  • Table 4 Further, since Comparative Examples 1 to 3 had a filament shape (diameter of about 1.8 mm), the water dispersion time was measured without processing. In Table 4, "non-dispersible" means that the filament did not break even after 60 minutes had passed.
  • Example 9 The raw materials shown in Table 5 were dissolved with 1,1,1,3,3,3-hexafluoro-2-propanol (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) to prepare a solution having a concentration of 5% by mass. ..
  • Two drops of this mixed solution were dropped onto a slide glass using a dropper and dried at 50 ° C. under reduced pressure (1 kPa or less) for 2 hours to prepare a film having a thickness of 25 ⁇ m.
  • the thickness of the slide glass before dropping the solution and the total thickness of the film and the slide glass were measured using a micrometer, and the thickness of the film was calculated from the difference.
  • Example 4 The same operation as in Example 9 was carried out except that two drops of the resin ⁇ solution shown in Table 5 were dropped onto a slide glass using a dropper to prepare a film having a thickness of 25 ⁇ m.
  • the resin composition 3 was pressed using a press machine (Lab Press P2-30T manufactured by Toyo Seiki Seisakusho Co., Ltd.) at 290 ° C. and 0.5 MPa for 2 minutes, and then at 290 ° C. and 20 MPa for 2 minutes. Then, the sheet was rapidly cooled to prepare a sheet having a thickness of 0.4 mm. The sheet was bent and broken in liquid nitrogen. The sheet was immersed in water at 80 ° C. for 30 seconds to elute the resin ⁇ on the fracture surface. Then, the sample was dried at 60 ° C. under reduced pressure (1 kPa or less) for 2 hours. After drying, the fracture surface of the sample was observed by SEM (VE-8800 manufactured by KEYENCE). A photograph of the SEM of the resin composition 3 is shown in FIG.
  • Polyester sulfone Solvay, Veradel 3300 PREM Ethylene-vinyl acetate-glycidyl methacrylate copolymer: manufactured by Sumitomo Chemical Co., Ltd., Bondfast 7B Ethylene-glycidyl methacrylate copolymer: Bondfast CG5001 manufactured by Sumitomo Chemical Co., Ltd. Ethylene-methyl acrylate-glycidyl methacrylate copolymer: Sumitomo Chemical Co., Ltd., Bondfast 7M Modified Styrene-Glycydyl Methacrylate Copolymer: BASF, JONCRYL ADR4468
  • the filaments of the resin composition 13 and the resin composition 14 are cut out by 5 to 10 cm, the cut filaments are put into 500 g of deionized water at 80 ° C. in a 500 mL beaker, and the resin is stirred with a magnetic stirrer at 300 rpm.
  • the time required for the filament to break was measured as the composition was dispersed in water. The results are shown in Table 6.
  • Example 12 When the filament of the resin composition 13 was supplied to a Fused Deposition Modeling 3D printer FUNMAT PRO410 manufactured by INTAMSYS and extruded from a heat nozzle having a temperature of 300 ° C., the nozzle could be discharged without clogging and melted. It was confirmed that the thing also solidified immediately.
  • Example 13 When the filament of the resin composition 14 was supplied to a Fused Deposition Modeling 3D printer FUNMAT PRO410 manufactured by INTAMSYS and extruded from a heat nozzle having a temperature of 300 ° C., the nozzle could be discharged without clogging and melted. It was confirmed that the thing also solidified immediately.
  • the resin composition obtained in the present invention has heat resistance and water solubility, and can be molded by heat melting.

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JP2018024850A (ja) * 2016-07-28 2018-02-15 花王株式会社 三次元造形用可溶性材料
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JP2000178481A (ja) * 1998-12-16 2000-06-27 Dainippon Printing Co Ltd 転写用電着膜形成液
JP2002161248A (ja) * 2000-11-28 2002-06-04 Dainippon Printing Co Ltd 接着方法
JP2003268235A (ja) * 2002-03-15 2003-09-25 Shimizu:Kk 樹脂組成物および水性電着塗料
JP2008534274A (ja) * 2005-04-07 2008-08-28 ガンブロ・ルンディア・エービー 濾過膜
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