CN105980431B - Aqueous urethane urea resin composition and method for producing the same - Google Patents

Aqueous urethane urea resin composition and method for producing the same Download PDF

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CN105980431B
CN105980431B CN201580008354.3A CN201580008354A CN105980431B CN 105980431 B CN105980431 B CN 105980431B CN 201580008354 A CN201580008354 A CN 201580008354A CN 105980431 B CN105980431 B CN 105980431B
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isocyanate
acid
parts
urethane prepolymer
molecular weight
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CN105980431A (en
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和田秀一
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DKS Co Ltd
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Dai Ichi Kogyo Seiyaku Co Ltd
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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
    • C09D175/04—Polyurethanes
    • 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
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/08—Processes
    • C08G18/0804—Manufacture of polymers containing ionic or ionogenic groups
    • C08G18/0819—Manufacture of polymers containing ionic or ionogenic groups containing anionic or anionogenic groups
    • C08G18/0823—Manufacture of polymers containing ionic or ionogenic groups containing anionic or anionogenic groups containing carboxylate salt groups or groups forming them
    • 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
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
    • C08G18/4236—Polycondensates having carboxylic or carbonic ester groups in the main chain containing only aliphatic groups
    • C08G18/4238—Polycondensates having carboxylic or carbonic ester groups in the main chain containing only aliphatic groups derived from dicarboxylic acids and dialcohols
    • 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
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/48—Polyethers
    • C08G18/4825—Polyethers containing two hydroxy groups
    • 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
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/48—Polyethers
    • C08G18/4854—Polyethers containing oxyalkylene groups having four carbon atoms in the alkylene group
    • 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
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
    • C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
    • C08G18/6633—Compounds of group C08G18/42
    • C08G18/6637—Compounds of group C08G18/42 with compounds of group C08G18/32 or polyamines of C08G18/38
    • C08G18/6648—Compounds of group C08G18/42 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/3225 or C08G18/3271 and/or polyamines of C08G18/38
    • C08G18/6651—Compounds of group C08G18/42 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/3225 or C08G18/3271 and/or polyamines of C08G18/38 with compounds of group C08G18/3225 or polyamines of C08G18/38
    • 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
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
    • C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
    • C08G18/6666—Compounds of group C08G18/48 or C08G18/52
    • C08G18/667—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38
    • C08G18/6681—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/32 or C08G18/3271 and/or polyamines of C08G18/38
    • C08G18/6685—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/32 or C08G18/3271 and/or polyamines of C08G18/38 with compounds of group C08G18/3225 or polyamines of C08G18/38
    • 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
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/72—Polyisocyanates or polyisothiocyanates
    • C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
    • C08G18/75—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic
    • C08G18/751—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring
    • C08G18/752—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group
    • C08G18/753—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group containing one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group having a primary carbon atom next to the isocyanate or isothiocyanate group
    • C08G18/755—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group containing one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group having a primary carbon atom next to the isocyanate or isothiocyanate group and at least one isocyanate or isothiocyanate group linked to a secondary carbon atom of the cycloaliphatic ring, e.g. isophorone diisocyanate
    • 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
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/72—Polyisocyanates or polyisothiocyanates
    • C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
    • C08G18/75—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic
    • C08G18/758—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing two or more cycloaliphatic rings
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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    • C08G2170/00—Compositions for adhesives
    • C08G2170/80—Compositions for aqueous adhesives

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  • Polymers & Plastics (AREA)
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  • Wood Science & Technology (AREA)
  • Manufacturing & Machinery (AREA)
  • Polyurethanes Or Polyureas (AREA)

Abstract

The invention provides an aqueous urethane urea resin composition, a preparation method thereof, an emulsifier and an emulsification method, wherein the preparation method can prepare the aqueous urethane urea resin composition with fine particle size, excellent storage stability and performance which is not inferior to the prior art even if no organic solvent is used, and the productivity is excellent because no organic solvent is used. The present invention relates to an aqueous urethane urea resin composition which is obtained by emulsifying and dispersing a urethane prepolymer containing no hydrophilic group and an isocyanate monomer in water in the presence of an isocyanate adduct at both ends of a dialkanol alkanoic acid and then subjecting the resultant to high molecular weight polymerization with a polyamine compound, wherein the residual NCO group content of a mixture of the urethane prepolymer containing no hydrophilic group, the isocyanate monomer and the isocyanate adduct at both ends of the dialkanol alkanoic acid is 3.5 to 9.5 mass%.

Description

Aqueous urethane urea resin composition and method for producing the same
Technical Field
The invention relates to an aqueous urethane urea resin composition, a preparation method thereof, an emulsifier and an emulsification method.
Background
Conventionally, aqueous polyurethane resins have been used in a wide range of applications as materials that can be used as adhesives, coating agents, paints, modifiers, adhesives, and the like. As such an aqueous polyurethane resin, it is known that the particle size can be made fine and the performance is excellent by a method of self-emulsifying and dispersing a urethane resin containing a hydrophilic group such as an anionic group, a cationic group, and a nonionic group in the skeleton thereof.
From the viewpoints of safety and hygiene, environmental protection, and resource saving, water-based resins have been widely used in various fields. In general, in the production of an aqueous polyurethane resin, a hydrophilic group-containing urethane prepolymer is synthesized in an organic solvent, emulsified in an anionic or cationic resin using a salt former, and then polymerized to a high molecular weight using a polyamine compound. The solvent removal involves a very large amount of energy and complicated operations, and is very uneconomical, and it is difficult to completely remove the organic solvent used from the resulting aqueous polyurethane resin.
Accordingly, various studies for producing aqueous polyurethane without using an organic solvent are being conducted. The following methods are disclosed: the running power is 2000kW/m3A method for producing an aqueous polyurethane by bringing the isocyanate group-terminated prepolymer into contact with water and mixing the prepolymer with the above continuous kneader (see patent document 1); a method for producing an aqueous polyurethane by stirring a urethane prepolymer with water using a vibration type stirring device (see patent document 2); a method in which an isocyanate group-terminated prepolymer is emulsified in water and then the molecular weight of the prepolymer is increased by an aminocarboxylic acid compound (see patent document 3); a method of emulsifying an isocyanate group-terminated prepolymer in water using an emulsifier in an auxiliary manner (see patent document 4); and a method in which an isocyanate group-terminated prepolymer is diluted with an unsaturated monomer and then emulsified in water (see patent document 5).
[ Prior art documents ]
[ patent document ]
[ patent document 1] Japanese patent laid-open No. 2004-292797
[ patent document 2] Japanese patent application laid-open No. 2009-79157
[ patent document 3] Japanese patent laid-open No. 2004-307721
[ patent document 4] Japanese patent laid-open No. Hei 9-52929
[ patent document 5] Japanese patent laid-open No. Hei 9-165425
Disclosure of Invention
Problems to be solved by the invention
In view of the above circumstances, the present inventors have made studies to enable synthesis without using an organic solvent, and in the method described in patent document 1, resin adhesion and contamination of peripheral devices (reaction devices, piping, etc.) in a continuous kneader, into which a highly viscous urethane resin liquid is introduced, are large; and because the high-temperature high-viscosity carbamate resin liquid and water are kneaded in the kneading machine, the temperature of the kneaded liquid is high, and isocyanate groups in the carbamate react with the water. In the method described in patent document 2, the resin adhesion and contamination of peripheral devices (such as a reaction device and piping) for introducing the high-viscosity urethane resin solution into the vibrating stirring device are large. In the method described in patent document 3, a large amount of an aminocarboxylic acid compound is used to make the particle diameter fine, which leads to a decrease in water resistance. In the method described in patent document 4, aggregates are generated in the step of reacting a large number of isocyanate groups with a polyamino compound by mixing a large number of isocyanate monomers. In addition, in the method described in patent document 5, since the viscosity of the highly viscous urethane resin liquid is lowered and the highly viscous urethane resin liquid is diluted with a large amount of unsaturated monomer, problems such as coarsening of the particle diameter of the emulsion and loss of the characteristics of the urethane resin are encountered.
Accordingly, the present inventors have conducted intensive studies and as a result, have found that when a dialkanolaminic acid (C) is used without being contained in a urethane skeleton, and the isocyanate adducts (D) at both ends of the dialkanolaminic acid (C) are used, the viscosity increase width is small even when the amount of the dialkanolaminic acid (C) to be used is increased, and an aqueous urethane urea resin can be produced without using an organic solvent, thereby completing the present invention. That is, the urethane prepolymer (a) containing no hydrophilic group and the isocyanate monomer (B) are stably emulsified in the isocyanate adduct (D) at both ends of the dialkanolamic acid (C) at a specific NCO group amount, and the molecular weight of the urethane prepolymer (a) and the isocyanate monomer (B) are stably increased by the polyamine compound.
An object of the present invention is to provide an aqueous urethane urea resin composition which has a fine particle size and excellent storage stability without using an organic solvent, and which has performance not inferior to that of the prior art, and which is excellent in productivity because an organic solvent is not used, and a method for producing the same.
Means for solving the problems
The present invention relates to an aqueous urethane urea resin composition, which is obtained by emulsifying and dispersing a urethane prepolymer (a) containing no hydrophilic group and an isocyanate monomer (B) in water in the presence of an isocyanate adduct (D) at both ends of a dialkanolaminic acid (C) and then polymerizing the resultant polymer with a polyamine compound (E); and the residual NCO group amount of the mixture of the urethane prepolymer (A) not containing a hydrophilic group, the isocyanate monomer (B), and the both-terminal isocyanate adduct (D) of the dialkanoalkanoic acid (C) is 3.5 to 9.5 mass%.
The invention is a method for producing an aqueous urethane urea resin composition, which does not substantially use an organic solvent; and a method for producing the aqueous urethane urea resin composition includes: a step of emulsifying a urethane prepolymer (a) containing no hydrophilic group and an isocyanate monomer (B) in the presence of an isocyanate adduct (D) at both ends of a dialkanolaminic acid (C); and a step of increasing the molecular weight of the polyamine compound (E); and the remaining NCO group amount of the mixture of the urethane prepolymer (A) not containing a hydrophilic group, the isocyanate monomer (B) and the both-terminal isocyanate adduct (D) of the dialkanoalkanoic acid (C) is 3.5 to 9.5% by mass.
In the emulsification step in the method for producing the aqueous urethane urea resin composition of the present invention, it is preferable that a mixture of the isocyanate adducts (D) at both ends of the dialkanolaminic acid (C), the urethane prepolymer (a) containing no hydrophilic group and the isocyanate monomer (B) is subjected to collision emulsification with emulsification water in an inline, rotor and stator mixer.
The present invention relates to a reactive emulsifier comprising the two terminal isocyanate adducts of dialkanoalkanoic acids.
The present invention relates to a method for emulsifying a urethane prepolymer (a) and an isocyanate monomer (B) each containing no hydrophilic group, which comprises using an isocyanate adduct (D) at both ends of a dialkanoalkanoic acid (C).
ADVANTAGEOUS EFFECTS OF INVENTION
Even if an organic solvent is not used, the particle size is fine, the storage stability is excellent, and the acid value can be arbitrarily adjusted, so that an aqueous urethane urea resin composition having performance not inferior to that of the conventional art can be produced. Since no organic solvent is used, productivity is also excellent. In addition, it is also possible to emulsify polyesters and polycarbonate polyols having active hydrogen atoms, which have been difficult to emulsify before. Such an aqueous urethane urea resin composition and a method for producing the same have not been provided yet. The present invention provides an aqueous urethane urea resin composition having such characteristics and a method for producing the same, and is industrially extremely useful.
Detailed Description
The aqueous urethane urea resin composition of the present invention is obtained by emulsifying and dispersing a urethane prepolymer (a) containing no hydrophilic group and an isocyanate monomer (B) in water in the presence of an isocyanate adduct (D) at both ends of a dialkanoalkanoic acid (C) and then polymerizing the resultant mixture with a polyamine compound (E).
In the present invention, the urethane prepolymer (a) containing no hydrophilic group is a urethane prepolymer containing no hydrophilic group such as anionic, cationic, nonionic or the like in the urethane resin skeleton, and is obtained by reacting a compound having an active hydrogen atom having 2 or more hydroxyl groups at the molecular end or in the molecule with an isocyanate monomer (B) so that the isocyanate group is 1.1 molar equivalent or more relative to the active hydrogen atom. In order to reduce the viscosity of the urethane prepolymer (a) and to obtain a stable emulsion, it is preferably 1.8 to 2.5 molar equivalents.
The compound having an active hydrogen atom in the present invention is not particularly limited, and examples thereof include: known examples of the hydroxyl group-containing compound include compounds having 2 or more hydroxyl groups at the molecular terminal or in the molecule, such as polyether, polyester, polyether ester, polycarbonate, polyolefin, polyacrylic acid, polyacetal, polybutadiene, and polysiloxane. Specific examples thereof include: polyhydric alcohols such as ethylene glycol, diethylene glycol, butylene glycol, propylene glycol, hexylene glycol, bisphenol a, bisphenol B, bisphenol S, hydrogenated bisphenol a, dibromobisphenol a, 1, 4-cyclohexanedimethanol, dihydroxyethyl terephthalate, dihydroxyethyl hydroquinone, trimethylolpropane, glycerol, and pentaerythritol; esters of alkylene derivatives of these polyhydric alcohols or of these polyhydric alcohols and alkylene derivatives with polycarboxylic acids, polycarboxylic anhydrides, or polycarboxylic esters; and polyol compounds such as polycarbonate polyol, polytetramethylene glycol, polycaprolactone polyol, polybutadiene polyol, polythioether polyol, polyacetal polyol, fluorine polyol, silicon polyol, castor oil polyol, acrylic polyol, and polyolefin polyol, and modified products thereof. These compounds may be used in 1 or 2 or more.
The number average molecular weight of the compound having an active hydrogen atom in the present invention is preferably 50 to 10,000, more preferably 500 to 5,000. When the particle diameter is within these ranges, the particle diameter of the emulsion becomes appropriate. In addition, in the case of production without using an organic solvent, from the viewpoint of making the urethane prepolymer low in viscosity, it is preferable that 20% by weight or less of the polyhydroxy compound having a number average molecular weight of more than 5,000 be used in the prepolymer; in the case of using a polyhydroxyl compound having a number average molecular weight of less than 500, it is preferable to set the average OHV of all polyols to be added to a range of 250mgKOH/g or less; when 3 or more active hydrogen atom compounds are used, it is preferable that the active hydrogen atom compounds are in the range of 1mmol equivalent/g (prepolymer) or less as 3 or more active hydrogen atom compounds.
The isocyanate monomer (B) in the present invention is not particularly limited, and examples thereof include organic polyisocyanates such as aliphatic, alicyclic and araliphatic which have been conventionally used. Specific examples thereof include: organic polyisocyanates such as 4, 4' -dicyclohexylmethane diisocyanate, isophorone diisocyanate, hydrogenated xylylene diisocyanate [ bis (isocyanatomethyl) cyclohexane ], hexamethylene diisocyanate, lysine diisocyanate, norbornane diisocyanate, xylylene diisocyanate, and the like, or mixtures of these compounds. The isocyanate monomer (B) also includes a polymer (dimer, trimer, etc.) of the organic polyisocyanate, a biuret modified product produced by the reaction of the organic polyisocyanate with water, and the like. These compounds may be used in 1 or 2 or more. Further, aromatic organic polyisocyanates such as diphenylmethane diisocyanate, tolylene diisocyanate, and naphthylene diisocyanate are not preferable because they react with emulsified water quickly and generate aggregates when reacting with polyamine compounds.
The dialkanoalkanoic acid compound (C) in the present invention is not particularly limited, and examples thereof include: 2, 2-dimethylolpropionic acid, 2-dimethylolbutyric acid (2, 2-dimethylolbutanoic acid), 2-dimethylolpentanoic acid (2, 2-dimethylolpentanoic acid), 2-dimethylolbutyric acid (2, 2-dimethylolbutanoic acid), 2-dimethylolpentanoic acid (2, 2-dimethylolpentanoic acid), and the like. These compounds may be used in 1 or 2 or more. Among these compounds, 2-dimethylolpropionic acid and 2, 2-dimethylolbutyric acid are preferable from the viewpoint of emulsion dispersibility.
In the dialkanoalkanoic acid compound (C) in the present invention, the carboxyl group in the dialkanoalkanoic acid (C) is preferably formed into a salt by a salt-forming agent from the viewpoint of emulsification dispersibility. The salt-forming agent is not particularly limited, and examples thereof include: metal hydroxides such as sodium hydroxide, calcium hydroxide, magnesium hydroxide, sodium carbonate, and potassium carbonate, and tertiary amine compounds such as ammonia, trimethylamine, triethylamine, dimethylaminoethanol, methyldiethanolamine, triethanolamine, triisopropanolamine, and morpholine. These compounds may be used in 1 or 2 or more.
The isocyanate adduct (D) at both ends of the dialkanoalkanoic acid (C) in the present invention is not particularly limited, and is, for example, obtained by reacting the isocyanate monomer (B) so that the isocyanate group is 1.1 molar equivalent or more relative to the dialkanoalkanoic acid (C). In order to obtain a stable emulsion, it is preferably 1.8 molar equivalents or more. The reaction of the isocyanate monomer (B) with the dialkanoalkanoic acid (C) may be carried out simultaneously with or separately from the reaction of the active hydrogen atom with the isocyanate monomer (B).
The polyamine compound (E) in the present invention is not particularly limited, and examples thereof include: hydrazides such as hydrazine and adipic acid hydrazide, ethylenediamine, propylenediamine, hexamethylenediamine, isophoronediamine, xylylenediamine, piperazine, diphenylmethanediamine, ethyltolylenediamine, diethylenetriamine, dipropylenetriamine, triethylenetetramine and tetraethylenepentamine. These compounds may be used in 1 or 2 or more.
In the aqueous urethane urea resin composition of the present invention, the residual NCO group amount of the mixture of the urethane prepolymer (a) not containing a hydrophilic group, the isocyanate monomer (B), and the both-terminal isocyanate adduct (D) of the dialkanoalkanoic acid (C) is 3.5 to 9.5% by mass, preferably 4.0 to 8.5% by mass. If the amount is less than 3.5% by mass, the molecular weight of the urethane prepolymer increases, and the viscosity increases, making emulsification difficult. In addition, in the range of more than 9.5 mass%, the molecular weight of the urethane prepolymer becomes too small, the amount of urethane bonds becomes large, and the viscosity becomes high, so that emulsification becomes difficult.
A method for producing an aqueous urethane urea resin composition according to an embodiment of the present invention is a method for producing an aqueous urethane urea resin composition substantially without using an organic solvent, the method including: a step of emulsifying a urethane prepolymer (a) containing no hydrophilic group and an isocyanate monomer (B) in the presence of an isocyanate adduct (D) at both ends of a dialkanolaminic acid (C); and a step of increasing the molecular weight of the polyamine compound (E); and the residual NCO group amount of the mixture of the urethane prepolymer (A) not containing a hydrophilic group, the isocyanate monomer (B), and the both-terminal isocyanate adduct (D) of the dialkanoalkanoic acid (C) is 3.5 to 9.5 mass%.
In the method for producing the aqueous urethane urea resin composition of the present invention, it is preferable that a mixture of the both-terminal isocyanate adduct (D) of the dialkanolamic acid (C), the urethane prepolymer (a) containing no hydrophilic group and the isocyanate monomer (B) is emulsified with water by collision emulsification in an inline, rotor and stator mixer, and then the molecular weight of the mixture is increased by the polyamine compound.
In the present invention, an inline, rotor and stator type mixer comprises: a fixed stator; and a rotor rotating at high speed with a small gap inside thereof. It is preferable to form the emulsion into fine particles by high shear efficiency due to the rotation speed. The inline, rotor, and stator type mixer is not particularly limited, and examples thereof include: a line homomixer (pipeline homomixer) (manufactured by planimex corporation), a homomixer line mill (homomic linemill) (manufactured by planimex corporation), a Milder (miller) (manufactured by pacific machine company), a rinse-aspirator (Cavitron) (manufactured by pacific machine company), a line mixer (manufactured by rui industries co., Ltd.), an inline mixer (inline mixer) (manufactured by Silverson (Silverson)), and the like.
In the present invention, the amount of the emulsified water is an amount necessary for the delivery emulsification of a stable oil in water type emulsion (O/W type emulsion), that is, preferably 70 parts by weight or more with respect to 100 parts by weight of the prepolymer. The method of adding the emulsified water is preferably a method of emulsifying the prepolymer by collision with the prepolymer in an inline, rotor, and stator mixer at once, rather than slowly adding the prepolymer, because: the temperature of the emulsion can be lowered at a single stroke, and the reaction between the isocyanate groups of the urethane prepolymer and the isocyanate monomer and water can be suppressed.
One embodiment of the present invention is a method for emulsifying a hydrophilic group-free urethane prepolymer (a) and an isocyanate monomer (B) using a both-terminal isocyanate adduct (D) of a dialkanolaminic acid (C). In the emulsification method, the temperature of the mixture of the urethane prepolymer (a) containing no hydrophilic group, the isocyanate monomer (B), and the isocyanate adduct (D) at both ends of the dialkanoalkanoic acid (C) is preferably 25 to 70 ℃ inclusive, and the temperature of the emulsification water is preferably in the range of 10 to 35 ℃. When the emulsifying water temperature is less than 10 ℃, the mixture of the urethane prepolymer (a) containing no hydrophilic group, the isocyanate monomer (B), and the isocyanate adduct (D) at both ends of the dialkanoalkanoic acid (C) rapidly increases in viscosity at the interface in contact with the emulsifying water, and thus coarse particles are generated, which is not preferable. The temperature of the emulsion is preferably 40 ℃ or lower. In the case where the temperature of the emulsion exceeds 40 ℃, the particle size of the emulsion becomes coarse. Further, the urethane prepolymer and the isocyanate group of the isocyanate monomer are not preferable because the reaction rate with water is high and the reaction with the polyamine compound is difficult to control thereafter.
The acid value of the mixture of the urethane prepolymer (A) containing no hydrophilic group, the isocyanate monomer (B) and the isocyanate adduct (D) at both ends of the dialkanoalkanoic acid (C) in the present invention is preferably from 3 to 40mgKOH/g, more preferably from 10 to 30 mgKOH/g. If the acid value is less than 10mgKOH/g, the particle size of the emulsion becomes coarse, and a surfactant is required to be used in combination. If the acid value is less than 3mgKOH/g, the particle size of the emulsion becomes coarse even when a surfactant is used in combination, which is not preferable. When the content of the isocyanate group exceeds 40mgKOH/g, the viscosity of the mixture of the urethane prepolymer (A) containing no hydrophilic group, the isocyanate monomer (B), and the isocyanate adduct (D) at both ends of the dialkanoalkanoic acid (C) becomes high, and emulsification becomes difficult, and the water resistance of the resulting aqueous urethane urea resin deteriorates, which is not preferable.
The viscosity of the mixture of the urethane prepolymer (A) containing no hydrophilic group, the isocyanate monomer (B) and the isocyanate adduct (D) at both ends of the dialkanoalkanoic acid (C) in the present invention is preferably 50000 (mPas/70 ℃ C.) or less, more preferably 30000 (mPas/70 ℃ C.) or less, and particularly preferably 20000 (mPas/70 ℃ C.) or less. If the viscosity exceeds 50000 (mPas/70 ℃), the viscosity of the mixture of the urethane prepolymer (A) containing no hydrophilic group, the isocyanate monomer (B) and the isocyanate adduct (D) at both ends of the dialkanoalkanoic acid (C) rapidly increases at the interface with emulsified water, and thus coarse particles are generated, which is not preferable.
One embodiment of the present invention is a reactive emulsifier comprising a di-terminal isocyanate adduct of a dialkanoalkanoic acid. The reactive emulsifier of the present invention can stably emulsify and disperse the urethane prepolymer (a) containing no hydrophilic group and the isocyanate monomer (B), and thus can reduce the viscosity of the urethane prepolymer without introducing a dialkanoalkanoic acid into the urethane skeleton. Polyol raw materials which are easily highly viscous such as polyester polyols, polycarbonate polyols, branched polyols, or the like can be used even without using an organic solvent. Therefore, it is useful as an adhesive or a coating agent. The coating can be used as a coating and an adhesive for other purposes.
Examples
The present invention will be specifically described below with reference to examples, but the present invention is not limited to these examples. Unless otherwise specified,% represents% by mass.
(evaluation method)
Urethane prepolymer temperature: the temperature just before emulsification was measured.
Temperature of emulsified water: the temperature just before emulsification was measured.
Emulsion temperature: the temperature immediately after emulsification was measured.
Weight of nonvolatile components: measured according to JIS K6828.
Viscosity: measured at 20 ℃ in accordance with JIS Z8803 using a B8H type viscometer (manufactured by Tokyo Meter) rotor No. 2.
Particle size: the particle size was measured by McClick (Microtrac) UPA-UZ152 (manufactured by Nikkiso Co., Ltd.), and the average value of 50% was calculated as the particle size.
(method of preparing test piece)
The resulting aqueous polyurethane resin dispersion was poured into a Teflon (registered trademark) coated petri dish so that the film thickness became 200 μm, and dried at 80 ℃ for 6 hours to prepare an evaluation sample.
(tensile Strength)
The evaluation sample was prepared by cutting the film into a size of a dumbbell test piece (No. 3). The test conditions were measured at a tensile rate of 100mm/min in accordance with JIS-K-6301.
(elongation)
The evaluation sample was prepared by cutting the film into a size of a dumbbell test piece (No. 3). The test conditions were measured at a tensile rate of 100mm/min in accordance with JIS-K-6301.
(Water resistance)
An evaluation sample was prepared by cutting the test film into a predetermined size (2cm × 4 cm). Tap water was used as the test solution. The test piece was immersed in the test solution at 20 ℃ for 24 hours, and the weight increase rate from the initial weight was determined by the following formula.
Weight gain (weight after impregnation-initial weight)/initial weight × 100
(example 1)
225 parts of difunctional polypropylene glycol (number average molecular weight 750), 13.4 parts of dimethylolpropionic acid and 177.9 parts of isophorone diisocyanate were added and reacted at 90 ℃ for 60 minutes to obtain a urethane prepolymer having an isocyanate group content of 8.1% and a carboxylic acid value of 13.5 mgKOH/g. After the obtained urethane prepolymer was cooled to 60 ℃, 10.1 parts of triethylamine was mixed, 670 parts of emulsifying water (20 ℃) was added, and the mixture was mixed and emulsified by a homomixer (a homomixer MARK2 manufactured by planimex corporation, the same as in examples 2 to 11 and comparative synthesis examples 1 to 3 below). The emulsion temperature was 30 ℃. Then, an aqueous solution prepared by diluting 22 parts of ethylenediamine with 198 parts of water was added to increase the molecular weight. The obtained emulsion had a nonvolatile content of 33.8%, a particle diameter of 0.06 μm, and a viscosity of 75 mPas/20 ℃.
(example 2)
165 parts of polytetramethylene glycol (number average molecular weight: 1000), 13.4 parts of dimethylolpropionic acid and 120.8 parts of isophorone diisocyanate were added and reacted at 90 ℃ for 60 minutes to obtain a urethane prepolymer having an isocyanate group content of 7.8% and a carboxylic acid value of 18.7 mgKOH/g. After the obtained urethane prepolymer was cooled to 60 ℃, 10.1 parts of triethylamine was mixed, 390 parts of emulsifying water (20 ℃) was added, and the mixture was mixed and emulsified by a homomixer. The emulsion temperature was 31 ℃. Then, an aqueous solution prepared by diluting 15 parts of ethylenediamine with 60 parts of water was added to increase the molecular weight. The obtained emulsion had a nonvolatile content of 40.6%, a particle diameter of 0.06 μm, and a viscosity of 60 mPas/20 ℃.
(example 3)
A urethane prepolymer having an isocyanate group content of 7.9% and a carboxylic acid value of 18.7mgKOH/g was obtained in the same manner as in example 2, except that a polyester polyol (number average molecular weight: 1000) containing 3-methyl-1, 5-pentanediol and adipic acid was used. After the obtained urethane prepolymer was cooled to 60 ℃, 10.1 parts of triethylamine was mixed, 390 parts of emulsifying water (20 ℃) was added, and the mixture was mixed and emulsified by a homomixer. The emulsion temperature was 30 ℃. Then, an aqueous solution prepared by diluting 15 parts of ethylenediamine with 60 parts of water was added to increase the molecular weight. The obtained emulsion had a nonvolatile content of 40.6%, a particle diameter of 0.09 μm and a viscosity of 50 mPas/20 ℃.
(example 4)
A urethane prepolymer having an isocyanate group content of 7.9% and a carboxylic acid value of 18.7mgKOH/g was obtained in the same manner as in example 2, except that a polycarbonate polyol (number average molecular weight: 1000) containing 1, 5-pentanediol and adipic acid was used. After the obtained urethane prepolymer was cooled to 70 ℃, 10.1 parts of triethylamine was mixed, 390 parts of emulsifying water (20 ℃) was added, and the mixture was mixed and emulsified by a homomixer. The emulsion temperature was 33 ℃. Then, an aqueous solution prepared by diluting 15 parts of ethylenediamine with 60 parts of water was added to increase the molecular weight. The obtained emulsion had a nonvolatile content of 40.6%, a particle diameter of 0.08 μm, and a viscosity of 40 mPas/20 ℃.
(example 5)
210 parts of polytetramethylene glycol (number average molecular weight 3000), 13.4 parts of dimethylolpropionic acid and 83 parts of isophorone diisocyanate were added and reacted at 90 ℃ for 60 minutes to obtain a urethane prepolymer having an isocyanate group content of 5.6% and a carboxylic acid value of 18.3 mgKOH/g. After the obtained urethane prepolymer was cooled to 60 ℃, 10.1 parts of triethylamine was mixed, 300 parts of emulsifying water (20 ℃) was added, and the mixture was mixed and emulsified in a homomixer. The emulsion temperature was 31 ℃. Then, an aqueous solution prepared by diluting 11 parts of ethylenediamine with 65 parts of water was added to increase the molecular weight. The obtained emulsion had a nonvolatile content of 45.8%, a particle diameter of 0.07 μm and a viscosity of 110 mPas/20 ℃.
(example 6)
200 parts of polyester polyol (having a number average molecular weight of 5000) containing 3-methyl-1, 5-pentanediol and adipic acid, 13.4 parts of dimethylolpropionic acid, and 68 parts of isophorone diisocyanate were added and reacted at 90 ℃ for 60 minutes to obtain a urethane prepolymer having an isocyanate group content of 5.0% and a carboxylic acid value of 19.9 mgKOH/g. After the obtained urethane prepolymer was cooled to 60 ℃, 10.1 parts of triethylamine was mixed, 280 parts of emulsified water (20 ℃) was added thereto, and the mixture was mixed and emulsified by a homomixer. The emulsion temperature was 32 ℃. Then, an aqueous solution prepared by diluting 9 parts of ethylenediamine with 100 parts of water was added to increase the molecular weight. The obtained emulsion had a nonvolatile content of 42.7%, a particle diameter of 0.12 μm and a viscosity of 55 mPas/20 ℃.
(example 7)
200 parts of trifunctional polypropylene glycol (number average molecular weight: 5000), 13.4 parts of dimethylolpropionic acid, and 78.2 parts of isophorone diisocyanate were added and reacted at 90 ℃ for 60 minutes to obtain a urethane prepolymer having an isocyanate group content of 5.6% and a carboxylic acid value of 19.2 mgKOH/g. After the obtained urethane prepolymer was cooled to 60 ℃, 10.1 parts of triethylamine was mixed, 300 parts of emulsifying water (20 ℃) was added, and the mixture was mixed and emulsified in a homomixer. The emulsion temperature was 31 ℃. Then, an aqueous solution prepared by diluting 10 parts of ethylenediamine with 80 parts of water was added to increase the molecular weight. The obtained emulsion had a nonvolatile content of 43.6%, a particle diameter of 0.06 μm, and a viscosity of 170 mPa. multidot.s/20 ℃.
(example 8)
200 parts of polytetramethylene glycol (number average molecular weight 3000), 13.4 parts of dimethylolpropionic acid, and 95 parts of 4, 4' -dicyclohexylmethane diisocyanate were added and reacted at 95 ℃ for 90 minutes to obtain a urethane prepolymer having an isocyanate group content of 5.3% and a carboxylic acid value of 18.2 mgKOH/g. After the obtained urethane prepolymer was cooled to 60 ℃, 10.1 parts of triethylamine was mixed, 370 parts of emulsified water (20 ℃) was added thereto, and the mixture was mixed and emulsified by a homomixer. The emulsion temperature was 30 ℃. Then, an aqueous solution prepared by diluting 10 parts of ethylenediamine with 60 parts of water was added to increase the molecular weight. The obtained emulsion had a nonvolatile content of 42.0%, a particle diameter of 0.07 μm, and a viscosity of 50 mPas/20 ℃.
(example 9)
240 parts of polyester polyol (number average molecular weight 3000) containing 3-methyl-1, 5-pentanediol and adipic acid, 13.4 parts of dimethylolpropionic acid, and 63 parts of hexamethylene diisocyanate were added and reacted at 85 ℃ for 45 minutes to obtain a urethane prepolymer having an isocyanate group content of 5.2% and a carboxylic acid value of 17.7 mgKOH/g. After the obtained urethane prepolymer was cooled to 60 ℃, 10.1 parts of triethylamine was mixed, and then 630 parts of emulsifying water (20 ℃) was added thereto, followed by mixing and emulsification using a homomixer. The emulsion temperature was 27 ℃. Then, an aqueous solution prepared by diluting 8 parts of 1, 3-propanediamine and 4 parts of diethylenetriamine in 130 parts of water was added to increase the molecular weight. The obtained emulsion had a nonvolatile content of 29.9%, a particle diameter of 0.16 μm, and a viscosity of 110 mPas/20 ℃.
(example 10)
250 parts of polyester polyol (number average molecular weight 1000) containing 3-methyl-1, 5-pentanediol and adipic acid, 13.4 parts of dimethylolpropionic acid, and 171 parts of isophorone diisocyanate were added and reacted at 90 ℃ for 60 minutes to obtain a urethane prepolymer having an isocyanate group content of 8.1% and a carboxylic acid value of 12.9 mgKOH/g. After the obtained urethane prepolymer was cooled to 60 ℃, 10.1 parts of triethylamine was mixed, 430 parts of emulsified water (20 ℃) was added thereto, and the mixture was mixed and emulsified by a homomixer. The emulsion temperature was 31 ℃. Then, an aqueous solution prepared by diluting 22 parts of ethylenediamine with 90 parts of water was added to increase the molecular weight. The obtained emulsion had a nonvolatile content of 46.3%, a particle diameter of 0.07 μm, and a viscosity of 20 mPas/20 ℃.
(example 11)
380 parts of polytetramethylene glycol (number average molecular weight: 1000), 13.4 parts of dimethylolpropionic acid and 215 parts of isophorone diisocyanate were added and reacted at 90 ℃ for 90 minutes to obtain a urethane prepolymer having an isocyanate group content of 6.7% and a carboxylic acid value of 9.2 mgKOH/g. After the obtained urethane prepolymer was cooled to 60 ℃, 10.1 parts of triethylamine was mixed, 610 parts of emulsifying water (20 ℃) was added, and the mixture was mixed and emulsified by a homomixer. The emulsion temperature was 30 ℃. Then, an aqueous solution prepared by diluting 26 parts of ethylenediamine with 250 parts of water was added to increase the molecular weight. The obtained emulsion had a nonvolatile content of 42.2%, a particle diameter of 0.40 μm, and a viscosity of 20 mPas/20 ℃.
(comparative Synthesis example 1)
60 parts of polyester polyol (number average molecular weight: 1000) containing 3-methyl-1, 5-pentanediol and adipic acid, 13.4 parts of dimethylolpropionic acid, 18 parts of 1, 4-butanediol, and 190 parts of 4, 4' -dicyclohexylmethane diisocyanate were added and reacted at 95 ℃ for 90 minutes to obtain a urethane prepolymer having an isocyanate group content of 11.0% and a carboxylic acid value of 19.9 mgKOH/g. After the obtained urethane prepolymer was cooled to 60 ℃, 10.1 parts of triethylamine was mixed, 300 parts of emulsifying water (20 ℃) was added, and the mixture was mixed and emulsified in a homomixer. The emulsion temperature was 31 ℃. Then, an aqueous solution prepared by diluting 18 parts of ethylenediamine with 60 parts of water was added to increase the molecular weight. The obtained emulsion had a nonvolatile content of 44.7%, a particle diameter of 3.2 μm, a viscosity of 50 mPas/20 ℃ and a large number of coarse particles.
(comparative Synthesis example 2)
240 parts of polyester polyol (number average molecular weight 12000) containing isophthalic acid, adipic acid and 1, 6-hexanediol, 13.4 parts of dimethylolpropionic acid and 53.5 parts of isophorone diisocyanate were added and reacted at 90 ℃ for 60 minutes to obtain a urethane prepolymer having an isocyanate group content of 3.3% and a carboxylic acid value of 18.3 mgKOH/g. After the obtained urethane prepolymer was cooled to 60 ℃, 10.1 parts of triethylamine was mixed, 300 parts of emulsifying water (20 ℃) was added, and the mixture was mixed and emulsified in a homomixer. The emulsion temperature was 32 ℃. Then, an aqueous solution prepared by diluting 6.1 parts of ethylenediamine with 30 parts of water was added to increase the molecular weight. The prepolymer had a low isocyanate group content and a high viscosity, and was therefore difficult to emulsify, and the obtained emulsion had a nonvolatile content of 47.9%, a particle diameter of 2.9 μm, a viscosity of 40 mPas/20 ℃ and very large number of coarse particles.
(comparative Synthesis example 3)
187.5 parts of difunctional polypropylene glycol (number average molecular weight 750), 13.4 parts of dimethylolpropionic acid and 90 parts of isophorone diisocyanate were added and reacted at 100 ℃ for 120 minutes to obtain a urethane prepolymer having an isocyanate group content of 1.7% and a carboxylic acid value of 19.3 mgKOH/g. After cooling the obtained urethane prepolymer to 80 ℃, 10.1 parts of triethylamine was mixed, and 580 parts of emulsified water (20 ℃) was added and mixed and emulsified by a homomixer, but the amount of coarse particles was very large. The emulsion temperature was 30 ℃. Then, an aqueous solution prepared by diluting 2.5 parts of ethylenediamine with 15 parts of water was added to increase the molecular weight. The obtained emulsion had a nonvolatile content of 32.7%, a particle diameter of 6.8 μm and a viscosity of 30 mPas/20 ℃.
Production example 1
For example 5, a confirmation study was conducted using an industrial production apparatus. After cooling a urethane prepolymer having an isocyanate group content of 5.6% and a carboxylic acid value of 18.3mgKOH/g to 60 ℃, a predetermined amount of triethylamine was mixed, and then mixed and emulsified with triethylamine in a ratio of 100/125 to the urethane prepolymer/emulsified water (20 ℃) by an inline, rotor, and stator mixer (inline homomixer manufactured by planimex corporation). The emulsion temperature was 32 ℃. Subsequently, an ethylenediamine diluted aqueous solution was added to increase the molecular weight. The obtained emulsion had a nonvolatile content of 45.8%, a particle diameter of 0.08 μm, and a viscosity of 100 mPas/20 ℃.
Production example 2
For example 5, a confirmation study was conducted using an industrial production apparatus. After cooling a urethane prepolymer having an isocyanate group content of 5.6% and a carboxylic acid value of 18.3mgKOH/g to 60 ℃, a predetermined amount of triethylamine was mixed, and then emulsified water was added to the mixture in a reaction vessel (1, stirring speed: 250rpm/min) at a ratio of 100/125 (20 ℃) which is the ratio of triethylamine to urethane prepolymer/emulsified water, followed by stirring and emulsification. The emulsion temperature was 31 ℃. Subsequently, an ethylenediamine diluted aqueous solution was added to increase the molecular weight. The obtained emulsion had a nonvolatile content of 45.8%, a particle diameter of 1.8 μm and a viscosity of 120 mPas/20 ℃ and, however, a large amount of coarse particles were produced and a large amount of resinate existed around the reaction vessel, which made it difficult to clean the emulsion.
(production example 3)
For example 5, a confirmation study was conducted using an industrial production apparatus. After cooling a urethane prepolymer having an isocyanate group content of 5.6% and a carboxylic acid value of 18.3mgKOH/g to 70 ℃, a predetermined amount of triethylamine was mixed, and then mixed and emulsified with triethylamine and urethane prepolymer/emulsified water (30 ℃) at 100/125 ratio by an inline, rotor, and stator mixer (in-line homomixer manufactured by planimex corporation). The emulsion temperature was 44 ℃. Subsequently, an ethylenediamine diluted aqueous solution was added to increase the molecular weight. The obtained emulsion had a nonvolatile content of 45.8%, a particle diameter of 1.3 μm, and a viscosity of 80 mPas/20 ℃.
[ Table 1]
Figure GDA0002277011520000151
Figure GDA0002277011520000161
Figure GDA0002277011520000171
In the examples in which the residual NCO group amount of the mixture of the urethane prepolymer (a) not containing a hydrophilic group, the isocyanate monomer (B), and the isocyanate adduct at both ends of the dialkanoalkanoic acid (C) (D) was 3.5 to 9.5 mass%, the particle diameter was fine, the dispersibility was excellent, and the film physical properties and properties were good. On the other hand, it is found that the comparative synthesis example 1 having a high residual NCO group content has a large particle diameter and also has poor dispersion stability. In comparative synthesis example 2, which has a low residual NCO group content, it is clear that the prepolymer has a high viscosity, a large particle diameter and poor dispersion stability. Further, in comparative synthesis example 3 having a low residual NCO group content, it is found that the viscosity is high, the particle diameter is large, and the dispersion stability is also poor due to the high molecular weight caused by the urethane bond.
Production examples 1 and 3, in which the residual NCO group content of the mixture of the urethane prepolymer (a) containing no hydrophilic group, the isocyanate monomer (B), and the isocyanate adduct at both ends of the dialkanoalkanoic acid (C) (D) was 3.5 to 9.5 mass%, were good in both the film properties and the properties. On the other hand, in production example 2 in which stirring was performed in the reaction vessel, it was found that the particle size was large, and the resin adhered to the periphery of the reaction vessel, which was a problem.

Claims (3)

1. An aqueous urethane urea resin composition which is obtained by emulsifying and dispersing a urethane prepolymer (A) containing no hydrophilic group and an isocyanate monomer (B), which are obtained by reacting a compound having a number average molecular weight of 500 to 5,000 and an active hydrogen atom with an isocyanate monomer (B) so that the isocyanate group becomes 1.8 to 2.5 molar equivalents relative to the active hydrogen atom, in water in the presence of an isocyanate adduct (D) at both ends of a dialkanol alkanoic acid (C) obtained by reacting an isocyanate monomer (B) so that the isocyanate group becomes 1.8 molar equivalents or more relative to the dialkanol alkanoic acid (C), and which is polymerized with a polyamine compound (E); and is
The remaining NCO group content of the mixture of the urethane prepolymer (A) containing no hydrophilic group, the isocyanate monomer (B) and the isocyanate adduct (D) at both ends of the dialkanol alkanoic acid (C) is 3.5 to 9.5% by mass, the acid value is 3 to 40mgKOH/g, and the viscosity is 50000mPa · s/70 ℃ or lower.
2. A method for producing an aqueous urethane urea resin composition, which does not use an organic solvent, comprising: an emulsifying step of emulsifying a urethane prepolymer (a) containing no hydrophilic group and an isocyanate monomer (B), which are obtained by reacting a compound having an active hydrogen atom and a number average molecular weight of 500 to 5,000 with an isocyanate monomer (B) so that the isocyanate group is 1.8 molar equivalents to 2.5 molar equivalents relative to the active hydrogen atom, in the presence of an isocyanate adduct (D) at both ends of a dialkanoalkanoic acid (C), which is obtained by reacting the isocyanate monomer (B) so that the isocyanate group is 1.8 molar equivalents to 1.8 molar equivalents relative to the dialkanoalkanoic acid (C); and a step of increasing the molecular weight of the polyamine compound (E); and a mixture of the urethane prepolymer (A) containing no hydrophilic group, the isocyanate monomer (B) and the isocyanate adduct (D) at both ends of the dialkanol alkanoic acid (C), wherein the residual NCO group content is 3.5 to 9.5% by mass, the acid value is 3 to 40mgKOH/g, and the viscosity is 50000mPa · s/70 ℃ or lower.
3. The method for producing an aqueous urethane urea resin composition according to claim 2, wherein the emulsifying step is a step of subjecting a mixture of a urethane prepolymer (a) not containing a hydrophilic group and an isocyanate monomer (B), which is obtained by reacting a dialkanoalkanoic acid (C) both-terminal isocyanate adduct (D) of a dialkanoalkanoic acid (C) obtained by reacting an isocyanate monomer (B) so that the isocyanate group becomes 1.8 molar equivalents or more relative to the dialkanoalkanoic acid (C), and an isocyanate monomer (B) so that the isocyanate group becomes 1.8 molar equivalents to 2.5 molar equivalents relative to the active hydrogen atom, to collision emulsification with emulsifying water in an inline, rotor, and stator mixer.
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