TWI558766B - Aqueous urethane urea resin composition and manufacturing method of the same, reactive emulsifier and emulsification method - Google Patents

Description

Water-based urethane urea resin composition, production method, and reactivity Emulsifier and emulsification method

The present invention relates to an aqueous urethane urea resin composition and a method for producing the same. Further, the present invention relates to a reactive emulsifier and an emulsification method.

Previously, aqueous polyurethane resins have been used as materials for adhesives, coating agents, coatings, modifiers, adhesives, and the like, and are used in a wide range of applications. As such a water-based polyurethane resin, it is known that a method of auto-emulsification dispersing a hydrophilic group such as an anionic, cationic or nonionic property in a urethane resin skeleton can be used to make a fine particle diameter. And excellent performance.

Water-based resins are popular in various fields in terms of safety, hygiene, environmental protection, and resource conservation. Usually, when a water-based polyurethane resin is produced, a hydrophilic group-containing urethane prepolymer is synthesized in an organic solvent, and an anionic or cationic resin is used for emulsification using a salt forming agent. The amine compound is produced by high molecular weight, but a solvent is required in this method. Solvent removal is accompanied by great energy and cumbersome operation, very uneconomical, and difficult to obtain from the aqueous polyamine The organic solvent used is completely removed in the urethane resin.

Therefore, various studies for producing aqueous polyurethanes without using an organic solvent are being carried out. A method of producing an aqueous polyurethane by contacting an isocyanate-based terminal prepolymer with water by using a continuous kneader having an operating power of 2000 kW/m ³ or more (see Patent Document 1) a method of producing an aqueous polyurethane by stirring a polyurethane prepolymer with water using a vibrating stirring device (refer to Patent Document 2); emulsifying an isocyanate-based terminal prepolymer in water; After that, a method of polymerizing an aminocarboxylic acid compound (see Patent Document 3); a method of assisting the use of an emulsifier to emulsify an isocyanate-based terminal prepolymer in water (see Patent Document 4); and isocyanate A method in which a base terminal prepolymer is diluted with an unsaturated monomer and then emulsified in water (see Patent Document 5).

[Prior Art Literature] [Patent Literature]

[Patent Document 1] Japanese Patent Laid-Open Publication No. 2004-292797

[Patent Document 2] Japanese Patent Laid-Open Publication No. 2009-79157

[Patent Document 3] Japanese Patent Laid-Open Publication 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

The present inventors have made it possible to use organic solvents without considering the above circumstances. In the case of the method of the synthesis, in the method disclosed in Patent Document 1, the resin for introducing the highly viscous urethane resin liquid into the peripheral device (reaction device, piping, etc.) in the continuous kneading machine The adhesion is large; and since the high-temperature highly viscous urethane resin liquid is kneaded with water in the kneading machine, the temperature of the kneading liquid is high, and the isocyanate group in the urethane reacts with water. Further, in the method disclosed in Patent Document 2, the resin attached to the peripheral device (reaction device, piping, etc.) for introducing the highly viscous urethane resin liquid into the vibrating stirring device is highly contaminated. In the method disclosed in Patent Document 3, in order to make the particle diameter fine, a large amount of the aminocarboxylic acid compound is used, thereby causing a decrease in water resistance. In the method disclosed in Patent Document 4, agglomerates are generated in a step of reacting a large amount of an isocyanate group with a polyamine-based compound by mixing a large amount of an isocyanate monomer. Further, in the method disclosed in Patent Document 5, since the highly viscous urethane resin liquid is made low in viscosity and is diluted by a large amount of unsaturated monomers, the emulsion particle size becomes thicker. In addition, problems such as the characteristics of the urethane resin are lost.

Therefore, the inventors of the present invention conducted active research and found that The dialkyl alcohol alkanoic acid (C) is not contained in the urethane skeleton, but the two-terminal isocyanate adduct (D) of the dialkanol alkanoic acid (C) is used, even if the dialkanol alkanoic acid is used. The amount of use of (C) is increased, and the degree of increase in viscosity is also small, and the aqueous urethane urea resin can be produced without using an organic solvent, thereby completing the present invention. That is, after setting the specific NCO base amount, the two-terminal isocyanate adduct (D) of the dialkanol alkanoic acid (C) will contain a hydrophilic group-containing urethane prepolymer (A), an isocyanate single The body (B) is stably emulsified and further stably polymerized using a polyamine compound.

It is an object of the present invention to provide an aqueous urethane urea resin group A product and a method for producing the same, which can produce an aqueous urethane urea resin composition having a fine particle diameter, excellent storage stability, and having properties superior to those of the prior art, without using an organic solvent, and Since it does not use an organic solvent, it is excellent in productivity.

The present invention relates to an aqueous urethane urea resin composition which is such that a hydrophilic group-free urethane prepolymer (A) and an isocyanate monomer (B) are used in a dialkyl alcohol alkanoic acid. (C) emulsified and dispersed in water in the presence of the isocyanate adduct (D) at both ends, polymerized by polyamine compound (E); and urethane prepolymer containing no hydrophilic group ( A) The residual NCO group amount of the mixture of the isocyanate monomer (B) and the di-terminal isocyanate adduct (D) of the dialkanol alkanoic acid (C) is from 3.5% by mass to 9.5% by mass.

The present invention relates to a process for producing a water-based urethane urea resin composition which does not substantially use an organic solvent; and a process for producing the aqueous urethane urea resin composition comprising: a dialkanol alkanoic acid a step of emulsifying a hydrophilic group-free urethane prepolymer (A) and an isocyanate monomer (B) in the presence of a terminal polyisocyanate adduct (D) of (C); using a polyamine compound (E) a step of performing a high molecular weight; and a terminal urethane prepolymer (A) having no hydrophilic group, an isocyanate monomer (B), and a terminal isocyanate adduct of a dialkanol alkanoic acid (C) The residual NCO group amount of the mixture of (D) is from 3.5% by mass to 9.5% by mass.

In the method for producing an aqueous urethane urea resin composition of the present invention The emulsification step is preferably a di-terminal isocyanate adduct (D) of a dialkanol alkanoic acid (C), a urethane prepolymer (A) having no hydrophilic group, and an isocyanate monomer (B). The mixture is emulsified with emulsified water in an on-line rotor stator mixer.

This invention relates to a reactive emulsifier comprising a two terminal isocyanate adduct of a dialkanol alkanoic acid.

The present invention also relates to a method for emulsification of a hydrophilic group-free urethane prepolymer (A) and an isocyanate monomer (B) using a two-terminal isocyanate adduct of a dialkanol alkanoic acid (C) (D).

Even if an organic solvent is not used, since the particle diameter is fine and the storage stability is excellent, and the acid value can be arbitrarily adjusted, an aqueous urethane urea resin composition having a performance which is inferior to the prior art can be produced. Since no organic solvent is used, productivity is also excellent. Further, a polyester having an active hydrogen atom and a polycarbonate polyol which have been previously difficult to be emulsified may be emulsified. Such a water-based urethane urea resin composition and a method for producing the same have not been provided so far. The present invention provides a water-based urethane urea resin composition having the above characteristics and a method for producing the same, which are extremely useful industrially.

The aqueous urethane urea resin composition of the present invention is a urethane prepolymer (A) and an isocyanate monomer (B) which are free from a hydrophilic group, and a dialkyl alcohol alkanoic acid. The both terminal isocyanate adduct (D) of (C) is emulsified and dispersed in water, and is polymerized by the polyamine compound (E).

In the present invention, the urethane prepolymer (A) which does not contain a hydrophilic group, A urethane prepolymer which does not contain an anionic, cationic or nonionic hydrophilic group in the urethane resin skeleton, and has a hydroxyl group having two or more hydroxyl groups at a molecular terminal or a molecule. The compound of the active hydrogen atom and the isocyanate monomer (B) are reacted so that the isocyanate group is 1.1 mole equivalent or more with respect to the active hydrogen atom. In order to set the urethane prepolymer (A) to a low viscosity, in order to obtain a stable emulsion, it is preferably set to 1.8 mol equivalent to 2.5 mol equivalent.

The compound having an active hydrogen atom in the present invention is not particularly limited, and examples thereof are exemplified. For example, well-known polyethers, polyesters, polyether esters, polycarbonates, polyolefins, polyacrylic acids, polyacetals, polybutadienes, polyoxyalkylenes are equal to the molecular terminal or have two or more hydroxyl groups in the molecule. compound of. Specific examples thereof include ethylene glycol, diethylene glycol, butanediol, propylene glycol, hexanediol, bisphenol A, bisphenol B, bisphenol S, hydrogenated bisphenol A, and dibromobisphenol A, 1. a polyhydric alcohol such as 4-cyclohexanedimethanol, dihydroxyethyl terephthalate, hydroquinone dihydroxyethyl ether, trimethylolpropane, glycerol or pentaerythritol; derived from the alkyl group of the polyol Or an esterified product of the polyol and the alkylene derivative with a polycarboxylic acid, a polycarboxylic acid anhydride, or a polycarboxylic acid ester; a polycarbonate polyol, a polytetramethylene glycol, a polycaprolactone Polyol compounds such as alcohol, polybutadiene polyol, polythioether polyol, polyacetal polyol, fluoropolyol, hydrazine polyol, castor oil polyol, acrylic polyol, polyolefin polyol, or the like thereof Body and so on. These compounds may be used alone or in combination of two or more.

Number average molecular weight of a compound having an active hydrogen atom in the present invention It is preferably in the range of 50 to 10,000, more preferably in the range of 500 to 5,000. If it is these ranges, the particle diameter of an emulsion becomes appropriate. Further, in the case of production without using an organic solvent, in the case of using a polyhydroxy compound having a number average molecular weight of more than 5,000 from the viewpoint of setting the urethane prepolymer to have a low viscosity Preferably, it is 20% by weight or less in the prepolymer; and in the case of using a polyhydroxy compound having a number average molecular weight of less than 500, it is preferred to set the average OHV of all the polyols to be added to 250 KOH mg/g. In the case of using three or more active hydrogen atom compounds, it is preferably in the range of 1 mmol equivalent/g (prepolymer) or less as three or more active hydrogen atom compounds.

The isocyanate monomer (B) in the present invention is not particularly limited, and for example, Organic polyisocyanates such as aliphatic, alicyclic, and aromatic aliphatics which have been conventionally used are listed. Specific examples thereof include 4,4'-dicyclohexylmethane diisocyanate, isophorone diisocyanate, hydrogenated xylylene diisocyanate [bis(isocyanatemethyl)cyclohexane], hexamethylene diisocyanate An organic polyisocyanate such as a diisocyanate, a norbornane diisocyanate or a xylylene diisocyanate, or a mixture of these compounds. Further, the isocyanate monomer (B) also includes a polypolymer (dimer, terpolymer, etc.) of the organic polyisocyanate or a biuret produced by the reaction of the organic polyisocyanate with water. Modify the body and so on. These compounds may be used alone or in combination of two or more. In addition, aromatic organic polyisocyanates such as diphenylmethane diisocyanate, toluene diisocyanate, and naphthyl diisocyanate are emulsified The reaction of water is fast, and in addition, coagulation occurs in the reaction with the polyamine compound, which is not preferable.

The dialkanol alkanoic acid compound (C) in the present invention is not particularly limited, and examples thereof are exemplified. For example, 2,2-dimethylolpropionic acid, 2,2-dimethylolbutanoic acid, 2,2-dimethylolpentanoic acid (2,2-dimethylolpentanoic) Acid), 2,2-dimethylolbutyric acid, 2,2-dimethylolvaleric acid, and the like. These compounds may be used alone or in combination of two or more. Among these compounds, 2,2-dimethylolpropionic acid and 2,2-dimethylolbutanoic acid are preferred from the viewpoint of emulsifying dispersibility.

Regarding the dialkylol alkanoic acid compound (C) in the present invention, emulsifying dispersibility From the viewpoint, the carboxyl group in the dialkanol alkanoic acid (C) is preferably a salt forming agent to form a salt. 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, or ammonia, trimethylamine, triethylamine, and dimethylamino groups. A tertiary amine compound such as ethanol, methyldiethanolamine, triethanolamine, triisopropanolamine or morpholine. These compounds may be used alone or in combination of two or more.

Two-terminal isocyanate adduct of dialkyl alkanolic acid (C) in the present invention (D) is not particularly limited. For example, the isocyanate monomer (B) is reacted so that the isocyanate group is 1.1 mole equivalent or more with respect to the dialkanol alkanoic acid (C). In order to obtain a stable emulsion, it is preferably 1.8 mol equivalent or more. The reaction of the isocyanate monomer (B) with the dialkanol alkanoic acid (C) may be carried out simultaneously with the reaction of the active hydrogen atom and the isocyanate monomer (B), or may be carried out separately.

The polyamine compound (E) in the present invention is not particularly limited, and for example, it can be listed. 肼: hydrazine, bismuth adipic acid, etc., ethylenediamine, propylenediamine, hexamethylenediamine, isophoronediamine, xylylenediamine, piperazine, diphenylmethanediamine, ethyl Toluene diamine, di-ethyltriamine, di-propyltriamine, tri-ethyltetramine, tetra-ethylpentamine, and the like. These compounds may be used alone or in combination of two or more.

The aqueous urethane urea resin composition of the present invention does not contain a hydrophilic group The residual NCO group amount of the mixture of the urethane prepolymer (A), the isocyanate monomer (B) and the di-terminal isocyanate adduct (D) of the dialkanol alkanoic acid (C) is 3.5% by mass to 9.5 mass%, preferably 4.0 mass% to 8.5% by mass. When the amount is less than 3.5% by mass, the molecular weight of the urethane prepolymer becomes large, so that the viscosity becomes high, so that emulsification becomes difficult. In addition, in the range of more than 9.5, the molecular weight of the urethane prepolymer becomes too small, the amount of the urethane bond increases, and the viscosity becomes high, so that emulsification becomes difficult.

Composition of aqueous urethane urea resin according to one embodiment of the present invention The method for producing a material is a method for producing an aqueous urethane urea resin composition which does not substantially use an organic solvent, and comprises: an isocyanate adduct (D) at both terminals of a dialkanol alkanoic acid (C) a step of emulsifying a hydrophilic group-free urethane prepolymer (A) and an isocyanate monomer (B); and a step of performing macromolecularization using the polyamine compound (E); The residual NCO group of the mixture of the hydrophilic urethane prepolymer (A), the isocyanate monomer (B) and the di-terminal isocyanate adduct (D) of the dialkanol alkanoic acid (C) is 3.5 mass. % to 9.5 mass%.

As a manufacturer of the aqueous urethane urea resin composition of the present invention The method is preferably a mixture of a terminal isocyanate adduct (D) of a dialkanol alkanoic acid (C), a urethane prepolymer (A) having no hydrophilic group, and an isocyanate monomer (B). After emulsification with emulsified water in an on-line rotor stator mixer, the polyamine compound is used for high molecular weight.

In the present invention, the in-line rotor stator mixer includes: a fixed stator; And a rotor that rotates at a high speed with a small gap inside. It is preferred because the high-shearing efficiency due to the rotational speed can achieve the micronization of the emulsion. The on-line rotor type stator mixer is not particularly limited, and examples thereof include a pipeline homomixer (manufactured by Primix) and a homomic line mill (spectrum line). Primix), Milder (manufactured by Pacific Aerospace Co., Ltd.), Cavitron (manufactured by Pacific Aerospace Co., Ltd.), and line mixer (manufactured by Mizuho Industrial Co., Ltd.) , inline mixer (infrared (Silverson) company).

In the present invention, the amount of emulsified water is a stable oil-based emulsion in water (oil in The water type emulsion, the O/W type emulsion, is required to carry out the emulsification, that is, 70 parts by weight or more based on 100 parts by weight of the prepolymer. In addition, the method of adding the emulsified water is preferably not slowly added to the prepolymer, but is immediately on the line. Rotor. Collision emulsification with the prepolymer in the stator mixer is because the temperature of the emulsion can be lowered at once, and the reaction between the urethane prepolymer and the isocyanate group of the isocyanate monomer and water can be suppressed.

One of the embodiments of the present invention is the use of two ends of a dialkanol alkanoic acid (C). An emulsion method of the hydrophilic group-free urethane prepolymer (A) and the isocyanate monomer (B) of the isocyanate adduct (D). In the emulsification method, the hydrophilic group-containing urethane prepolymer (A), the isocyanate monomer (B), and the di-terminal isocyanate adduct (D) of the dialkanol alkanoic acid (C) The temperature of the mixture is preferably from 25 ° C to 70 ° C, and the temperature of the emulsified water is preferably in the range of from 10 ° C to 35 ° C. If the temperature of the emulsified water is less than 10 ° C, the hydrophilic group-containing urethane prepolymer (A), the isocyanate monomer (B), and the di-terminated isocyanate adduct of the dialkanol alkanoic acid (C) When the mixture of (D) is in contact with the emulsified water, the viscosity rises sharply, so that coarse particles are generated, which is not preferable. The temperature of the emulsion is preferably set to 40 ° C or lower. When the temperature of the emulsion exceeds 40 ° C, the particle size of the emulsion becomes coarse. Further, the reaction speed of the urethane prepolymer and the isocyanate group of the isocyanate monomer with water is fast, and the subsequent reaction control with the polyamine compound becomes difficult, which is not preferable.

Hydrophilic group-free urethane prepolymer (A), isocyanide in the present invention The acid value of the mixture of the acid ester monomer (B) and the terminal isocyanate addition product (D) of the dialkanol alkanoic acid (C) is preferably from 3 mgKOH/g to 40 mgKOH/g, more preferably from 10 mgKOH/g to 30 mgKOH. /g. When the acid value is less than 10 mgKOH/g, the particle diameter of the emulsion becomes coarse, and it is necessary to use a surfactant in combination. When the acid value is less than 3 mgKOH/g, the particle size of the emulsion becomes coarse even if the surfactant is used in combination, which is not preferable. Further, when it exceeds 40 mgKOH/g, the hydrophilic group-containing urethane prepolymer (A), the isocyanate monomer (B), and the di-terminated isocyanate (C) are both terminal isocyanate adducts (D). The viscosity of the mixture becomes high, the emulsification becomes difficult, and the resulting aqueous urethane is obtained. The water resistance of the urea resin is deteriorated, so it is not preferable.

Hydrophilic group-free urethane prepolymer (A), isocyanide in the present invention The viscosity of the mixture of the acid ester monomer (B) and the terminal isocyanate adduct (D) of the dialkanol alkanoic acid (C) is preferably 50,000 (mPa.s / 70 ° C) or less, more preferably 30,000 (mPa). Below .s/70 ° C), it is particularly preferably 20,000 (mPa.s / 70 ° C) or less. If it is more than 50,000 (mPa.s / 70 ° C), the hydrophilic group-containing urethane prepolymer (A), the isocyanate monomer (B), and the di-terminated isocyanate of the dialkanol alkanoic acid (C) When the mixture of the adduct (D) is in contact with the emulsified water, the viscosity rises sharply, so that coarse particles are generated, which is not preferable.

One of the embodiments of the present invention is a di-terminal heterodimer comprising a dialkanol alkanoic acid. A reactive emulsifier for cyanate ester adducts. The reactive emulsifier of the present invention can stably emulsifie and disperse the hydrophilic group-free urethane prepolymer (A) and the isocyanate monomer (B), so that it is not necessary to introduce the dialkanol alkanoic acid into the amine. In the urethane skeleton, the urethane prepolymer can be made low-viscosity. Even if an organic solvent is not used, a polyol material which is easy to be highly viscous such as a polyester polyol, a polycarbonate polyol or a branched polyol can be used. Therefore, it can be used as an adhesive or a coating agent. Other uses can also be used as coatings and adhesives.

[Examples]

Hereinafter, the invention will be specifically described by way of examples, and the invention is not limited to the examples. In addition, % means mass% unless otherwise specified.

(evaluation method)

Urethane prepolymer temperature: The temperature before emulsification is determined.

Emulsified water temperature: Determine the temperature before emulsification.

Emulsion temperature: The temperature immediately after emulsification was measured.

Weight of non-volatile components: Measured in accordance with JIS K 6828.

Viscosity: Measured at 20 ° C using a B8H type viscometer (manufactured by Tokyo Keiki Co., Ltd.) Rotor No. 2 in accordance with JIS Z8803.

Particle size: Measurement was carried out by using Microtrac UPA-UZ152 (manufactured by Nikkiso Co., Ltd.), and a 50% average value was calculated as the particle diameter.

(Method of making test piece)

The obtained polyurethane dispersion aqueous dispersion was placed in a Teflon (registered trademark) coated petri dish so that the film thickness was 200 μm, and dried at 80 ° C for 6 hours to prepare an evaluation sample. .

(Tensile Strength)

An evaluation sample was prepared by cutting the film into the size of a dumbbell-shaped test piece (No. 3). The test conditions were measured in accordance with JIS-K-6301 at a tensile speed of 100 mm/min.

(Elongation)

An evaluation sample was prepared by cutting the film into the size of a dumbbell-shaped test piece (No. 3). The test conditions were measured in accordance with JIS-K-6301 at a tensile speed of 100 mm/min.

(water resistance)

An evaluation sample was prepared by cutting the test film into a predetermined size (2 cm × 4 cm). Tap water was used as the test solution. The test piece was placed in a test solution at 20 ° C After immersing for 24 hours, the weight increase rate with respect to the initial weight was calculated by the following formula.

Weight gain rate = (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 the reaction was carried out at a temperature of 90 ° C for 60 minutes to obtain an isocyanate group content. A urethane prepolymer having a carboxyl acid value of 13.5 mg KOH/g was 8.1%. After cooling the obtained urethane prepolymer to 60 ° C, 10.1 parts of triethylamine was mixed, and then 670 parts of emulsified water (20 ° C) was added, and the mixture was made by a homomixer (Primix). The homomixer MARK2 was mixed and emulsified in the following Examples 2 to 11 and Comparative Synthesis Example 1 to Comparative Synthesis Example 3. The emulsion temperature was 30 °C. Then, an aqueous solution obtained by diluting 22 parts of ethylenediamine in 198 parts of water was added for high molecular weight. The obtained emulsion has a nonvolatile content of 33.8%, a particle diameter of 0.06 μm, and a viscosity of 75 mPa. s / 20 ° C.

(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 the reaction was carried out at a temperature of 90 ° C for 60 minutes to obtain an isocyanate group. A urethane prepolymer having a content of 7.8% and a carboxylic acid value of 18.7 mg KOH/g. After cooling the obtained urethane prepolymer to 60 ° C, 10.1 parts of triethylamine was mixed, and then emulsified water (20 ° C) was added 390. The mixture was emulsified by a homomixer. The emulsion temperature was 31 °C. Then, an aqueous solution obtained by diluting 15 parts of ethylenediamine in 60 parts of water was added to carry out high molecular weight. The obtained emulsion has a nonvolatile content of 40.6%, a particle diameter of 0.06 μm, and a viscosity of 60 mPa. s / 20 ° C.

(Example 3)

An isocyanate group content of 7.9%, a carboxyl group was obtained in the same manner as in Example 2, except that a polyester polyol containing 3-methyl-1,5-pentanediol and adipic acid (number average molecular weight: 1,000) was used. A urethane prepolymer having an acid value of 18.7 mg KOH/g. After the obtained urethane prepolymer was cooled to 60 ° C, 10.1 parts of triethylamine was mixed, and then 390 parts of emulsified water (20 ° C) was added, and the mixture was emulsified by a homomixer. The emulsion temperature was 30 °C. Then, an aqueous solution obtained by diluting 15 parts of ethylenediamine in 60 parts of water was added to carry out high molecular weight. The obtained emulsion has a nonvolatile content of 40.6%, a particle diameter of 0.09 μm, and a viscosity of 50 mPa. s / 20 ° C.

(Example 4)

An isocyanate group content of 7.9% and a carboxyl acid value of 18.7 were obtained in the same manner as in Example 2 except that a polycarbonate polyol containing 1,5-pentanediol and adipic acid (number average molecular weight: 1,000) was used. A methacrylate prepolymer of mgKOH/g. After the obtained urethane prepolymer was cooled to 70 ° C, 10.1 parts of triethylamine was mixed, and then 390 parts of emulsified water (20 ° C) was added, and the mixture was emulsified by a homomixer. The emulsion temperature was 33 °C. Then, an aqueous solution obtained by diluting 15 parts of ethylenediamine in 60 parts of water was added to carry out high molecular weight. The obtained emulsion has a nonvolatile content of 40.6%, a particle diameter of 0.08 μm, and a viscosity of 40 mPa. s / 20 ° C.

(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 the reaction was carried out at a temperature of 90 ° C for 60 minutes to obtain an isocyanate group. A urethane prepolymer having a content of 5.6% and a carboxylic acid value of 18.3 mg KOH/g. After cooling the obtained urethane prepolymer to 60 ° C, 10.1 parts of triethylamine was mixed, and then 300 parts of emulsified water (20 ° C) was added, and the mixture was emulsified by a homomixer. The emulsion temperature was 31 °C. Then, an aqueous solution obtained by diluting 11 parts of ethylenediamine in 65 parts of water was added for high molecular weight. The obtained emulsion has a nonvolatile content of 45.8%, a particle diameter of 0.07 μm, and a viscosity of 110 mPa. s / 20 ° C.

(Example 6)

200 parts of a polyester polyol (number average molecular weight: 5000) containing 3-methyl-1,5-pentanediol and adipic acid, 13.4 parts of dimethylolpropionic acid, and 68 parts of isophorone diisocyanate were added. The reaction was carried out at a temperature of 90 ° C for 60 minutes to obtain a urethane prepolymer having an isocyanate group content of 5.0% and a carboxyl acid value of 19.9 mgKOH/g. After the obtained urethane prepolymer was cooled to 60 ° C, 10.1 parts of triethylamine was mixed, and then 280 parts of emulsified water (20 ° C) was added, and the mixture was emulsified by a homomixer. The emulsion temperature was 32 °C. Then, an aqueous solution obtained by diluting 9 parts of ethylenediamine in 100 parts of water was added for high molecular weight. The obtained emulsion has a nonvolatile content of 42.7%, a particle diameter of 0.12 μm, and a viscosity of 55 mPa. s / 20 ° C.

(Example 7)

Adding trifunctional polypropylene glycol (number average molecular weight of 5000) 200 parts, two 13.4 parts of hydroxymethylpropionic acid and 78.2 parts of isophorone diisocyanate were reacted at a temperature of 90 ° C for 60 minutes to obtain a urethane having an isocyanate group content of 5.6% and a carboxyl acid value of 19.2 mgKOH/g. Prepolymer. After cooling the obtained urethane prepolymer to 60 ° C, 10.1 parts of triethylamine was mixed, and then 300 parts of emulsified water (20 ° C) was added, and the mixture was emulsified by a homomixer. The emulsion temperature was 31 °C. Then, an aqueous solution obtained by diluting 10 parts of ethylenediamine in 80 parts of water was added for high molecular weight. The obtained emulsion has a nonvolatile content of 43.6%, a particle diameter of 0.06 μm, and a viscosity of 170 mPa. s / 20 ° C.

(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 the temperature was 90 minutes at 95 ° C for 90 minutes. The reaction obtained a urethane prepolymer having an isocyanate group content of 5.3% and a carboxylic acid value of 18.2 mgKOH/g. After cooling the obtained urethane prepolymer to 60 ° C, 10.1 parts of triethylamine was mixed, and then 370 parts of emulsified water (20 ° C) was added, and the mixture was emulsified by a homomixer. The emulsion temperature was 30 °C. Then, an aqueous solution obtained by diluting 10 parts of ethylenediamine in 60 parts of water was added to carry out high molecular weight. The obtained emulsion has a nonvolatile content of 42.0%, a particle diameter of 0.07 μm, and a viscosity of 50 mPa. s / 20 ° C.

(Example 9)

Adding 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 , the reaction was carried out at a temperature of 85 ° C for 45 minutes to obtain an isocyanate group. A urethane prepolymer having a content of 5.2% and a carboxyl acid value of 17.7 mgKOH/g. After the obtained urethane prepolymer was cooled to 60 ° C, 10.1 parts of triethylamine was mixed, and then 630 parts of emulsified water (20 ° C) was added, and the mixture was emulsified by a homomixer. The emulsion temperature was 27 °C. Then, an aqueous solution obtained by diluting 8 parts of 1,3-propanediamine and 4 parts of di-ethyltriamine in 130 parts of water was added for high molecular weight. The obtained emulsion has a nonvolatile content of 29.9%, a particle diameter of 0.16 μm, and a viscosity of 110 mPa. s / 20 ° C.

(Embodiment 10)

Adding 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 The reaction was carried out at a temperature of 90 ° C for 60 minutes to obtain a urethane prepolymer having an isocyanate group content of 8.1% and a carboxyl acid value of 12.9 mgKOH/g. After cooling the obtained urethane prepolymer to 60 ° C, 10.1 parts of triethylamine was mixed, and then 430 parts of emulsified water (20 ° C) was added, and the mixture was emulsified by a homomixer. The emulsion temperature was 31 °C. Then, an aqueous solution obtained by diluting 22 parts of ethylenediamine in 90 parts of water was added for high molecular weight. The obtained emulsion has a nonvolatile content of 46.3%, a particle diameter of 0.07 μm, and a viscosity of 20 mPa. s / 20 ° C.

(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 the reaction was carried out at 90 ° C for 90 minutes to obtain an isocyanate group. A urethane prepolymer having a content of 6.7% and a carboxylic acid value of 9.2 mgKOH/g. Cooling the resulting urethane prepolymer After the temperature was 60 ° C, 10.1 parts of triethylamine was mixed, and then 610 parts of emulsified water (20 ° C) was added, and the mixture was emulsified by a homomixer. The emulsion temperature was 30 °C. Then, an aqueous solution obtained by diluting 26 parts of ethylenediamine in 250 parts of water was added to carry out high molecular weight. The obtained emulsion has a nonvolatile content of 42.2%, a particle diameter of 0.40 μm, and a viscosity of 20 mPa. s / 20 ° C.

(Comparative Synthesis Example 1)

Adding polyester polyol (number average molecular weight of 1000) containing 3-methyl-1,5-pentanediol and adipic acid to 60 parts, dimethylolpropionic acid 13.4 parts, and 1,4-butanediol 18 190 parts of 4,4'-dicyclohexylmethane diisocyanate, and reacted at 95 ° C for 90 minutes to obtain a urethane pre-ester having an isocyanate group content of 11.0% and a carboxyl acid value of 19.9 mg KOH/g. Polymer. After cooling the obtained urethane prepolymer to 60 ° C, 10.1 parts of triethylamine was mixed, and then 300 parts of emulsified water (20 ° C) was added, and the mixture was emulsified by a homomixer. The emulsion temperature was 31 °C. Then, an aqueous solution obtained by diluting 18 parts of ethylenediamine in 60 parts of water was added for high molecular weight. The obtained emulsion has a nonvolatile content of 44.7%, a particle size of 3.2 microns, and a viscosity of 50 mPa. s / 20 ° C, a lot of coarse particles.

(Comparative Synthesis Example 2)

Adding 240 parts of polyester polyol (number average molecular weight: 12,000) containing isophthalic acid and adipic acid and 1,6-hexanediol, 13.4 parts of dimethylolpropionic acid, and 53.5 parts of isophorone diisocyanate The reaction was carried out at a temperature of 90 ° C for 60 minutes to obtain a urethane prepolymer having an isocyanate group content of 3.3% and a carboxyl acid value of 18.3 mgKOH/g. After cooling the obtained urethane prepolymer to 60 ° C, triethylamine 10.1 was mixed. Then, 300 parts of emulsified water (20 ° C) was added, and the mixture was emulsified by a homomixer. The emulsion temperature was 32 °C. Then, an aqueous solution obtained by diluting 6.1 parts of ethylenediamine in 30 parts of water was added for high molecular weight. The prepolymer is difficult to emulsify due to its low content of isocyanate groups and high viscosity. The obtained emulsion has a nonvolatile content of 47.9%, a particle size of 2.9 microns and a viscosity of 40 mPa. s / 20 ° C, a lot 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 the reaction was carried out at a temperature of 100 ° C for 120 minutes to obtain an isocyanate group content. 1.7% of a urethane prepolymer having a carboxylic acid value of 19.3 mgKOH/g. After the obtained urethane prepolymer was cooled to 80 ° C, 10.1 parts of triethylamine was mixed, and then 580 parts of emulsified water (20 ° C) was added, and the mixture was emulsified by a homomixer, but the amount of coarse particles was very large. The emulsion temperature was 30 °C. Then, an aqueous solution obtained by diluting 2.5 parts of ethylenediamine in 15 parts of water was added for high molecular weight. The obtained emulsion has a nonvolatile content of 32.7%, a particle diameter of 6.8 μm, and a viscosity of 30 mPa. s / 20 ° C.

(Manufacturing Example 1)

For Example 5, a confirmation study was carried out using an industrial manufacturing apparatus.

After cooling the urethane prepolymer having an isocyanate group content of 5.6% and a carboxyl acid value of 18.3 mgKOH/g to 60 ° C, a predetermined amount of triethylamine was mixed, and then an on-line rotor type mixer was used. A pipe homogenizer manufactured by Primix Co., Ltd. was mixed and emulsified at a ratio of triethylamine mixed urethane prepolymer/emulsified water (20 ° C) = 100/125. The emulsion temperature was 32 °C. Then, Tim The aqueous solution was diluted with ethylenediamine to carry out high molecular weight. The obtained emulsion has a nonvolatile content of 45.8%, a particle diameter of 0.08 μm, and a viscosity of 100 mPa. s / 20 ° C.

(Manufacturing Example 2)

For Example 5, an industrial manufacturing facility was used to carry out the confirmation study.

After cooling the urethane prepolymer having an isocyanate group content of 5.6% and a carboxyl acid value of 18.3 mgKOH/g to 60 ° C, a predetermined amount of triethylamine was mixed and then in the reaction vessel (1, stirring speed: 250 rpm/min), emulsified water was added at a ratio of triethylamine mixed urethane prepolymer/emulsified water (20 ° C)=100/125 to carry out stirring emulsification. The emulsion temperature was 31 °C. Then, an aqueous solution of ethylenediamine was added to dilute the aqueous solution to carry out high molecular weight. The obtained emulsion has a nonvolatile content of 45.8%, a particle diameter of 1.8 μm, and a viscosity of 120 mPa. s / 20 ° C, but a large amount of coarse particles are produced, and a large amount of resin is present around the reactor, which is difficult to clean.

(Manufacturing Example 3)

For Example 5, an industrial manufacturing facility was used to carry out the confirmation study. After cooling the urethane prepolymer having an isocyanate group content of 5.6% and a carboxyl acid value of 18.3 mgKOH/g to 70 ° C, a predetermined amount of triethylamine was mixed, and then an on-line rotor type mixer was used. A pipeline homomixer manufactured by Primix Co., Ltd. was mixed and emulsified at a ratio of triethylamine mixed urethane prepolymer/emulsified water (30 ° C) = 100/125. The emulsion temperature was 44 °C. Then, an aqueous solution of ethylenediamine was added to dilute the aqueous solution to carry out high molecular weight. The obtained emulsion has a nonvolatile content of 45.8%, a particle diameter of 1.3 μm, and a viscosity of 80 mPa. s / 20 ° C.

About urethane prepolymer (A) without hydrophilic group, isocyanate single An example in which the residual NCO group amount of the mixture of the terminal (B) and the terminal isocyanate adduct (D) of the dialkanol alkanoic acid (C) is from 3.5% by mass to 9.5% by mass, and the particle diameter is fine and the dispersibility is excellent. The physical properties and properties of the membrane were good. On the other hand, in Comparative Synthesis Example 1 in which the residual NCO group content was high, it was found that the particle diameter was large and the dispersion stability was also poor. Further, in Comparative Synthesis Example 2 in which the residual NCO group content was low, it was found that the prepolymer had high viscosity, large particle diameter, and poor dispersion stability. Further, in Comparative Synthesis Example 3 in which the residual NCO group content was low, it was found that the high molecular weight due to the urethane bond was high, the viscosity was high, the particle diameter was large, and the dispersion stability was also poor.

About urethane prepolymer (A) without hydrophilic group, isocyanate single Production Example 1 and Production Example 3 in which the residual NCO group amount of the mixture of the terminal (B) and the terminal isocyanate adduct (D) of the dialkanol alkanoic acid (C) is from 3.5% by mass to 9.5% by mass, and the physical properties of the film and Good traits. On the other hand, in Production Example 2 in which stirring was carried out in the reaction vessel, it was found that the particle diameter was large and the resin was adhered to the periphery of the reaction vessel, which was disadvantageous.

Claims (4)

An aqueous urethane urea resin composition which is such that a hydrophilic group-free urethane prepolymer (A) and an isocyanate monomer (B) are used in a dialkanol alkanoic acid (C). An aqueous urethane urea resin composition obtained by emulsification and dispersion in water in the presence of a terminal isocyanate adduct (D), which is polymerized by a polyamine compound (E), and which does not contain a hydrophilic group. The residual NCO group amount of the mixture of the acid ester prepolymer (A), the isocyanate monomer (B), and the terminal isocyanate adduct (D) of the dialkanol alkanoic acid (C) is 3.5% by mass to 9.5% by mass, And the acid value of the mixture of the hydrophilic group-containing urethane prepolymer (A), the isocyanate monomer (B) and the di-terminal isocyanate adduct (D) of the dialkanol alkanoic acid (C) has an acid value of 9.2. MgKOH/g~40 mgKOH/g. A method for producing a water-based urethane urea resin composition, which does not use an organic solvent, and a method for producing the aqueous urethane urea resin composition, comprising: two of a dialkanol alkanoic acid (C) a step of emulsifying a hydrophilic group-free urethane prepolymer (A) and an isocyanate monomer (B) in the presence of a terminal isocyanate adduct (D); and using a polyamine compound (E) a step of high molecular weight; and a hydrophilic group-containing urethane prepolymer (A), an isocyanate monomer (B), and a di-terminal isocyanate adduct (D) of a dialkanol alkanoic acid (C) The residual NCO base amount of the mixture is 3.5% by mass to 9.5% by mass, and the hydrophilic group-free urethane prepolymer (A), the isocyanate monomer (B), and the dialkanol alkanoic acid (C) are both The acid value of the mixture of terminal isocyanate adducts (D) is 9.2 mgKOH/g to 40 mgKOH/g. The method for producing an aqueous urethane urea resin composition according to claim 2, wherein the emulsification step is a di-terminal isocyanate addition product (D) of a dialkanol alkanoic acid (C), The mixture of the hydrophilic group-free urethane prepolymer (A) and the isocyanate monomer (B) and the emulsified water were subjected to collision emulsification in an on-line rotor stator mixer. An emulsion method of a hydrophilic group-free urethane prepolymer (A) and an isocyanate monomer (B), which does not use an organic solvent, and uses a two-terminal isocyanate addition of a dialkanol alkanoic acid (C) a mixture of the terminal (D) and the hydrophilic group-free urethane prepolymer (A), the isocyanate monomer (B) and the di-terminal isocyanate adduct (D) of the dialkanol alkanoic acid (C) The acid value is 9.2 mgKOH/g to 40 mgKOH/g.