JPH0689094B2 - Nonionic urethane resin emulsion giving improved physical properties - Google Patents

Description

TECHNICAL FIELD The present invention relates to a nonionic urethane resin emulsion having excellent emulsion stability and improved physical properties such as water resistance, hot water resistance and solvent resistance. is there.

(Prior Art) Many urethane resin emulsions have been conventionally known. These are those in which hydrophilic groups such as anions, cations and nonions are introduced into the urethane resin skeleton for self-emulsion dispersion, or a large amount of an emulsifier is added to the hydrophobic resin to forcibly disperse in water. .

(Problems to be Solved by the Invention) Regarding the self-emulsifying type in which a hydrophilic group is introduced into the skeleton, it has become possible in recent years to obtain an aqueous dispersion having a high molecular weight and a high cross-linking structure, and improvements have been made. It is impossible to completely avoid the influence of the hydrophilic group, and particularly the hot water resistance and the moist heat resistance are not satisfactory.

On the other hand, for those forcibly dispersing the hydrophobic resin with an emulsifier, since an essentially large amount of emulsifier is required, the physical properties of the film are often unsatisfactory, and if the amount of emulsifier is reduced to solve this problem, The emulsification dispersibility and product stability were poor, and it was not suitable for practical use.

That is, as a method for dispersing a hydrophobic urethane prepolymer containing a free isocyanate group in water in the presence of an emulsifier and then chain-extending with a polyamine compound, for example, JP-B-48-13356 and JP-B-61-56260 are proposed. ing.

However, these methods usually have a high free isocyanate group content (low molecular weight) of the prepolymer to be used for emulsification, so that the molecular weight change before and after the polyamine chain extension is large, and the balance of the emulsification system is disturbed, which tends to deteriorate product stability. Therefore, the hydrophilicity of the resin skeleton itself is increased, or it is necessary to increase the amount of emulsifier or to use an ionic emulsifier in combination, so that the water resistance and hot water resistance of the product film are often poor.

(Means for Solving Problems) The present inventors provide a urethane resin emulsion that improves the above-mentioned drawbacks of the conventional urethane resin emulsion, stably disperses in water, and provides improved physical properties. For the purpose of the above, the present invention has been achieved as a result of earnestly studying the adjustment conditions of the urethane polymer before emulsification and the type of the agent to be used. That is, it is obtained by reacting one or more compounds having a molecular weight of 200 to 10,000 having two or more active hydrogen atoms with an excess amount of polyisocyanate, and optionally a low molecular weight chain extender having two or more active hydrogen atoms. In a urethane resin emulsion obtained by chain extending a free isocyanate group-containing urethane polymer, in the presence of an emulsifier and water, with a polyamine compound containing two or more primary and / or secondary amino groups in one molecule, The content of free isocyanate groups obtained by reacting the urethane polymer at an NCO / OH molar ratio of 1.2 to 1.02 is 1.5 to 0.2% by weight.
And a urethane polymer having an oxyethylene chain content of 5 to 20% by weight, wherein the emulsifier is a polyoxyethylene arylphenol ether type nonionic surfactant having an HLB of 6 to 18 and is 2 to 15% by weight based on the urethane resin. It is a nonionic urethane resin emulsion giving improved physical properties, characterized by being blended as described above.

The free isocyanate group-containing urethane polymer used in the present invention includes at least one compound having a molecular weight of 200 to 10,000 having two or more active hydrogen atoms and an excess amount of polyisocyanate, and optionally two or more active hydrogens. A urethane polymer having a free isocyanate group content of 1.5 to 0.2% by weight and an oxyethylene chain content of 5 to 20% by weight, which is obtained by reacting with a low molecular weight chain extender having an atom, can be mentioned.

A compound having a molecular weight of 200 to 10,000 having two or more active hydrogen atoms has two or more hydroxyl groups at the end or in the molecule,
Those containing a carboxyl group, an amino group, a mercapto group, etc., and are generally known polyethers, polyesters, polyetheresters, polythioethers, polyacetals, polybutadienes, etc., preferably polyethers having two or more hydroxyl groups at the terminals. , Polyester.

Examples of the polyether include polyoxyethylene glycol, polyoxypropylene glycol, polyoxyethylene propylene glycol, ethylene glycol, propylene glycol, glycerin, trimethylolpropane, pentaerythritol, sorbitol and other polyols, ethylene oxide, propylene oxide, butylene oxide. And one or more adducts (random or block) of alkylene oxide, polyoxytetramethylene glycol, which is a ring-opening polymer of tetrahydrofuran, and the like.

Polyesters such as ethylene glycol, propylene glycol, butylene glycol, hexylene glycol, diethylene glycol, glycerin, trimethylol propane and other polyols and succinic acid, glutaric acid, adipic acid, maleic acid, fumaric acid, phthalic acid and other polyvalent Examples thereof include saturated or unsaturated carboxylic acids or condensation products thereof with acid anhydrides. Among them, polyethylene adipate diol, polybutylene adipate diol, polyhexylene adipate diol, polydiethylene adipate diol and the like having a molecular weight of 1,000 to 2,000 adipate diols are particularly useful.

Such a molecular weight of 200 to 10 having two or more active hydrogen atoms,
Since the urethane polymer contains 5 to 20% by weight of an oxyethylene chain, it is necessary to appropriately select or combine 000 compounds so as to satisfy the range.

As the polyisocyanate, all aromatic, aliphatic or alicyclic polyisocyanates which have been conventionally used can be used. Examples thereof include polyisocyanates such as tolylene diisocyanate, xylylene diisocyanate, diphenylmethane diisocyanate, naphthalene diisocyanate, hexamethylene diisocyanate, dicyclohexylmethane diisocyanate, isophorone diisocyanate, mixtures thereof, and dimers or trimers thereof. Of these, tolylene diisocyanate, diphenylmethane diisocyanate, hexamethylene diisocyanate and dicyclohexylmethane diisocyanate are particularly preferable.

Next, the low molecular weight chain extender having two or more active hydrogen atoms is a polyhydric alcohol agent such as ethylene glycol, propylene glycol, butanediol, neopentyl glycol, hexadiol, diethylene glycol, and trimethylolpropane. Are blended together.

A molecular weight of 200 to 1 having two or more active hydrogen atoms
The reaction of 0,000 compounds with an excess amount of polyisocyanate, and optionally a low molecular weight chain extender having two or more active hydrogen atoms, is carried out by a conventionally known one-step or multi-step isocyanate polyaddition reaction method at 50-120. Carry out under the temperature condition of ° C.

In this case, if necessary, a reaction control agent such as phosphoric acid, benzoic acid, p-toluenesulfonic acid, adipic acid, phthalic anhydride, benzoyl chloride, a reaction catalyst such as dibutyltin dilaurate, stannas octoate, triethylamine, triethylenediamine, etc. Further, an organic solvent that does not react with an isocyanate group may be added in the reaction step or after the reaction is completed.

These organic solvents are acetone, methyl ethyl ketone,
Tetrahydrofuran, dioxane, dimethylformamide, ethyl acetate, toluene, xylene, methylene chloride and the like.

In addition, if necessary, after the reaction step or after the reaction, an antioxidant,
It is also possible to add a stabilizer such as an ultraviolet absorber.

When reacting the urethane polymer, the NCO / OH molar ratio is 1.2.
˜1.02, preferably 1.15 to 1.05, and the resulting urethane polymer preferably has a free isocyanate group content of 1.5 to 0.2% by weight.

When NCO / OH is 1.2 or more, or when the free isocyanate group content is 1.5% or more, the emulsion stability and aging stability of the product after polyamine chain extension become poor, and NCO / OH is 1.
When the content of 02 or less or the free isocyanate group content is 0.2% or less, it takes an extremely long time to complete the reaction, and the viscosity is increased, so that a large amount of an organic solvent is required, which is inferior in economical efficiency, and in some cases, a high molecular weight, Due to high cross-linking, uniform emulsion dispersion is difficult.

Further, the resulting urethane polymer desirably contains from 5 to 20% by weight of oxyethylene chains.

When the oxyethylene chain content in the urethane polymer is 5% or less, the hydrophobicity of the polymer skeleton is too strong to make uniform emulsification and dispersion impossible, and when it is 20% or more, the emulsification and dispersibility is good, but the product It is not possible to obtain a urethane resin emulsion which significantly deteriorates the physical properties of the film, particularly water resistance, is excellent in emulsion stability for this purpose, and has improved physical properties such as water resistance, hot water resistance and solvent resistance.

Next, the emulsifier used in the present invention is a polyoxyethylene arylphenol ether type nonionic surfactant having an HLB of 6 to 18, such as monostyrenated phenol, distyrenated phenol, tristyrenated phenol or a mixture thereof. Examples thereof include ethylene oxide adducts such as oxide adducts, tribenzylphenol, benzylphenylphenol, cumylphenol, and the like. Particularly preferable emulsifiers are ethylene oxide adducts of distyrenated (mono-, di-, or tri) phenol or a mixture thereof. Examples of the products include those in the range of HLB8-17. Only by using these emulsifiers can the objects of the invention be achieved.

Conventional nonionic surfactants such as polyoxyethylene alkyl ether type, polyoxyethylene alkylphenol ether type, polyoxyethylene propylene ether type, higher alcohol polyethylene glycol ether type and aliphatic polyethylene glycol ester type are the chains of the present invention. It is inferior in emulsifying power to a hydrophobic urethane resin skeleton such as an extension polymer, and has a large foaming property, so that there are problems in uniform emulsification and dispersion, temporal emulsion stability, and workability, and it cannot be used.

Further, the use of anionic surfactants such as sulfuric acid ester salts and phosphoric acid ester salts of ethylene oxide adducts such as alkylphenols and higher alcohols, alkylbenzene sulfonates, sulfosuccinic acid diesters, etc., or the combination with the nonionic surfactants However, it cannot be used in the present invention because it significantly deteriorates the product film performance, especially the water resistance and the hot water resistance.

Next, primary and / or 2 in one molecule used in the present invention
The polyamine compound containing two or more primary amino groups is the same as that used in the usual urethane emulsion production, and examples thereof include ethylenediamine, tetramethylenediamine, hexamethylenediamine, diethylenetriamine, triethylenetetramine, piperazine, hydrazine and tolylenediene. Amine and xylylenediamine are preferred.

Examples of the nonionic urethane resin emulsion according to the present invention include urethane resin emulsions obtained by chain extending the urethane polymer with the polyamine compound in the presence of the emulsifier and water.

The amount of the emulsifier used is preferably 2 to 15% by weight based on the urethane resin.

If the amount used is less than 2%, uniform emulsion dispersion is impossible,
When it is 15% or more, the emulsified dispersion is good, but the water resistance of the product film is deteriorated.

The amount of the polyamine compound used is an amount containing 0.5 to 1.5 equivalents of amino groups, preferably 0.7 to 1.2 equivalents, relative to the free isocyanate groups in the urethane polymer.

The emulsifying and dispersing method in the present invention is not particularly limited, and a urethane polymer, a polyamine compound, water and an emulsifier may be added in any order, and the resulting mixture may be emulsified by using an emulsifying and dispersing device such as a homomixer and a homogenizer. In order to suppress side reactions between the isocyanate groups in the water and water as much as possible and to promote effective chain extension reaction with polyamine compounds, for example, 1) mix an emulsifier with urethane polymer and gradually add water with stirring to emulsify and disperse Then, a method of adding a polyamine compound, 2) a method of mixing an emulsifier with a urethane polymer, adding a mixture of a polyamine compound and water with stirring, and emulsifying and dispersing are preferable.

At this time, phosphoric acid, benzoyl chloride or the like can be added as a urethanization reaction control agent in order to control a side reaction of water and an isocyanate group.

The reaction of the urethane polymer with water and the polyamine compound proceeds at the same time as the emulsification and dispersion, and is usually 60 to 120 at 30 to 50 ° C.
The reaction is completed in minutes.

When the emulsified dispersion contains an organic solvent, if necessary, it is distilled off under reduced pressure at 30 to 70 ° C. to obtain a milky white nonionic urethane resin emulsion.

(Effect of the present invention) The nonionic urethane resin emulsion of the present invention is excellent in emulsion stability, and has various physical properties such as water resistance, hot water resistance, solvent resistance and strength of the film, compared with the conventional urethane emulsion of the same type. Has achieved a significant improvement, and is comparable to solvent-based polyurethanes.

Therefore, the nonionic urethane resin emulsion of the present invention can be used for a wide range of applications such as fiber knitted woven fabric, non-woven fabric, wood, paper, leather, impregnation of metal, coating, adhesive, paint, vehicle for ink, etc. It has high utility value in the field of synthetic leather and artificial leather.

Since the nonionic urethane resin emulsion of the present invention is nonionic, other aqueous resin emulsions such as vinyl acetate, ethylene vinyl acetate copolymer,
Acrylic ester resin emulsion and natural rubber, SB
Since it has good compatibility with rubber latexes such as R and NBR, it is also useful as a modifier for these.

Further, since the nonionic urethane resin emulsion of the present invention has a heat-sensitive gelling property, it can be used for manufacturing various cast products.

(Examples) Hereinafter, the present invention will be described with reference to Examples, but the present invention is not limited thereto.

Example 1 Polybutylene adipate diol (average molecular weight 1000) 18
0 parts, polyoxyethylene propylene random copolymer glycol (average molecular weight 3400 oxyethylene chain content 80 wt
%) 20 parts, 3.8 parts of 1,4-butanediol, 3.8 parts of trimethylolpropane and 143.8 parts of methyl ethyl ketone were added with 79.9 parts of dicyclohexylmethane diisocyanate and reacted at 75 ° C. for 90 minutes to give a free isocyanate group content of 1.03.
% Urethane resin in methyl ethyl ketone was obtained. Into this solution, polyoxyethylene arylphenol ether type nonionic surfactant (HLB = 15) 14.4 which is an ethylene oxide adduct of distyrenated phenol is added.
After adding and mixing 20 parts of water, 301.9 parts of water is added to emulsify and disperse, 42.4 parts of a 5% aqueous solution of ethylenediamine is added, and after stirring for 60 minutes, metal ethyl ketone is distilled off at 40 to 50 ° C under reduced pressure with an evaporator. , Average particle size 1.2μm, solid content about 49
% Of a milky white urethane resin emulsion was obtained.

Example 2 Polybutylene dipentate diol (average molecular weight 1000) 180
Parts, polyoxyethylene propylene random copolymer glycol (average molecular weight 3400 oxyethylene chain content 80 wt
%) 35.1 parts, 1,4 butane diol 3.8 parts, trimethylol propane 3.8 parts and methyl ethyl ketone 151 parts to a mixture was added dicyclohexylmethane diisocyanate 80.5 parts and reacted at 75 ° C. for 90 minutes to give a free isocyanate group content 1.04.
% Urethane resin in methyl ethyl ketone was obtained. To this solution, polyoxyethylene arylphenol ether type nonionic surfactant (HLB = 15) 15.2 which is an ethylene oxide adduct of distyrenated phenol is added.
Parts, and 303 parts of water were added to emulsify, 45.1 parts of a 5% aqueous solution of ethylenediamine was added thereto, the mixture was stirred for 60 minutes, the solvent was distilled off in the same manner as in Example 1, the average particle diameter was 1.0 μm, and the solid content was about 50%.
To obtain a milky white urethane resin emulsion.

Example 3 Polybutylene adipate diol (average molecular weight 1000) 18
0 parts, polyoxyethylene propylene random copolymer glycol (average molecular weight 3400 oxyethylene chain content 80 wt
%) 60 parts, 3.8 parts of 1,4 butanediol, 3.8 parts of trimethylolpropane and 166 parts of methyl ethyl ketone were added with 84.3 parts of dicyclohexylmethane diisocyanate,
The reaction was carried out at 75 ° C. for 90 minutes to obtain a methyl ethyl ketone solution of a urethane polymer having a free isocyanate group content of 1.07%. 16.0 parts of polyoxyethylene arylphenol ether type nonionic surfactant (HLB = 15), which is an ethylene oxide adduct of distyrenated phenol, and 3 parts of water
After adding 36.8 parts and emulsifying, 5% of ethylenediamine was added to this.
After adding 49.1 parts of the aqueous solution and stirring for 60 minutes, the solvent was distilled off to obtain a milky white urethane resin emulsion having an average particle diameter of 0.85 μm and a solid content of about 50%.

Comparative Example 1 Polybutylene adipate diol (average molecular weight 1000) 18
0 parts, polyoxyethylene propylene random copolymer glycol (average molecular weight 3400 oxyethylene chain content 80 wt
%) 10 parts, 3.8 parts of 1,4-butanediol, 3.8 parts of trimethylolpropane and 138.2 parts of methyl ethyl ketone were added with 78.8 parts of dicyclohexylmethane diisocyanate and reacted at 75 ° C. for 90 minutes to give a free isocyanate group content of 1.05.
% Urethane resin in methyl ethyl ketone was obtained. To this solution, a polyoxyethylene arylphenol ether type nonionic surfactant (HLB = 15) 13.8 which is an ethylene oxide adduct of distyrenated phenol is added.
And 290.2 parts of water were added for emulsification, 41.5 parts of a 5% aqueous solution of ethylenediamine was added thereto, and the mixture was stirred for 60 minutes, and then the solvent was distilled off. The obtained emulsified dispersion had a coarse particle size and was non-uniform.

Comparative Example 2 Polybutylene adipate diol (average molecular weight 1000) 18
0 parts, polyoxyethylene propylene random copolymer glycol (average molecular weight 3400 oxyethylene chain content 80 wt
%) 105 parts, 3.8 parts of 1,4-butanediol, 3.8 parts of trimethylolpropane and 191 parts of methyl ethyl ketone were added with 89.4 parts of dicyclohexylmethane diisocyanate and reacted at 75 ° C for 90 minutes to give a free isocyanate group content of 1.04.
% Urethane resin in methyl ethyl ketone was obtained. To this solution, a polyoxyethylene arylphenol ether type nonionic surfactant (HLB = 15), which is an ethylene oxide adduct of distyrenated phenol, is added to 19.1.
Part, water 401 parts, and after emulsifying, add 56.8 parts of a 5% aqueous solution of ethylenediamine to the mixture, stir for 60 minutes, evaporate the solvent, and obtain a milky white urethane resin emulsion with an average particle size of 0.5 μm and a solid content of about 50%. Got

Example 4 In Example 2, the emulsifier “a polyoxyethylene arylphenol ether type nonionic surfactant (HLB which is an ethylene oxide adduct of distyrenated phenol)
= 15) 15.2 parts ”is a polyoxyethylene arylphenol ether type nonionic surfactant (HLB = 15) 45. which is an ethylene oxide adduct of distyrenated phenol.
6 parts ”was used, and the same operation as in Example 2 was carried out to obtain a milky white urethane resin emulsion having an average particle size of 0.9 μm and a solid content of about 50%.

Comparative Example 3 In Example 2, the emulsifier “a polyoxyethylene arylphenol ether type nonionic surfactant (HLB which is an ethylene oxide adduct of distyrenated phenol)
= 15) 15.2 parts "is a polyoxyethylene arylphenol ether type nonionic surfactant (HLB = 15) 4.6 which is an ethylene oxide adduct of distyrenated phenol.
The procedure was exactly the same as in Example 2 except that "part" was used.

A non-uniform dispersion having a coarse particle size was obtained.

Comparative Example 4 In Example 2, the emulsifier “polyoxyethylene arylphenol ether type nonionic surfactant (HLB which is an ethylene oxide adduct of distyrenated phenol)
= 15) 15.2 parts ”is a polyoxyethylene arylphenol ether type nonionic surfactant (HLB = 15) 60. which is an ethylene oxide adduct of distyrenated phenol.
The procedure was the same as in Example 2 except that "8 parts" was used to obtain a milky white urethane resin emulsion having an average particle size of 0.9 µm and a solid content of about 50%.

Comparative Example 5 In Example 1, "14.4 parts of polyoxyethylene arylphenol ether type nonionic surfactant (HLB = 15), which is an ethylene oxide adduct of distyrenated phenol," was used as an emulsifier with an ethylene oxide adduct of nonylphenol. A polyoxyalkylphenol ether type nonionic surfactant (HLB = 15) 2.9 parts, a polyoxyethylene propylene ether type nonionic surfactant (HLB = 7.5) 11.5 in which ethylene oxide is added to polyoxypropylene glycol having an average molecular weight of 2,000. Department
The procedure of Example 1 was repeated, except that A non-uniform dispersion having a coarse particle size was obtained.

Comparative Example 6 In Example 1, “polyoxyethylene arylphenol ether type nonionic surfactant (HLB = 15) 14.4 parts which is an ethylene oxide adduct of distyrenated phenol” as an emulsifier was replaced with “sulfosuccinic acid diester type anionic surfactant”. The same operation as in Example 1 was performed except that 7.2 parts of the agent and 7.2 parts of polyoxyalkylphenol ether type nonionic surfactant (HLB = 12) which is an ethylene oxide adduct of nonylphenol were used. A slightly non-uniform urethane resin emulsion having an average particle diameter of 2.1 μm was obtained.

Comparative Example 7 Polybutylene adipate diol (average molecular weight 1000) 18
0 parts, polyoxyethylene propylene random copolymer glycol (average molecular weight 3400 oxyethylene chain content 80 wt
%) 33.4 parts, 1,4 butanediol 3.8 parts, trimethylolpropane 3.8 parts and methyl ethyl ketone 146.6 parts 72.2 parts of dicyclohexylmethane diisocyanate was added to a mixture and reacted at 75 ° C for 90 minutes to give a free isocyanate group content of 0.18.
% Urethane resin in methyl ethyl ketone was obtained. Into this solution, polyoxyethylene arylphenol ether type nonionic surfactant (HLB = 15) 14.4 which is an ethylene oxide adduct of distyrenated phenol is added.
Parts and 301.4 parts of water were added to obtain a non-uniform dispersion. When 7.6 parts of a 5% aqueous solution of ethylenediamine was further added, gelation occurred.

Comparative Example 8 Polybutylene adipate diol (average molecular weight 1000) 18
0 parts, polyoxyethylene propylene random copolymer glycol (average molecular weight 3400 oxyethylene chain content 80 wt
%) 36.0 parts, 1,4 butanediol 3.8 parts, trimethylolpropane 3.8 parts and methyl ethyl ketone 156.5 parts To the mixture was added dicyclohexylmethane diisocyanate 89.3 parts and reacted at 75 ° C for 90 minutes to give a free isocyanate group content of 1.81.
% Urethane resin in methyl ethyl ketone was obtained. Into this solution, a polyoxyethylene arylphenol ether type nonionic surfactant (HLB = 15) 15.6 which is an ethylene oxide adduct of distyrenated phenol is added.
And 328.5 parts of water are added to emulsify, 81.0 parts of a 5% aqueous solution of ethylenediamine is added thereto, the mixture is stirred for 60 minutes and the solvent is distilled off to obtain a slightly coarse milky white urethane resin emulsion having an average particle diameter of 1.8 μm. It was The urethane resin emulsion left a white precipitate on the bottom when left for 2 days.

Example 5 Polyoxytetramethylene glycol (average molecular weight 100
0) 180 parts, polyethylene glycol (average molecular weight 600) 1
To a mixture of 4.8 parts, polyoxyethylene propylene random copolymer glycol (average molecular weight 3400) 14.8 parts, 1,4 butanediol 3.0 parts, trimethylol propane 5.1 parts and methyl ethyl ketone 147.6 parts was added diphenylmethane diisocyanate 77.5 parts, and the mixture was heated to 75 ° C. at 60 ° C. A partial reaction was performed to obtain a methyl ethyl ketone solution of a urethane polymer having a free isocyanate group content of 0.36%. To this solution, 14.8 parts of polyoxyethylene arylphenol ether type nonionic surfactant (HLB = 8), which is an ethylene oxide adduct of distyrenated phenol, and polyoxyethylene arylphenol ether, which is an ethylene oxide adduct of distyrenated phenol, are added. Type nonionic surfactant (HLB = 1
5) 14.8 parts, 324.7 parts of water were added and emulsified, 15.2 parts of a 5% aqueous solution of ethylenediamine was added, the mixture was stirred for 60 minutes, the solvent was distilled off, and a milky white urethane having an average particle diameter of 1.2 μm and a solid content of about 50%. A resin emulsion was obtained.

Example 6 Polybutylene adipate diol (average molecular weight 1000) 18
0 parts, polyethylene glycol (average molecular weight 600) 14.8
Parts, polyoxyethylene propylene random copolymer glycol (average molecular weight 3400) 14.8 parts, 1,4 butanediol
Tolylene diisocyanate 67 in a mixture of 4.9 parts, 7.1 parts of trimethylolpropane and 144.7 parts of methyl ethyl ketone.
8 parts was added and reacted at 75 ° C. for 80 minutes to obtain a methyl ethyl ketone solution of a urethane polymer having a free isocyanate group content of 1.43%. To this solution, a polyoxyethylene arylphenol ether type nonionic surfactant (HLB = 1%), which is an ethylene oxide adduct of distyrenated phenol, is added.
3) After adding 28.9 parts and 318.3 parts of water to emulsify, add 59.2 parts of a 5% aqueous solution of ethylenediamine, stir for 60 minutes, distill off the solvent, and give a milky white urethane with an average molecular diameter of 1.35 μm and a solid content of about 45%. A resin emulsion was obtained.

Example 7 With respect to each urethane resin emulsion obtained in Examples 1 to 6 and Comparative Examples 1 to 7, the dispersion state, stability over time, and water resistance and hot water resistance of the formed film were comparatively examined. First result
Shown in the table.

Claims (1)

[Claims] 1. A molecular weight of 20 having two or more active hydrogen atoms.
A free isocyanate group-containing urethane polymer obtained by reacting one or more compounds of 0 to 10,000 with an excess amount of polyisocyanate, and optionally a low molecular weight chain extender having two or more active hydrogen atoms is used as an emulsifier and water. In a urethane resin emulsion obtained by chain extension of a polyamine compound containing two or more primary and / or secondary amino groups in one molecule, the urethane polymer having an NCO / OH molar ratio of 1.2 to 1.02. Free isocyanate group content obtained by reacting with 1.5-0.2% by weight
And a urethane polymer having an oxyethylene chain content of 5 to 20% by weight, wherein the emulsifier is a polyoxyethylene arylphenol ether type nonionic surfactant having an HLB of 6 to 18 and is 2 to 15% by weight based on the urethane resin. A nonionic urethane resin emulsion giving improved physical properties, characterized by being blended as follows.