JPS62241902A - Production of water-based resin composition - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

Detailed Description of the Invention [Field of Industrial Application] The present invention relates to a method for producing an aqueous resin composition, and more specifically, in the presence of a urethane emulsion having a particle size of 0.001 μ to 0.035 μ, The present invention relates to a method for producing an aqueous resin composition characterized by radically polymerizing a monomer having a polymerizable unsaturated bond.

[Conventional technology and problems]

Conventionally, monomers with polymerizable unsaturated bonds such as vinyl acetate, acrylic esters, and styrene are mixed with potassium persulfate, hydrogen peroxide, benzoyl peroxide, and alkylhydrocarbons in an aqueous medium containing an emulsifier. A method of radical emulsion polymerization using peroxides as a polymerization catalyst or, depending on the case, in combination with a reducing agent such as sodium bisulfite or pyrosulfite, is known. or fumarate) long-chain alkyl or alkylphenoxy (or alkoxy) polyethoxyethyl esters, or long-chain alkyl or alkylphenoxy (or alkoxy) polyethoxyethyl esters of sulfopropyl itaconate; , maleic acid adduct of liquid polybutadiene, or alkyl sulfoxide of acrylic acid-acrylonitrile copolymer, or acrylic acid-
Polymer compounds such as alkyl sulfoxides of acrylamide copolymers or modified vinyl acetate polymers,
Methods of using them as so-called polymeric emulsifiers, radical graft emulsion polymerization to these polymeric emulsifiers, emulsion polymerization in the absence of emulsifiers, etc. are known.

However, these known methods have economic disadvantages due to the long reaction time required for radical polymerization, the difficulty in obtaining a highly concentrated emulsion polymer, and the need to use a large amount of emulsifier relative to the polymerizable monomer. This may significantly reduce the physical properties of the polymer itself, or cause problems with product odor due to unreacted monomers remaining in the emulsion polymer, problems with foaming of emulsions or latex, and problems with emulsification. It is not possible to solve the disadvantages such as sedimentation of coarse particles generated in the polymer, or decrease in stability of so-called emulsion or latex, and also because the emulsifier, which is a hydrophilic substance, remains in the product. The surface gloss, water resistance, mechanical properties, etc. of the dry resin obtained from these emulsions or latexes are poor, and when a polymeric emulsifier is used, the viscosity of the aqueous solution of the emulsifier itself is high, causing emulsion polymerization. It is very inconvenient to operate and the viscosity of the emulsion polymer produced is high, which has been a major problem in the field of application of emulsions or latex.

On the other hand, a method is known in which a monomer having a polymerizable unsaturated bond is radically polymerized in the presence of a gel-like aqueous polyurethane dispersion or in the presence of an oligourethane salt. Generally, when polyurethane has a strong crosslinking bond and is in the so-called gel-like state, the aqueous dispersion becomes very unstable, and radical emulsion polymerization cannot be performed in the presence of such an unstable gel-like aqueous dispersion. The resulting resin emulsion or latex becomes extremely unstable, and furthermore, when an emulsifier is used in the presence of an aqueous polyurethane dispersion in an amount of less than 10% based on the monomer having a polymerizable unsaturated bond, Uniform radical emulsion polymerization was not possible.

In addition, oligourethane salts are linear oligomers with a low molecular weight of about 1,500 to 20,000, and if the tensile strength of the resin is about 20 kg/cm2 or less, such a low molecular weight can cause poor mechanical performance. The oligourethane salt has a strong negative effect on the physical properties of the dried film of the resin emulsion obtained by radical emulsion polymerization in the presence of the oligourethane salt with excellent physical properties, and the resin emulsion or latex with excellent physical properties is I couldn't get it.

[Means for solving problems]

In order to solve the above-mentioned problems found in radical emulsion polymerization reactions and their products, the present inventors have conducted intensive research and found that in the presence of a urethane emulsion with a particle size of 0.001μ to 0.035μ, The present inventors have discovered that radical polymerization of monomers having polymerizable unsaturated bonds is extremely effective, and have completed the present invention.

That is, the present invention relates to a monomer having a polymerizable unsaturated bond in the presence of 3 to 80% by weight (solid content) of one or more types of urethane emulsion having a particle size of 0.001μ to 0.035μ. The present invention relates to a method for producing an aqueous resin composition characterized in that 97 to 20% by weight of the composition is radically polymerized.

The urethane emulsion used in the present invention can be manufactured by various methods, and a typical manufacturing method is, for example, as follows.

■ Polymerization products such as tetrahydrofuran, propylene oxide, and ethylene oxide, polyethers that are copolymerization products,
Dehydration condensation reaction between polyhydric alcohols such as ethylene glycol, propylene glycol, butanediol, and hexanediol and polyhydric carboxylic acids such as maleic acid, succinic acid, adipic acid, and phthalic acid, or ring-opening polymerization reaction of cyclic esters. The obtained polyhydroxyl compound represented by polyester, polyacetal, polyester amide, polythioether, etc., and aromatic polyisocyanate such as 1.5-naphthalene diisocyanate, 4,4'-diphenylmethane diisocyanate, phenylene diisocyanate, toluene diisocyanate, or hexa Polyisocyanates represented by aliphatic diisocyanates such as methylene diisocyanate, dicyclohexylmethane diisocyanate, and xylylene diisocyanate, as well as the above-mentioned polyhydric alcohols and low-molecular polyamines such as ethylene diamine, propylene diamine, diethylene triamine, hexamethylene diamine, and xylylene diamine. A urethane polymer solution is obtained by reacting with a chain extender represented by in an inert organic solvent such as tetrahydrofuran, acetone, methyl ethyl ketone, ethyl acetate, or toluene, and this is poured into water containing an appropriate amount of emulsifier and mixed. , a method of distilling off the inert organic solvent to obtain an aqueous polyurethane.

■ A urethane prepolymer containing free isocyanate groups produced from a polyhydroxyl compound and excess polyisocyanate is chain-extended in water containing an active hydrogen compound such as low-molecular polyamines or polyhydric alcohol and an emulsifier. A method of obtaining water-based polyurethane by emulsification.

■ A method in which a urethane prepolymer containing free isocyanate groups is emulsified in water using tertiary amines as a catalyst, and chain-extended with water to obtain aqueous polyurethane.

■ A urethane prepolymer with terminal isocyanate groups containing a salt-forming compound such as N,N-dimethylethanolamine is dispersed in water containing a neutralizing agent and an emulsifier, and then low-molecular-weight polyamines are added to extend the chain to form a water-based polyurethane. How to get it.

■ A prepolymer with a terminal hydroxyl group obtained from a polyhydroxyl compound and a polyisocyanate, or a compound with a terminal amino group obtained by reacting a diamine with a urethane prepolymer with a terminal isocyanate group is emulsified in water using an emulsifier. After that, polyisocyanate is added to polymerize it to obtain water-based polyurethane.

■Urethane prepolymer with terminal isocyanate groups,
A method of obtaining an aqueous polyurethane by reacting a compound having a tertiary amino group such as N-alkyl jetanolamine or triethanolamine, then neutralizing it with an acid, and emulsifying it in water.

■Urethane prepolymer with terminal isocyanate groups,
A method of reacting a compound having a tertiary amino group such as N-alkylgetanolamine, quaternizing the tertiary amino group with an alkylating agent, and then mixing with water to obtain an aqueous polyurethane.

(2) A method in which a urethane polymer containing a halogen group or a sulfonic acid group is reacted with a tertiary amine and then mixed with water to obtain a water-based polyurethane.

■ React the hydroxyl or amino groups of polyurethane containing primary and/or tertiary hydroxyl and/or amino groups with a compound that produces a salt after ring opening, such as a cyclic dicarboxylic anhydride, sultones, or lactones. A method in which water-based polyurethane is obtained by neutralizing the polyurethane with a base and then mixing it with water.

[Phase] A method of obtaining an aqueous polyurethane by chain-extending a urethane prepolymer with terminal isocyanate groups produced from a water-soluble polyhydroxyl compound and a polyisocyanate in an aqueous solution of a polyfunctional amine.

■ A urethane prepolymer with a terminal isocyanate group is reacted with an aqueous solution of an alkali or ammonium salt of a diaminocarboxylic acid, such as a compound having an amino group or hydroxyl group and a sulfonic acid group or a carboxyl group, and emulsification is carried out at the same time as chain extension to obtain an aqueous polyurethane. Method.

[Phase] A method of obtaining aqueous polyurethane by reacting a polyhydroxyl compound, a compound having a quaternary ammonium group and a hydroxyl group in the molecule, a compound having an epoxy group and a hydroxyl group in the molecule, and a polyisocyanate and mixing with water. .

0 A method in which a urethane prepolymer having terminal isocyanate groups is reacted with a hydroxyl compound having a quaternary ammonium base and mixed with water to obtain an aqueous polyurethane.

[Phase] A method of obtaining water-based polyurethane by reacting polyoxyethylene glycol or a water-soluble glycol, which is a ring-opened copolymer of propylene oxide and ethylene oxide, with polyisocyanate.

■ A urethane prepolymer containing carboxyl groups and isocyanate groups manufactured from a polyhydroxyl compound having carboxyl groups and polyisocyanate is mixed with an aqueous solution of a basic substance, and at the same time it is neutralized and chain-extended with water or low-molecular polyamines to form an aqueous solution. How to get polyurethane.

[Phase] A polyurethaneurea polyamine is produced by reacting a polyalkylene polyamine such as diethylene triamine with a urethane prepolymer having terminal isocyanate groups,
A method of obtaining an aqueous polyurethane by adding an aqueous acid solution to this, or adding epihalohydrin to the polyurethaneurea polyamine and then adding an aqueous acid solution.

(2) A method of obtaining an aqueous polyurethane by reacting the above polyurethaneurea polyamine, its alkyl (C+z~Cm!) isocyanate adduct, or its epihalohydrin adduct with a cyclic dicarboxylic acid anhydride, and then mixing with an aqueous solution of a basic substance.

[Phase] The above polyurethaneurea polyamine or its epihalohydrin adduct is reacted with sultones or lactones, or with monohalogenated sodium carboxylate, or with (meth)acrylic acid ester or acrylonitrile, and then hydrolyzed. and then mixed with water to obtain water-based polyurethane.

[Phase] A polyurethaneurea polyamine is produced by reacting a polyalkylene polyamine such as diethylene triamine with a urethane prepolymer having terminal isocyanate groups obtained from a polyhydroxyl compound containing polyoxyethylene glycol and a polyisocyanate, and this is mixed with water. , or a method in which epihalohydrin is added to the polyurethaneurea polyamine and then mixed with water to obtain a water-based polyurethane.

In addition to the aqueous polyurethane produced by the method shown in the representative examples above, polyurethane that stably exists with a particle size of 0.001 .mu.m to 0.035 .mu.m can be effectively used in the present invention.

Among the above, the aqueous polyurethane obtained by the method of [Phase] to 0 is particularly useful.

The particle size according to the present invention is 0. Urethane emulsilane with a QO of 1 μm to 0.035 μm is a transparent or semitransparent colloidal dispersion, and Tyndall phenomenon is observed when irradiated with laser light. or,
Due to Rayleigh scattering, it appears blue-white in reflected light and yellow-red in transmitted light.

As the monomer having a polymerizable unsaturated bond used in the present invention, a radically polymerizable compound is used. α, β-unsaturated carboxylic acid amides such as amide, maleic acid amide, maleic acid imide, methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, butyl acrylate, butyl methacrylate, stearyl methacrylate, hydroxyethyl Acrylate, hydroxypropyl acrylate, 2-aminoethyl methacrylate hydrochloride, dimethylaminoethyl methacrylate, methoxymethyl methacrylate, chloromethyl methacrylate, dichlorotriazinyl aminoethyl methacrylate, and esters of maleic acid, fumaric acid, itaconic acid, etc., α,
Esters of β-unsaturated carboxylic acids, substituted amides of unsaturated carboxylic acids such as methylol acrylamide, methylol methacrylamide, methoxymethyl acrylamide, α, β- such as acrylonitrile, methacrylaterile, etc.
In addition to unsaturated carboxylic acids such as nitrile, vinyl acetate, vinyl chloride, and vinyl chloroacetate, divinyl compounds, vinylidene compounds, aromatic vinyl compounds represented by styrene, and heterocyclic vinyl compounds represented by vinylpyridine and vinylpyrrolidone. Vinyl ketone compounds, vinyl ether compounds, vinylamide compounds, monoolefin compounds such as ethylene and propylene, conjugated diolefin compounds such as butadiene, isoprene and chlorobrene, allyl compounds such as allyl alcohol and allyl acetate, and monoolefin compounds such as glycidyl methacrylate. One or more monomers selected from the group of monomers are used.

Particle size 0.001 to 0.035 produced by the above method
Polymerization catalysts used in the radical emulsion polymerization of the monomers having polymerizable unsaturated bonds mentioned above in the presence of μ urethane emulsion include potassium persulfate, ammonium persulfate, hydrogen peroxide, and benzoyl peroxide. ,t
-butyl hydroperoxide, succinic acid hydroperoxide, cumene hydroperoxide,
Peroxides such as p-methane hydroperoxide, di-tert-butyl hydroperoxide, and tert-butyl perbenzoic acid, or 2,2°-azobis(2-amidinopropane) hydrochloride, azobiscyclohexanecarbonitrile, etc. Preferred representative examples include azobis-based initiators, and if necessary, ethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, pentaethylenehexamine, monoethanolamine, jetanolamine, triethanolamine, propylenediamine, Water-soluble amines such as diethylamine and monoethylamine, pyrosulfite, sodium bisulfite, sodium formaldehyde sulfoxylate, etc. are used as activators in combination with polymerization catalysts, and as polymerization degree regulators, organic halogen compounds, nitro compounds, alkyl Mercaptans, diisopropylxanthate, etc. can also be used.

In the emulsion polymerization reaction according to the present invention, the particle size o according to the present invention,
In the presence of a urethane emulsion of ooiμ to 0.035μ, the above-mentioned polymerizable monomers, catalysts, catalyst activators, polymerization regulators, etc. are appropriately combined, using known methods without special devising. <Implemented.

In addition, in the present invention, the particle size is 0.001μ to 0.035μ.
The mixing ratio of μ's urethane emulsion and polymerizable monomer is 97 to 20!1% of the polymerizable monomer, and the particle size is 0.0%.
01μ~0.035μ urethane emulsion 3~80
Weight % (solid content).

If the amount of the urethane emulsion with m diameter o, ooiμ ~ 0.035μ is less than 3% by weight, it is difficult to maintain emulsion dispersion stability, and if it exceeds 80% by weight, emulsion dispersion stability is sufficient. Due to the relative increase in precursors, the precursors are relatively low polymers and contain many hydrophilic groups, so the application performance of the obtained emulsion polymer is poor, especially the water resistance is significantly poor. .

On the other hand, when a urethane emulsion with a particle size larger than 0.035 μm is used, it is difficult to maintain emulsion dispersion stability and the resulting emulsion polymer has poor stability. In addition, the obtained emulsion polymer has poor permeability to absorbent substrates, coating film density, gloss, water resistance, etc.

Furthermore, 0,00 used in the emulsion polymerization reaction according to the present invention
Since the urethane emulsion of 1μ to 0.035μ itself functions as a surfactant, there is no need to use a protective colloid or surfactant in the emulsion polymerization reaction, but the stability of the resin emulsion silane or latex produced may be affected. It goes without saying that conventionally known protective colloids and surfactants can be used to improve the properties of the resin as long as they do not adversely affect the physical properties of the resulting resin.

Furthermore, depending on the use for which the resin emulsion silane or latex is used, commonly used antifoaming agents, antifungal agents, fragrances, fluorescent whitening agents, antioxidants, ultraviolet absorbers, reinforcing agents,
In addition to fillers, pigments, antistatic agents, antiblocking agents, flame retardants, plasticizers, lubricants, organic solvents, tackifiers, thickeners, foaming agents, colorants, etc., epoxy compounds as crosslinking agents, A compound having a methylol group or an alkoxymethyl group, a catalyst, etc. can be blended into the resin emulsion silane or latex.

Since the resin composition obtained by the method of the present invention has a high concentration and excellent emulsifying and dispersing properties, it has excellent general stability of emulsion silane, such as storage stability and mechanical stability. or,
It also exhibits excellent permeability to absorbent bases.

On the other hand, when this is used as a coating film, a dense coating film can be obtained, and it has excellent properties such as water resistance, gloss, adhesion, transparency, and tensile strength.
Excellent mechanical properties.

In addition, the film obtained from this resin composition has the excellent properties of urethane, such as elasticity, adhesion, and abrasion resistance.
The excellent properties of vinyl polymers, such as hardness, airtightness,
Properties such as water resistance are combined, and arbitrary properties can be expressed depending on the manufacturing conditions.

The resin emulsion or latex produced by the method of the present invention can be applied to fiber materials, nonwoven fabrics, paper, leather, rubber, wood, metal, asphalt, concrete, plaster, ALC.
By impregnating boards, ceramic siding materials, glass, glass fibers, plastics, etc., or applying them to these surfaces and drying, you can obtain performance improvement effects such as surface coating, adhesion, and texture improvement. Coating agents for barcode labels (POS labels), civil engineering and construction related products, inks, paints, various binders,
It can be advantageously used in adhesives, paper processing agents, cement admixtures, and fields where rubber latex and resin emulsion silanes are generally applied.

〔Example〕

Next, the present invention will be specifically explained with reference to reference examples and examples, but it goes without saying that the present invention is not limited thereto.

In addition, all parts and percentages in the examples are based on weight unless otherwise specified.

Reference example-1 Propylene oxide adduct of bisphenol A (hydroxyl value 2
60.4) 1916 parts, methyl ethyl ketone 1485
Part and 2.4-) Mixture of lylene diisocyanate and 2゜6-lylene diisocyanate 80720 1548
Place 75 parts in a round bottom flask equipped with a stirrer and thermometer.
The reaction was carried out at ℃ for 4 hours to obtain a urethane prepolymer solution containing 7.55% of free isocyanate M.

Meanwhile, in another flask, 374 parts of methyl ethyl ketone, 12.3 parts of diethylenetriamine, 21.1 parts of N-methylaminopropylamine, and 15.5 parts of di-n-butylamine were added.
400 parts of the above-mentioned urethane prepolymer solution was gradually added to this while stirring from the dropping funnel over 1 hour, and the mixture was reacted at 50°C for 30 minutes to form a polyurethane urea. A polyamine solution was obtained.

An infrared absorption spectrum was measured using a drop of this solution, and it was determined that <225
No absorption of 0c■-1 was observed.

Subsequently, 24 parts of succinic anhydride dissolved in 120 parts of methyl ethyl ketone was added to this polyurethaneurea polyamine solution and reacted at 50°C for 30 minutes, and then 7.7 parts of caustic soda was dissolved in 900 parts of water. In addition, 40-5
Methyl ethyl ketone was distilled off under reduced pressure at 0°C.

Next, water was added to adjust the concentration to obtain a uniform, stable, low-viscosity polyurethane emulsion with a resin content of 30%.

The obtained polyurethane emulsion is transparent and has a Tyndall phenomenon when irradiated with a laser beam, and has a particle size of 0.
It was 0.006μ.

In addition, the particle size is C0ULTBRELHCTRONIC3I
NC made C0ULTII! Measured with RAODEL N4.

Reference Example-2 382 parts of methyl ethyl ketone, 31.6 parts of N-methylaminopropylamine, and 23.2 parts of di-n-butylamine were placed in a flask and mixed uniformly, and the urethane prepolymer synthesized in Reference Example-1 was added to the mixture. 400 parts of the solution was gradually added from the dropping funnel over 1 hour with stirring, and the mixture was heated to 50°C.
A polyurethaneurea polyamine solution was obtained by reacting for 30 minutes.

An infrared absorption spectrum was measured using a drop of this solution, and it was determined that <225
No absorption at 0 cm-' was observed.

Subsequently, 17.9% was added to this polyurethaneurea polyamine solution.
Part of succinic anhydride dissolved in 90 parts of methyl ethyl ketone was added, reacted at 50°C for 30 minutes, and then 7.2
Dissolve 1 part of caustic soda in 860 parts of water and add
Methyl ethyl ketone was distilled off under reduced pressure at 50°C.

Next, water was added to adjust the concentration to obtain a uniform, stable, low-viscosity polyurethane emulsion with a resin content of 30%.

The obtained polyurethane emulsion is transparent and has a Tyndall phenomenon when irradiated with a laser beam, and has a particle size of 0.
It was 03μ.

Reference Example-3 A urethane prepolymer solution containing 7.74% of free isocyanate groups was obtained by reacting with the same ingredients as in Reference Example-1.

In a separate flask, add 386 parts of methyl ethyl ketone and 25.
3 parts of diethylenetriamine and 31.7 parts of dibutylamine were added and mixed uniformly, and 400 parts of the above urethane prepolymer solution was gradually added to this while stirring from the dropping funnel over a period of 1 hour. The reaction was carried out at ℃ for 30 minutes to obtain a polyurethaneurea polyamine solution.

An infrared absorption spectrum was measured using a drop of this solution, and it was determined that <225
No absorption at 0 cm-' was observed.

Subsequently, 24.6 was added to this polyurethaneurea polyamine solution.
Part of succinic anhydride dissolved in 125 parts of methyl ethyl ketone was added and reacted at 50°C for 30 minutes, then 6.
Dissolve 4 parts of caustic soda in 910 parts of water and add
Methyl ethyl ketone was distilled off under reduced pressure at ~50°C.

Next, water was added to adjust the concentration to obtain a uniform, stable, low-viscosity polyurethane emulsion with a resin content of 30%.

The obtained polyurethane emulsion was cloudy and had a particle size of 0.
．． It was 04μ.

Example-1 257,111 parts (solid content: 33.3 parts) of the urethane emulsion with a particle size of 0.006μ obtained in Reference Example-1 was placed in a round-bottomed flask equipped with a nitrogen introduction tube, a dropping funnel, a stirrer, and a thermometer. Add 187 parts of exchanged water, adjust the pH of the system to 10 with sodium carbonate, then replace the system with nitrogen thoroughly and heat to 60°C.
Styrene/2-ethylhexyl acrylate-35/65 mixed monomer (weight ratio) 10 parts, potassium versalphate 0.1 part, sodium bisulfite 0.05
After addition of 90 parts of styrene/2-ethylhexyl acrylate-35/65 mixed monomer (weight ratio) from the dropping funnel over 1 hour, the temperature was further increased to 60°C. It was aged for 1 hour.

The mixture was cooled to room temperature, and the precipitates generated during polymerization were filtered through a 100-mesh wire gauze to obtain a stable emulsion free from unreacted styrene odor.

The amount of precipitates generated during polymerization was 0.09 of the monomer charged.
% (hereinafter referred to as polymerization stability), and the viscosity is 38 cps.
(Using a B-type viscometer, 25°C, same below), pH 9.1
(measured for a 5% emulsion, the same applies hereinafter), mechanical stability 0.03% (Take the emulsion in a tall beaker, stir it at 400° rpm 15a+in with a lab mixer, measure the amount of coagulated material produced, and determine the solid content of the emulsion. An extremely stable emulsion was obtained with a polymerization rate of 100% (expressed in %).

Example 2 Using 111 parts (solid content 33.3 parts) of the urethane emulsion with a particle size of 0.03μ obtained in Reference Example 2, the same formulation as in Example 1 was used to create an emulsion with no unreacted monomer odor. A stable emulsion was obtained.

Polymerization stability is 0.11%, viscosity 33 cps s
An extremely stable emulsion with a pH of 9.3 and a mechanical stability of 0.04% was obtained with a polymerization rate of 100% Example-3 Urethane emulsion 17.5 with a particle size of 0.006μ obtained in Reference Example-1 part (solid content 5 parts) and 1 part ion-exchanged water
97 parts were placed in a flask and followed by the same formulation as in Example 1 to obtain a stable emulsion free of unreacted monomer odor.

Polymerization stability is 0.35%, viscosity 40cps,
A very stable emulsion with a pH of 9.1 and a mechanical stability of 0.06% was obtained. Polymerization rate 100% Example-4 997,778 parts of the urethane emul with a particle size of 0.006 μ obtained in Reference Example-1 (solid content 233.3 parts) and 117 parts of ion-exchanged water were placed in a flask, and the following Example-1 and A stable emulsion without unreacted monomer odor was obtained using the same formulation.

Polymerization stability is 0.01%, viscosity is 30 cps,
A very stable emulsion was obtained with a pH of 9.5 and a mechanical stability of 0.01%, with a polymerization rate of 100%.Comparative Example-1 111 parts of the 0.04μ urethane emulsion obtained in Reference Example-3 (solid content 33. 3 parts), and the following examples -
An emulsion was obtained using the same recipe as in Example 1.

Polymerization stability is 0.85%, particle size 43cps,
pH 8.6, mechanical stability 0.4%, polymerization rate 9
9.6% Comparative Example-2 6.7 parts (solid content 2 parts) of the urethane emulsion with a particle size of 0.03μ obtained in Reference Example-2 and 197 parts of ion-exchanged water
A portion of the mixture was placed in a flask, and an emulsion was obtained using the same recipe as in Example-1.

Polymerization stability is 1.6%, viscosity 38 cps, p
H8.9, mechanical stability 0.3%. Polymerization rate 99
．． 3%.

Comparative Example-3 Using 1889 parts (solid content: 567 parts) of the urethane emulsion with a particle size of 0.03 μ obtained in Reference Example-2, an emulsion was obtained according to the same recipe as in Example-1.

Polymerization stability is 0.01%, viscosity 45 cps,
An emulsion with a pf of 19.6 and a mechanical stability of 0.01% was obtained. Polymerization rate: 100% The physical properties of the emulsions obtained in Examples 1 to 4 and Comparative Examples 1 to 3 were evaluated by the method shown below.

The results are shown in Table 1.

As shown in Table 1, the particle size is 0.001 μ to 0.035
Products using μ urethane emulsions have extremely excellent physical properties.

Furthermore, in Comparative Example 2, the amount of urethane emulsion of 0.001 μm to 0.035 μm used was small, so the emulsion dispersibility, permeability, and adhesion of the obtained emulsion were poor.

On the other hand, Comparative Example 3 is a case where a large amount of 0.001μ to 0.035μ urethane emulsion is used.

In such a case, the urethane emulsion with o, ooiμ to 0.035μ has a relatively low molecular weight and high hydrophilic group density, and therefore has poor water resistance.

Power 11 Drunk Analyzer (1) Gloss An aqueous resin composition was applied to a glossy glass plate, and after drying, it was measured with a gloss needle of Suga Test Instruments.

A few examples using the same gloss meter are shown for reference.

Material gloss The larger the number, the better the gloss.

(2) A film obtained by putting an aqueous resin composition in a water-resistant Teflon-coated dish and drying it was immersed in water at 25° C. for 7 days, and changes in state were observed.

O mark: Paint film swelling rate within 5% and no change such as whitening Δ mark: Paint film swelling ratio 5% to 10% with no change such as whitening or slight whitening × mark: Paint film (3) Storage stability of emulsion The aqueous resin composition was placed in a mayonnaise bottle and left in a thermostat at 50° C., and changes in state were observed.

× mark: Sedimentation of coarse particles, thickening, and gum-up are observed within 1 week at 50°C.

Δ mark: Sedimentation of coarse particles, thickening, and gum-up are observed within 2 weeks at 50°C.

O mark: Stable at 50°C for 2 weeks or more.

(4) 400 with the viscosity of the permeable emulsion adjusted to 10 cps
ml was placed in a 500*1 beaker, and a Kubota Fire Prevention Siding I449 unpainted board cut into an appropriate size was immersed in the beaker for 2 hours, then taken out and dried overnight at 80°C to prepare a sample. Penetration was measured using the following formulation.

Using an X-ray microanalyzer (model JCXA-733, manufactured by JEOL Ltd.) to measure the distribution of carbon, which is the most abundant carbon in the resin, the center of the specimen was cut and the cut surface was measured using an X-ray microanalyzer (model JCXA-733, manufactured by JEOL Ltd.). Those in which carbon distribution is observed are indicated as permeated and marked with an ○, and those in which no carbon distribution is observed are indicated as not permeated and indicated as marked with an X.

(5) Adhesion Using the sample obtained in section (4), JIS K5400-1
The test was carried out in accordance with the base material test described in ``General Test Methods for Paints'' published in 1979.

However, by canting 2X2CII at 4 fin intervals, making a total of 25 basal eyes, those with 25 to 20 attached are marked with an O.
Those with 20 to 10 adherents are indicated by a Δ mark, and those with 10 or less adhesion are indicated by an X mark.

(6) Polymerization rate Measure the residual upper limit by gas chromatography, I asked for more.

(%)

Claims (1)

[Claims] 1. One or more types of urethane emulsion with a particle size of 0.001μ to 0.035μ 3 to 80% by weight (solid content)
Monomer 97 having a polymerizable unsaturated bond in the presence of
A method for producing an aqueous resin composition, which comprises radically polymerizing up to 20% by weight.