JPS63280702A - Production of self dispersion-type aqueous vinyl resin - Google Patents

Abstract

PURPOSE:To obtain the titled homogeneous and stable resin with small particle size, by solution polymerization in a solvent between each specific two kinds of monomer to prepare a uniform copolymer followed by distilling off the solvent to effect phase inversion into an aqueous system. CONSTITUTION:A solution polymerization is carried out in an alcohol and/or ketone solvent (e.g., isopropanol, methyl ethyl ketone), between (A) 0.5-15.0wt.% of a monomer with polymerizable double bond, carrying salt-formable group [e.g., N-(3-sulfopropyl)-N-methacryloyloxyethyl-N,N-dimethyl ammonium betaine] and (B) 99.5-85.0wt.% of a second monomer with polymerizable double bond, copolymerizable with the monomer A (e.g. methyl acrylate) to prepare a uniform copolymer followed by adding, if needed, a neutralizing agent to said copolymer to ionize the salt-forming group and then adding water followed by distilling off the above-mentioned solvent to effect phase inversion into an aqueous system, thus obtaining the objective resin.

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Field of Application] The present invention relates to a method for producing a self-dispersed aqueous vinyl resin having uniform and small particle size, which is characterized by a phase inversion method.

[Conventional technology and problems]

Conventionally, aqueous resin dispersions are mostly produced by emulsion polymerization, and several percent of emulsifiers are used to maintain stability of the polymerization reaction and the resulting aqueous resin dispersion.

Normally, in order to obtain an aqueous resin dispersion with a small particle size using this formulation, a relatively large amount of emulsifier is required.

However, the emulsifier used exhibits harmful side effects such as lowering the water resistance, adhesion, adhesion, weather resistance, mechanical strength, etc. of the film after drying.

Soap-free emulsion polymerization is attracting attention as a method for improving these problems. The details of such polymerization methods are described in many documents, such as Yamazaki et al.'s "New Developments and Problems of Synthetic Polymer Latex" [Chemical Industry Data (
Tokyo Tech Examination News) vol 13 (4) P3 (197
As described in 8)), the aqueous resin dispersion obtained by soap-free emulsion polymerization has the problem of extremely poor storage stability and mechanical stability, and is not practical.

Further, for example, Japanese Patent Publication No. 49-36942 discloses that the interpolymer is composed of an aqueous colloidal dispersion of ammonia-pulverized particles of a monomeric interpolymer.
000 to 150,000 and at least 20 weight percent of methyl methacrylate and alkyl acrylates having 4 to 16 carbon atoms and methacrylates having 6 to 16 carbon atoms. 0 to 75% by weight of an ester selected from the group consisting of alkyl acids, and 0 to 40% by weight of an ethylenically unsaturated copolymerizable monomer selected from the group consisting of styrene, vinyl acetate and vinyl chloride; an acid selected from the group consisting of 1 to 8 weight percent acrylic acid, 1 to 8 weight percent methacrylic acid, 4 to 8 weight percent maleic acid, and 4 to 8 weight percent itaconic acid; At least about 30 mole percent of the acid is in the form of ammonium salt and at least about 95 percent of the particles have a diameter of 0.5 mm.
The colloidal dispersion of this invention has a size in the range of 0.01 to 0.1 μm, but the colloidal dispersion of the present invention is prepared by subjecting an alkali-swollen carboxylic acid-modified acrylic polymer latex to vigorous mechanical processing at high temperatures. This is a method of dividing particles after shearing force, and the operation is complicated, and water-based resins with small particle sizes can only be used under extremely limited conditions such as the amount of carboxylic acid monomer in the copolymer and the degree of alkali neutralization. There is a problem that a dispersion cannot be obtained, and this type of method not only has difficulty in obtaining a uniform particle size distribution, but also has problems with the stability of the dispersion, such as sedimentation of coarse particles.

Furthermore, for example, JP-A No. 58-136647 discloses a monomer consisting of 2 to 20% by weight of an unsaturated monomer having an acidic group and 98 to 80% by weight of another unsaturated monomer copolymerizable therewith. After synthesizing a copolymer with a weight average molecular weight of 104 to 106,
Unreacted substances or unreacted substances and medium are removed to prepare a solid material substantially free of unreacted substances and medium, and this copolymer is added with an aqueous alkali solution such as aqueous ammonia or caustic soda.
A method is disclosed in which a translucent dispersion is obtained by neutralizing at a temperature of 40 to 95°C and then gradually adding water while stirring. Not only is it difficult to obtain a uniform particle size distribution, but there are also problems with the stability of the dispersion, such as sedimentation of coarse particles.

Polymers with particularly high glass transition temperatures (e.g. styrene,
methyl methacrylate, etc.), this tendency is remarkable.

[Means for solving problems]

The present inventors have conducted intensive research into a method for producing a self-dispersed aqueous vinyl resin with a uniform, stable, and small particle size that solves the above problems. The present invention was achieved by successfully obtaining a self-dispersing water-based vinyl resin with a small amount of water.

That is, the present invention includes 0.5 to 15.0% by weight of a monomer having a polymerizable double bond having a salt form or a base group, and a monomer having a polymerizable double bond that can be copolymerized with the monomer having a polymerizable double bond. Body 99.5
~85.0% by weight is subjected to solution polymerization in an alcohol-based and/or ketone-based solvent to obtain a homogeneous copolymer.Next, a neutralizing agent is added to this copolymer as necessary to add a salt-forming group. This relates to a method for producing a stable self-dispersed water-based vinyl resin, which is characterized by ionizing the resin, then adding water, distilling off the alcoholic and/or ketone solvent, and inverting the phase to an aqueous system. .

Examples of the monomer having a salt-forming group and a polymerizable double bond used in the present invention include anionic monomers, cationic monomers, amphoteric monomers, and the like. More specifically, the anionic monomers include unsaturated carboxylic acid monomers, unsaturated sulfonic acid monomers, unsaturated phosphoric acid monomers, etc.
Cationic monomers include unsaturated tertiary amine-containing monomers and unsaturated ammonium salt-containing monomers, and amphoteric monomers include N-(3-sulfopropyl)-N-methacryloxyethyl-N, Examples include N-dimethylammonium betaine, N-(3-sulfopropyrun-N-methacrylamidoprobyl-N), N-dimethylammonium betaine, 1-(3-sulfopropyl)-2-vinylpyridinium betaine, and the like.

Specifically, among the anionic monomers, unsaturated carboxylic acid monomers include acrylic acid, methacrylic acid, crotonic acid, itaconic acid, maleic acid, fumaric acid,
Examples include citraconic acid and their anhydrides.

Examples of unsaturated sulfonic acid monomers include styrene sulfonic acid, 2-acrylamide-2-methylpropanesulfonisoquasido, 3-sulfopropyl(meth)acrylic acid ester, bis(3-sulfopropyl)-itaconine quasi There are sodoesters and their salts. or,
Others include sulfuric acid monoester of 2-hydroxyethyl (meth)acrylic acid and its salts.

Unsaturated phosphoric acid monomers include vinylphosphonic acid, vinylphosphate, acid phosphoxyethyl (meth)
Acrylate, 3-chloro-2-acid phosphoxypropyl (meth)acrylate, acid phosphoxypropyl (meth)acrylate, bis(methacryloxyethyl) phosphate, diphenyl-2-methacryloyloxyethyl phosphate, diphenyl-2 -acryloyloxyethyl phosphate, dibutyl-2-methacryloyloxyethyl phosphate, dibutyl-2-acryloyloxyethyl phosphate, dioctyl-2-(meth)acryloyloxyethyl phosphate, and the like.

Examples of cationic monomers include unsaturated tertiary amine-containing monomers and unsaturated ammonium salt-containing monomers. Specifically, vinylpyridine, 2-methyl-5-vinylpyridine, 2-ethyl-5- Monovinylpyridine Ll'T such as vinylpyridine; Styrenes having a dialkylamino group such as N,N-dimethylaminostyrene, N,N-dimethylaminomethylstyrene iN,N-dimethylaminoethyl methacrylate, N,N-dimethylamino Ethyl acrylate, N,N-diethylaminoethyl methacrylate, N,N-diethylaminoethyl acrylate, N,N-dimethylaminopropyl methacrylate, N,N-dimethylaminopropyl acrylate,
N,N-diethylaminopropyl methacrylate, N,
Esters having a dialkylamino group of acrylic acid or methacrylic acid such as N-diethylaminopropyl acrylate; vinyl ethers having a dialkylamino group such as 2-dimethylaminoethyl vinyl ether lff
1N-(N'.

N“-dimethylaminoethyl)methacrylamide, N-
(N', N'-dimethylaminoethyl) acrylamide, N-(N', N'-diethylaminoethyl) methacrylamide, N-(N', N''-diethylaminoethyl) acrylamide, N-(N', N' -dimethylaminopropyl)methacrylamide, N-(N',
N'-dimethylaminopropyl)acrylamide, N-
(N'.

N'-diethylaminopropyl) methacrylamide, N
- Acrylamides or methacrylamides having a dialkylamino group such as (N', N''-diethylaminopropyl)acrylamide, or alkyl halides (alkyl group has 1 to 18 carbon atoms, halogen is chlorine, bromine, iodine), Benzyl halides, such as benzyl chloride or bromide, alkyl- or tri-sulfonic acids, such as methanesulfonic acid,
Those quaternized with known quaternizing agents such as alkyl esters of benzenesulfonic acid or toluenesulfonic acid (alkyl group having 1 to 18 carbon atoms) and dialkyl sulfate (alkyl group having 1 to 4 carbon atoms), etc. Can be mentioned.

In the present invention, the blending ratio of the monomer having a polymerizable double bond having a salt-forming group and the monomer having a polymerizable double bond that can be copolymerized with the monomer is 0.5 to 15.0.
% by weight, the latter being 99.5-85.0% by weight. The amount of monomers with weightable double bonds with salt-forming groups is 0
．． If it is less than 5% by weight, a uniform and stable self-dispersing aqueous resin dispersion with a small particle size cannot be obtained. On the other hand, if the weight exceeds 15 weight, a resin having practical water resistance cannot be obtained.

Examples of monomers having a polymerizable double bond that can be copolymerized with the monomer having a polymerizable double bond having a salt-forming group used in the present invention include methyl acrylate, ethyl acrylate, and acrylic acid. Acrylics such as isopropyl, n-butyl acrylate, isobutyl acrylate, n-amyl acrylate, isoamyl acrylate, n-hexyl acrylate, 2-ethylhexyl acrylate, n-octyl acrylate, decyl acrylate, and dodecyl acrylate. Acid esters, methyl methacrylate, ethyl methacrylate, propyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, n-amyl methacrylate, n-hexyl methacrylate, n-octyl methacrylate, 2-ethylhexyl methacrylate, decyl methacrylate,
methacrylic acid esters such as dodecyl methacrylate,
Styrene, vinyltoluene, 2-methylstyrene, 1-
Styrenic monomers such as butylstyrene and chlorostyrene; hydroxy group-containing monomers such as hydroxyethyl acrylate and hydroxypropyl acrylate; ) Epoxy group-containing monomers such as acrylic threads, glycidyl acrylate, glycidyl methacrylate, (meth)acrylic acid esters bonded with fluorinated alkyl groups represented by the following formula %, etc., acrylonitrile, etc. It can be selected from one or more types.

Examples of alcoholic solvents used in the present invention include methanol, ethanol, n-propanol, isopropanol, n-butanol, secondary butanol, tertiary butanol, isobutanol, diacetone alcohol,
Examples include 2-iminoethanol, and isopropanol is preferred.

Examples of ketone solvents include acetone, methyl ethyl ketone, diethyl ketone, dipropyl ketone, methyl isobutyl ketone, and methyl isopropyl ketone.1. Preferably it is methyl ethyl ketone.

These may be used alone or in a mixture of two or more. If necessary, a high boiling point hydrophilic organic solvent may be used in combination.

Examples of high-boiling hydrophilic organic solvents include phenoxyethanol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol 7-ethyl ether, diethylene glycol diethyl ether, diethylene glycol monobutyl ether, 3-methyl-3 -Methoxybutanol, etc.

As the initiator used here, a known radical initiator is used. For example, hydroperoxides represented by t-butyl hydroperoxide, dialkyl peroxides represented by di-t-butyl peroxide, diacyl peroxides represented by acetyl peroxide, and t-butyl peracetate. filtrate esters, ketone peroxides such as methyl ethyl ketone peroxide, and 2,2'-azobis(isobutyronitrile), 2,2''-azobis(2
, 4-dimethylvaleronitrile), 1,1°-azobis(cyclohexane-1-carbonitrile), and the like.

In order to obtain a uniform and stable self-dispersed aqueous resin dispersion using each of the above raw materials, for example, a reactor equipped with a stirrer, a reflux condenser, a dropping funnel, a thermometer, and a nitrogen gas introduction tube is prepared. , 0.5 to 15.0% by weight of a monomer having a polymerizable double bond having a salt-forming group, and 99.5 to 85% of a monomer having a polymerizable double bond that can be copolymerized therewith. 0% by weight, and the radical initiator is 0.05 to 0.05% based on the total
Obtaining a homogeneous copolymer using 0.5% by weight and optionally a chain transfer agent and one or more alcoholic and ketone solvents in a nitrogen gas stream from 50°C to refluxing the solvent; Next, a neutralizing agent is added to this copolymer as necessary to ionize the salt-forming groups (not necessary if the salt-forming groups are already ionized), then water is added, and then an alcohol-based and/or ketone-based solvent is added to the copolymer. It is obtained by distilling off and inverting the phase to an aqueous system.

The monomer having a polymerizable double bond having a salt-forming group is preferably in the range of 0.5 to 15.0% by weight, and 0.5% by weight.
If it is less than that, a stable self-dispersing aqueous vinyl resin cannot be obtained. On the other hand, if it exceeds 15% by weight, the water resistance of the coating film will be poor.

As a method for obtaining a homogeneous copolymer, it is preferable to control the dropwise addition rate of the hexamer so as to keep the monomer ratio in the reaction system as constant as possible. Specifically, all or a portion of the highly copolymerizable monomer with a slow reaction rate is initially charged into the reactor, and a monomer with a fast reaction rate is dropped into the reactor, or, A monomer with a slow reaction rate and a portion of a monomer with a fast reaction rate are charged into a reactor, and the composition is kept as constant as possible, and the monomer with a fast reaction rate is added dropwise to match the consumption rate of the monomer with a fast reaction rate. etc., a homogeneous copolymer can be obtained.

To obtain such a homogeneous copolymer, among the polymerization methods such as emulsion polymerization method, suspension polymerization method, precipitation polymerization method, bulk polymerization method, and solution polymerization method, precipitation polymerization method, bulk polymerization method, and solution polymerization method are used. It is particularly preferable to carry out solution polymerization in an alcohol-based or ketone-based solution that is effective as a phase inversion solvent, and is industrially advantageous.

The number average molecular weight of the self-dispersed aqueous vinyl resin obtained in the present invention is preferably 10,000 to 500,000. The reason for this is that if it is less than io or ooo, the physical properties of the coating film will be poor, and if it exceeds 500,000, the viscosity will become high, causing problems in the phase inversion step, etc., and a stable self-dispersed water-based vinyl resin with a gfQ degree cannot be obtained.

The self-dispersed aqueous vinyl resin obtained in the present invention has almost complete transparency in transmitted light, and exhibits Tyndall phenomenon characteristic of colloids when irradiated with laser light.

The particle size of the uniform and stable self-dispersed aqueous vinyl resin obtained in the present invention is preferably 0.001 to 0.1 μ, more preferably 0.001 to 0.06 μ.

The self-dispersed water-based vinyl resin obtained in the present invention can be used for textiles,
Non-woven fabric, paper, wood, leather, rubber, plastic, metal,
Glass, concrete, plaster, ceramic siding materials,
By impregnating it into ALC plates, etc., or applying it to their surfaces, you can obtain the effects of improving properties such as surface coating, adhesion, and texture improvement. )
It can be advantageously used in fields where industrial coating agents, civil engineering and construction, inks, paints, powder emulsions, and rubber latex and resin emulsions are generally applied.

Furthermore, since it is structurally a polymeric surfactant, it has a wide range of uses as a general surfactant in addition to being used as a binder. For example, it is used as a protective colloid for emulsion polymerization, a dispersant for coal and calcium carbonate, a flocculant, a binder, a surface modifier, and the like.

〔Example〕

Next, the present invention will be specifically explained with reference to Examples and Comparative 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.

Example 1 In a reactor equipped with a stirrer, reflux condenser, dropping funnel, thermometer, and nitrogen introduction tube, 500 parts of methyl ethyl ketone, 123.5 parts of methyl methacrylate, 293.7 parts of n-butyl acrylate, and 82.2 parts of acrylic acid were added. Charge 8 parts and remove dissolved oxygen by flowing nitrogen gas.

Meanwhile, 253 parts of methyl ethyl ketone from which dissolved oxygen has been removed, 253 parts of methyl methacrylate, and 0.5 part of azobisisobutyronitrile are charged into the dropping funnel.

After heating the reactor to 83±3° C., a solution of 1.0 part of azobisisobutyronitrile dissolved in 10 parts of methyl ethyl ketone is added, and the monomer is added dropwise from the dropping funnel in accordance with the consumption rate of methyl methacrylate.

After dropping the monomer, add 1 azobisisobutyronitrile
．． A solution of 5 parts of azobisisobutyronitrile dissolved in 10 parts of methyl ethyl ketone was added, and the mixture was further aged for 2 hours.A solution of 0.7 parts of azobisisobutyronitrile dissolved in 10 parts of methyl ethyl ketone was added again, and the reaction was continued for 4 hours to form a homogeneous copolymer. A polymer was obtained.

Next, 120 parts of triethylamine was added to this copolymer to neutralize it, and then 2,700 parts of ion-exchanged water were added, and the methyl ethyl ketone was distilled off under reduced pressure, preferably below 50°C, to form a transparent self-dispersed water-based vinyl resin. I got it.

Example-2 In the same manner as in Example-1, 500 parts of methyl ethyl ketone, 131.4 parts of methyl methacrylate, 338.3 parts of n-butyl acrylate, and 30.4 parts of acrylic acid were charged, and dissolved oxygen was removed by flowing nitrogen gas. do.

On the other hand, 281.2 parts of methyl ethyl ketone from which dissolved oxygen has been removed, 281.2 parts of methyl methacrylate, and 0.56 parts of azobisisobutyronitrile are charged into the dropping funnel.

After heating the reactor to 83±3° C., a solution of 1.0 part of azobisisobutyronitrile dissolved in 10 parts of methyl ethyl ketone is added, and the monomer is added dropwise from the dropping funnel in accordance with the consumption rate of methyl methacrylate.

After dropping the monomer, add 1 azobisisobutyronitrile
．． 5 parts dissolved in 10 parts of methyl ethyl ketone was added, and after further aging for 2 hours, 0.
A solution of 7 parts dissolved in 10 parts of methyl ethyl ketone was added, and the reaction was continued for 4 hours to obtain a homogeneous copolymer.

Next, 43 parts of triethylamine was added to this copolymer to neutralize it, and then 2,550 parts of ion-exchanged water was added to obtain a transparent self-dispersed aqueous vinyl resin using the same formulation as in Example-1.

Example-3 400 parts of isopropyl alcohol as in Example-1,
153.8 parts of methyl methacrylate, 340.8 parts of n-butyl acrylate, and 5.4 parts of acrylic acid were charged, and nitrogen gas was introduced to remove dissolved oxygen.

On the other hand, 269 parts of isopropyl alcohol from which dissolved oxygen has been removed, 269 parts of methyl methacrylate, and 5.4 parts of azobisisobutyronitrile are charged into the dropping funnel.

After heating the reactor to 83±3° C., 1.0 part of azobisisobutyronitrile dissolved in 100 parts of isopropyl alcohol is added, and the monomer is added dropwise from the dropping funnel in accordance with the consumption rate of methyl methacrylate. After monomer dropwise addition, a slurry of 1.5 parts of azobisisobutyronitrile mixed with 10 parts of isopropyl alcohol was added, and after further reaction for 2 hours, 0.7 parts of azobisisobutyronitrile was mixed with 10 parts of isopropyl alcohol again. A slurry was added thereto, and the reaction was continued for 4 hours to obtain a homogeneous copolymer.

Next, 8 parts of triethylamine was added to this copolymer to neutralize it, and then 2,400 parts of ion-exchanged water was added to obtain a transparent 4-self-dispersed aqueous vinyl resin using the same formulation as in Example-1.

Example-4 Same as Example-1, 500 parts of methyl ethyl ketone, 166.7 parts of methyl methacrylate, 280 parts of n-butyl acrylate, 53 parts of dimethylaminoethyl methacrylate.
．． 3 parts were charged and nitrogen gas was introduced to remove dissolved oxygen.

Meanwhile, 166.7 parts of methyl ethyl ketone from which dissolved oxygen has been removed, 166.7 parts of methyl methacrylate, and 0.33 parts of azobisisobutyronitrile are charged into the dropping funnel.

After heating the reactor to 83±3° C., a solution of 1.0 part of azobisisobutyronitrile dissolved in 10 parts of methyl ethyl ketone is added, and the monomer is added dropwise from the dropping funnel in accordance with the consumption rate of methyl methacrylate. After monomer dropwise addition, 1.3 parts of azobisisobutyronitrile dissolved in 710 parts of methyl ethyl ketone was added, and after further aging for 2 hours, a solution of 0.7 parts of azobisisobutyronitrile dissolved in 10 parts of methyl ethyl ketone was added. After addition, the reaction was continued for 4 hours to obtain a homogeneous copolymer.

Next, 35 parts of 70% glycolic acid was added to this copolymer to neutralize it, and then 2140 parts of ion-exchanged water was added to Example-1.
A transparent self-dispersed water-based vinyl resin was obtained using the same formulation as above.

Comparative Example 1 In the same manner as in Example 1, 500 parts of methyl ethyl ketone, 131.6 parts of methyl methacrylate, 236.8 parts of n-butyl acrylate, and 131.6 parts of acrylic acid were charged, and dissolved oxygen was removed by flowing nitrogen gas.

- 157.9 parts of methyl ethyl ketone from which dissolved oxygen has been removed, 157.9 parts of methyl methacrylate, and 0.4 parts of azobisisobutyronitrile are charged into a funnel under force.

After heating the reactor to 83±3° C., a solution of 1.0 part of azobisisobutyronitrile dissolved in 10 parts of methyl ethyl ketone is added, and the monomer is added dropwise from the dropping funnel in accordance with the consumption rate of methyl methacrylate. After monomer dropwise addition, 1.4 parts of azobisisobutyronitrile dissolved in 10 parts of methyl ethyl ketone was added, and after further aging for 2 hours, a solution of 0.7 parts of azobisisobutyronitrile dissolved in 10 parts of methyl ethyl ketone was added. After addition, the reaction was continued for 4 hours to obtain a homogeneous copolymer.

Next, 185 parts of triethylamine was added to this copolymer to neutralize it, and then 2,600 parts of ion-exchanged water was added to Example-1.
A transparent self-dispersed water-based vinyl resin was obtained using the same formulation as above.

Comparative Example 2 In the same manner as in Example 1, 500 parts of methyl ethyl ketone, 153.8 parts of methyl methacrylate, 340.8 parts of n-butyl acrylate, and 2.3 parts of acrylic acid were charged, and dissolved oxygen was removed by flowing nitrogen gas.

Meanwhile, 269 parts of methyl ethyl ketone from which dissolved oxygen has been removed, 269 parts of methyl methacrylate, and 0.54 parts of azobisisobutyronitrile are charged into a dropping funnel.

After heating the reactor to 83±3° C., a solution of 1.0 part of azobisisobutyronitrile dissolved in 710 parts of methyl ethyl ketone is added, and the monomer is added dropwise from the dropping funnel in accordance with the consumption rate of methyl methacrylate. After monomer dropwise addition, 1.5 parts of azobisisobutyronitrile dissolved in 10 parts of methyl ethyl ketone was added, and after further aging for 2 hours, a solution of 0.7 parts of azobisisobutyronitrile dissolved in 10 parts of methyl ethyl ketone was added. After addition, the reaction was continued for 4 hours to obtain a homogeneous copolymer.

Next, 3.4 parts of triethylamine was added to this copolymer to neutralize it, and then 2,400 parts of ion-exchanged water was added to Example-1.
A milky white self-dispersed aqueous vinyl resin was obtained using the same formulation.

The physical properties of the aqueous resins obtained in Examples 1 to 4 and Comparative Examples 1 to 2 were evaluated by the method shown below.

The results are shown in Table 1.

Obtainable and negative wide (1) Particle size C0IJLTERELECTRONIC3INC made C
Measured with 0LILT store MODEL, N4.

(2) Properties Describes the properties observed with the naked eye of water-based resins.

(3) High-temperature storage stability After the aqueous resin was left in a constant temperature chamber kept at a temperature of 40° C.±2° C. for one month, the external appearance was observed and classified into three grades: ◯, △, and ×.

O: No change at all 61 Stable for more than one week at 40°C, thickening or precipitation occurring within one month at 40°C.

×: Separation or a large amount of precipitate was generated within one week at 40°C.

(4) Dilute with distilled water so that the dilution stability resin content is 1%, and
Dragon, put it in a glass tube with a length of 30 cm and seal it tightly, and observed the condition after 24 hours, ○, △.

It was divided into three stages: ×.

O: Uniform with no separation or sedimentation △: A small amount of sedimentation is observed, but within practical level After adding 100 g of resin and stirring for 5 minutes under a load of 10 kg, the aqueous resin was filtered through a 100-mesh wire gauze, the aggregate was dried at 105° C. for 3 hours, the weight was determined, and the mechanical stability was determined using the following formula.

(6) After coating the aqueous resin composition on a glossy glass plate and drying it, the Suga test m
The shiny needle of @ was measured. Those with better gloss than the uncoated glass plate were marked with a circle, and those with poorer gloss were marked with an x.

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

The larger the number, the better the gloss.

(7) 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 one day, and changes in state were observed.

O: Swelling rate of the coating film is within 5% and there is no change such as whitening. Δ: Swelling rate of the coating film is 5% to 10% and there is no change such as whitening. ×: Swelling rate of the coating film is that there is no change such as whitening. Items with large surface changes such as whitening at 10% or more (8) Permeability (preparation of specimen) Onoda ordinary Portland cement, standard sand (produced in Toyoura, Yamaguchi Prefecture) and water in a ratio of 1:1:0.5 part by weight. The mixture was mixed with a universal mixer (Model 50M-03-R: manufactured by Inn Eiyo Seisakusho) at low speed for 1 minute and high speed for 2 minutes, packed into a 4X4X16 inch mold, and demolded after 2 days. It was dried at ℃ for 3 hours, cooled after drying, and stored in a desiccator.

(Test method) 100 mZ of 15% aqueous solution of aqueous resin composition was placed in a diameter of approximately 6 cm.
m beaker, and add 60 m of the above mortar specimen to it.
The wet emulsion was soaked for 60 minutes, taken out after 60 minutes, cut parallel to the surface of the 4X4C11 sheet at 1.5 cm from the bottom, and dried at 50°C for 3 hours.The penetration depth of the wet emulsion was measured using the following method.

(Measurement method) The cut surface was measured using an X-ray microanalyzer (JCXA-733
Measure the distribution of the carbon that is most abundant in the resin using a mold (manufactured by Japan Electronics Technical Service ■), and mark the part with a large amount of carbon as having penetrated, and indicate the carbon distribution. Items that are not recognized are marked with an X, indicating that they have not penetrated.

(9) Adhesion Using the specimen obtained in section (8), 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, cut the 'l x 'l cm into 4111 intervals to make a total of 25 base lines and cut the ones with 25 to 20 adhered to ○.
Those with 20 to 10 adherents are indicated with a △ mark, and those with 10 or less are indicated with an X mark.

Claims (1)

[Claims] 1. 0.5 to 15.0% by weight of a monomer having a polymerizable double bond having a salt-forming group, and 99.5 to 85% of a monomer having a polymerizable double bond that can be copolymerized therewith. .0% by weight is subjected to solution polymerization in an alcohol and/or ketone solvent to obtain a homogeneous copolymer, and then a neutralizing agent is added to this copolymer as necessary to ionize the salt-forming groups. A method for producing a stable self-dispersing aqueous vinyl resin, which comprises: adding water, distilling off the alcoholic and/or ketone solvent and inverting the phase to an aqueous system.