JPH0696603B2 - Method for producing self-dispersing aqueous vinyl resin - Google Patents

Description

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

[Prior Art and Problems] Conventionally, most of the aqueous resin dispersions are produced by an emulsion polymerization method, and several percent of an emulsifier is used to keep the polymerization reaction and the stability of the produced aqueous resin dispersions. .

Usually, if an attempt is made to obtain an aqueous resin dispersion having a small particle diameter with this formulation, a relatively large amount of emulsifier is required.

However, the emulsifier used shows harmful side effects such as reduction in water resistance, adhesion, adhesiveness, weather resistance, mechanical strength and the like of the film after drying.

The soap fuller emulsion polymerization method has been attracting attention as a method for improving these problems. The details of such a polymerization method are described in many documents, for example, “New Development and Problems of Synthetic Polymer Latex” by Yamazaki et al. [Chemical Industry Material (Tokyo Tech News) vol 13 (4) P3 (1978). ], The aqueous resin dispersion obtained by soap-free emulsion polymerization is not practical because it has a problem that the storage stability and mechanical stability are extremely poor.

Further, for example, in Japanese Patent Publication No. Sho 49-36942, a monomer interpolymer of ammonia-consisting of an aqueous colloidal dispersion of ground particles, said interpolymer is 10,000-150,
A group having a weight average molecular weight of 000 and at least 20% by weight of methyl methacrylate, an alkyl acrylate having 4 to 16 carbon atoms and an alkyl methacrylate having 6 to 16 carbon atoms. 0 to 75% by weight of the ester selected from 0 to 40% by weight and 1 to 8% by weight of the ethylenically unsaturated copolymerizable monomer selected from the group consisting of styrene, vinyl acetate and vinyl chloride. Acrylic acid,
1 to 8% by weight of methacrylic acid, 4 to 8% by weight of maleic acid and 4 to 8% by weight of an acid selected from the group consisting of itaconic acid, at least about 30 mol% of which is ammonium salt. Although it is disclosed that the morphology and at least about 95% of the number of particles have a size in the range of 0.01 to 0.1μ in diameter, the colloidal dispersions of this invention are alkali swollen carboxylic acid modified. The method of dividing the particles of acrylic polymer latex under high temperature under vigorous mechanical shearing is complicated operation, and
There is a problem that an aqueous resin dispersion having a small particle size can be obtained only under extremely limited conditions such as the amount of carboxylic acid monomer in the copolymer and the degree of alkali neutralization. It is difficult to obtain a uniform particle size distribution, and there are problems with the stability of the dispersion, such as the precipitation of coarse particles.

Further, for example, in JP-A-58-136647, it is composed 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. Weight average molecular weight 10
After synthesizing the copolymer of ⁴ to 10 ^6, the unreacted substance or the unreacted substance and the medium are removed to prepare a solid substance substantially free of the unreacted substance and the medium. water,
A method of obtaining a translucent dispersion by adding an aqueous alkali solution such as caustic soda and performing a neutralization treatment at a temperature of 40 to 95 ° C., and then gradually dropping water with stirring is disclosed. Not only is it difficult to obtain a uniform particle size distribution, but there are problems with the stability of the dispersion, such as the precipitation of coarse particles.

Especially polymers with high glass transition temperatures (eg styrene,
This tendency is remarkable for methyl methacrylate and the like.

[Means for solving problems]

The inventors of the present invention have made extensive studies on a method for producing a uniform and stable self-dispersible aqueous vinyl resin having a small particle size, which has solved the above problems, and as a result of earnest research, a uniform and stable particle size characterized by a phase inversion method. The present invention succeeded in obtaining a self-dispersion type aqueous vinyl resin having a small size.

That is, the present invention is a monomer having a polymerizable double bond having a salt-forming group 0.5 to 15.0% by weight, and a monomer having a polymerizable double bond copolymerizable therewith 99.5 to 85.0% by weight
And are subjected to solution polymerization in an alcohol-based and / or ketone-based solvent to obtain a homogenous copolymer, and then, to this copolymer,
A stable self-dispersing type characterized by adding a neutralizing agent as necessary to ionize a salt-forming group, subsequently adding water, and then distilling off an alcohol-based and / or ketone-based solvent to invert the phase to an aqueous system. It relates to a method for producing an aqueous vinyl resin.

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

Specifically, as the unsaturated carboxylic acid monomer among the anionic monomers, acrylic acid, methacrylic acid, crotonic acid, itaconic acid, maleic acid, fumaric acid, citraconic acid, etc., or their anhydrides, etc. is there.

Unsaturated sulfonic acid monomers include styrene sulfonic acid, 2-acrylamido-2-methylpropane sulphonic acid, 3-sulphopropyl (meth) acryl acid ester, bis- (3-sulphopropyl) -itaconic acid ester, etc. And its salt. Also other 2-
There are sulfuric acid monoesters of hydroxyethyl (meth) acrylic acid and salts thereof.

Unsaturated phosphoric acid monomers include vinylphosphonic acid, vinylphosphate, acid phosphoxyethyl (meth)
Acrylate, 3-chloro-2-acid phosphoroxypropyl (meth) acrylate, acid phosphoroxypropyl (meth) acrylate, bis (methacryloxyethyl) phosphate, diphenyl-2-methacryloyloxyethyl phosphate, diphenyl-2-acryle Examples thereof include loyloxyethyl phosphate, dibutyl-2-methacryloyloxyethyl phosphate, dibutyl-2-acryloyloxyethyl phosphate, dioctyl-2- (meth) acryloyloxyethyl phosphate.

Examples of the cationic monomer include unsaturated tertiary amine-containing monomers and unsaturated ammonium salt-containing monomers, and specifically, vinyl pyridine, 2-methyl-5-vinyl pyridine, 2-ethyl-5- Monovinylpyridines such as vinylpyridine; Styrenes having a dialkylamino group such as N, N-dimethylaminostyrene and N, N-dimethylaminomethylstyrene; N, N-dimethylaminoethyl methacrylate, N, N-dimethylaminoethyl 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; N-
(N ', N'-dimethylaminoethyl) methacrylamide, N- (N', N'-dimethylaminoethyl) acrylamide, N- (N ', N'-diethylaminoethyl) methacrylamide, N- (N', N'-diethylaminoethyl) acrylamide, N- (N ', N'-dimethylaminopropyl)
Dialkylamino such as methacrylamide, N- (N ', N'-dimethylaminopropyl) acrylamide, N- (N', N'-diethylaminopropyl) methacrylamide, N- (N ', N'-diethylaminopropyl) acrylamide Acrylamides or methacrylamides having a group, or alkyl halides thereof (alkyl group having 1 to 18 carbon atoms, chlorine, bromine, iodine as halogen), benzyl halides such as benzyl chloride or benzyl bromide, alkyl or aryl sulfones Known quaternizing agents such as acids, for example, alkyl esters of methanesulfonic acid, benzenesulfonic acid or toluenesulfonic acid (alkyl groups having 1 to 18 carbon atoms), and dialkyl sulfates (alkyl groups having 1 to 4 carbon atoms). Examples include quaternized ones.

In the present invention, the compounding ratio of the monomer having a polymerizable double bond having a salt-forming group and the monomer having a polymerizable double bond copolymerizable with the former is 0.5 to 15.0% by weight, the latter is 99.5-85.0% by weight. When the amount of the salt-forming group-containing monomer having a weightable double bond is less than 0.5% by weight, a uniform and stable self-dispersing aqueous resin dispersion having a small particle size cannot be obtained. On the other hand, if it exceeds 15% by weight, a practical resin having water resistance cannot be obtained.

Examples of the monomer having a polymerizable double bond copolymerizable 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. Isopropyl, n-butyl acrylate, isobutyl acrylate, n-amyl acrylate, isoamyl acrylate, n-hexyl acrylate, acrylic acid
Acrylic esters such as 2-ethylhexyl, n-octyl acrylate, decyl acrylate, dodecyl acrylate, methyl methacrylate, ethyl methacrylate, propyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, n-methacrylate Methacrylic acid esters such as amyl, n-hexyl methacrylate, n-octyl methacrylate, 2-ethylhexyl methacrylate, decyl methacrylate, dodecyl methacrylate, styrene, vinyltoluene, 2-methylstyrene, 1-butylstyrene, chloro Styrene-based monomers such as styrene, hydroxy group-containing monomers such as hydroxyethyl acrylate and hydroxypropyl acrylate, N-substituted (meth) acryl such as N-methylol (meth) acrylamide, N-butoxymethyl (meth) acrylamide Monomer, glycidyl acrylate, epoxy group-containing monomers such as glycidyl methacrylate, and, the following equation _{CH 2 = CHCOOC 2 H 4 C} 6 F 13, CH 2 = CHCOOC 2 H 4 C 8 F 17, CH 2 = CHCOOC 2 _{H 4 C 10 F 21, CH} 2 = CHCOOC 2 H 4 C 12 F 25, CH 2 = C (CH 3) COOC 2 H 4 C 6 F 13, CH 2 = C (CH 3) COOC 2 H 4 C
₈ F ₁₇ , CH ₂ = C (CH ₃ ) COOC ₂ H ₄ C ₁₀ F ₂₁ , CH ₂ = C (CH ₃ ) COOC ₂ H ₄ C ₁₂ F ₂₅ , CH ₂ = CHCOOC ₂ H ₄ CF _{2 6} H, CH ₂ = CHCOOC ₂ H ₄ CF _{2 8} H, CH ₂ = C (CH ₃ ) COOC ₂ H ₄ CF _{2 6} H, CH ₂ = C (CH ₃ ) COOC ₂ H ₄ CF _{2 8} H, etc. It can be selected from one or more of (meth) acrylic acid ester having a fluorinated alkyl group bonded thereto and acrylonitrile.

Examples of the alcohol solvent used in the present invention include methanol, ethanol, n-propanol, isopropanol, n-butanol, secondary butanol, tertiary butanol, isobutanol, diacetone alcohol, 2-iminoethanol and the like. And is preferably isopropanol.

Examples of the ketone solvent include acetone, methyl ethyl ketone, diethyl ketone, dipropyl ketone, methyl isobutyl ketone, methyl isopropyl ketone, and the like, and methyl ethyl ketone is preferable.

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

As the high boiling hydrophilic organic solvent, phenoxyethanol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol diethyl ether, diethylene glycol monobutyl ether, 3-methyl-3- Methoxybutanol and the like.

As the initiator used here, a known radical initiator is used. For example, hydroperoxides typified by t-butyl hydroperoxide, dialkyl peroxides typified by dit-butyl peroxide, diacyl peroxides typified by acetyl peroxide, and t-butyl peracetate. Representative peroxyesters, ketone peroxides typified by methyl ethyl ketone peroxide, and 2,2'-azobis (isobutyronitrile), 2,2'-azobis (2,4-dimethylvaleronitrile), 1 , 1'-Azobis (cyclohexane-1
-Carbonitrile) and other azo polymerization initiators.

In order to obtain a uniform and stable self-dispersing aqueous resin dispersion using each of the above raw materials, for example, a stirrer, a reflux condenser, a dropping funnel, a thermometer, and a reactor equipped with a nitrogen gas introduction pipe are prepared. And 0.5 to 15.0% by weight of a monomer having a polymerizable double bond having a salt-forming group, 99.5 to 85.0% by weight of a monomer having a polymerizable double bond capable of being copolymerized therewith, and radical initiation. The agent is used in an amount of 0.05 to 0.5% by weight with respect to the total amount of monomers and, if necessary, a chain transfer agent, and one or more alcohol-based and ketone-based solvents in a nitrogen gas stream.
℃ ~ under a solvent reflux to obtain a homogeneous copolymer, then add a neutralizing agent, etc. to this copolymer if necessary to ionize the salt-forming group (not necessary if already ionized), It is obtained by adding water and adding water, and then distilling off the alcohol-based and / or ketone-based solvent to invert the phase into an aqueous system.

The monomer having a polymerizable double bond having a salt-forming group is
A preferable range is 0.5 to 15.0% by weight, and if it is less than 0.5% by weight, 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 becomes poor.

As a method for obtaining a homogenous copolymer, it is preferable to control the dropping rate of the monomer so as to keep the monomer ratio in the reaction system as constant as possible. Specifically, all or a part of the monomer having a slow copolymerization property and a slow reaction rate is initially charged into the reactor, and a monomer having a high reaction rate is dropped into the reactor, or Charge a slow monomer and a part of the fast-reacting monomer into the reactor, keep the composition as constant as possible and adjust the consumption rate of the fast-reacting monomer to a homogeneous rate by dropping the fast-reacting monomer. A copolymer is obtained.

In order to obtain such a homogeneous copolymer, among the polymerization formulations such as emulsion polymerization method, suspension polymerization method, precipitation polymerization method, bulk polymerization method, solution polymerization method, precipitation polymerization method, bulk polymerization method, solution polymerization method, etc. Is particularly preferable, and solution polymerization is particularly preferable in an alcohol-based or ketone-based solution effective as a phase inversion solvent, and industrially advantageous.

The number average molecular weight of the self-dispersible aqueous vinyl resin obtained in the present invention is preferably 10,000 to 500,000. The reason for this is 10,00
If it is less than 0, the physical properties of the coating film are inferior, and if it exceeds 500,000, the viscosity becomes high and it interferes with the phase inversion process and the like, and a stable self-dispersing aqueous vinyl resin at high concentration cannot be obtained.

The self-dispersible water-based vinyl resin obtained in the present invention has almost perfect transparency for transmitted light, and has a Tyndall phenomenon peculiar to colloid when irradiated with laser light.

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

The self-dispersible aqueous vinyl resin obtained in the present invention is a woven fabric,
Non-woven fabric, paper, wood, leather, rubber, plastic, metal,
Glass, concrete, plaster, ceramic siding material,
ALC plate, etc. can be impregnated or coated on the surface to obtain properties such as surface coating, adhesion and texture improvement, as well as filming liquid for cathode ray tubes, bar code label (POS label). ) Coating agents, civil engineering and construction related materials, inks, paints, powder emulsions, and rubber latex and resin emulsions can be advantageously used in the fields to which they are generally applied.

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

〔Example〕

Next, the present invention will be specifically described with reference to Examples and Comparative Examples, but it goes without saying that the present invention is not limited thereto.
All parts and% in the examples are on a weight basis unless otherwise specified.

Example-1 Stirrer, reflux condenser, dropping funnel, thermometer, 500 parts of methyl ethyl ketone, 123.5 parts of methyl methacrylate, 293.7 parts of n-butyl acrylate in a reactor equipped with a nitrogen introducing tube.
And 82.8 parts of acrylic acid are charged and nitrogen gas is flowed to remove dissolved oxygen.

On the other hand, 253 parts of methyl ethyl ketone from which dissolved oxygen is 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 prepared by dissolving 1.0 part of azobisisobutyronitrile in 10 parts of methyl ethyl ketone is added, and a monomer is added dropwise from a dropping funnel according to the consumption rate of methyl methacrylate.

Azobisisobutyronitrile 1.
Add 5 parts dissolved in 10 parts methyl ethyl ketone,
Aged for another 2 hours, again azobisisobutyronitrile 0.7
One part dissolved in 10 parts of methyl ethyl ketone was added, and the reaction was continued again for 4 hours to obtain a homogeneous copolymer.

Next, 120 parts of triethylamine was added to the copolymer for neutralization, and subsequently 2700 parts of ion-exchanged water were added, and then methyl ethyl ketone was distilled off under reduced pressure, preferably at 50 ° C or lower, to give a transparent self-dispersing aqueous vinyl resin. Got

Example-2 Methyl ethyl ketone 500 parts, methyl methacrylate 131.4 parts, n-butyl acrylate 338.3 as in Example-1.
And 30.4 parts of acrylic acid are charged and nitrogen gas is flowed to remove dissolved oxygen.

On the other hand, 281.2 parts of methyl ethyl ketone from which dissolved oxygen is 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 prepared by dissolving 1.0 part of azobisisobutyronitrile in 10 parts of methyl ethyl ketone is added, and a monomer is added dropwise from a dropping funnel according to the consumption rate of methyl methacrylate.

Azobisisobutyronitrile 1.
Add 5 parts dissolved in 10 parts methyl ethyl ketone,
After further aging for 2 hours, 0.7 parts of azobisisobutyronitrile 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 for neutralization, and then 2550 parts of ion-exchanged water was added to obtain a transparent self-dispersible aqueous vinyl resin with the same formulation as in Example-1.

Example-3 As in Example-1, 400 parts of isopropyl alcohol, 153.8 parts of methyl methacrylate, 34 parts of n-butyl acrylate
0.8 parts and 5.4 parts of acrylic acid are charged and nitrogen gas is flowed 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., a solution prepared by dissolving 1.0 part of azobisisobutyronitrile in 100 parts of isopropyl alcohol is added, and a monomer is added dropwise from a dropping funnel according to the consumption rate of methyl methacrylate. After the monomer was added dropwise, 1.5 parts of azobisisobutyronitrile made into a slurry with 10 parts of isopropyl alcohol was added, and further 2 parts were added.
After the reaction for time, 0.7 part of azobisisobutyronitrile made into a slurry with 10 parts of isopropyl alcohol was added again, and the reaction was continued for 4 hours to obtain a homogeneous copolymer.

Next, 8 parts of triethylamine was added to the copolymer for neutralization, and subsequently 2400 parts of ion-exchanged water was added to obtain a transparent self-dispersible aqueous vinyl resin with the same formulation as in Example-1.

Example-4 As in Example-1, methyl ethyl ketone 500 parts, methyl methacrylate 166.7 parts, n-butyl acrylate 280 parts,
Dissolve oxygen by charging 53.3 parts of dimethylaminoethyl methacrylate and flowing nitrogen gas.

On the other hand, 166.7 parts of methyl ethyl ketone from which dissolved oxygen is removed, 166.7 parts of methyl methacrylate and 0.33 part of azobisisobutyronitrile are charged into the dropping funnel.

After heating the reactor to 83 ± 3 ° C., a solution prepared by dissolving 1.0 part of azobisisobutyronitrile in 10 parts of methyl ethyl ketone is added, and a monomer is added dropwise from a dropping funnel according to the consumption rate of methyl methacrylate. After completing the monomer addition, 1.3 parts of azobisisobutyronitrile was added to methyl ethyl ketone 1
What was dissolved in 0 part was added, and after aging for 2 hours, 0.7 part of azobisisobutyronitrile dissolved in 10 parts of methyl ethyl ketone was added, and the reaction was continued for 4 hours to obtain a homogeneous copolymer.

Next, 35 parts of 70% glycolic acid was added to the copolymer for neutralization, and then 2140 parts of ion-exchanged water was added to obtain a transparent self-dispersing aqueous vinyl resin with the same formulation as in Example-1.

Comparative Example-1 Methyl ethyl ketone 500 parts, methyl methacrylate 131.6 parts, n-butyl acrylate 236.8 in the same manner as in Example-1.
And 131.6 parts of acrylic acid are charged and nitrogen gas is flowed to remove dissolved oxygen.

Meanwhile, a dropping funnel is charged with 157.9 parts of methyl ethyl ketone from which dissolved oxygen is removed, 157.9 parts of methyl methacrylate and 0.4 part of azobisisobutyronitrile.

After heating the reactor to 83 ± 3 ° C., a solution prepared by dissolving 1.0 part of azobisisobutyronitrile in 10 parts of methyl ethyl ketone is added, and a monomer is added dropwise from a dropping funnel according to the consumption rate of methyl methacrylate. After completion of dropping the monomer, add 1.4 parts of azobisisobutyronitrile to 1 part of methyl ethyl ketone.
What was dissolved in 0 part was added, and after aging for 2 hours, 0.7 part of azobisisobutyronitrile dissolved in 10 parts of methyl ethyl ketone was added, and the reaction was continued for 4 hours to obtain a homogeneous copolymer.

Next, 185 parts of triethylamine was added to the copolymer for neutralization, and subsequently 2600 parts of ion-exchanged water was added to obtain a transparent self-dispersing aqueous vinyl resin with the same formulation as in Example-1.

Comparative Example-2 Methyl ethyl ketone 500 parts, methyl methacrylate 153.8 parts, n-butyl acrylate 340.8 as in Example-1.
And 2.3 parts of acrylic acid are charged and nitrogen gas is flowed to remove dissolved oxygen.

On the other hand, 269 parts of methyl ethyl ketone from which dissolved oxygen is removed, 269 parts of methyl methacrylate and 0.54 part of azobisisobutyronitrile are charged into the dropping funnel.

After heating the reactor to 83 ± 3 ° C., a solution prepared by dissolving 1.0 part of azobisisobutyronitrile in 10 parts of methyl ethyl ketone is added, and a monomer is added dropwise from a dropping funnel according to the consumption rate of methyl methacrylate. After completion of dropping the monomers, 1.5 parts of azobisisobutyronitrile was added to 1 part of methyl ethyl ketone.
What was dissolved in 0 part was added, and after aging for 2 hours, 0.7 part of azobisisobutyronitrile dissolved in 10 parts of methyl ethyl ketone was added, and the reaction was continued for 4 hours to obtain a homogeneous copolymer.

Next, 3.4 parts of triethylamine was added to the copolymer for neutralization, and then 2400 parts of ion-exchanged water was added to obtain a milky white self-dispersing aqueous vinyl resin in the same formulation as in Example-1.

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

The results are shown in Table 1.

Physical property evaluation method (1) Grain size Measured with COULTER MODEL N4 made by COULTER ELECTRONICS INC.

(2) Properties Describe the properties of the aqueous resin observed with the naked eye.

(3) Stability at high temperature The aqueous resin was left in a thermostat kept at a temperature of 40 ° C ± 2 ° C for 1 month, and then the appearance was observed and classified into three grades, ○, △, and ×.

◯: Completely unchanged Δ: Stable at 40 ° C. for 1 week or more, and increased viscosity or precipitate generated at 40 ° C. within 1 month.

X: Separation or large amount of precipitate generation within 40 minutes at 40 ° C.

(4) Dilution stability Dilute with distilled water so that the resin content is 1%, and then dilute it to 7 m inside diameter.
A glass tube with a length of 30 cm and a length of 30 cm was placed in the glass tube, and the tube was sealed. After 24 hours, the state was observed and classified into three stages of ○, △, and ×.

◯: Separation and sedimentation were not observed and uniform Δ: A small amount of sedimentation was observed, but within the practical level ×: Separation and a large amount of sediment were outside the practical level (5) Mechanical stability (Marlon tester) Aqueous to the Marlon tester receiver Add 100 g of resin, stir for 5 minutes with a load of 10 kg, filter the aqueous resin with a 100 mesh wire net,
The agglomerate is dried at 105 ° C. for 3 hours, the weight is obtained, and the mechanical stability is obtained by the following formula.

(6) Hikarizawa The aqueous resin composition was applied to a glass plate, dried, and then measured with a gloss meter of Suga Test Instruments Co., Ltd. Those having a gloss higher than that of the uncoated glass plate were marked with a circle, and those having a lower gloss were marked with a cross.

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

The larger the number, the better the gloss.

(7) Water resistance A film obtained by putting the aqueous resin composition in a Teflon-coated dish and drying it was immersed in water at 25 ° C for 1 day, and the state change was observed.

◯: No change such as whitening within a swelling rate of 5% of the coating film Δ: Swelling rate of the coating film of 5% to 10% with no change such as whitening or slightly whitening ×: Swelling rate of the coating film Large surface changes such as whitening at 10% or more (8) Permeability (Preparation of specimens) Onoda Ordinary Portland Cement, standard sand (produced by Toyoura, Yamaguchi Prefecture) and water in a ratio of 1: 1: 0.5 parts by weight Kneading with a universal mixing stirrer (5DM-03-R type: manufactured by Sanei Seisakusho Co., Ltd.) for 1 minute at low speed and 2 minutes at high speed, packed in a 4 × 4 × 16 cm mold and molded, and then removed after 2 days Molded, dried at 80 ° C. for 3 hours, cooled after drying, and stored in a desiccator.

(Test method) 100 ml of a 15% aqueous solution of the aqueous resin composition was placed in a beaker having a diameter of about 6 cm, and the mortar sample was immersed in the beaker for 60 minutes,
After 5 minutes, it was taken out, the lower 1.5 cm was cut parallel to the 4 × 4 cm plane, and dried at 50 ° C. for 3 hours. The depth of penetration of the emulsion was measured by the following method.

(Measurement method) The distribution of carbon contained in the resin was measured using an X-ray microanalyzer (JCXA-733, manufactured by JEOL Technical Service Co., Ltd.) on the cut surface, and a large amount of carbon was distributed. Those that have penetrated are marked with a circle, and those with no carbon distribution are marked with a cross.

(9) Adhesion property The test piece obtained in the item (8) was used in accordance with the cross-cut test described in JIS K5400-1979 "General test method for paints".

However, cut 2 x 2 cm into 4 mm intervals to make a total of 25 squares.
Items with 25 to 20 adhered are indicated by ○, those with 20 to 10 adhered are indicated by Δ, and those with 10 or less are indicated by ×.

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 85.0% by weight of a monomer having a polymerizable double bond copolymerizable therewith. Is subjected to solution polymerization in an alcohol-based and / or ketone-based solvent to obtain a homogeneous copolymer, and then a neutralizing agent is optionally added to this copolymer to ionize the salt-forming group, followed by water. The method for producing a stable self-dispersible water-based vinyl resin, characterized in that the alcohol-based and / or ketone-based solvent is distilled off and the phase is converted into an aqueous system after the addition of