JPH0255775A - Aqueous resin composition - Google Patents

Abstract

PURPOSE:To obtain the title composition excellent in solvent resistance, noncombustibility, adhesion to an inorganic substrate, etc., and useful for a coating material or an adhesive by mixing a methylolated cationic and/or nonionic water-soluble polymer with colloidal alumina. CONSTITUTION:This composition is prepared by adding colloidal alumina (e.g., alumina sol) to a methylolated cationic and/or nonionic water-soluble polymer obtained by copolymerizing, for example, an N-substituted methylolated alpha,beta- monoethylenically unsaturated carboxylic acid amide (e.g., N-methylolacrylamide) and/or its derivative with a mixture containing an amino or nitrogenous hetero- cyclic alpha,beta-monoethylenically unsaturated compound (e.g., N,N-dimethylaminoethyl methacrylate or vinylpyridine) and/or its derivative with, optionally, a polymerizable organic monomer (e.g., butyl methacrylate).

Description

Detailed Description of the Invention Object of the Invention (Industrial Field of Application) The present invention relates to a novel aqueous resin composition, particularly to an aqueous resin composition that provides a film with excellent water resistance, solvent resistance, and mechanical properties. .

(Prior Art) Recently, paints and the like have become water-based due to environmental pollution and health and safety concerns, and water-based paints are replacing conventional solvent-based paints. Under these circumstances, water-based paints are also required to have a high level of coating film performance, and among these, improving the durability of the coating film is becoming essential.

Conventionally, methods for obtaining aqueous resin compositions include emulsion polymerization, and a method of polymerizing a water-soluble resin in an aqueous medium.

A method of polymerizing a water-soluble resin in an organic medium and converting it into an aqueous medium has been used. However, the emulsion polymerization method uses emulsifiers and water-soluble polymer substances.

These effects result in decreased resistance and loss of flexibility, and since resin particles are dispersed in the coating solution, they tend to penetrate into the porous substrate and have poor film-forming properties. be. Also, water-soluble resin alone is water resistant.

It has poor solvent resistance and tends to lack resin flexibility.

In many cases, it was not put to practical use.

As a method to improve this point, we first proposed a method to improve this point.
proposed the invention described in Publication No. 39. This was sufficiently satisfactory in terms of water resistance. However, the most important thing for emuldigon paints is to significantly improve their durability so that they can obtain a film that is as hard as possible and has good film-forming properties.To this end, various proposals have been made to date. One method is to add a membrane-forming agent to a polymer emulsion with a relatively high glass transition point.This method requires careful consideration of the stability and volatility of the emulsion polymer, making it extremely difficult to select one. A method called multi-stage polymerization has also been proposed.This is an emulsion in which the core layer has a polymer composition with a high glass transition point and the shell layer has a polymer composition with a relatively low glass transition point.This method Although the performance is efficiently expressed in the region where the amount of emulsifier is relatively low,
When used as a paint, it is necessary to further add an emulsifier, a water-soluble resin, etc. to improve the stability of the paint, resulting in significantly poor water resistance and a decrease in physical properties. Furthermore.

Apart from such multi-stage polymerization, blending of a polymer emulsion with a high glass transition point and a polymer emulsion with a low glass transition point has been proposed, but the compatibility of the emulsions with each other is poor and the durability of the coating film is still a step away. .

In addition to being used as a dispersion stabilizer for these polymer emulsions, water-soluble resins can also be used alone, but although they have good film-forming properties, they have problems with durability. In order to improve these problems, a method of introducing a crosslinking group into a water-soluble resin has been proposed, but there is a problem with the storage stability of the paint.

As described above, paints using only organic polymers have limitations, and therefore blends or reactions of inorganic silica and organic polymers have been proposed. For example, by using colloidal silica as the inorganic silica and blending it with an organic polymer, it is durable and nonflammable.

Proposals have been made to improve blocking resistance. However, this method has the disadvantage that the mutual bond between the inorganic silica and the organic polymer is weak and the coating film deteriorates in the long term. Therefore, attempts have been made to use alkoxysilanes in combination as a method to improve these drawbacks. However, this method has the disadvantage that the long-term storage stability of the paint is poor. On the other hand, as a method to solve these drawbacks, a method has been proposed in which a heptamer having a polymerizable unsaturated double bond having an alkoxysilane group is used and emulsion polymerized with other monomers in one step. However, even in this method, there are many aggregates during emulsion polymerization, and workability is poor. Therefore, improvement cannot be achieved unless a large amount of emulsifier is used. Therefore, it has the disadvantage that water resistance and physical properties are significantly inferior.

Although it has been confirmed that alkoxysilane is effective for strengthening the mutual bond between inorganic silica and organic polymer, it has various drawbacks. As a solution to these drawbacks, the present inventors have previously developed α in which the silica contains at least one methylol group.

Easily binds to an organic polymer, especially an acrylic copolymer, containing β-monoethylenically unsaturated carboxylic acid amide and/or its derivative in the molecule, and moreover, silica and acrylic copolymer can be stably obtained in a one-component state. proposed.

This has an affinity for inorganic materials such as concrete and slate, but has the disadvantage of poor permeability.

(Problems to be Solved by the Invention) As a result of intensive study, the present inventors found that colloidal alumina (
It was discovered that colloidal alumina (colloidal alumina) easily binds to a water-soluble organic polymer containing at least one methylol group, and that a composite of colloidal alumina and water-soluble organic polymer can be stably obtained in a single liquid state. The present invention improves the various drawbacks mentioned above and improves the coating moldability of organic polymers.

Advantages such as flexibility and hardness of colloidal alumina,
It has solvent resistance and non-combustibility, has a strong film, and penetrates into concrete, slate boards, etc. very well.
The present invention provides a resin composition useful as a completely new industrial coating material, which has characteristics such as high adhesiveness.

"Structure of the Invention" (Means for Solving the Problems) The present invention provides that a cationic and/or nonionic water-soluble resin containing a methylol group and colloidal alumina at least partially combine with the methylol group in a water-soluble polymer. This is an aqueous resin composition formed by bonding via a condensation reaction with hydroxyl groups on the surface of colloidal alumina. That is, it is a resin composition containing an aqueous composite.

The water-soluble polymer is not particularly limited, but in consideration of industrial value, vinyl polymers, epoxy polymers, etc. are suitable in terms of physical properties, cost, etc.

Examples of vinyl polymers that are cationic and/or nonionic water-soluble polymers containing methylol groups include (a) α,β-monoethylenically unsaturated carboxylic acid amides containing N-substituted methylol groups and/or their α, β- derivatives and amino groups or nitrogen-containing heterocycles
A method of copolymerizing a mixture each containing a monoethylenically unsaturated compound and or a derivative thereof in an organic solvent, followed by neutralization with an acid and converting the solvent to water, (b) containing an N-substituted methylol group A mixture containing an α,β-monoethylenically unsaturated carboxylic acid amide and/or a derivative thereof and a vinyl monomer containing a halogenated alkyl group is copolymerized in an organic solvent, and then an amine compound and/or a phosphine compound is copolymerized. quaternary chlorination, a method of converting the solvent into water, (c) an α,β-monoethylenically unsaturated carboxylic acid amide containing an N-substituted methylol group and or a derivative thereof and a vinyl monomer having an epoxy group, respectively; (d) α containing an N-substituted methylol group; There is a method in which a mixture containing a β-monoethylenically unsaturated carboxylic acid amide and/or a derivative thereof and a vinyl monomer having a quaternary cation group is polymerized in an aqueous medium.

As the α,β-monoethylenically unsaturated carboxylic acid amide containing an N-substituted methylol group (a), (b), (C), and (d), 2 N-methylolacrylamide, N-methylolmethacrylamide .

N-dimethylolmethacrylamide and its derivatives include N-n-butoxymethylmethacrylamide, N-
Examples include n-butoxymethylacrylamide, N-ethoxymethylacrylamide, N-ethoxymethylmethacrylamide, N-methoxymethylacrylamide, and N-methoxymethylmethacrylamide.

Examples of the α,β-monoethylenically unsaturated compound having an amino group or a nitrogen-containing heterocycle in (a) include allylamine, N,N-dimethylethyl methacrylate, N,
Examples include N-diethyl ethyl methacrylate-vinyl pyridine.

As the acid (a), an inorganic acid radical, an organic acid radical, etc. can be used. For example, the inorganic acid radicals are PO,'-,
HP○a", Hz PO4-, CI-, Br5O,"
-, H3O, -, No, and CH as an organic acid group
s COO-, Cz Hs coo-, CH, CH(O
H) COO-, C'b Hs 5O8-.

Examples of the vinyl monomer containing a halogenated alkyl group (b) include chloromethylstyrene, polytetraethylstyrene, and 3-chloro2hydroxypropyl methacrylate.

Examples of the amine compounds (b) and (C) include pyridine, ammonia, triethylamine, and ethanolamines such as dimethylethanolamine and triethanolamine.

The phosphine compounds (b) and (C) are as follows.

Triethylphosphine, triphenylphosphine.

Examples include.

Examples of the vinyl monomer having an epoxy group (C) include glycidyl acrylate, glycidyl methacrylate, and methylglycidyl acrylate.

In addition, as the polymerizable organic monomer here.

For example, the following are used, but 1. Usually, physical properties,
A mixture thereof is used for various purposes.

Alkyl ester (C1-22) of acrylic acid ester M: For example, methyl acrylate, ethyl acrylate, n-butyl acrylate, is.

-Butyl acrylate, tert-butyl acrylate, 2-ethylhexyl acrylate, and the like.

Alkyl esters (1-22 carbon atoms) of methacrylic acid: for example, methyl methacrylate, ethyl methacrylate, n-butyl methacrylate.

Examples include 1so-butyl methacrylate-1-, tert-butyl methacrylate, 2-ethylhexyl methacrylate, and the like.

Hydroxyl group-containing vinyl monomers: Examples include hydroxyethyl acrylate, hydroxyethyl methacrylate, hydroxypropyl acrylate, and hydroxypropyl methacrylate.

Other monomers include, for example, silicon (meth)acrylate fluoroalkyl (meth)acrylate styrene, vinyltoluene, acrylonitrile vinyl dichloride, vinyl acetate, vinylidene chloride, vinylpyrrolidone, and the like.

The vinyl monomer having a quaternary cation group (d) is 1
For example, by reacting a vinyl monomer having an epoxy group with an amine compound and a protonic acid, or by reacting an α,β-monoethylenically unsaturated compound having an amino group or a nitrogen-containing heterocycle with a protonic acid or a halide. can get. Examples of the vinyl monomer having an epoxy group include those described in (c) above. Examples of the amine compound include those described in (b) and (C) above. Examples of protonic acids include inorganic acids such as hydrochloric acid, hydrobromic acid, sulfuric acid, phosphoric acid, and halonic acid; organic acids such as formic acid, acetic acid, propionic acid, butyric acid, and lactic acid. Among them, the dissociation constant (pKa value) is lXl0
-' or more are preferred. Examples of the α,β-monoethylenically unsaturated compound having an amino group or a nitrogen-containing heterocycle include those described in (a) above. Examples of the halide include methyl iodide, methyl bromide, and monochlorotrimethylsilane.

In addition, examples of the nonionic water-soluble resin having a methylol group include α,β-monoethylenically unsaturated carboxylic acid amide containing an N-substituted methylol group (a), (b), (c), and (d). It is obtained by copolymerizing the above-mentioned hydroxyl group-containing vinyl monomers. Other examples include polymers of α, β-monoethylenically unsaturated carboxylic acid amide containing N-substituted methylol groups in the presence of polyvinyl alcohol or cellulose derivatives.

As the organic solvent used in the polymerization reaction of the present invention, any solvent that can dissolve the polymer can be used, and water-miscible organic solvents are preferably used. for example.

Alcohols such as methanol, ethanol, and isopropanol; Ketones such as a, methyl isobutyl ketone; ethylene glycol methyl ether,
Ethylene glycol monoethyl ether.

Examples include glycol ethers such as ethylene glycol monobutyl ether, ethylene glycol monoethyl ether acetate, ethylene glycol monobutyl ether acetate, and diethylene glycol monobutyl ether. Furthermore, it is also possible to use water or the like in combination, if necessary.

In addition, examples of polymerization catalysts that can be used include organic peroxides such as benzoyl peroxide, perbutyl octate, and t-butyl hydroperoxide, azobisisobutyronitrile (AIBN), azobiscyanovaleric acid, etc.
,2. Examples include azo compounds such as '7zobis(2-7midinopropane) dihydrochloride.

The cationic water-soluble polymer containing a methylol group is an addition polymer of an epoxy compound and an amino group-containing compound.
Examples of graded products include 1) A method in which a polyadduct of an epoxy resin and a primary monoamine and/or a secondary diamine is neutralized with an acid, and then the water-soluble polymer is methylolized. 2) Methylolation. A method of neutralizing a polyadduct of an epoxy resin and a primary monoamine and/or a secondary diamine with an acid; c) A method of neutralizing a polyadduct of an epoxy resin and a methylolated primary monoamine and/or a secondary diamine; There is a method of neutralizing the polyadduct with an acid, and (2) a method of neutralizing the amine adduct of a phenol novolak type epoxy resin and/or a talesol novolac type epoxy resin with an acid.

Further, as the epoxy resin, for example, those listed below are used. Bisphenol A type epoxy resin, brominated bisphenol A type epoxy resin, hydrogenated bisphenol A type epoxy resin, bisphenol F type epoxy resin, linear aliphatic type epoxy resin.

Alicyclic epoxy resin, epoxidized polybutadiene.

Examples include polyglycidylamine.

Examples of the primary amine include monoethanolamine, ethylamine, butylamine, and benzylamine.

Examples include aniline 26.

Examples of the secondary diamine include N, N'-dimethylaminoethane. The acid mentioned in (a) above can be used as the neutralizing acid here.

Colloidal alumina, also called alumina sol, is a colloidal liquid of alumina and has a rod-like shape.

Its size is 100 mμ x 10 mμ, and it is usually supplied as an aqueous dispersion and can be used as it is. As the alumina sol, for example, those commercially available under the trade name Alumina Sol-100, Alumina Sol-200 (manufactured by Nissan Chemical Industries, Ltd.) or the alumina sol As series (manufactured by Catalysts Kasei Co., Ltd.) can be used.

If the cationic and/or nonionic water-soluble polymer containing a methylol group is a vinyl polymer, add 100% by weight of the α,β-monoethylenically unsaturated carboxylic acid amide having an N-substituted methylol group to the water-soluble polymer. It is necessary that the content be at least 1 part by weight per part. In addition, when the cationic water-soluble polymer containing a methylol group is a quaternized product of an addition polymer of an epoxy compound and an amino group-containing compound, the average number of methylol groups per molecule in the water-soluble polymer is It is necessary to have at least one. This is because the reactivity with the OH groups on the alumina sol surface is insufficient, resulting in poor durability of the coating film.

This is because a strong organic-inorganic bond cannot be obtained and the durability of the coating film is poor. Also, the alumina sol used is water-soluble resin 1
It can be used in an amount of 0.1 to less than 1000 parts by weight per 00 parts by weight. Preferably it is 1 to 100 parts by weight. If it is less than 0.1 part by weight, the reactivity with the OH groups on the surface of the alumina sol will be too low, resulting in poor coating film durability, and a strong organic-inorganic bond will not be obtained, resulting in poor coating film durability. . on the other hand,
If it exceeds too many parts by weight, the continuous film properties will be insufficient, cracks will occur, and the durability of the coating film will be poor.

The reason why the composition of the present invention has excellent effects on the physical properties of the coating film is not necessarily clear, but the OH groups present on the alumina sol surface and the methylol groups contained in the water-soluble resin react to form a strong crosslinking bond. is formed.

Furthermore, when the alumina sol is coated on a metal substrate and heat-treated, the remaining OH groups on the surface of the alumina sol and the O on the surface of the metal substrate and inorganic material.
This is presumably because it also reacts with H groups to form strong organic-inorganic composite bonds.

The water-soluble or water-dispersible resin composition according to the present invention is as follows.

Although the main component is the composite resin obtained as described above, an amino resin and/or an epoxy resin can be further blended as necessary.

Such additive resin acts as a crosslinking agent, and is crosslinked and cured by dehydration condensation reaction or addition reaction with the functional groups remaining in the composite resin, forming a stronger film.

It can provide water resistance, alkali resistance, acid resistance, and solvent resistance. Such amino resins include conventionally known urea-formaldehyde condensation products modified with monohydric alcohols such as methanol or butanol, respectively;
Examples include monomeric and polymeric melamine resins, benzoguanamine resins, and the like. Further, the epoxy resin can be crosslinked by an addition reaction between the epoxy group in its molecule and the methylol group or amine group in the composite resin to form a stronger film. As such epoxy resin.

The average molecular weight is at least about 350. Preferably about 350
-3,000 and polyphenol glycidyl ethers having an epoxy equivalent of 150-3,000, preferably 200-2,000. The above-mentioned amino resin and (
or) The blending ratio of the epoxy resin and the composite resin is 40/60 to 5/95, preferably 30/70 in terms of 2 weight percentages.
~10/90.

If the amount of the amino resin and/or epoxy resin used exceeds the above range, it will be difficult to fully exhibit the inherent performance of the composite resin, and if it is less than the above range, the effect as a crosslinking agent will not be sufficient.

The composition of the present invention optionally contains pigments and fillers.

Plasticizer, R-material dispersant, solvent, thickener, preservative, antifoaming agent,
Additives such as leveling agents can also be used together.

Further, the composition of the present invention may be mixed with other cationic and/or nonionic aqueous resin dispersions, if necessary.

The composition of the present invention can be used on plastic substrates, metallized paper, and cloth.

It can be used in paints, adhesives, etc. that can be applied to inorganic substrates. It is particularly effective for metals, inorganic base materials, etc.

The alumina sol composite aqueous resin composition obtained in the present invention as described above is transparent or translucent and highly flexible, and has the advantages of 5 organic polymers such as coating formability and flexibility, and the hardness and solvent resistance of alumina sol. sex.

It is a completely new industrial coating material with characteristics such as nonflammability. Note that the aqueous resin composition of the present invention can range from water-soluble to water-dispersible depending on the materials used.

Next, examples will be shown. However, all 2 parts indicate parts by weight.

Example 1 1) Butyl methacrylate 45 parts 2) N,
N-dimethylaminoethyl metal acrylate 50 parts 3) N-methylolacrylamide 5 parts 4) Isopropyl alcohol 150 parts 5) AIBN
Part 2 6) Water
20 parts 7) Acetic acid 20
Part 8) Water 400 parts 9) Alumina sol-200 (manufactured by Nichiryo Kagaku Co., Ltd. 2 solid content 10%)
155 parts Pour 1/2 of 1) to 5) into a reaction vessel previously saturated with nitrogen gas, and heat at 80°C.
Heat until.

The remaining 1/2 was added dropwise over 2 hours. Continue stirring for 4 hours until the non-volatile content reaches 40%, then 6).

7) was added dropwise over 10 minutes. Thereafter, the mixture of 8) and 9) was added dropwise over 20 minutes, and the temperature was raised to azeotropically distill the isopropyl alcohol until the nonvolatile content reached 20%. It is water soluble. A stable alumina sol composite aqueous resin was obtained. Approximately 100% of this water-based resin was then applied to a glass plate.
When it was coated in micron (μm) and heat treated for 110° cxio minutes and immersed in toluene, it swelled only slightly. Furthermore, the adhesion of cellophane tape was tested by coating it on a calcium silicate plate, and it was found to be good. The tensile strength measured by Tensilon was 150 Kg/cm'', and the elongation at break was 50%.

Example 2 1) 3-chloro-2-hydroxypropyl methacrylate 60 parts 2) Butyl methacrylate 35 parts 3) N-butoxymethylacrylamide 5 parts 4) Isopropyl alcohol 150 parts 5) AIBN
5 parts 6) Triethylamine 34 parts 7) Water 40 parts 8) Water
400 parts 9) Alumina sol-100 (manufactured by Nissan Chemical Co., Ltd., solid content 10%)
1) ~ 15 parts to a reaction vessel previously saturated with nitrogen gas
Add 1/2 of 5) and heat to 80°C.

The remaining 1/2 was added dropwise over 2 hours. Continue stirring for 4 hours until the non-volatile content reaches 40%, then 6).

7) was added dropwise over 10 minutes, and then a mixture of 8) and 9) was added dropwise over 20 minutes, and then the temperature was raised to azeotropically distill the isopropyl alcohol until the nonvolatile content reached 20%. A stable alumina sol composite aqueous resin was obtained. When this aqueous resin was applied to a glass plate in a thickness of about 100 microns, heat treated at 150°C for 10 minutes, and immersed in toluene, only slight swelling occurred. Furthermore, the adhesion of cellophane tape was tested by coating it on a calcium silicate plate, and it was found to be good.

Example 3 1) Butyl methacrylate 60 parts 2) Glycidyl methacrylate 35 parts 3) N-methylolacrylamide 5 parts 4) Isopropyl alcohol 150 parts 5) AIBN
Part 1 6) Pyridine
20 parts 7) Acetic acid
15 parts 8] Water 20 parts 9) Water 400 parts 10) Alumina sol - 10,025 parts 1/2 of 1) to 5) were charged into a reaction vessel previously saturated with nitrogen gas, and heated to 80°C.

The remaining 1/2 was added dropwise over 2 hours. Continue stirring for 4 hours until the nonvolatile content reaches 40% (6), 7).

8) was added and reacted at 80°C for 2 hours. after that,
After the mixture of 9) and 10) was added dropwise over 20 minutes, the temperature was raised to azeotropically distill the isopropyl alcohol until the nonvolatile content reached 20%. A stable alumina sol composite aqueous resin was obtained. Then, when this water-based resin was temporarily coated on glass to a thickness of about 100 microns, heat treated for 11o"cxio, and immersed in toluene, it swelled only slightly. Furthermore, it was coated on a calcium silicate plate and the adhesion of cellophane tape was tested. It turned out to be good.

Example 4 1) Methacryloyloxyethyltrimethylammonium chloride 60 parts 2) Butyl methacrylate 35 parts 3) N-methoxymethylacrylamide 5 parts 4) Isopropyl alcohol 75 parts 5) Water
75 parts 6) V-50 (2,2-azobis(2-aminodibroban) dihydrochloride
1 part 7) Water 440 parts 8)
Alumina sol - 10015 parts 1/2 of 1) to 6) were charged into a reaction vessel previously saturated with nitrogen gas, and heated to 80°C.

The remaining 1/2 was added dropwise over 2 hours. Continue stirring for 4 hours until the non-volatile content reaches 40%, then 7).

After the mixture of 8) was added dropwise over 20 minutes, the temperature was raised to azeotropically distill the isopropyl alcohol until the nonvolatile content reached 20%. A stable alumina sol composite aqueous resin was obtained. When this aqueous resin was applied to a glass plate in a thickness of about 100 microns, heat treated at 110° C. for 10 minutes, and immersed in toluene, only slight swelling occurred. Furthermore, the adhesion of cellophane tape was tested by coating it on a calcium silicate plate, and it was found to be good.

Example 5 1) 2-Hydroxyethyl acrylate 60 parts 2) Acrylamide 35 parts 3) N-methylolacrylamide 5 parts 4) Isopropyl alcohol 75 parts 5) Benzoyl peroxide
Part 5 6) Water
75 parts 7) Water 440 parts 8
) Alumina sol - 2005 parts Pour 1/2 of 1) to 6) into a reaction vessel previously saturated with nitrogen gas, and heat to 80°C.

The remaining 1/2 was added dropwise over 2 hours. Continue stirring for 4 hours. After the non-volatile content reaches 40%, add the mixture of 7) and 8) dropwise over 20 minutes. Raise the temperature and azeotropically distill the isopropyl alcohol until the non-volatile content reaches 20%. I let it happen. A stable alumina sol composite aqueous resin was obtained.

Then, 100 g of this aqueous resin was added to hexamethoxymethylol melamine (manufactured by Mitsui Toatsu Chemical Co., Ltd., trade name Suimeru #3).
50) After adding 20g, apply it on a polished mild steel plate so that the film thickness after drying is about 30 microns, and then apply 180'
Baked at C for 40 minutes. The obtained coated plate was soaked in bone for 14 days, but no abnormalities such as whitening or blistering were observed in the coated film.

Example 6 1) Epon 828 60 parts 2) N
-Butoxymethylacrylamide 10 parts 3) Benzoyl peroxide 1 part 4) Isopropyl alcohol 150 parts 5) Jetanolamine
38 parts 6) Lactic acid
32 parts 7) Water 440 parts 8) Alumina sol - 10015 parts 1) to 4) were charged into a reaction vessel previously saturated with nitrogen gas, heated to 80° C., and reacted for 2 hours. After that, 5) and 6) were added dropwise over 20 minutes, and then 2
Allowed time to react. After that, the mixture of 7) and 8) was added dropwise over 20 minutes, and the temperature was raised to azeotropically reduce the non-volatile content to 2.
The isopropyl alcohol was drained until it became 0%.

A stable alumina sol composite aqueous resin was obtained. Then, approximately 100 microns of this water-based resin was coated on a glass plate and
When it was heat-treated at °C for 10 minutes and immersed in toluene, it swelled only slightly. Furthermore, the adhesion of cellophane tape was tested by coating it on a calcium silicate plate, and it was found to be good.

Comparative Example 1 1) Butyl methacrylate 50 parts 2) N
, N dimethylaminoethyl metal acrylate 50 parts 3) Isopropyl alcohol 150 parts 4) A
IBN 2 parts 5) Acetic acid
20 parts 6) Water
20 parts 7) Water 4
00 parts 8) Alumina sol - 20055 parts 1/2 of 1) to 4) were charged into a reaction vessel previously saturated with nitrogen gas, and heated to 80'C.

The remaining 1/2 was added dropwise over 2 hours. Continue to stir for 4 hours until the non-volatile content reaches 40%, then 5).

6) is added dropwise over 10 minutes. Thereafter, the mixture of 7) and 8) was added dropwise over 20 minutes, and the temperature was raised to azeotropically distill the isopropyl alcohol until the nonvolatile content reached 20%. A stable alumina sol composite aqueous resin was obtained. Then, apply approximately 100 microns of this water-based resin to a glass plate.
When it was heat treated at 10° C. for 10 minutes and immersed in toluene, it immediately dissolved. Furthermore, when the adhesiveness of cellophane tape was tested by coating it on a calcium silicate plate, the coating film peeled off.

The tensile strength by Tensilon is 100g/cm2. The elongation at break was 5%.

Comparative Example 2 1) 3-chloro-2-hydroxypropyl methacrylate 60 parts 2) Butyl methacrylate 35 parts 3) N-butoxymethylacrylamide 5 parts 4) Isopropyl alcohol 150 parts 5) AIBN
Part 5 6) Triethylamine
34 parts 7) Water 440 parts 1) to 5) in a reaction vessel previously saturated with nitrogen gas
/2 and heat it to 80°C.

The remaining 1/2 was added dropwise over 2 hours. Continue stirring for 4 hours until the non-volatile content reaches 40%, then 6).

After adding 7) dropwise over 20 minutes, the temperature was raised to azeotropically distill the isopropyl alcohol until the nonvolatile content reached 20%. A transparent water-soluble resin was obtained. Then, apply approximately 100 microns of this water-soluble resin to a glass plate and hold it at an angle of 150°.
When it was heat treated for C×10 minutes and immersed in toluene, it immediately dissolved. Furthermore, when the adhesiveness of cellophane tape was tested by coating it on a calcium silicate plate, the coating film peeled off.

Comparative Example 3 1) Methacryloyloxyethyltrimethylammonium chloride 60 parts 2) Butyl methacrylate 4 parts 0 parts 3) Isopropyl alcohol 75 parts 4) Water
75 parts 5) V-50 3 parts 6) Water 440 parts 7) Alumina sol - 100 15 parts 1/2 of 1) to 5) were charged into a reaction vessel previously saturated with nitrogen gas and heated to 80°C.

The remaining 1/2 was added dropwise over 2 hours. Continue stirring for 4 hours until the non-volatile content reaches 40%, then 6).

After adding 7) dropwise over 20 minutes, the temperature was raised to azeotropically distill the isopropyl alcohol until the nonvolatile content reached 20%. A stable alumina sol composite aqueous resin was obtained. This aqueous resin was applied to a glass plate in a thickness of about 100 microns, heat treated at 110° C. for 10 minutes, and immediately dissolved when immersed in toluene. Furthermore, when the adhesiveness of cellophane tape was tested by coating it on a calcium silicate plate, the coating film peeled off.

Comparative Example 4 1) 2-Hydroxyethyl acrylate) 612) Acrylamide 40 parts 3) Isopropyl alcohol 75 parts 4) Benzoyl peroxide 5 parts 5) Water
75 parts 6) Water 4
40 parts 7) Alumina sol-20015 parts 1/2 of 1) to 5) were charged into a reaction vessel previously saturated with nitrogen gas, and heated to 80°C.

The remaining 1/2 was added dropwise over 2 hours. Continue stirring for 4 hours until the non-volatile content reaches 40%, then 6).

After the mixture of 7) was added dropwise over 20 minutes, the temperature was raised to azeotropically distill the isopropyl alcohol until the nonvolatile content reached 20%. A stable alumina sol composite aqueous resin was obtained. This aqueous resin was applied to a glass plate in a thickness of about 100 microns, heat treated at 110° C. for 10 minutes, and immediately dissolved when immersed in toluene. Furthermore, when the seven-roteb adhesion was tested by coating it on a calcium silicate plate, the coating film peeled off.

"Effects of the Invention" From the above results, the alumina sol composite aqueous resin of the present invention has excellent solvent resistance and adhesion to inorganic substrates, and since it is a cationic type, it has excellent corrosion resistance to substrates.
It has been found to be extremely useful in paints for metals, inorganic building materials, and organic building materials because of its good resistance to microbial parasitism.

Claims (1)

[Scope of Claims] 1. An aqueous resin composition characterized by containing a cationic and/or nonionic water-soluble polymer containing a methylol group and colloidal alumina. 2.Claim 1, wherein the cationic and/or nonionic water-soluble polymer containing a methylol group is a vinyl polymer.
The aqueous resin composition described. 3. The aqueous resin composition according to claim 1, wherein the cationic water-soluble polymer containing a methylol group is a quaternized product of an addition polymer of an epoxy compound and an amino group-containing compound.