JP2000044807A - Resin composition, its production and coated product - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a resin composition excellent in preservation stability, and capable of providing a coating membrane excellent in high hardness, scrape resistance, chemical resistance, fouling resistance, weather resistance or the like by including a specific water-soluble resin and a specified siloxane composition. SOLUTION: This resin composition comprises (A) a water-soluble resin having a siloxane bond, and (B) a siloxane composition of the formula SiOaXbYc X is a hydrolyzable group; Y is a nonhydrolyzable group; 0<=(a)<=1.4; (b)/[(b)+(c)]=0.01-1.0, with the proviso that 2(a)+(b)+(c)=4}. The compounding ratio of the components A to B is preferably (99.99/0.01)-(1/99), more preferably (97/3)-(40/60) expressed in terms of weights of nonvolatile components in both. The resin composition is obtained by mixing the components A and B at a room temperature to 200 deg.C, and aging the obtained mixture at pH 2-11, preferably pH 6-11 at 0-200 deg.C, preferably 40-90 deg.C for 1-8 hr.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an aqueous resin composition, a method for producing the same, and use thereof. More specifically, a resin composition containing the siloxane composition in an amount of 0.1 to 99% by weight of the total resin solids, which can provide a coating composition or a coating material having excellent storage stability, especially a siloxane composition Is a resin composition containing from 0.1 to 60% by weight, and is used as a top coating material, a top coating, a surface treatment agent, etc., such as a metal such as iron or an inorganic siding board, and adheres to a substrate. Or a resin composition containing a siloxane composition in an amount of 60 to 99% by weight, which is a heat-resistant coating agent. Further, the present invention provides a useful one as an aqueous inorganic additive which imparts heat resistance, high hardness, abrasion resistance and chemical resistance to a resin.

[0002]

2. Description of the Related Art In recent years, a resin composition containing various polymers such as an acrylic resin and an organic silicon composition has attracted attention as a material having both organic and inorganic advantages. Resin compositions containing these components are generally used as organic solvents for higher alcohols, ketones, esters, and aromatics because of compatibility between components, storage stability of liquids, and physical properties of coating films. One type or two or more types are mixed and used in large quantities.

[0003]

Since these organic solvents volatilize during coating and pose a problem in the protection of the global environment, there is a worldwide movement to regulate their use. In particular, when coating metal, cement or various ceramic base materials, volatilization of the solvent is more problematic because a relatively high temperature treatment is required and volatilization of the solvent causes a danger of ignition. Therefore, development of a resin composition containing an organic silicon composition using an aqueous solvent has been desired. However, when an aqueous solvent is used, the affinity between the organosilicon composition and the organic polymer in the curable composition is generally not sufficient, and the organosilicon composition has poor compatibility with water. An organic solvent is indispensable in the solvent, and the organic solvent cannot be excluded. In addition, the resin composition using an aqueous solvent may solidify during storage, which makes it difficult to put it into practical use.

[0004]

The present inventors have made intensive studies in view of the above problems, and as a result, have found that a resin composition obtained by blending a specific siloxane composition and a specific water-soluble resin is obtained. The inventors have found that the above problems can be solved, and have reached the present invention. That is, the present invention provides a resin composition obtained by blending the following (1) and (2), (1) a water-soluble resin having a siloxane bond, (2) a general formula (A): represented by SiO _a X _b Y _c . (Wherein X is a hydrolyzable group, Y is a non-hydrolyzable group, 0 ≦ a ≦ 1.4, b / (b + c) = 0.01-1.
0, where 2a + b + c = 4. General formula (B): SiO _{a ′} X _{b ′} Y _{c ′} (where X is a hydrolyzable group, Y is a non-hydrolyzable group, and 1.4 <a ′ <2, b ′ / ( b ′ + c ′) = 0.0
1 to 1.0, where 2a '+ b' + c '= 4. A) a resin composition comprising a siloxane component represented by

[0005] A coating composition comprising a pigment and / or powder dispersed in any one of the above resin compositions, and an epoxy resin, a polyisocyanate resin, or a melamine Resin, or aziridine,
An oxazoline ring, or a curable resin composition characterized by comprising a resin having a carbodiimide group,
And the following (1) and (2), pH 2-11, temperature 0
A method for producing a resin composition, which comprises blending and aging in the range of 200 ° C., (1) a water-soluble resin having a siloxane bond, and (2) a siloxane composition represented by the general formula (A). ): SiO _a X _b Y _c (where X is a hydrolyzable group, Y is a non-hydrolyzable group, 0 ≦ a ≦ 1.4, b / (b + c) = 0.01 to 1.
0, where 2a + b + c = 4. ), Coated articles obtained by applying the above-mentioned curable resin composition on a substrate, and coated articles obtained by applying the above-mentioned coating composition onto a substrate. That is, the inventors have found that a film obtained by applying and curing the above resin composition can provide a film having high hardness, solvent resistance and chemical resistance, and have reached the present invention.

[0006]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in detail. (1) Description of Water-Soluble Resin Having Siloxane Bond The water-soluble resin having a siloxane bond that can be used in the present invention is a resin having a siloxane bond (indicated by (Si—O) n), It is not particularly limited as long as it dissolves in. `` Dissolved in water '' means that when the resin component and water are mixed, it has a colorless and transparent appearance,
A resin that can be uniformly dissolved. As the form, any of a water-soluble synthetic resin and an aqueous synthetic resin emulsion can be used, and even those called by the names of synthetic resin aqueous solution, synthetic resin aqueous dispersion, aqueous dispersion, latex, etc. are uniform in appearance. Also includes those that are transparent.

The type of resin used as the resin component of the water-soluble synthetic resin is not particularly limited as long as it is a water-soluble resin, and examples thereof include the following. Acrylic resin, acrylic / styrene copolymer resin, vinyl acetate resin,
Vinyl acetate / acrylic copolymer resin, vinyl acetate partially saponified vinyl alcohol resin, vinyl alcohol resin, ethylene / vinyl acetate copolymer resin, olefin resin, vinyl chloride resin, vinylidene chloride resin, vinyl chloride / acrylic copolymer resin, styrene A resin such as a radical polymerizable resin such as a butazine copolymer resin or an ionic polymerizable resin can be used, and a condensed resin such as a urethane resin, a polyester resin, a nylon resin, a phenoxy resin, or an epoxy resin can also be used.

A water-soluble resin having a siloxane bond can be obtained by hydrolyzing and condensing a resin having a hydrolyzable silyl group in an aqueous or solvent system. Further, the hydrolyzable silyl group before hydrolysis may be in any form, and may be a polymer having an alkoxysilyl group, an acetoxysilyl group, an oximesilyl group, or an amidosilyl group represented by the following general formula (C). Any water-soluble synthetic resin having a siloxane bond, which is obtained by preliminarily hydrolytic condensation, can be used.

[0009]

[0010]

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[0011] (R2 to R6 are a hydrocarbon group having 1 to 8 carbon atoms or a phenyl group) Rg: a hydrocarbon group having 1 to 8 carbon atoms or a phenyl group As a method for synthesizing these water-soluble resins and a method for making them water-soluble, The following known methods can be mentioned.

Water-solubilization 1) Aqueous solution polymerization method A water-soluble resin is obtained by radical polymerization (including solution polymerization and emulsion polymerization) of a radically polymerizable monomer in an aqueous medium or a mixture thereof with a hydrophilic solvent. Method 2) Post aqueous solution method A method of obtaining a water-soluble resin by adding and dissolving a water-soluble polymer having a large amount of hydrophilic functional groups obtained by radical polymerization or condensation reaction in water.

Whether the water-soluble synthetic resin is obtained by any of the above-mentioned production methods depends on the type of the synthetic resin. For example, acrylic resin and acrylic styrene copolymer resin are produced by emulsion polymerization, solution polymerization or aqueous solution polymerization. Among them, a water-soluble resin of an acrylic resin (including an acrylic resin and a styrene copolymer resin) and a water-soluble resin of a urethane resin are preferable from the viewpoint of coating film properties.

The method of introducing a siloxane bond for the purpose of stabilizing the mixture and for exhibiting the physical properties includes a radical double bond having a hydrolyzable silyl group, such as alkoxysilane, acetoxysilane, oximesilane, or amidosilane, or a chain transfer agent. A method in which mercaptoalkoxysilane, mercaptoacetoxysilane, mercaptooximesilane, mercaptoamidosilane, and the like, which are effective, are copolymerized during radical polymerization and then hydrolyzed and condensed.

A method in which the above-mentioned silane having a radical double bond with a polyolefin resin is grafted in the presence of a radical initiator, followed by hydrolysis and condensation. Amine alkoxysilane, amine oxime silane, amine amide silane, amine acetoxy silane, glycidyl alkoxy silane, glycidyl acetoxy silane, glycidyl oxime silane, glycidyl amide silane, isocyanate alkoxy silane, isocyanate alkoxy silane having reactivity with various functional groups Silane, isocyanate-oxime silane, isocyanate-amide silane, chloroalkoxysilane,
Chloroacetoxysilane, chlorooxime silane, chloramidosilane, alkoxysilane having a carboxyl group, acetoxysilane, oxime silane, amide silane, etc. are used at the time of resin polymerization or after resin polymerization, and then bonded to the resin, followed by hydrolysis and condensation. There is a method and a method of reacting and bonding after the resin production to carry out hydrolysis and condensation.

For example, after a glycidyl group is introduced into a resin to give an aminosilane, or a carboxyl group of the resin is reacted with glycidylsilane, the resin is hydrolyzed and condensed in the presence of water to have a siloxane bond. In addition, a stable water-soluble resin in which a hydrolyzable silyl group and / or silanol group remains partially can be obtained. The amount of the above-mentioned hydrolyzable silyl group to be introduced is as follows.
It is preferable to use the alkoxysilanes, acetoxysilanes, oxime silanes, and amidosilanes in an amount of 0.1 to 70 parts by weight, more preferably 1 to 30 parts by weight, per 100 parts by weight.

When the amount of the alkoxy group-containing silane, acetoxy group-containing silane, oxime group-containing silane and amide group-containing silane introduced into the resin is less than 0.1 part by weight based on 100 parts by weight of the total amount of the resin monomer. In addition, the water-soluble resin composition obtained by blending the siloxane composition described below has poor storage stability and a small effect of developing coating properties such as hardness, chemical resistance and weather resistance. On the other hand, if the amount of the resin monomer exceeds 70 parts by weight based on 100 parts by weight of the total amount of the resin monomer, the water-soluble resin itself easily gels and a stable polymer cannot be obtained. Hereinafter, these will be described in detail.

(Water-soluble resin having siloxane bond by emulsion polymerization method)
It can be produced by a usual emulsion polymerization method. As the monomer component used for the polymerization, one or more of acrylic acid esters, methacrylic acid esters, styrene or derivatives thereof, acrylonitrile, vinyl acetate and other vinyl monomers, or diene monomers such as butadiene, chloroprene and isoprene are used. A radical double bond monomer having a hydrolyzable silyl group as an essential component
Alternatively, a mercaptosilane having a hydrolyzable silyl group or a hydrolyzable silane having glycidyl having a reactivity can be selected and used.

Specific examples of the methacrylic acid ester include:
Examples thereof include methyl methacrylate, ethyl methacrylate, n-butyl methacrylate, t-butyl methacrylate, i-butyl methacrylate, and 2-ethylhexyl methacrylate. Specific examples of the acrylate include methyl acrylate, ethyl acrylate, n-butyl acrylate, i-butyl acrylate, 2-ethylhexyl acrylate, octyl acrylate, and the like. Esters and acrylates are usually used alone or as a mixture of two or more. Examples of the styrene derivative include styrene,
α-methylstyrene, vinyltoluene and the like.

Other vinyl monomers include (meth)
Acrylonitrile, (meth) acrylamide, N-methylol (meth) acrylamide, (meth) acrylic acid 2
-Hydroxyethyl, glycidyl (meth) acrylate,
-N, N-dimethylaminoethyl acrylate, -N, N-diethylaminoethyl acrylate, methoxyethyl (meth) acrylate, butoxyethyl (meth) acrylate, vinyl acetate, vinyl propionate, vinyl vasateate, Vinyl chloride and the like.

Specific examples of the alkoxysilanes having a hydrolyzable silyl group, acetoxysilanes, oxime silanes and amidosilanes include alkoxysilyl group-containing unsaturated monomers such as vinyltrimethoxysilane and vinyltriethoxysilane. , Methylvinyldimethoxysilane, dimethylvinylmethoxysilane, dimethylvinylethoxysilane, methylvinyldiethoxysilane, vinyltris (methoxyethoxy) silane, vinyltriacetoxysilane, methylvinyldiacetoxysilane, dimethylvinylacetoxysilane, 3-methacryloxy Propyltrimethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropyldimethylmethoxysilane, 3-methacryloxypropyltriethoxysilane, 3 Methacryloxy propyl methyl diethoxy silane, 3-methacryloxypropyl dimethyl ethoxysilane, 3-methacryloxypropyl tri oxime silane can be exemplified.

Examples of the hydrolyzable silyl group-containing monomer having a chain transfer effect include 3-mercaptopropyltrimethoxysilane, 3-mercaptopropyltriethoxysilane, 3-mercaptopropylmethyldimethoxysilane,
3-mercaptopropylmethyldiethoxysilane, 3-
Mercaptopropyldimethylmethoxysilane, 3-mercaptopropyldimethylethoxysilane, 3-mercaptopropyltriacetoxysilane, 3-mercaptopropylmethyldiacetoxysilane, 3-mercaptopropyldimethylacetoxysilane, 3-mercaptopropyltrioximesilane, etc. Can do things.

Furthermore, aminoalkoxysilanes and aminoacetoxysilanes reactive with various functional groups include N- (2-aminoethyl) -3-aminopropyltrimethoxysilane and N- (2-aminoethyl)- 3-aminopropyltriethoxysilane, N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane,
N- (2-aminoethyl) -3-aminopropylmethyldiethoxysilane, N- (2-aminoethyl) -3-aminopropyldimethylmethoxysilane, N- (2-aminoethyl) -3-propyldimethylethoxysilane , N
-(2-aminoethyl) -3-aminopropyltriacetoxysilane and the like can be mentioned.

As the alkoxysilanes and acetoxysilanes having a glycidyl group, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-glycidylsilane Sidoxypropyldimethylmethoxysilane, 3-glycidoxypropyldimethylethoxysilane, 3-glycidoxypropyltriacetoxysilane and the like can be mentioned.

Further, chloro-containing alkoxysilanes, acetoxysilanes such as 3-chloropropyltrimethoxysilane, 3-chloropropyltriethoxysilane, 3-chloropropylmethyldimethoxysilane,
Examples thereof include chloropropylmethyldiethoxysilane, 3-chloropropyldimethylmethoxysilane, 3-chloropropyldimethylethoxysilane, and 3-chloropropyltriacetoxysilane. Other than these silanes having a hydrolyzable silyl group, oxime silanes,
Amidosilanes can also be used. These silanes having a hydrolyzable silyl group are represented by the following general formula (D), and can be used alone or in combination of two or more.

[0026]

[0027]

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[0028]

[0029]

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[0030] (R2 to R6 are a hydrocarbon group having 1 to 8 carbon atoms or a phenyl group) Rg: a hydrocarbon group having 1 to 8 carbon atoms or a phenyl group

In emulsion polymerization of these monomers, it is necessary to copolymerize a radical polymerizable monomer having hydrophilicity in order to stabilize the produced emulsion particles during polymerization and to dissolve them in water. Examples of the radical polymerizable monomer having hydrophilicity include anionic, cationic, nonionic and zwitterionic monomers. In the anionic monomer, a monomer having a carboxyl group in the molecule is used.
Examples thereof include maleic acid, fumaric acid, crotonic acid, itaconic acid, acrylic acid, methacrylic acid and the like.

Similarly, monomers having a sulfonic acid group in the molecule include vinylsulfonic acid, (meth) allylsulfonic acid, styrenesulfonic acid, (meth) acrylic acid-2-ethylsulfonic acid, and acrylamide-2-acid.
Methyl propane sulfonic acid and the like. Similarly, examples of the monomer having a phosphoric acid group in the molecule include (meth) acrylic acid-2-hydroxyethyl phosphate.

These anionic monomers can be used as salts of organic amines such as ammonia, trimethylamine and monoethanolamine, and salts of alkali metals such as sodium and potassium. Examples of the cationic monomer include dimethylaminomethyl (meth) acrylate,
Diethylaminoethyl (meth) acrylate, dimethylaminoethyl (meth) acrylate, dimethylaminopropyl (meth) acrylate, methacrylamidopropyltrimethylammonium chloride, 2-hydroxypropyltrimethylammonium methacrylate,
Diallyldimethylammonium chloride and p-vinylbenzylammonium chloride.

Examples of nonionic monomers include (meth) acrylamide, N-methylol (meth) acrylamide, N, N-dimethyl (meth) acrylamide, acryloylmorpholine, diacetone acrylamide, vinylpyrrolidone, vinyloxazolidone, Examples thereof include hydroxyethyl (meth) acrylate and hydroxypropyl (meth) acrylate.

Of these radically polymerizable monomers having a hydrophilic group, anionic monomers or cationic monomers are preferable in consideration of the stability in the PH region. When a nonionic monomer is introduced in a necessary amount to stabilize the emulsion, there is a problem in terms of water resistance of the film.
If the amount of these hydrophilic monomers used is too small, the stability during emulsion polymerization is reduced, and it becomes impossible to dissolve in water during neutralization.If the amount is too large, the water resistance of the dried film deteriorates. 5 to 100 parts by weight of polymerizable monomer
It is used in an amount of from 50 to 50 parts by weight, preferably from 10 to 30 parts by weight.

The emulsion polymerization reaction is carried out by supplying a monomer and a polymerization initiator all at once or continuously at a predetermined temperature while stirring in an aqueous medium in the presence of an emulsifier. The amount of the emulsifier used is usually 0.05 to 10 parts by weight, preferably 0.1 to 5 parts by weight, based on 100 parts by weight of the total amount of the polymerizable monomer.
Used in the range of parts by weight, specific examples include stearylamine hydrochloride, lauryltrimethylammonium chloride, cationic emulsifiers such as trimethyloctadodecylammonium chloride, potassium oleate, sodium lauryl sulfate, sodium dodecylbenzenesulfonate, alkanesulfonic acid Sodium, sodium alkylnaphthalene sulfonate, sodium dialkyl sulfosuccinate, sodium polyoxyethylene alkyl ether sulfate, sodium polyoxyethylene alkyl allyl ether sulfate, polyoxyethylene alkyl ether phosphate, polyoxyethylene alkyl allyl ester Anionic emulsifiers such as terphosphates, polyoxyethylene alkyl ethers, polyoxyethylene alkyl allyl esters; Ether, polyoxyethylene polyoxypropylene block polymers -, polyethylene glycol - Le fatty acid esters, nonionic emulsifiers such as polyoxyethylene sorbitan fatty acid esters, lauryl betaine, is amphoteric emulsifiers such as lauryl dimethyl amine oxide and the like.

Emulsifiers having a polymerizable double bond in the molecular structure and commercially available as so-called reactive emulsifiers can also be used. The amount of the reactive emulsifier to be used is generally 10 parts by weight or less, preferably 8 parts by weight or less, more preferably 5 parts by weight or less based on 100 parts by weight of the total amount of the polymerizable monomer. Examples of the reactive emulsifier include (Adekariasope SE-10N) manufactured by Asahi Denka Kogyo Co., Ltd., (Latemul S-180) manufactured by Kao Corporation, and Sanyo Chemical Industry Co., Ltd.
(Eaminol JS-2), Daiichi Kogyo Seiyaku Co., Ltd. (Aqualon HS-10), Nippon Emulsifier Co., Ltd. (Antox MS-60), and the like.

If necessary, various mercaptans, α
A chain transfer agent such as methylstyrene and alkyl halide may be used. It is used mainly for controlling the molecular weight of the polymer with a chain transfer agent to improve water solubility. The amount used is 0.01 to 100 parts by weight of the total amount of the polymerizable monomer.
When the amount is less than 0.01 part by weight, the effect of reducing the molecular weight is small, and when the amount exceeds 10 parts by weight, polymerization is inhibited, and a problem is caused in the polymerizability.

In addition, a water-soluble polymer such as polyvinyl alcohol, hydroxyethyl cellulose, a water-soluble acrylic copolymer, and a copolymer of sodium styrene sulfonate may be used alone or in combination with the above-mentioned emulsifier. Can be. The monomer concentration at the time of polymerization is usually 30 to 70 in total.
%, Preferably 35 to 65% by weight. Examples of the polymerization initiator include generally used radical polymerization initiators such as persulfates such as ammonium persulfate and potassium persulfate, and 2,2′-azobisisobutylnitrile. , 2 '
Examples thereof include azo-based polymerization initiators such as (2,4-dimethylvaleronitrile) and peroxide-based polymerization initiators such as benzoyl peroxide and lauryl peroxide.

The amount of the radical polymerization initiator used is 0.2 to 10 parts by weight, preferably 0.3 to 5 parts by weight, based on 100 parts by weight of the total amount of the polymerizable monomer. The reaction time during the polymerization is usually 2 to 16 hours, and the temperature during the polymerization is usually 6 hours.
0-100 ° C. In the neutralization step, the temperature is usually 0
It is carried out under conditions of up to 90 ° C., and raising the temperature makes it possible to shorten the time of water-solubilization. In the case of using a nonionic monomer, this step is not required.

In this neutralization step, the introduced alkoxysilyl group is hydrolyzed and condensed, and a water-soluble resin having a partial siloxane bond can be obtained at the same time. The degree of neutralization may be, for example, in the case of a carboxyl group-containing water-soluble resin, the carboxyl group may be neutralized in an amount of 20 mol% or more, preferably 30% by weight or more, more preferably 80% by weight or more. It only has to be neutralized.

The neutralizing agent used for neutralization is a basic compound such as ammonia or an organic amine in the case of an anionic monomer, and specific examples of the organic amine are alkylamines such as monomethylamine, diethylamine and triethylamine. Monoethanolamine, diethanolamine,
Alkanolamines such as triethanolamine, dimethylaminoethanol and diethylaminoethanol. Examples include morpholine, pyridine, piperazine and the like.

Also, inorganic water-soluble alkalis can be used, for example, sodium hydroxide, potassium hydroxide, etc.
Furthermore, sodium hydrogen carbonate, pyrophosphoric acid and the like can be mentioned. In the case of a cationic monomer, it can be solubilized by neutralizing an amino group with an inorganic acid or an organic acid as a water-solubilizing agent. It may be neutralized in an amount of at least 30 mol% by weight, preferably at least 30 mol%, more preferably at least 8 mol%.
What is necessary is just to neutralize 0 mol% or more. At this time, the neutralizing agent used is an organic acid such as formic acid, acetic acid, propionic acid, succinic acid, citric acid and malic acid. In addition, inorganic acids such as hydrochloric acid, phosphoric acid, sulfuric acid, and nitric acid can also be used.

The nonionic monomer is a monomer capable of solubilizing the resin without neutralizing the monomer, but the amount required for water solubilization is 7 to 50 parts by weight based on 100 parts by weight of the total polymerizable monomer. , More preferably 15 to 50
Parts by weight. The weight average molecular weight of the water-soluble resin having a siloxane bond obtained by the emulsion polymerization method is 500 to 500.
000, preferably 1,000 to 100,000.

(Water-soluble synthetic resin having siloxane bond by solution polymerization method) When the solution polymerization method is adopted, it is necessary to carry out the polymerization in a water-soluble organic solvent in consideration of the subsequent steps of imparting water solubility and water dispersibility. Is preferred. Examples of such a water-soluble organic solvent include alcohols such as methyl alcohol, ethyl alcohol, isopropyl alcohol, normal propyl alcohol, and butyl alcohol; ketones such as methyl ethyl ketone; ethylene glycol monomethyl ether; ethylene glycol monoethyl ether; Examples thereof include ethers such as monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, and propylene glycol monobutyl ether.

As the polymerizable monomer to be used, the same monomers as those shown in the above-mentioned emulsion polymerization can be used. In order to make the monomer water-soluble later, the monomer that imparts anionic property requires 5 to 50 parts by weight based on 100 parts by weight of the total amount of the polymerizable monomer, and 7 to 50 parts by weight for a nonionic monomer. Parts, if it is a cationic monomer, 5
Requires ~ 50 parts by weight.

In particular, when an unsaturated carboxylic acid is used among the anionic monomers, the amount used is 5 to 50 parts by weight, preferably 10 to 40 parts by weight, based on 100 parts by weight of the entire polymerizable monomer. If it is less than 5 parts by weight, poor water-solubilization water solubilization will result, and if it exceeds 50 parts by weight, the water resistance of the film,
The alkali resistance becomes poor. The degree of neutralization may be such that the carboxyl group contained is neutralized by 20 mol% or more, preferably 30 mol% or more, more preferably 80 mol% or more. .

The neutralizing agent used for neutralization is a basic compound such as ammonia or an organic amine in the case of an anionic monomer, and specific examples of the organic amine are alkylamines such as monomethylamine, diethylamine and triethylamine. Monoethanolamine, diethanolamine,
Alkanolamines such as triethanolamine, dimethylaminoethanol and diethylaminoethanol. Examples include morpholine, pyridine, piperazine and the like.

Also, inorganic water-soluble alkalis can be used, such as sodium hydroxide and potassium hydroxide.
Furthermore, sodium hydrogen carbonate, pyrophosphoric acid and the like can be mentioned. In the case of a cationic monomer, it can be solubilized by neutralizing an amino group with an inorganic acid or an organic acid as a water-solubilizing agent. It may be neutralized in an amount of at least 30 mol% by weight, preferably at least 30 mol%, more preferably at least 8 mol%.
What is necessary is just to neutralize 0 mol% or more. At this time, the neutralizing agent used is an organic acid such as formic acid, acetic acid, propionic acid, succinic acid, citric acid and malic acid. In addition, inorganic acids such as hydrochloric acid, phosphoric acid, sulfuric acid, and nitric acid can also be used.

The nonionic monomer is a monomer capable of solubilizing the resin without neutralizing itself, but the amount required for water solubilization is 7 to 50 parts by weight based on 100 parts by weight of the total polymerizable monomer. , More preferably 15 to 50
Parts by weight. Further, a chain transfer agent such as various mercaptans, α-methylstyrene, and alkyl halide may be used as needed. It is used mainly for controlling the molecular weight of the polymer with a chain transfer agent to improve water solubility. The amount used is 0.01 to 100 parts by weight of the total amount of the polymerizable monomer.
To 10 parts by weight.

In the polymerization method, a mixture of the above-mentioned alkoxyl group-containing monomer and other hydrophilic group monomers and other ethylenically unsaturated monomers in the above-mentioned hydrophilic solvent or water and / or a mixture thereof is used. It is divided and / or charged in a lump, and the above-mentioned polymerization initiator is added to promote radical polymerization. The monomer concentration during the polymerization is 30 to 7 in total.
0% by weight, preferably 35 to 65% by weight, and the radical polymerization initiator is 0.1 to 10 parts by weight, preferably 0.3 to 5 parts by weight based on 100 parts by weight of the total amount of the polymerizable monomer. The reaction time is 2 to 16 hours, and the reaction temperature during polymerization is usually 60 to 100 ° C.

The water-solubilization depends on the type of the above-mentioned hydrophilic monomer, but as a step, the polymerized resin is cationically and anionically converted to a water-soluble neutralizing agent and water by adding a neutralizing agent and water. Is obtained. In the neutralization step, the temperature is usually 0
It is carried out under conditions of up to 90 ° C., and raising the temperature makes it possible to shorten the time of water-solubilization. In the case of using a nonionic monomer, the step is not required. The weight average molecular weight of the water-soluble resin having a siloxane bond obtained by a solution polymerization method is 500 to 500,000.
And preferably from 1,000 to 100,000.

(2) Description of the siloxane composition of the general formula (A) The siloxane composition used in the aqueous composition of the present invention is represented by the general formula (A): SiO _a X _b Y _c (where X is a hydrolysis And Y is a non-hydrolyzable group, 0 ≦ a ≦ 1.4, b / (b + c) = 0.01 to 1.
0, where 2a + b + c = 4. ).

In the present invention, the siloxane composition to be used in combination with the above-mentioned water-soluble resin having a siloxane bond may be any siloxane composition satisfying 0 ≦ a ≦ 1.4. is there. The coefficient a is a coefficient indicating the degree of siloxane condensation of the siloxane composition. When a = 0, the monomer is a silicon composition monomer having no siloxane bond. When a> 0, the oligomer has a siloxane bond. As the siloxane composition used in the present invention, a monomer and / or oligomer of the silicon composition may be used alone, or a mixture of one or more of these may be used.

In the general formula (A), a siloxane composition using these silicon compositions alone or as a mixture is represented by a chemical formula. When a> 1.4, the siloxane composition has a high viscosity and is easily gelled, and the storage stability is significantly reduced, so that it becomes difficult to use the composition. When a = 2, silica (Si) having no X or Y organic functional group described later is used.
O ₂ ). Silicas having a = 2, such as colloidal silica and fumed silica, are particulate silicas having no organic functional groups. Therefore, storage stability when a water-soluble resin used in the present invention is blended to form a coating composition. Although the properties are good, the effects of improving high hardness, solvent resistance and chemical resistance when formed into a coating film cannot be expected.

The range of the coefficient a is 0 ≦ a ≦ 1.4,
Preferably 0.5 ≦ a ≦ 1.4, more preferably 0.6
≦ a ≦ 1.2, when the water-soluble resin composition obtained by blending and aging this with a water-soluble resin has high hardness, solvent resistance, and chemical resistance when formed into a film or a film. And the like are most preferable because they exhibit remarkable functions. X is a hydrolyzable group, which is a group capable of forming a siloxane bond by a hydrolytic condensation reaction or the like. Examples of such a group include a halogen group, a hydrogen group, a hydroxyl group, an OR group and the like, and one or more of these groups. As the halogen group, -F, -Cl, -Br, -I
And the like. As the OR group, R represents an alkyl group, a cycloalkyl group, an alkoxyalkyl group, an aryl group,
It is one or more of an aralkyl group and an alkylpolyoxyalkylenyl group. Representative examples of R are shown below.

Examples of the alkyl group include methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, 2-ethylhexyl, octyl,
A decyl group or the like may be mentioned, and it may be linear or branched. Examples of the cycloalkyl group include a cyclohexyl group, a cyclobutyl group, a cyclopentyl group, and the like. Examples of the alkoxyalkyl group include a methoxyethyl group, an ethoxyethyl group, a butoxyethyl group, and the like.

As the aryl group, for example, a phenyl group,
Examples include a tolyl group and a xylyl group. Examples of the aralkyl group include a benzyl group and a phenethyl group. Examples of the alkylpolyoxyalkylenyl group include CH
_{3 - (OCH 2 CH 2)} n-, C 2 H 5 - (OCH 2 C
_{H 2) n -, CH 3} - (OCH 2 CHCH 3) n -, C
_{2 H 5 - (OCH 2 CHCH} 3) n - , and the like.

When X is a halogen group, hydrogen halide is by-produced by hydrolysis, and when X is a hydrogen group, hydrogen is by-produced. Therefore, it is necessary to pay attention to their flammability, corrosiveness and toxicity. . For this reason, X is preferably an OR group. Considering the ease of forming a siloxane bond by the reaction with the aqueous resin and the hydrolytic condensation of the siloxane composition itself, R represents a methyl group, an ethyl group, a propyl group, It is preferable to select from one or more butyl groups. Thereby, the water-soluble resin composition obtained by blending and aging with the water-soluble resin is highly crosslinked in the process of forming a film or a coating film, and the resulting coating film has high hardness, solvent resistance, chemical resistance, etc. The function expression is most remarkable.

Y is a non-hydrolyzable group, an alkyl group,
It is one or more of a cycloalkyl group, an alkoxyalkyl group, an alkenyl group, an aryl group, an aralkyl group, an alkylpolyoxyalkylenyl group, an acyl group, an acyloxyalkyl group and a glycidyloxyalkyl group.
Representative examples of Y are shown below. As the alkyl group,
For example, a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, a 2-ethylhexyl group, an octyl group, a decyl group and the like can be mentioned.

Examples of the cycloalkyl group include a cyclohexyl group, a cyclobutyl group, a cyclopentyl group and the like. Examples of the alkoxyalkyl group include a methoxyethyl group, an ethoxyethyl group, a butoxyethyl group, and the like. Examples of the alkenyl group include a vinyl group, a 1-propenyl group, a 2-propenyl group, a 1-butenyl group, a 2-butenyl group, and the like.

As the aryl group, for example, a phenyl group,
Examples include a tolyl group and a xylyl group. Examples of the aralkyl group include a benzyl group and a phenethyl group. Examples of the alkylpolyoxyalkylenyl group include CH
_{3 - (OCH 2 CH 2)} n-, C 2 H 5 - (OCH 2 C
_{H 2) n -, CH 3} - (OCH 2 CHCH 3) n -, C
_{2 H 5 - (OCH 2 CHCH} 3) n - , and the like.

Examples of the acyl group include an acetyl group and a propionyl group. Examples of the acyloxyalkyl group include an acryloyloxypropyl group and a methacryloyloxypropyl group. The glycidyloxyalkyl group includes, for example, a glycidyloxypropyl group. Further, as the epoxy ring-containing group, a β (3 · 4-epoxycyclohexyl) ethyl group and the like can be mentioned.

Y contributes to improving the storage stability of the water-soluble resin composition obtained by blending and aging the water-soluble resin, improving the flexibility of the resulting coating film, and improving the compatibility with the water-soluble resin. In view of these characteristics, a wide range of selection is possible. Selection of X and Y of the siloxane composition used in the water-soluble resin composition of the present invention can be appropriately performed according to the purpose of use of the water-soluble resin composition. That is,
For compatibility and storage stability with the water-soluble resin component in the water-soluble resin composition of the present invention, and also for expressing functions such as high hardness, flexibility, solvent resistance, and chemical resistance in the obtained coating film. You only have to take that into consideration.

The ratio between X and Y is represented by b / (b + c) and is in the range of 0.01 to 1.0 molar ratio. Preferably 0.
The molar ratio is in the range of 1 to 1.0, more preferably 0.5 to 1.0.
~ 1.0. When a siloxane composition having a molar ratio of b / (b + c) <0.01 is blended and aged with a water-soluble resin to form a water-soluble resin composition, the resulting coating film has scratch resistance, solvent resistance, and resistance to water. This is a problem because the ability to express functions such as chemical properties is poor.

In particular, 0.6 ≦ a ≦ 1.2, b / (b + c)
= 0.5 to 1.0 molar ratio (provided that 2a + b + c = 4) when the siloxane composition used in the present invention is blended and aged in a water-soluble resin to form a water-soluble resin composition. In addition, the storage stability of the liquid is excellent, and functions such as scratch resistance, solvent resistance, and chemical resistance when a coating film is formed are most remarkable.

These general formulas (A): SiOa Xb Yc
Specific examples of the siloxane composition represented by, for example, tetramethoxysilane, tetraethoxysilane, tetra-n-propoxysilane, tetraisopropoxysilane, tetra-n-butoxysilane, tetraisobutoxysilane, tetra-t- Tetraalkoxysilane compositions such as butoxysilane and tetraphenoxysilane and / or partially hydrolyzed condensates thereof.

Methyltrimethoxysilane, methyltriethoxysilane, methyltripropoxysilane, methyltriisopropoxysilane, ethyltrimethoxysilane,
Ethyltriethoxysilane, ethyltripropoxysilane, ethyltriisopropoxysilane, propyltrimethoxysilane, propyltriethoxysilane, butyltrimethoxysilane, butyltriethoxysilane, pentyltrimethoxysilane, pentyltriethoxysilane,
Hexyltrimethoxysilane, hexyltriethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, phenyltripropoxysilane, phenyltriisopropoxysilane, benzyltrimethoxysilane, benzyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane , 3-glycidoxypropyltriethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltriethoxysilane, 3
-Methacryloxypropyltrimethoxysilane, 3-methacryloxypropyltriethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-mercaptopropyltriethoxysilane, 3-aminopropyltriethoxysilane And / or trialkoxysilane compounds such as N- (2-aminoethyl) -3-aminopropyltrimethoxysilane and 3-ureidopropyltriethoxysilane and / or partially hydrolyzed condensates thereof.

Dimethyldimethoxysilane, dimethyldiethoxysilane, diethyldimethoxysilane, diethyldiethoxysilane, diphenyldimethoxysilane, diphenyldiethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, -Dialkoxysilane compounds such as mercaptopropylmethyldimethoxysilane, 3-aminopropylmethyldimethoxysilane, N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane and / or partial hydrolysis condensates thereof.

Chlorosilanes such as methyltrichlorosilane, vinyltrichlorosilane, phenyltrichlorosilane, methyldichlorosilane, dimethyldichlorosilane, dimethylchlorosilane, methylvinyldichlorosilane, 3-chloropropylmethyldichlorosilane, diphenyldichlorosilane, and methylphenyldichlorosilane Compounds and / or partially hydrolyzed condensates thereof.

These siloxane compositions may be used alone or in combination of two or more. (3) Mixing and Aging of a Water-Soluble Resin Having a Siloxane Bond and a Siloxane Composition According to the present invention, a water-soluble resin having a siloxane bond and a siloxane composition described above are blended and aged under a specific condition. Compared to an aqueous resin composition in which a siloxane composition is simply added to an aqueous resin or a hydrolyzable silyl group-containing aqueous resin, the obtained siloxane composition can be obtained even if the amount of the siloxane composition is greatly increased. The storage stability of the contained aqueous resin composition is good, and the coating film obtained by applying this to various substrates has high hardness, scratch resistance,
It exhibits excellent properties such as chemical resistance and weather resistance.

The water-soluble resin having a siloxane bond of the present invention and the siloxane composition may be mixed at room temperature to 200 ° C., and the mixing method is not particularly limited. Industrially, for example, a method in which both are charged and mixed well into a device capable of mixing or stirring such as a mixer or a reactor, or a water-soluble resin having a siloxane bond is stirred, A method of gradually adding, mixing and blending the siloxane composition may be used.

The present invention is characterized in that after the above-mentioned blending, the resulting blended solution is aged by heating at pH 2 to 11 at a liquid temperature of 0 to 200 ° C. for 1 to 8 hours. In a water-soluble resin having a siloxane bond, hydrolysis and condensation further proceed, and the siloxane bond is formed by partially reacting with the water-soluble resin having a siloxane bond. It is possible to obtain a water-soluble resin composition having good storage stability and having a sea-island structure in which a particulate siloxane composition having an inertia radius of 20 to 200 ° partially bonded is uniformly dispersed. The aging conditions are preferably 40 to 90 ° C and 1 to 8 hours.
r. The pH of the system is more preferably PH6-1.
It is one. The water-soluble resin composition thus obtained can be further added with water or various other solvents or a dispersion medium after aging. Furthermore, it is also possible to completely remove the solvent after the aging to completely remove the solvent.

The mixing ratio of the water-soluble resin having a siloxane bond and the siloxane composition is such that the weight ratio of the water-soluble resin having a siloxane bond / siloxane composition =
99.99 / 0.01 to 1/99, preferably 97/3
４０40/60. When the mixing ratio of the water-soluble resin having a siloxane bond / siloxane composition is 99.99 / 0.0
In the case of 1 to 40/60, the characteristics of the obtained resin composition show properties (film-forming ability, light resistance, durability, waterproofness) in which the properties on the resin side are strong and inorganic properties are added thereto. on the other hand,
When the mixing ratio of the water-soluble resin having a siloxane bond / siloxane composition is 39/61 to 1/99, the film-forming ability as a thick film is weak, and inorganic properties (heat resistance, high hardness, high strength) and the like are poor. Show properties.

In the present invention, a stabilizer, PH,
It may contain additives such as a regulator, a surfactant, and a viscosity modifier. In addition, known additives such as pigments, fillers, dispersants, preservatives, fungicides, and plasticizers, and curing agents described below may be added. In addition, a water-soluble resin composition having a high compounding ratio of the siloxane composition can be used by being added to a coating agent or a paint as an anti-blocking additive or an additive for improving surface hardness of the paint.

(4) Description of Curing Agent A curing agent can be added to the water-soluble resin composition of the present invention in order to further improve chemical resistance, film hardness and weather resistance.
As the curing agent, it has reactivity with functional groups (for example, carboxyl group, hydroxyl group, sulfonic acid group, amino group) on the resin side and functional groups (for example, silanol group and hydrolyzable silyl group) on the siloxane composition side. The resin is not particularly limited as long as it has a functional group (for example, epoxy group, glycidyl group, isocyanate group, aziridine, oxazoline ring, carbodiimide group).

Examples of the type of resin include epoxy resin, polyisocyanate resin, aziridine, melamine resin, aziridine, a resin having an oxazoline ring, and a resin having a carbodiimide group. Resin forms include solvent-based resin and water-based resin (water-dispersed type and water-soluble type)
Any of a resin and a bulk resin can be used, but an aqueous resin is particularly preferable. The above curing agents can be used alone or in combination of two or more. It is preferable that the curing agent compounding liquid has a pot life in use. However, either a method of using one liquid and a method of mixing and using two liquids before use may be used. In the case of the latter method, it is sufficient that the pot life of the blended liquid is about 10 hours to 3 days.

The compounding amount of the curing agent may be such that the functional group of the curing agent is 10/1 to 1/4 in molar ratio with respect to the functional groups on the resin side and the siloxane composition side, and preferably 3/1 to 1/4.
It is 1/2. When the molar ratio of the functional group is less than 10/1, the effect of improving the performance by mixing the curing agent cannot be obtained, and when it is more than 1/4, the stability of the curing agent compounding solution becomes poor, and the pot life during use becomes poor. It may not be obtained and may lead to gelation.

The above-described resin composition of the present invention can be applied to various substrates to obtain coated articles. Further, a coated product obtained by coating a base material with a coating composition obtained by dispersing a pigment or other powder in the resin composition of the present invention to obtain a coating can be obtained. As a coating method of such a water-soluble resin composition,
Impregnation method for base material and wire rod such as polymer, metal and ceramic,
A coating composition formed by spin coating, spraying, or the like, or coated with the above pigment, filler, dispersant, or the like, is applied to a metal building material, an inorganic building material, or a hardened cement material by using a roll coater, Car
The coating film can be formed with a ten coater or a sprayer, and a heating step can be taken. Furthermore, it is also possible to directly spray-coat inorganic building materials, metal building materials, tiles, etc. at the construction site. The water-soluble resin composition of the present invention has excellent storage stability of the liquid, and the resulting coating film has characteristics of high hardness, solvent resistance, chemical resistance, and weather resistance. Hereinafter, the present invention will be described more specifically with reference to examples.

Example 1 (Synthesis of Water-Soluble Resin Having Siloxane Bond)
400 g of ethyl alcohol is charged into a two-liter four-necked flask equipped with a temperature controller, a thermometer, a reflux condenser, a dropping funnel and a nitrogen gas inlet tube, and heated to 75 ° C. while introducing nitrogen gas. After raising the temperature and adding 1.6 g of AIBN (2,2′-azobisisobutylnitrile), 100 g of butyl acrylate, 200 g of methyl methacrylate,
A monomer mixture obtained by stirring and mixing 60 g of methacrylic acid and 40 g of 3-methacryloxypropyltrimethoxysilane was added dropwise from a dropping funnel over 5 hours to carry out polymerization at 75 ° C.

After completion of the dropwise addition, 0.8 g of ADVN (2,2 'azobis 2,4-dimethylvaleronitrile) dissolved in 2 g of ethyl alcohol was added, the mixture was aged at 80 ° C. for 3 hours, and cooled to 25% 20 g of ammonium water and 200 g of ion-exchanged water were added to obtain a water-soluble resin A-1 having a siloxane bond. The obtained water-soluble resin A-1 was a transparent aqueous solution having a nonvolatile content of 40.1%, a pH of 8.0 and a viscosity of 1000 cP.

(Blending and Aging) The water-soluble resin A- prepared above was placed in a two-liter four-necked flask equipped with a stirrer, a temperature controller, a thermometer, a reflux condenser, and a dropping funnel.
1: 1000 g and 100 g of ion-exchanged water were charged, the temperature was raised, and at an internal temperature of 60 ° C., a dropping funnel was used to prepare a siloxane composition MKC silicate MS51 (polymethoxysiloxane manufactured by Mitsubishi Chemical Corporation: weight Average molecular weight 500-80
0, 100 g of SiO _0.8 (OMe) _2.4 ) was gradually added dropwise over 30 minutes while stirring, and aged at the same temperature for 5 hours with stirring. The product A-2 was obtained. This water-soluble resin composition A-2
Has a nonvolatile content of 40.5%, a pH of 8.0, a viscosity of 3,000
It was a clear aqueous solution of cP.

(Solvent removal) Stirrer, temperature controller, thermometer,
Into a two-liter four-necked flask equipped with a reflux condenser or a rectification tower and a dropping funnel was charged 1000 g of the water-soluble resin composition A-2 prepared above, and the temperature was raised to an internal temperature of 80 g. 450 g was taken out while removing the ethyl alcohol out of the system under reduced pressure for 5 hours while azeotropically boiling at ℃. 460 g of deionized water gradually over 30 minutes with stirring
The solution was dropped and completely solubilized for 2 hours with stirring at the same temperature.
Then, it cooled and obtained the water-soluble resin composition A-3. This water-soluble resin composition-1 has a nonvolatile content of 40.2%, PH
8.0, viscosity 5000cP, ethyl alcohol 0.3%
Was a clear aqueous solution. Ethyl alcohol was measured by gas chromatography.

The water solubility of Example 1 having a siloxane bond
Analysis of Resin A-1 and Water-soluble Resin Composition A-2 1) Confirmation of Degree of Siloxane Condensation by Si-NMR The degree of condensation in the present invention is measured by Si-NMR.
Can be easily known. Tetramethylsilane
The chemical shift value of
The hydrolysis condensate of silane (tetrafunctional) is
Value, giving 5 groups of peaks between -75 and -120 ppm
For each Q₀, Q₁, Q_Two, Q_Three, Q _FourCalled.
Each peak is derived from the number of siloxanes, as follows:₀Is
Monomer having zero siloxane, Q₁Is the number of siloxane
There is one, Q_TwoMeans two siloxanes, Q_ThreeIs Shiroki
Three suns, Q_FourIndicates a product with four siloxanes
You. Calculate the area ratio of each of these peaks and calculate
By calculation, the degree of condensation a is determined. Silica (S
iO_Two)), A = 2.

A = A × 0 + B × 0.5 + C × 1.0 + D
× 1.5 + E × 2 Each area ratio of Q ₀ , Q ₁ , Q ₂ , Q ₃ , Q ₄ is represented by A: B:
C: D: E. However, A + B + C + D + E = 1 Also, the siloxane formation degree of tetrafunctional methyl silicate can be determined from the following equation.

Degree of siloxane formation (%) = (a / 2) × 100 Chemical shift value of trifunctional 3-methacryloxypropyltrimethoxysilane (hereinafter referred to as A-174) used in Examples of the present invention. Is −41 to −70 ppm
Gives four groups of peaks, Q ₀ ′, Q ₁ ′,
_They are referred to as Q ₂ ′ and Q ₃ ′.

As in the tetrafunctional case, each peak is derived from the number of siloxanes, and Q ₀ ′ is a monomer having zero siloxane, Q ₁ ′ is a monomer having one siloxane, and
Q ₂ ′ represents a substance having two siloxanes, and Q ₃ ′ represents a substance having three siloxanes. By determining the area ratio of each of these peaks and calculating according to the following equation, the degree of condensation a ′
Is found. When all three functional groups form a siloxane bond, a '= 1.5.

A ′ = A ′ × 0 + B ′ × 0.5 + C ′ ×
1.0 + D ′ × 1.5 The area ratio of Q ₀ ′, Q ₁ ′, Q ₂ ′, Q ₃ ′ is A ′:
B ': C': D '. However, A ′ + B ′ + C ′ + D ′ = 1 Further, the siloxane formation degree of trifunctional A-174 can be determined from the following equation.

Degree of siloxane formation (%) = (a ′ / 1.5) × 100 Thus, the Si-NM of the trifunctional substance and the tetrafunctional substance
Since the R peak has different chemical shift values, it is possible to observe each state (condensation degree) separately.

(Si-NM of MKC silicate MS51)
R measurement) MKC silicate MS51 which is a partially hydrolyzed condensate of tetramethoxysilane used in Example 1
The i-NMR was measured, and the chemical shifts of Q ₀ , Q ₁ , Q ₂ , Q ₃ , and Q ₄ were 77 to 79, 85 to 67, respectively.
It was confirmed at the positions of 92 to 96, 100 to 104 and 106 to 120 ppm. From these peak area ratios, the siloxane condensation degree a = 0.80 and the siloxane formation degree 40.0%
I knew it was.

[0091]

[Table 1]

(A-174 Si-NM of hydrolysis condensate)
R measurement) used in the synthesis of the water-soluble resin A-1 of Example 1,
A homopolymer which was a partially hydrolyzed condensate of only A-174 was synthesized, and the Si-NMR of this product was measured.
The chemical shift of Q ₀ ′, Q ₁ ′, Q ₂ ′, Q ₃ ′ is
-41.0, -50.0, -59.0, -6 respectively
It was confirmed at 8.5 ppm. From this, trifunctional A
The -174 homopolymer has a chemical shift value different from that of tetrafunctional methyl silicate, and it was confirmed that the respective siloxane condensation degrees and siloxane formation degrees can be determined. (Si-NMR measurement of water-soluble resin A-1) The result of Si-NMR measurement of the water-soluble resin A-1 of Example 1 is shown below.

[0093]

[Table 2]

From the results, it was confirmed that about 77% of the hydrolyzable silyl group (derived from A-174) of the water-soluble resin A-1 had a siloxane bond. (Si-NMR measurement of water-soluble resin composition A-2) Example 1 in which MS51 was blended and aged with the above-mentioned water-soluble resin A-1.
Of the water-soluble resin composition A-2 is shown below.

[0095]

[Table 3]

[0096]

[Table 4]

[0097] MS51 (siloxane composition), among the water-soluble resin A-1 having a siloxane bond, significantly increased Q _4, increased significantly to 40% to about 98% siloxane formed of substantially silica The hydrolysis-condensation reaction has progressed to a state close to. On the other hand, the hydrolyzable silyl group (A-174) on the water-soluble resin side also has an increased Q ₃ ′, and the degree of siloxane formation has been increased from 76.9% to 82.7%.

From these results, the water-soluble resin A-1 having a siloxane bond was blended with MS51 by the method of the present invention.
By aging, MS51 undergoes a hydrolysis-condensation reaction and exists in a state close to silica particles, and a part of the MS51 is siloxane-bonded to a hydrolyzable silyl group of a water-soluble resin. It is considered to be liquid. This means that when the water-soluble resin F-1 having no siloxane bond and MS51 described later or the aqueous resin A-1 having a siloxane bond and MS51 are simply blended at room temperature, the resin component and the MS51 component are stable. Since it does not have a siloxane bond, it can be inferred from the fact that the mixed composition eventually undergoes hydrolytic condensation of MS51, eventually leading to gelation.

2) Confirmation of molecular weight change by GPC analysis (Water-soluble resin A-1 having siloxane bond and MS5
GPC measurement of 1) Water-soluble resin A-1 has a peak top at molecular weights of 2700 and 8400. -MS51 It has a peak top at a molecular weight of 350 to 480. (GPC measurement of water-soluble resin composition A-2) Molecular weight 270
It has peak tops near 0 and 100,000, and has a molecular weight of 8400 for water-soluble resin A-1 and a molecular weight of 3 for MS51.
It was confirmed that the peak top around 50 to 480 disappeared. From this, the molecular weight of the water-soluble resin A-1 is 84
It is considered that a substance having a molecular weight of about 100,000 reacted with the substance at about 00 and MS51.

3) Confirmation of fine particles by small-angle X-ray scattering method [Small-angle X-ray scattering method] The presence of fine particles can be easily confirmed by means such as small-angle scattering X-rays. That is, due to the presence of the microparticles, the scattering intensity I in which the diffraction intensity distribution of the incident X-ray indicates central scattering in the incident line direction, ie, small angle X-ray scattering, is given by the following Guinier's equation.

[0101] I (h) = C · exp (-h 2 Rg 2/3) (I: scattering intensity, h: scattering vector (= 4πsinθ /
λ), Rg: radius of gyration of the microparticle, C: Const,
lambda: 1.5418 Å, theta: the spread angle) taking common logarithm of the expression of both sides of the above Guinier, logI (h) = logC- (h 2 Rg 2/3) next, therefore, if there are small particles , Measure the scattering intensity and plot a log-log graph against the scattering vector (the resulting plot is called a Guinier plot);
By calculating the inclination, the radius of inertia of the fine particles can be obtained. When the inclination of the Guinier plot, and k k = -Rg ^2/3 radius of gyration Rg of the relationship are obtained.

When the scattering intensity is sufficient, a distance distribution function is obtained by Fourier transform of the scattering vector, and the radius of inertia can be determined from the peak position, and the shape and its variation can be determined from the peak width. The radius of inertia in the present invention refers to this value when the Guinier plot is a substantially straight line and the radius of inertia is determined to be one from its slope. When the Guinier plot is a curve, and the slope of the Guineer plot does not determine one radius of inertia, a distance distribution function is obtained by Fourier transform of a scattering vector, and the radius of inertia obtained from the peak position is used.

The radius of inertia Rg has a correlation with the particle radius r,
In the case of spherical particles, the following relationship holds. Rg ² = 3/5 · r ^{2 When} twice the particle radius r is substantially equal to the correlation length lc, there is a relationship that the scatterer in the sample is monodisperse and spherical,
The correlation length lc is obtained by the following equation. lc = ∫ [I (h) hdh] / ∫ [I (h) h ² dh] The radius of gyration of the fine particles was determined by the small-angle scattering X-ray analysis shown below.

[Small Angle Scattering X-Ray Analysis Conditions] X-ray generator: RU-200B (Rotating Cathode Type) manufactured by Rigaku Corporation X-ray source: Cu-Kα ray Flat graphite incident monochromator used Current, voltage: 40 kV, 200 mA Optical system: Kratky camera manufactured by Rigaku Denki Co., Ltd. U-slit Width: 70 μm Height: 15 mm Detector: PSPC (Position-sensitive proportional counter) manufactured by Rigaku Denki Co., Ltd. Light receiving slit: 8 mm height Integration time: 4000 seconds Number of channels: 512 (45. 7ch / deg.) Distance from sample to detector: 300mm

[Measurement Results] The measurement results of MS51 The result was that the radius of inertia was 4 ° or less, but since this value is below the lower limit of detection in this analysis method, it can be said that there is no particle formation. Measurement result of water-soluble resin A-1 The radius of inertia was 12.6 ° and the correlation length was 28.6 °. Measurement result of water-soluble resin composition A-2 The radius of inertia was 42.6 ° and the correlation length was 61.5 °.

[0106]

[Table 5]

The siloxane composition of Example 1 (MS51)
Has a radius of inertia Rg of about 13 ° and a correlation length Lc of about 29 °. Meanwhile, MS
The water-soluble resin composition A-2 obtained by blending and aging 51 is
Inertia radius Rg about 43 °, correlation length Lc about 62 °, MS5
The scattering intensity was clearly higher than that of the water-soluble resin A-1 before one compounding, and the presence as particles was confirmed. A water-soluble resin composition A prepared by blending and aging MS51
-2, the distance distribution function is asymmetrical, and if twice the radius of inertia is approximately equal to the correlation length, the particles are considered to be monodisperse and nearly spherical, so the particles in this system are not monodisperse, It is presumed to have an irregular shape.

4) Summary of Analysis From the analysis results of Si-NMR, GPC and small angle X-ray scattering, the added siloxane composition itself (MS51) grows to several tens of degrees or more and is almost close to silica (SiO ₂ ). Despite the state, it is considered that the liquid is stabilized because it is partially siloxane-bonded to the resin side, and the whole liquid does not gel.

Example 2 (Synthesis of Water-Soluble Resin Having Siloxane Bond)
400 g of isopropyl alcohol was charged into a two-liter four-necked flask equipped with a temperature controller, a thermometer, a reflux condenser, a dropping funnel and a nitrogen gas inlet tube, and heated to 75 ° C. while introducing nitrogen gas. After raising the temperature and adding 1.6 g of AIBN, a monomer mixture obtained by stirring and mixing 100 g of butyl acrylate, 220 g of methyl methacrylate, 60 g of methacrylic acid, 20 g of 3-methacryloxypropyltrimethoxysilane, and 5 g of lauryl mercaptan. Was added dropwise from a dropping funnel over 5 hours to carry out polymerization at 75 ° C.

After completion of the dropwise addition, 0.8 g of ADVN was dissolved in 2 g of isopropyl alcohol and added. The mixture was aged at 80 ° C. for 3 hours, cooled and cooled, 20 g of 25% ammonium water, 800 g of ion-exchanged water and 400 g of isopropyl alcohol.
r-containing water-soluble resin B-1 having a siloxane bond
I got The obtained water-soluble resin B-1 had a nonvolatile content of 20.1.
%, PH 8.0 and viscosity 100 cP.

(Blending and aging) The water-soluble resin B- prepared above was placed in a 2-liter four-necked flask equipped with a stirrer, a temperature controller, a thermometer, a reflux condenser, and a dropping funnel.
1: 1000 g and 50 g of ion-exchanged water were charged, the temperature was raised, and at an internal temperature of 60 ° C., using a dropping funnel, a siloxane composition MKC silicate MS51 (manufactured by Mitsubishi Chemical Corporation).
While stirring 50 g, gradually drop it over 30 minutes,
Further, aging was performed at the same temperature for 5 hours with stirring, and then the mixture was cooled to obtain a water-soluble resin composition B-2. This water-soluble resin composition B-2 has a nonvolatile content of 20.5% and a pH of 8.
0 and a transparent aqueous solution having a viscosity of 200 cP.

(Solvent removal) Stirrer, temperature controller, thermometer,
Into a two-liter four-necked flask equipped with a reflux condenser or a rectification tower and a dropping funnel was charged 1000 g of the water-soluble resin composition B-2 prepared above, and the temperature was raised to an internal temperature of 90%. 850 g was taken out while removing isopropyl alcohol from the system under reduced pressure for 5 hours while azeotroping at ℃.
It takes 30 minutes while further stirring, and gradually deionized water 8
50 g was added dropwise, and the mixture was completely dissolved in water for 2 hours with stirring at the same temperature, and then cooled to obtain a water-soluble resin composition B-3. This water-soluble resin composition B-3 has a nonvolatile content of 21.2.
%, PH 8.0, viscosity 5000 cP, and 0.3% isopropyl alcohol. In addition, isopropyl alcohol was measured by gas chromatography.

Example 3 (Synthesis of Water-Soluble Resin Having Siloxane Bond)
400 g of butyl cellosolve was charged into a two-liter four-necked flask equipped with a temperature controller, a thermometer, a reflux condenser, a dropping funnel and a nitrogen gas inlet tube, and the temperature was raised to 75 ° C. while introducing nitrogen gas. After heating and adding 1.6 g of AIBN, 20 g of butyl acrylate and 1 g of methyl methacrylate were added.
80 g, 80 g of acrylic acid, 120 g of 3-acryloxypropyltrimethoxysilane, lauryl mercaptan 8
g was stirred and mixed, and a monomer mixture obtained was dropped from a dropping funnel over 5 hours to carry out polymerization at 75 ° C. After completion of the dropwise addition, 0.8 g of ADVN was dissolved in 2 g of butyl cellosolve, added, and aged at 80 ° C. for 3 hours.
20 g of ammonium water and 400 g of ion-exchanged water were added to obtain a water-soluble resin C-1 having a siloxane bond.
The obtained water-soluble resin C-1 has a nonvolatile content of 33.1%, PH
It was a clear aqueous solution with a viscosity of 3000 cP and a pH of 8.0.

(Blending and Aging) The water-soluble resin B- prepared above was placed in a two-liter four-necked flask equipped with a stirrer, a temperature controller, a thermometer, a reflux condenser, and a dropping funnel.
1: 1000 g and ion-exchanged water 330 g were charged and heated to an internal temperature of 60 ° C. using a dropping funnel to prepare a siloxane composition MKC silicate MS51 (Mitsubishi Chemical Corporation)
) Was gradually added dropwise over 30 minutes with stirring, and aged at the same temperature for 5 hours under stirring.
Then, it cooled and obtained the water-soluble resin composition C-2. This water-soluble resin composition C-2 has a nonvolatile content of 33.5%, PH
It was a clear aqueous solution having a viscosity of 8.0 cP and a viscosity of 6000 cP.

Example 4 (Synthesis of Water-Soluble Resin Having Siloxane Bond)
400 g of isopropyl alcohol was charged into a two-liter four-necked flask equipped with a temperature controller, a thermometer, a reflux condenser, a dropping funnel and a nitrogen gas inlet tube, and heated to 75 ° C. while introducing nitrogen gas. After raising the temperature and adding 1.6 g of AIBN, a monomer obtained by stirring and mixing 100 g of 2-ethylhexyl acrylate, 200 g of methyl methacrylate, 60 g of dimethylaminoethyl methacrylate, and 40 g of 3-methacryloxypropyltrimethoxysilane. The mixture was dropped from a dropping funnel over 5 hours, and polymerization was carried out at 75 ° C. After completion of the dropping, 0.8 g of ADVN was dissolved in 2 g of isopropyl alcohol and added, and the mixture was aged at 80 ° C. for 3 hours. After cooling, 10 g of acetic acid and 400 g of ion-exchanged water were added. 1 was obtained. The obtained water-soluble resin D-1 has a nonvolatile content of 33.1%,
It was a clear aqueous solution having a pH of 6.0 and a viscosity of 1800 cP.

(Mixing and aging) The water-soluble resin D- prepared above was placed in a two-liter four-necked flask equipped with a stirrer, a temperature controller, a thermometer, a reflux condenser, and a dropping funnel.
1: 1000 g and 100 g of ion-exchanged water were charged and heated to an internal temperature of 60 ° C. using a dropping funnel to prepare a siloxane composition MKC silicate MS56 (polymethoxysiloxane manufactured by Mitsubishi Chemical Corporation: weight Average molecular weight 1000-1
400, 100 g of SiO _1.0 (OMe) _2.0 ) was gradually added dropwise with stirring over 30 minutes, and aged at the same temperature for 5 hours with stirring. The product D-2 was obtained. This water-soluble resin composition D
-2: Non-volatile content 33.5%, PH 8.0, viscosity 300
It was a clear aqueous solution of 0 cP.

Example 5 (Synthesis of Water-Soluble Resin Having Siloxane Bond)
400 g of isopropyl alcohol was charged into a two-liter four-necked flask equipped with a temperature controller, a thermometer, a reflux condenser, a dropping funnel and a nitrogen gas inlet tube, and heated to 75 ° C. while introducing nitrogen gas. After heating and adding 1.6 g of AIBN, 40 g of butyl acrylate, 200 g of methyl methacrylate, 160 g of hydroxyethyl methacrylate
g, 3-methacryloxypropyltrimethoxysilane 4
g was stirred and mixed, and a monomer mixture obtained was dropped from a dropping funnel over 5 hours to carry out polymerization at 75 ° C. After completion of the dropwise addition, 0.8 g of ADVN was dissolved in 2 g of isopropyl alcohol and added, and the mixture was aged at 80 ° C. for 3 hours. After cooling, 2 g of triethylamine and 400 g of ion-exchanged water were added. 1 was obtained.
The obtained water-soluble resin E-1 has a nonvolatile content of 33.1%, PH
It was a clear aqueous solution with a viscosity of 7.0 and a viscosity of 1000 cP.

(Blending and Aging) The water-soluble resin E- prepared above was placed in a two-liter four-necked flask equipped with a stirrer, a temperature controller, a thermometer, a reflux condenser, and a dropping funnel.
1: 1000 g and 30 g of ion-exchanged water were charged, the temperature was raised, and at an internal temperature of 60 ° C., using a dropping funnel, a siloxane composition MKC silicate MS51 (manufactured by Mitsubishi Chemical Corporation).
While stirring 30 g, gradually drop it over 30 minutes,
Further aging for 5 hours under stirring at the same temperature,
Upon cooling, a water-soluble resin composition E-2 was obtained. This water-soluble resin composition E-2 has a nonvolatile content of 33.5%, PH of 8.0,
It was a transparent aqueous solution having a viscosity of 3000 cP.

Comparative Example 1 The same monomer composition and operation as in Example 1 except that 3-methacryloxypropyltrimethoxysilane (A-174) was omitted in the section of synthesis of the water-soluble resin A-1 in Example 1. Was carried out to obtain a water-soluble resin F-1 having no siloxane bond. The obtained water-soluble resin F-1 had a nonvolatile content of 38.5.
%, PH 8.0, and a viscosity of 500 cP.

Comparative Example 2 The water-soluble resin F-1 obtained in Comparative Example 1 was mixed with 500 g of M
50 g of KC silicate MS51 (manufactured by Mitsubishi Chemical Corporation) was added dropwise over 30 minutes at room temperature and with stirring, the temperature was raised to 60 ° C., and the mixture was aged with stirring at PH 8.0, and the water-soluble resin composition F was obtained.
During the synthesis of -2, the whole liquid gelled after 30 minutes.

Comparative Example 3 The water-soluble resin A-1 obtained in Example 1 was added to 500 g of M
50 g of KC silicate MS51 (manufactured by Mitsubishi Chemical Corporation) was added dropwise at room temperature and with stirring over 30 minutes to synthesize a water-soluble resin composition A-4 that had just been blended and had not been subjected to aging. The obtained water-soluble resin A-4 had a nonvolatile content of 45.2.
%, PH 7.8, and a viscosity of 1200 cP.

Comparative Example 4 400 g of isopropyl alcohol was charged into a two-liter four-necked flask equipped with a stirrer, a temperature controller, a thermometer, a reflux condenser, a dropping funnel and a nitrogen gas inlet tube. The temperature was raised to 75 ° C while introducing gas, and AIBN
After adding 1.6 g, a monomer mixture obtained by stirring and mixing 20 g of methyl methacrylate, 60 g of methacrylic acid, 320 g of 3-methacryloxypropyltrimethoxysilane, and 5 g of lauryl mercaptan was dropped from the dropping funnel for 5 hours. The mixture was added dropwise to carry out polymerization at 75 ° C. After dropping, A
0.8 g of DVN is dissolved in 2 g of isopropyl alcohol and added, and the mixture is aged at 80 ° C. to synthesize the water-soluble resin G-1.
Could not get.

Example 6 Preparation of Coating Solution and Evaluation of Clear Coating Film The water-soluble resin obtained in Examples 1 to 5 and Comparative Examples 1 to 3 and the solid content concentration in the water-soluble resin composition were reduced to 20%. Water was appropriately blended to prepare a coating liquid having a viscosity of 100 cp or less. The viscosity increase or the gelation state of these coating liquids when they were stored at 50 ° C. for 2 weeks were confirmed as a result of standing stability, and the M in the preparation of each water-soluble resin composition.
Table 1 shows the mixing stability when S51 was added.

Further, 100 g of these coating liquids
(Examples 1 to 4 and Comparative Example 1) were added to a water-soluble epoxy resin (manufactured by Nagase Kasei Co., Ltd.) Denacol EX to improve water resistance.
-521 (polyglycerol polyglycidyl ether)
After mixing 10 g, the coating liquid 1 of Example 5
After mixing 5 g of PAPI135: 5 g of a polyisocyanate resin (manufactured by Dow Polyurethane Nippon Co., Ltd.) with 00 g, spray coating is performed at a coating amount of 100 g / m ² using a glass substrate, and cured at 40 ° C. for 30 minutes. Table 2 shows the evaluation results of the resulting clear coating films.

Example 7 Preparation of paint and evaluation of coating film 100 g of each coating solution of Examples 1 to 4 and Comparative Example 1
10 g of a water-soluble epoxy resin (manufactured by Nagase Kasei Co., Ltd.) Denacol EX-521 (polyglycerol polyglycidyl ether) and titanium paste SD-7042 (manufactured by Dainippon Ink and Chemicals, Inc.) paste)
5 g were blended and stirred to prepare each paint. Also, 5 g of polyisocyanate resin (manufactured by Dow Polyurethane Japan Co., Ltd.) PAPI135: 5 g and titanium paste SD-70 manufactured by Dainippon Ink Co., Ltd. were added to the coating solution of Example 5.
5 g of 42 (60% water-dispersed titanium paste) was mixed and stirred to prepare each paint. Using a slate plate as a base material, a chlorinated rubber sealer (manufactured by Asahi Denka Co., Ltd.) was spray-coated at 100 g / m ² wet,
After standing for a day, each of the above-prepared paints is 250 to 300 g /
Spray coating was performed with m ² wet and cured at 40 ° C. for 30 minutes to form a coating film. Table 3 shows the evaluation results of these coating films. The test method for evaluating the coating film is described below.

Test Method 1 (Warm Water Resistance) The appearance when the sample was completely immersed in warm water at 60 ° C. for 10 days and was pulled up, and the appearance after drying at room temperature were determined. A: No peeling. ：: Pinhole-shaped peeling occurred. Δ: Partial peeling occurred. ×: Peeling occurred entirely.

Test Method 2 (Solvent Resistance) A paper towel was sufficiently impregnated with tetrahydrofuran (hereinafter referred to as THF), methyl ethyl ketone (hereinafter referred to as MEK) or methanol to form a film or a coating film on the test piece. Was rubbed 50 times, the surface condition was observed, and evaluated based on the following criteria. A: No whitening or blistering. ：: slight whitening occurred. Δ: Whitening and blistering occurred simultaneously. ×: Film and coating film dissolved.

Test Method 3 (Pencil Hardness) After drawing a line at an angle of 45 ° on the film or coating surface of the sample with a pencil for various hardness, the surface was erased with an eraser, and the coating surface of the coating surface was scratched and erased. The hardness of the pencil which cannot be scratched and which cannot be scratched was defined as the hardness of the coating film. Test method 4 (Initial gloss of paint film) Each paint coated plate was measured with a gloss meter (incident angle 60 degrees, reflection angle 60 degrees).
Was measured.

Test Method 5 (Gloss of coating film) Each paint-coated plate was measured for 200 days with a sunshine weathering tester.
The test piece irradiated with UV light for 0 hr was measured with a gloss meter (incidence angle: 60 degrees, reflection angle: 60 degrees) to determine what percentage of the initial gloss was. Test Method 6 (Color difference of coating film) Each paint-coated plate was tested with a sunshine weathering tester for 200 hours.
The test piece irradiated with UV light for 0 hr was measured with a color difference meter, and the difference from the initial color difference was measured.

Test Method 7 (Contamination) Each paint-coated plate was placed on an outdoor exposure table at a 45 ° southward angle of 1 °.
After standing for one year, the degree of contamination was evaluated according to the following criteria. ◎ The stain on the coating film surface is hardly noticeable without washing with water. ○ Dirt on the surface of the coating film was removed by light washing. Δ: The surface of the coating film was strongly stained by washing with water. × The stain on the coating film surface cannot be removed by washing with water.

Sunshine weathering tester Toyo Seiki Seisakusho Co., Ltd. Ci35 xenon lamp-type weathermeter gloss meter Suga Testing Machine Co., Ltd. UGV-50D digital variable angle glossmeter Color difference meter Minolta camera Co., Ltd. CR-300 colorimeter

[0132]

[Table 6]

[0133]

[Table 7] Each coating solution was added with water to a solid content of 20% (viscosity 1
(Less than 00 cp).

[0134]

[Table 8]

[0135]

The water-soluble resin composition or the coating composition containing the same according to the present invention comprises a conventional water-based resin composition containing a hydrolyzable silyl group and a water-based resin composition obtained by simply adding a siloxane compound thereto. Compared with the resin composition, the storage stability is extremely good, and the coating film obtained by curing this resin has excellent functions such as high hardness, scratch resistance, chemical resistance, stain resistance, weather resistance and heat resistance. It is particularly useful in applications such as coating agents, paints, and adhesives.

 ──────────────────────────────────────────────────続 き Continuing from the front page (72) Daisuke Miki, Inventor 1-13-13, Shodida, Hirakata City, Osaka Prefecture Inside Chuo Rika Kogyo Co., Ltd. (72) Inventor Takeshi Sawai 1-1 Kurosaki Castle Stone, Yawatanishi-ku, Kitakyushu-shi Mitsubishi Chemical Corporation Kurosaki Office

Claims (14)

[Claims] 1. A resin composition comprising the following (1) and (2): (1) a water-soluble resin having a siloxane bond (2) a siloxane composition represented by the general formula (A): _a general formula (A): SiO _a X _b Y _c (where X is a hydrolyzable group, and Y is A hydrolyzable group, 0 ≦ a ≦ 1.4, b / (b + c) = 0.01 to 1.
0, where 2a + b + c = 4. ) 2. The resin composition according to claim 1, wherein (1) is a water-soluble resin having a pH of 2 to 11. 3. The resin composition according to claim 1, wherein (1) is a water-soluble resin obtained by neutralizing a resin having a carboxyl group. 4. The resin composition according to claim 1, wherein (1) is a water-soluble resin comprising a resin having a hydroxyl group. 5. The resin composition according to claim 1, wherein (1) is a water-soluble resin obtained by neutralizing a resin having a sulfonic acid group. 6. The siloxane composition of (2), wherein c
= 0, wherein the resin composition according to any one of claims 1 to 5. 7. A general formula (B): SiO _{a ′} X _{b ′} Y _{c ′} (wherein X is a hydrolyzable group, Y is a non-hydrolyzable group, and 1.4 <a ′ <2; b ′ / (b ′ + c ′) = 0.0
1 to 1.0, where 2a '+ b' + c '= 4. A resin composition comprising a siloxane component represented by the formula (1): 8. The resin composition according to claim 7, wherein the siloxane component forms fine particles having an inertial radius of 20 ° to 200 ° according to a small-angle X-ray scattering method. 9. A coating composition comprising a pigment and / or powder dispersed in the resin composition according to claim 1. 10. A resin composition according to claim 1, further comprising an epoxy resin, a polyisocyanate resin, a melamine resin, or a resin having an aziridine, oxazoline ring, or carbodiimide group. Characteristic curable resin composition. 11. The following (1) and (2) are adjusted to pH 2-1.
1. A method for producing a resin composition, wherein compounding and aging are performed in a temperature range of 0 to 200 ° C. (1) a water-soluble resin having a siloxane bond (2) a siloxane composition represented by the general formula (A): _a general formula (A): SiO _a X _b Y _c (where X is a hydrolyzable group, and Y is A hydrolyzable group, 0 ≦ a ≦ 1.4, b / (b + c) = 0.01 to 1.
0, where 2a + b + c = 4. ) 12. The resin composition according to claim 11, wherein an organic solvent is present when compounding (1) and (2), and compounding and aging are performed within a temperature range of 0 to 200 ° C. Method of manufacturing a product. 13. A coated product obtained by coating the curable resin composition according to claim 10 on a substrate. 14. A coated product obtained by coating the coating composition according to claim 9 on a substrate.