JPH11209473A - Water-base resin, production thereof, and water-base curable resin composition containing same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a water-base resin which is excellent in curability and storage stability and forms a cured coating film excellent in gloss retention and durability such as stain resistance in outdoor exposure and resistance to acid rain, a process for producing the same, and a water-base curable resin compsn. contg. the same. SOLUTION: A mixture and/or a condensate formed from (A) a polysiloxane having Si-bonded hydrolyzable groups and/or Si-bonded hydroxyl groups and cycloalkyl groups bonded to at least 10 mol.% of the total Si atoms and (B-1) a polymer having acidic or basic groups is partially or completely neutralized with a basic or acidic compd. and then is dispersed or dissolved in a water-base medium, thus giving the objective water-base resin.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

TECHNICAL FIELD The present invention relates to a novel and useful aqueous resin, a novel and useful method for producing the aqueous resin,
The present invention relates to a novel and useful aqueous curable resin composition containing the aqueous resin as an essential component. More specifically, a mixture and / or condensate composed of a specific polysiloxane containing a cycloalkyl group and a specific polymer containing an acid group or a basic group is neutralized with a basic compound or an acidic compound. After being squeezed, an aqueous resin obtained by dispersing or dissolving in an aqueous medium, a method for producing the aqueous resin and containing the aqueous resin as an essential component, an aqueous curable resin composition,

Furthermore, at least one selected from the group consisting of a specific polysiloxane containing a cycloalkyl group and an anionic group, a cationic group and a nonionic group.
Aqueous resin obtained by dispersing or dissolving a mixture and / or condensate consisting of a specific polymer having various kinds of hydrophilic groups in an aqueous medium, a method for producing the aqueous resin, and an essential component comprising the aqueous resin Containing as an aqueous curable resin composition,

[0003] In particular, a cured product excellent in various properties such as solvent resistance, chemical resistance and water resistance as well as so-called durability, such as gloss retention, exposure contamination resistance and acid rain resistance. The present invention relates to an aqueous resin which can be formed, and has both excellent curability and excellent storage stability, and also relates to a method for producing the aqueous resin. Comprising, as an essential component, in particular, an aqueous curable resin composition which is excellent in curability, and which can provide a cured product excellent in various properties including durability as described above. Also concerns.

[0004] The composition of the present invention is effectively used for various applications such as various paints, fiber treatment agents, adhesives and sealing agents for building exteriors, building materials, heavy-duty corrosion prevention and vehicles. You can do it.

[0005]

2. Description of the Related Art Heretofore, aqueous curable resin compositions for paints have been prepared by using a vinyl polymer having both a basic group or an acid group and a so-called functional group such as a hydroxyl group. An aqueous resin obtained by neutralizing with a compound or a basic compound and then dispersing or dissolving in an aqueous medium, and various curing agents such as epoxy resins, isocyanate resins and amino resins. Aqueous curable resin composition (JP-A-4-359075, JP-A-6-1948, JP-T-8-51000)
0, European Patent EP 661320-A1) is widely used.

However, such a cured coating film obtained from an aqueous curable resin composition using a conventionally used aqueous resin as a so-called base resin component has, among other things, gloss retention during exposure, exposure resistance, and the like. In applications where the so-called durability such as pollution resistance and acid rain resistance is inadequate and therefore high durability is required, it can be used and applied almost completely. Absent,
There is a problem.

[0007] The present inventors have conducted research to solve such problems, and as a result, in addition to a polymer having both a hydrolyzable silyl group and an acid group, or a polymer having both a hydrolyzable silyl group and an acid group, After a condensation reaction between a polymer having a functional group other than these two types of functional groups and a polysiloxane having a hydroxyl group bonded to a silicon atom and / or a hydrolyzable group bonded to a silicon atom, a base is formed. Aqueous resin obtained by dispersing or dissolving a resin obtained by partially or completely neutralizing with a reactive compound in an aqueous medium is found to be excellent in curability and storage stability. An aqueous curable resin composition containing
It has been found that it gives a cured coating with excellent durability such as gloss retention, acid resistance, acid rain resistance and exposure contamination resistance,
First, a patent application was filed (Japanese Patent Application No. 8-197478).
issue).

However, in such an aqueous resin,
In order to ensure long-term storage stability, it is necessary to use a polysiloxane having an aryl group bonded to 10 mol% or more of all silicon atoms. Therefore, gloss retention during long-term exposure is required. It was found that the level was not at a satisfactory level.

[0009]

SUMMARY OF THE INVENTION However, the present inventors have completely solved the above-mentioned various problems in the conventional technology, and have completely eliminated the various disadvantages or defects in the conventional technology. In order to solve it, we started research earnestly.

[0010] Accordingly, an object of the present invention is to provide a cured product excellent in durability such as long-term gloss retention, exposure contamination resistance and acid rain resistance. And to provide a new and useful aqueous resin itself having excellent storage stability and the like, and also to provide a method for producing such an aqueous resin. An object of the present invention is to provide a novel and useful aqueous curable resin composition which provides a cured coating film having extremely excellent durability, which contains a useful aqueous resin.

Therefore, the present inventors have conducted further studies in order to solve the above-mentioned problems, and as a result,

A hydrolyzable group bonded to a silicon atom and / or
Or a specific polysiloxane having a hydroxyl group bonded to a silicon atom and having a cycloalkyl group bonded to 10 mol% or more of all silicon atoms, and a polymer having an acid group or a basic group. The mixture and / or condensate

Alternatively, in addition to the polysiloxane, an acid group or a basic group, a combination of the acid group or the basic group, a hydrolyzable group bonded to a silicon atom, and a hydroxyl group bonded to a silicon atom. After partially or completely neutralizing a mixture and / or a condensate comprising a polymer having a functional group other than the three groups together with a basic compound or an acidic compound, the mixture is dispersed or dispersed in an aqueous medium. Aqueous resin obtained by dissolving,

Alternatively, a mixture and / or condensate comprising the polysiloxane and a polymer having at least one kind of hydrophilic group selected from the group consisting of an anionic group, a cationic group and a nonionic group is prepared. Or, in addition to at least one hydrophilic group selected from the group consisting of an anionic group, a cationic group, and a nonionic group, the hydrophilic group, a hydrolyzable group bonded to a silicon atom, and a silicon atom An aqueous resin obtained by dispersing or dissolving a mixture and / or condensate of a polymer having a functional group other than the three types of groups with a hydroxyl group bonded to an aqueous medium is particularly preferable. , Found excellent in curability and long-term storage stability, and established a method for producing the aqueous resin,

An aqueous curable resin composition containing the aqueous resin as an essential component is to provide a cured product having extremely high gloss retention in addition to being excellent in acid rain resistance, exposure contamination resistance and the like. The present invention has been completed here by ascertaining that the problem to be solved by the present invention as described above can be brilliantly solved.

[0016]

That is, the present invention basically has a hydrolyzable group bonded to a silicon atom and / or a hydroxyl group bonded to a silicon atom, and one of all silicon atoms.
A mixture and / or condensate comprising a polysiloxane (A) having a cycloalkyl group bonded to at least 0 mol% and a polymer (B-1) having an acid group or a basic group,
Aqueous resin (W-1) obtained by partially or completely neutralizing with a basic compound or an acidic compound and then dispersing or dissolving in an aqueous medium, the aqueous resin (W-
1) The composition containing the aqueous resin (W-1) as an essential component, and the aqueous resin (W-
It is an object of the present invention to provide an aqueous curable resin composition containing 1) and a compound (C) having a functional group that reacts with a functional group contained in the aqueous resin (W-1),

In addition, a polysiloxane having a hydrolyzable group bonded to a silicon atom and / or a hydroxyl group bonded to a silicon atom, and having a cycloalkyl group bonded to at least 10 mol% of all silicon atoms ( A) and, in addition to the acid or basic group, the acid group or the basic group, a hydrolyzable group bonded to a silicon atom, and a hydroxyl group bonded to a silicon atom. A mixture and / or condensate consisting of the polymer (B-2) also having a functional group of
Aqueous resin (W-2) obtained by partially or completely neutralizing with a basic compound or an acidic compound and then dispersing or dissolving in an aqueous medium;
2) The composition containing the aqueous resin (W-2) as an essential component, and the aqueous resin (W-
2) and an aqueous curable resin composition containing a compound (C) having a functional group that reacts with a functional group contained in the aqueous resin (W-2).

Further, a polysiloxane (A) having a hydrolyzable group bonded to a silicon atom and / or a hydroxyl group bonded to a silicon atom, and having a cycloalkyl group bonded to at least 10 mol% of all silicon atoms (A ) And an anionic group,
Polymers having at least one hydrophilic group selected from the group consisting of cationic groups and nonionic groups (B-
An aqueous resin (W) obtained by dispersing or dissolving a mixture and / or a condensate of
-3), a method for producing the aqueous resin (W-3) and a composition containing the aqueous resin (W-3) as an essential component, and further, the aqueous resin (W-3) and the aqueous resin ( W-3)
It is an object of the present invention to provide an aqueous curable resin composition which also contains a compound (C) having a functional group that reacts with a functional group contained in

Further, a polysiloxane having a hydrolyzable group bonded to a silicon atom and / or a hydroxyl group bonded to a silicon atom, and having a cycloalkyl group bonded to at least 10 mol% of all silicon atoms ( A) and an anionic group,
Selected from the group consisting of a cationic group and a nonionic group, in addition to at least one hydrophilic group, the hydrophilic group,
A mixture and / or condensate of a polymer (B-4) having both a hydrolyzable group bonded to a silicon atom and a hydroxyl group bonded to a silicon atom, which also has a functional group other than the three types of groups. (W-4) obtained by dispersing or dissolving in a water-based medium, a method for producing the water-based resin (W-4), and a composition containing the water-based resin (W-4) as an essential component Further, an aqueous curable resin composition containing the aqueous resin (W-4) and a compound (C) having a functional group that reacts with a functional group contained in the aqueous resin (W-4) will be provided. It is assumed that.

<< Configuration >>

Hereinafter, the present invention will be described in further detail.
I will explain.

The aqueous resin (W-1) according to the present invention has a hydrolyzable group bonded to a silicon atom and / or a hydroxyl group bonded to a silicon atom, and has an amount of not less than 10 mol% of all silicon atoms. A polysiloxane (A) having a cycloalkyl group bonded thereto and a polymer having an acid group or a basic group (B-
An aqueous resin obtained by partially or completely neutralizing the mixture and / or condensate of 1) with a basic compound or an acidic compound, and then dispersing or dissolving in an aqueous medium.

Further, the aqueous resin (W-2) according to the present invention has a hydrolyzable group bonded to a silicon atom and / or a hydroxyl group bonded to a silicon atom, and has one of all silicon atoms.
A polysiloxane (A) having a cycloalkyl group bonded to at least 0 mol%, an acid group or a basic group, and the acid group or the basic group, and a hydrolyzable group bonded to a silicon atom; A mixture and / or a condensate consisting of a hydroxyl group bonded to a silicon atom, and a polymer (B-2) which also has a functional group other than the three types of groups, are partially or partially mixed with a basic compound or an acidic compound. It is an aqueous resin obtained by being neutralized or completely neutralized and then dispersed or dissolved in an aqueous medium.

Further, the aqueous resin (W-3) according to the present invention
Is a polysiloxane (A) having a hydrolyzable group bonded to a silicon atom and / or a hydroxyl group bonded to a silicon atom, and having a cycloalkyl group bonded to at least 10 mol% of all silicon atoms. At least one selected from the group consisting of anionic groups, cationic groups and nonionic groups
It is an aqueous resin obtained by dispersing or dissolving a mixture and / or condensate comprising a polymer (B-3) having a kind of hydrophilic group in an aqueous medium.

Further, the aqueous resin (W-
4) is a polysiloxane (A) having a hydrolyzable group bonded to a silicon atom and / or a hydroxyl group bonded to a silicon atom, and having a cycloalkyl group bonded to 10 mol% or more of all silicon atoms. ) And at least one hydrophilic group selected from the group consisting of an anionic group, a cationic group and a nonionic group, a hydrophilic group, a hydrolyzable group bonded to a silicon atom, and a silicon atom And a polymer (B-4) having a functional group other than the three types of groups together with a hydroxyl group bonded to
It is an aqueous resin obtained by dispersing or dissolving in an aqueous medium.

Such aqueous resins (W-1), (W-2),
As a precursor for preparing (W-3) or (W-4), each of the polymers (B-1), (B-2), (B-3) or (B-4) and Mixtures and / or condensates with siloxane (A) are used.

Therefore, such precursors include:
Polymer (B-1), (B-2), (B-3) or (B
-4) and a mere mixture of polysiloxane (A), (B-1), (B-2), (B-3) or (B-4) and (A) are chemically bonded. Each of the condensate, polymer (B-1), (B-2), (B-3) or (B-4) and polysiloxane (A)
There are the above-mentioned condensates, expediently, three kinds of mixtures, etc.
From the viewpoint of the curability and durability of the obtained aqueous resin, it is particularly preferable that at least a part of the aqueous resin contains a condensate.

The bonding mode of each of the polymers (B-1) to (B-4) in the condensate and the polysiloxane (A) is represented by the following structural formula (SI)
Although a mode such as I) or the following structural formula (S-III) can be adopted, from the viewpoint of achieving a high degree of durability, it is particularly preferable to employ a bonding mode of the structural formula (S-II). .

[0029]

Embedded image (However, in the formula, the carbon atom is a polymer (B-1), (B
-2), a part of the segment derived from each of (B-3) and (B-4), and the silicon atom bonded only to the oxygen atom is a part of the segment derived from the polysiloxane (A). Shall be constituted. )

[0030]

Embedded image (However, in the formula, the carbon atom is a polymer (B-1), (B
-2), a part of the segment derived from each of (B-3) and (B-4), and the silicon atom bonded only to the oxygen atom is a part of the segment derived from the polysiloxane (A). Shall be constituted. )

Aqueous resins (W-1), (W-2), (W-
3) The polysiloxane (A) which is one of the constituent components of the precursor of (W-4) is at least 10 mol%, preferably 20 mol%, of all the silicon atoms constituting the polysiloxane. As described above, it is more preferable that a cycloalkyl group is bonded to at least 40 mol% of silicon atoms from the viewpoint of the stability of the obtained aqueous resin.

The polysiloxane (A) has the following structural formula (S-IV)

[0033]

Embedded image (However, R ¹ in the formula is at least one kind selected from the group consisting of an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group and an alkenyl group, which may or may not have a substituent. It represents a monovalent organic group.)

Having the structure shown as an essential unit structure, that is, having a branched structure,
From the viewpoint of the durability of the cured product obtained from the composition of the present invention,
Particularly preferred.

Further, aqueous resins (W-1), (W-2),
Polymers (B-1), (B-2), and (B-) which are the other components of the precursor of (W-3) or (W-4).
3) or (B-4) includes an acrylic polymer, a fluoroolefin polymer, a vinyl ester polymer,
There are various vinyl polymers such as an aromatic vinyl polymer or a polyolefin polymer, and further, a polymer other than a vinyl polymer such as a polyester polymer, an alkyd polymer or a polyurethane polymer. There is coalescence.

Among these, particularly preferred are vinyl polymers and polyurethane polymers, and particularly preferred among vinyl polymers are acrylic polymers and fluoroolefin polymers. Is mentioned.

The aqueous resins (W-1) and (W-
In preparing (2), (W-3) or (W-4), the polysiloxane (A) and the polymer (B-1), (B
-2), (B-3) or (B-4) is derived from the polysiloxane (A) contained in each of the aqueous resins (W-1) to (W-4). Segment: The weight ratio of the segment derived from each of the polymers (B-1), (B-2), (B-3) and (B-4) is about 5:95 to 95: 5. Preferably, it is set to be 10:90 to 90:10, more preferably, to be 10:90 to 80:20.

In the aqueous resins (W-1) to (W-4), the segments derived from each of the polymers (B-1), (B-2), (B-3) and (B-4) are If the weight ratio is set to be less than about 5%, the alkali resistance of the cured product obtained from the composition of the present invention is lowered or cracks are easily generated because the polysiloxane component is too large. And the polymer (B
-1), (B-2), (B-3) or (B-4), when the weight ratio of the segment derived from each of them is excessively larger than about 95%, the poly is absolutely necessary. Since the amount of the siloxane component is too small, the durability of the obtained cured product such as exposure stain resistance and gloss retention is reduced.

The polysiloxane (A) or the polymer (b-1), (b-2), (b-3) or (b-4) described later binds to a silicon atom contained in the polysiloxane (A). The term "hydrolysable group" as used herein refers to a group that easily undergoes hydrolysis and is eliminated to form a hydroxyl group bonded to a silicon atom, that is, a silanol group. Typical examples thereof include an alkoxy group and a substituted group. Alkoxy group, acyloxy group, halogen atom,
Examples include an alkenyloxy group, a phenoxy group, a mercapto group, an amino group, an amide group, an aminooxy group, an iminooxy group, and a hydrogen atom.

And, among these hydrolyzable groups,
One particularly preferred example is an alkoxy group.

As the acid group contained in the polymer (B-1) or (B-2), various known and commonly used acid groups are introduced. Among them, only typical ones are exemplified. If it is, a carboxyl group, a phosphate group, an acidic phosphate group,
Examples include a phosphorous acid group, a sulfonic acid group or a sulfinic acid group.

Then, the polymer (B-3) or (B-
As the anionic group contained in 4), various known and commonly used anionic groups may be introduced.
As described above, there can be mentioned those obtained by neutralizing a known and commonly used acid group with a basic compound.

Representative examples of the basic compound used for neutralizing the above-mentioned acid group to convert it into an anionic group include methylamine, dimethylamine, trimethylamine, ethylamine, diethylamine, triethylamine, and the like. Various organic amines such as 2-aminoethanol or 2-dimethylaminoethanol; various inorganic basic substances such as ammonia, lithium hydroxide, sodium hydroxide or potassium hydroxide;

Various quaternary ammonium hydroxides such as tetramethylammonium hydroxide, tetra-n-butylammonium hydroxide and trimethylbenzylammonium hydroxide are exemplified.

As the basic group contained in the polymer (B-1) or (B-2), various types of known and commonly used basic groups are introduced. If it stops, a primary amino group, a secondary amino group, a tertiary amino group, a quaternary ammonium hydroxide group, etc. will be mentioned.

Further, the polymer (B-3) or (B-4)
Various known and commonly used cationic groups are introduced as the cationic group contained therein, and particularly preferred examples include those obtained by neutralizing a known and commonly used basic group with an acidic compound as described above. .

Representative examples of acidic compounds used for neutralizing such basic groups include various carboxylic acids such as formic acid, acetic acid, propionic acid and lactic acid; monomethyl phosphate or dimethyl phosphate Various mono- or diesters of phosphoric acid, such as;

Various organic sulfonic acids such as methanesulfonic acid, benzenesulfonic acid or dodecylbenzenesulfonic acid; and various inorganic acids such as hydrochloric acid, sulfuric acid, nitric acid or phosphoric acid.

Further, the polymer (B-3) or (B-
Examples of the polyether chain as a nonionic group contained in 4) include various polyoxyalkylene chains such as a polyoxyethylene chain, a polyoxypropylene chain, and a polyoxybutylene chain. (Oxyethylene-oxypropylene) chains, in which the oxyalkylene moiety is randomly copolymerized,
Alternatively, various types such as a polyoxyethylene-polyoxypropylene chain in which different polyoxyalkylene chains are bonded in a block shape are exemplified.

Then, the polymer (B-1) or (B-
In 2), the amount of the acid group or basic group introduced is
The number of moles of acid groups or basic groups per 1,000 g of the polymer (B-1) or (B-2) is about 0.1
Molar to about 10 moles is appropriate, preferably 0.2 to 5 moles, and most preferably 0.3 to 3 moles.

Then, the polymer (B-3) or (B-
As the hydrophilic group introduced in 4), the above-described anionic group, cationic group or nonionic group may be used alone, or a combination of anionic group or cationic group and nonionic group may be used. It may be.

When such an anionic group or a cationic group is introduced into the polymer (B-3) or (B-4) as a hydrophilic group, the amount of the anionic group or the cationic group may be,
The number of moles of the anionic group or the cationic group per 000 gram is suitably in the range of about 0.1 mol to about 10 mol, and preferably in the range of 0.2 to 5 mol. Most preferably, it is in the range of 0.3 to 3 mol.

Further, the polymer (B-3) or (B-4)
In the case where a polyether chain as a nonionic group is introduced as a hydrophilic group, the amount of the introduction is about 10 to about 990 g in terms of the number of polyether chains per 1,000 g of the polymer. Is appropriate, preferably within the range of 20 to 900 grams, and most preferably within the range of 40 to 800 grams.

Further, the polymer (B-3) or (B-
4) In the case where both an anionic group or a cationic group and a polyether chain as a nonionic group are introduced as hydrophilic groups, the introduction amount when each is introduced alone is in the range described above. It is preferable to introduce each.

Further, the polymer (B-1) or (B-2)
In addition to the acid group or the basic group, it is also possible to introduce a polyether chain as a nonionic group as a hydrophilic group.
A suitable number of grams of polyether chains per 0 gram is about 10 to about 990 grams, preferably 20 to 900 grams, and most preferably 40 to 800 grams. A range of grams is appropriate.

Introduced into the above-mentioned polymer (B-2)
An acid group or a basic group, a hydrolyzable group bonded to a silicon atom, and a hydroxyl group bonded to a silicon atom, which are functional groups other than three types of groups [hereinafter referred to as a functional group (Fu-1)] And only a typical one is exemplified as a hydroxyl group bonded to a carbon atom, a hydroxyl group bonded to a carbon atom and blocked (hereinafter also referred to as a blocked hydroxyl group), a carboxyl group, and a block. Carboxyl group, carboxylic anhydride group, primary amino group, secondary amino group, tertiary amino group, cyclocarbonate group, epoxy group, oxazoline group, primary amide group, secondary amide group, carbamate group and Structural formula (SI) of

[0057]

Embedded image

And the like.

However, when an acid group is introduced into the polymer (B-2) as a precursor functional group of the anionic group, the above-mentioned various functional groups (Fu-1) are added to the polymer (B-2). ), The carboxyl group, the blocked carboxyl group and the carboxylic anhydride group are not used as the functional group (Fu-1). When a basic group is introduced as a precursor functional group of a cationic group into the polymer (B-2), the above-mentioned various functional groups (Fu-
In 1), the primary amino group, the secondary amino group, and the tertiary amino group are not used as the functional group (Fu-1).

The secondary amide group among the functional groups (Fu-1) is an N-hydroxymethylamide group, an N-alkoxymethylamide group having an alkoxy group having 1 to 8 carbon atoms, or the following: Structural formula (SV)

[0061]

Embedded image —C (O) —NH—CH (OR ² ) —COOR ³ (SV)

(Wherein R ² represents a hydrogen atom, an alkyl group or an aryl group having 1 to 8 carbon atoms, and R ³ represents an alkyl group or an aryl group having 1 to 8 carbon atoms) And.)

It also includes the functional group represented by

Further, these functional groups correspond to the polymer (B-
In 2), only one kind may be contained, or two or more kinds may be contained.

Among the above-mentioned functional groups (Fu-1), particularly preferred are a hydroxyl group, a blocked hydroxyl group, a carboxyl group, a blocked carboxyl group, a carboxylic acid anhydride group, a tertiary amino group, Examples thereof include a carbonate group, an epoxy group, a primary amide group, a secondary amide group, a carbamate group, and a functional group represented by the aforementioned structural formula (SI).

The polymer of the functional group (Fu-1) (B-
2) The amount of solids introduced into the polymer is 1.0
A suitable range is from about 0.1 to about 5 moles, preferably from 0.2 to 3 moles, and even more preferably from 0.3 to 2 moles per 100 grams. It is.

Further, at least one hydrophilic group selected from the group consisting of an anionic group, a cationic group and a nonionic group introduced into the polymer (B-4) is bonded to a silicon atom. Only the typical examples of the functional group other than the three types of groups (hereinafter, also referred to as functional group (Fu-2)), which are conveniently a hydrolyzable group and a hydroxyl group bonded to a silicon atom, are only given as examples. If the functional group (F
Various functional groups exemplified as typical examples of u-1) are given.

Further, these functional groups correspond to the polymer (B-
In 4), only one kind may be contained, or two or more kinds may be contained.

Among the above-mentioned functional groups (Fu-2), particularly preferred are a hydroxyl group bonded to a carbon atom, a blocked hydroxyl group, a tertiary amino group, a carboxyl group,
Examples include a block carboxyl group, a carboxylic acid anhydride group, a cyclocarbonate group, an epoxy group, a primary amide group, a secondary amide group, a carbamate group, or a functional group represented by the aforementioned structural formula (SI).

The functional group (Fu-2) polymer (B-
4) The amount of the solids introduced into the polymer is 1,0
A suitable range is from about 0.1 to about 5 moles, preferably from 0.2 to 3 moles, and even more preferably from 0.3 to 2 moles per 100 grams. It is.

Next, the aqueous resins (W-1) and (W-1)
The method for preparing (-2), (W-3) or (W-4) will be described.

First, the aqueous resin (W-1) or (W-
Among the preparation methods 2), the polysiloxane (A) which is particularly preferred as the precursor thereof as described above.
A method for preparing a condensate in which is bonded to the polymer (B-1) or (B-2) via the bond represented by the structural formula (SI) will be described.

The aqueous resin (W-1) or (W-
Examples of the method for preparing 2) include (a) a free acid group or a free basic group (hereinafter, a free acid group and a free basic group are also collectively referred to as a polar group), a silicon atom A polymer having both a hydrolyzable group and / or a hydroxyl group bonded to a silicon atom, or a polar group and a hydrolyzable group and / or a hydroxyl group bonded to a silicon atom, The polymer also containing the functional group (Fu-1) described above is reacted with the above-mentioned polysiloxane (A), and the water bonded to the silicon atom contained in the polysiloxane (A) and each of the above-mentioned polymers is reacted. After preparing a condensate by bonding via a bond represented by the structural formula (S-II) by a reaction between a decomposable group and / or a hydroxyl group bonded to a silicon atom, the polar group contained is converted to a basic compound or Acid compound In neutralizing allowed, then method in which dispersed or dissolved in an aqueous medium,

(B) having a radical polymerizable double bond, and having the double bond, a hydrolyzable group bonded to a silicon atom and / or a hydroxyl group bonded to a silicon atom, and A polysiloxane having a cycloalkyl group bonded to at least 10 mol% of atoms is represented by the following structural formula (S-V
A compound bonded in the bonding mode shown in I) is used as one of the copolymerization components, and is combined with a vinyl monomer having a free acid group or a vinyl monomer having a free basic group. By copolymerizing a vinyl monomer containing a monomer as an essential component, or in addition to the polysiloxane containing a double bond and a vinyl monomer having a polar group, A monomer having a functional group (Fu-1) as an essential component is copolymerized with a vinyl monomer to prepare a condensed form of a vinyl polymer and a polysiloxane. After, the contained polar group is neutralized with a basic compound or an acidic compound,
Then, a method of dispersing or dissolving in an aqueous medium,
Etc.

[0075]

Embedded image (However, in the formula, a carbon atom is one of carbon atoms constituting a double bond, or a carbon atom constituting a substituent bonded to a double bond, and a silicon atom bonded only to an oxygen atom Is derived from polysiloxane.)

Next, the aqueous resin (W-3) or (W-
Among the preparation methods 4), the polysiloxane (A) which is particularly preferable as the precursor thereof as described above.
A method for preparing a condensate in which is bonded to the polymer (B-3) or (B-4) via the bond represented by the structural formula (S-II) will be described.

The aqueous resin (W-3) or (W-
As a method for preparing 4), for example, (c) bonding at least one hydrophilic group selected from the group consisting of a neutralized acid group, a neutralized basic group and a nonionic group to a silicon atom A polymer having both a hydrolyzable group and / or a hydroxyl group bonded to a silicon atom, or a hydrophilic group and a hydrolyzable group bonded to a silicon atom and / or a hydroxyl group bonded to a silicon atom. Functional groups (Fu-
2) is reacted with the above-mentioned polysiloxane (A) to form a hydrolyzable group and / or a silicon atom contained in the polysiloxane (A) and each polymer contained in each of the above-mentioned polymers. A method of forming a condensate by bonding via a bond represented by the structural formula (S-II) by a reaction between hydroxyl groups bonded to a silicon atom, and then dispersing or dissolving in an aqueous medium;

(D) having a radically polymerizable double bond, having the double bond, a hydrolyzable group bonded to a silicon atom and / or a hydroxyl group bonded to a silicon atom, and A polysiloxane having a cycloalkyl group bonded to at least 10 mol% of the atoms is represented by the structural formula (S
-VI) is used as one of the copolymerization components, and a vinyl monomer containing a neutralized acid group, a neutralized base, Monomer having at least one hydrophilic vinyl monomer selected from the group consisting of a vinyl monomer having a hydrophilic group and a vinyl monomer having a nonionic group as an essential component By copolymerizing the above-mentioned compounds, or in addition to the above-mentioned polysiloxane containing a double bond and the above-mentioned vinyl monomer having a hydrophilic group, it contains the above-mentioned functional group (Fu-2). The monomer to be formed is also copolymerized with a vinyl monomer containing as an essential component to prepare a condensed form of the vinyl polymer and polysiloxane, and then dispersed or dispersed in an aqueous medium. How to dissolve, There is.

In the above methods (a) and (c), a polymer other than polysiloxane has a hydrolyzable group bonded to a silicon atom and / or a hydroxyl group bonded to a silicon atom as a functional group for complexing. It is particularly convenient to introduce a hydrolyzable group bonded to a silicon atom among these functional groups.

The hydrolyzable group bonded to the silicon atom includes the following general formula (S-VII)

[0081]

Embedded image

[0082] (wherein, R ⁴ in the formula is an alkyl group, a monovalent organic group such as an aryl group or an aralkyl group, R ⁵
Represents a hydrolyzable group such as a hydrogen atom, a halogen atom, an alkoxy group, a substituted alkoxy group, an acyloxy group, a phenoxy group, an aryloxy group, a mercapto group, an amino group, an amide group, an aminooxy group, an iminooxy group or an alkenyloxy group. And a is 0 or 1
Or, it is assumed to be an integer of 2. )

It is particularly convenient to introduce the compound in the form of a hydrolyzed silyl group as shown in the above.

Such a hydrolyzable silyl group is formed by the covalent bond of the hydrolyzable silyl group itself directly to a carbon atom or by a covalent bond to a carbon atom via a siloxane bond. Assume that it is bonded to the polymer.

Of the various methods (a) to (d) described above, the method (a) or (c) is particularly preferred from the viewpoint of simplicity of preparation.

Among the aqueous resins (W-1) and (W-2), specific examples of the condensate used when preparing the type having only an anionic group as a hydrophilic group by the method (A) Typical preparation methods include (1) a polymer having both a hydrolyzable silyl group and an acid group (b-
1) or a polymer (b-2) containing a hydrolyzable silyl group, an acid group and the above functional group (Fu-1), and a hydrolyzable group bonded to a silicon atom and / or a silicon atom A polysiloxane (A) having a hydroxyl group and having 10 mol% of all silicon atoms is subjected to a condensation reaction to form a condensate (c)
-1) or a method for obtaining (c-2),

(2) In the process of preparing the polysiloxane (A) in the presence of the polymer (b-1) or (b-2), the polymer (b-1) or (b-2) ) And polysiloxane (A) are subjected to a condensation reaction to form a condensate (c-
3) or a method for obtaining (c-4),

(3) In the presence of the polysiloxane (A), the polymer (b-1) or the polymer (b-
In the course of performing the reaction for preparing 2), the polysiloxane (A) is subjected to a condensation reaction with the polymer (b-1) or (b-2) to obtain a condensate (c-5) or (c-6). Method,

(4) In the process of carrying out the reaction for preparing the polymer (b-1) or (b-2) and the reaction for preparing the polysiloxane (A) in parallel, the polymer (b- 1) or (b-2) and polysiloxane (a-
Various methods, such as a method of partially or completely neutralizing the composite resin (c-7) or (c-8) obtained by compounding 1) with a basic compound, may be used.

The polymer (b-1) or (b-
Specific examples of the acid group introduced in 2) include, in addition to the various free acid groups described above, a carboxylic acid anhydride group, a phosphoric acid anhydride group, a sulfonic acid anhydride group, or a carboxylic acid-sulfonic acid mixed acid. An acid anhydride group represented by an anhydride group and the like, and further easily converted to a free acid group such as a silyl ester group, a tert-butyl ester group or a 1-alkoxyethyl ester group. Examples of the form of the ester group include a so-called blocked acid group represented by a carboxyl group, a phosphoric acid group, an acidic phosphate group, a phosphorous acid group or a sulfonic acid group.

Among the various acid groups as described above, only particularly desirable ones are exemplified as a carboxyl group, a block carboxyl group or a carboxylic anhydride group.

Introduced into the above-mentioned polymer (b-2)
Examples of the functional group (Fu-1) include those exemplified as those that can be introduced into the polymer (B-2).

Further, these functional groups are formed by the polymer (b-
In 2), only one kind may be contained, or two or more kinds may be contained.

Among the various functional groups mentioned above, particularly desirable ones are a hydroxyl group bonded to a carbon atom, a block hydroxyl group, a tertiary amino group, a cyclocarbonate group, an epoxy group, a primary amide group and a secondary amide group. , A carbamate group or a functional group represented by the aforementioned structural formula (S-I).

The condensation reaction between the polysiloxane (A) and the polymer (b-1) or (b-2) is carried out in a medium containing an organic solvent having an alcoholic hydroxyl group as an essential component. It is preferred to do so.

The above (b-1) or (b-2)
When the condensation reaction between (A) and (A) is carried out in a medium not containing an alcoholic hydroxyl group-containing organic solvent, the resulting composite resin solution inevitably thickens, and the subsequent neutralization step with a basic compound In such cases, gelation or the like easily occurs, and it is necessary to pay sufficient attention.

In particular, at the time of such a condensation reaction in a medium containing no alcoholic hydroxyl group-containing organic solvent, a hydrolyzable silyl group is added to the polymer (b-1) or (b-2). If an attempt is made to introduce 0.05 mol or more in terms of the number of moles per 1,000 g of the polymer, gelation may occur in such a complexing process.

On the other hand, in a medium containing an alcoholic hydroxyl group-containing organic solvent as an essential component, (b-1)
Alternatively, in the case where the condensation reaction between (b-2) and (A) is carried out, gelation does not occur during the condensation reaction or during the neutralization process with a basic compound, and the desired aqueous resin is obtained. Can be prepared safely and easily.

Examples of such organic solvents containing an alcoholic hydroxyl group, which are particularly typical, include various water-soluble organic solvents such as methanol, ethanol, normal (n-) propanol and iso (i-) propanol. Alcohols: ethylene glycol, propylene glycol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol mono-n-butyl ether, propylene glycol
Various water-soluble glycols such as n-propyl ether and glycol ethers.

Next, the various condensates (c-1) to
The method for preparing (c-8) will be described in detail.

First, when preparing the condensates (c-1) to (c-8), the polymer (b-1) or (b
-2) is prepared, and typical examples of such various polymers include various polymers similar to those described above for the polymer (B-1) or (B-2). Among them, particularly preferred are vinyl-based polymers or polyurethane-based polymers, and particularly preferred vinyl-based polymers are acrylic-based polymers and fluoroolefin-based polymers. Can be

First, the polymer (b-1) or (b
-2) the method for preparing a vinyl polymer,
It will be described.

Among the various vinyl polymers, the condensate (c-1), (c-3), (c-5) or (c-
In order to prepare the polymer (b-1) which is a precursor of 7), for example, (i) a vinyl monomer (m-1) having a hydrolyzable silyl group and hydrophilicity are imparted. Or a vinyl monomer having an acid group (m-2) for copolymerization, or a monomer of both types (two types) described above and a copolymerizable with these monomers. Other monomers (m-
3) and the method of copolymerizing

(Ii) In the presence of a chain transfer agent having a hydrolyzable silyl group and / or a radical polymerization initiator having a hydrolyzable silyl group, a vinyl monomer (m-
2) is polymerized or the monomer (m-2)
And another monomer (m-3) that can be copolymerized,

(Iii) In the presence of a chain transfer agent having a hydrolyzable silyl group and / or a radical polymerization initiator having a hydrolyzable silyl group, a vinyl monomer (m-
(1) and (m-2) are copolymerized, or (m-) is added in the presence of a chain transfer agent having a hydrolyzable silyl group and / or a radical polymerization initiator having a hydrolyzable silyl group.
A method of copolymerizing 1) and (m-2) with another monomer (m-3) copolymerizable with these monomers,

(Iv) Various isocyanate group-containing compounds such as 3-isocyanatopropyltriethoxysilane are added to a previously prepared vinyl polymer having both an acid group and a hydroxyl group bonded to a carbon atom. Various methods known in the art can be applied, such as a method of reacting a silane compound, but from the viewpoint of simplicity, of these,
In particular, the methods (i) to (iii) are preferable.

Next, among the various vinyl polymers, (b) which is a precursor of the condensate (c-2), (c-4), (c-6) or (c-8), In order to prepare -2), for example, (v) the above-described functional group (Fu-1)
And a vinyl monomer having a hydrolyzable silyl group (m-1) and a vinyl monomer having an acid group (m-2). Or share weight,
This is a method of copolymerizing (m-1), (m-2), (m-4), and another monomer (m-3) copolymerizable with these monomers. And,

(Vi) In the presence of a chain transfer agent having a hydrolyzable silyl group and / or a radical polymerization initiator having a hydrolyzable silyl group, a vinyl monomer (m-
2) and (m-4) are copolymerized, or both monomers are copolymerized with another monomer (m-3) capable of being copolymerized,

(Vii) In the presence of a chain transfer agent having a hydrolyzable silyl group and / or a radical polymerization initiator having a hydrolyzable silyl group, a vinyl monomer (m-
1), (m-2) and (m-4) are copolymerized, or in the presence of a chain transfer agent having a hydrolyzable silyl group and / or a radical polymerization initiator having a hydrolyzable silyl group. , (M-1), (m-2) and (m-4), and other monomers (m-
3) and the method of copolymerizing

(Viii) 3-isocyanate was added to a previously prepared vinyl polymer having three kinds of functional groups of an acid group, a functional group (Fu-1), and a hydroxyl group bonded to a carbon atom. Such as propyltriethoxysilane, a method of reacting various isocyanate group-containing silane compounds, and the like, various known and commonly used methods can be applied, but from the viewpoint of simplicity, among these, in particular,
Each of the methods (v) to (vii) is preferable.

Each of the polymers (b-1) and (b-
The hydrolyzable silyl group-containing vinyl monomer (m-1) used when preparing 2) is a hydrolyzable silyl group represented by the structural formula (S-VII) as described above. A monomer having a vinyl trimethoxysilane, vinyl triethoxy silane, vinyl tri-n-butoxy silane, and vinyl trimethoxy silane. Methyldimethoxysilane, vinyltris (2-methoxyethoxy) silane, allyltrimethoxysilane, 2-trimethoxysilylethylvinylether, 2-triethoxysilylethylvinylether, 2- (methyldimethoxysilyl) ethylvinylether, 3-trimethoxysilylpropyl Vinyl ether or 3-triethoxysilylpropyl vinyl ether,

Or 3- (methyldimethoxysilyl) propyl vinyl ether, 3- (meth) acryloyloxypropyltrimethoxysilane, 3- (meth) acryloyloxypropyltriethoxysilane, 3- (meth)
Acryloyloxypropylmethyldimethoxysilane or 3- (meth) acryloyloxypropylmethyldichlorosilane.

Further, the polymer (b-1) or (b-
The chain transfer agent having a hydrolyzable silyl group used in the reaction for preparing 2) includes a hydrolyzable silyl group as described above and a mercapto group, a chlorine atom, a bromine atom or an iodine atom. It refers to a compound having a group or an atom activated by a so-called free radical.

As typical examples of such chain transfer agents, only typical ones are exemplified. 3-mercaptopropyltrimethoxysilane, 3-mercaptopropyltriethoxysilane, 3-mercaptopropylmethyldimethoxysilane, 3-mercaptopropyl Methyldichlorosilane, 3-mercaptopropyldimethylchlorosilane, 3
-Bromopropyltrimethoxysilane or 3-bromopropyltriethoxysilane.

Furthermore, (b-1) or (b-
The radical polymerization initiator having a hydrolyzable silyl group as described above, which is used when preparing 2), refers to a compound having a hydrolyzable silyl group as described above in a molecule. Yes, and if we only exemplify particularly representative ones of these,

2,2'-azobis- (2-methyl-4-
Trimethoxysilylbutyronitrile), 2,2'-azobis- (2-methyl-4-triethoxysilylbutyronitrile), 2,2'-azobis- (2-methyl-4-dimethoxymethylsilylbutyronitrile) ) Or 2,
In addition to various things such as 2'-azobis- (2-methyl-4-diethoxymethylsilylbutyronitrile),
Various azo initiators having an active hydrogen-containing group such as 2,2'-azobis [2- (hydroxymethyl) propionitrile] or 4,4'-azobis (4-cyanovaleric acid); Hydrolyzable silyl via an amide bond or a urethane bond in a form such as can be obtained by reacting with isocyanatosilane, such as 3-isocyanatopropyltriethoxysilane or 3-isocyanatopropylmethyldimethoxysilane. Various azo compounds, such as an azo compound having a group bonded thereto;

Or tert-butylperoxy-
2,2-dimethyl-3-trimethoxysilylpropanoate, tert-butylperoxy-2,2-dimethyl-3-triethoxysilylpropanoate, tert-
Butylperoxy-2,2-dimethyl-3-dimethoxymethylsilylpropanoate, tert-butylperoxy-2,2-dimethyl-3-diethoxymethylsilylpropanoate, tert-butylperoxy-3-methyl -5-trimethoxysilyl hexanoate or t
Various peroxides such as tert-butylperoxy-4-ethyl-5-trimethoxysilylhexanoate.

The acid-containing vinyl monomer (m-) used in preparing the polymer (b-1) or (b-2)
Among the 1), only typical examples of the vinyl monomer containing a free carboxyl group are exemplified below, and (meth) acrylic acid, 2-carboxyethyl (meth) acrylate, crotonic acid, Various unsaturated carboxylic acids, such as itaconic acid, maleic acid or fumaric acid;

Monomethyl itaconate, mono-itaconate
n-butyl, monomethyl maleate, mono-maleic acid
n-butyl, monomethyl fumarate, mono-n-fumarate
Various monoesters (half esters) of saturated dicarboxylic acids and saturated monohydric alcohols such as butyl; monovinyl esters of various saturated dicarboxylic acids such as monovinyl adipate or monovinyl succinate;

It contains various saturated polycarboxylic acid anhydrides such as succinic anhydride, glutaric anhydride, phthalic anhydride or trimellitic anhydride, and contains hydroxyl groups bonded to various carbon atoms as described later. It is an addition reaction product with a vinyl-based monomer, and furthermore, various kinds of monomers such as those obtained by an addition reaction of various carboxyl group-containing monomers and lactones as described above. And the like.

The acid group-containing vinyl monomer (m-) used in preparing the polymer (b-1) or (b-2)
Of the monomers 1) having a block carboxyl group, only typical ones are exemplified, and trimethylsilyl (meth) acrylate, dimethyl-te
JP-A-62-254 such as rt-butylsilyl (meth) acrylate or trimethylsilyl crotonate.
Various silyl ester group-containing vinyl monomers as disclosed in JP 876;

1-ethoxyethyl (meth) acrylate, 1-n-butoxyethyl (meth) acrylate, 2
Various hemiacetal ester groups or hemiketal ester groups such as -methoxy-2- (meth) acryloyloxypropane or 2- (meth) acryloyloxytetrahydrofuran, as disclosed in JP-A-5-222134. Containing monomers; or t
tert-butyl (meth) acrylate or tert
And various tert-butyl ester group-containing monomers such as -butyl crotonate.

The acid group-containing vinyl monomer (m-) used in preparing the polymer (b-1) or (b-2)
Among the 1), if only a typical example of the carboxylic acid anhydride group-containing monomer is exemplified, maleic anhydride, citraconic anhydride or itaconic anhydride may be used.
Anhydrides of various unsaturated polycarboxylic acids; anhydrides of various unsaturated monocarboxylic acids, such as acrylic acid or methacrylic anhydride; or various unsaturated carboxylic acids, such as acrylic acid or methacrylic acid. Mixed anhydrides with various saturated carboxylic acids, such as acetic acid, propionic acid or benzoic acid.

As described above, the vinyl polymer (b-2) has, as a functional group (Fu-1), a hydroxyl group bonded to a carbon atom, a block hydroxyl group, a tertiary amino group, a cyclocarbonate group, and an epoxy group. Various functional groups such as a group, a primary amide group, a secondary amide, a carbamate group, and a functional group represented by the structural formula (SI) are introduced.

When the functional group (Fu-1) is introduced by each of the methods (v) to (vii), various vinyl monomers (m-4) containing the functional group are used. However, among them, if only a particularly typical example of a hydroxyl group-containing vinyl monomer bonded to a carbon atom is exemplified,

Hydroxyalkyl (meth) acrylates such as 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate or 4-hydroxybutyl (meth) acrylate;
Hydroxyl-containing vinyl ethers bonded to various carbon atoms, such as hydroxyethyl vinyl ether or 4-hydroxybutyl vinyl ether;

Hydroxyl-containing allyl ethers bonded to various carbon atoms such as 2-hydroxyethyl allyl ether; hydroxyl-containing monomers bonded to various carbon atoms as described above, and ε-caprolactone, etc. Adducts with various lactones; epoxide-containing unsaturated monomers such as glycidyl (meth) acrylate; and acetic acid. Such as adducts with various acids,

Further, various unsaturated carboxylic acids represented by (meth) acrylic acid and the like, and represented by "Cardura E" (trade name of Shell, Netherlands) and the like. Other than the epoxide compounds of α-olefins, there are hydroxyl-containing monomers bonded to carbon atoms, such as adducts with various monoepoxy compounds.

Of the vinyl monomers (m-4), only those which are particularly typical as vinyl monomers having a blocked hydroxyl group are exemplified, and 2-trimethylsiloxyethyl (meth) acrylate, JP-A-62-283, such as 2-trimethylsiloxypropyl (meth) acrylate, 4-trimethylsiloxybutyl (meth) acrylate, 2-trimethylsiloxyethyl vinyl ether or 4-trimethylsiloxybutyl vinyl ether
Various silyl ether group-containing vinyl monomers as disclosed in Japanese Patent No. 163;

2- (1-ethoxy) ethoxyethyl (meth) acrylate, 2- (1-n-butoxy) ethoxyethyl (meth) acrylate, 2- [2- (meth) acryloyloxy] ethoxytetrahydrofuran or 2,2 Various vinyl monomers containing an acetal group or a ketal group, such as -dimethyl-4- (meth) acryloyloxymethyldioxolane, as disclosed in JP-A-4-41515;

Or 3- [2- (meth) acryloyloxy] ethyloxazolidine, 2,2-dimethyl-3-
[2- (meth) acryloyloxy] ethyloxazolidine or 2-isobutyl-2-methyl-3- [2-
(Meth) acryloyloxy] ethyl oxazolidine, and various oxazolidine group-containing vinyl monomers.

Among the vinyl monomers (m-4), only typical examples of cyclocarbonate group-containing vinyl monomers are given below.

2,3-carbonatepropyl (meth) acrylate, 2-methyl-2,3-carbonatepropyl (meth) acrylate, 3,4-carbonatebutyl (meth) acrylate, 3-methyl-3,4-carbonatebutyl (Meth) acrylate, 4-methyl-3,4
-Carbonate butyl (meth) acrylate, 4,5-
Carbonate pentyl (meth) acrylate, 6,7-
Carbonate hexyl (meth) acrylate, 5-ethyl-5,6-carbonate hexyl (meth) acrylate or 7,8-carbonate octyl (meth) acrylate, 2,3-carbonate propyl vinyl ether, di (2,3-carbonate propyl) A 5-membered cyclocarbonate group-containing vinyl monomer such as malate or di (2,3-carbonatepropyl) itaconate;

Further, [5-N- (meth) acryloylcarbamoyloxy] methyl-5-ethyl-1,3-
Dioxan-2-one, 5- [N- {2- (meth) acryloyloxy} ethylcarbamoyloxy] methyl-
5-ethyl-1,3-dioxan-2-one, 5-ethyl-5- (meth) acryloyloxymethyl-1,3-
6-membered cyclocarbonate group-containing vinyl monomers such as dioxan-2-one or 4- (5-ethyl-2-oxo-1,3-dioxan-5-yl) methoxymethylstyrene.

Of the vinyl monomers (m-4), only glycidyl (meth) acrylate, methyl glycidyl (meth) acrylate and methyl glycidyl (meth) are exemplified as particularly typical epoxy-containing vinyl monomers. Acrylate, 3,4-
Epoxycyclohexylmethyl (meth) acrylate,
Various compounds such as vinylcyclohexene oxide, glycidyl vinyl ether, methyl glycidyl vinyl ether or allyl glycidyl ether.

Among the vinyl monomers (m-4), only typical examples of the vinyl monomer containing a primary amide group or a secondary amide group are exemplified, and (meth) acrylamide , N-isopropyl (meth) acrylamide, N-methyl (meth) acrylamide, N-
Vinyl formamide, methyl (meth) acrylamide glycolate, methyl (meth) acrylamide glycolate methyl ether, N-methylol (meth) acrylamide, Nn-butoxymethyl (meth) acrylamide, 2-isocyanatoethyl (meth) acrylate And various compounds such as addition products of acetylacetone or acetoacetic esters with acetylacetone.

Of the vinyl monomers (m-4), only typical examples of carbamate group-containing vinyl monomers are given below.

Methyl N- (meth) acryloylcarbamate, ethyl N- (meth) acryloylcarbamate,
Ethyl N- [2- (meth) acryloyloxy] ethylcarbamate, 2-carbamoyloxyethyl (meth)
Acrylate, 2- (N-methylcarbamoyloxy)
Ethyl (meth) acrylate, 2- (N-ethylcarbamoyloxy) ethyl (meth) acrylate or 3
Addition reaction product of 2-isopropenyl-α, α-dimethylbenzyl isocyanate and 2-hydroxypropyl carbamate; addition reaction product of 2-isocyanatoethyl (meth) acrylate and phenol; 2-isocyanatoethyl (meth) Various compounds such as an addition reaction product of acrylate and ethanol; or an addition reaction product of 2-isocyanatoethyl (meth) acrylate and methyl ethyl ketoxime.

Of the vinyl monomers (m-4), only typical examples of the vinyl monomer having a functional group represented by the aforementioned structural formula (SI) are given. For example, various isocyanate group-containing vinyl monomers such as 2-isocyanatoethyl (meth) acrylate or 3-isopropenyl-α, α-dimethylbenzyl isocyanate, and ε-caprolactam or γ-butyrolactam, Various compounds such as addition products with various amide compounds.

Among the vinyl monomers (m-4), only typical ones having a tertiary amino group are exemplified.

2-dimethylaminoethyl (meth) acrylate, 2-diethylaminoethyl (meth) acrylate, 2-di-n-propylaminoethyl (meth) acrylate, 3-dimethylaminopropyl (meth) acrylate, 4-dimethylamino Various tertiary amino group-containing (meth) acrylates, such as butyl (meth) acrylate or N- [2- (meth) acryloyloxy] ethylmorpholine;

Various tertiary amino group-containing aromatic vinyl monomers such as vinylpyridine, N-vinylcarbazole or N-vinylquinoline;

N- (2-dimethylamino) ethyl (meth) acrylamide, N- (2-diethylamino) ethyl (meth) acrylamide, N- (2-di-n-propylamino) ethyl (meth) acrylamide, N- (3-
Dimethylamino) propyl (meth) acrylamide, N
Various (meth) acrylamides containing a tertiary amino group, such as-(4-dimethylamino) butyl (meth) acrylamide or N- [2- (meth) acrylamido] ethylmorpholine;

N- (2-dimethylamino) ethylcrotonamide, N- (2-diethylamino) ethylcrotonamide, N- (2-di-n-propylamino) ethylcrotonamide, N- (3- Various tertiary amino group-containing crotonamides, such as dimethylamino) propylcrotonamide or N- (4-dimethylamino) butylcrotonamide;

Various tertiary amino group-containing vinyl ethers such as 2-dimethylaminoethyl vinyl ether, 2-diethylaminoethyl vinyl ether, 3-dimethylaminopropyl vinyl ether and 4-dimethylaminobutyl vinyl ether.

Further, the aforementioned (i) to (iii)
Alternatively, according to the methods (v) to (vii), the vinyl-based monomer (m-1), vinyl-based monomer (m-1), which can be used when preparing the vinyl-based polymer (b-1) or (b-2) If only other typical vinyl monomers (m-3) which can be copolymerized with the system monomers (m-2) and (m-4) are exemplified,

Methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, 2-ethylhexyl (meth) acrylate or lauryl (meth) acrylate Like
Various esters of a primary or secondary alkyl alcohol having ₁ to ₂₂ carbon atoms with (meth) acrylic acid;

Benzyl (meth) acrylate or 2
-Various aralkyl (meth) acrylates, such as phenylethyl (meth) acrylate; various cycloalkyl (meth) acrylates, such as cyclohexyl (meth) acrylate or isobornyl (meth) acrylate; 2-methoxyethyl (meth) Various ω-alkoxyalkyl (meth) acrylates, such as acrylate or 4-methoxybutyl (meth) acrylate;

Various aromatic vinyl monomers such as styrene, p-tert-butylstyrene, α-methylstyrene or vinyltoluene; vinyl acetate, vinyl propionate, vinyl pivalate, vinyl versatate or benzoate Various carboxylic acid vinyl esters such as vinyl acid;

Various alkyl esters of crotonic acid, such as methyl crotonate or ethyl crotonate; dimethyl maleate, di-n-butyl malate, dimethyl fumarate, di-n-butyl fumarate, dimethyl itaconate or di- dialkyl esters of various unsaturated dibasic acids, such as n-butyl itaconate;

Various cyano group-containing monomers such as (meth) acrylonitrile or crotononitrile; various kinds of monomers such as vinyl fluoride, vinylidene fluoride, tetrafluoroethylene, chlorotrifluoroethylene or hexafluoropropylene. Fluoroolefins;
Various chlorinated olefins, such as vinyl chloride or vinylidene chloride; various α, such as ethylene, propylene, isobutylene, 1-butene or 1-hexene
-Olefins;

Various alkyl vinyl ethers such as ethyl vinyl ether, n-butyl vinyl ether, isobutyl vinyl ether or n-hexyl vinyl ether; various cycloalkyl vinyl ethers such as cyclopentyl vinyl ether, cyclohexyl vinyl ether or 4-methylcyclohexyl vinyl ether;

Tertiary amide group-containing monomers such as N, N-dimethyl (meth) acrylamide, N- (meth) acryloylmorpholine, N- (meth) acryloylpyrrolidine and N-vinylpyrrolidone.

By using the various monomers listed above, the vinyl polymer (b-1) or (b-2)
Can be applied using various known polymerization methods, such as a solution polymerization method, a non-aqueous dispersion polymerization method or a bulk polymerization method, and among them, in particular,
The simplest method is a solution radical polymerization method in an organic solvent.

As the polymerization initiator which can be used in applying the solution radical polymerization method, various known and commonly used compounds can be used, of course, but only typical ones among them will be exemplified. If you stop,

Various types such as 2,2'-azobis (isobutyronitrile), 2,2'-azobis (2,4-dimethylvaleronitrile) and 2,2'-azobis (2-methylbutyronitrile) Azo compounds;

Or tert-butyl peroxypivalate, tert-butyl peroxybenzoate, te
rt-butylperoxy-2-ethylhexanoate,
Benzoyl peroxide, lauroyl peroxide, acetyl peroxide,

Various peroxides such as di-tert-butyl peroxide, dicumyl peroxide, tert-butyl hydroperoxide, cumene hydroperoxide, methyl ethyl ketone peroxide or diisopropyl peroxycarbonate.

As the organic solvent that can be used when applying the solution radical polymerization method, any of known and commonly used organic solvents can be used.
Of course, it may be used alone or in combination of two or more, but in order to smoothly proceed with the subsequent condensation reaction with the polysiloxane (A), it has various alcoholic hydroxyl groups as described above. It is desirable to contain an organic solvent as an essential component.

Among such organic solvents, those having no alcoholic hydroxyl group, and particularly representative ones, are exemplified by n-hexane, n-heptane, n-octane, cyclohexane, cyclopentane or cyclopentane. Various aliphatic or alicyclic hydrocarbons such as octane;

Various aromatic hydrocarbons such as toluene, xylene or ethylbenzene; methyl formate, ethyl formate, ethyl acetate, n-butyl acetate or n-acetate
Various esters such as amyl, ethylene glycol monomethyl ether acetate or ethylene glycol monoethyl ether acetate or ethylene glycol monobutyl ether acetate;

Various ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, methyl n-amyl ketone or cyclohexanone; or, such as dimethoxyethane, tetrahydrofuran, dioxane, diisopropyl ether or di-n-butyl ether;
Various ethers; various chlorinated hydrocarbons such as chloroform, methylene chloride, carbon tetrachloride, trichloroethane or tetrachloroethane;
Furthermore, N-methylpyrrolidone, dimethylformamide, dimethylacetamide, ethylene carbonate and the like are used.

The vinyl polymer (b-1) or (b-
When preparing 2), if the amount of the acid group-containing monomer used is large, gelation often occurs during polymerization, so care must be taken.

In order to prevent such gelation, ethyl orthoacetate, ethyl ortho-n-butylate,
Various hydrolyzable esters such as ethyl orthoformate, ethyl orthopropionate or methyl orthoformate may be used in combination with the above-mentioned solvents.

By applying a known and commonly used solution radical polymerization method by using monomers, polymerization initiators and organic solvents as described above, the desired various vinyl-based compounds can be obtained. Polymer (b-1) or (b-
2) can be prepared.

As described above, the amount of hydrolyzable silyl groups to be introduced into the vinyl polymer (b-1) or (b-2) is determined by the solid content of each polymer. As the number of moles of the hydrolyzable silyl group per 1,000 grams, a range of about 0.005 to about 3 moles is appropriate, and a range of 0.01 to 2 moles is suitable. Even more preferably, a range of 0.05 to 1 mol is appropriate.

When the amount is less than about 0.005 mol, the durability and the like of the coating film obtained from the composition of the present invention are inevitably reduced, while the amount exceeds about 3 mol and becomes too large. In such a case, the condensates (c-1) to (c-
In the preparation of 8), the viscosity of the reaction solution is increased, and there is an inconvenience such that gelation occurs.

Accordingly, a hydrolyzable silyl group-containing monomer, a hydrolyzable silyl group-containing chain transfer agent or a hydrolyzable silyl group is introduced so that the preferable amount of hydrolyzable silyl group as described above is introduced. It is necessary to appropriately set the amount of the group-containing polymerization initiator to be used.

The amount of the acid group to be introduced into the vinyl polymer (b-1) or (b-2) is determined based on the amount of the acid group per 1,000 g of the solid content of each polymer. The number of moles is suitably from about 0.1 to about 10 moles, preferably from 0.2 to 5 moles, and most preferably from 0.3 to 3 moles. Within the range is appropriate.

Therefore, it is necessary to appropriately set the amount of the vinyl monomer containing an acid group so that the above-mentioned preferable amount of the acid group is introduced.

Further, at least one vinyl monomer among the vinyl monomers (m-4) having a functional group (Fu-1) to be introduced into the vinyl polymer (b-2). The amount of the monomer to be copolymerized is in the range of about 0.1 to about 5 mol, as the number of moles of the functional group per 1,000 g of the solid content of the vinyl polymer (b-2). Such an amount is appropriate, preferably in the range of 0.2 to 3 mol, and more preferably in the range of 0.3 to 2 mol.

The vinyl polymer (b-1)
Alternatively, the number average molecular weight of (b-2) is about 500
To within about 200,000, preferably 1,
A range of 000 to 50,000 is appropriate, and a range of 1,500 to 20,000 is more preferable.

When the number average molecular weight of the vinyl polymer (b-1) or (b-2) is less than about 500, the mechanical strength of the cured product obtained from the composition of the present invention is inevitable. And so on, while about 200,
If it is too high exceeding 000, the appearance of the cured product obtained from the composition of the present invention is inevitably deteriorated.

As the vinyl polymer (b-1), in the presence of a polymer other than the vinyl polymer such as a polyester resin or an alkyd resin having a polymerizable unsaturated double bond, the above-mentioned various polymers are used. It is also possible to use a polyester resin or an alkyd resin obtained by polymerizing according to the methods (i) to (iii) in the form of a grafted vinyl polymer segment.

As the vinyl polymer (b-2), in the presence of a polymer other than the vinyl polymer such as a polyester resin or an alkyd resin having a polymerizable unsaturated double bond, the above-mentioned various polymers are used. It is also possible to use a polyester resin or an alkyd resin obtained by polymerizing according to the methods (v) to (vii) described above, in the form of a grafted vinyl polymer segment.

To prepare a polyurethane polymer of the polymer (b-1), in addition to various dihydroxy compounds and various diisocyanate compounds, as a raw material component for introducing a hydrolyzable silyl group, Using a diamine compound having a hydrolyzable silyl group or a monoamine compound having a hydrolyzable silyl group, further, as a raw material component for introducing an acid group, an acid group such as dimethylolpropionic acid or dimethylolbutanoic acid JP-A-51-90391 uses various known and commonly used raw material components such as a compound having a hydroxyl group bonded to a carbon atom.
JP-A-55-73729 or JP-A-55-73729.
What is necessary is just to apply the method described in 0-255817.

Further, to prepare the polyurethane polymer of the polymer (b-2), the polyurethane polymer (b-1) used in preparing the above-mentioned polyurethane polymer (b-1) has already been listed. In addition to various known and commonly used raw materials,
Various compounds having one or two groups having the above-mentioned functional group (Fu-1) and having an active hydrogen which reacts with an isocyanate group can be used as a raw material component by using a known and commonly used compound. Various methods may be applied.

One or two groups having a functional group (Fu-1) and having an active hydrogen which reacts with an isocyanate group, which are used in preparing the polyurethane polymer (b-2), are used. If only typical compounds are exemplified, 4-hydroxymethyl-1,3-dioxolan-2-one, N-methyldiethanolamine, N-ethyldiethanolamine, glycidol, 2-hydroxyethyl Compounds having both various functional groups and a hydroxyl group bonded to a carbon atom, such as carbamate or 2-hydroxypropyl carbamate.

The amount of the hydrolyzable silyl group to be introduced into the polyurethane polymer (b-1) or (b-2) prepared by the above-mentioned method is as follows. For about 1,000 grams of solid content, about 0.0
A range of from about 0.05 to about 3 moles is suitable, preferably a range of from 0.01 to 2 moles, and even more preferably a range of from 0.05 to 1 mole.

If the amount is less than about 0.005 mol, the polyurethane polymer (b-1) or (b-
The condensation reaction between 2) and the polysiloxane (A) hardly progresses, and as a result, the durability and the like of the cured product obtained from the composition of the present invention is reduced, while about 3 If the molar ratio is too large, the solution viscosity at the time of the above-described complexing reaction will increase, and eventually, inconveniences such as causing gelation will be observed. Is also not preferred.

The amount of the acid group to be introduced into the polyurethane polymer (b-1) or (b-2) is as follows:
The number of moles of the acid group per 1,000 g of the solid content of each polymer is suitably in the range of about 0.1 to about 10 moles, and preferably in the range of 0.2 to 5 moles. Is most suitable, and most preferably in the range of 0.3 to 3 mol.

Further, a polyurethane polymer (b-
2) a hydroxyl group, a block hydroxyl group, a tertiary amino group, a cyclocarbonate group, an epoxy group, a primary amide group, a secondary amide group, a carbamate group or a structural formula described above, each of which is to be introduced into a carbon atom. A functional group (Fu) represented by a functional group represented by (SI) and the like.
The amount of the -1) introduced may be a polyurethane polymer (b-
The number of moles of the functional group per 1,000 grams of the solid content in 2) is suitably in the range of about 0.1 to about 5 moles, and preferably in the range of 0.2 to 3 moles. However, even more preferably, a range of 0.3 to 2 mol is appropriate.

The polyurethane polymer (b-1) or (b-2) has a number average molecular weight of about 500 to
The range of about 100,000 is preferably 1,0.
The range of from 00 to 50,000 is suitable, and the range of from 1,500 to 30,000 is more preferable.

When the number average molecular weight of the polyurethane polymer (b-1) or (b-2) is less than about 500, the mechanical strength of the coating film obtained from the composition of the present invention is inevitably reduced. Will be inferior, while about 100,0
If it gets too high beyond 00,
In either case, the appearance of the cured product obtained from the composition of the present invention is deteriorated, and in either case, it is not preferable.

[0184] The compound having a hydroxyl group bonded to a silicon atom and / or a hydrolyzable group bonded to a silicon atom, which is used in preparing the condensates (c-1) to (c-8), and Polysiloxane (A) in which a cycloalkyl group is bonded to 10 mol% or more of a silicon atom is generally referred to as a silanol group.
Or having a hydrolyzable group bonded to a silicon atom, and
The term refers to various linear, branched or cyclic polysiloxanes in which a cycloalkyl group is bonded to 10 mol% or more of all silicon atoms constituting the polysiloxane.

Among these various polysiloxanes, they are represented by the structural formula (S-IV) as described above in view of excellent curability of the aqueous resin of the present invention and durability of a cured product obtained from the composition of the present invention. A polysiloxane having a branched structure or a cyclic structure having a structure as an essential unit structure is particularly preferable.

Typical examples of the polysiloxane (A) include a silicon compound containing at least one cycloalkyl group bonded to a silicon atom and at least two hydrolyzable groups bonded to a silicon atom. And a hydrolyzable condensate of a silicon compound containing, as an essential component, a silicon compound having at least three hydrolyzable groups bonded to a silicon atom in one molecule, or a partial hydrolyzable condensate. In addition, it is prepared so that a cycloalkyl group is bonded to 10 mol% or more of all silicon atoms.

A silicon compound containing at least one cycloalkyl group bonded to a silicon atom and at least two hydrolyzable groups bonded to a silicon atom, which is used in preparing the polysiloxane (A). Various known and commonly used compounds can be used, but if only typical ones are exemplified, the following general formula (S-VIII) can be used.

[0189]

Embedded image ^{(R 6) (R 7)} b SiR 8 3-b (S-VIII)

(Wherein R ⁶ represents a cycloalkyl group, and R ⁷ represents an alkyl group, a cycloalkyl group, which may or may not have a substituent, respectively)
R ⁸ represents a halogen atom, an alkoxy group, a substituted alkoxy group, an acyloxy group, a phenoxy group, a mercapto group, an amino group, an amide group, an aminooxy group, an iminooxy group, and a monovalent organic group such as an aryl group, an aralkyl group or an alkenyl group. Alternatively, it represents a hydrolyzable group such as an alkenyloxy group, and b is an integer of 0 or 1. ).

Representative examples of the silicon compound represented by the general formula (S-VIII) include trifunctional silanes such as cyclopentyltrimethoxysilane, cyclopentyltriethoxysilane, cyclohexyltrimethoxysilane or cyclohexyltriethoxysilane. Various cycloalkyl trialkoxysilanes as compounds; bifunctional silane compounds such as cyclopentylmethyldimethoxysilane, cyclopentylmethyldiethoxysilane, cyclohexylmethyldimethoxysilane, cyclohexylmethyldiethoxysilane or cyclohexylethyldiethoxysilane Various alkylcycloalkyl dialkoxysilanes; dicyclopentyldimethoxysilane, dicyclopentyldiethoxysilane, dicyclohexyl Such as dimethoxysilane or dicyclohexyl diethoxysilane, various dicycloalkyl dialkoxysilane such as bifunctional silane compound;

Cycloalkyltrichlorosilanes as trifunctional silane compounds such as cyclopentyltrichlorosilane or cyclohexyltrichlorosilane: Alkylcycloalkyl as bifunctional silane compounds such as cyclopentylmethyldichlorosilane or cyclohexylmethyldichlorosilane Dichlorosilanes; further, various dicycloalkyldichlorosilanes as bifunctional silane compounds such as dicyclopentyldichlorosilane or dicyclohexyldichlorosilane.

As the above-mentioned silicon compound having at least three hydrolyzable groups bonded to a silicon atom in one molecule, which is used in preparing the polysiloxane (A), known silicon compounds can be used. Any of these can be used, but if only typical ones are exemplified, the following general formula (S-IX) can be used.

[0194]

Embedded image R ⁹ _b SiR ¹⁰ _4-b (S-IX)

(However, R ⁹ in the formula may be an alkyl group, which may or may not have a substituent.
R ¹⁰ is a halogen atom, an alkoxy group, a substituted alkoxy group, an acyloxy group, a phenoxy group, a mercapto group, an amino group, an amide group, an aminooxy group, an iminooxy group. Alternatively, it represents a hydrolyzable group such as an alkenyloxy group, and b is an integer of 0 or 1. )

A partially hydrolyzed condensate obtained by partial hydrolysis and condensation of one of these silicon compounds; or a partially hydrolyzed condensation of a mixture of two or more of these silicon compounds. The resulting partial co-hydrolysis condensate;

Or (CH ₃ CH ₂ O) ₃ SiCH ₂ C
H ₂ Si (OCH ₂ CH ₃ ) ₃ or (CH ₃ CH ₂ O) ₃
Compounds having three or more hydrolyzable groups bonded to silicon atoms in one molecule, such as SiCH ₂ CH ₂ CH ₂ Si (OCH ₂ CH ₃ ) ₃ .

As the silicon compound represented by the general formula (S-IX) described above, only typical ones are exemplified, and examples thereof include tetraethoxysilane, tetramethoxysilane and tetra-n-butoxysilane. , Various tetraalkoxysilanes;

Methyltrimethoxysilane, methyltriethoxysilane, methyltri-n-butoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, ethyltri-n-butoxysilane, n-propyltrimethoxysilane, n-propyltriethoxysilane , N-butyltrimethoxysilane or n-butyltriethoxysilane,

Phenyltrimethoxysilane, phenyltriethoxysilane, phenyltri-n-butoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, vinyltri-n-butoxysilane, vinyltris (2-methoxyethoxy) silane or allyltrimethoxy Silane,

2-trimethoxysilylethyl vinyl ether, 2-triethoxysilylethyl vinyl ether,
3-trimethoxysilylpropyl vinyl ether, 3-
Various organotrialkoxysilanes such as triethoxysilylpropyl vinyl ether, 3- (meth) acryloyloxypropyltrimethoxysilane or 3- (meth) acryloyloxypropyltriethoxysilane;

Tetrahalogenosilanes such as tetrachlorosilane or tetrabromosilane; methyltrichlorosilane, ethyltrichlorosilane, n-propyltrichlorosilane, vinyltrichlorosilane, 3- (meth) silane
Such as acryloyloxypropyltrichlorosilane,
Various organotrichlorosilanes;

Alternatively, various acetoxysilanes such as tetraacetoxysilane, methyltriacetoxysilane, and phenyltriacetoxysilane are used.

In preparing the polysiloxane (A), dimethyldimethoxysilane, dimethyldiethoxysilane and dimethyldimethoxysilane are added to the above-mentioned various silicon compounds represented by the general formulas (S-VIII) and (S-IX). Dimethyldi-n-butoxysilane, diethyldimethoxysilane, diethyldiethoxysilane, di-n-propyldimethoxysilane, di-n-propyldiethoxysilane, di-n-butyldimethoxysilane or di-n-butyldiethoxysilane,

Diphenyldimethoxysilane, diphenyldiethoxysilane, diphenyldi-n-butoxysilane, methylphenyldimethoxysilane, methylphenyldiethoxysilane, vinylmethyldimethoxysilane,
-(Methyldimethoxysilyl) ethyl vinyl ether,
A so-called bifunctional silicon compound having two hydrolyzable groups bonded to a silicon atom in one molecule, such as 3- (methyldimethoxysilyl) propyl vinyl ether or 3- (meth) acryloyloxypropylmethyldimethoxysilane;

Alternatively, trimethylmethoxysilane, trimethylethoxysilane, triethylmethoxysilane,
So-called monofunctional having only one hydrolyzable group bonded to a silicon atom in one molecule, such as triethylethoxysilane, triphenylmethoxysilane, triphenylethoxysilane, trimethylchlorosilane, triethylchlorosilane or triphenylchlorosilane. A silicon compound can also be used in combination.

In order to prepare a polysiloxane having a cycloalkyl group and a branched structure, which is a particularly preferred example of the polysiloxane (A), from the various silicon compounds described above, the general formula (S-VIII) ), A trifunctional silane compound containing a cycloalkyl group is used as an essential silicon compound;
Alternatively, among the silicon compounds represented by the general formula (S-VIII), a bifunctional silane compound containing a cycloalkyl group and a hydrolyzable compound bonded to a silicon atom represented by the general formula (S-IX) Groups at least 3 per molecule
Hydrolysis condensation or partial hydrolysis condensation may be performed by using the silicon compound having the same as the essential silicon compound.

At that time, the cycloalkyl group-containing 3
A functional silane compound or a bifunctional silane compound containing a cycloalkyl group is used in 10 of the total silane compounds.
Mol% or more, preferably 20 mol% or more, and more preferably 40 mol% or more.

The aqueous resin (W-1) or (W-
From the viewpoint of the curability and durability of 2), 10 mol% or more, preferably 20 mol% or more, more preferably 30 mol% or more of all silicon atoms constituting the polysiloxane (A) It is particularly preferable to form a unit structure represented by the following structural formula (S-4).

Therefore, in preparing the polysiloxane (A), at least 10 mol%, preferably at least 20 mol%, more preferably at least 30 mol% of all silane compounds used are methyltrialkoxysilanes, Particularly preferred is a trifunctional silane compound such as methyltrichlorosilane, cyclohexyltrialkoxysilanes or cyclohexyltrichlorosilane.

Phenyltrialkoxysilanes, phenyltrichlorosilane, diphenyldialkoxysilanes,
Although various phenylsilanes such as diphenyldichlorosilane, methylphenyldialkoxysilanes or methylphenyldichlorosilane can be used in combination,
These should be used in proportions which do not impair the gloss retention characteristic of the present invention.

The polysiloxane (A) can be obtained by hydrolytic condensation or partial hydrolytic condensation of the silicon compound as described above. In this case, a catalyst may or may not be used. However, from the viewpoint of facilitating the progress of these condensation reactions, it is desirable to use a catalyst.

In the case where a catalyst is used,
Any of known and commonly used catalysts can be used,
Moreover, they may be used alone or in combination of two or more.

As typical examples of such catalysts, only typical ones may be mentioned, such as hydrochloric acid, sulfuric acid or phosphoric acid.
Various inorganic acids; various organic acids such as p-toluenesulfonic acid, monoisopropyl phosphate or acetic acid;

Various inorganic bases such as sodium hydroxide or potassium hydroxide; various titanates such as tetraisopropyl titanate or tetrabutyl titanate; various tin carboxylates such as dibutyltin dilaurate or tin octylate Acid salts;

Metal carboxylate such as naphthenate or octylate of various metals such as iron, cobalt, manganese or zinc; various aluminum compounds such as aluminum trisacetylacetonate;

1,8-diazabicyclo [5.4.0] undecene-7 (DBU), 1,5-diazabicyclo [4.3.0] nonene-5 (DBN), 1,4-diazabicyclo [2.2 .2] octane (DABCO), tri-n-butylamine or dimethylbenzylamine,
Butylamine, octylamine,

Various amine compounds such as monoethanolamine, diethanolamine, triethanolamine, imidazole, 1-methylimidazole, 2,4-dimethylimidazole or 1,4-diethylimidazole;

Tetramethylammonium salt, tetrabutylammonium salt, trimethyl (2-hydroxypropyl) ammonium salt, cyclohexyltrimethylammonium salt, tetrakis (hydroxylmethyl) ammonium salt, dilauryldimethylammonium salt, trioctylmethylammonium salt or o- Various quaternary ammonium salts, such as trifluoromethylphenyltrimethylammonium salt,

Further, as typical counter anions,
Quaternary ammonium salts having chloride, bromide, carboxylate, hydroxide or the like, respectively.

The amount of the catalyst used is in the range of about 0.0001 to about 10% by weight, preferably 0.0005 to 3% by weight, based on the silicon compound subjected to hydrolysis or partial hydrolysis. %, Particularly preferably 0.0005 to 1% by weight.

The amount of water used in the above reaction is about 0.05 mol or more, preferably 0 mol or more, per 1 mol of the hydrolyzable group bonded to the silicon atom of the silicon compound. .1 mol or more is appropriate, and more preferably 0.2 mol or more.

When the amount is less than 0.05 mol, the rate of hydrolysis is remarkably slowed down, which is not preferable for practical use. However, the amount of water is 5 mol, 10 mol, or silicon atom. Use in a large excess with respect to 1 mol of the hydrolyzable group bonded to the compound has no problem.

The addition of the catalyst and water is as follows:
It is needless to say that the catalyst and water may be added at a time or separately, and may be added in the form of a mixture of the catalyst and water, or may be added separately.

The reaction temperature of this reaction is from 0 ° C. to 1
About 50 ° C. is appropriate, preferably 20 ° C. to 100 ° C.
C. is appropriate, and the reaction can be carried out under any conditions of normal pressure, increased pressure or reduced pressure.

Then, by-products of the reaction, such as alcohol and water, respectively, are successively carried out.
Polysiloxane (A) and polymer (b-1) or (b-
If there is a problem with the condensation reaction step 2) or the stability of the resulting aqueous resin, it can be removed out of the system by means such as distillation. If there is no problem,
As it is, it can be left in the system without any problems.

In such a reaction, various known and commonly used organic solvents may or may not be used, but the polymer (b-1) or (b-2) In order to allow the condensation reaction step to proceed smoothly, it is desirable to use a medium containing an organic solvent having various alcoholic hydroxyl groups as an essential component as described above.

Then, using a medium containing such an organic solvent having an alcoholic hydroxyl group as an essential component,
When preparing the polysiloxane (A), the concentration of the silicon compound having at least three hydrolyzable groups bonded to silicon atoms in one molecule in the organic solvent is about 5% by weight or more. Is desirable.

Next, of the aqueous resin (W-1) or (W-2) used in the present invention, a condensate (c) as a precursor in preparing a type having an anionic group as a hydrophilic group The methods (1) to (4) described above, which are the preparation methods of -1) to (c-8), will be described in detail.

First, the method (1) described above means that the polymer (b-1) or (b-2) and the polysiloxane (A) are subjected to a condensation reaction to form the condensate (c).
-1) or (c-2).

Here, a catalyst can be added in order to smoothly progress the condensation reaction between the polymer (b-1) or (b-2) and the polysiloxane (A). As such, various catalysts already listed as those used in preparing the polysiloxane (A) can be used as they are.

The amount of the catalyst used in the case of condensing by the method (1) may be selected from the polymer (b-1) or (b)
-2) and about 0.0001 to about 10% by weight based on the total amount of the polysiloxane (A),
Preferably, the range is 0.0005 to 3% by weight, and particularly preferably, the range is 0.0005 to 1% by weight.

In the case where the catalyst used in the process of preparing the polysiloxane (A) remains in (A), the catalyst remains particularly in (A) without adding a catalyst. It is possible to accelerate the condensation reaction by using only the catalyst.

In the method (1), in order for the condensation reaction between the polymer (b-1) or (b-2) and the polysiloxane (A) to proceed smoothly, The hydrolysis of the hydrolyzable silyl group contained in each of the union (b-1) and (b-2) and the hydrolyzable group bonded to a silicon atom contained in the polysiloxane (A) in some cases It is desirable that the hydrolysis of the compound proceeds smoothly, and it is therefore particularly desirable to carry out such a condensation reaction in the presence of water.

When water used in preparing the polysiloxane (A) remains in (A),
In particular, it is possible to carry out the condensation reaction only with water remaining in (A) without adding water.

The amount of water used in carrying out the condensation reaction is determined by the amount of the hydrolyzable group contained in the hydrolyzable silyl group bonded to each of the polymers (b-1) and (b-2). Is at least about 0.05 mol, preferably at least 0.1 mol, per mol of the total amount of the hydrolyzable groups bonded to the silicon atoms present in the polysiloxane (A). It is suitable, and more preferably 0.5 mol or more.

[0237] When the amount is less than about 0.05 mol, the rate of hydrolysis tends to be remarkably slowed down, which is not preferable.

Also, even if the amount of water used is set to a large excess,
As long as no inconvenience such as insolubles coming out during the reaction occurs, the complexing reaction can be performed without any problem.
When the polysiloxane (A) has a hydrolyzable group bonded to a silicon atom, the amount of water used is generally about 1 mol of the hydrolyzable group contained in (A). , 10
It is suitably set to not more than 5 moles, preferably not more than 5 moles, more preferably not more than 3.5 moles,

When there is no hydrolyzable group bonded to a silicon atom in (A), the polymer (b-1)
Or 50 mol per mol of the hydrolyzable group contained in the hydrolyzable silyl group bonded to each of (b-2).
It is suitably set to 0 mol or less, preferably 300 mol or less, more preferably 200 mol or less.

In the method (1), a suitable reaction temperature for performing the condensation reaction is about 0 to 150 ° C., and preferably about 20 to 100 ° C.

Next, the above-mentioned method (2) refers to a method in the presence of the above-mentioned polymer (b-1) or (b-2).
In the course of performing the reaction for preparing the polysiloxane (A),
This is a method of preparing a condensate (c-3) or (c-4) by subjecting (b-1) or (b-2) to a condensation reaction with (A).

The condensate (c) was obtained by the method (2) described above.
In preparing -3) or (c-4), a catalyst for promoting hydrolytic condensation of silicon compounds may or may not be used. It is desirable to use a catalyst in order to allow the reaction to proceed promptly and at the same time to smoothly proceed the condensation reaction between the resulting (A) and (b-1) or (b-2).

As such a catalyst, those exemplified as usable in the preparation of the above (A) can be used.

The amount of the catalyst used is in the range of about 0.000001 to about 10% by weight, preferably 0.00000% by weight, based on the silicon compound as the raw material of (A).
The range of 5 to 5% by weight is particularly preferably 0.000 to 5% by weight.
A range of 1 to 1% by weight is appropriate.

In preparing the condensate by the method (2), the hydrolysis reaction of the silicon compound as a raw material of (A) was allowed to proceed smoothly, and the produced (A) and (b)
In order to smoothly progress the condensation reaction with (-1) or (b-2), the reaction is usually performed in a form to which water is added. At this time, the amount of water to be added depends on the amount of the hydrolyzable group contained in the hydrolyzable silyl group bonded to the polymer (b-1) or (b-2) and the amount of silicon atom present in the silicon compound. The amount is preferably about 0.05 mol or more, preferably 0.1 mol or more, and more preferably 0.5 mol or more, based on 1 mol of the total amount of the compound and the hydrolyzable group bonded thereto. The above is appropriate.

If the amount is less than about 0.05 mol, the rate of hydrolysis tends to be extremely slow, and therefore it is not preferable.

Further, even if the amount of water used is set to a large excess, the condensation reaction can be carried out without hindrance as long as no inconvenience such as precipitation of insolubles occurs during the reaction. It is appropriate to set the amount of water used to about 10 mol or less, preferably 5 mol or less, more preferably 3.5 mol or less, based on 1 mol of the total amount of the functional groups. And

Further, the reaction conditions for preparing the condensate by the method (2) and the method for adding the catalyst and water may be the same as those employed in the preparation of the above (A).

Next, the above-mentioned method (3) refers to the step of carrying out the reaction for preparing the above-mentioned polymer (b-1) or (b-2) in the presence of the above-mentioned polysiloxane (A). A condensation reaction between the polymer (b-1) or (b-2) and (A) to prepare a condensate (c-5) or (c-6).

Here, a condensation reaction is carried out in the process of preparing each of the polymers (b-1) and (b-2), and when preparing a condensate with (A), (b-
The hydrolysis reaction of the hydrolyzable silyl group contained in each of 1) and (b-2) is promoted, and the polysiloxane (A) and the polymer (b-1) or (b-
A catalyst can be added in order to allow the condensation reaction with each of 2) to proceed smoothly, and such a catalyst can be used when preparing the polysiloxane (A) in the same manner as in the method (1) described above. Various catalysts which have already been listed as those used in the above can be used as they are.

The amount of the catalyst used in the case of condensing by the method (3) is based on the total amount of the polymer (b-1) or (b-2) and the polysiloxane (A). A range of about 0.0001 to about 10% by weight, preferably a range of 0.0005 to 3% by weight, and particularly preferably a range of 0.0005 to 1% by weight is appropriate.

When the catalyst used in the process of preparing the polysiloxane (A) remains in (A) in the same manner as in the above (1), no additional catalyst is added. In both cases, the condensation reaction can be promoted only by the catalyst remaining in (A).

In the method (3), (b-
From the viewpoint of smoothly proceeding the condensation reaction between 1) or (b-2) and (A), it is desirable to add water to the reaction system as in the method (1) described above. And
The amount of the water conforms to the method (1).

The addition of these catalysts and water is as follows:
It is needless to say that the catalyst and water may be added at a time or separately, and may be added in the form of a mixture of the catalyst and water, or may be added separately.

In the method (3), a suitable reaction temperature for preparing each of the polymers (b-1) and (b-2) is about 0 to 150 ° C., preferably, About 20 ° C to 120 ° C is appropriate.

Further, the method (4) described above is that the reaction for preparing the polymer (b-1) or (b-2) and the reaction for preparing the polysiloxane (A) are carried out in the same reaction system. In the step (a), (b-1) or (b-2) and (A) are condensed in a parallel
This is a method for preparing (7) or (c-8), and this condensation reaction may be carried out according to the above-mentioned methods (1) to (3).

In preparing each of the condensates (c-1) to (c-8) by the methods (1) to (4), the polymer (b-1) or (b-2) and the polymer The proportion of the siloxane (A) used is such that the ratio of the segment derived from the polymer (B-1) or (B-2) to the polysiloxane segment derived from the polysiloxane (A) falls within the preferred range as described above. What is necessary is just to set.

Furthermore, in the method of (3) or (4), the conditions for preparing the polymer (b-1) or (b-2), or (b-1) or (b-2) The target properties of (b-1) or (b-2)
The method for preparing must conform to the conditions or properties described above.

Further, in the method of (1) to (4),
When preparing each of the condensates (c-1) to (c-8), the total concentration of each component is determined by the concentration of each of the condensates (c-1) to (c-8) produced by the reaction. At the end of the condensation reaction, to a concentration of about 5% by weight or more,
Preferably at least 10% by weight, more preferably 2% by weight.
It is desirable to set it to be 0% by weight or more.

The concentration can be adjusted using a medium containing an organic solvent having an alcoholic hydroxyl group as an essential component as described above.

In the partial or complete neutralization reaction of the acid groups contained in the condensates (c-1) to (c-8) prepared by the methods (1) to (4), various The basic compounds of the formula (I) are used. Typical examples thereof include those used when introducing an anionic group into the polymer (B-1) or (B-2). And the like.

Among these various basic compounds, it is particularly desirable to use ammonia or various organic amines.

The amount of the basic compound to be added is at least as large as that of the condensates (c-1) to (c-8).
It is an amount capable of imparting water dispersibility, and is a condensate (c
-1) the ratio of the number of equivalents of the basic compound to the number of equivalents of the acid groups contained in (c-8),

That is, the basic compound / “acid group contained in each of the condensates (c-1) to (c-8)”
It is appropriate that the equivalent ratio is about 0.1 or more,
The amount within a range that does not impair the coating film performance is preferably approximately in the range of 0.1 to 3, and most preferably 0.3 to 2.

The reaction temperature of the neutralization reaction is 0
C. to about 150.degree. C. is appropriate, and preferably 20.degree.
100 ° C. is appropriate, and the reaction can be carried out under any conditions of normal pressure, increased pressure or reduced pressure.

As described above, the condensates (c-1) to
A partially or completely neutralized product of each of the basic compounds (c-8) can be prepared, but the organic solvent contained in such a partially or completely neutralized product can be prepared without removing it. As it is, it can be dispersed or dissolved in an aqueous medium, and if necessary, can be removed by a distillation operation or the like.

The condensate (c-1) thus obtained
To each of (c-8) or the completely neutralized product,
By dispersing or dissolving in an aqueous medium, of the aqueous resin (W-1) or (W-2), a type having only an anionic group as a hydrophilic group is prepared.

In order to prepare the aqueous resin (W-1) or (W-2) from the respective partial or complete neutralized products of the condensates (c-1) to (c-8), various known and commonly used resins are used. Method can be applied. For example, simply add water or a mixture of water and a water-soluble organic solvent to the partially or completely neutralized product, or convert the partially or completely neutralized product to water or a mixture of water and a water-soluble organic solvent. The desired aqueous resin (W-1) or (W-2) can be prepared by dispersing or dissolving it in an aqueous medium by adding it.

If necessary, the organic solvent contained in the aqueous resin (W-1) or (W-2) thus prepared may be partially or partially heated or reduced. By completely removing the resin, the aqueous resin (W-1) or (W-2) having a low organic solvent content or containing no organic solvent can be prepared.

Next, of the aqueous resin (W-3) or (W-4), a type having only an anionic group as a hydrophilic group was used in the preparation of the above-mentioned method (c). Typical examples of the method for preparing the condensate to be prepared include (5) a polymer (b-3) prepared in advance and having both a hydrolyzable silyl group and an acid group, or a hydrolyzable polymer. The polymer (b-4) containing the functional group (Fu-2) in addition to the silyl group and the acid group is partially or completely neutralized with a basic compound, and then And the above-mentioned polysiloxane (A), followed by a condensation reaction to form a condensate (c-9) or (c-1).
0) a method of preparing

(6) The polymer (b-3) or the polymer (b
(B-3) or (b-4) and (A) are subjected to a condensation reaction in the course of carrying out the reaction for preparing the polysiloxane (A) in the presence of the basic compound and the condensate ( a method for preparing (c-11) or (c-12),

(7) In the course of carrying out the reaction for preparing the polymer (b-3) or the polymer (b-4) in the co-presence of the polysiloxane (A) and the basic compound, (b- 3)
Or a method for preparing a condensate (c-13) or (c-14) by subjecting (b-4) and (A) to a condensation reaction,

(8) A reaction for preparing the polymer (b-3) or the polymer (b-4) in the presence of a basic compound,
(B-3) or (b-4) and (a-2) in the course of carrying out the reaction for preparing the polysiloxane (A) in parallel.
And a condensation reaction to form a condensate (c-15) or (c-
16), and the like.

The polymer (b-3) or (b-
Examples of the acid group introduced in 4) include the various acid groups described above as those used in the preparation of the aqueous resin (W-1) or (W-2). Carboxyl groups, blocked carboxyl groups, carboxylic anhydride groups, and the like are only examples of desirable ones.

As the functional group other than the acid group among the functional groups (Fu-2) to be introduced into the polymer (b-4), it may be introduced into the polymer (B-4). Various things exemplified as possible things are mentioned.

Next, the method for preparing the condensates (c-9) to (c-16) will be described in detail.

First, when preparing the condensates (c-9) to (c-16), the polymer (b-3) or (b-4) is prepared as a precursor thereof. As typical examples of the polymer of (B-1), polymers (B-1) and (B-
Various types are mentioned in the same manner as those described above for 2), and among them, particularly preferable are:
Examples thereof include a vinyl polymer or a polyurethane polymer, and particularly preferable vinyl polymers include an acrylic polymer and a fluoroolefin polymer.

First, a method for preparing a vinyl polymer of the polymer (b-3) or (b-4) will be described.

Among such vinyl polymers, the condensate (c-9), (c-11), (c-13) or (c-
To prepare the polymer (b-3), which is the precursor of 15), monomers, polymerization initiators and organic compounds exemplified as those used in the preparation of the polymer (b-1) are used. The methods (i) to (iv) may be applied as they are using solvents, but from the viewpoint of simplicity, among these, the methods (i) to (iii) are particularly applied. Is preferred.

Then, among such vinyl polymers, the polymer (b-4) which is a precursor of the condensate (c-10), (c-12), (c-14) or (c-16) Is prepared using the monomers, polymerization initiators and organic solvents exemplified as those used in the preparation of the polymer (b-2), and (v) to (viii). May be applied as it is, but from the viewpoint of simplicity, it is particularly preferable to apply each of the methods (v) to (vii).

Further, a hydrolyzable silyl group to be introduced into the vinyl polymer (b-3) or (b-4),
The amount of each of the functional groups other than the acid group in the acid group or the functional group (Fu-2) is determined according to the amount introduced when preparing the polymer (b-1) or (b-2). Good.

Further, these vinyl polymers (b-3)
The number average molecular weight of (b-4) also conforms to the preferred range in the case of the vinyl polymer (b-1) or (b-2).

As the vinyl polymer (b-3), in the presence of a polymer other than the vinyl polymer such as a polyester resin or an alkyd resin having a polymerizable unsaturated double bond, the above-mentioned various polymers are used. It is also possible to use a polyester resin or an alkyd resin obtained by polymerizing according to the methods (i) to (iii) in the form of a grafted vinyl polymer segment.

As the vinyl polymer (b-4), in the presence of a polymer other than the vinyl polymer such as a polyester resin or an alkyd resin having a polymerizable unsaturated double bond, the above-mentioned various polymers are used. It is also possible to use a polyester resin or an alkyd resin obtained by polymerizing according to the methods (v) to (vii) described above, in the form of a grafted vinyl polymer segment.

The method for preparing the polyurethane polymer of the polymers (b-3) and (b-4) is the same as the method for preparing the polyurethane polymer (b-1) or (b-2) described above. Applicable as it is.

The polysiloxane (A), which is the other component of the condensates (c-9) to (c-16), was prepared by preparing the aqueous resin (W-1) or (W-2). What was illustrated as what is used at the time of can be used.

Next, the aqueous resin (W-3) or (W-
Among 4), the above-mentioned methods (5) to (8), which are preparation methods of the type having an anionic group, will be described in detail.

First, the above-mentioned method (5) means that the polymer (b-3) or (b-4) is partially or completely neutralized with a basic compound, and then polysiloxane is used. This is a method of preparing a condensate (c-9) or (c-10) by mixing (A) and subjecting it to a condensation reaction.

In conducting the condensation reaction of the respective partially or completely neutralized products of the polymer (b-3) or (b-4) with the polysiloxane (A), the partially or completely neutralized product is obtained. The neutralized acid group itself contained in the product is the polymer (b-3) or (b-4) and the polysiloxane (A)
Since it functions as a catalyst for the condensation reaction with
There is no need to add a condensation reaction catalyst.

In the method (5), the condensation reaction between the partially or completely neutralized product of the polymer (b-3) or (b-4) and the polysiloxane (A) is carried out. In order for the polymer to proceed smoothly, the polymer (b)
-3) or (b-4), the hydrolysis of the hydrolyzable silyl group contained in the partially or completely neutralized product, and the silicon atom contained in the polysiloxane (A) as the case may be. It is desirable that the hydrolysis of the hydrolyzable group bonded to the compound proceed smoothly. Therefore, it is particularly desirable to carry out such a condensation reaction in the presence of water.

When water used in preparing the polysiloxane (A) remains in (A),
In particular, it is possible to carry out the condensation reaction only with water remaining in (A) without adding water.

The amount of water used in carrying out the condensation reaction is determined based on the amount of the hydrolyzable group contained in the hydrolyzable silyl group bonded to each of the polymers (b-3) and (b-4). Is at least about 0.05 mol, preferably at least 0.1 mol, per mol of the total amount of the hydrolyzable groups bonded to the silicon atoms present in the polysiloxane (A). It is suitable, and more preferably 0.5 mol or more.

When the amount is less than about 0.05 mol, the rate of hydrolysis is liable to be remarkably reduced.

Further, even if the amount of water used is set to a large excess,
As long as no inconvenience such as insolubles coming out during the reaction occurs, the complexing reaction can be performed without any problem.
When the polysiloxane (A) has a hydrolyzable group bonded to a silicon atom, the amount of water used is generally about 1 mol of the hydrolyzable group contained in (A). , 10
It is suitably set to not more than 5 moles, preferably not more than 5 moles, more preferably not more than 3.5 moles,

When there is no hydrolyzable group bonded to a silicon atom in (A), the polymer (b-3)
Or 50 mol per 1 mol of the hydrolyzable group contained in the hydrolyzable silyl group bonded to each of (b-4).
It is suitably set to 0 mol or less, preferably 300 mol or less, more preferably 200 mol or less.

In the method (5), when the partial or complete neutralization of the acid groups in the polymer (b-3) or (b-4) is carried out before the condensation reaction, the condensation product (C
Various basic compounds exemplified as those used in the neutralization reaction of -1) to (c-8) can be used,
In particular, it is desirable to use ammonia or various organic amines.

The amount of the basic compound to be added is such that at least water dispersibility can be imparted to the condensate (c-9) or (c-10) obtained. The ratio of the number of equivalents of the basic compound to the number of equivalents of acid groups contained in the polymer (b-3) or (b-4),

That is, it is appropriate to set the equivalent ratio of the basic compound / “acid group contained in the polymer (b-3) or (b-4)” to about 0.1 or more. As an amount not impairing the coating film performance, preferably, generally,
The range of 0.1 to 3 is appropriate, and most preferably the range of 0.3 to 2 is appropriate.

The reaction temperature of the neutralization reaction is 0
C. to about 150.degree. C. is appropriate, and preferably 20.degree.
100 ° C. is appropriate, and the reaction can be carried out under any conditions of normal pressure, increased pressure or reduced pressure.

Further, in the method (5), the reaction temperature of the condensation reaction which is carried out subsequent to the neutralization reaction is suitably from about 0 to 150 ° C., preferably from 20 to 150 ° C.
About 100C to about 100C is appropriate.

Next, the above-mentioned method (6) means that the above-mentioned polymer (b-3) or (b-4) is reacted with a polysiloxane (A) in the presence of a basic compound. In the process, a partially neutralized product or a completely neutralized product of (b-3) or (b-4) is subjected to a condensation reaction with (A) to give a condensate (c-11) or (c-
This is a method for preparing 12).

The condensate (c) is obtained by the method (6) described above.
In preparing -11) or (c-12), a neutralized acid group present in the reaction system promotes hydrolytic condensation of silicon compounds, so that it is not necessary to use a catalyst.

In preparing the condensate by the method (6), the hydrolysis reaction of the silicon compound as the raw material of (A) was allowed to proceed smoothly, and the produced (A) and (b)
In order to smoothly carry out the condensation reaction between the partially neutralized product or the completely neutralized product of (-3) or (b-4), the reaction is usually carried out in the form of adding water. At this time, the amount of water added is determined based on the polymer (b-3) or (b-
4) with respect to 1 mol of the total amount of the hydrolyzable group contained in the hydrolyzable silyl group bonded to the silicon compound and the hydrolyzable group bonded to the silicon atom, which is present in the silicon compound.
About 0.05 mol or more, preferably 0.1 mol or more is suitable, and more preferably 0.5 mol or more.

[0304] When the amount is less than about 0.05 mol, the rate of hydrolysis is liable to be remarkably slowed down.

Further, even if the amount of water used is set to a large excess, the compounding reaction can be carried out without any trouble as long as inconvenience such as insoluble matter is precipitated during the reaction.
The amount of water used is generally set to 10 mol or less, preferably 5 mol or less, more preferably 3.5 mol or less, based on 1 mol of the total amount of the above-mentioned hydrolyzable groups. Is appropriate and

Further, the reaction conditions for preparing the condensate by the method (6) and the method of adding water are as described in the above (A).
May be used according to the method employed in the preparation of.

In the method (6), as the basic compound to be added in advance, various compounds exemplified as those used in the method (5) can be used.

In this method, the amount of the basic compound used is the same as that in the method (5).

The method (7) is a reaction for preparing the polymer (b-3) or (b-4) in the presence of the polysiloxane (A) and a basic compound. Is carried out, the polymer (b-3) or (b
-4) by subjecting each partially neutralized product or fully neutralized product to a condensation reaction with (A) to obtain a condensate (c-1)
This is a method for preparing 3) or (c-14).

In the method (7), when the basic compound coexisting with the reaction system is the polymer (b-3) or (b)
-4) It functions as a catalyst for the condensation reaction between the neutralized product and the polysiloxane, so that it is not necessary to further add a catalyst for the condensation reaction.

In the method (7), (b-
From the viewpoint of smoothly proceeding the condensation reaction between the partially neutralized product or the completely neutralized product of (3) or (b-4) and (A), the reaction is carried out in the same manner as in the above-mentioned method (5). It is desirable to add water to the system. The amount of the water conforms to the method (5). And
Water may be added all at once or in portions.

In the method (7), a suitable reaction temperature for preparing each of the polymers (b-3) and (b-4) is about 0 to 150 ° C., preferably, About 20 ° C to 120 ° C is appropriate.

Further, as the basic compound to be added in advance in the method (7), the various basic compounds described in the method (5) can be used as they are, but among them, particularly, , Ammonia or organic amines are preferred.

The amount of the basic compound to be added is as follows.
This is based on the method (5) described above.

Further, the above-mentioned method (8) includes a reaction for preparing the polymer (b-3) or (b-4) in the presence of a basic compound, and a method for preparing the polysiloxane (A). In the same reaction system in parallel with each other by condensing (A-3) and (B-3) or (b-4) each partially or completely neutralized product. And a method for preparing a condensate (c-15) or (c-16), wherein the neutralization reaction and the complexation reaction may be carried out according to the above-mentioned methods (5) to (7).

In preparing each of the condensates (c-9) to (c-16) by the methods (5) to (8), the polymer (b-3) or (b-4) and the polymer The proportion of the siloxane (A) to be used is such that the ratio of the segment derived from the polymer (B-3) or (B-4) to the polysiloxane segment derived from the polysiloxane (A) falls within the preferred range as described above. What is necessary is just to set.

Further, in the method (7) or (8), the conditions for preparing the polymer (b-3) or (b-4), or (b-3) or (b-4) respectively The target properties of (b-3) or (b-4)
The method for preparing must conform to the conditions or properties described above.

Further, in the method of (5) to (8),
In preparing each of the condensates (c-9) to (c-16), the total concentration of each component is determined by the concentration of each of the condensates (c-9) to (c-16) produced by the reaction. ,
It is desirable to set the concentration at the end of the complexing reaction to about 5% by weight or more, preferably 10% by weight or more, and more preferably 20% by weight or more.

The adjustment of the concentration can be performed by using a medium containing an organic solvent having an alcoholic hydroxyl group as an essential component as described above.

As described above, the condensates (c-9) to
The organic solvent contained in (c-16) can be dispersed or dissolved in water as it is without removing it, or can be removed by a distillation operation or the like as necessary.

The condensate (c-9) thus obtained
By dispersing or dissolving each of (c-16) in an aqueous medium, a type having only an anionic group as a hydrophilic group in the aqueous resin (W-3) or (W-4) is prepared. You.

To prepare the aqueous resin (W-3) or (W-4) from each of the condensates (c-9) to (c-16), the aqueous resin (W-1) or (W- Various known and commonly used methods exemplified as applied in the preparation of 2) can be applied.

If necessary, the organic solvent contained in the aqueous resin (W-3) or (W-4) thus prepared is partially or partially heated or / and reduced in pressure. By completely removing the resin, the aqueous resin (W-3) or (W-4) having a low organic solvent content or containing no organic solvent can be prepared.

As described above, the aqueous resins (W-1) to (W-4) containing an anionic group can be prepared, but in the various methods (1) to (4) described above, Except that a basic group is introduced into the polymer (b-1) or (b-2) instead of the acid group in the same manner as in the various methods (1) to (4). Is prepared, and then the basic group contained in the condensate is neutralized with an acidic compound, and then dispersed or dissolved in an aqueous medium by the method described above to obtain the desired cationic group. Aqueous resin (W-1) or (W-
2) can be prepared.

In the various methods (5) to (8) described above, a basic group may be substituted for the polymer (b-
(5) to (5) except that the compound is introduced into (3) or (b-4) and an acidic compound is used instead of the basic compound.
(8) A condensate with polysiloxane (A) containing a cationic group is prepared in the same manner as the various methods described above, and then dispersed or dissolved in an aqueous medium by the method described above. The aqueous resin (W-3) or (W-4) containing the intended cationic group
Can be prepared.

In order to introduce a basic group into the vinyl polymer among the polymers (b-1) to (b-4), various amino group-containing vinyl monomers may be copolymerized. .

Representative examples of the vinyl monomer containing an amino group used at that time include, in addition to the various tertiary amino group-containing monomers described above, 2-tert-
-Butylaminoethyl (meth) acrylate or 2
2 such as -tert-butylaminoethyl crotonate
(Meth) acrylic esters or crotonic esters containing a secondary amino group.

In order to introduce a basic group into the polyurethane polymer among the polymers (b-1) to (b-4), N-methyldiethanolamine or N-ethyldiethanolamine is used in the preparation of the polyurethane resin. Such a dihydroxy compound having a tertiary amino group may be used in combination.

The amount of the basic group introduced into (b-1) to (b-4) is determined by the method described in (1) to (8). What is necessary is just to follow the amount of the acidic group to be performed.

The functional group (Fu-
1) the amount of the functional group (Fu-2) introduced into (b-4)
, The number average molecular weight of (b-1) to (b-4),
The usage ratio of (1) or (b-2) to polysiloxane (A), the usage ratio of (b-3) or (b-4) to polysiloxane (A), and the like are (1) to (8). Various methods may be used.

Further, in the above-mentioned various methods (5) to (8), a nonionic polyether chain is introduced as a hydrophilic group in place of the neutralized acid group, thereby obtaining a nonionic group. Aqueous Resin Containing Functional Group (W-3)
Or (W-4) can be prepared.

Of the aqueous resin (W-3) or (W-4) containing a nonionic group, to prepare a vinyl polymer, a vinyl monomer containing various polyether chains as described above is used. The monomer may be used as a copolymer component.

Further, by combining the above-mentioned method of preparing an aqueous resin containing an anionic group or a cationic group with a method of introducing a nonionic group, the anionic group or the cationic group and the nonionic group can be combined. Can be prepared.

The aqueous resin prepared as described above (W
Of the functional groups contained in the aqueous resin (W-1), the functional groups contained in the aqueous resin (W-1) include a mixture of the polysiloxane (A) and the polymer (B-1) and / or a condensate. Derived from a hydroxyl group bonded to a silicon atom and a hydrolyzable group bonded to a silicon atom optionally contained, and additionally an acid group neutralized by a basic compound or a basic group neutralized by an acidic compound As well as any free acid groups or free basic groups that may be present.

Among the aqueous resins (W-3), the functional groups contained in the aqueous resin containing an anionic group or a cationic group as a hydrophilic group include polysiloxane (A) and polymer (B-3). A hydroxyl group bonded to a silicon atom and an optionally contained hydrolyzable group bonded to a silicon atom, which are derived from a mixture and / or a condensate thereof, and an acid group or an acid neutralized by a basic compound. These are the basic groups neutralized by the compound as well as any free acid groups or free basic groups contained.

The functional group contained in the aqueous resin containing only a nonionic group as a hydrophilic group among the aqueous resin (W-3) includes polysiloxane (A) and polymer (B-3). And / or a hydrolyzable group bonded to a silicon atom, which is optionally contained, derived from a mixture and / or a condensate of the above.

As the functional group contained in the aqueous resin (W-2), a hydroxyl group bonded to a silicon atom, which is derived from a mixture and / or condensate of the polysiloxane (A) and the polymer (B-2), and In some cases, there is a hydrolyzable group bonded to the contained silicon atom, and in addition, an acid group neutralized by a basic group or a basic group neutralized by an acidic compound, and optionally a free group contained therein. There is an acid group or a free basic group, and further, as other functional groups, a hydroxyl group bonded to a carbon atom, a block hydroxyl group,
Cyclocarbonate group, epoxy group, primary amide group, 2
And at least one of a functional amide group, a carbamate group and a functional group (Fu-1) represented by the structural formula (S-I).

Among the aqueous resins (W-4), the functional groups contained in the aqueous resin containing an anionic group or a cationic group as a hydrophilic group include polysiloxane (A) and polymer (B-4). A hydroxyl group bonded to a silicon atom and optionally a hydrolyzable group bonded to a silicon atom, which are derived from a mixture and / or a condensate of
In addition, there are an acid group neutralized by a basic group or a basic group neutralized by an acidic compound, and optionally a free acid group or a free basic group contained therein. As a hydroxyl group bonded to a carbon atom, a blocked hydroxyl group, a carboxyl group, a blocked carboxyl group, a carboxylic anhydride group, a tertiary amino group,
Cyclocarbonate group, epoxy group, primary amide group, 2
And at least one of a functional amide group, a carbamate group and a functional group (Fu-2) represented by the structural formula (S-I).

Among the aqueous resin (W-4), the functional group contained in the aqueous resin having only a nonionic group as a hydrophilic group includes a mixture of polysiloxane (A) and polymer (B-4) and / or Or a hydroxyl group, a blocked hydroxyl group, a carboxyl group, or a blocked carboxyl group bonded to a carbon atom, in addition to a hydroxyl group bonded to a silicon atom and optionally a hydrolyzable group bonded to a silicon atom contained in the condensate. Group, carboxylic acid anhydride group, tertiary amino group, cyclocarbonate group, epoxy group, primary amide group, secondary amide group, carbamate group or structural formula (S-
It is at least one of the functional groups (Fu-2) as shown in I).

In preparing the aqueous resins (W-1) to (W-4), each of the polymers (b-1) to (b-4) was treated with a blocked acid as a precursor functional group of an anionic group. When a group or an acid anhydride group is introduced, the aqueous resin (W-1)
In the process of preparing (W-4), it is necessary to convert at least a part of them into neutralized acid groups which are anionic groups.

In preparing the aqueous resin (W-4), when a blocked acid group or acid anhydride group is to be introduced as a functional group (Fu-2) into the polymer (B-2). Is that at least a part of the blocked acid groups or acid anhydride groups is prepared in the process of preparing a mixture and / or condensate, and further, at the stage of dispersing or dissolving them in water, It may be converted to a free acid group by hydrolysis, thermal decomposition or alcoholysis.

Further, the aqueous resin (W-2) or (W-
When preparing 4), a block hydroxyl group, an epoxy group or a cyclocarbonate group is introduced into the polymer (B-2) or (B-4) as the functional group (Fu-1) or (Fu-2), respectively. If this is the case, at least during the step of preparing the mixture and / or the condensate and also at the step of dispersing or dissolving them in water, at least a part of these functional groups may be subjected to hydrolysis or alcoholysis. May be converted to a free hydroxyl group.

The type of the block hydroxyl group, epoxy group or cyclocarbonate group, the above-mentioned conditions of the condensation reaction, the conditions of mixing with (C) described later, or the subsequent dispersion or dispersion in water Depending on the conditions of dissolution, such various functional groups may be completely converted to free hydroxyl groups.

The aqueous resin (W-
To prepare the aqueous curable resin composition of the present invention from each of 1) to (W-4), one of (W-1) to (W-1)
Since each of (W-4) itself has a self-curing property, a self-curing resin composition containing (W-1) to (W-4) as essential components is used. All you have to do is

In two, for each of (W-1) to (W-4), the aqueous resin (W-1) to (W-1)
By compounding compound (C) having a functional group that reacts with the functional group contained in (W-4), (W-
What is necessary is just to set it as the curable resin composition which also utilizes the crosslinking reaction between the functional group contained in each of 1)-(W-4) and the functional group contained in compound (C).

The compound (C) used in the preparation of the latter type of curable resin composition includes the above-mentioned aqueous resins (W-1) to (W-4) contained in each of the aqueous resins (W-1) to (W-4). And various known compounds having at least one functional group that reacts with various functional groups such as isocyanate. If only typical representative examples of such functional groups are given, isocyanate is used. Groups, blocked isocyanate groups, hydroxyl groups bonded to carbon atoms, blocked hydroxyl groups, carboxyl groups, blocked carboxyl groups, carboxylic anhydride groups, amino groups, cyclocarbonate groups, chain carbonate groups, epoxy groups, primary amide groups,
Secondary amide group, carbamate group, oxazoline group, N-
Hydroxymethylamino group, N-alkoxymethylamino group, carbonyl group, acetoacetyl group, silanol group, hydrolyzable group bonded to silicon atom, or the following structural formula (SV)

[0347]

Embedded image —C (O) —NH—CH (OR ² ) —COOR ³ (SV)

(Wherein R ² represents a hydrogen atom, an alkyl group or an aryl group having 1 to 8 carbon atoms, and R ³ represents an alkyl group or an aryl group having 1 to 8 carbon atoms) Shall be shown.)

And the like.

The functional group contained in the compound (C) is appropriately selected according to the type of the functional group contained in each of the aqueous resins (W-1) to (W-4). You. If only a typical example is exemplified as such a combination, a silanol group-silanol group,
Silanol group-alkoxysilyl group, alkoxysilyl group-alkoxysilyl group, carboxyl group-epoxy group, carboxyl group-cyclocarbonate group, tertiary amino group-epoxy group, hydroxyl group bonded to carbon atom-N-hydroxymethylamino group, Hydroxyl group bonded to carbon atom-
It is an isocyanate group or a hydroxyl-blocked isocyanate group bonded to a carbon atom.

As the compound (C), an aqueous resin (W
Depending on the functional groups contained in each of -1) to (W-4), those having two or more of the various functional groups described above may be used. As the compound (C), various resins can be used in addition to the compound having a relatively low molecular weight. However, only typical examples of such resins are described below. In this case, various kinds of vinyl polymers such as acrylic resin and fluororesin, as well as polyester resin, alkyd resin, polyurethane resin, epoxy resin and the like can be used. When a compound having two or more kinds of the above functional groups is used as the compound (C), it is particularly convenient to use a vinyl polymer as the compound (C). It is.

As the compounds (C), only typical ones are exemplified. Compounds having a hydroxyl group bonded to a silicon atom and / or a hydrolyzable group bonded to a silicon atom, and an isocyanate in one molecule Compound having both a group and a hydrolyzable group bonded to a silicon atom, compound having both an epoxy group and a hydrolyzable group bonded to a silicon atom in one molecule, bonding to an amino group and a silicon atom in one molecule A compound having a hydrolyzable group, a polyisocyanate compound, a blocked polyisocyanate compound, a polyepoxy compound, a polycyclocarbonate compound, an amino resin, a compound containing a primary or secondary amide group, a polycarboxy compound, a polyhydroxy compound, Polyaziridine compound, polyacrylate compound, polycarbodiimide compound, block A compound having an acid group, a polyamine compound, a compound having at least two carboxylic anhydride groups or a polyoxazoline compound, and these various compounds may be used alone or in combination of two or more. Of course, it is possible.

Of these, particularly preferred are a compound having a hydroxyl group bonded to a silicon atom and / or a hydrolyzable group bonded to a silicon atom, a compound having an isocyanate group and a hydrolyzable group bonded to a silicon atom in one molecule. A compound having an epoxy group and a hydrolyzable group bonded to a silicon atom in one molecule, a polyisocyanate compound, a blocked polyisocyanate compound, a polyepoxy compound, a polycyclocarbonate compound, an amino resin, Examples thereof include a primary or secondary amide group-containing compound, a polycarboxy compound, and a polyhydroxy compound.

Of the above-mentioned silicon compounds having a hydroxyl group bonded to a silicon atom and / or a hydrolyzable group bonded to a silicon atom, only particularly typical ones are exemplified. A silicon compound represented by the formula (S-VIII) or (S-IX); a hydrolyzate or a hydrolytic condensate of these silicon compounds; a portion obtained by one kind of partial hydrolytic condensation of these silicon compounds Hydrolyzed condensates; or partial co-hydrolyzed condensates obtained by partial hydrolytic condensation of two or more of these silicon compounds.

Of these, only particularly typical examples of the silicon compound are tetramethoxysilane and tetraethoxysilane, partially hydrolyzed condensates thereof, and partially hydrolyzed condensates thereof. Or a linear, branched or cyclic, or ladder-shaped silicone resin having a hydroxyl group bonded to a silicon atom and / or a hydrolyzable group bonded to a silicon atom.

If only one of the above-mentioned compounds having an isocyanate group and a hydrolyzable group bonded to a silicon atom in one molecule is specifically exemplified, only the following compounds should be exemplified.

Silicon compounds such as 3-isocyanatopropyltrimethoxysilane, 3-isocyanatopropylmethyldimethoxysilane, 3-isocyanatopropyltriethoxysilane or 3-isocyanatopropylmethyldiethoxysilane;

Alternatively, various copolymers comprising a hydrolyzable silyl group-containing vinyl monomer as described above and an isocyanate group-containing vinyl monomer as described later, or both of these copolymers may be used. With various vinyl monomers such as (meth) acrylic, vinylester, vinylether, aromatic vinyl or fluoroolefin, which can be copolymerized with both monomers. Various vinyl copolymers, such as acrylic copolymers, vinyl ester copolymers or fluoroolefin copolymers, each having an isocyanate group and a hydrolyzable silyl group, which are obtained by copolymerization. And polymers.

Only those compounds which are particularly typical as compounds having both an epoxy group and a hydrolyzable group bonded to a silicon atom in one molecule are described below.

Silicon compounds such as 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropyltriethoxysilane or 3-glycidoxypropylmethyldiethoxysilane; A partial hydrolyzed condensate obtained by one kind of partial hydrolytic condensation of a silicon compound; or a partial cohydrolyzed condensate obtained by two or more kinds of partial hydrolytic condensation of these silicon compounds;

"EGM-202" [trade name of a cyclic polysiloxane having a methoxy group bonded to a silicon atom and 3-glycidoxypropyl, manufactured by Dow Corning Toray Silicone Co., Ltd.]; "KP-392" [trade name of partially hydrolyzed condensate of 3-glycidoxypropyltrimethoxysilane manufactured by Shin-Etsu Chemical Co., Ltd.];

Alternatively, various copolymers composed of various epoxy group-containing vinyl monomers as described above and various hydrolyzable silyl group-containing vinyl monomers as described above, or various copolymers thereof. Are copolymerized with (meth) acrylic, vinyl ester, vinyl ether, aromatic vinyl or fluoroolefin vinyl monomers, respectively, which can be copolymerized with both monomers. Various vinyl copolymers, such as acrylic copolymers, vinyl ester copolymers or fluoroolefin copolymers, each having both an epoxy group and a hydrolyzable silyl group, which are obtained by polymerization. And the like.

Only typical examples of the above-mentioned polyisocyanate compounds are given below. Tolylene diisocyanate or diphenylmethane-4,4 '
Various aromatic diisocyanates, such as diisocyanates;

Various aralkyl diisocyanates, such as meta-xylylene diisocyanate or α, α, α ′, α′-tetramethyl-meta-xylylene diisocyanate;

Such as hexamethylene diisocyanate, lysine diisocyanate, 1,3-bisisocyanatomethylcyclohexane, 2-methyl-1,3-diisocyanatocyclohexane, 2-methyl-1,5-diisocyanatocyclohexane or isophorone diisocyanate , Various aliphatic or alicyclic diisocyanates;

There are various prepolymers having an isocyanate group obtained by subjecting various polyisocyanates as described above to an addition reaction with polyhydric alcohols,

Various prepolymers having an isocyanurate ring obtained by subjecting various polyisocyanates as described above to cyclization and trimerization;

Various polyisocyanates having a biuret structure, obtained by reacting various polyisocyanates as described above with water;

Further, various vinyl monomers having an isocyanate group alone such as 2-isocyanatoethyl (meth) acrylate, 3-isopropenyl-α, α-dimethylbenzyl isocyanate or (meth) acryloyl isocyanate may be used. Polymer;

Alternatively, these isocyanate group-containing vinyl monomers can be copolymerized with the monomers to be (meth) acrylic, vinyl ester, vinyl ether, aromatic, vinyl or fluoroolefin, respectively. Obtained by copolymerizing with vinyl monomers, etc.

Various vinyl copolymers such as an isocyanate group-containing acrylic copolymer, a vinyl ester copolymer or a fluoroolefin copolymer, respectively.

Among these polyisocyanates, in particular, from the viewpoint of weather resistance and the like, aliphatic, aralkyl or alicyclic diisocyanate compounds, and various types of polyisocyanate compounds derived from these various diisocyanate compounds. The use of a prepolymer or a vinyl polymer containing an isocyanate group is particularly desirable.

If only typical representative examples of the above-mentioned blocked polyisocyanate compounds are given as examples, various polyisocyanate compounds as described above can be blocked with various blocking agents as described later. Various block polyisocyanate compounds obtained by letting

The compounds include a class of compounds in which an isocyanate group is regenerated by heat, such as various compounds having a uretdione structure obtained by cyclizing and dimerizing an isocyanate group.

[0387] Particularly, only typical representative blocking agents used for preparing the blocked polyisocyanate compound are exemplified by methanol,
Various alcohols such as ethanol, benzyl alcohol or lactate;

Various phenolic hydroxyl group-containing compounds such as phenol, salicylate or cresol; or various amides such as ε-caprolactam, 2-pyrrolidone or acetanilide;

Alternatively, there are various oximes such as acetone oxime or methyl ethyl ketoxime, and further various active methylene compounds such as methyl acetoacetate, ethyl acetoacetate or acetylacetone.

As the above-mentioned polyepoxy compounds, only typical ones are exemplified, and ethylene glycol, hexanediol, neopentyl glycol,
Polyglycidyl ethers of various aliphatic or cycloaliphatic polyols, such as trimethylolpropane, trimethylolethane, glycerin, pentaerythritol, sorbitol or hydrogenated bisphenol A;

Hydroquinone, catechol, resorcinol,
Polyglycidyl ethers of various aromatic diols such as bisphenol A, bisphenol S or bisphenol F; aromatic diol derivatives such as ethylene oxide or propylene oxide adducts of aromatic diols as described above. Diglycidyl ethers;

Polyglycidyl ethers of various polyether polyols such as polyethylene glycol, polypropylene glycol or polytetramethylene glycol; polyglycidyl ethers of tris (2-hydroxyethyl) isocyanurate; adipic acid, butanetetracarboxylic acid Polyglycidyl esters of various aliphatic or aromatic polycarboxylic acids, such as, for example, propanetricarboxylic acid, phthalic acid, terephthalic acid or trimellitic acid;

Bisepoxides of various hydrocarbon dienes, such as butadiene, hexadiene, octadiene, dodecadiene, cyclooctadiene, α-pinene or vinylcyclohexene; bis (3,4-epoxycyclohexylmethyl) adipate or 3, Various alicyclic polyepoxy compounds such as 4-epoxycyclohexylmethyl-3,4-epoxycyclohexylcarboxylate; or epoxidized various diene polymers such as polybutadiene or polyisoprene;

"Denacol EX-612" [trade name of sorbitol polyglycidyl ether manufactured by Nagase Kasei Kogyo Co., Ltd.]; "EGM-400" [3-glycidide manufactured by Toray Dow Corning Silicone Co., Ltd.] Trade name of cyclic polysiloxane having xypropyl];

Alternatively, various homopolymers of the various epoxy group-containing vinyl monomers described above or these epoxy group-containing vinyl monomers can be copolymerized with the monomers. Acrylic copolymers each having an epoxy group, such as those obtained by copolymerizing with (meth) acrylic, vinyl ester, vinyl ether, aromatic vinyl or fluoroolefin vinyl monomers And vinyl-based copolymers such as vinyl ester-based copolymers and fluoroolefin-based copolymers.

If only typical representative examples of the polycyclocarbonate compound are given, various polyepoxy compounds as described above may be reacted with carbon dioxide, for example, in the presence of a catalyst to obtain the epoxy compound. 5-membered ring cyclocarbonate group-containing polycyclocarbonate compound obtained by converting a group into a cyclocarbonate group; or homopolymers of various cyclocarbonate group-containing vinyl monomers as described above

Alternatively, the cyclocarbonate group-containing vinyl monomer can be copolymerized with the monomer.
(Meth) acrylic, vinyl ester, vinyl ether, aromatic vinyl or fluoroolefin vinyl monomers obtained by copolymerization, each having a cyclocarbonate group, acrylic copolymer, Vinyl copolymers such as vinyl ester copolymers and fluoroolefin copolymers.

Subsequently, if only typical examples of the above-mentioned amino resins are given, only

An alkylol group obtained by reacting various amino group-containing compounds such as melamine, benzoguanamine, acetoguanamine, urea or glycouril with various aldehyde compounds (or aldehyde-supplying substances) such as formaldehyde or acetaldehyde. Various amino resins having:

Alternatively, various alkoxyalkyl groups obtained by reacting such an amino resin having an alkylol group with various lower alcohols such as methanol, ethanol, n-butanol or i-butanol (isobutanol). Containing amino resin.

If only typical examples of the primary or secondary amide group-containing compound are given as examples, the functional group used in preparing the vinyl polymer (b-2) described above may be used. Various vinyl monomers having a primary or secondary amide group as already exemplified as a part of the vinyl monomer (m-4) containing a group (Fu-1) Homopolymer

Alternatively, these primary or secondary amide group-containing vinyl monomers can be copolymerized with the monomers to form (meth) acrylic, vinyl ester, vinyl ether, and aromatic vinyl, respectively. Acrylic copolymers, vinyl ester copolymers or fluoroolefin copolymers having a primary or secondary amide group, obtained by copolymerization with vinyl or fluoroolefin vinyl monomers, etc. Various vinyl copolymers, such as coalescing.

Further, if only typical examples of the polycarboxy compound are exemplified, oxalic acid,
Low molecular weight compounds such as malonic acid, succinic acid, glutaric acid, adipic acid, sebacic acid, azelaic acid, phthalic acid, terephthalic acid, isophthalic acid, tartronic acid, malic acid, tartaric acid or citric acid; Furthermore,

As a part of the acid group-containing vinyl monomer used in the preparation of the vinyl polymer (b-1), various vinyl compounds having a carboxyl group as exemplified above may be used. Homopolymer of monomer

Alternatively, such a carboxyl group-containing vinyl monomer can be copolymerized with the monomer to form a (meth) acrylic, vinyl ester, vinyl ether, aromatic vinyl or fluoroolefin vinyl, respectively. Obtained by copolymerizing with monomers and the like,
Having a carboxyl group, various acrylic copolymers,
Various vinyl copolymers such as a vinyl ester copolymer or a fluoroolefin copolymer are included.

As the above-mentioned polyhydroxy compounds, only typical ones are exemplified, and various low-molecular compounds such as ethylene glycol, propylene glycol, butylene glycol and glycerin, and the like. Or a functional group (F) used for preparing a vinyl polymer (b-2) such as polypropylene glycol.
As a part of the vinyl monomer (m-4) having u-1), homopolymers of various vinyl monomers having a hydroxyl group bonded to a carbon atom as already exemplified.

Alternatively, a hydroxyl group-containing vinyl monomer bonded to such a carbon atom can be copolymerized with the monomer to form a (meth) acrylic, vinyl ester, vinyl ether, aromatic vinyl or aromatic vinyl, respectively. Various acrylic copolymers, vinyl ester copolymers or fluoroolefin copolymers having hydroxyl groups bonded to carbon atoms, obtained by copolymerizing with fluoroolefin vinyl monomers, etc. And various vinyl copolymers.

Compound (C) was converted from aqueous resin (W-1) to
When compounded with each of (W-4), this compound (C) is itself a water-soluble compound, a water dispersion, or a compound having a certain degree of hydrophilicity. In this case, a composition in which the compound (C) is uniformly dissolved or uniformly dispersed in each of the aqueous resins (W-1) to (W-4) can be obtained.

However, when the hydrophilicity of the compound (C) is low, even if the compound (C) is to be mixed with each of the aqueous resins (W-1) to (W-4), the composition in the form of a uniformly dissolved or dispersed form. However, in such a case, the compound (C) can be obtained by introducing a so-called hydrophilic group or the like into the compound (C) by various known and commonly used methods. ) The hydrophilicity of the composition itself can be improved, and a composition having a uniform shape can be obtained.

When the compound (C) is a polymer, the compound (C) may be used in any form of a solventless liquid, an organic solvent solution, an aqueous solution or an aqueous dispersion. Can be. When the compound (C) itself is a vinyl polymer, it is also suitable to use it as an emulsion polymer.

The above aqueous resins (W-1) to (W-4)
In order to prepare an aqueous curable resin composition comprising the compound (C) and the compound (C), the compound (C) is prepared by adding a hydroxyl group bonded to a silicon atom and / or a hydrolyzable group bonded to a silicon atom. When the compound is a compound having 100% solid content of each of the aqueous resins (W-1) to (W-4).
The solid content of the compound (C) is in the range of about 0.1 to about 200 parts by weight, preferably 0.5 part by weight,
To 150 parts by weight, more preferably 1 to 100 parts by weight.
What is necessary is just to mix | blend so that it may be in the range of a weight part.

If the compound (C) is a compound having both an isocyanate group and a hydrolyzable group bonded to a silicon atom in one molecule, a polyisocyanate compound or a blocked polyisocyanate compound, the aqueous resin (W-1) to (W-4),
With respect to one equivalent of a functional group which reacts with an isocyanate group or a blocked isocyanate group, respectively,

The amount of each isocyanate group or blocked isocyanate group contained in the compound (C) is in the range of about 0.1 to about 10 equivalents, preferably
Within the range of 0.3 to 5 equivalents, more preferably 0.5 to 2 equivalents.
What is necessary is just to mix | blend the said compound (C) so that it may be in the range of an equivalent.

When the compound (C) is a compound having both an epoxy group and a hydrolyzable group bonded to a silicon atom in one molecule, a polyepoxy compound or a polycyclocarbonate compound, an aqueous resin (W-1)-
With respect to one equivalent of a functional group which reacts with an epoxy group or a cyclocarbonate group, respectively, contained in each of (W-4),

The total amount of the epoxy group and / or cyclocarbonate group contained in the compound (C) is:
Within the range of about 0.2 to about 5.0 equivalents, preferably 0.5
The compound (C) may be blended so as to be in a range of from to 3.0 equivalents, more preferably in a range of from 0.7 to 2 equivalents.

Subsequently, when the compound (C) is an amino resin in particular, the aqueous resins (W-1) to (W-
The solids content of the compound (C) is in the range of about 5 to about 200 parts by weight, preferably in the range of 10 to 150 parts by weight, more preferably 100 parts by weight of each solid of 4). The amount may be in the range of 15 to 100 parts by weight.

When the compound (C) is a compound having a primary or secondary amide group, it is contained in each of the aqueous resins (W-1) to (W-4). For one equivalent of a functional group that reacts with a primary or secondary amide group,

The amount of the primary or secondary amide group contained in the compound (C) is in the range of about 0.2 to about 5.0 equivalents, preferably in the range of 0.5 to 3.0 equivalents. More preferably, compound (C) may be blended so as to be in the range of 0.7 to 2 equivalents.

Further, when the compound (C) is a polycarboxy compound, the aqueous resin (W-1)
To (W-4) relative to one equivalent of the functional group that reacts with the carboxyl group contained in each of

The amount of carboxyl group contained in the compound (C) is in the range of about 0.2 to about 5.0 equivalents, preferably in the range of 0.5 to 3.0 equivalents, more preferably
The compound (C) may be blended so as to be in the range of 0.7 to 2 equivalents.

When the compound (C) is a polyhydroxy compound, the aqueous resin (W-1)
With respect to one equivalent of the functional group that reacts with the hydroxy group contained in each of (W-4),

The amount of hydroxyl group contained in the compound (C) is in the range of about 0.2 to about 5.0 equivalents, preferably
Within the range of 0.5 to 3.0 equivalents, more preferably 0.7
What is necessary is just to mix | blend a compound (C) so that it may be in the range of-2 equivalents.

Prepared as described above, each
The aqueous curable resin composition of the present invention containing the aqueous resins (W-1) to (W-4) as essential components, or the aqueous resins (W-1) to (W-4), respectively. Further, the aqueous curable resin composition of the present invention into which the compound (C) is also blended can be used as a clear composition containing no color pigment, and can be any of various known or commonly used organic or It can also be used as a coloring composition containing an inorganic pigment.

Typical examples of the above-mentioned pigments include carbon black, phthalocyanine blue, phthalocyanine green and quinacridone red.
Various organic pigments; various metal oxide inorganic pigments such as titanium oxide, iron oxide, titanium yellow or copper chrome black; and inorganic flake pigments such as aluminum flake or pearl mica. No.

The aqueous curable resin composition of the present invention further comprises a curing catalyst, a flow regulator, a dye, a leveling agent, a rheology control agent, an ultraviolet absorber, an antioxidant or a plasticizer. It can be used in a form in which various known and commonly used additives are mixed.

Among the above-mentioned additives, only those which are particularly typical as curing catalysts are exemplified, and those which are used in the preparation of the polysiloxane (A) as described above have already been mentioned. Various catalysts such as those described above can be used. In addition to these compounds, tetramethylphosphonium salts, tetraethylphosphonium salts, tetrapropylphosphonium salts, tetrabutylphosphonium salts, trimethyl (2-hydroxypropyl)
Various compounds such as phosphonium salts, triphenylphosphonium salts or benzylphosphonium salts having various anions as a counter anion such as, for example, fluoride, chloride, bromide or carboxylate can also be used.

In the case where each of the aqueous resins (W-1) to (W-4) has an anionic group or a cationic group as a hydrophilic group, such an anionic group or a cationic group is bonded to a silicon atom. Since it functions as a condensation catalyst for a hydroxyl group, that is, a silanol group, crosslinking by condensation of a silanol group can be achieved at room temperature without adding a curing catalyst. To further improve curability,
What is necessary is just to add the curing catalyst as described above.

When the aqueous resin (W-3) or (W-4) is
When the polymer has only a nonionic group as a hydrophilic group, crosslinking by condensation of silanol groups is very slow at room temperature. Therefore, in order to crosslink such a resin at room temperature by condensation of silanol groups, it is preferable to add a curing catalyst as described above.

The curable resin composition of the present invention containing each of the aqueous resins (W-1) to (W-4), or (W-
When a curing catalyst is added to the curable resin composition of the present invention containing the compound (C) in addition to each of 1) to (W-4), the amount of the curing catalyst to be added is determined by the amount of the composition For 100 parts by weight of the total amount of resin solids contained in
In the range of 0.01 to 15 parts by weight, preferably 0.05 to
It is appropriate to set it in the range of 10 parts by weight, particularly preferably in the range of 0.1 to 5 parts by weight.

The aqueous curable resin composition according to the present invention thus obtained is composed of the aqueous resin (W-1)
Depending on the type of (W-4), the presence or absence of the component (C), or in the case where the component (C) is added, the optimum curing conditions differ depending on the type and amount of the component. And let it dry for about 3-10 days,

Alternatively, by baking at a temperature range of about 80 to about 250 ° C. for about 30 seconds to about 2 hours, a cured product having high practicality can be obtained.

The water-based resin according to the present invention comprises the water-based resin as an essential component, because the water-based resin according to the present invention provides a cured product having extremely excellent durability and the like. Can be used mainly for various paints, such as paints for automotive top coatings, paints for architectural exteriors, paints for building materials, etc., and further for adhesives, inks, impregnants for fibers and papers, and It can be used for a wide range of applications, such as for surface treatment agents.

[0421]

Next, the present invention will be described more specifically with reference examples, examples and comparative examples. However, the present invention is in no way limited to only these illustrative examples. is not. In the following, all parts and percentages are by weight unless otherwise specified.

Reference Example 1 [Example of Preparation of Control Resin 1]

First, 470 parts of isopropanol (IPA) was charged into a reaction vessel equipped with a thermometer, a reflux condenser, a stirrer, a dropping funnel, and a nitrogen inlet tube, and the temperature was raised to 80 ° C. while passing nitrogen gas. did.

Next, at the same temperature, one of styrene (ST)
00 parts, 300 of methyl methacrylate (MMA)
Parts, 304 parts of n-butyl methacrylate (BMA)
186 parts of n-butyl acrylate (BA), 3-methacryloyloxypropyltrimethoxysilane (MPT
MS), 30 parts of acrylic acid (AA), IPA
Of tert-butylperoxy-2-ethylhexanoate (TBPO) was added dropwise over 4 hours.

After the completion of the dropwise addition, the mixture was stirred at the same temperature for 16 hours to provide a carboxyl group and a trimethoxysilyl group having a nonvolatile content of 52.5% and a number average molecular weight of 11,900. To obtain a solution of the target polymer. Hereinafter, this is abbreviated as (R-1).

In a reaction vessel similar to the above, 364 parts of phenyltrimethoxysilane (PTMS), 534 parts of methyltrimethoxysilane (MTMS) and 54 parts of IPA were added.
4 parts were charged and heated to 80 ° C.

Next, at the same temperature, 9.3 parts of “AP-3” (trade name of isopropyl acid phosphate manufactured by Daihachi Chemical Industry Co., Ltd.) and 311 parts of ion-exchanged water were added to 5 The mixture was added dropwise over a period of minutes and stirred at the same temperature for 4 hours to prepare a cohydrolysis condensate of PTMS and MTMS. The reaction mixture Te following nuclear magnetic resonance analysis ⁽¹ H-NMR), hydrolysis of PTMS and MTMS was confirmed that the progress of 100%.

Thereafter, 959 parts of the polymer (R-1) was added, and the mixture was stirred at the same temperature for 4 hours to prepare a condensate of the polysiloxane and the polymer (R-1). .
When this condensate was analyzed by ¹ H-NMR, it was found that the hydrolysis of the trimethoxysilyl group contained in the polymer (R-1) had progressed 100%.

Then, at the same temperature, triethylamine (T
A mixture of 56 parts of EA) and 1,345 parts of ion-exchanged water was added dropwise over 30 minutes, and then the mixture was distilled under reduced pressure to remove non-volatile components of 39% except for alcohols such as methanol (MEOH) and IPA. 0.3% of an aqueous resin was obtained. Hereinafter, this is abbreviated as Control Resin 1.

Thereafter, this control resin 1 was heated at 40 ° C.
After storage for one month, no abnormalities such as gelation and precipitation of a precipitate were observed, and it was found that the storage stability was excellent.

Reference Example 2 [Preparation Example of Polymer (R-2)] In a reaction vessel similar to that of Reference Example 1, 470 parts of IPA were charged, and the temperature was raised to 80 ° C. under a nitrogen gas flow.

Next, at the same temperature, 100 parts of ST, MM
A 300 parts, BMA 364 parts, BA 186 parts, A
A mixture consisting of 50 parts of A, 450 parts of IPA and 50 parts of TBPO was added dropwise over 4 hours.

After completion of the dropwise addition, stirring was carried out at the same temperature for 16 hours to obtain a carboxyl-containing control resin 2 having a nonvolatile content of 53.4% and a number average molecular weight of 10,200. To obtain a solution of a polymer to be used in the preparation of Hereinafter, this is abbreviated as (R-2).

Reference Examples 3 to 5 [Polymers (R-3) to (R-
Preparation example of 5)]

The polymerization was carried out in the same manner as in Reference Example 2 except that the kind and the amount of the monomer used and the amount of the polymerization initiator were changed as shown in Table 1, and the polymerization was carried out. Polymers (R-3) to (R-5) having the property values shown and used for preparing a control resin were obtained. The polymers are abbreviated as shown in the table.

[0436]

[Table 1]

<< Footnote to Table 1 >> "PEGMA": Abbreviation of methoxypolyethylene glycol methacrylate having a number average molecular weight of about 1,000 "DMAEMA": Abbreviation of 2-dimethylaminoethyl methacrylate "HEMA" abbreviation for 2-hydroxyethyl methacrylate "AIBN" abbreviation for azobisisobutyronitrile

[0438]

[Table 2]

<< Footnote to Table 1 >> [R] obtained in Reference Example 3
"-3" is a polymer to be used when preparing the control resin 3.

"R-4" obtained in Reference Example 4 is a polymer to be used when preparing Control Resin 4.

"R-5" obtained in Reference Example 5 is a polymer to be used when preparing Control Resin 5.

Reference Example 6 [Preparation Example of Control Resin 2] In the same reaction vessel as Reference Example 1, the polymer (R-2)
273 parts were charged. Next, a mixture of 49 parts of TEA and 1,000 parts of ion-exchanged water was dropped therein over 30 minutes under stirring at room temperature, and then IPA as a solvent was removed by vacuum distillation. As a result, a control aqueous resin having a nonvolatile content of 34.5% was obtained. Hereinafter, this is abbreviated as Control Resin 2.

Reference Example 7 [Preparation Example of Control Resin 3] In the same reaction vessel as in Reference Example 1, the polymer (R-3)
289 parts were charged. Next, a mixture of 29 parts of acetic acid and 1,000 parts of ion-exchanged water was added dropwise thereto at room temperature under stirring over 30 minutes.
By removing the solvent IPA, the non-volatile content becomes 3
A control aqueous resin of 6.1% was obtained. Hereinafter, this is abbreviated as control resin 3.

Reference Example 8 [Preparation Example of Control Resin 4] In the same reaction vessel as Reference Example 1, the polymer (R-4)
252 parts were charged. Next, a mixture of ion-exchanged water and 1,000 parts was dropped into the mixture at room temperature under stirring over 30 minutes, and the solvent IP was distilled off under reduced pressure.
By removing A, a control aqueous resin having a non-volatile content of 35.7% was obtained. Hereinafter, this is abbreviated as control resin 4.

Reference Example 9 [Preparation Example of Control Resin 5] In the same reaction vessel as Reference Example 1, the polymer (R-5)
266 parts were charged. Then, at room temperature and under stirring, 49 parts of TEA and 1,000 parts of ion-exchanged water are added dropwise over 30 minutes, and then IPA as a solvent is removed by distillation under reduced pressure. , With a nonvolatile content of 35.3
% Of a control aqueous resin was obtained. Hereinafter, this is abbreviated as Control Resin 5.

Example 1 [Preparation example of aqueous resin (W-1)]

[0447] This example shows one illustrative example for preparing the aqueous resin (W-1).

First, IP was placed in the same reaction vessel as in Reference Example 1.
A of 470 parts was charged at 80 ° C. under nitrogen gas ventilation.
The temperature rose.

Next, at the same temperature, 100 parts of ST, MM
300 copies of A, 304 copies of BMA, 186 copies of BA, M
A mixture of 30 parts of PTMS, 80 parts of AA, 450 parts of IPA and 50 parts of TBPO was added dropwise over 4 hours.

After the completion of the dropwise addition, the mixture was stirred at the same temperature for 16 hours to provide a carboxyl group and a trimethoxysilyl group having a nonvolatile content of 52.5% and a number average molecular weight of 11,900. To obtain a solution of the target polymer. Hereinafter, this is abbreviated as (b-1-1).

In a similar reaction vessel, 358 parts of cyclohexyltrimethoxysilane (CHTMS) and MTM were added.
534 parts of S and 544 parts of IPA
The temperature was raised to ° C.

Subsequently, at the same temperature, 9.2 of “AP-3” was obtained.
And 307 parts of ion-exchanged water were added dropwise over 5 minutes, and the mixture was stirred at the same temperature for 4 hours to prepare a cohydrolytic condensate of CHTMS and MTMS. ¹ H-NMR
Thus, the hydrolysis of CHTMS and MTMS is 100%
I confirmed that it was progressing.

Thereafter, 95 of the polymer (b-1-1) was obtained.
Nine parts were added, and the mixture was stirred at the same temperature for 4 hours to prepare a condensate of the polysiloxane and the polymer (b-1-1). When this condensate was analyzed by ¹ H-NMR, it was found that the hydrolysis of the trimethoxysilyl group contained in the polymer (b-1-1) had progressed 100%.

Next, at the same temperature, a mixture of 56 parts of TEA and 1,347 parts of ion-exchanged water was added dropwise over 30 minutes, and then distilled under reduced pressure to remove alcohols such as MEOH and IPA. Thus, a target aqueous resin having a nonvolatile content of 40.3% was obtained. Hereinafter, this is abbreviated as (W-1-1).

Thereafter, the aqueous resin (W-1-1)
Was stored at 40 ° C. for one month, and no abnormalities such as gelation and precipitation of a precipitate were observed, indicating that the product was excellent in storage stability.

Example 2 (Same as above) First, a 3 l-liter stainless steel autoclave, the inside of which was replaced with nitrogen gas, was placed in a stainless steel autoclave.
0 parts, 130 parts of monobutyl maleate, 110 parts of vinyl acetate, 310 parts of ethyl vinyl ether, 60 parts of vinyl tris (β-methoxyethoxy) silane, and 50 parts of tert-butyl peroxypivalate as a polymerization initiator And was charged.

Next, 400 parts of the liquefied and collected chlorotrifluoroethylene was injected into the flask. By continuing the reaction at 60 ° C. for 15 hours with stirring, a carboxyl group and tris (β) having a nonvolatile content of 51.2% and a number average molecular weight of 9,900 are obtained.
A solution of the desired fluorocopolymer having both (-methoxyethoxy) silyl groups was obtained. Hereinafter, this is referred to as (b-1-2)
Abbreviated.

In the same reaction vessel as in Reference Example 1, CHTMS was added.
358 parts, MTMS 534 parts, and IPA 51 parts
Two parts were charged and heated to 80 ° C.

Subsequently, at the same temperature, 9.2 parts of “AP-3” and 307 parts of ion-exchanged water were added dropwise over 5 minutes, and the mixture was stirred at the same temperature for 4 hours. CHT
A co-hydrolysis condensate of MS and MTMS was prepared. ¹ H-
NMR confirmed that the hydrolysis of CHTMS and MTMS had progressed 100%.

Thereafter, 98 of polymer (b-1-2) was obtained.
3 parts were added, and the mixture was stirred at the same temperature for 4 hours to prepare a condensate of the polysiloxane and the polymer (b-1-2). When this condensate was analyzed by ¹ H-NMR, the hydrolysis of the tris (β-methoxyethoxy) silyl group contained in the polymer (b-1-2) had progressed 100%. It has been found.

Next, at the same temperature, a mixture of 35 parts of TEA and 1,347 parts of ion-exchanged water was added dropwise over 30 minutes, and then distilled under reduced pressure to remove alcohols such as MEOH and IPA. Thus, a target aqueous resin having a nonvolatile content of 40.1% was obtained. Hereinafter, this is abbreviated as (W-1-2).

Thereafter, the aqueous resin (W-1-2)
Was stored at 40 ° C. for one month, and no abnormalities such as gelation and precipitation of a precipitate were observed, indicating that the product was excellent in storage stability.

Example 3 (Same as above) First, 190 parts of cyclohexylmethyldimethoxysilane (CHMDMS), 571 parts of MTMS, and 470 parts of IPA were charged into the same reaction vessel as in Reference Example 1, and nitrogen was added. The temperature was raised to 80 ° C. under the gas flow.

Then, at the same temperature, 8.4 of “AP-3”
And parts, and 282 parts of ion-exchanged water was added dropwise in about 5 minutes, at the same temperature, the mixture was stirred during 4 hours, ¹ H-
By NMR, the hydrolysis of CHMDMS and MTMS is
It was confirmed that the progress was 100%.

Thereafter, at the same temperature, 100 parts of ST, M
300 parts of MA, 327 parts of BMA, 186 parts of BA,
A mixture consisting of 57 parts of AA, 30 parts of MPTMS, 350 parts of IPA and 50 parts of TBPO was added dropwise over 4 hours, and after completion of the addition, the mixture was stirred at the same temperature for 16 hours to carry out the polymerization reaction. To obtain a condensate of a polysiloxane and an acrylic polymer. The condensate was analyzed by ¹ H-NMR, and the MPT
It was confirmed that the hydrolysis reaction of the trimethoxysilyl group derived from MS had progressed 100%.

Then, at the same temperature, a mixture of 80 parts of TEA and 1,964 parts of ion-exchanged water was added dropwise over 30 minutes to neutralize the carboxyl groups, and then distilled under reduced pressure. By removing alcohols such as MEOH and IPA, a target aqueous resin having a nonvolatile content of 40.0% was obtained. Hereinafter, this is abbreviated as (W-1-3).

Thereafter, the aqueous resin (W-1-3)
Was stored at 40 ° C. for one month, and no abnormalities such as gelation and precipitation of a precipitate were observed, indicating that the product was excellent in storage stability.

Example 4 (Same as above) First, CHTMS 67 was placed in the same reaction vessel as in Reference Example 1.
9 parts, 1,445 parts of MTMS, 425 parts of dimethyldimethoxysilane (DMDMS) and 1,66 parts of IPA
1 part and heated to 80 ° C. under nitrogen gas flow.

Then, at the same temperature, 28.
A mixture of 6 parts and 960 parts of ion exchanged water, 100 parts of ST, 300 parts of MMA, 284 parts of BMA, BA
186 parts, AA 100 parts, MPTMS 30 parts, I
A mixture consisting of 350 parts of PA and 50 parts of TBPO was added dropwise over 4 hours.

After the completion of the dropwise addition, the polymerization reaction was continued by stirring at the same temperature for 16 hours to obtain a composite resin. When this composite resin was analyzed by ¹ H-NMR, it was confirmed that the hydrolysis reaction of the trimethoxysilyl group derived from CHTMS, MTMS, DMDMS and MPTMS had progressed by 100%.

Then, at the same temperature, 140 parts of TEA,
A mixture of ion-exchanged water and 3,240 parts was dropped over 30 minutes to neutralize the carboxyl groups, and then distilled under reduced pressure to remove alcohols such as MEOH and IPA. The desired aqueous resin was obtained in an amount of 0.9%. Hereinafter, this is abbreviated as (W-1-4).

Thereafter, the aqueous resin (W-1-4)
Was stored at 40 ° C. for one month, and no abnormalities such as gelation and precipitation of a precipitate were observed, indicating that the product was excellent in storage stability.

Example 5 (Same as above) First, 373 parts of 2,2-dimethyl-3-hydroxypropyl-2,2-dimethyl-3-hydroxypropionate and N- 39 parts of methyldiethanolamine, 417 parts of toluene and 0.44 parts of dibutyltin dioctate were charged, and the temperature was raised to 80 ° C. while passing dry nitrogen gas.

Then, at the same temperature, a mixture of 519 parts of isophorone diisocyanate and 519 parts of toluene was added dropwise over 1 hour, and after completion of the addition, the mixture was stirred at the same temperature for 4 hours. It was confirmed that the isocyanate concentration was almost the same as the theoretical value.

Thereafter, at the same temperature, a mixture of 64 parts of 3-aminopropyltrimethoxysilane and 64 parts of toluene was added dropwise over 10 minutes. The mixture was stirred for a while, and after confirming that the isocyanate group had disappeared by infrared absorption spectroscopy (IR analysis), 50 parts of toluene and 450 parts of IPA were added, and the nonvolatile content was 43.
A solution of a polyurethane-based polymer having 3% and having a number average molecular weight of 5,400 and having both an amino group and a trimethoxysilyl group was obtained. Hereinafter, this is abbreviated as (b-1-3).

In the same reaction vessel as in Reference Example 1, CHMDM was added.
134 parts of S, 403 parts of MTMS and 57 parts of IPA
Two parts were charged and heated to 80 ° C.

Next, at the same temperature, 5.9 of “AP-3”
And 199 parts of ion-exchanged water were added dropwise over 5 minutes, and the mixture was stirred at the same temperature for 4 hours to obtain CHM.
A co-hydrolysis condensate of DMS and MTMS was prepared. ¹ H
Analyze the reaction mixture by NMR-CHMD
It was confirmed that hydrolysis of MS and MTMS had progressed 100%.

Subsequently, here, the obtained polymer (b-1)
-3) was added, and the mixture was stirred at the same temperature for 4 hours to give polysiloxane and polymer (b-
A condensate with 1-3) was prepared.

Next, when the condensate was analyzed by ¹ H-NMR, the hydrolysis of the trimethoxysilyl group contained in the polymer (b-1-3) proceeded 100%. Turned out to be.

Subsequently, at the same temperature, a mixture of 19.1 parts of acetic acid and 1,300 parts of ion-exchanged water was added dropwise over 30 minutes, and then MEOH, IPA,
By removing alcohols such as n-butanol and toluene, a target aqueous resin having a nonvolatile content of 40.1% was obtained. Hereinafter, this is abbreviated as (W-1-5).

Thereafter, the aqueous resin (W-1-5)
Was stored at 40 ° C. for one month, and no abnormalities such as gelation and precipitation of a precipitate were observed, indicating that the product was excellent in storage stability.

Example 6 [Preparation example of aqueous resin (W-2)]

This example shows one illustrative example for preparing the aqueous resin (W-2).

First, C was placed in the same reaction vessel as in Reference Example 1.
748 parts of HTMS, 1,006 parts of MTMS, and I
1,164 parts of PA were charged, and the temperature was raised to 80 ° C. under nitrogen gas flow.

Then, at the same temperature, 17.AP-3.
8 parts and 598 parts of ion-exchanged water were added dropwise in about 5 minutes, and stirred at the same temperature for 4 hours to obtain CHTMS and M
A co-hydrolysis condensate of TMS was prepared. ^{By 1} H-NMR, it was confirmed that the hydrolysis of CHTMS and MTMS had progressed 100%.

Thereafter, at the same temperature, 100 parts of ST, M
250 parts of MA, 184 parts of BMA, 186 parts of BA,
50 parts of AA, 50 parts of HEMA, 30 parts of MPTMS
Parts, 150 parts of PEGMA, 350 parts of IPA and T
A mixture consisting of 50 parts of BPO was added dropwise over 4 hours, and after completion of the addition, the polymerization reaction was continued by stirring at the same temperature for 16 hours to obtain a polysiloxane and an acrylic polymer. To give a condensate.

The condensate was analyzed by ¹ H-NMR, and it was confirmed that the hydrolysis of the trimethoxysilyl group derived from MPTMS had progressed 100%.

Next, at the same temperature, 2,6
After dropping 73 parts over 30 minutes, ME was distilled off under reduced pressure.
By removing alcohols such as OH and IPA, a target aqueous resin having a nonvolatile content of 35.0% was obtained. Hereinafter, this is abbreviated as (W-2-1).

Thereafter, the aqueous resin (W-2-1)
Was stored at 40 ° C. for one month, and no abnormalities such as gelation and precipitation of a precipitate were observed, indicating that the product was excellent in storage stability.

Example 7 (same as above)

First, IP was placed in the same reaction vessel as in Reference Example 1.
A of 470 parts was charged at 80 ° C. under nitrogen gas ventilation.
The temperature rose.

Next, at the same temperature, 100 parts of ST, MM
300 copies of A, 284 copies of BMA, 186 copies of BA, 2
-50 of hydroxyethyl methacrylate (HEMA)
Parts, 80 parts of AA, 450 parts of IPA and tert-
A mixture of 50 parts of butylperoxy-2,2-dimethyl-3-trimethoxysilylpropanoate (TBPOTMS) was added dropwise over 4 hours.

After completion of the dropwise addition, the mixture was stirred at the same temperature for 16 hours to give a carboxyl group, a hydroxyl group and a trimethoxysilyl group having a nonvolatile content of 53.8% and a number average molecular weight of 12,100. Was obtained. Hereinafter, this is abbreviated as (b-2-1).

In the same reaction vessel as in Reference Example 1, polymer (b)
2-1) 938 parts, CHTMS 377 parts and MTM
507 parts of S and 566 parts of IPA
The temperature was raised to ° C.

Next, at the same temperature, 9.0 of “AP-3” was obtained.
And parts, and 301 parts of ion-exchanged water was added dropwise over 5 minutes, at the same temperature, the mixture was stirred during 4 hours, ¹ H-
NMR confirmed that the hydrolysis of the trimethoxysilyl group, CHTMS and MTMS contained in the polymer (b-2-1) had progressed 100%.

Thereafter, at the same temperature, 57 parts of TEA and 1,350 parts of ion-exchanged water were added dropwise over 30 minutes, and then vacuum distillation was performed to remove alcohols such as MEOH and IPA. Thus, a target aqueous resin having a nonvolatile content of 40.1% was obtained. Hereinafter, this is abbreviated as (W-2-2).

Thereafter, the aqueous resin (W-2-2)
Was stored at 40 ° C. for one month, and no abnormalities such as gelation and precipitation of a precipitate were observed, indicating that the product was excellent in storage stability.

Example 8 (Same as above) First, a polymer (b-2-2) was prepared. 470 parts of IPA was charged into the same reaction vessel as in Reference Example 1, and the temperature was raised to 80 ° C. under nitrogen gas flow.

Subsequently, at the same temperature, 100 parts of ST, MM
300 parts of A, 284 parts of BMA, 186 parts of BA, H
50 parts of EMA and 80 parts of AA and 450 parts of IPA
Of TBPO and 50 parts of TBPO were added dropwise over 4 hours.

After completion of the dropwise addition, the mixture was stirred at the same temperature for 16 hours to obtain a carboxyl group, a hydroxyl group and a trimethoxysilyl group having a nonvolatile content of 55.1% and a number average molecular weight of 11,100. Was obtained. Hereinafter, this is abbreviated as (b-2-2).

Subsequently, a polysiloxane was prepared.
The same reaction vessel as in Example 1 was charged with 377 parts of CHTMS and 507 parts of MTMS, and the temperature was raised to 80 ° C. Then, at the same temperature, 9.0 parts of “AP-3” were ion-exchanged. A mixture of water and 301 parts was added dropwise over about one hour.

After the completion of the dropwise addition, the mixture was stirred at the same temperature for 4 hours to obtain a target polysiloxane (co-hydrolyzed condensate of CHTMS and MTMS) having a number average molecular weight of 1,200. Hereinafter, this is abbreviated as (a-1).

Finally, 915 parts of the polymer (b-2-2) and 1,783 parts of the polysiloxane (a-1) were mixed at room temperature, and then, at the same temperature, TEA
Of a mixture of 57 parts of
After dropwise addition over 0 minutes, MEOH, I
By removing alcohols such as PA, a target aqueous resin having a nonvolatile content of 41.0% was obtained. Hereinafter, this is abbreviated as (W-2-3).

Thereafter, the aqueous resin (W-2-3)
Was stored at 40 ° C. for one month, and no abnormalities such as gelation and precipitation of a precipitate were observed, indicating that the product was excellent in storage stability.

Example 9 [Preparation example of aqueous resin (W-3)]

This example shows one illustrative example for preparing the aqueous resin (W-3).

First, TE was placed in the same reaction vessel as in Reference Example 1.
A mixture of 50 parts of A and 470 parts of IPA was charged, and the temperature was raised to 80 ° C. while passing nitrogen gas.

Next, at the same temperature, 100 parts of ST, MM
300 copies of A, 314 copies of BMA, 186 copies of BA, A
A mixture of 80 parts of A, 20 parts of 3-methacryloyloxypropyloxydimethylethoxysilane, 450 parts of IPA and 50 parts of TBPO was added dropwise over 4 hours.

After the completion of the dropwise addition, the mixture was stirred at the same temperature for 16 hours to obtain a carboxyl group neutralized with TEA having a nonvolatile content of 50.5% and a number average molecular weight of 14,800. A solution of the target polymer having both dimethylmethoxysilyl groups was obtained. Hereinafter, this is referred to as (b-
Abbreviated as 3-1).

In a similar reaction vessel as above, 3 CHTMS was added.
58 parts, 534 parts of MTMS and 506 parts of IPA were charged and heated to 80 ° C.

Then, at the same temperature, 307 of ion-exchanged water
Was added dropwise over 5 minutes, and the mixture was stirred at the same temperature for 4 hours to prepare a cohydrolysis condensate of CHTMS and MTMS. By ¹ H-NMR of the reaction mixture, CH
It was confirmed that hydrolysis of TMS and MTMS had progressed 100%.

Thereafter, 95 of the polymer (b-3-1) was obtained.
9 parts were added, and the mixture was stirred at the same temperature for 4 hours to prepare a condensate of the polysiloxane and the polymer (b-3-1). When this condensate was analyzed by ¹ H-NMR, it was found that hydrolysis of the dimethylmethoxysilyl group contained in the polymer (b-3-1) had progressed 100%.

Then, at the same temperature, 1,3
After the mixture with 47 parts was dropped over 30 minutes, the target aqueous resin having a non-volatile content of 35.6% was obtained by vacuum distillation except for alcohols such as MEOH and IPA.
Hereinafter, this is abbreviated as (W-3-1).

Thereafter, the aqueous resin (W-3-1)
Was stored at 40 ° C. for one month, and no abnormalities such as gelation and precipitation of a precipitate were observed, indicating that the product was excellent in storage stability.

Example 10 (same as above)

First, a mixture of 52 parts of acetic acid and 470 parts of IPA was charged into the same reaction vessel as in Reference Example 1, and the temperature was raised to 80 ° C. under a nitrogen gas flow.

Then, at the same temperature, 100 parts of ST, MM
300 parts of A, 234 parts of BMA, 186 parts of BA, M
30 parts of PTMS, 150 parts of 2-dimethylaminoethyl methacrylate (DMAEMA) and 450 parts of IPA
And a mixture of 50 parts of AIBN was added dropwise over 4 hours.

After completion of the dropwise addition, the mixture was stirred at the same temperature for 16 hours to obtain a dimethylamino group neutralized with acetic acid having a nonvolatile content of 51.1% and a number average molecular weight of 13,200. And a solution of the target polymer having both trimethoxysilyl groups. Hereinafter, this is referred to as (b-3-
Abbreviated as 2).

In the same reaction vessel as in Reference Example 1, the polymer (b)
-3-2) 978 parts, CHTMS 377 parts and MTM
525 parts of S and 566 parts of IPA
The temperature was raised to ° C.

Next, at the same temperature, the ion-exchanged water 301
Was added dropwise over 5 minutes and stirred at the same temperature for 4 hours, and then the polymer (b-3) was analyzed by ¹ H-NMR.
-2) trimethoxysilyl group, CHT contained in
It was confirmed that hydrolysis of MS and MTMS had progressed 100%.

Thereafter, at the same temperature, 1,350 parts of ion-exchanged water was added dropwise over 30 minutes, and then distilled under reduced pressure to remove alcohols such as MEOH and IPA.
A target aqueous resin having a nonvolatile content of 37.0% was obtained. Hereinafter, this is abbreviated as (W-3-2).

Then, the aqueous resin (W-3-2)
Was stored at 40 ° C. for one month, and no abnormalities such as gelation and precipitation of a precipitate were observed, indicating that the product was excellent in storage stability.

Example 11 (same as above)

First, C was placed in the same reaction vessel as in Reference Example 1.
748 parts of HTMS, 1,006 parts of MTMS, and I
1,164 parts of PA were charged, and the temperature was raised to 80 ° C. under nitrogen gas flow.

Next, at the same temperature, 17.
8 parts and 598 parts of ion-exchanged water were added dropwise in about 5 minutes, and the mixture was stirred at the same temperature for 4 hours to prepare a co-hydrolysis condensate of CHTMS and MTMS. ¹ H-NMR
Thus, the hydrolysis of CHTMS and MTMS is 100%
I confirmed that it was progressing.

Subsequently, at the same temperature, 100 parts of ST, M
300 parts of MA, 184 parts of BMA, 186 parts of BA,
30 parts of MPTMS, 200 parts of PEGMA, and IPA
Of 350 parts of TBPO and 50 parts of TBPO,
The solution was dropped over 4 hours, and after the dropping, the same temperature was maintained at 16 ° C.
The polymerization reaction was continued by stirring for a certain time to obtain a condensate of the polysiloxane and the acrylic polymer.

This condensate was analyzed by ¹ H-NMR, and it was confirmed that the hydrolysis reaction of the trimethoxysilyl group derived from MPTMS had progressed 100%.

Next, at the same temperature, 2,6
After dropping 73 parts over 30 minutes, ME was distilled off under reduced pressure.
By removing alcohols such as OH and IPA, a target aqueous resin having a non-volatile content of 36.7% was obtained. Hereinafter, this is abbreviated as (W-3-3).

Thereafter, the aqueous resin (W-3-3)
Was stored at 40 ° C. for one month, and no abnormalities such as gelation and precipitation of a precipitate were observed, indicating that the product was excellent in storage stability.

Example 12 [Preparation example of aqueous resin (W-4)]

[0531] This example shows one illustrative example for preparing the aqueous resin (W-4).

First, a mixture of 52 parts of acetic acid and 470 parts of IPA was charged into the same reaction vessel as in Reference Example 1, and the temperature was raised to 80 ° C. under a stream of nitrogen gas.

Next, at the same temperature, 100 parts of ST, MM
300 copies of A, 184 copies of BMA, 186 copies of BA, H
A mixture of 50 parts of EMA, 150 parts of DMEMA, 30 parts of MPTMS, 450 parts of IPA and 50 parts of AIBN was added dropwise over 4 hours.

After completion of the dropwise addition, the mixture was stirred at the same temperature for 16 hours to obtain a dimethylamino group neutralized with acetic acid having a nonvolatile content of 50.9% and a number average molecular weight of 12,700. And a solution of the target polymer having both trimethoxysilyl groups. Hereinafter, this is referred to as (b-4-
Abbreviated as 1).

In the same reaction vessel as in Reference Example 1, the polymer (b)
4-1) 990 parts, CHTMS 377 parts and MTM
507 parts of S and 513 parts of IPA
The temperature was raised to ° C.

Next, at the same temperature, 301 of ion-exchanged water
Was added dropwise over 5 minutes and stirred at the same temperature for 4 hours, and then the polymer (b-4) was analyzed by ¹ H-NMR.
-1) trimethoxysilyl group contained in
It was confirmed that hydrolysis of MS and MTMS had progressed 100%.

[0537] Thereafter, at the same temperature, 1,350 parts of ion-exchanged water was added dropwise over 30 minutes, and then alcohols such as MEOH and IPA were removed by distillation under reduced pressure.
A target aqueous resin having a nonvolatile content of 40.1% was obtained. Hereinafter, this is abbreviated as (W-4-1).

Then, the aqueous resin (W-4-1)
Was stored at 40 ° C. for one month, and no abnormalities such as gelation and precipitation of a precipitate were observed, indicating that the product was excellent in storage stability.

Examples 13 to 30 First, a mixture of a part of each of the aqueous resins (W-1) to (W-4), a pigment, and ethylene glycol monobutyl ether (EGMBE) was prepared by using a sand mill. Disperse and prepare various mill bases having a pigment weight concentration (PWC) of 60%, and then add all the remaining water bases (W-1) to (W-4) to the mill base and mix. Various white bases were prepared.

Then, water is added to each of these white bases, if necessary, and the compound (C) is further blended to obtain a PWC of 35%.
Various white paints were prepared.

Aqueous resins (W-1) to (W-4) used for each white paint prepared as described above
The amounts of each of the pigment, EGMBE, and compound (C) used are as shown in Table 2.

Each of the white paints thus obtained was dried on a coated steel sheet which had been previously coated with a polyester / melamine paint and baked, and which had been water-polished. The composition was applied with an applicator so that the film thickness became about 40 μm, and cured under the curing conditions shown in the same table to obtain various cured coating films.

Each of the coating films obtained using the aqueous curable resin composition according to the present invention,
The appearance was excellent. Each coating film was evaluated for various properties. The results are
The results are shown in Table 2.

Comparative Examples 1 to 8 First, a mixture of a part of the control resins 1, 2, 3, 4 or 5, a pigment and EGMBE was dispersed by using a sand mill to obtain a PWC of 60%. Various millbases were prepared and then the control resin 1,
Various white bases were prepared by adding and mixing all of the remainder of 2, 3, 4 or 5.

Then, by blending water and, if necessary, compound (C) with each of these white bases, PWC can be reduced to 35%.
A variety of control white paints were prepared.

The control resin 1, 2, 3, 4 or 5 used in each of the white paints thus prepared was used.
And the amounts of the pigment, ethylene glycol monobutyl ether and compound (C) used are as shown in the table.

Each of the white paints thus obtained was applied in the same manner as in Example 9 and cured under the curing conditions shown in the same table to obtain various types of paints.
A cured control coating was obtained.

[0548] The control resin 1, thus obtained,
Each of the coating films using the curable composition for control containing 2, 3, 4 or 5 was excellent in appearance. Each coating film was evaluated for various properties. The results are, collectively,
It is shown in Table 2.

[0549]

[Table 3]

<< Footnotes to Table 2 >> All numerical values indicating the usage ratios of the raw materials are parts by weight.

“CR-97” is the same as “Taipec CR-
97 ", which is a trade name of rutile titanium oxide manufactured by Ishihara Sangyo Co., Ltd.

[0552]

[Table 4]

<< Footnote to Table 2 >>"Weatherresistance" refers to the 60-degree specular reflectance (%) of the coating film after exposure for 4,000 hours using a sunshine weatherometer.
Is divided by the same gloss value of the coating film when not exposed, and multiplied by 100 (gloss retention:
%).

[0554] The higher the value, the better the weather resistance.

“Stain resistance” indicates the color difference (ΔE) between an unwashed coating film after exposure for two months outdoors and a coating film without exposure.

[0556] The closer the value is to zero, the better the stain resistance.

[0557] "Acid resistance" means that the test was carried out as a substitute test for "acid rain resistance", and 0.1 ml of a 10% sulfuric acid aqueous solution was placed on the surface of each cured coating film. The test plate was placed in a hot air dryer at 60 ° C. for 30 minutes.
After holding for a minute, the coating film surface was washed with water and dried, and the state of the surface was visually evaluated and determined.

[0558] The criteria for evaluation judgment at that time are as follows.

◎: no etching…: slight etching was observed Δ: gloss was reduced ×: etching was remarkable

[0560] "Alkali resistance" means that each test plate was immersed in a 5% aqueous sodium hydroxide solution at room temperature for 24 hours, and then the coating film surface was separately washed with water and dried. The surface state is visually evaluated and determined.

[0561]

[Table 5]

<< Footnotes to Table 2 >> Each numerical value indicating the usage ratio of raw materials is a part by weight.

[0563]

[Table 6]

[0564]

[Table 7]

<< Footnotes to Table 2 >> All numerical values indicating the usage ratios of the raw materials are parts by weight.

"GPTMS": abbreviation for 3-glycidoxypropyltrimethoxysilane

[0567]

[Table 8]

[0568]

[Table 9]

Footnotes in Table 2 >> Each numerical value indicating the usage ratio of raw materials is part by weight.

[0570]

[Table 10]

[0571]

[Table 11]

<< Footnotes to Table 2 >> All numerical values indicating the usage ratios of the raw materials are parts by weight.

[EX-612] is "Denacol EX"
-612 ", which is a trade name of sorbitol polyglycidyl ether manufactured by Nagase Kasei Kogyo Co., Ltd.

“EGM-400” is a product of Dow Corning Silicone Toray Silicone Co., Ltd.
It is a trade name of a cyclic polysiloxane having a glycidoxypropyl group.

[0575]

[Table 12]

[0576]

[Table 13]

<< Footnotes in Table 2 >> All numerical values indicating the usage ratios of the raw materials are parts by weight.

“AN-210” is the same as “Aquanate 21”.
0 ", a trade name of self-emulsifying polyisocyanate manufactured by Nippon Polyurethane Industry Co., Ltd .; isocyanate content = 17.0%.

[0579]

[Table 14]

[0580]

[Table 15]

<< Footnotes to Table 2 >> Each numerical value indicating the usage ratio of raw materials is a part by weight.

“S-695” is “Watersol S”
-695 ", a trade name of an aqueous solution of methyl etherified methylol melamine resin manufactured by Dainippon Ink and Chemicals, Inc .; non-volatile content = 66%.

[0583]

[Table 16]

[0584]

[Table 17]

<< Footnotes to Table 2 >> All numerical values indicating the usage ratio of raw materials are parts by weight.

“BN-08” is “Elastron BN”
-08 ", a trade name of blocked isocyanate manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd .; non-volatile content = 34.5
%.

[0587]

[Table 18]

Example 31

In this example, various water-based resins are evaluated for storage stability.

The various aqueous resins (W-1), (W-2), (W-3) and (W-3) obtained in Examples 1 to 8 were obtained.
-4) was stored at 40 ° C. for one month, and then various white bases were prepared in the same manner as in Examples 13 to 30. Then, water was further added as necessary.
By blending the compound (C), various white paints having a PWC of 35% were prepared.

The water-based resins (W-1), (W-2), and (W-
The use ratios of 3) or (W-4), the pigment, ethylene glycol monobutyl ether and the compound (C) are as already shown in Table 2.

Next, in the same manner as in Examples 13 to 30,
Each of the white paints was applied on a test coated plate, and then cured under the curing conditions shown in the same table to obtain various cured coating films.

The aqueous curable resin composition according to the present invention containing a white base prepared from the aqueous resin after being stored at 40 ° C. for one month and obtained at 40 ° C. Each of the coating films was particularly excellent in appearance, and the performance of each coating film was hardly different from the results shown in the same table.

From these various facts, it can be seen that the aqueous resin (W-
1), (W-2), (W-3) or (W-4)
Especially, it can be easily understood that the storage stability is excellent.

[0595]

The aqueous resin according to the present invention has both excellent curability and excellent storage stability, and contains such an excellent aqueous resin as an essential component. The aqueous curable resin composition according to the present invention can form a cured coating film having excellent so-called durability, such as gloss retention during exposure, exposure stain resistance, and acid rain resistance. It is extremely practical.

Claims (19)

[Claims] 1. A polysiloxane (A) having a hydrolyzable group bonded to a silicon atom and / or a hydroxyl group bonded to a silicon atom and having a cycloalkyl group bonded to at least 10 mol% of all silicon atoms. ) And a polymer (B-1) having an acid group or a basic group and / or a condensate are partially or completely neutralized with a basic compound or an acidic compound, and then neutralized in an aqueous medium. Aqueous resin obtained by dispersing or dissolving in water. 2. A polysiloxane (A) having a hydrolyzable group bonded to a silicon atom and / or a hydroxyl group bonded to a silicon atom and having a cycloalkyl group bonded to at least 10 mol% of all silicon atoms. ), An acid group or a basic group, the acid group or the basic group, a hydrolyzable group bonded to a silicon atom, and a hydroxyl group bonded to a silicon atom.
Polymer (B-2) having a functional group other than the three types of groups.
An aqueous resin obtained by partially or completely neutralizing a mixture and / or condensate of the following with a basic compound or an acidic compound, and then dispersing or dissolving in an aqueous medium. 3. A polysiloxane (A) having a hydrolyzable group bonded to a silicon atom and / or a hydroxyl group bonded to a silicon atom and having a cycloalkyl group bonded to at least 10 mol% of all silicon atoms. ) And a polymer (B-3) having at least one kind of hydrophilic group selected from the group consisting of an anionic group, a cationic group and a nonionic group, and / or a condensate, An aqueous resin obtained by dispersing or dissolving in water. 4. A polysiloxane (A) having a hydrolyzable group bonded to a silicon atom and / or a hydroxyl group bonded to a silicon atom, and having a cycloalkyl group bonded to at least 10 mol% of all silicon atoms. ) And at least one hydrophilic group selected from the group consisting of an anionic group, a cationic group and a nonionic group, a hydrophilic group, a hydrolyzable group bonded to a silicon atom, and a silicon atom A mixture and / or a condensate consisting of a polymer (B-4) having a functional group other than the three types of groups, together with a hydroxyl group bonded to the polymer, is obtained by dispersing or dissolving the mixture in an aqueous medium. Aqueous resin. 5. The polymer (B-
1) wherein at least one of (B-2), (B-3) or (B-4) is selected from the group consisting of a vinyl polymer, a polyester polymer, an alkyd polymer and a polyurethane polymer; The aqueous resin according to any one of claims 1 to 4, which is a seed polymer. 6. The aqueous resin according to claim 1, wherein the hydrolyzable group bonded to the silicon atom is an alkoxy group. 7. The functional group other than the above three groups, which is an acid group or a basic group, a hydrolyzable group bonded to a silicon atom, and a hydroxyl group bonded to a silicon atom, is a carbon atom. A hydroxyl group, a blocked hydroxyl group, a carboxyl group, a blocked carboxyl group, a carboxylic anhydride group, a tertiary amino group, a cyclocarbonate group, an epoxy group, a primary amide group, a secondary amide group, a carbamate group and The following structural formula (S-I) The aqueous resin according to claim 2, which is at least one kind of functional group selected from the group consisting of functional groups represented by 8. At least one hydrophilic group selected from the group consisting of an anionic group, a cationic group and a nonionic group, a hydrolyzable group bonded to a silicon atom, and a bond to a silicon atom Functional groups other than the three types described above are preferably a hydroxyl group bonded to a carbon atom, a blocked hydroxyl group, a carboxyl group, a blocked carboxyl group, a carboxylic anhydride group, a tertiary amino group, and a cyclocarbonate. Group, epoxy group, primary amide group, secondary amide group, carbamate group and the following structural formula (S-I) The aqueous resin according to claim 4, which is at least one kind of functional group selected from the group consisting of functional groups represented by the following. 9. A polysiloxane (A) having a hydrolyzable group bonded to a silicon atom and / or a hydroxyl group bonded to a silicon atom, and having a cycloalkyl group bonded to at least 10 mol% of all silicon atoms. ) And a polymer (B-1) having an acid group or a basic group and / or a condensate are partially or completely neutralized with a basic compound or an acidic compound, and then neutralized in an aqueous medium. Aqueous resin (W-1) characterized by being dispersed or dissolved in water
Manufacturing method. 10. A polysiloxane (A) having a hydrolyzable group bonded to a silicon atom and / or a hydroxyl group bonded to a silicon atom, and having a cycloalkyl group bonded to at least 10 mol% of all silicon atoms. ), An acid group or a basic group, and the acid group or the basic group, a hydrolyzable group bonded to a silicon atom, and a hydroxyl group bonded to a silicon atom. A polymer having a functional group (B-
The aqueous resin (W-) characterized in that the mixture and / or the condensate of (2) is partially or completely neutralized with a basic compound or an acidic compound, and then dispersed or dissolved in an aqueous medium. 2) Manufacturing method. 11. A polysiloxane (A) having a hydrolyzable group bonded to a silicon atom and / or a hydroxyl group bonded to a silicon atom, and having a cycloalkyl group bonded to at least 10 mol% of all silicon atoms. ) And a polymer (B-3) having at least one kind of hydrophilic group selected from the group consisting of an anionic group, a cationic group and a nonionic group, and / or a condensate, A method for producing an aqueous resin (W-3), characterized by being dispersed or dissolved in water. 12. A polysiloxane (A) having a hydrolyzable group bonded to a silicon atom and / or a hydroxyl group bonded to a silicon atom and having a cycloalkyl group bonded to at least 10 mol% of all silicon atoms. ) And at least one hydrophilic group selected from the group consisting of an anionic group, a cationic group and a nonionic group, a hydrophilic group, a hydrolyzable group bonded to a silicon atom, and a silicon atom A mixture and / or a condensate consisting of a polymer (B-4) having a functional group other than the three types of groups, together with a hydroxyl group bonded to the polymer, is dispersed or dissolved in an aqueous medium. A method for producing an aqueous resin (W-4). 13. The polymer (B-
1), (B-2), (B-3) or (B-4) is selected from the group consisting of a vinyl polymer, a polyester polymer, an alkyd polymer and a polyurethane polymer;
The method according to any one of claims 9 to 12, which is at least one polymer. 14. The method according to claim 9, wherein the hydrolyzable group bonded to the silicon atom is an alkoxy group. 15. The functional group other than the three types of the above-mentioned acid group or basic group, the hydrolyzable group bonded to a silicon atom, and the hydroxyl group bonded to a silicon atom is preferably a carbon atom. A hydroxyl group, a blocked hydroxyl group, a carboxyl group, a blocked carboxyl group, a carboxylic anhydride group, a tertiary amino group, a cyclocarbonate group, an epoxy group, a primary amide group, a secondary amide group, a carbamate group and The following structural formula (S-I) The production method according to claim 10, wherein the production method is at least one kind of functional group selected from the group consisting of functional groups represented by 16. At least one hydrophilic group selected from the group consisting of an anionic group, a cationic group and a nonionic group, a hydrolyzable group bonded to a silicon atom, and a bond to a silicon atom Functional groups other than the three types described above are preferably a hydroxyl group bonded to a carbon atom, a blocked hydroxyl group, a carboxyl group, a blocked carboxyl group, a carboxylic anhydride group, a tertiary amino group, and a cyclocarbonate. Group, epoxy group, primary amide group, secondary amide group, carbamate group, and the following structural formula (S-I) 13. The production method according to claim 12, which is at least one kind of functional group selected from the group consisting of functional groups represented by 17. A curable resin composition comprising the aqueous resin according to claim 1 as an essential component. 18. An aqueous curable resin composition containing the aqueous resin according to claim 1 and a compound (C) having a functional group which reacts with the aqueous resin as an essential component. . 19. The compound having a functional group that reacts with a functional group contained in an aqueous resin, wherein the compound (C) has a hydroxyl group bonded to a silicon atom and / or a hydrolyzable group bonded to a silicon atom. Compound having both isocyanate group and hydrolyzable group bonded to silicon atom in one molecule, compound having both epoxy group and hydrolyzable group bonded to silicon atom in one molecule, polyisocyanate compound, block poly Isocyanate compound, polyepoxy compound, polycyclocarbonate compound, amino resin,
The aqueous curable resin composition according to claim 18, which is at least one compound selected from the group consisting of a primary or secondary amide group-containing compound, a polycarboxy compound, and a polyhydroxy compound.