JPH11209694A - Electrodeposition paints and painted objects - Google Patents

Abstract

(57) [Problem] An object of the present invention is to provide an electrodeposition paint and a coated product which form a cured coating film having excellent durability such as gloss retention, exposure contamination resistance and acid rain resistance. SOLUTION: An electrodeposition paint containing as an essential component an aqueous resin containing an anionic group or a cationic group comprising a polysiloxane and a polymer other than the polysiloxane,
Alternatively, an electrodeposition paint containing the aqueous resin and a compound having a functional group that reacts with a functional group contained in the aqueous resin as essential components.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

TECHNICAL FIELD The present invention relates to a new and useful electrodeposition paint. More specifically, the present invention relates to an aqueous resin (W) containing an anionic group or a cationic group, which comprises a polysiloxane (A) and a polymer (B) other than the polysiloxane, and is made aqueous. The present invention relates to an electrodeposition paint as an essential component, or an electrodeposition paint containing an aqueous resin and a compound having a functional group that reacts with a functional group contained in the aqueous resin, as an essential component, and has a gloss retention property. The present invention relates to an electrodeposition coating material that provides a cured coating film having excellent solvability, such as resistance to exposure contamination and acid rain, as well as solvent resistance, chemical resistance, and water resistance.

[0002]

2. Description of the Related Art As an electrodeposition paint, various resins such as acrylic resin, modified epoxy or modified polybutadiene, which contain an aqueous resin containing an anionic group or a cationic group as a base resin component, Have been used. Electrodeposition paints containing an acrylic resin as a base resin component and containing an amino resin or a blocked polyisocyanate as a curing agent have been widely used for outdoor use such as for building materials.

[0003] However, cured coating films obtained from such electrodeposition coatings have insufficient durability such as gloss retention upon exposure, resistance to exposure contamination and resistance to acid rain. There is a problem that it cannot be used for the required applications.

However, various studies have been made to solve such problems. For example, a composition for an electrodeposition coating composition using a fluorine-based resin as a base resin component (Japanese Patent Application Laid-Open No.
No. 59676, JP-A-3-39369) or a composition for an electrodeposition coating composition using a fluororesin as a base resin component and blending an organoalkoxysilane as a curing agent (JP-A-1-75575). ) Have been proposed, but the effect of improving various performances is still insufficient, and further improvement in performance is desired.

[0005]

However, the present inventors have started intensive studies in order to completely solve the various problems in the conventional technology as described above.

[0006] Therefore, the problem to be solved by the present invention is not only excellent in durability such as gloss retention, exposure contamination resistance and acid rain resistance, but also in addition to the above-mentioned durability, solvent resistance. An object of the present invention is to provide an electrodeposition paint having extremely high practicality that gives a cured coating film having excellent properties such as water resistance, chemical resistance and water resistance.

[0007]

Means for Solving the Problems Accordingly, the present inventors have:
Focusing on the problem to be solved by the invention as described above, as a result of intensive research, it has been found that a polysiloxane and a polymer other than the polysiloxane are used, and that the anionic group or the cationic Electrodeposition paint containing an aqueous resin containing a group as an essential component,

Alternatively, an aqueous resin comprising a polysiloxane and a polymer other than the polysiloxane and containing an anionic group or a cationic group, and a functional group which reacts with a functional group contained in the aqueous resin are used. The electrodeposition coating containing a compound having an essential component, among others, has been found to provide a cured coating film having excellent durability, such as gloss retention, acid rain resistance, and exposure stain resistance. The present invention has now been completed with the assurance that the problem to be solved can be solved brilliantly.

That is, the present inventors will provide an electrodeposition coating material comprising a polysiloxane and a polymer other than the polysiloxane, and containing an aqueous resin containing an anionic group or a cationic group as an essential component. And

An aqueous resin comprising a polysiloxane and a polymer other than the polysiloxane and containing an anionic group or a cationic group, and a functional group which reacts with a functional group contained in the aqueous resin. It is an object of the present invention to provide an electrodeposition paint containing a compound having the same as an essential component.

[0011]

DETAILED DESCRIPTION OF THE INVENTION The present invention relates, in part, to an aqueous resin comprising an anionic group or a cationic group, which comprises a polysiloxane and a polymer other than the polysiloxane, and which is made aqueous. It is intended to provide an electrodeposition paint containing as a component,

The second is an aqueous resin comprising a polysiloxane and a polymer other than the polysiloxane and containing an anionic group or a cationic group, and
It is intended to provide an electrodeposition coating containing a compound having a functional group that reacts with a functional group contained in the aqueous resin as an essential component,

[0013] Thirdly, the above-mentioned aqueous resin is a polysiloxane segment having a hydrolyzable group bonded to a silicon atom and / or a hydroxyl group bonded to a silicon atom (A-
An aqueous solution obtained by dispersing or dissolving 1) and a composite resin (C-1) composed of a polymer segment (B-1) having a hydrophilic group as an anionic group or a cationic group in an aqueous medium. It is intended to provide an electrodeposition paint such as resin (W-1),

Fourth, the aqueous resin is a polysiloxane segment having a hydrolyzable group bonded to a silicon atom and / or a hydroxyl group bonded to a silicon atom (A-
In addition to 1) and a hydrophilic group such as an anionic group or a cationic group, the hydrophilic group, a hydrolyzable group bonded to a silicon atom, and a hydroxyl group bonded to a silicon atom,
Aqueous resin (W-2) obtained by dispersing or dissolving a composite resin (C-2) composed of a polymer segment (B-2) having a functional group other than a type group in an aqueous medium It is intended to provide an electrodeposition paint that is

Fifth, the aqueous resin has a silicon atom having an aryl group or a cycloalkyl group and a hydrolyzable group bonded together and / or a silicon atom having an aryl group or a cycloalkyl group and a hydroxyl group bonded together. A composite resin (C-3) composed of a polysiloxane segment (A-2) and a polymer segment (B-1) having a hydrophilic group that is an anionic group or a cationic group;
A polysiloxane (p) having a hydrolyzable group bonded to a silicon atom and / or a hydroxyl group bonded to a silicon atom,
After mixing and, if necessary, condensing,
It is intended to provide an electrodeposition paint such as an aqueous resin (W-3) obtained by dispersing or dissolving in an aqueous medium,

Sixth, the aqueous resin is a polysiloxane segment (A-2) having a silicon atom having an aryl group and a hydrolyzable group bonded together and / or a silicon atom having an aryl group and a hydroxyl group bonded together. And a hydrophilic group such as an anionic group or a cationic group, a hydrophilic group, a hydrolyzable group bonded to a silicon atom, and a hydroxyl group bonded to a silicon atom. A composite resin (C-4) composed of a polymer segment (B-2) also having the following functional group; and a polysiloxane having a hydrolyzable group bonded to a silicon atom and / or a hydroxyl group bonded to a silicon atom. (P) is mixed, and if necessary, condensed, and then dispersed or dissolved in an aqueous medium to provide an electrodeposition coating material which is an aqueous resin (W-4). It is an.

In the present invention, the polysiloxane segment (A-1) preferably has the following structural formula (SI):

[0018]

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 is intended to provide an electrodeposition coating material which is a polysiloxane segment having a structure represented by a monovalent organic group as an essential unit structure.

The above-mentioned polysiloxane (p) has the following structural formula (SI)

[0020]

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 is intended to provide an electrodeposition coating material which is a polysiloxane having a structure represented by a monovalent organic group as an essential unit structure.

An object of the present invention is to provide an electrodeposition coating material in which the polymer segment (B-1) or (B-2) is a segment derived from a vinyl polymer and / or a polyurethane polymer. There is

The above-mentioned functional groups other than the three types of the hydrophilic group, which is an anionic group or a cationic group, a hydrolyzable group bonded to a silicon atom, and a hydroxyl group bonded to a silicon atom, are present. A hydroxyl group bonded to a carbon atom, a blocked hydroxyl group, an epoxy group, a cyclocarbonate group,
Secondary amide group, secondary amide, carbamate group and the following structural formula (S-II)

[0023]

Embedded image And at least one kind of functional group selected from the group consisting of functional groups represented by

The compound (D) having a functional group which reacts with a functional group contained in the aqueous resin is a compound having a hydroxyl group bonded to a silicon atom and / or a hydrolyzable group bonded to a silicon atom, one molecule At least one selected from the group consisting of a compound having both a blocked isocyanate group and a hydrolyzable group bonded to a silicon atom, a blocked polyisocyanate compound, an amino resin, a primary or secondary amide group-containing compound and a polyhydroxy compound. 1
To provide an electrodeposition paint that is a kind of compound,

The above-mentioned composite resin (C-1) is a polymer having both a hydrolyzable group bonded to a silicon atom and / or a hydroxyl group bonded to a silicon atom and a polar group such as an acid group or a basic group. A composite resin (c-1) obtained by subjecting (b-1) to a condensation reaction with a polysiloxane (a-1) having a hydrolyzable group bonded to a silicon atom and / or a hydroxyl group bonded to a silicon atom, The purpose of the present invention is to provide an electrodeposition paint that is obtained by partially or completely neutralizing with a basic compound or an acidic compound,

The above-mentioned composite resin (C-2) comprises, in addition to a hydrolyzable group bonded to a silicon atom and / or a hydroxyl group bonded to a silicon atom, and a polar group such as an acid group or a basic group, A polymer (b-2) having both a hydrolyzable group bonded to an atom, a hydroxyl group bonded to a silicon atom and a polar group, which is conveniently a functional group other than the three groups, and a hydrolysis bonded to a silicon atom A composite resin (c-2) obtained by subjecting a polysiloxane (a-1) having a functional group and / or a hydroxyl group bonded to a silicon atom to a condensation reaction is partially neutralized or neutralized with a basic compound or an acidic compound. It is intended to provide an electrodeposition paint that can be obtained by completely neutralizing,

The above-mentioned hydrolyzable group bonded to a silicon atom, a hydroxyl group bonded to a silicon atom and a polar group,
A functional group other than a group of types, a hydroxyl group bonded to a carbon atom,
A blocked hydroxyl group, epoxy group, cyclocarbonate group, primary amide group, secondary amide, carbamate group and the following structural formula (S-II)

[0028]

Embedded image And at least one kind of functional group selected from the group consisting of functional groups represented by

The polysiloxane segment (A-
(1) to provide an electrodeposition coating material in which the polysiloxane segment has an aryl group and / or a cycloalkyl group bonded to 10 mol% or more of all silicon atoms.

Further, the present invention aims to provide an electrodeposition coating material in which the hydrolyzable group bonded to the silicon atom is an alkoxy group.

The present invention also provides a coated article covered with the electrodeposition paint.

<< Structure >> The present invention is further described below.
It will be described in detail. The base resin component constituting the electrodeposition coating composition of the present invention, comprising a polysiloxane (A) and a polymer other than the polysiloxane (B), and containing an anionic group or a cationic group obtained by making this an aqueous solution. The aqueous resin (W) to be used is a mixture of a polysiloxane and a polymer other than the polysiloxane, a condensate of the polysiloxane and a polymer other than the polysiloxane, or a polymer other than the polysiloxane and the polysiloxane. And a condensate of the above, and a polysiloxane moiety and / or a polymer moiety other than polysiloxane, into which an anionic group or a cationic group is introduced, is dissolved in an aqueous medium. Alternatively, a dispersed form is referred to.

From the viewpoint of durability, it is preferable that the polysiloxane and the polymer other than the polysiloxane are at least partially condensed.

It is particularly preferable that the above-mentioned anionic group or cationic group is introduced into a polymer portion other than polysiloxane, from the viewpoint of easy introduction.

More specific examples of the preferred aqueous resin (W) as described above include a polysiloxane segment (A-1) having a hydrolyzable group bonded to a silicon atom and / or a hydroxyl group bonded to a silicon atom. A composite resin (C-1) composed of a polymer segment (B-1) having a hydrophilic group such as an anionic group or a cationic group,
Aqueous resin (W-1) obtained by dispersing or dissolving in an aqueous medium,

The polysiloxane segment (A-
In addition to 1) and a hydrophilic group such as an anionic group or a cationic group, the hydrophilic group, a hydrolyzable group bonded to a silicon atom, and a hydroxyl group bonded to a silicon atom,
A composite resin (C-2) composed of a polymer segment (B-2) also having a functional group (hereinafter, also referred to as a functional group (Fu-1)) other than the kinds of groups is dispersed in an aqueous medium. Or an aqueous resin obtained by dissolving (W-2),

A polysiloxane segment having a silicon atom having an aryl group or a cycloalkyl group and a hydrolyzable group bonded together and / or a silicon atom having an aryl group or a cycloalkyl group and a hydroxyl group bonded together (A-
2) and a composite resin (C-3) composed of a polymer segment (B-1) having a hydrophilic group that is an anionic group or a cationic group, and a hydrolyzable group bonded to a silicon atom and / or An aqueous resin (W-3) obtained by mixing and, if necessary, condensing a polysiloxane (p) having a hydroxyl group bonded to a silicon atom, and then dispersing or dissolving in an aqueous medium;

Further, in addition to the aforementioned polysiloxane segment (A-2) and a hydrophilic group such as an anionic group or a cationic group, the functional group (Fu-1)
The composite resin (C-4) composed of the polymer segment (B-2) also having the above and the above-mentioned polysiloxane (p) are mixed, and if necessary, condensed, and then mixed with an aqueous medium. Aqueous resin (W-4) obtained by dispersing or dissolving in it is exemplified.

The aqueous resins (W-1), (W-2),
In the composite resin (C-1), (C-2), (C-3) or (C-4), which is a precursor of (W-3) or (W-4), respectively, a polysiloxane is used. Bonding mode between segment (A-1) and polymer segment (B-1), bonding mode between polysiloxane segment (A-1) and polymer segment (B-2), polysiloxane segment (A-2) Of the polymer segment (B-1) or the polysiloxane segment (A
-2) and the polymer segment (B-2) may be bonded to each other by the following structural formula (S-III) or the following structural formula (S-IV). From the viewpoint of achieving the above, it is particularly preferable to employ the bonding mode of the structural formula (S-III).

[0040]

Embedded image (However, in the formula, the carbon atom is a polymer segment (B-
The silicon atom constituting a part of 1) or (B-2) and bonded only to an oxygen atom is a polysiloxane segment (A
-1) or a part of (A-2). )

[0041]

Embedded image (However, in the formula, the carbon atom is a polymer segment (B-
1) or a part of (B-2), while the silicon atom is a polysiloxane segment (A-1) or (A-2).
-2). )

The polysiloxane segment (A) constituting the composite resin (C-1) or (C-2) which is a precursor of the aqueous resin (W-1) or (W-2)
-1) or the aqueous resin (W-3) or (W-
Polysiloxane (p) used in preparing 4)
Has the following structural formula (S-I)

[0043]

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. Having a structure represented by the following formula:
That is, having a branched structure, from the viewpoint of the durability of the cured coating film obtained from the electrodeposition paint of the present invention,
Particularly preferred.

The polysiloxane segment (A-
As 1), 10 mol% or more, preferably 20 mol% or more, more preferably 40 mol% or more of all silicon atoms constituting the polysiloxane segment have an aryl group and / or a cycloalkyl group. It is suitable that the groups are bonded from the viewpoint of the stability of the obtained aqueous resin and, consequently, the electrodeposition coating composition of the present invention.

The aqueous resin (W-3) or (W-
The composite resin (C-3) or (C-
Polysiloxane segment (A-2) constituting 4)
Is a group having a silicon atom in which an aryl group or a cycloalkyl group and a hydrolyzable group are bonded together and / or a silicon atom in which an aryl group or a cycloalkyl group is bonded to a hydroxyl group, and is linear, branched or cyclic. It may have any structure.

The polysiloxane segment (A-
The aryl group bonded to the silicon atom contained in 1) or (A-2) refers to an aromatic residue such as a phenyl group, a p-tolyl group, or a naphthyl group.
From the viewpoint of practicality, a phenyl group is particularly preferable.

The composite resins (C-1), (C-2), (C-
3) or the other component of (C-4),
As the polymer segment (B-1) or (B-2), an acrylic polymer, a fluoroolefin polymer,
There are polymers derived from various vinyl polymers such as vinyl ester polymers, aromatic vinyl polymers or polyolefin polymers, and furthermore, polyester polymers, alkyd polymers or polyurethane polymers. Some are derived from polymers other than vinyl polymers such as coalescing.

Among these, particularly preferred are a vinyl polymer segment and a polyurethane polymer segment, and particularly preferred among the vinyl polymer segments are an acrylic polymer segment and a fluoropolymer segment. An olefin-based polymer segment is exemplified.

The aqueous resin (W-1) or (W-
Polysiloxane segment (A-1) in 2)
And the polymer segment (B-1) or (B-2) in a weight ratio of (A-1) :( B-1) or (B-2) of 5:95 to 95: 5. It is good to set so as to be about 10:90 to 90:10, more preferably 10:90 to 80:20.

A polymer prepared when preparing the aqueous resin (W-3) or (W-4), which constitutes the composite resin (C-3) or (C-4) which is a precursor thereof. As the weight ratio of the segment (B-1) or (B-2) and the polysiloxane segment (A-2), the weight ratio of (B-1) or (B-2) :( A-2) is used. , 5:
Preferably, it is 10:99 so as to be about 95 to 99: 1.
90 to 95: 5, more preferably 2
What is necessary is just to set so that it may become 0: 80-90: 10.

Further, the aqueous resin (W-3) or (W-
In 4), the total amount of the polysiloxane derived from the polysiloxane (p) and the polysiloxane segment (A-2), and the polymer segment (B-1) or (B-2)
So that the weight ratio of [(A-2) + (p) -derived polysiloxane] :( B-1) or (B-2) 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), if the weight ratio of the polymer segment (B-1) or (B-2) is set to be less than about 5%, the polymer is inevitable. Since the amount of the siloxane component is too large, the alkali resistance and flexibility of the cured coating film obtained from the electrodeposition coating composition of the present invention may decrease, while the polymer segment (B-
When the weight ratio of 1) or (B-2) is too large exceeding about 95%, the cured coating film is inevitably exposed to stain and has a high glossiness because the polysiloxane component is too small. Either case is not preferred, because the durability of the film, such as resistance or acid rain resistance, is lowered.

Further, in the aqueous resin (W-3) or (W-4), the polysiloxane derived from the polysiloxane (p) and the polysiloxane segment (A-2)
The proportion occupied by the polysiloxane segment (A-2) in the total polysiloxane component is 5 to 90 mol%, preferably 10 to 80 mol%, as mol% of silicon atoms constituting the total polysiloxane. Mol%, more preferably 15 to 75 mol%, is preferably an aqueous resin (W
This is preferred from the viewpoint of the balance of (-3) or (W-4) and the curability.

The polysiloxane segment (A-
1) or (A-2), or the polysiloxane (a-1), (a-2) or (p),
-1) or (b-2), and a hydrolyzable group bonded to a silicon atom contained in the polymer (b-3) or (b-4) described below easily hydrolyzes. A hydroxyl group which has been received and eliminated and bonded to a silicon atom, that is, a silanol group, is referred to as a group which is represented by an alkoxy group, a substituted alkoxy group, an acyloxy group,
Examples include a halogen atom, 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.

The polymer segment (B-1) or (B-
As the anionic group contained in 2), various well-known and commonly used anionic groups are introduced. Particularly preferred are:
Various acid groups neutralized with a basic compound are exemplified.

Representative examples of such an acid group include a carboxyl group, a phosphoric acid group, an acidic phosphate group, a phosphite group, a sulfonic acid group and a sulfinic acid group. Particularly preferred.

Representative examples of the basic compound used for neutralizing an acid group to convert it into an anionic group as described above include methylamine, dimethylamine, trimethylamine, ethylamine, diethylamine, triethylamine. 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.

Of these basic compounds, various organic amines and ammonia are particularly preferred.

The polymer (B-1) or (B-2)
As the cationic group contained therein, various kinds of known and commonly used cationic groups are introduced, and particularly preferred examples include a basic group neutralized with an acidic compound.

Representative examples of such basic groups include primary amino groups, secondary amino groups, tertiary amino groups, and quaternary ammonium hydroxide groups.

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 and phosphoric acid.

Of the various acidic compounds described above, carboxylic acids are particularly preferred.

The polymer segment (B-1) or (B-
The amount of the anionic group or the cationic group introduced in 2) is about 0.1 mol to about 0.1 mol as the number of moles of the anionic group or the cationic group per 1,000 g of the polymer segment. Set to be within the range of 10 mol, preferably within the range of 0.2 to 5 mol, most preferably within the range of 0.3 to 3 mol,

Moreover, the aqueous resins (W-1) to (W-4)
The amount of the anionic group or cationic group introduced per 1,000 g of the solid content is in the range of about 0.08 mol to about 5 mol, preferably in the range of 0.15 to 3 mol. Most preferably, 0.2 to 2
It is appropriate to set so as to be within the range of mole.

The polymer segment (B-1) or (B-
The amount of the anionic group or cationic group introduced per 1,000 g of 2) is less than 0.1 mol or the solid content of the aqueous resins (W-1) to (W-4). When the introduction amount of the anionic group or the cationic group per 1,000 g is less than 0.08 mol,
The stability of the electrodeposition coating composition of the present invention is reduced, and conversely, the introduction of an anionic group or a cationic group introduced per 1,000 g of the polymer segment (B-1) or (B-2). When the amount exceeds 10 mol or the aqueous resin (W-1)
When the introduction amount of the anionic group or the cationic group per 1,000 g of the solid content of (W-4) exceeds 5 mol, the water resistance of the cured coating film obtained from the electrodeposition coating composition of the present invention is improved. It is not preferable because chemical resistance is reduced.

A functional group other than the three groups, which is a hydrophilic group, a hydrolyzable group bonded to a silicon atom, and a hydroxyl group bonded to a silicon atom, is introduced into the polymer segment (B-2). Only typical examples of (Fu-1) are exemplified, and a hydroxyl group bonded to a carbon atom and a hydroxyl group bonded to a carbon atom and blocked (hereinafter, referred to as “Fu-1”).
A blocked hydroxyl group), a carboxyl group, a blocked carboxyl group (hereinafter also referred to as a blocked carboxyl group), a carboxylic anhydride group, a primary amino group, a secondary amino group, a tertiary amino group, a cyclocarbonate group, an epoxy group An oxazoline group, a primary amide group, a secondary amide group,
A carbamate group and the following structural formula (S-II)

[0070]

Embedded image

And the like.

The secondary amide group may be an N-hydroxymethylamide group, an N-alkoxymethylamide group having an alkoxy group having 1 to 8 carbon atoms, or the following structural formula (SV)

[0073]

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.)

And the functional group represented by the formula:

Among these functional groups, particularly preferred are a hydroxyl group bonded to a carbon atom, a blocked hydroxyl group, an epoxy group, a cyclocarbonate group, a primary amide group, a secondary amide, a carbamate group, and the above-mentioned groups. And a functional group represented by the structural formula (S-II).

Further, these functional groups may contain only one kind in the polymer segment (B-2).
More than one species may be included.

The amount of the functional group (Fu-1) to be introduced into the polymer segment (B-2) is in the range of about 0.1 to about 5 mol per 1,000 g of the solid content of the polymer. Is appropriate, preferably in the range of 0.2 to 3 mol, and more preferably, in the range of 0.3 to 2 mol.

Next, a method for preparing the aqueous resin (W-1) or (W-2) will be described.

First, the aqueous resin (W-1) or (W-
2) Among them, the composite resin (C-1) which is a precursor thereof
Alternatively, as (C-2), the polysiloxane segment (A-1) and the polymer segment (B-1) or (B-2), which are particularly preferable as described above, are represented by the structural formula (S-III) described above. The preparation method in the case of using a compound conjugated through the bond shown in ()) will be described.

The composite resin (C-1) or (C-
As a method for preparing 2), for example, (a) a polar group such as a free acid group or a free basic group, and a hydrolyzable group bonded to a silicon atom and / or a hydroxyl group bonded to a silicon atom are used. Having a polar group, a hydrolyzable group bonded to a silicon atom and / or a hydroxyl group bonded to a silicon atom, and a hydrolyzable group bonded to the polar group and a silicon atom and a hydroxyl group bonded to a silicon atom Functional groups other than the three types of groups [hereinafter, also referred to as functional groups (Fu-2)]
And a polysiloxane (a-
1), and the polysiloxane (a-1) and a hydrolyzable group bonded to a silicon atom and / or a hydroxyl group bonded to a silicon atom contained in each of the above polymers are reacted with each other to form a structural formula ( A method of neutralizing the contained free acid group or free basic group with a basic compound or an acidic compound after forming a complex through the bond shown in S-III),

(B) A polymer having both a hydrophilic group, which is a neutralized acid group or a neutralized basic group, and a hydrolyzable group bonded to a silicon atom and / or a hydroxyl group bonded to a silicon atom. Or a polymer containing the above-mentioned functional group (Fu-1) in addition to the hydrophilic group and a hydrolyzable group bonded to a silicon atom and / or a hydroxyl group bonded to a silicon atom; a-1) to react with each other to form a polysiloxane (a-1) and a hydrolyzable group bonded to a silicon atom and / or a hydroxyl group bonded to a silicon atom contained in each of the above-described polymers. A method of forming a complex through a bond represented by the formula (S-III):

(C) A compound having a radically polymerizable double bond, wherein the double bond and the polysiloxane are bonded in a bonding mode represented by the following structural formula (S-VI): Used as one of the polymerization components, and a vinyl monomer having a polar group such as a vinyl monomer having a free acid group or a vinyl monomer having a free basic group. By copolymerizing a vinyl monomer contained as an essential component, or in addition to the polysiloxane containing a double bond and a vinyl monomer having a polar group, the above-described functional group (Fu -2) is copolymerized with a vinyl monomer containing an essential component thereof to form a complex, and then a free acid group or a free basic group contained is converted to a base. Neutralize with acidic or acidic compounds Method,

[0084]

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 Constitutes a part of polysiloxane)

(D) Polysiloxane containing a double bond as described above and a hydrophilic monomer containing a neutralized acid-containing vinyl monomer or a neutralized basic group-containing vinyl monomer By copolymerizing a vinyl monomer containing a hydrophilic group-containing vinyl monomer as an essential component, or having a polysiloxane containing the double bond and a hydrophilic group described above. A method of forming a complex by copolymerizing a vinyl-based monomer containing, as an essential component, the monomer containing the functional group (Fu-1) in addition to the vinyl-based monomer, Etc.

In the above method (a) or (b), 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)

[0088]

Embedded image

(Wherein R ⁴ is an alkyl, cycloalkyl, aryl or aralkyl group).
R ⁵ represents 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. Represents a hydrolyzable group such as a group, and a is an integer of 0, 1 or 2. )

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

Such a hydrolyzable silyl group can be 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.

Among the various methods (a) to (d) described above, the method (a) is particularly preferred from the viewpoint of simplicity of preparation, and the aqueous resin (W-1) or ( The method for preparing W-2) will be described in detail.

Among the aqueous resins (W-1) and (W-2), those having an anionic group as a hydrophilic group include
As a more specific method in the case of using the composite resin (C-1) or (C-2) prepared by the method (A) as a precursor, a typical one is (1) hydrolyzing method. Polymer having both decomposable silyl group and acid group (b-
1) or a polymer (b-2) containing a hydrolyzable silyl group, an acid group and the above functional group (Fu-2), and a hydrolyzable group bonded to a silicon atom and / or bonded to a silicon atom Composite resin (c-1) or (c-) obtained by subjecting polysiloxane (a-1) having a hydroxyl group to a condensation reaction.
2) partially neutralizing or completely neutralizing with a basic compound, and then dispersing or dissolving in an aqueous medium,

(2) In the presence of the polymer (b-1) or (b-2), the polysiloxane (a-
In the process of preparing 1), the polymer (b-1) or (b-
The composite resin (c-3) or (c-4) obtained by complexing 2) with polysiloxane (a-1) is partially or completely neutralized with a basic compound, and then aqueous A method of dispersing or dissolving in a medium,

(3) The above-mentioned polysiloxane (a-1)
In the process of carrying out the reaction for preparing the polymer (b-1) or the polymer (b-2) in the presence of the polysiloxane (a-1) and the polymer (b-1) or (b- Composite resin (c-5) or (c) obtained by compounding 2)
-6) is partially or completely neutralized with a basic compound, and then dispersed or dissolved in an aqueous medium.

(4) In the process of performing the above-mentioned reaction for preparing the polymer (b-1) or (b-2) and the above-mentioned reaction for preparing the polysiloxane (a-1) in parallel, (B-1) or (b-2) and a polysiloxane (a-
A method in which the composite resin (c-7) or (c-8) obtained by complexing 1) is partially or completely neutralized with a basic compound, and then dispersed or dissolved in an aqueous medium; And various other methods.

The polymer (b-1) or (b-
Specific examples of the acid group introduced in 2) include the various free acid groups described above, and among these, a carboxyl group is particularly preferred.

Examples of the carboxyl group include, in addition to a free acid group, an acid anhydride group represented by a carboxylic acid anhydride group, a phosphoric acid anhydride group, a sulfonic acid anhydride group or a carboxylic acid-sulfonic acid mixed acid anhydride group. Further, for example, a so-called blocked carboxyl group may be used as an ester group which is easily converted to a free acid group, such as a silyl ester group, a tert-butyl ester group or a 1-alkoxyethyl ester group. Can also be introduced.

Introduced into the above-mentioned polymer (b-2)
Representative functional groups (Fu-2) include 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 cyclocarbonate group, an epoxy group, An oxazoline group, a primary amide group, a secondary amide group, a carbamate group and the following structural formula (S-II)

[0100]

Embedded image

And the like.

The secondary amide group may be an N-hydroxymethylamide group, an N-alkoxymethylamide group having an alkoxy group having 1 to 8 carbon atoms, or the following structural formula (SV)

[0103]

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.)

And the functional group represented by the formula:

Of these functional groups (Fu-2), particularly preferred are a hydroxyl group bonded to a carbon atom,
Examples include a blocked hydroxyl group, an epoxy group, a cyclocarbonate group, a primary amide group, a secondary amide, a carbamate group, and a functional group represented by the aforementioned structural formula (S-II).

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.

In the above-mentioned step of compounding the polymer (b-1) or (b-2) with the polysiloxane (a-1), an organic solvent having an alcoholic hydroxyl group is contained as an essential component. It is preferable to carry out in a medium.

The above (b-1) or (b-2)
When the complexing step of (a-1) and (a-1) is performed in a medium that does not contain an alcoholic hydroxyl group-containing organic solvent, the resulting composite resin solution inevitably thickens,
Gelation or the like in the subsequent neutralization step with a basic compound is likely to occur, and it is necessary to pay sufficient attention.

In particular, when the complexation is carried out in a medium containing no alcoholic hydroxyl group-containing organic solvent, the polymer (b
If it is attempted to introduce a hydrolyzable silyl group into the -1) or (b-2) in an amount of 0.05 mol or more per 1,000 g of the polymer, such a complex is formed. Gelation may occur during the process.

On the other hand, in a medium containing an alcoholic hydroxyl group-containing organic solvent as an essential component, (b-1)
Alternatively, when performing the complexing step of (b-2) and (a-1), the gelation in the complexing process or the neutralization process with a basic compound does not occur. The aqueous resin to be prepared can be prepared safely and easily.

As the alcoholic hydroxyl group-containing organic solvent, only typical ones are exemplified, and various water-soluble organic solvents such as methanol, ethanol, normal (n-) propanol and iso (i-) propanol may be used. 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 above-mentioned various composite resins (c-1)
Among the preparation methods of (c-8) to (c-8), (c-
The preparation method of 1) and (c-2) will be described in detail.

First, the composite resin (c-1) or (c-
When preparing 2), the polymer (b-1) or (b-2) as described above is prepared. As a typical example of such various polymers, a polymer segment (B- 1)
Alternatively, various kinds of compounds similar to those described above for (B-2) may be mentioned, and among them, particularly preferable ones are vinyl-based polymers or polyurethane-based polymers. Of these, acrylic polymers and fluoroolefin polymers are particularly desirable.

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

Among the vinyl polymers, (c-1)
In order to prepare the polymer (b-1) which is a precursor of, for example, (i) a vinyl monomer (m-1) having a hydrolyzable silyl group and a hydrophilic monomer (m-1) for imparting hydrophilicity A vinyl-based monomer having an acid group (m-2) may be copolymerized with the monomer, or both types (two types) may be copolymerized with other monomers capable of copolymerizing with these monomers. 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 kinds of isocyanate groups 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, to prepare (b-2) which is a precursor of (c-2) among the various vinyl polymers, for example, (v) the functional group ( Fu-
2) having a vinyl monomer (m-4), a vinyl monomer having a hydrolyzable silyl group (m-1), and a vinyl monomer having an acid group (m-2). Or (m-1), (m-2) and (m-4), and other monomers (m-3) copolymerizable with these monomers;
It is a method of copolymerizing

(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) A vinyl polymer having three kinds of functional groups, which are prepared in advance, having an acid group, a functional group (Fu-2), and a hydroxyl group bonded to a carbon atom, is added with 3-
Such as isocyanatopropyltriethoxysilane,
Various methods known in the art can be applied, such as a method of reacting various isocyanate group-containing silane compounds, but from the viewpoint of simplicity, among them,
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, a vinyl triethoxy silane, a vinyl tri-n-butoxy silane, and a vinyl trimethoxy silane. Methyldimethoxysilane, vinyltris (2-methoxyethoxy) silane, 2-trimethoxysilylethyl vinyl ether,
-Triethoxysilylethyl vinyl ether, 3-trimethoxysilylpropyl vinyl ether or 3-triethoxysilylpropyl vinyl ether,

3- (meth) acryloyloxypropyltrimethoxysilane, 3- (meth) acryloyloxypropyltriethoxysilane, 3- (meth) acryloyloxypropylmethyldimethoxysilane or 3- (meth) acryloyloxypropylmethyldimethoxysilane
(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 below. 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 the functional group (Fu-2), a hydroxyl group bonded to a carbon atom, a block hydroxyl group, an epoxy group, a cyclocarbonate group, and a primary amide. And various functional groups such as a group, a secondary amide, a carbamate group, and a functional group represented by the structural formula (S-II).

When the functional group (Fu-2) 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. And adducts with various lactones.

Among the vinyl monomers (m-4), only those which are particularly representative as the vinyl monomers having a blocked hydroxyl group are exemplified, and 2-trimethylsiloxyethyl (meth) acrylate, JP-A-62-2831, such as 4-trimethylsiloxybutyl (meth) acrylate, 2-trimethylsiloxyethyl vinyl ether or 4-trimethylsiloxybutyl vinyl ether
Various silyl ether group-containing vinyl monomers as disclosed in JP-A-63-63;

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.

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

Containing a 5-membered cyclocarbonate group such as 2,3-carbonatepropyl (meth) acrylate, 2-methyl-2,3-carbonatepropyl (meth) acrylate or 3,4-carbonatebutyl (meth) acrylate Vinyl monomers; and [5-
N- (meth) acryloylcarbamoyloxy] methyl-5-ethyl-1,3-dioxan-2-one or 5- [N- {2- (meth) acryloyloxy} ethylcarbamoyloxy] methyl-5-ethyl-1 And 3-membered cyclocarbonate group-containing vinyl monomers such as dioxan-2-one.

Among the vinyl monomers (m-4), glycidyl (meth) acrylate, glycidyl (meth) acrylate, and the like are only examples of particularly typical epoxy group-containing vinyl monomers (m-4). Methyl glycidyl (meth) acrylate,
Various compounds such as 3,4-epoxycyclohexylmethyl (meth) acrylate, 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 include (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 those particularly representative as the carbamate group-containing vinyl monomers will be exemplified.

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.

Among the vinyl monomers (m-4), only typical examples of the vinyl monomer having a functional group represented by the structural formula (S-II) described above 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-
Various compounds such as addition products with various amide compounds such as butyrolactam.

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, and 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 or cyclohexyl 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 various monomers as 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 compounds can be used. Of course, only typical ones are 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,
Various peroxides such as benzoyl peroxide, di-tert-butyl peroxide, cumene hydroperoxide 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.
Needless to say, the polysiloxane (a-1) may be used alone or in combination of two or more.
In order to allow the complexing reaction to proceed smoothly, it is desirable to contain an organic solvent having various alcoholic hydroxyl groups as an essential component as described above.

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 various ethers such as dimethoxyethane, tetrahydrofuran or di-n-butyl ether; For example, pyrrolidone, dimethylformamide, dimethylacetamide or ethylene carbonate.

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 well-known and commonly used solution radical polymerization method using the monomers, polymerization initiators and organic solvents, respectively, as described above, it is possible to obtain various vinyl-based compounds of interest. Polymer (b-1) or (b-
2) can be prepared.

As described above, the amount of the hydrolyzable silyl group to be introduced into the vinyl polymer (b-1) or (b-2) is determined based on 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 of the cured coating film obtained from the electrodeposition coating composition of the present invention is inevitably reduced, while the amount exceeding about 3 mol is too large. In the case where the amount increases, the viscosity of the reaction solution increases during the preparation of the composite resin (c-1) or (c-2), which may cause inconvenience such as gelation. Any of these cases is not preferred.

Therefore, a hydrolyzable silyl group-containing monomer, a hydrolyzable silyl group-containing chain transfer agent or a hydrolyzable silyl group is introduced so that a preferable amount of the 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-2) 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.

Further, these vinyl polymers (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 cured coating film obtained from the electrodeposition coating composition of the present invention is inevitably used. Target strength and so on, while about 20
If the value is too high exceeding 000, the appearance of the cured coating film 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 a 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, in preparing the polyurethane polymer of the polymer (b-2), the polyurethane polymer (b-1) used for preparing the above-mentioned polyurethane polymer (b-1) has already been listed. In addition to various known and commonly used raw materials,
Using various compounds having one or two groups having the above-mentioned functional group (Fu-2) and having an active hydrogen which reacts with an isocyanate group as a raw material component, Various methods may be applied.

One or two groups having a functional group (Fu-2) 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 as the compounds having 4-hydroxymethyl-1,3-dioxolan-2-one, glycidol,
Compounds having both various functional groups and a hydroxyl group bonded to a carbon atom, such as 2-hydroxyethyl carbamate or 2-hydroxypropyl carbamate.

The amount of the hydrolyzable silyl group to be introduced into the polyurethane-based 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.

When the amount is less than about 0.005 mol, the polyurethane polymer (b-1) or (b-
The complexing reaction between 2) and the polysiloxane (a-1) hardly progresses, and as a result, the durability and the like of the cured coating film obtained from the electrodeposition paint of the present invention decrease. On the other hand, if the amount is more than about 3 mol and is too large, the solution viscosity during the above-described complexing reaction increases, and as a result, inconveniences such as causing gelation are recognized. In any case, it is not preferable.

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, the polyurethane polymer (b-
2) a hydroxyl group, a block hydroxyl group, a cyclocarbonate group, an epoxy group, a primary amide group, a secondary amide group, a carbamate group or a structural formula (S-II) described above, each of which is to be introduced into a carbon atom. The introduction amount of the functional group (Fu-2) represented by the functional group represented by the following formula is expressed as the number of moles of the functional group per 1,000 g of the solid content of the polyurethane polymer (b-2). A range of about 0.1 to about 5 moles is appropriate, preferably a range of 0.2 to 3 moles, and more preferably a range of 0.3 to 2 moles. It is.

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 cured coating film obtained from the electrodeposition coating composition of the present invention is inevitable. And so on, while about 10
If it exceeds 000 and becomes too high, the appearance of the cured coating film is inevitably deteriorated.

The polysiloxane (a-) 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 composite resin (c-1) or (c-2). 1) means various linear, branched or cyclic polysiloxanes having a hydroxyl group bonded to a silicon atom and / or a hydrolyzable group bonded to a silicon atom, generally called a silanol group. Is designated.

Among these various polysiloxanes, the structural formula (S) as described above is preferred because of the excellent curability of the electrodeposition paint used in the present invention and the excellent durability of the cured coating film obtained from the electrodeposition paint of the present invention. Polysiloxane having a branched or cyclic structure having the structure represented by -I) as an essential unit structure is particularly preferred.

Representative examples of the polysiloxane (a-1) include a hydrolyzable group bonded to a silicon atom,
A hydrolyzed condensate of the silicon compound prepared by hydrolyzing and condensing at least three silicon compounds in one molecule, or a hydrolyzed condensate of the silicon compound, which is prepared by partially hydrolyzing and condensing the silicon compound. Partial hydrolysis condensates and the like can be mentioned.

The silicon compound having at least three hydrolyzable groups bonded to a silicon atom in one molecule, which is used when preparing the polysiloxane (a-1), is a known and commonly used silicon compound. Although any of them can be used, if only typical ones among them are exemplified, the following general formula (S-VIII) can be used.

[0193]

Embedded image R ⁶ _b SiR ⁷ _4-b (S-VIII)

(However, R ⁶ in the formula may be an alkyl group, which may or may not have a substituent.
R ⁷ represents a monovalent organic group such as a cycloalkyl group, an aryl group, an aralkyl group or an alkenyl group;
B represents 0 or 1, and represents a hydrolyzable group such as 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 or an alkenyloxy group. It is assumed to be an integer. )

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

As the silicon compounds represented by the above-mentioned general formulas, only typical ones are exemplified. Various tetraalkoxy compounds such as tetraethoxysilane, tetramethoxysilane or tetra-n-butoxysilane may be used. Silanes;

Methyltrimethoxysilane, methyltriethoxysilaneethyltrimethoxysilane n-propyltrimethoxysilane, n-propyltriethoxysilane,
n-butyltrimethoxysilane or n-butyltriethoxysilane,

Cyclopentyltrimethoxysilane, cyclopentyltriethoxysilane, cyclohexyltrimethoxysilane, cyclohexyltriethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, phenyltri-n-butoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane , Vinyltris (2-methoxyethoxy) silane or allyltrimethoxysilane,

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, cyclopentyltrichlorosilane, cyclohexyltrichlorosilane, phenyltrichlorosilane, vinyltrichlorosilane, 3- (meth ) Various organotrichlorosilanes, such as acryloyloxypropyltrichlorosilane;

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

Among these silicon compounds having a hydrolyzable group, those particularly preferred for use in preparing the polysiloxane (a-1) include tetraalkoxysilanes and organotrialkoxysilanes, And partial co-hydrolysis condensates thereof, and various chlorosilanes.

When a large amount of a tetrafunctional silicon compound typified by tetraethoxysilane is used as the silicon compound, the polymer (b-1) or (b-2) and the polysiloxane (a-1) It is desirable to use a trifunctional silicon compound such as an organotrialkoxysilane or an organotrichlorosilane as a main component, since gelation is likely to occur in the complexing step or the neutralization step with a basic compound.

When preparing the polysiloxane (a-1), dimethyldimethoxysilane, dimethyldiethoxysilane,
Diethyldimethoxysilane, di-n-propyldimethoxysilane, di-n-butyldimethoxysilane or di-n-butyldiethoxysilane,

Diphenyldimethoxysilane, diphenyldiethoxysilane, methylphenyldimethoxysilane,
Methylphenyldiethoxysilane, 2- (methyldimethoxysilyl) ethyl vinyl ether, 3- (methyldimethoxysilyl) propyl vinyl ether or 3-
A so-called bifunctional silicon compound having two hydrolyzable groups bonded to a silicon atom in one molecule, such as (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.

By subjecting various silicon compounds as described above to hydrolysis condensation or partial hydrolysis condensation,
A hydrolysis condensate or a partial hydrolysis condensate used as the polysiloxane (a-1) can be obtained. In this case, a catalyst may or may not be used. It is desirable to use a catalyst from the viewpoint of facilitating the condensation reaction.

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 carboxyls 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,

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

Various quaternary ammonium salts such as tetramethylammonium salt, tetrabutylammonium salt, dilauryldimethylammonium salt or trioctylmethylammonium 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 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 preferably about 0.05 mol or more, more preferably 0 mol, per 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 practically preferable. 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 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.

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.
If a problem is caused in the step of compounding the polysiloxane (a-1) with the polymer (b-1) or (b-2) or in the stability of the obtained aqueous resin, a means such as distillation is used. Therefore, it can be removed from the system, and if there is no problem, it can be left in the system as it is without any problem.

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) It is desirable to use a medium containing an organic solvent having various alcoholic hydroxyl groups as an essential component as described above in order to allow the complexing step to proceed smoothly.

Using a medium containing such an organic solvent having an alcoholic hydroxyl group as an essential component,
When preparing the polysiloxane (a-1), at least 3 hydrolyzable groups bonded to silicon atoms are contained in one molecule.
The concentration of the silicon compound in the organic solvent is preferably about 5% by weight or more.

Further, as the polysiloxane (a-1),
Commercially available polysiloxanes can also be used, and examples of such polysiloxanes include, but are not limited to, those which are commercially available as polysiloxanes containing silanol groups or methoxy groups bonded to silicon atoms, such as "TSR-
160 or 165] (trade name of Toshiba Silicone Co., Ltd.), "SH-6018" [Dow Corning Toray Co., Ltd.
Product name manufactured by Silicone Co., Ltd.], “GR-100, 90
8 or 950 "[trade name manufactured by Showa Denko KK], etc., having a linear, cyclic, branched or ladder (type) structure. And so on.

Among the polysiloxanes described above, from the viewpoint of the stability of the aqueous resins (W-1) and (W-2), 10 mol% of the total silicon atoms constituting the polysiloxane (a-1) As described above, it is appropriate to use one in which an aryl group and / or a cycloalkyl group is bonded to preferably 20 mol% or more, more preferably 40 mol% or more of silicon atoms.

The aqueous resins (W-1) and (W-
From the viewpoint of the curability and durability of 2), polysiloxane (a
10 mol% or more, preferably 20 mol% or more, and more preferably 30 mol% or more of all silicon atoms constituting -1) are methyltrialkoxysilanes, methyltrichlorosilane, cyclohexyltrialkoxysilanes, It is appropriate to use those derived from trifunctional silane compounds, such as cyclohexyltrichlorosilane, phenyltrialkoxylans or phenyltrichlorosilane.

Next, among the aqueous resins (W-1) and (W-2) used in the present invention, the above-mentioned preparation methods (1) to (1) which are of a type in which an anionic group is a hydrophilic group are used. 4) The method will be described in detail.

Next, from the polymer (b-1) or (b-2) and the polysiloxane (a-1), the aqueous resin (W-1) or (W-1) was prepared by the method (1). Among W-2), a method of preparing a type having an anionic group as a hydrophilic group will be described in detail.

(1) In preparing by the following method,
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-1). As such a catalyst, Various catalysts, such as those already listed as those used in preparing the polysiloxane (a-1),
It can be used as it is.

(1) The amount of the catalyst used in the case of forming a composite by the method described in (1) above is the total amount of each of the polymer (b-1) or (b-2) and the polysiloxane (a-1). Is preferably in the range of about 0.0001 to about 10% by weight, more preferably in the range of 0.0005 to 3% by weight, and particularly preferably in the range of 0.0005 to 1% by weight. is there.

When the catalyst used in the process of preparing the polysiloxane (a-1) remains in (a-1), the (a-) 1)
It is possible to accelerate the condensation reaction only with the catalyst remaining therein.

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

When the water used in preparing the polysiloxane (a-1) remains in the (a-1), the water (a-1) can be obtained without any additional water. It is also possible to carry out the condensation reaction only with water remaining in the above.

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). Present in the polysiloxane (a-1),
About 0.05 mol or more, preferably 0.1 mol, per 1 mol of the total amount with the hydrolyzable group bonded to the silicon atom.
1 mol or more is suitable, and more preferably 0.5 mol or more.
More than a mole is appropriate.

If the amount is less than about 0.05 mol, the rate of hydrolysis is liable to be remarkably slowed down.

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 a hydrolyzable group bonded to a silicon atom is present in the polysiloxane (a-1), use of water is based on 1 mol of the hydrolyzable group contained in (a-1). It is appropriate to set the amount to generally less than 10 mol, preferably less than 5 mol, more preferably less than 3.5 mol;

In the case where (a-1) has no hydrolyzable group bonded to a silicon atom, the polymer (b-
With respect to 1 mol of the hydrolyzable group contained in the hydrolyzable silyl group bonded to each of 1) or (b-2),
It is appropriate to set the amount to 500 mol or less, preferably 300 mol or less, and 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.

Further, according to the method (1), the composite resin (c-1) or (c
In the partial or complete neutralization reaction of the acid group in -2), it is preferable to use ammonia or various organic amines as various basic compounds as described above.

The amount of the basic compound to be added is at least as large as that of the polymer (b-1) or (b-
2) and an amount capable of imparting water dispersibility to the condensation reaction product of the polysiloxane (a-1),
A ratio of the number of equivalents of the basic compound to the number of equivalents of acid groups contained in the condensation reaction product of the polymer (b-1) or (b-2) and (a-1),

That is, the equivalent ratio of the basic compound / "acid groups in the condensation reaction product of each of the above-mentioned polymer (b-1) or (b-2) with (a-1)" is about 0. Although it is appropriate that the amount is 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 3. A range of 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.

As described above, a partially or completely neutralized product of the composite resin (c-1) or (c-2) with a basic compound can be prepared. The organic solvents contained therein can be dispersed or dissolved in water as they are without being removed, or can be removed by a distillation operation or the like as necessary.

The thus obtained composite resin (c-
By dispersing or dissolving the respective partially or completely neutralized products of 1) or (c-2) in water, the anionic group in the aqueous resin (W-1) or (W-2) is converted to a hydrophilic one. A type having a base is prepared.

The composite resin (c-1) or (c-2),
The aqueous resin (W
In order to prepare -1) or (W-2), various known and commonly used methods 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 mix the partially or completely neutralized product with water or water and a water-soluble organic solvent. By adding to the above mixture, the desired aqueous resin (W-1) or (W-2) can be prepared by dispersing or dissolving in water.

Further, if necessary, the organic solvent contained in the aqueous resin (W-1) or (W-2) thus prepared is partially or 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, a method for preparing the above-mentioned aqueous resin (W-3) or (W-4) will be described.

First, as a composite resin (C-3) or (C-4) which is a precursor of the aqueous resin (W-3) or (W-4), a polymer which is particularly preferable as described above, A method for preparing a compound in which the segment (B-1) or (B-2) and the polysiloxane segment (A-2) are complexed via the bond represented by the structural formula (S-III) will be described.

The composite resin (C-3) or (C-
As a method for preparing 4), for example, (e) a polar group having a free acid group or a free basic group, a hydrolyzable group bonded to a silicon atom and / or a hydroxyl group bonded to a silicon atom. A polymer containing the above functional group (Fu-2) in addition to the above-mentioned compound or a polar group and a hydrolyzable group bonded to a silicon atom and / or a hydroxyl group bonded to a silicon atom, and an aryl group or a cycloalkyl A polysiloxane (a-2) having a silicon atom in which a group and a hydrolyzable group are bonded together and / or a silicon atom in which an aryl group or a cycloalkyl group and a hydroxyl group are bonded together, to form a polysiloxane (a-2) ) And a reaction between the hydrolyzable group bonded to the silicon atom and / or the hydroxyl group bonded to the silicon atom contained in each of the above-mentioned polymers. After then conjugated via binding II), a method of neutralizing the free acid groups or free base groups contained in the basic compound or acidic compound,

(F) A polymer having both a neutralized acid group or a neutralized basic group, a hydrophilic group, a hydrolyzable group bonded to a silicon atom and / or a hydroxyl group bonded to a silicon atom, or In addition to the hydrophilic group and the hydrolyzable group bonded to the silicon atom and / or the hydroxyl group bonded to the silicon atom, a polymer containing the functional group (Fu-1) described above and the polysiloxane (a- 2) to form a polysiloxane (a-2) and a hydrolyzable group bonded to a silicon atom contained in each of the above-mentioned polymers and / or
Or a method of forming a complex through a bond of the structural formula (S-III) by a reaction between hydroxyl groups bonded to silicon atoms,

(G) An aryl group having a radically polymerizable double bond and wherein the double bond and polysiloxane are bonded in the bonding mode represented by the structural formula (S-VI) Alternatively, a polysiloxane having a silicon atom in which a cycloalkyl group and a hydrolyzable group are bonded together and / or a silicon atom in which an aryl group or a cycloalkyl group and a hydroxyl group are bonded together are used as one of the copolymerization components. And a vinyl monomer containing a polar group-containing vinyl monomer, which is a vinyl monomer having a free acid group or a vinyl monomer having a free basic group, as an essential component Or the above-mentioned functional group (Fu) in addition to the double bond-containing polysiloxane and the polar group-containing vinyl monomer.
-2) is copolymerized with a vinyl monomer containing an essential component thereof to form a complex, and then a free acid group or a free basic group contained is converted to a base. (H) having a radical polymerizable double bond, wherein the double bond and the polysiloxane are bonded by a bonding mode represented by the structural formula (S-VI). A polysiloxane having a silicon atom having a bonded aryl group or cycloalkyl group and a hydrolyzable group bonded together and / or a silicon atom having an aryl group or cycloalkyl group bonded to a hydroxyl group bonded together is used as a copolymer component. Use this as one, and
A vinyl monomer containing a neutralized acid group-containing vinyl monomer or a hydrophilic group-containing vinyl monomer such as a neutralized basic group-containing vinyl monomer as an essential component By copolymerizing with the monomers, or
In addition to the polysiloxane having a double bond and the vinyl-based monomer having a hydrophilic group, the functional group (Fu-
There is a method in which a monomer containing 1) is copolymerized with a vinyl-based monomer containing the monomer as an essential component to form a complex.

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

It is particularly convenient to introduce the hydrolyzable group bonded to the silicon atom in the form of the hydrolyzable silyl group described above, as in the methods (a) and (b). is there.

Of the above-mentioned various methods (e) to (h), the method (e) is particularly simple. Hereinafter, the aqueous resin (W-3) or (W-4) to which this method is applied The method for preparing is described in detail.

In the composite resin (C-3) or (C-4), a type containing an anionic group as a hydrophilic group in the case of preparing the type by the above-mentioned method (e) represents a more specific method. Typically,

(5) In addition to the previously prepared polymer (b-3) having both a hydrolyzable silyl group and an acid group or both a hydrolyzable silyl group and an acid group, A polymer (b-4) also containing a group (Fu-2),
The acid group contained in the composite resin (c-9) or (c-10) obtained by subjecting the polysiloxane (a-2) to a condensation reaction is partially or completely neutralized with a basic compound. Method,

(6) The polymer (b-3) or the polymer (b
(B-3) or (b-4) during the reaction for preparing the polysiloxane (a-2) in the presence of (-4)
A method of partially or completely neutralizing an acid group contained in a composite resin (c-11) or (c-12) obtained by subjecting a compound (a-2) to a condensation reaction with a basic compound,

(7) In the course of carrying out the reaction for preparing the polymer (b-3) or the polymer (b-4) in the presence of the polysiloxane (a-2), (b-3) or (b-3) (B-
4) a method of partially or completely neutralizing an acid group contained in the composite resin (c-13) or (c-14) obtained by subjecting (a-2) to a condensation reaction with a basic compound;

(8) The polymer (b-3) or the polymer (b
In the process of performing the reaction for preparing -4) and the reaction for preparing polysiloxane (a-2) in parallel, (b-3)
Alternatively, the acid group contained in the composite resin (c-15) or (c-16) obtained by subjecting (b-4) and (a-2) to a condensation reaction is partially or completely neutralized with a basic compound. There is a method of neutralizing.

The polymer (b-3) or (b-
Examples of the acid group introduced in 4) include the various acid groups described above as those introduced during the preparation of the aqueous resin (W-1) or (W-2). Desirable are a carboxyl group, a block carboxyl group or a carboxylic anhydride group.

As the functional group (Fu-2) introduced into the polymer (b-4), the polymer (b-2)
Examples of those that can be introduced into the above are the various examples already exemplified.

Of the above methods (5) to (8), the composite resin (C-3) can be obtained by the representative method (5).
Alternatively, the method of preparing (C-4) will be described in detail.

(5) Composite resin (C-3)
Alternatively, when preparing (C-4), a polymer (b-3) or (b-4) is prepared as a precursor thereof, and a typical example of such various polymers is a polymer Although various types are mentioned similarly to what was mentioned above about segment (B-1) and (B-2), Among them, especially preferable thing is a vinyl-type polymer or a polyurethane-type polymer, Further, among the vinyl polymers, particularly preferable ones 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.

In preparing the polymer (b-3), which is a precursor of the composite resin (c-9), of the vinyl polymer, the polymer (b-1) is used in the preparation of the polymer (b-1). The methods (i) to (iv) may be applied as they are using monomers, polymerization initiators and organic solvents exemplified as those described above, but from the viewpoint of simplicity, these methods are used. Among them, it is particularly preferable to apply each of the methods (i) to (iii).

Then, among such vinyl polymers, the polymer (b-4) which is a precursor of the composite resin (c-10)
(V) to (viii) using the monomers, polymerization initiators and organic solvents exemplified as those used in the preparation of the polymer (b-1). The method can be applied as it is, but from the point of simplicity,
Among these, 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 the acid group or the functional group (Fu-2) may be in accordance with the amount introduced when preparing the polymer (b-1) or (b-2).

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

Then, the polymer (b-3) or (b-4)
Of the acid groups and functional groups (Fu-2) to be introduced into the polyurethane polymer and the number average molecular weight of the polymer are determined by the polyurethane polymer (b-1) or (b-
This is in accordance with the preferred range in the case of 2).

Next, the composite resin (c-9) or (c-
Polysiloxane having a silicon atom in which an aryl group or a cycloalkyl group and a hydrolyzable group are bonded together and / or a silicon atom in which an aryl group or a cycloalkyl group and a hydroxyl group are bonded together, which is the other component of 10) ( a-2) will be described.

If only typical examples of such a polysiloxane (a-2) are given, only at least one of an aryl group or a cycloalkyl group may be used.
A hydrolyzable condensate of the silicon compound, which is prepared by hydrolyzing and condensing a silicon compound having at least one silicon atom bonded to at least two hydrolyzable groups together in one molecule, or And a partially hydrolyzed condensate of the silicon compound, which is prepared by partially hydrolyzing and condensing the silicon compound.

As described above, polysiloxane (a-2)
As a silicon compound having at least one silicon atom per molecule in which at least one aryl group or cycloalkyl group and at least two hydrolyzable groups are bonded together, Any of various known and commonly used compounds can be used, but if only typical ones among them are exemplified, the following general formula (S-IX)

[0277]

Embedded image ^{_{R 8 R 9 c SiR 10 3}} -c (S-IX)

(Wherein, R ⁸ in the formula is an aryl group or a cycloalkyl group, and R ⁹ is an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group, which may or may not have a substituent. And at least one monovalent organic group selected from the group consisting of
¹⁰ 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, a mercapto group, an amino group, an amide group, an aminooxy group, an iminooxy group or an alkenyloxy group. And c 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

[0280]

Embedded image

Or

[0282]

Embedded image

At least one of the aryl groups, such as
And silicon compounds having at least two hydrolyzable groups bonded together in one molecule.

As the silicon compound represented by the general formula (S-IX) as described above, only typical ones are exemplified, and examples thereof include phenyltrimethoxysilane, phenyltriethoxysilane and phenyltributoxysilane. , Various phenyl trialkoxysilanes;
Various alkylphenyl dialkoxysilanes such as methylphenyldimethoxysilane, methylphenyldiethoxysilane, ethylphenyldimethoxysilane or ethylphenyldiethoxysilane; various diphenyldialkoxys such as diphenyldimethoxysilane or diphenyldiethoxysilane Silanes;

Various cycloalkyl trialkoxysilanes such as cyclopentyltrimethoxysilane, cyclopentyltriethoxysilane, cyclohexyltrimethoxysilane or cyclohexyltriethoxysilane; cyclopentylmethyldimethoxysilane, cyclopentylmethyldiethoxysilane, cyclohexylmethyldimethoxysilane, Various alkylcycloalkyl dialkoxysilanes such as cyclohexylmethyldiethoxysilane or cyclohexylethyldiethoxysilane; various dicycloalkyls such as dicyclopentyldimethoxysilane, dicyclopentyldiethoxysilane, dicyclohexyldimethoxysilane or dicyclohexyldiethoxysilane Alkyl dialkoxy silanes;

Various monophenyl- or diphenylchlorosilanes such as phenyltrichlorosilane, methylphenyldichlorosilane, ethylphenyldichlorosilane or diphenyldichlorosilane; cyclopentyltrichlorosilane, cyclohexyltrichlorosilane, cyclopentylmethyldichlorosilane, cyclohexylmethyl Various monocycloalkyl- or dicycloalkylchlorosilanes, such as dichlorosilane, dicyclopentyldichlorosilane or dicyclohexyldichlorosilane;

Various monophenyl- or diphenylacetoxysilanes such as phenyltriacetoxysilane, methylphenyldiacetoxysilane, ethylphenyldiacetoxysilane or diphenyldiacetoxysilane; or cyclopentyltriacetoxysilane, cyclohexyltriacetoxysilane, cyclopentyl Various monocycloalkyl- or dicycloalkylacetoxysilanes such as methyldiacetoxysilane, cyclohexylmethyldiacetoxysilane, dicyclopentyldiacetoxysilane or dicyclohexyldiacetoxysilane.

Of these silicon compounds having an aryl group and a hydrolyzable group, only those particularly preferred as compounds used for preparing the polysiloxane (a-2) are exemplified by phenyl. Trialkoxysilane, alkylphenyldialkoxysilane, diphenyldialkoxysilane, cyclohexyl trialkoxysilane, alkylcyclohexyldialkoxysilane,
Dicyclohexyldialkoxysilane, phenyltrichlorosilane, alkylphenyldichlorosilane, diphenyldichlorosilane, cyclohexyltrichlorosilane, alkylcyclohexyldichlorosilane or dicyclohexyldichlorosilane, partial hydrolysis condensates thereof or partial cohydrolysis condensates thereof, etc. It is.

In preparing the polysiloxane (a-2), in addition to the various silicon compounds described above, trimethylmethoxysilane, trimethylethoxysilane, triethylmethoxysilane, triethylethoxysilane, triphenylmethoxysilane, Such as triphenylethoxysilane, trimethylchlorosilane, triethylchlorosilane or triphenylchlorosilane,
A so-called monofunctional silicon compound having only one hydrolyzable group bonded to a silicon atom in one molecule, or methyltriethyl, which can be used when preparing a polysiloxane (a-1), Trifunctional silicon compounds having no aryl group or cycloalkyl group such as methoxysilane, methyltriethoxysilane or methyltri-n-butoxysilane, further, dimethyldimethoxysilane, dimethyldiethoxysilane or dimethyldi-n-butoxysilane And a bifunctional silicon compound having no aryl group or cycloalkyl group.

By subjecting the above-mentioned various silicon compounds to hydrolysis-condensation or partial hydrolysis-condensation, a hydrolysis-condensation product or a partial hydrolysis-condensation product used as polysiloxane (a-2) can be obtained. However, its preparation may be performed according to the above-mentioned method for preparing polysiloxane (a-1).

Further, as the polysiloxane (a-2), those prepared as described above may be used,
Commercially available polysiloxanes can also be used.

Only typical representative examples of such commercially available polysiloxanes include, but are not limited to, "TSR" which is commercially available as a polysiloxane having a silicon atom to which a phenyl group is bonded in addition to a hydroxyl group or a methoxy group.
-160 or 165 "(trade name of Toshiba Silicone Co., Ltd.) or" SH-6018 "(trade name of Dow Corning Silicone Co., Ltd.). Hydrolytic condensates or partial hydrolytic condensates having a cyclic or branched structure.

The polymer (b-3) or (b-
In order to prepare a type having an anionic group in the composite resin (C-3) or (C-4) from the method (5) from the method 4) and the polysiloxane (a-2), In the method (1), the polymer (b-1) or (b)
The polymer (b-3) or (b-4) is used instead of -2), and the polysiloxane (a-1) is used.
Except that polysiloxane (a-2) is used instead of
The reaction is carried out according to the method (1), and the composite resin (c-
9) or (c-10) is prepared, and then the acid group contained in the composite resin is partially or completely neutralized with a basic compound in the same manner as in the method (1). I just need.

According to the method (5), the composite resin (c-
The ratio of the polymer (b-3) or (b-4) and the polysiloxane (a-2) used in the preparation of each of (9) and (c-10) depends on the resulting composite resin (C-
3) or the polymer segment (B-) in (C-4)
The ratio of 1) or (B-2) to the polysiloxane segment (A-2) may be set so as to be within the above-described preferable range.

Further, in the method (5), in preparing the composite resin (c-9) or (c-10), an organic solvent may or may not be used. In order to easily perform the above-mentioned processes, it is desirable to use various organic solvents, such as those already listed as usable when preparing the vinyl polymer (b-1).

In the method (5), the composite resin (c-
In the preparation of 9) or (c-10), the total concentration of each component is determined by combining the composite resin (c-9) or (c-10) produced by the reaction with each other at the time of completion of the composite reaction. The concentration is about 5% by weight or more, preferably 1%.
It is desirable to set it to 0% by weight or more, and more preferably to 20% by weight or more. The adjustment of the concentration can be performed with various organic solvents as described above.

As described above, among the composite resins (C-3) and (C-4), the type having an anionic group can be prepared. The organic solvents contained in the composite resin are as follows. , Without removing, as described above,
It can be mixed with a polysiloxane (p) having a hydrolyzable group bonded to a silicon atom and / or a hydroxyl group bonded to a silicon atom. Prior to mixing with the polysiloxane (p), a distillation operation or the like is performed. It can also be removed.

The thus obtained composite resin (C-
3) or (C-4) is mixed with a polysiloxane (p) having a hydrolyzable group bonded to a silicon atom and / or a hydroxyl group bonded to a silicon atom, and further, if necessary, condensed. By dispersing or dissolving in a medium, the aqueous resin (W-3) or (W-
4) is prepared.

The polysiloxane (p) used at that time
As the polysiloxane (a-1) or (a-2) described above, various commercially available polysiloxanes such as polysiloxane can be used. Among them, methyltrialkoxysilane, The fact that it is prepared using a trifunctional silane compound having a methyl group as an organic group such as methyltrichlorosilane or methyltriacetoxysilane as an essential raw material component indicates the curability of the electrodeposition paint of the present invention. Particularly preferred is the solvent resistance of the cured coating film.

In the polysiloxane (p), the proportion of silicon atoms derived from trifunctional silane having a methyl group in all silicon atoms is preferably 20 mol% or more, and more preferably 30 mol%. The above is more preferable, and furthermore, 50 mol% or more is particularly preferable.

The polysiloxane (p) as described above,
The mixture with the above-described composite resin (C-3) or (C-4), or (p), and if necessary, (C)
3) or a part of a hydrolyzable group bonded to a silicon atom and / or a part of a hydroxyl group bonded to a silicon atom in (p) obtained by condensation with (C-4).
3) Dispersing or dissolving a condensation reaction product in a form in which a hydrolyzable group bonded to a silicon atom and / or a hydroxyl group bonded to a silicon atom in (C-4) is partially dehydrated and condensed. Water-based resin (W-3)
Or (W-4) is obtained.

The ratio of (C-3) or (C-4) and (p) used at that time is determined based on the aqueous resin (W-
3) or (W-4), the ratio of the total amount of the polysiloxane segment (A-2) and the polysiloxane derived from (p) to the ratio of the polymer segment (B-1) or (B-2) is as described above. What is necessary is just to set it in the preferable range as mentioned above.

To prepare the aqueous resin (W-3) or (W-4) from a mixture or condensation reaction product of the composite resin (C-3) or (C-4) and the polysiloxane (p) What is necessary is just to carry out according to the above-mentioned method as a prescription applied when preparing aqueous resin (W-1) or (W-2) from composite resin (C-1) or (C-2).

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 (5) described above, In place of the acid group, a basic group is replaced with a polymer (b-1) to (b)
-4) and aqueous resins (W-1) to (W-4) containing a cationic group are prepared by using an acidic compound instead of a basic compound as a neutralizing agent. I can do it.

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. .

Typical examples of the vinyl monomer containing an amino group include 2-tert.
-Butylaminoethyl (meth) acrylate or 2
2 such as -tert-butylaminoethyl crotonate
(Meth) acrylic acid ester or crotonic acid ester containing a secondary amino group; 2-dimethylaminoethyl (meth) acrylate, 2-diethylaminoethyl (meth) acrylate, 2-di-n-propylaminoethyl (meth) acrylate, Various tertiary amino group-containing (meth) acrylates such as 3-dimethylaminopropyl (meth) acrylate, 4-dimethylaminobutyl (meth) acrylate or N- [2- (meth) acryloyloxy] ethylmorpholine ;

Various tertiary amino group-containing aromatic vinyl monomers such as vinyl pyridine, N-vinyl carbazole or N-vinyl quinoline;

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

Various tertiary amino groups, such as N- (2-dimethylamino) ethylcrotonamide, N- (2-diethylamino) ethylcrotonamide or N- (4-dimethylamino) butylcrotonamide Crotonic amides;

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.

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.

Then, the amount of the basic group introduced into (b-1) to (b-4) and the amount of the functional group (Fu-2) introduced into (b-2) or (b-4) , (B-1) to (b-
4) Number average molecular weight, (b-1) or (b-2) and the use ratio of polysiloxane (a-1), (b-3) or (b-4) and polysiloxane (a-2) The ratio of use with the polysiloxane (p) may be in accordance with various methods (1) to (5).

The aqueous resin prepared as described above (W
Among the functional groups contained in the aqueous resin (W-1), the hydroxyl group derived from the composite resin (C-1) and bonded to a silicon atom and, if necessary, are contained in the aqueous resin (W-1). There is a hydrolyzable group bonded to the silicon atom, and in addition, an acid group neutralized by a basic compound or a basic group neutralized by an acidic compound, and optionally a free acid group or a free acid group contained therein. It is a basic group.

The functional groups contained in the aqueous resin (W-3) include a composite resin (C-3) and a polysiloxane (p).
And a hydroxyl group bonded to a silicon atom and a hydrolyzable group bonded to a silicon atom that may be contained, both of which are neutralized by a basic compound derived from (C-3). Acid group or a basic group neutralized by an acidic compound, and optionally a free acid group or a free basic group contained therein.

The functional group contained in the aqueous resin (W-2) includes a hydroxyl group bonded to a silicon atom derived from the composite resin (C-2) and a hydrolysis bonded to a silicon atom contained in some cases. There is an acid group, and in addition, there are an acid group neutralized by a basic group or a basic group neutralized by an acidic compound, and a free acid group or a free basic group optionally contained, Other functional groups are represented by a hydroxyl group, a block hydroxyl group, a primary amide group, a secondary amide group, a carbamate group, or a structural formula (S-II) derived from the composite resin (C-2) and bonded to a carbon atom. At least one of the functional groups (Fu-2).

The functional groups contained in the aqueous resin (W-4) include a composite resin (C-4) and a polysiloxane (p).
A hydroxyl group bonded to a silicon atom and a hydrolyzable group bonded to a silicon atom contained in some cases, and an acid group neutralized by a basic group derived from (C-4) Alternatively, there are a basic group neutralized by an acidic compound and a free acid group or a free basic group contained as the case may be, and further, other functional groups derived from the composite resin (C-4) At least one of a hydroxyl group, a block hydroxyl group, a primary amide group, a secondary amide group, a carbamate group or a functional group (Fu-2) represented by the structural formula (S-II) bonded to a carbon atom It is.

In preparing the aqueous resins (W-1) to (W-4), each of the polymers (b-1) to (b-4) was used as a precursor functional group of an anionic group as a blocked acid. 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.

Further, the aqueous resin (W-2) or (W-
When preparing block hydroxyl group, epoxy group or cyclocarbonate group as the functional group (Fu-2) into the polymer segment (B-2) when preparing 4), the composite resin (C-2) ) Or (C-4), and at the stage of dispersing or dissolving them in water, at least a part of these functional groups are converted to free hydroxyl groups by hydrolysis or alcoholysis. Sometimes converted.

Then, the kind of the block hydroxyl group, epoxy group or cyclocarbonate group, or the condition of the above-mentioned complexing reaction, the condition of mixing with (D) described later, or the subsequent dispersion in water Depending on the conditions of dissolution or the like, such various functional groups may be completely converted to free hydroxyl groups.

The aqueous resin (W-
In order to prepare the electrodeposition coating composition of the present invention from each of 1) to (W-4), in part, each of (W-1) to (W-4) itself is self-curing. From a place that has sex,
What is necessary is just to make a self-hardening paint containing each of (W-1) to (W-4) as an essential component,

In two, for each of (W-1) to (W-4), the above-mentioned aqueous resin (W-1) to (W-1)
By compounding compound (D) having a functional group that reacts with the functional group contained in (W-4), (W-
A curable paint that also utilizes a crosslinking reaction between the functional groups contained in each of 1) to (W-4) and the functional groups contained in compound (D) may be used.

The compound (D) used in the preparation of the latter type of curable paint is the same as the aqueous resin (W
-1) to (W-4), each of which refers to various known and commonly used compounds having at least one functional group that reacts with the various functional groups described above. If only typical representative examples of the functional group are given, an epoxy group, a cyclocarbonate group, a blocked isocyanate group, a primary amide group,
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)

[0323]

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) A functional group as shown in the following.

The functional group contained in the compound (D) 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, epoxy-carboxyl group, carboxyl group-cyclocarbonate group, carboxyl group-oxazoline group, carboxyl group-carbodiimide group, hydroxyl group bonded to carbon atom-acryloyl group,
A hydroxyl group-N-hydroxymethylamino group bonded to a carbon atom, a hydroxyl group-N-alkoxymethylamino group bonded to a carbon atom or a hydroxyl group-blocked isocyanate group bonded to a carbon atom.

As the compound (D), 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 (D), various resins can be used in addition to a 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.

As the compounds (D), 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 a block per molecule. A compound having both an isocyanate group and a hydrolyzable group bonded to a silicon atom,
Block polyisocyanate compound, polycyclocarbonate compound, polyepoxy compound, amino resin, primary or secondary amide group-containing compound, polyhydroxy compound, polyaziridine compound, polyacrylate compound,
Polycarbodiimide compounds, polyoxazoline compounds, etc., and these various compounds may be used alone or in combination of two or more.

Among 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, and a compound having a blocked isocyanate group and a hydrolyzable group bonded to a silicon atom in one molecule. And a polyhydroxy compound, a compound having a functional group, a blocked polyisocyanate compound, an amino resin, a compound containing a primary or secondary amide group, and the like.

Among 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 typical ones are exemplified. Silicon compounds represented by the formula (S-VIII) or the general formula (S-IX); hydrolysates or hydrolyzed condensates of these silicon compounds;
A partial hydrolyzed condensate obtained by one kind of partial hydrolytic condensation of these silicon compounds; or a partial cohydrolyzed condensate obtained by two or more kinds of partial hydrolytic condensation of these silicon compounds.

Of these, only particularly typical examples of the silicon compound are tetramethoxysilane and tetraethoxysilane, partially hydrolyzed condensates thereof, and partially co-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 the above-described compounds having a blocked isocyanate group and a hydrolyzable group bonded to a silicon atom in one molecule are specifically exemplified, only compounds which are particularly typical are described below.

Various silicon containing an isocyanate group such as 3-isocyanatopropyltrimethoxysilane, 3-isocyanatopropylmethyldimethoxysilane, 3-isocyanatopropyltriethoxysilane or 3-isocyanatopropylmethyldiethoxysilane There are compounds obtained by reacting a compound with an isocyanate group blocking agent.

Representative examples of the blocking agent used for preparing a compound having both a blocked isocyanate group and a hydrolyzable group bonded to a silicon atom include methanol, ethanol, benzyl alcohol and lactic acid ester. Various alcohols, such as;

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

Alternatively, it includes various oximes such as acetone oxime or methyl ethyl ketoxime, and various active methylene compounds such as methyl acetoacetate, ethyl acetoacetate or acetylacetone.

Examples of the above-mentioned blocked polyisocyanate compounds include compounds obtained by reacting various known and commonly used polyisocyanate compounds with various blocking agents as described above to block isocyanate groups, and various polyisocyanate compounds. There is a class of compounds in which an isocyanate group is regenerated by heat, such as compounds having various uretdione structures obtained by cyclizing and dimerizing an isocyanate group of the compound.

If only typical representative examples of the polyisocyanate compound used in preparing such a blocked polyisocyanate compound are given, examples include 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;

Examples of various prepolymers having isocyanate groups, which are obtained by subjecting various polyisocyanates as described above to an addition reaction with polyhydric alcohols,

Various prepolymers having an isocyanurate ring obtained by cyclizing and trimerizing various polyisocyanates as described above;

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, and are respectively (meth) acrylic, vinyl ester, vinyl ether, aromatic, vinyl, or fluoroolefin-based. 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.

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.

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

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 may be used. 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-2), 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.

When the compound (D) is a polymer, the compound (D) may be used in any form of a solventless liquid, an organic solvent solution, an aqueous solution or an aqueous dispersion. Can be.

When preparing an electrodeposition coating composition containing each of the aqueous resins (W-1) to (W-4) and the compound (D) as an essential component, the compound (D) may be a silicon-containing compound. In the case of a compound having a hydroxyl group bonded to an atom and / or a hydrolyzable group bonded to a silicon atom, 100% of each solid content of the aqueous resins (W-1) to (W-4)
The solid content of the compound (D) is about 1 part by weight,
It may be in the range of from about 200 to about 200 parts by weight, preferably in the range of from 3 to 150 parts by weight, more preferably in the range of from 5 to 100 parts by weight.

When the compound (D) is a compound having both a blocked isocyanate group and a hydrolyzable group bonded to a silicon atom in one molecule or a blocked polyisocyanate compound, the aqueous resin (W- 1)-(W
-4), the amount of the blocked isocyanate group contained in the compound (D) is about 0.1 to about 10 equivalents relative to 1 equivalent of the functional group which reacts with the blocked isocyanate group. Within the range, preferably from 0.3 to
The compound (D) may be blended in a range of 5 equivalents, more preferably in a range of 0.5 to 2 equivalents.

When the compound (D) is an amino resin, the solid of the compound (D) is added to 100 parts by weight of the solids of each of the aqueous resins (W-1) to (W-4). The amount is in the range of about 5 to about 200 parts by weight, preferably 1
Within the range of 0 to 150 parts by weight, more preferably 15 to 1 part by weight.
What is necessary is just to mix | blend so that it may be in the range of 00 weight part.

When the compound (D) is a compound other than the above compounds such as a compound having a primary or secondary amide group, a polyhydroxy compound or a blocked polyisocyanate, the aqueous resin (W-1) (W-4)
The amount of the functional group contained in the compound (D) is about 0.2 with respect to 1 equivalent of the functional group reacting with the functional group contained in the various compounds (D) contained in each of the compounds. The compound (D) is blended so as to be in a range of from about 5.0 to about 5.0 equivalents, preferably in a range of from 0.5 to 3.0 equivalents, and more preferably in a range of from 0.7 to 2 equivalents. I just need.

The electrodeposition coating composition of the present invention can be used as a clear composition containing no coloring pigment, or can be used as a coloring composition containing a conventional pigment.

Typical examples of pigments used for coloring paints include various organic pigments such as carbon black, phthalocyanine blue, phthalocyanine green or quinacridone red; titanium oxide, iron oxide And various metal oxide-based inorganic pigments such as titanium yellow or copper chrome black; and extender pigments such as clay or talc.

The electrodeposition coating composition of the present invention may further contain a known and commonly used compound such as a curing catalyst, a flow control agent, a dye, a leveling agent, a rheology control agent, an ultraviolet absorber, an antioxidant or a plasticizer. Various additives can be blended.

Of 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-1) described above are already used. Various catalysts such as those described above can be used. In addition to these compounds, tetramethylphosphonium salts, tetraethylphosphonium salts, tetrabutylphosphonium salts, trimethyl (2-hydroxypropyl) phosphonium salts, Various compounds such as triphenylphosphonium salts or benzylphosphonium salts having various anions as a counter anion, such as fluoride, chloride, bromide or carboxylate, can also be used.

These various catalysts are appropriately selected according to the type of the hydrophilic group contained in the aqueous resins (W-1) to (W-4) in order to maintain the stability of the electrodeposition bath. Must be used.

When the above-described curing catalyst is added, the amount of the curing catalyst is 0.01 to 15 parts by weight based on 100 parts by weight of the total amount of the resin solids contained in the electrodeposition paint. , Preferably in the range of 0.05 to 10 parts by weight, particularly preferably in the range of 0.1 to 5 parts by weight.

Further, for the purpose of improving the stability of the electrodeposition coating composition of the present invention and improving the smoothness of the coating film, various organic solvents as described above can be added. Particularly preferred solvents are hydrophilic solvents such as various alcohols, glycol ethers or ketones.

The above-mentioned aqueous resins (W-1) to (W-4)
In order to prepare the electrodeposition coating composition of the present invention, these aqueous resins are diluted with water or water containing a hydrophilic solvent, if necessary, to give a resin solids concentration of 2 to 40%, preferably 4%. It may be adjusted so as to be about 20%.

Compound (D) and aqueous resins (W-1) to (W)
In order to obtain the electrodeposition paint of the present invention from each of -4),
The compound (D) is itself water-soluble,
When it is an aqueous dispersion or one having a certain degree of hydrophilicity, the compound (D) and each of the aqueous resins (W-1) to (W-4) are simply used. Only by mixing, it is possible to obtain an electrodeposition coating in the form of uniformly dissolved or uniformly dispersed.

However, if it is not possible to obtain a uniformly dissolved or uniformly dispersed electrodeposition coating due to the low hydrophilicity of the compound (D) or the like, (W
-1) or a composite resin (C-
(C) which is a precursor of 1) or (C-2) or (W-3)
A mixture or condensate of -3) with polysiloxane (p), or a mixture or condensate of (W-4) precursor (C-4) with polysiloxane (p), and (D) ) Is dissolved or dispersed in water or water containing a hydrophilic solvent, whereby an electrodeposited paint in a form of uniformly dissolved or uniformly dispersed can be obtained.

The substrate as a coated object to which the electrodeposition coating composition of the present invention is applied may be any substrate as long as various conductive materials are used. Metals such as iron, copper, aluminum;
Plated steel sheets plated with zinc, tin, chromium or aluminum; Chemical conversion-treated metals obtained by subjecting the surfaces of the various metals to a chemical conversion treatment with chromic acid or phosphoric acid; Various types of electrolysis such as anodized aluminum Metal to be treated.

In order to apply the electrodeposition coating composition of the present invention to various objects to be coated as described above, a known and commonly used method can be applied.

In order to apply an electrodeposition coating prepared from an aqueous resin containing a cationic group, a voltage may be applied between the coating material and a counter electrode using the object to be coated as a cathode, or an aqueous solution containing an anionic group may be applied. In order to apply the electrodeposition paint prepared from the resin, a voltage may be applied between the object to be coated and the counter electrode as an anode.

In this case, the temperature of the electrodeposition bath containing the electrodeposition paint of the present invention is preferably about 15 to 35 ° C., the applied voltage is 50 to 400 volts, and the application time is
The coating may be performed under conditions of about 30 seconds to 10 minutes.

The coated product thus obtained is baked at a temperature of about 100 to 180 ° C. for about 10 to 30 minutes in a state of being washed with water or after being washed with water, so that it is resistant to exposure contamination and acid. A coated article having a cured coating film having excellent durability such as raininess can be obtained.

[0374]

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 [Preparation Example of Compound (D)] In a reaction vessel equipped with a thermometer, a reflux condenser, a stirrer, a dropping funnel and a nitrogen introducing tube, burnock DN-980S [Dainippon Ink and Chemicals, Inc. Non-yellowing polyisocyanate resin, isocyanate group content = 20.7%, active ingredient = 100%], 57.4 parts of ethylene glycol monoethyl ether acetate (EGMA), and 1 of dibutyltin diacetate Then, the temperature was raised to 80 ° C. under nitrogen gas flow. Then, 47.2 parts of methyl ethyl ketoxime was added to 3 parts while stirring at the same temperature.
It was dropped in 0 minutes. Next, the reaction was continued at the same temperature for 10 hours until the isocyanate group was completely reacted, to obtain a solution of a blocked isocyanate having a nonvolatile content (hereinafter abbreviated as NV) of 70.0%. Hereinafter, this is abbreviated as compound (D-1).

Reference Example 2 [Preparation Example of Compound (D)] In a reaction vessel similar to that of Reference Example 1, 700 parts of ethylene glycol monoethyl ether (EGME) was charged, and the temperature was raised to 80 ° C. while passing nitrogen gas. Warmed.

Then, at the same temperature, one of styrene (ST)
00 parts, 300 of methyl methacrylate (MMA)
Parts, 250 parts of n-butyl methacrylate (BMA)
100 parts of n-butyl acrylate (BA), 200 parts of N-butoxymethylacrylamide (BMAM) and 50 parts of acrylic acid (AA), 300 parts of EGME and tert-butyl peroxy-2-ethylhexanoate ( A mixture consisting of 50 parts of TBPO) was added dropwise over 4 hours.

After the completion of the dropwise addition, stirring was continued at the same temperature for 16 hours to obtain an NV of 51.5% and
A solution of a polymer having both a secondary amide group and a carboxyl group and having a number average molecular weight (hereinafter abbreviated as Mn) of 9,800 was obtained. Hereinafter, this is abbreviated as compound (D-2).

Reference Example 3 [Preparation Example of Polysiloxane (p)] In a reaction vessel similar to Reference Example 1, 2,428 parts of methyltrimethoxysilane (MTMS) was charged, and the temperature was raised to 80 ° C. At the same temperature, a mixture of 0.3 part of "AP-3" (trade name of isopropyl acid phosphate, manufactured by Daihachi Chemical Industry Co., Ltd.) and 354 parts of deionized water was applied for about 1 hour. And dropped.

After completion of the dropwise addition, stirring was carried out at the same temperature for 4 hours, and then methanol (MEO) was distilled off under reduced pressure.
By removing H), the content of methoxy groups becomes about 35
%, The target polysiloxane (partial hydrolysis condensate of MTMS) having Mn of 1,000 was obtained. Hereinafter, this is abbreviated as polysiloxane (p-1).

Reference Example 4 [Preparation Example of Polysiloxane (p)] In a reaction vessel similar to Reference Example 1, 2,201 parts of MTMS and 475 of phenyltrimethoxysilane (PTMS) were placed.
And heated to 80 ° C., and then at the same temperature,
A mixture of 0.3 parts of "AP-3" and 368 parts of deionized water was added dropwise over about one hour.

After completion of the dropwise addition, stirring was carried out at the same temperature for 4 hours, and then the alcohols such as MEOH and isopropyl alcohol (IPA) were removed by distillation under reduced pressure. % And
The target polysiloxane having an Mn of 1,200 (M
Partial co-hydrolysis condensate of TMS and PTMS) was obtained.
Hereinafter, this is abbreviated as polysiloxane (p-2).

Example 1 In this example, an aqueous resin containing an anionic group (W-
The present invention relates to an electrodeposition paint prepared from 1).

An aqueous resin containing an anionic group (W-
470 parts of IPA was charged into the same reaction vessel as in Preparation Reference Example 1 of 1), and the temperature was raised to 80 ° C. under nitrogen gas flow.

Next, at the same temperature, 100 parts of ST, MM
300 copies of A, 327 copies of BMA, 186 copies of BA, 3
-Methacryloyloxypropyltrimethoxysilane (MPTMS) 30 parts, AA 57 parts, IPA 450
And a mixture of 50 parts of TBPO was added dropwise over 4 hours.

After the completion of the dropwise addition, stirring was continued at the same temperature for 16 hours to obtain an NV of 53.5% and
A solution of the target polymer having Mn of 11,900 and having both a carboxyl group and a trimethoxysilyl group was obtained. Less than,
This is abbreviated as polymer (b-1-1).

In the same reaction vessel as above, 46
7 parts and 402 parts of IPA were charged and heated to 80 ° C.

Then, at the same temperature, 4.0 of “AP-3” was obtained.
And 127 parts of deionized water were added dropwise over 5 minutes and stirred at the same temperature for 4 hours to prepare a hydrolysis-condensation product of PTMS. Nuclear magnetic resonance analysis of reaction products ( ¹ H-N
MR), it was confirmed that the hydrolysis of PTMS had progressed 100%.

Thereafter, the polymer (b-1-1) of 1,
300 parts were added and 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%.

Then, at the same temperature, triethylamine (T
A mixture of 56 parts of EA) and 1,437 parts of deionized water was dropped over 30 minutes, and then distilled under reduced pressure to obtain ME.
NV is 3 except for alcohols such as OH and IPA.
9.3% of the target aqueous resin was obtained. Hereinafter, this is abbreviated as aqueous resin (W-1-1).

Preparation of Mill Base 100 parts of aqueous resin (W-1-1), "Typek C
R-97 "[trade name of rutile-type titanium oxide manufactured by Ishihara Sangyo Co., Ltd.] and a mixture consisting of 91.7 parts of EGME and 87.3 parts of EGME were dispersed in a sand mill to obtain a pigment having a NV of 60% and a pigment weight concentration of 60%. (Hereinafter abbreviated as PWC) to give a white mill base with 70%. Hereinafter, this mill base is abbreviated as mill base (M-1).

Preparation of Electrodeposition Coating and Cured Coating A mixture consisting of 145.4 parts of the aqueous resin (W-1-1) and 71.4 parts of the mill base (M-1) was mixed with an NV of 10
% And dispersed in deionized water so that the PWC is 30%.
% Of a white electrodeposition paint was prepared. Using this paint, an electrodeposition coating was carried out under the conditions of a bath temperature of 25 ° C., an applied voltage of 150 volts, and an applied time of 3 minutes, using an alumite-treated aluminum plate as an anode. Next, the aluminum plate was sufficiently washed with water, and baked at 180 ° C. for 20 minutes to obtain a coated plate having a white cured coating film having a thickness of 22 μm. Table 1 shows the results of various performance evaluations of the cured film thus obtained.

Example 2

This example relates to an electrodeposition coating prepared from an aqueous resin (W-1) containing an anionic group.

Preparation of Electrodeposition Coating and Cured Coating Film 120 parts of the aqueous resin (W-1-1) prepared in Example 1, 71.4 parts of the mill base (M-1) and “D” as the component (D) A mixture comprising 10 parts of methyl silicate MS-51 [containing a methoxy group bonded to a silicon atom with a methyl silicate condensate manufactured by Mitsubishi Chemical Corporation]
Disperse in deionized water so that NV is 10%,
A white electrodeposition paint having a PWC of 30% was prepared. Using this paint, an alumite-treated aluminium plate was subjected to electrodeposition coating in the same manner as in Example 1. Next, the aluminum plate is sufficiently washed with water,
After baking for 20 minutes, a coated plate having a white cured coating film having a thickness of 20 μm was obtained. Table 1 shows the results of various performance evaluations of the cured film thus obtained.

Embodiment 3

This example relates to an electrodeposition coating prepared from an aqueous resin (W-1) containing an anionic group.

An aqueous resin containing an anionic group (W-
Preparation of 1) In a reaction vessel similar to that of Reference Example 1, 272 parts of PTMS, M
138 parts of TMS, 280 parts of cyclohexyltrimethoxysilane (CHTMS) and 1,034 parts of IPA were charged, and the temperature was raised to 80 ° C. under nitrogen gas flow.

Next, at the same temperature, 6.0 of “AP-3” was obtained.
Of ST and 203 parts of deionized water and 10 parts of ST
0 parts, MMA 300 parts, BMA 327 parts, BA 1
86 parts, 57 parts of AA and 30 parts of MPTMS and IP
A mixture consisting of 350 parts of A and 50 parts of TBPO was each added dropwise over 4 hours.

After 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 100% of the hydrolysis reaction of the trimethoxysilyl group derived from PTMS, MTMS, CHTMS and MPTMS had progressed.

Thereafter, at the same temperature, a mixture of 80 parts of TEA and 2,036 parts of deionized water was dropped 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 an NV of 40.0% was obtained. Hereinafter, this is abbreviated as aqueous resin (W-1-2).

Preparation of Mill Base 100 parts of aqueous resin (W-1-2), "Typek C
A mixture consisting of 93.3 parts of R-97 and 88.9 parts of EGME was dispersed in a sand mill to give an NV of 60%.
Thus, a white mill base having a PWC of 70% was obtained. Less than,
This mill base is abbreviated as mill base (M-2).

Preparation of Electrodeposition Paint and Cured Coating A mixture consisting of 142.9 parts of an aqueous resin (W-1-2) and 71.4 parts of a mill base (M-2) was mixed with an NV of 10
% In deionized water so that the PWC is 3%.
A 0% white electrodeposition paint was prepared. Except for using this paint, electrodeposition coating, washing with water and baking were performed in the same manner as in Example 1 to obtain a coated plate having a white cured coating film having a thickness of 22 μm. Table 1 shows the results of various performance evaluations of the cured film thus obtained.

Embodiment 5

This example relates to an electrodeposition paint prepared from an aqueous resin (W-1) containing an anionic group.

An aqueous resin containing an anionic group (W-
Preparation of 1) In a stainless steel autoclave having an internal volume of 3 liters, the inside of which was replaced with nitrogen gas, 920 parts of IPA, 68 parts of monobutyl maleate and 12 parts of vinyl acetate were added.
0 parts, 352 parts of ethyl vinyl ether, 60 parts of vinyl tris (β-methoxyethoxy) silane, and 50 parts of tert-butyl peroxypivalate as a polymerization initiator were charged.

Next, 400 parts of the liquefied and collected chlorotrifluoroethylene was injected into the flask. The reaction was allowed to continue for 15 hours at 60 ° C. with stirring, so that NV was 51.3% and Mn was 10,1.
Thus, a solution of the desired fluorocopolymer having both a carboxyl group and a trimethoxysilyl group was obtained. Hereinafter, this is abbreviated as (b-1-2).

In the same reaction vessel as in Reference Example 1, 354 parts of PTMS, 141 parts of MTMS, and 303 parts of IPA were placed.
Then, the temperature was raised to 80 ° C.

Subsequently, at the same temperature, 4.5 parts of “AP-3” and 152 parts of deionized water were added dropwise over 5 minutes, and the mixture was stirred at the same temperature for 4 hours. Later
^{By 1} H-NMR, it was confirmed that hydrolysis of PTMS and MTMS had progressed 100%.

Thereafter, the polymer (b-1-2) of 1,
377 parts were added, and the mixture was stirred at the same temperature for 4 hours to prepare a condensate of polysiloxane and polymer (b-1-2). When this condensate was analyzed by ¹ H-NMR, it was found that the hydrolysis of the trimethoxysilyl group contained in the polymer (b-1-2) had progressed 100%.

Subsequently, at the same temperature, a mixture of 26 parts of TEA and 1,424 parts of deionized water was added dropwise over 30 minutes, followed by vacuum distillation to remove alcohols such as MEOH and IPA. Thus, a target aqueous resin having an NV of 40.5% was obtained. Hereinafter, this is referred to as an aqueous resin (W-1-
Abbreviated as 3). Millbase 100 parts of prepared aqueous resin (W-1-3), "Typek C
A mixture consisting of 94.5 parts of "R-97" and 90 parts of EGME was dispersed in a sand mill to give an NV of 60%,
A white mill base with a WC of 70% was obtained. Hereinafter, this mill base is abbreviated as mill base (M-3).

Preparation of Electrodeposition Coating and Cured Coating A mixture consisting of 141.1 parts of an aqueous resin (W-1-3) and 71.4 parts of a mill base (M-3) was mixed with an NV of 10
% In deionized water so that the PWC is 3%.
A 0% white electrodeposition paint was prepared. Except for using this paint, electrodeposition coating, washing with water and baking were performed in the same manner as in Example 1 to obtain a coated plate having a white cured coating film having a thickness of 23 μm. Table 1 shows the results of various performance evaluations of the cured film thus obtained.

Example 5 [Electrodeposition paint containing cationic group]

This example relates to an electrodeposition paint prepared from an aqueous resin (W-1) containing a cationic group.

An aqueous resin containing a cationic group (W-
Preparation of 1) Into the same reaction vessel as in Reference Example 1, 2,2-dimethyl-3-
373 parts of hydroxypropyl-2,2-dimethyl-3-hydroxypropionate, 39 parts of N-methyldiethanolamine, 417 parts of EGMA and 0.44 part of dibutyltin dioctate were charged, and the mixture was blown with dry nitrogen gas. Then, the temperature was raised to 80 ° C.

Then, at the same temperature, a mixture of 519 parts of isophorone diisocyanate and 519 parts of EGMA 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 group concentration was almost reduced to the theoretical value.

Thereafter, at the same temperature, a mixture consisting of 64 parts of 3-aminopropyltrimethoxysilane and 64 parts of EGMA was added dropwise over 10 minutes. Stirring was performed for a while, and after confirming that the isocyanate group had disappeared by infrared absorption spectrum analysis, 50 parts of EGMA and 45 parts of IPA were confirmed.
By adding 0 parts, a solution of a polyurethane-based polymer having an amino group and a trimethoxysilyl group having an NV of 43.3% and an Mn of 5,400 was obtained. Hereinafter, this is abbreviated as polymer (b-1-3).

In the same reaction vessel as in Reference Example 1, 306 parts of MTMS and cyclohexylmethyldimethoxysilane (C
198 parts of HMDMS) and 572 parts of IPA were charged and heated to 80 ° C.

Then, at the same temperature, 5.3 of “AP-3”
And 178 parts of deionized water were added dropwise over 5 minutes and stirred at the same temperature for 4 hours.

Thereafter, the reaction mixture was analyzed by ¹ H-NMR, and it was confirmed that hydrolysis of MTMS and CHMDMS had progressed 100%.

Subsequently, the obtained polymer (b-1)
-3) was added thereto, and the mixture was stirred at 80 ° C. for 4 hours to give polysiloxane and polymer (b-
A condensate with 1-3) was prepared. This condensate, ¹ H-
NMR analysis revealed that hydrolysis of the trimethoxysilyl group contained in the polymer (b-1-3) had progressed 100%.

Subsequently, at the same temperature, a mixture of 19.1 parts of acetic acid and 1,411 parts of deionized water was added dropwise over 30 minutes, and then alcohols such as MEOH and IPA were distilled under reduced pressure. , The NV is 39.7
% Of the target aqueous resin. Hereinafter, this is abbreviated as aqueous resin (W-1-4).

Preparation of Mill Base 100 parts of aqueous resin (W-1-4), "Typek C
A mixture consisting of 92.6 parts of R-97 "and 88.2 parts of EGME was dispersed in a sand mill to give an NV of 60%.
Thus, a white mill base having a PWC of 70% was obtained. Less than,
This mill base is abbreviated as mill base (M-4).

Preparation of Electrodeposition Coating and Cured Coating A mixture comprising 143.9 parts of an aqueous resin (W-1-4) and 71.4 parts of a mill base (M-4) was mixed with an NV of 10
% In deionized water so that the PWC is 3%.
A 0% white electrodeposition paint was prepared. Using this paint, an electrodeposition coating was carried out under the conditions of a bath temperature of 25 ° C., an applied voltage of 150 volts, and an applied time of 3 minutes, using an alumite-treated aluminum plate as a cathode. Next, after sufficiently washing the aluminum plate with water, baking was performed at 140 ° C. for 20 minutes to obtain a coated plate having a white cured coating film having a thickness of 21 μm. Table 1 shows the results of various performance evaluations of the cured film thus obtained.

Embodiment 6

This example relates to an electrodeposition paint prepared from an aqueous resin (W-2) containing an anionic group.

A water-based resin containing an anionic group (W-
Preparation of Composite Resin (c-2) as Precursor of 2) 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.

Next, at the same temperature, 100 parts of ST, MM
300 copies of A, 277 copies of BMA, 186 copies of BA, 2
-50 of hydroxyethyl methacrylate (HEMA)
Parts, 30 parts of 3-methacryloyloxypropylmethyldiethoxysilane (MPMDE), 57 parts of AA, IP
A mixture consisting of 450 parts of A and 50 parts of TBPO was added dropwise over 4 hours.

After completion of the dropwise addition, stirring was continued at the same temperature for 10 hours to obtain an NV of 52.5% and
A solution of an acrylic polymer having a Mn of 10,800 and having a hydroxyl group, a carboxyl group, and a methyldiethoxysilyl group was obtained. Hereinafter, this is abbreviated as (b-2-1).

In the same reaction vessel as above, CHTMS 4
67 parts and 402 parts of IPA were charged and heated to 80 ° C.

Then, at the same temperature, 4.0 of “AP-3” was obtained.
And 127 parts of deionized water were added dropwise over 5 minutes and stirred at the same temperature for 4 hours to prepare a hydrolysis condensate of CHTMS. ¹ H-NMR analysis of the reaction product confirmed that the hydrolysis of CHTMS had progressed 100%.

Thereafter, the polymer (b-2-1) of 1,
300 parts were added and stirred at the same temperature for 4 hours to prepare a composite resin of polysiloxane and polymer (b-2-1). When this condensate was analyzed by ¹ H-NMR, it was found that hydrolysis of the methyldiethoxysilyl group contained in the polymer (b-2-1) had progressed 100%. Hereinafter, this composite resin is referred to as (c-2-
Abbreviated as 1).

An electrodeposition coating composition containing an aqueous resin (W-2)
100 parts of the prepared composite resin (c-2-1) and 7 parts of the compound (D-1) which is the blocked isocyanate prepared in Reference Example 1.
And a mixture consisting of 21.8 parts of "Taipec CR-93" was dispersed by a sand mill to obtain a white composition having a PWC of 30%.

Next, 100 parts of this white composition and TE
A mixture of 2.2 parts of A was dispersed in deionized water so that the NV became 10%, and a white electrodeposition paint containing an aqueous resin (W-2) having a PWC of 30% and a blocked isocyanate was obtained. Prepared. Except for using this paint, electrodeposition coating, washing with water and baking were performed in the same manner as in Example 1 to obtain a coated plate having a white cured coating film having a thickness of 23 μm. Table 1 shows the results of various performance evaluations of the cured film thus obtained.

Embodiment 7

The present example relates to an electrodeposition coating prepared from an aqueous resin (W-2) containing an anionic group.

The composite resin prepared in Example 6 (c-2-
100 parts of 1), 17.7 of the compound (D-2) which is an acrylic resin containing a secondary amide group prepared in Reference Example 2
And a mixture consisting of 23.6 parts of "Taipec CR-93" was dispersed with a sand mill to obtain a white composition having a PWC of 30%.

Next, 100 parts of this white composition and TE
A mixture of 2.5 parts of A was dispersed in deionized water so that the NV became 10%, and a white resin containing an aqueous resin (W-2) having a PWC of 30% and a compound (D-2) was obtained. An electrodeposition paint was prepared. Use this paint and at 150 ° C 2
Electrodeposition coating, washing with water, and baking were performed in the same manner as in Example 1 except that the baking conditions for 0 minutes were applied, to obtain a coated plate having a white cured coating film having a thickness of 22 μm. Table 1 shows the results of various performance evaluations of the cured film thus obtained.

Embodiment 8

The present example relates to an electrodeposition coating prepared from an aqueous resin (W-2) containing an anionic group.

The composite resin prepared in Example 6 (c-2-
11. 100 parts of 1), and “Watersol S-695” as a component (D) [trade name of an aqueous solution of methyl etherified methylol melamine resin manufactured by Dainippon Ink and Chemicals, NV = 66%]. 3 copies and "Taipec C
A mixture comprising 23.2 parts of R-93 "was dispersed by a sand mill to obtain a white composition having a PWC of 30%.

Next, 100 parts of this white composition and TE
A mixture of 2.1 parts of A was dispersed in deionized water so that the NV became 10%, and a white electrodeposition paint containing an aqueous resin (W-2) having a PWC of 30% and a melamine resin was obtained. Prepared. Electrodeposition coating, washing with water and baking were carried out in the same manner as in Example 1 except that this paint was used and baking conditions of 150 ° C. for 20 minutes were applied.
A coated plate having a μm white cured coating film was obtained. Table 1 shows the results of various performance evaluations of the cured film thus obtained.

Embodiment 9

This example relates to an electrodeposition coating prepared from an aqueous resin (W-2) containing an anionic group.

The aqueous resin containing an anionic group (W-
Preparation of Composite Resin (c-2) as Precursor of 2) 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.

Next, at the same temperature, 100 parts of ST, MM
300 copies of A, 227 copies of BMA, 186 copies of BA, B
50 parts of MAM, 30 parts of MPMDE, 57 parts of AA,
A mixture consisting of 450 parts of IPA and 50 parts of TBPO was added dropwise over 4 hours.

After the completion of the dropwise addition, stirring was continued at the same temperature for 10 hours to obtain an NV of 52.0% and
A solution of an acrylic polymer having a secondary amide group, a carboxyl group, and a methyldiethoxysilyl group having a Mn of 11,500 was obtained. Hereinafter, this is abbreviated as (b-2-2).

467 parts of CHTMS, 402 of IPA
Parts, 4.0 parts of "AP-3" and 127 parts of deionized water
In the same manner as in Example 6, a hydrolyzed condensate of CHTMS was prepared.

Thereafter, 1,1 of the polymer (b-2-2)
300 parts were added and stirred at the same temperature for 4 hours to prepare a composite resin of polysiloxane and polymer (b-2-2). When this condensate was analyzed by ¹ H-NMR, it was found that hydrolysis of the methyldiethoxysilyl group contained in the polymer (b-2-2) had progressed 100%. Hereinafter, this composite resin is abbreviated as (c-2-2).

An electrodeposition paint and a water-based resin (W-2) containing
Preparation of cured coating film A mixture consisting of 100 parts of the composite resin (c-2-2) and 19.7 parts of "Taipec CR-93" was dispersed in a sand mill to obtain a white composition having a PWC of 30%. Was.

Next, 100 parts of this white composition and TE
A mixture of 2.3 parts of A was dispersed in deionized water so that the NV became 10% to prepare a white electrodeposition paint containing an aqueous resin (W-2) having a PWC of 30%. Electropainting, rinsing and baking were performed in the same manner as in Example 1 except that this paint was used and baking conditions of 150 ° C. for 20 minutes were applied, and a white cured coating film having a thickness of 23 μm was obtained. A painted plate was obtained. Table 1 shows the results of various performance evaluations of the cured film thus obtained.

Example 10 In this example, an aqueous resin containing an anionic group (W-
The present invention relates to an electrodeposition paint prepared from 3).

Preparation of Aqueous Resin (W-3) In the same reaction vessel as in Reference Example 1, propylene glycol-
124 parts of n-propyl ether (PNP) and IPA
Of 186 parts, and the temperature was raised to 80 ° C. while passing nitrogen gas.

Next, at the same temperature, 100 parts of ST, MM
A 300 parts, BMA 274 parts, BA 186 parts, M
30 parts of PTMS and 110 parts of AA, 31 parts of PNP
A mixture of 0 parts and 50 parts of TBPO was added dropwise over 4 hours.

After the completion of the dropwise addition, stirring was continued at the same temperature for 16 hours to obtain an NV of 55.9%, and
A solution of an acrylic polymer having a Mn of 12,300 and having both a carboxyl group and a trimethoxysilyl group was obtained.
Hereinafter, this is abbreviated as polymer (b-3-1).

Subsequently, 354 parts of PTMS and 310 parts of IPA were charged into the same reaction vessel as in Reference Example 1, and the temperature was raised to 80 ° C. Then, at the same temperature, "AP-
A mixture of 2.9 parts of "3" and 96 parts of deionized water,
It was added dropwise over 5 minutes and stirred at the same temperature for 4 hours to prepare a hydrolysis-condensation product of PTMS.

After that, the reaction mixture was analyzed by ¹ H-NMR, and the hydrolysis of PTMS was 100%.
I confirmed that it was progressing.

Further, 660 parts of the polymer (b-3-1) was added to the hydrolyzed condensate, and the mixture was stirred at the same temperature for 4 hours to obtain a polysiloxane obtained from PTMS. , A condensation reaction with the polymer (b-3-1) is carried out, and then, at the same temperature, 62 parts of TEA is added dropwise over 5 minutes while stirring to neutralize the carboxyl group, thereby obtaining a complex. A resin was prepared. Hereinafter, this is abbreviated as composite resin (C-3-1).

The composite resin thus obtained was analyzed by ¹ H-NMR to find that the polymer (b-3-1)
The hydrolysis of the trimethoxysilyl group contained in it,
It turned out that it was progressing 100%.

[0460] 1,189 parts of the composite resin (C-3-1) and 5 of the polysiloxane (p-1) prepared in Reference Example 3
05 parts were mixed at room temperature, and then 1,317 parts of deionized water was added dropwise to the obtained mixture over 30 minutes, and then alcohols such as MEOH and IPA were removed by distillation under reduced pressure. As a result, a target aqueous resin having an NV of 40.2% was obtained. Hereinafter, this is referred to as an aqueous resin (W-
Abbreviated as 3-1).

Preparation of Electrodeposition Paint and Cured Coating 100 parts of water-based resin (W-3-1)
A mixture consisting of 17.2 parts of "-93" and 74.1 parts of EGME was dispersed by a sand mill, and the NV was 10%.
Was diluted with deionized water to obtain a white electrodeposition paint having a PWC of 30%.

Next, using this paint, and
Electrodeposition, washing with water and baking were carried out in the same manner as in Example 1 except that the baking conditions at 20 ° C. for 20 minutes were applied.
A coated plate having a white cured coating film having a thickness of 23 μm was obtained. Table 1 shows the results of various performance evaluations of the cured film thus obtained.

Embodiment 11

This example relates to an electrodeposition paint prepared from an aqueous resin (W-3) containing an anionic group.

Preparation of Aqueous Resin (W-3) In a reaction vessel similar to that of Reference Example 1, 354 parts of PTMS and 310 parts of PNP were charged, and the temperature was raised to 80 ° C. A mixture of 2.9 parts of "-3" and 96 parts of deionized water was added dropwise over 5 minutes, and stirred at the same temperature for 4 hours to prepare a hydrolysis-condensation product of PTMS. . ^The reaction mixture was analyzed by ¹ H-NMR, and it was confirmed that hydrolysis of PTMS had progressed 100%.

Subsequently, 784 parts of the polymer (b-1-2) prepared in Example 4 was added thereto, and the mixture was stirred at the same temperature for 4 hours to give PT.
A polysiloxane obtained from MS and a polymer (b-1-
The condensation reaction with 2) was carried out, and then, at the same temperature, 15 parts of TEA was added dropwise over 5 minutes while stirring to neutralize the carboxyl group, thereby preparing a composite resin. Hereinafter, this is abbreviated as composite resin (C-3-2).

The composite resin thus obtained was subjected to ¹ H-NM
Analysis by R revealed that the hydrolysis of the trimethoxysilyl group contained in the polymer (b-1-2) had progressed 100%.

[0469] 1,562 parts of the composite resin (C-3-2) and the polysiloxane (p-
505 parts of 1) were mixed at room temperature, and 1500 parts of deionized water was added dropwise to the obtained mixture over 30 minutes, and then alcohols such as MEOH and IPA were distilled under reduced pressure. , The NV is 40.1
% Of the target aqueous resin. Hereinafter, this is abbreviated as aqueous resin (W-3-2).

Preparation of Electrodeposition Coating and Cured Coating 100 parts of aqueous resin (W-3-2)
A mixture consisting of 17.2 parts of "-93" and 73.8 parts of EGME was dispersed in a sand mill, and the NV was 10%.
Was diluted with deionized water to obtain a white electrodeposition paint having a PWC of 30%.

Next, using this paint, and
Electrodeposition, washing with water and baking were carried out in the same manner as in Example 1 except that the baking conditions at 20 ° C for 20 minutes were applied.
A coated plate having a white cured coating film having a thickness of 21 μm was obtained. Table 1 shows the results of various performance evaluations of the cured film thus obtained.

Example 12

This example relates to an electrodeposition paint prepared from an aqueous resin (W-3) containing an anionic group.

Preparation of Aqueous Resin (W-3) In a similar reaction vessel as in Reference Example 1, 1,467 of CHTMS was added.
Parts, 124 parts of PNP and 186 parts of IPA were charged, and the temperature was raised to 80 ° C. under nitrogen gas flow.

Next, at the same temperature, 100 parts of ST, MM
300 parts of A, 279 parts of BMA, 186 parts of BA and 135 parts of AA, 310 parts of PNP 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 2 hours, and then, at the same temperature, a mixture of 11.6 parts of "AP-3" and 388 parts of deionized water was added for 5 minutes. , Followed by stirring at the same temperature for 18 hours.

Then, at the same temperature, 140 parts of TEA
A composite resin was prepared by neutralizing the carboxyl group by dropping over 5 minutes. Hereinafter, this is abbreviated as composite resin (C-3-3). This composite resin is referred to as ¹ H-N
Analysis by MR confirmed that 100% of the hydrolysis reaction of the trimethoxysilyl group derived from CHTMS and TBPOTMS bound to the acrylic resin had progressed.

[0477] 842 parts of the composite resin (C-3-3) and 586 parts of the polysiloxane (p-2) prepared in Reference Example 4 were mixed at room temperature, and then the resulting mixture was deionized. After dropping 1,211 parts of water over 30 minutes and removing methanol and alcohols such as IPA by vacuum distillation, NV becomes 40.2%.
The desired aqueous resin was obtained. Hereinafter, this is referred to as an aqueous resin (W-3-
Abbreviated as 3).

Preparation of electrodeposition paint and cured coating film 100 parts of water-based resin (W-3-3)
A mixture consisting of 17.2 parts of "-93" and 74.1 parts of EGME was dispersed by a sand mill, and the NV was 10%.
Was diluted with deionized water to obtain a white electrodeposition paint having a PWC of 30%.

Next, using this paint, and
Electrodeposition, washing with water and baking were carried out in the same manner as in Example 1 except that the baking conditions at 20 ° C. for 20 minutes were applied.
A coated plate having a white cured coating film having a thickness of 23 μm was obtained. Table 1 shows the results of various performance evaluations of the cured film thus obtained.

Embodiment 13

This example relates to an electrodeposition paint prepared from an aqueous resin (W-4) containing an anionic group.

Preparation of Aqueous Resin (W-4) In a reaction vessel similar to that of Reference Example 1, 884 parts of PTMS, P
124 parts of NP and 186 parts of IPA were charged, and the temperature was raised to 80 ° C. while passing nitrogen gas.

Next, at the same temperature, 100 parts of ST, MM
A 300 parts, BMA 224 parts, BA 186 parts, A
A 110 parts, HEMA 50 parts, MPTMS 30
A mixture of parts, 310 parts of PNP and 50 parts of TBPO was added dropwise over 4 hours.

After completion of the dropwise addition, the mixture was stirred at the same temperature for 2 hours, and then, at the same temperature, a mixture of 7.2 parts of "AP-3" and 241 parts of deionized water was added for 5 minutes. , Followed by stirring at the same temperature for 18 hours. Then, at the same temperature, 154 parts of TEA was added dropwise over 5 minutes to neutralize the carboxyl groups, thereby obtaining a composite resin. This is hereinafter referred to as a composite resin (C
-4-1).

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

[0486] 1,182 parts of the composite resin (C-4-1) and the polysiloxane (p-
505 parts of 1) were mixed at room temperature, and 1,317 parts of deionized water was added dropwise to the obtained mixture over 30 minutes, and then MEOH and IPA were distilled under reduced pressure.
NV is 40.
2% of the target aqueous resin was obtained. Hereinafter, this is referred to as an aqueous resin (W-4-1).

Preparation of Electrodeposition Paint and Cured Coating Film 100 parts of aqueous resin (W-4-1), 4.7 parts of compound (D-1) prepared in Reference Example 1, 83.7 parts of EGME, A white paint obtained by dispersing a mixture consisting of 18.6 parts of “Typek CR-97” with a sand mill
Dispersed in 13 parts of deionized water, NV is 10% and P
A white electrodeposition paint having a WC of 30% was prepared.

Then, electrodeposition coating, washing with water and baking were carried out in the same manner as in Example 1 except that this coating material was used to obtain a coated plate having a white cured coating film having a thickness of 22 μm. Table 1 shows the results of various performance evaluations of the cured film thus obtained.

Embodiment 14

This example relates to an electrodeposition paint prepared from an aqueous resin (W-4) containing an anionic group.

The aqueous resin prepared in Example 13 (W-4-
100 parts of 1), 1 of "Watersol S-695"
0.8 parts, 94.2 parts of EGME and "Taipek
A white paint obtained by dispersing a mixture consisting of 20.3 parts of "CR-97" with a sand mill was dispersed in 471 parts of deionized water to obtain a white electrodeposition paint having an NV of 10% and a PWC of 30%. Prepared.

Next, using this paint, and
Electrodeposition, washing with water and baking were carried out in the same manner as in Example 1 except that the baking conditions at 20 ° C. for 20 minutes were applied.
A coated plate having a white cured coating film having a thickness of 22 μm was obtained. Table 1 shows the results of various performance evaluations of the cured film thus obtained.

Embodiment 15

This example relates to an electrodeposition paint prepared from an aqueous resin (W-4) containing an anionic group.

Preparation of Aqueous Resin (W-4) In a reaction vessel similar to that of Reference Example 1, 884 parts of PTMS, P
124 parts of NP and 186 parts of IPA were charged, and the temperature was raised to 80 ° C. while passing nitrogen gas.

Next, at the same temperature, 100 parts of ST, MM
A 300 parts, BMA 174 parts, BA 186 parts, A
A 110 parts, BMAM 100 parts, MPTMS 30
A mixture of parts, 310 parts of PNP and 50 parts of TBPO was added dropwise over 4 hours.

After completion of the dropwise addition, the mixture was stirred at the same temperature for 2 hours, and then, at the same temperature, a mixture of 7.2 parts of "AP-3" and 241 parts of deionized water was added for 5 minutes. , Followed by stirring at the same temperature for 10 hours. Then, at the same temperature, 154 parts of TEA was added dropwise over 5 minutes to neutralize the carboxyl groups, thereby obtaining a composite resin. This is hereinafter referred to as a composite resin (C
-4-2).

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

[0499] 1,182 parts of the composite resin (C-4-2) and the polysiloxane (p-
505 parts of 1) were mixed at room temperature, and 1,317 parts of deionized water was added dropwise to the obtained mixture over 30 minutes, and then MEOH and IPA were distilled under reduced pressure.
NV is 40.
5% of the target aqueous resin was obtained. Hereinafter, this is abbreviated as aqueous resin (W-4-2).

Preparation of electrodeposition paint and cured film 100 parts of aqueous resin (W-4-2), 75.
A mixture consisting of 9 parts and 17.4 parts of "Taipec CR-97" was dispersed in a sand mill, and the white paint obtained was dispersed in 386 parts of deionized water to give an NV of 10%.
A white electrodeposition paint having a PWC of 30% was prepared.

Next, using this paint, and
Electrodeposition, washing with water and baking were carried out in the same manner as in Example 1 except that the baking conditions at 20 ° C. for 20 minutes were applied.
A coated plate having a white cured coating film having a thickness of 22 μm was obtained. Table 1 shows the results of various performance evaluations of the cured film thus obtained.

Embodiment 16

This example relates to an electrodeposition paint prepared from an aqueous resin (W-4) containing a cationic group.

Preparation of Aqueous Resin (W-4) In a reaction vessel similar to that in Reference Example 1, 377 parts of methylphenyldimethoxysilane (MPDMS), 388 parts of cyclohexylmethyldimethoxysilane (CHMDMS), P
124 parts of NP and 186 parts of IPA were charged, and the temperature was raised to 80 ° C. under nitrogen gas ventilation.

Next, at the same temperature, 100 parts of ST, MM
200 copies of A, 194 copies of BMA, 186 copies of BA, 2
240 parts of dimethylaminoethyl methacrylate, H
50 parts of EMA, 30 parts of MPTMS, 310 parts of PNP
Part and 5 of azobisisobutyronitrile (AIBN)
A mixture of 0 parts was added dropwise over 4 hours.

After completion of the dropwise addition, the mixture was stirred at the same temperature for 2 hours, and then, at the same temperature, a mixture of 6.7 parts of "AP-3" and 223 parts of deionized water was added. The mixture was added dropwise over a period of minutes, followed by stirring at the same temperature for 18 hours.

Next, at the same temperature, 83 parts of acetic acid was added dropwise over 5 minutes to neutralize the tertiary amino group, thereby obtaining a composite resin. Hereinafter, this is abbreviated as composite resin (C-4-3). When this composite resin was analyzed by ¹ H-NMR, the hydrolysis of the trimethoxysilyl group derived from MPDMS, CHMDMS and MPTMS was 100%.
It was confirmed that it was progressing.

[0509] 1,106 parts of the composite resin (C-4-3) and the polysiloxane (p-
505 parts of 1) were mixed at room temperature. Then, 1,324 parts of deionized water was added dropwise to the obtained mixture over 30 minutes, and then MEOH and IPA were distilled under reduced pressure.
NV is 40.
4% of the target aqueous resin was obtained. Hereinafter, this is abbreviated as aqueous resin (W-4-3).

100 parts of aqueous resin (W-4-3), 4 parts of compound (D-1) prepared in Reference Example 1, 8 parts of EGME
3.7 parts and 18.6 of "Taipek CR-97"
Parts of a mixture obtained by dispersing a mixture consisting of 3 parts by a sand mill and dispersing the mixture in 413 parts of deionized water.
A white electrodeposition paint having a PWC of 30% at 0% was prepared.

Next, electrodeposition coating, washing with water and baking were carried out in the same manner as in Example 1 except that this paint was used and the alumite-treated aluminum plate as an object to be coated was used as a cathode, to give a film thickness of 22 μm. A coated plate having a white cured coating film was obtained. Table 1 shows the results of various performance evaluations of the cured film thus obtained. Comparative Example 1

The present comparative example relates to an acrylic resin-based electrodeposition paint prepared from an aqueous resin containing an anionic group.

As a vinyl monomer, 100 parts of ST,
300 copies of MMA, 307 copies of BMA, 186 copies of BA
Parts, 50 parts of HEMA and 57 parts of AA, except that the acrylic polymer (b-2-
As in the case of the preparation of 1), the NV was 52.7%,
In addition, a solution of an acrylic polymer having a hydroxyl group and a carboxyl group and having Mn of 11,800 was obtained. Hereinafter, this is abbreviated as polymer (R-1).

100 parts of the polymer (R-1), the compound (D-) which is a blocked isocyanate prepared in Reference Example 1
9.9 parts of 1) and 2 of "Taipek CR-93"
The mixture consisting of 5.5 parts was dispersed in a sand mill to obtain a PWC.
Was 30%.

Then, 100 parts of this white composition and TE
A mixture of 3.8 parts of A was dispersed in deionized water so that the NV became 10% to prepare a white electrodeposition paint containing a comparative acrylic resin having a PWC of 30% and a blocked isocyanate. . Other than using this paint,
Electrodeposition coating, water washing and baking were performed in the same manner as in Example 6 to obtain a coated plate having a white cured coating film having a thickness of 21 μm. Table 1 shows the results of various performance evaluations of the cured film thus obtained.

Comparative Example 2

[0516] The present comparative example relates to an acrylic resin-based electrodeposition paint prepared from an aqueous resin containing an anionic group.

[0517] 1 of the polymer (R-1) prepared in Comparative Example 1
A mixture consisting of 00 parts, 14.1 parts of "Watersol S-695" and 26.6 parts of "Taipec CR-93" was dispersed by a sand mill to obtain a white composition having a PWC of 30%.

Then, 100 parts of this white composition and TE
A mixture of 3.6 parts of A was dispersed in deionized water so that the NV became 10% to prepare a white electrodeposition paint containing a comparative acrylic resin and a melamine resin having a PWC of 30%. . Except for using this paint, electrodeposition coating, washing with water and baking were performed in the same manner as in Example 8 to obtain a coated plate having a white cured coating film having a thickness of 22 μm. Table 1 shows the results of various performance evaluations of the cured film thus obtained.

Comparative Example 3

This comparative example relates to an acrylic resin-based electrodeposition coating prepared from an aqueous resin containing a cationic group.

Preparation of Aqueous Resin (W-4) In a reaction vessel similar to that of Reference Example 1, 500 parts of PNP, IP
A at 200 ° C. under nitrogen gas ventilation.
The temperature rose.

Then, at the same temperature, 100 parts of ST, MM
200 parts of A, 224 parts of BMA, 186 parts of BA, 2
240 parts of dimethylaminoethyl methacrylate, H
50 parts of EMA, 300 parts of PNP and 5 parts of AIBN
A mixture of 0 parts was added dropwise over 4 hours.

After the completion of the dropwise addition, stirring was continued at the same temperature for 13 hours to obtain an NV of 50.2% and a Mn of 9,80.
A solution of an acrylic polymer containing a tertiary amino group and a hydroxyl group was obtained. Hereinafter, this polymer is abbreviated as (R-2).

100 parts of the polymer (R-2), the compound (D-) which is a blocked isocyanate prepared in Reference Example 1
9.9 parts of 1) and 2 of "Taipek CR-93"
A mixture consisting of 4.5 parts was dispersed in a sand mill to obtain a PWC.
Was 30%.

Next, a mixture of 100 parts of this white composition and 3.4 parts of acetic acid was dispersed in deionized water so that the NV became 10%, and a comparative acrylic resin having a PWC of 30% was used. And a white electrodeposition coating composition containing the isocyanate and a blocked isocyanate. Except for using this paint, electrodeposition coating, washing with water and baking were carried out in the same manner as in Example 16 to obtain a coated plate having a white cured coating film having a thickness of 21 μm. Table 1 shows the results of various performance evaluations of the cured film thus obtained.

[0526]

[Table 1]

<< Footnotes in Table 1 >>"Weatherresistance": measured by Sunshine Weatherometer
After 3,000 hours of exposure, 6
The gloss value, which is the 0-degree specular reflectance (%), is divided by the same gloss value of the coating film at the time of non-exposure, and is divided by 100.
This is a value obtained by multiplying (gloss retention:%). The larger the value, the better the weather resistance.

"Stain resistance": The color difference (ΔE) between the unwashed coating film after exposure for two months outdoors and the coating film without exposure was displayed. The closer the value is to zero, the better the stain resistance.

[0529] "Acid resistance": This test is performed as a substitute test for "acid rain resistance", and 0.1 ml of a 10% sulfuric acid aqueous solution is placed on the surface of each cured coating film. After the test plate was held under the following conditions, the surface of the coating film was washed with water and dried, and the state of the surface was visually evaluated and judged. The criteria for evaluation at that time are as follows.

Holding condition A: Hold at 25 ° C. for 1 day Holding condition B: Hold in a hot-air dryer at 60 ° C. for 30 minutes

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

[0532]

[Table 2]

[0533]

[Table 3]

[0534]

[Table 4]

[0535]

The electrodeposition paint of the present invention obtained as described above gives a cured coating film having extremely excellent durability such as gloss retention, exposure stain resistance and acid rain resistance. It is extremely practical for coating metals used in various outdoor applications such as building materials.

Claims (17)

[Claims] 1. An aqueous resin containing an anionic group or a cationic group, which comprises a polysiloxane (A) and a polymer (B) other than the polysiloxane, and is made aqueous.
An electrodeposition paint comprising (W) as an essential component. 2. The electrodeposition paint according to claim 1, further comprising a compound (D) having a functional group that reacts with a functional group contained in the aqueous resin (W) as an essential component. 3. The polysiloxane segment (A-1) wherein the aqueous resin (W) has a hydrolyzable group bonded to a silicon atom and / or a hydroxyl group bonded to a silicon atom.
And an aqueous resin obtained by dispersing or dissolving a composite resin (C-1) composed of a polymer segment (B-1) having a hydrophilic group as an anionic group or a cationic group in an aqueous medium ( The electrodeposition paint according to claim 1, wherein the composition is W-1). 4. The polysiloxane segment (A-1) wherein the aqueous resin (W) has a hydrolyzable group bonded to a silicon atom and / or a hydroxyl group bonded to a silicon atom.
And a hydrophilic group such as an anionic group or a cationic group, a hydrophilic group, a hydrolyzable group bonded to a silicon atom, and a hydroxyl group bonded to a silicon atom. Polymer segment (B-
Aqueous resin (W-) obtained by dispersing or dissolving the composite resin (C-2) composed of
The electrodeposition paint according to claim 1, wherein the composition is 2). 5. The aqueous resin (W) has a silicon atom having an aryl group or a cycloalkyl group and a hydrolyzable group bonded together and / or a silicon atom having an aryl group or a cycloalkyl group and a hydroxyl group bonded together. A composite resin (C-3) composed of a polysiloxane segment (A-2), a polymer segment (B-1) having a hydrophilic group such as an anionic group or a cationic group, and water bonded to a silicon atom An aqueous resin (W) obtained by mixing a polysiloxane (p) having a decomposable group and / or a hydroxyl group bonded to a silicon atom, and, if necessary, condensing and then dispersing or dissolving in an aqueous medium. The electrodeposition paint according to claim 1, wherein the composition is -3). 6. The polysiloxane segment (A-2) wherein the aqueous resin (W) has a silicon atom having an aryl group and a hydrolyzable group bonded together and / or a silicon atom having an aryl group and a hydroxyl group bonded together. And a hydrophilic group such as an anionic group or a cationic group, a hydrophilic group, a hydrolyzable group bonded to a silicon atom, and a hydroxyl group bonded to a silicon atom. A composite resin (C-4) composed of a polymer segment (B-2) also having the following functional group; and a polysiloxane having a hydrolyzable group bonded to a silicon atom and / or a hydroxyl group bonded to a silicon atom. 3. An aqueous resin (W-4) obtained by mixing (p), further condensing, if necessary, and then dispersing or dissolving in an aqueous medium. The electrodeposition paint according to the above. 7. The polysiloxane segment (A)
-1) has the following structural formula (SI): (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. The electrodeposition coating composition according to claim 3, wherein the polysiloxane segment has a structure represented by a monovalent organic group) as an essential unit structure. 8. The polysiloxane (p) has the following structural formula (SI): (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. 7. A polysiloxane having a structure represented by a monovalent organic group) as an essential unit structure.
The electrodeposition paint according to the above. 9. The polymer segment (B-1) or (B-2) is a segment derived from a vinyl polymer and / or a polyurethane polymer. The electrodeposition paint according to the above. 10. A functional group other than the three types of the above-described hydrophilic group, which is an anionic group or a cationic group, a hydrolyzable group bonded to a silicon atom, and a hydroxyl group bonded to a silicon atom. Has a hydroxyl group bonded to a carbon atom, a blocked hydroxyl group, an epoxy group, a cyclocarbonate group,
A primary amide group, a secondary amide group, a carbamate group, and
The following structural formula (S-II) 7. It is at least one kind of functional group selected from the group consisting of functional groups represented by the following:
The electrodeposition paint according to the above. 11. The compound (D) having a functional group that reacts with a functional group contained in the aqueous resin is a compound having a hydroxyl group bonded to a silicon atom and / or a hydrolyzable group bonded to a silicon atom. At least one selected from the group consisting of a compound having both a blocked isocyanate group and a hydrolyzable group bonded to a silicon atom in the molecule, a blocked polyisocyanate compound, an amino resin, a primary or secondary amide group-containing compound, and a polyhydroxy compound. 3. The electrodeposition coating composition according to claim 2, which is one kind of compound. 12. The composite resin (C-1) has both a hydrolyzable group bonded to a silicon atom and / or a hydroxyl group bonded to a silicon atom and a polar group such as an acid group or a basic group. Composite resin (c-1) obtained by subjecting a polymer (b-1) to a condensation reaction with a polysiloxane (a-1) having a hydrolyzable group bonded to a silicon atom and / or a hydroxyl group bonded to a silicon atom 4. The electrodeposition coating composition according to claim 3, which is obtained by partially or completely neutralizing) with a basic compound or an acidic compound. 13. The composite resin (C-2) further comprises a hydrolyzable group bonded to a silicon atom and / or a hydroxyl group bonded to a silicon atom, and a polar group such as an acid group or a basic group. A polymer (b-2) having both a hydrolyzable group bonded to a silicon atom, a hydroxyl group bonded to a silicon atom, and a polar group. A composite resin (c-2) obtained by subjecting a polysiloxane (a-1) having a hydrolyzable group and / or a hydroxyl group bonded to a silicon atom to a condensation reaction is partially reacted with a basic compound or an acidic compound. The electrodeposition paint according to claim 4, wherein the paint is obtained by summing or completely neutralizing. 14. A hydrolyzable group bonded to a silicon atom, a hydroxyl group bonded to a silicon atom, and a polar group,
A functional group other than the three groups is a hydroxyl group bonded to a carbon atom, a blocked hydroxyl group, an epoxy group, a cyclocarbonate group, a primary amide group, a secondary amide, a carbamate group, and the following structural formula (S-II) ) 14. The electrodeposition coating composition according to claim 13, which is at least one kind of functional group selected from the group consisting of functional groups represented by 15. The polysiloxane segment (A-1) is a polysiloxane segment in which an aryl group and / or a cycloalkyl group is bonded to 10 mol% or more of all silicon atoms. The electrodeposition paint according to claim 3. 16. The electrodeposition according to claim 3, wherein the hydrolyzable group bonded to the silicon atom is an alkoxy group. paint. 17. A coated article coated with the electrodeposition coating composition according to claim 1. Description: