JPH11209693A - Process for forming coating film and article coated thereby - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a process for forming a coating film whereby a cured coating film excellent in so-called comprehensive durability, such as gloss retention, resistance to staining due to outdoor exposure, and acid and alkali resistance, and having very high image sharpness is obtd. SOLUTION: In this process, a curable clear coating compsn. contg., as an essential ingredient, a water-base resin obtd. by dispersing or dissolving a composite resin comprising a polysiloxane and a polymer other than a polysiloxane in water is applied to a substrate or a precoated substrate and is cured.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for forming a new and useful coating film and a coated article coated by the coating film forming method. More specifically, the present invention contains, as an essential component, an aqueous resin (A) obtained by dispersing or dissolving a composite resin composed of a polysiloxane and a polymer other than the polysiloxane in an aqueous medium, or In addition to the aqueous resin (A), a compound having a functional group that reacts with a functional group contained in the aqueous resin also contains, as an essential component, a curable clear coating, which is used as a top coating. In particular, the present invention relates to a novel and highly practical method for forming a coating film capable of forming a coating film having excellent so-called durability, such as gloss retention, exposure contamination resistance, and acid rain resistance. The present invention also relates to a coated article coated by such a method for forming a coating film.

The method of forming a coating film according to the present invention is particularly suitable for use as a top coat for automobiles or for repair painting of automobiles, as well as for painting exterior walls of buildings or painting of building materials. It is used for a purpose, and therefore, as a painted object, an object painted on various base materials such as an automobile, a building material, or an outer wall of a building is an object.

[0003]

2. Description of the Related Art In recent years, based on demands for global environmental protection and work environment improvement, water-curable water-curable resins containing a small amount of organic solvents have been volatilized into the atmosphere from conventional organic solvent-containing paints. It has become necessary to substitute a water-based paint based on a resin composition.

Heretofore, aqueous paints based on aqueous curable resin compositions include vinyl-based paints having both a basic group or an acid group and a so-called functional group such as a hydroxyl group bonded to a carbon atom. After neutralizing the polymer with an acidic compound or a basic compound, and then dispersing or dissolving in water, an aqueous resin and various curing agents such as an epoxy resin, an isocyanate resin or an amino resin are used. Aqueous curable resin (JP-A-4-35907)
No. 5, JP-A No. 6-1948, JP-A No. 8-51.
No. 000, EP-661320-A1) are widely used.

[0005] However, in such a method of forming a coating film in which an aqueous coating material based on an aqueous curable resin composition as hitherto used as a top coating material is used, the resulting cured coating film is obtained. Is inferior in so-called durability, such as gloss retention during exposure, exposure contamination resistance, and acid rain resistance, and cannot be applied to applications that require a high degree of durability. There's a problem.

[0006]

SUMMARY OF THE INVENTION However, the present inventors have enthusiastically started research to solve various problems in the conventional technology as described above.

[0007] Accordingly, the problem to be solved by the present invention is, among other things, an extremely practical method capable of forming a cured coating film having excellent durability such as gloss retention, exposure contamination resistance and acid rain resistance. Another object of the present invention is to provide a method for forming a coating film having a high coating quality, and a coated article coated by such a method for forming a coating.

[0008]

Means for Solving the Problems Accordingly, the present inventors have:
As a result of intensive studies, aiming at the problem to be solved by the invention as described above, a composite resin composed of a polysiloxane and a polymer other than the polysiloxane is dispersed or dissolved in an aqueous medium to obtain a composite resin. Aqueous resin (A)
Is contained as an essential component, or the water resin (A)
In addition, a compound having a functional group that reacts with the functional group contained in the aqueous resin (A) also contains as an essential component,
Curable clear paint,

It has been found that, when this is used as a topcoat, a hard coating film having excellent gloss retention, acid rain resistance, and resistance to exposure contamination and the like, and having extremely high sharpness is provided. It has been found that a coated article coated by such a method for forming a coating film is extremely excellent in various performances such as durability, and, consequently, the problem to be solved by the invention as described above is solved brilliantly. Now that the present invention has been completed, the present invention has been completed.

That is, the present invention basically provides a composite resin comprising a polysiloxane and a polymer other than the polysiloxane in an aqueous medium on a substrate or on a substrate on which a film has been formed in advance. A curable clear coating material (I) containing, as an essential component, an aqueous resin (A) obtained by being dispersed or dissolved in

Alternatively, an aqueous resin (A) obtained by dispersing or dissolving a composite resin comprising a polysiloxane and a polymer other than the polysiloxane in an aqueous medium, and a functional group contained in the aqueous resin (A) A curable clear coating material (I) containing, as an essential component, a compound having a functional group that reacts with a curable clear coating material (I), and then curing or coating the substrate, or a substrate on which a film has been formed in advance. On the base coat paint (II) containing a pigment and the above-mentioned curable clear paint (I) are successively applied, and then two layers of coating films formed from both paints are simultaneously applied. It is an object of the present invention to provide a method of forming a coating film which is dried or cured, in particular, can provide a cured coating film having excellent durability and the like, and is extremely practical.

Still another object of the present invention is to provide a coated product obtained by coating a base material or a base material on which a coating is formed in advance by the respective coating methods as described above.

Here, first, the above-mentioned curable clear coating material (I) used in carrying out the coating film forming method of the present invention is a composite resin composed of polysiloxane and a polymer other than polysiloxane. Aqueous resin obtained by dispersing or dissolving in an aqueous medium (A)
May be contained as an essential component,

Further, the aqueous resin (A) and the aqueous resin (A)
Some compounds also contain, as an essential component, a compound having a functional group that reacts with the functional group contained in the above.

More specifically, the water-soluble resin (A), which is an essential component of the curable clear coating (I), includes a hydrolyzable group bonded to a silicon atom and / or a hydroxyl group bonded to a silicon atom. And a polymer segment (B-) having at least one hydrophilic group selected from the group consisting of an anionic group, a cationic group, and a nonionic group for aqueous conversion. An aqueous resin (W-1) obtained by dispersing or dissolving the composite resin (C-1) composed of 1) in an aqueous medium;

Alternatively, the polysiloxane segment (A-1) is selected from the group consisting of an anionic group, a cationic group, and a nonionic group for aqueous conversion.
In addition to at least one type of hydrophilic group, the compound also has functional groups other than the three types of the hydrophilic group, a hydrolyzable group bonded to a silicon atom, and a hydroxyl group bonded to a silicon atom. An aqueous resin (W-2) obtained by dispersing or dissolving a composite resin (C-2) composed of a polymer segment (B-2) in an aqueous medium;

In addition, a polysiloxane segment (A-2) 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 a composite resin (C-3) composed of the polymer segment (B-1) described above, and a hydrolyzable group bonded to a silicon atom and / or a silicon atom for imparting room-temperature curability. An aqueous resin (W-3) obtained by mixing and, if necessary, condensing a polysiloxane (p) having a hydroxyl group, and then dispersing or dissolving in water.

Further, the above-mentioned polysiloxane segment (A-2) and the above-mentioned polymer segment (B-
The aqueous resin obtained by mixing the composite resin (C-4) composed of 2) and the above-mentioned polysiloxane (p), further condensing as necessary, and then dispersing or dissolving in water ( W-4).

Such 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 in the form of the following structural formula (S-I) or the following structural formula (S-
IV) can be employed, but from the viewpoint of providing a method for forming a cured coating film having excellent durability, it is particularly preferable to employ the bonding mode of the structural formula (SI).

[0020]

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). )

[0021]

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-II)

[0023]

Embedded image R ¹ (wherein R ¹ is at least one 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; A monovalent organic group of any kind.) As an essential unit structure, that is, a cured film having excellent durability should have a branched structure. It is particularly preferred in that it provides a method.

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 group is bonded from the viewpoint of the stability of the obtained aqueous resin.

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 above-mentioned 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.

When preparing the aqueous resin (W-3) or (W-4), the composite resin (C-3) which is a precursor thereof is used.
Or the ratio of the polysiloxane segment (A-2) and the polymer segment (B-1) or (B-2) constituting (C-4) is (A-2): (B-1). Alternatively, the weight ratio with (B-2) is about 1:99 to 95: 5, preferably 5:95 to 90:10, and more preferably 10:90 to 80: 2
What is necessary is just to set it to 0.

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.

The polymer segment (B-1) or (B-
If the weight ratio of 2) is set to be less than about 5%,
In any case, since the amount of the polysiloxane component is too large, the alkali resistance of the cured coating film formed by the method of the present invention is lowered or cracks are easily generated. On the other hand, the polymer segment (B-1) Or (B-
If the weight ratio of 2) is too large, exceeding about 95%, the cured coating film formed by the method of the present invention must have an anti-pollution property due to too little polysiloxane component. Either case is not preferable because durability such as gloss retention is reduced.

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 polysiloxane (p), and further polysiloxane (a-1) described later.
Alternatively, in (a-2), the polymer (b-
1), (b-2), (b-3) or (b-4)
The contained hydrolyzable group bonded to a silicon atom refers to a group that easily undergoes hydrolysis and is eliminated to form a hydroxyl group bonded to a silicon atom, that is, a silanol group. Examples thereof include an alkoxy group, a substituted alkoxy group, an acyloxy group, 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.

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

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 the basic group include a primary amino group, a secondary amino group, a tertiary amino group and a quaternary ammonium hydroxide group.

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

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

Furthermore, as a nonionic group contained in the polymer segment (B-1) or (B-2),
Examples of the polyether chain include various polyoxyalkylene chains such as a polyoxyethylene chain, a polyoxypropylene chain, and a polyoxybutylene chain, and the above-mentioned oxy groups such as a poly (oxyethylene-oxypropylene) chain. Various types such as a type in which an alkylene portion is randomly copolymerized, or a type in which different polyoxyalkylene chains such as a polyoxyethylene-polyoxypropylene chain are bonded in a block shape are exemplified.

As the hydrophilic group contained in the polymer segment (B-1) or (B-2), the aforementioned anionic group, cationic group or nonionic group may be used alone. However, it is also possible to use an anionic group or a cationic group in combination with a nonionic group.

The polymer segment (B-1) or (B-
2) In the case where such an anionic group or a cationic group is introduced as a hydrophilic group, the amount of the anionic group or the cationic group is defined as the number of moles of the anionic group or the cationic group per 1,000 g of the polymer segment. About 0.1 mol ~
A range of about 10 moles is suitable, and preferably
A range of 0.2 to 5 mol is appropriate, and most preferably a range of 0.3 to 3 mol.

In the case where only a polyether chain as a nonionic group is introduced as a hydrophilic group into the polymer segment (B-1) or (B-2), the amount to be introduced is as follows. Gram of polyether chains per 1,000 grams of
0 g is appropriate, and preferably 20 g.
A range of 〜900 grams is suitable, most preferably a range of 40-800 grams.

Further, when both an anionic group or a cationic group and a polyether chain as a nonionic group are introduced as hydrophilic groups into the polymer segment (B-1) or (B-2), It is preferable to introduce each of them within the above-mentioned range as the introduction amount when each is introduced alone.

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). [Hereinafter, it is also referred to as a functional group (Fu). ], Only a typical example is exemplified, and a hydroxyl group bonded to a carbon atom, a hydroxyl group bonded to a carbon atom and blocked (hereinafter also referred to as a blocked hydroxyl group), a carboxyl group, and a blocked Carboxyl group (hereinafter,
A carboxylic acid 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 And the following structural formula (S-III)

[0050]

Embedded image

And the like.

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

[0053]

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:

However, the polymer segment (B-
When 2) has a cationic group as a hydrophilic group,
Among such functional groups, an amino group such as a primary amino group, a secondary amino group or a tertiary amino group may be further introduced as a functional group (Fu) into the polymer segment (B-2). Absent.

When the polymer segment (B-2) has an anionic group as a hydrophilic group, a carboxyl group such as a carboxyl group, a block carboxyl group, or a carboxylic acid anhydride group or a carboxyl group among such functional groups. The functional group derived from the group is a functional group (F
As u), it is not further introduced into the polymer segment (B-2).

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

Among the above-mentioned functional groups (Fu), particularly preferred are a hydroxyl group bonded to a carbon atom, a blocked hydroxyl group, a tertiary amino group, a carboxyl group, a blocked carboxyl group, a carboxylic anhydride group, and a cyclocarbonate group. An epoxy group, a primary amide group, a secondary amide group, a carbamate group, or a functional group represented by the structural formula (S-III) described above.

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

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 (SI) 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-
Examples of the method for preparing 2) include (a) at least one polar group selected from the group consisting of a free acid group, a free basic group and a nonionic group, and a hydrolyzable group bonded to a silicon atom. And / or a polymer having both a hydroxyl group bonded to a silicon atom or a polar group and a hydrolyzable group bonded to a silicon atom and / or a hydroxyl group bonded to a silicon atom. A polymer containing a functional group other than an acid group (including a block acid group and an acid anhydride) or a basic group, and a hydrolyzable group bonded to a silicon atom and / or a hydroxyl group bonded to a silicon atom The polysiloxane (a-1) was reacted with a hydrolyzable group and / or a silicon atom bonded to a silicon atom contained in the polysiloxane (a-1) and each polymer described above. After forming a complex through a bond represented by the structural formula (SI) by a reaction between acid groups, the contained free acid group or free basic group is neutralized with a basic compound or an acidic compound. Method,

(B) at least one hydrophilic group selected from the group consisting of a neutralized acid group, a neutralized basic group and a nonionic group, and a hydrolyzable group and / or In addition to the polymer having both a hydroxyl group bonded to a silicon atom or a hydrophilic group and a hydrolyzable group bonded to a silicon atom and / or a hydroxyl group bonded to a silicon atom, the polymer also contains the functional group (Fu) described above. Is reacted with the above-mentioned polysiloxane (a-1) to form a hydrolyzable group and / or silicon bonded to a silicon atom contained in the polysiloxane (a-1) and each of the above-mentioned polymers. A method of forming a complex through a bond represented by the structural formula (SI) by a reaction between hydroxyl groups bonded to atoms,

(C) A compound having a radically polymerizable double bond, and the double bond and the polysiloxane being bonded in a bonding mode represented by the following structural formula (S-VI), Used as one of the polymerization components, and a vinyl monomer containing a free acid group, a vinyl monomer having a free basic group, and a vinyl monomer containing a nonionic group By copolymerizing a vinyl monomer containing at least one polar group selected from the group consisting of a vinyl monomer as an essential component, or a polysiloxane containing the double bond And a vinyl group monomer having a polar group, and a functional group (F
u) by copolymerizing with a vinyl monomer containing as an essential component a monomer containing a functional group other than an acid group (including a block acid group and an acid anhydride) or a basic group After the complexation, a method of neutralizing the contained free acid group or free basic group with a basic compound or an acidic compound,

[0066]

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 having a double bond as described above, a vinyl monomer having a neutralized acid group, a vinyl monomer having a neutralized basic group, and a nonion By copolymerizing vinyl monomers containing at least one hydrophilic vinyl monomer as an essential component selected from the group consisting of vinyl monomers containing a functional group, or In addition to the above-mentioned polysiloxane containing a double bond and the above-mentioned vinyl-based monomer having a hydrophilic group, a vinyl-based monomer containing, as an essential component, the above-mentioned monomer containing a functional group (Fu) There is a method of forming a complex by copolymerizing with monomers.

In the above methods (a) and (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)

[0070]

Embedded image

[0071] (wherein, R ⁴ in the formula is an alkyl group, a monovalent organic group such as an aryl group or an aralkyl group, R ⁵
Represents a hydrolyzable group such as a hydrogen atom, a halogen atom, an alkoxy group, a substituted alkoxy group, an acyloxy group, a phenoxy group, an aryloxy group, a mercapto group, an amino group, an amide group, an aminooxy group, an iminooxy group or an alkenyloxy group. And a is 0 or 1
Or, it is assumed to be an integer of 2. )

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

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

Among the aqueous resins (W-1) and (W-2), those having only an anionic group as a hydrophilic group are prepared by using the composite resin prepared by the method (a) as a precursor. Typical examples of the more specific method in the case of (1) are (1) a polymer (b-1) having both a hydrolyzable silyl group and an acid group or a hydrolyzable silyl group and an acid group. A polymer (b-2) containing a functional group other than an acid group among the functional groups (Fu), and a polysiloxane having a hydrolyzable group bonded to a silicon atom and / or a hydroxyl group bonded to a silicon atom Composite resin (c-1) or (c-2) obtained by subjecting (a-1) to a condensation reaction
Is partially neutralized or completely neutralized with a basic compound, and then dispersed or dissolved 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 neutralized or completely neutralized with a basic compound, and then dispersed or dissolved in an aqueous medium.

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

In the various methods (1) to (4) described above, the neutralized acid is introduced by neutralizing the acid group using a basic compound. Instead of using raw materials containing acid groups or polymers containing acid groups and basic compounds, use raw materials having neutralized acid groups or polymers having neutralized acid groups By doing so, the aqueous resin (W-1) or (W-2) containing an anionic group can be prepared.

The polymer (b-1) or (b-
Specific examples of the acid group introduced in 2) include, in addition to the above-mentioned various free acid groups,

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.
So-called blocked carboxyl groups and phosphoric acid groups, respectively, are easily converted into free acid groups such as silyl ester groups, tert-butyl ester groups or 1-alkoxyethyl ester groups. And a blocked acid group represented by an acid phosphate group, a phosphorous acid group or a sulfonic acid group.

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

The polymer (b-2) is introduced
Examples of the functional group other than the acid group in the functional group (Fu) include various groups exemplified as those which can be introduced into the polymer segment (B-2).

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

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

Further, the polysiloxane (a
The step of compounding -1) with the polymer (b-1) or (b-2) is preferably performed in a medium containing an organic solvent having an alcoholic hydroxyl group as an essential component.

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, and the resulting complex resin Gelation and the like in the neutralization step are likely to occur, and it is necessary to pay sufficient attention.

In particular, when such complexing 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.

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

Next, the above-mentioned various composite resins (c-1)
The preparation method of (c-8) will be described in detail.

First, when preparing the composite resins (c-1) to (c-8), the polymer (b-1) or (b-2) as described above is prepared. Typical examples of the polymer include various kinds of polymers similar to those described above for the polymer segment (B-1) or (B-2). Among them, particularly preferred is vinyl. Examples of the vinyl polymer include an acrylic polymer and a fluoroolefin-based polymer.

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

Of these various vinyl polymers,
(C-1), (c-3), (c-5) or (c-7)
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, among the various vinyl polymers, (c-2), (c-4), (c-6) or (c-
In order to prepare (b-2) which is a precursor of 8), for example, (v) a vinyl monomer (m) having a functional group other than an acid group among the functional groups (Fu) described above (m -4) and 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);
Other monomers copolymerizable with these monomers (m-
3) and the 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-based polymer having three kinds of functional groups prepared in advance, namely, an acid group, a functional group other than the acid group among the functional groups (Fu), and a hydroxyl group bonded to a carbon atom. For the coalescence, various known and commonly used methods, such as a method of reacting various isocyanate group-containing silane compounds such as 3-isocyanatopropyltriethoxysilane, can be applied, but from the viewpoint of simplicity. Of these, the methods (v) to (vii) are particularly preferable.

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

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

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

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

Further, (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 group-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 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-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) includes, as the functional group other than the acid group in the functional group (Fu), a hydroxyl group bonded to a carbon atom, a block hydroxyl group,
Various functional groups such as a primary amino group, a cyclocarbonate group, an epoxy group, a primary amide group, a secondary amide, a carbamate group, and a functional group represented by the structural formula (S-III) are introduced.

When a functional group other than an acid group among the functional groups (Fu) is introduced by each of the above-mentioned methods (v) to (vii), various vinyl monomers containing such a functional group are introduced. (M-4) is used. Among them, if only a particularly typical example of a hydroxyl group-containing vinyl monomer bonded to a carbon atom is given,

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

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

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

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

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

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

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

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

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

Of the vinyl monomers (m-4), only typical examples of epoxy group-containing vinyl monomers are given as examples. Glycidyl (meth) acrylate, methylglycidyl (meth) Acrylate, 3,4-
Epoxycyclohexylmethyl (meth) acrylate,
Various compounds such as vinylcyclohexene oxide, glycidyl vinyl ether, methyl glycidyl vinyl ether or allyl glycidyl ether.

Of 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 typical ones as the carbamate group-containing vinyl monomers are 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.

Of the vinyl monomers (m-4), only typical examples of the vinyl monomers having a functional group represented by the structural formula (S-III) 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.

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

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

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

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

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

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

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

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

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

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

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

Various cyano group-containing monomers such as (meth) acrylonitrile or crotononitrile; various 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, cyclohexyl vinyl ether or 4-methylcyclohexyl vinyl ether;

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

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

As the polymerization initiator which can be used in applying the solution radical polymerization method, various known 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,
Benzoyl peroxide, lauroyl peroxide, acetyl peroxide,

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

As the organic solvent that can be used when applying the solution radical polymerization method, any of the 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 typical 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 ketones such as dimethoxyethane, tetrahydrofuran, dioxane, diisopropyl ether or di-n-butyl ether
Various ethers; various chlorinated hydrocarbons such as chloroform, methylene chloride, carbon tetrachloride, trichloroethane or tetrachloroethane;
Furthermore, N-methylpyrrolidone, dimethylformamide, dimethylacetamide, ethylene carbonate and the like are used.

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

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

By applying a known and commonly used solution radical polymerization method 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 and the like of the coating film formed by the method of the present invention are inevitably reduced, while the amount exceeds about 3 mol and becomes too large. In this case, the composite resins (c-1) to (c
In the preparation of -8), the viscosity of the reaction solution is increased, and there is a disadvantage that gelation occurs.

Accordingly, a hydrolyzable silyl group-containing monomer, a hydrolyzable silyl group-containing chain transfer agent or a hydrolyzable silyl group is introduced so that the above-mentioned preferable amount of hydrolyzable silyl group 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, of the vinyl monomer (m-4) having a functional group other than an acid group among the functional groups (Fu) to be introduced into the vinyl polymer (b-2) The copolymerization amount of at least one vinyl monomer is from about 0.1 to about 0.1 mol per mol of the functional group per 1,000 g of the solid content of the vinyl polymer (b-2). A suitable amount is within the range of 5 moles, and preferably is in the range of 0.
A range of 2 to 3 mol is appropriate, and even more preferably, a range of 0.3 to 2 mol is appropriate.

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 these vinyl polymers (b-1) or (b-2) is less than about 500, the mechanical properties of the cured coating film formed by the method of the present invention are inevitable. The strength becomes poor, while about 20
If it is too high exceeding 000, the appearance of the cured coating film formed by the method of the present invention is inevitably deteriorated.

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

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

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

Further, to prepare the polyurethane polymer of the polymer (b-2), the polyurethane polymer (b-1) is used as described above. In addition to various known and commonly used raw materials,
Various compounds having a functional group other than an acid group among the above functional groups (Fu) and having one or two groups having active hydrogen that reacts with an isocyanate group are used as raw material components. Various known and commonly used methods may be used.

The polyurethane polymer (b-2) has a functional group other than an acid group among the functional groups (Fu) used for preparing the polyurethane polymer (b-2), and has an active hydrogen which reacts with an isocyanate group. If only a typical compound having one or two groups is exemplified, 4
-Hydroxymethyl-1,3-dioxolan-2-one, glycidol, 2-hydroxyethyl carbamate or 2-hydroxypropyl carbamate,
Examples include compounds having both various functional groups and a hydroxyl group bonded to a carbon atom.

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 formed by the method of the present invention decrease, On the other hand, if the amount is more than about 3 mol, the solution viscosity at the time of the above-mentioned complexing reaction increases, and as a result, inconvenience such as causing gelation may be recognized. In either 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 tertiary amino group, a cyclocarbonate group, an epoxy group, a primary amide group, a secondary amide group, a carbamate group or a structural formula described above, each of which is to be introduced into a carbon atom. (S-II
The introduction amount of the functional group other than the acid group in the functional group (Fu) represented by the functional group represented by I),
1,000 of the solid content of the polyurethane polymer (b-2)
From about 0.1 to about 5 moles of functional groups per gram
Molar range is appropriate, preferably 0.2-3.
A mole range is appropriate, and even more preferably, a range of 0.3 to 2 moles is appropriate.

The polyurethane polymer (b-1) or (b-2) has a number average molecular weight of about 500 to 500.
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 cured film formed by the method of the present invention must have a mechanical strength. Becomes inferior, while about 10
If it exceeds 000 and becomes too high, the appearance of the cured coating film formed by the method of the present invention is inevitably deteriorated.

Hydroxyl groups bonded to silicon atoms and / or hydroxyl groups used in preparing the composite resins (c-1) to (c-8)
Alternatively, polysiloxane (a-1) having a hydrolyzable group bonded to a silicon atom refers to a hydroxyl group bonded to a silicon atom and / or a hydrolyzable group bonded to a silicon atom, which is generally called a silanol group. It refers to various polysiloxanes having a group, such as linear, branched or cyclic.

Among these various polysiloxanes, the curability of the curable clear coating material (I) used in carrying out the method of forming a coating film of the present invention and the curability of the cured coating film formed by the method of the present invention are also described. From the viewpoint of excellent durability, a polysiloxane having a branched structure or a cyclic structure having the structure represented by the structural formula (S-II) as an essential unit structure as described above is particularly preferable.

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.

[0179]

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

(Wherein R ⁶ in the formula is 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
Compounds having three or more hydrolyzable groups bonded to silicon atoms in one molecule, such as SiCH ₂ CH ₂ CH ₂ Si (OCH ₂ CH ₃ ) ₃ .

As the silicon 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, methyltriethoxysilane, methyltri-n-butoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, ethyltri-n-butoxysilane, n-propyltrimethoxysilane, n-propyltriethoxysilane , N-butyltrimethoxysilane or n-butyltriethoxysilane,

Cyclopentyltrimethoxysilane, cyclopentyltriethoxysilane, cyclohexyltrimethoxysilane, cyclohexyltriethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, phenyltri-n-butoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane , Vinyltri-n-butoxysilane, 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.

Of 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,
Dimethyldi-n-butoxysilane, diethyldimethoxysilane, diethyldiethoxysilane, di-n-propyldimethoxysilane, di-n-propyldiethoxysilane, di-n-butyldimethoxysilane or di-n-
Butyldiethoxysilane,

Diphenyldimethoxysilane, diphenyldiethoxysilane, diphenyldi-n-butoxysilane, methylphenyldimethoxysilane, methylphenyldiethoxysilane, cyclopentylmethyldimethoxysilane, cyclopentylmethyldiethoxysilane, cyclohexylmethyldimethoxysilane, cyclohexylmethyldiphenyl Ethoxysilane, vinylmethyldimethoxysilane,
Two hydrolyzable groups bonded to a silicon atom in one molecule, such as 2- (methyldimethoxysilyl) ethyl vinyl ether, 3- (methyldimethoxysilyl) propyl vinyl ether or 3- (meth) acryloyloxypropylmethyldimethoxysilane A so-called bifunctional silicon compound;

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.

Here, when 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.

Examples of such catalysts include only typical ones, such as hydrochloric acid, sulfuric acid or phosphoric acid.
Various inorganic acids; various organic acids such as p-toluenesulfonic acid, monoisopropyl phosphate or acetic acid;

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

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

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

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

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

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

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

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

When the amount is less than 0.05 mol, the rate of hydrolysis is remarkably slowed down, which is not preferable in practical use. However, when 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, are successively performed.
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 this 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 above-mentioned polysiloxanes, from the viewpoint of the stability of the aqueous resin (W-1) or (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.

Further, the aqueous resin (W-1) or (W-
From the viewpoint of the curability of the curable clear coating material (I) containing 2) as an essential component and the durability of the cured coating film formed by the method of the present invention, the polysiloxane (a-1) is constituted. 10% by mole or more, preferably 20% by mole or more, more preferably 30% by mole or more of all silicon atoms to be formed are methyltrialkoxysilanes, methyltrichlorosilane, cyclohexyltrialkoxysilanes, cyclohexyltrichlorosilane, phenyl 3 such as trialkoxylans or phenyltrichlorosilane
It is appropriate to use one derived from a functional silane compound.

Next, of the aqueous resin (W-1) or (W-2), which is an essential component of the curable clear coating composition (I) used in carrying out the method for forming a coating film of the present invention. The above-mentioned methods (1) to (4), which are methods of preparing an anionic group as a hydrophilic group, will be described in detail.

First, the above-mentioned method (1) means that the polymer (b-1) or (b-2) and the polysiloxane (a-1) are subjected to a condensation reaction to form a complex. And preparing the composite resin (c-1) or (c-2), and then partially or completely neutralizing the acid group contained in the composite resin with a basic compound.

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

(1) The amount of the catalyst used when the composite is formed 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.

In the case where the catalyst used in the process of preparing the polysiloxane (a-1) remains in (a-1), (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 for 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.

[0222] When the amount is less than about 0.05 mol, the rate of hydrolysis is liable to be remarkably reduced.

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;

When there is no hydrolyzable group bonded to a silicon atom in (a-1), 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., 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), various basic compounds can be used, but only typical ones among them can be used. Methylamine, dimethylamine, trimethylamine, ethylamine, diethylamine, triethylamine, n-butylamine, tri-n-butylamine,
Various organic amine compounds represented by 2-amino-2-methylpropanol, 2-aminoethanol or 2-dimethylaminoethanol;

Or various inorganic basic substances represented by sodium, potassium hydroxide and the like, including ammonia; and tetramethylammonium hydroxide, tetra-n-
Various quaternary ammonium hydroxides represented by butylammonium hydroxide, trimethylbenzylammonium hydroxide, and the like.

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

The amount of the basic compound added is at least as large as the amount 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 (a-1) with each of the polymers (b-1) or (b-2)” 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, and the reaction can be carried out under any conditions of normal pressure, increased pressure or reduced pressure.

Next, the above-mentioned method (2) refers to a method in the presence of the above-mentioned polymer (b-1) or (b-2).
In the course of carrying out the reaction for preparing the polysiloxane (a-1), the (b-1) or (b-2) and (a-1) are subjected to a condensation reaction to form a composite, thereby forming a composite resin (c
-3) or (c-4), and then the acid groups contained in the composite resin are partially or completely neutralized with a basic compound.

In preparing the composite resin (c-3) or (c-4) by the method (2), a silicon compound having at least three hydrolyzable groups bonded to silicon atoms in one molecule May be used for promoting the hydrolysis and condensation of silicon compounds containing as an essential component, or may not be used, but at the same time, the hydrolysis reaction of the silicon compounds proceeds rapidly. It is desirable to use a catalyst from the viewpoint of smoothly progressing the condensation reaction between the resulting (a-1) and (b-1) or (b-2).

As such a catalyst, the aforementioned (a-1)
The ones exemplified as usable in the preparation of can be used.

As the amount of the catalyst used, (a-1)
About 0.000001 based on the silicon compound
To about 10% by weight, preferably 0.000%.
The range of 005 to 5% by weight is particularly preferably 0.0 to 5% by weight.
The range of 001 to 1% by weight is appropriate.

Further, in preparing the composite resin by the method (2), the hydrolysis reaction of the silicon compound as the raw material of (a-1) was allowed to proceed smoothly, and the produced (a-
In order for the condensation reaction between 1) and (b-1) or (b-2) to proceed smoothly, the reaction is usually carried out in the form of adding water. The amount of water added at that time depends on the polymer (b
-1) or the total amount of the hydrolyzable group contained in the hydrolyzable silyl group bonded to (b-2) and the hydrolyzable group present in the silicon compound and bonded to the silicon atom. About 0.05 mol or more, preferably 0.1 mol or more, and more preferably 0.5 mol or more are suitable for 1 mol of the above.

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

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

Further, the reaction conditions for preparing the composite resin by the method (2) and the method of adding the catalyst and water may be the same as those employed in the preparation of the above (a-1). .

In the method (2), as the neutralizing basic compound, various compounds exemplified as those usable in the method (1) can be used.

In this method, the reaction conditions for the neutralization reaction, such as the amount of the basic compound used, are the same as those in the method (1).

Next, the above-mentioned method (3) is a reaction for preparing the above-mentioned polymer (b-1) or (b-2) in the presence of the above-mentioned polysiloxane (a-1). In the process, the polymer (b-1) or (b-2) and (a)
-1) to form a complex by a condensation reaction with
In this method, the composite resin (c-5) or (c-6) is prepared, and then the acid groups contained in the composite resin are partially or completely neutralized with a basic compound.

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

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

When the catalyst used in the process of preparing the polysiloxane (a-1) remains in (a-1) in the same manner as in the above (1), particularly, Can be used to promote the condensation reaction only with the catalyst remaining in (a-1).

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

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

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

Further, in the method (3), the partial or complete neutralization reaction of the acid group in the composite resin (c-5) or (c-6), which is performed subsequent to the condensation reaction, is as described above. Although various basic compounds described in the method (1) can be used as they are, it is particularly preferable to use ammonia or organic amines.

The amount of the basic compound or the acidic compound to be added and the reaction conditions for the neutralization in the neutralization are in accordance with the method (1).

Furthermore, the method (4) is the same as the reaction for preparing the polymer (b-1) or (b-2) and the reaction for preparing the polysiloxane (a-1) in the same manner. In the process performed in parallel in the reaction system, (b-1)
Alternatively, (b-2) and (a-1) are condensed to form a composite, and the composite resin (c-7) or (c-
8), and then partially or completely neutralize the acid groups contained in the composite resin with a basic compound, wherein the complexation reaction and the neutralization reaction are as described in (1) to (9) above. (3) The method may be performed according to the method described in (3).

In preparing each of the composite resins (c-1) to (c-8) by the methods (1) to (4), the polymer (b-1) or (b-2) and the polymer The ratio of the siloxane (a-1) to the polymer segment (B
The ratio between (-1) or (B-2) and the polysiloxane segment (A-1) may be set so as to fall within the above-described preferred range.

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

Further, the methods (1) to (4)
In preparing each of the composite resins (c-1) to (c-8), the total concentration of each component is determined by the respective concentrations of the composite resins (c-1) to (c-8) produced by the reaction. ,
It is desirable to set the concentration at the end of the complexing reaction to about 5% by weight or more, preferably 10% by weight or more, and more preferably 20% by weight or more.

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

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

The thus obtained composite resin (c-
By dispersing or dissolving the respective partially or completely neutralized products of 1) to (c-8) in water, only the anionic group of the aqueous resin (W-1) or (W-2) becomes hydrophilic. A type having a functional group is prepared.

From each of the composite resins (c-1) to (c-8) or the completely neutralized product, the aqueous resin (W-1)
Alternatively, in order to prepare (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 a mixture of water and a water-soluble organic solvent. The desired aqueous resin (W-1) or (W-2) can be prepared by dispersing or dissolving in an aqueous medium by adding the compound to the aqueous medium.

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, the aqueous resin (W-3) or (W-4), which is an essential component of the curable clear coating composition (I) used in carrying out the method for forming a coating film of the present invention, is used. The preparation method 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 (SI) will be described.

The composite resin (C-3) or (C-
Examples of the method for preparing 4) include (e) a hydrolyzable group bonded to a silicon atom and at least one polar group selected from the group consisting of a free acid group, a free basic group and a nonionic group; And / or a polymer having a hydroxyl group bonded to a silicon atom, or a polar group, a hydrolyzable group bonded to a silicon atom and / or a hydroxyl group bonded to a silicon atom, A polymer containing a functional group other than a group or a basic group, and 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 Is reacted with the polysiloxane (a-2) having an atom to bond to the polysiloxane (a-2) and the silicon atom contained in each of the above polymers. Hydrolyzable group and / or structure by the reaction of hydroxyl groups with each other bonded to the silicon atom (S-
A method of forming a complex through the bond of I), and then neutralizing a free acid group or a free basic group contained therein with a basic compound or an acidic compound;

(F) At least one hydrophilic group selected from the group consisting of a neutralized acid group, a neutralized basic group and a nonionic group, and a hydrolyzable group and / or silicon bonded to a silicon atom A polymer having both a hydroxyl group bonded to an atom or a polymer containing the above-mentioned functional group (Fu) 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. The union is reacted with the above-mentioned polysiloxane (a-2) to form a hydrolyzable group and / or a silicon atom bonded to a silicon atom contained in the polysiloxane (a-2) and each of the above-mentioned polymers. A method of forming a complex through a bond of the structural formula (SI) by a reaction between the bonded hydroxyl groups,

(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 is used as one of the copolymerization components. And a vinyl monomer containing a free acid group,
Vinyl containing, as an essential component, a vinyl monomer having at least one polar group selected from the group consisting of a vinyl monomer having a free basic group and a vinyl monomer having a nonionic group Of the above-mentioned functional group (Fu) by copolymerizing a monomer with a monomer, or in addition to the above-mentioned polysiloxane having a double bond and a vinyl monomer having a polar group. After copolymerization with a vinyl monomer containing a monomer containing a functional group other than a group or a basic group as an essential component, to form a complex, the contained free acid group or free Neutralizing the basic group with a basic compound or an acidic compound,

(H) An aryl group having a radical 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 is used as one of the copolymerization components. And at least one selected from the group consisting of a vinyl monomer having a neutralized acid group, a vinyl monomer having a neutralized basic group, and a vinyl monomer having a nonionic group. By copolymerizing a vinyl monomer containing a kind of hydrophilic group-containing vinyl monomer as an essential component, or a polysiloxane containing the double bond. In addition to a vinyl monomer having a hydrophilic group and a vinyl monomer having a functional group (Fu) as an essential component in addition to a vinyl monomer having a hydrophilic group, There is a method to make it.

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.

Representative of the more specific method in the case where the type having only an anionic group as a hydrophilic group in the composite resin (C-3) or (C-4) is prepared by the above method (e). 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) which also contains a functional group other than an acid group in the group (Fu), and the polysiloxane (a-
Composite resin (c-9) obtained by subjecting 2) to a condensation reaction
Or a method of partially or completely neutralizing the acid group contained in (c-10) with a basic compound,

(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.

In the various methods (5) to (8) described above, the neutralized acid group is introduced by neutralizing the acid group using a basic compound. Instead of using raw materials containing acid groups or polymers containing acid groups and basic compounds, use raw materials having neutralized acid groups or polymers having neutralized acid groups By doing so, the composite resin (C-3) or (C-4) containing an anionic group can be prepared.

The polymer (b-3) or (b-
As the acid group introduced in 4), the acid group described above as used in the preparation of the aqueous resin (W-1) or (W-2),
Various acid groups and the like can be mentioned. Among them, particularly preferable ones are a carboxyl group, a block carboxyl group and a carboxylic anhydride group.

The functional group (Fu) other than the acid group introduced into the polymer (b-4) can be introduced into the polymer segment (B-2). Various examples are given as examples.

Next, the composite resins (c-9) to (c-16)
The method of preparing is described in detail.

First, the composite resins (c-9) to (c-16)
Is prepared as a precursor of the polymer (b-3) or (b-4). A typical example of such various polymers is a polymer segment (B-1). )
And various types similar to those described above for (B-2), and among them, particularly preferred are vinyl-based polymers and polyurethane-based polymers. Of these, acrylic polymers and fluoroolefin polymers are particularly desirable.

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

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

Then, among such vinyl polymers, the polymer (b-4) which is a precursor of the composite resin (c-10), (c-12), (c-14) or (c-16) Is prepared using the monomers, polymerization initiators and organic solvents exemplified as those used in the preparation of the polymer (b-1), and (v) to (viii). May be applied as it is, but from the viewpoint of simplicity, it is particularly preferable to apply each of the methods (v) to (vii).

Further, a hydrolyzable silyl group to be introduced into the vinyl polymer (b-3) or (b-4),
A functional group other than an acid group in the acid group or the functional group (Fu),
As each amount, the polymer (b-1) or (b-
What is necessary is just to follow the quantity introduce | transduced at the time of preparation of 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 polymers (b-3) and (b-4) is the same as the method for preparing the polyurethane polymer (b-1) or (b-2) described above. Applicable as it is.

Next, the composite resins (c-9) to (c-1)
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 6) ( a-2) will be described.

If only particularly typical examples of such polysiloxane (a-2) are given as examples, 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, the 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)

[0289]

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. It is selected from the group consisting of alkenyl groups and at least one monovalent organic group, R ¹⁰
Is a hydrogen atom, a halogen atom, an alkoxy group, a substituted alkoxy group, an acyloxy group, a phenoxy group, a mercapto group,
It represents a hydrolyzable group such as 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;

Alternatively,

[0293]

Embedded image

Or

[0295]

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. Examples of the silicon compound 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 compounds particularly desirable as compounds used in 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 various silicon compounds as described above 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).

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.

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

First, in order to prepare the composite resin (C-3) or (C-4) by the method (5), the polymer (b-1) or (b) is prepared by the method (1) described above. −
In place of 2), respectively, polymer (b-3) or (b)
(1) except that polysiloxane (a-2) is used in place of polysiloxane (a-1).
The reaction is carried out according to the following method to prepare a composite resin (c-9) or (c-10), and then the acid group contained in the composite resin is converted into a base in the same manner as in the method (1). Partial or complete neutralization may be carried out with a sex compound.

In order to prepare the composite resin (C-3) or (C-4) by the method (6), the polymer (b-1) or (b) may be prepared by the method (2).
The polymer (b-3) or (b-4) is used instead of -2), and the polysiloxane (a-1) is used.
The reaction was carried out according to the method (2) except that the reaction for preparing polysiloxane (a-2) was carried out instead of the reaction for preparing the compound (c-2) to prepare the composite resin (c-11) or (c-12). Then, similarly to the method (1), the acid group contained in the composite resin may be partially or completely neutralized with a basic compound.

In the method described in (7) above, the composite resin (C
To prepare (3) or (C-4), the above (3)
In this method, polysiloxane (a-2) is used in place of polysiloxane (a-1), and polymer (b-
The reaction is performed according to the method (2) except that the reaction for preparing the polymer (b-3) or (b-4) is performed instead of the reaction for preparing 1) or (b-2), respectively. Then, the composite resin (c-13) or (c-14) is prepared, and then the acid group contained in the composite resin is partially changed with a basic compound in the same manner as in the method (1). What is necessary is just to sum or to completely neutralize.

According to the method (8), the composite resin (C
To prepare (-3) or (C-4), the above (4)
A reaction for preparing a polysiloxane (a-2) in place of the polysiloxane (a-1), and
A method according to (4), except that the reaction for preparing the polymer (b-3) or (b-4) is performed instead of the reaction for preparing the polymer (b-1) or (b-2), respectively. To prepare a composite resin (c-15) or (c-16), and then convert the acid group contained in the composite resin to a basic compound in the same manner as in the method (1). Then, partial or complete neutralization may be performed.

The polymer (b-3) or (b-4) for preparing each of the composite resins (c-9) to (c-16) by the method (5) to (8), The ratio of use with the siloxane (a-2) depends on the 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 (7) or (8), conditions for preparing the polymer (b-3) or (b-4), or (b-3) or (b-4) The target properties of (b-3) or (b-4) must conform to the conditions or properties described above.

Further, among the methods (5) to (8),
In preparing the composite resins (c-9) to (c-16),
Organic solvents may or may not be used,
In order to easily perform stirring and the like, it is desirable to use various organic solvents as already listed as those that can be used in preparing the vinyl polymer (b-1).

In the methods (5) to (8), when preparing the composite resins (c-9) to (c-16), the total concentration of each component is adjusted by the composite resin (c- 9)
(C-16) to a concentration of about 5% by weight or more, preferably 1% at the end of the complexation reaction.
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, and 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 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. The aqueous resin (W-3) or (W-4) is prepared by dispersing or dissolving in water.

The polysiloxane (p) used at that time is the above-mentioned polysiloxane (a-1)
Alternatively, (a-2), furthermore, various types such as commercially available polysiloxanes can be used, and among these, a methyl group as an organic group such as methyltrialkoxysilane, methyltrichlorosilane or methyltriacetoxysilane can be used. That is prepared using a trifunctional silane compound having
Particularly preferred is the curability of the curable clear coating material (I) used when carrying out the method for forming a coating film of the present invention, and the durability of the cured coating film formed by the method of the present invention. .

In the polysiloxane (p), the proportion of silicon atoms derived from trifunctional silane having a methyl group bonded to all silicon atoms is preferably at least 20 mol%, and more preferably at least 30 mol%. The above is more preferred, and the proportion is more preferably 50 mol% or more.

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) or by dispersing or dissolving a condensation reaction product in a form in which a hydrolyzable group bonded to a silicon atom and / or a part of a hydroxyl group bonded to a silicon atom in (C-4) is partially dehydrated. And an aqueous resin (W-3) or (W-4).

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) Various known methods can be applied.
For example, adding water or a mixture of water and a water-soluble organic solvent to the mixture or the condensation reaction product,
Alternatively, by adding the mixture or the condensation reaction product to water or a mixture of water and a water-soluble organic solvent and dispersing or dissolving in an aqueous medium,
The desired aqueous resin (W-3) or (W-4) can be produced.

If necessary, the organic solvent contained in the aqueous resin (W-3) or (W-4) thus prepared may be partially or completely removed by heating and / or reduced pressure. The aqueous resin (W-3) or (W-4) having a low organic solvent content or containing no organic solvent can be prepared.

As described above, the aqueous resins (W-1) to (W-4) containing an anionic group can be prepared. In the various methods (1) to (8) described above, By introducing a basic group instead of an acid group into the polymers (b-1) to (b-4), and using an acidic compound as a neutralizing agent instead of the basic compound, Aqueous resins (W-1) to (W-4) containing a functional group can be prepared.

Further, in the various methods (1) to (8) described above, a nonionic polyether chain is introduced as a hydrophilic group in place of the neutralized acid group, thereby obtaining a nonionic group. Aqueous resin containing functional group (W-1)
~ (W-4) can be prepared.

Further, by combining the above-described method of preparing an aqueous resin containing an anionic group or a cationic group with the method of introducing a nonionic group, it is possible to combine an anionic group or a cationic group with a nonionic group. Can be prepared.

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, As a functional group other than these, a hydroxyl group bonded to a carbon atom, 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 derived from the composite resin (C-2) It is at least one kind of a functional group (Fu) as shown by (S-III).

The functional groups contained in the aqueous resin (W-4) include the composite resin (C-4) and the 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) , A hydroxyl group bonded to a carbon atom, a block hydroxyl group, a cyclocarbonate group,
It is at least one of an epoxy group, a primary amide group, a secondary amide group, a carbamate group and a functional group (Fu) represented by the structural formula (S-III).

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.

The aqueous resin (W-2) or (W-
When preparing 4), a blocked acid group or acid anhydride group was used as the functional group (Fu) in the polymer segment (B-
When it is intended to introduce in 2), at least a part of the blocked acid group or acid anhydride group is
In the step of synthesizing the composite resin (C-2) or (C-4), and further in the step of dispersing or dissolving the same in water, free acid groups are produced by hydrolysis, thermal decomposition or alcoholysis. May be converted to

Further, the aqueous resin (W-2) or (W-
In preparing 4), when a block hydroxyl group, epoxy group or cyclocarbonate group is to be introduced as a functional group (Fu) into the polymer segment (B-2),
At the stage of synthesizing 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 may be hydrolyzed or subjected to alcoholysis. May be converted to a free hydroxyl group.

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 water-based resin (W-
In order to prepare a curable clear coating material (I) to be used in performing the method for forming a coating film of the present invention from each of 1) to (W-4), one of (W- 1)-(W-
Each of 4) may be a self-curing clear coating containing each of (W-1) to (W-4) as an essential component from a place having self-curing property by itself,

In the 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-
What is necessary is just to set it as the hardening clear coating which also utilizes the crosslinking reaction between the functional group contained in each of 1)-(W-4) and the functional group contained in compound (D).

The compound (D) used in the preparation of the latter type of the curable clear coating material (I) is contained in each of the above-mentioned aqueous resins (W-1) to (W-4). It refers to various known and commonly used compounds having at least one functional group that reacts with the various functional groups as described above, and only typical representative examples of such functional groups may be used. , Isocyanate group, blocked isocyanate group, hydroxyl group bonded to carbon atom, blocked hydroxyl group, carboxyl group, blocked carboxyl group, carboxylic anhydride group, amino group, cyclocarbonate group, chain carbonate group, epoxy group, primary amide Group, secondary amide group, carbamate group, oxazoline group, N-hydroxymethylamino group, N-alkoxymethylamino group, Group, acetoacetyl group, a silanol group, a hydrolyzable group or the following structural formula bonded to the silicon atom (S-V)

[0336]

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

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

And the like.

The functional group contained in the compound (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, carboxyl group-epoxy group, carboxyl group-cyclocarbonate group, tertiary amino group-epoxy group, hydroxyl group bonded to carbon atom-N-hydroxymethylamino group, Hydroxyl group bonded to carbon atom-
It is an isocyanate group or a hydroxyl-blocked isocyanate group bonded to a carbon atom.

As the compound (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. When a compound having two or more functional groups described above is used as the compound (D), it is particularly convenient to use a vinyl polymer as the compound (D). It is.

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

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

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

If only one of the above-mentioned compounds having an isocyanate group and a hydrolyzable group bonded to a silicon atom in one molecule is specifically exemplified, only compounds which are particularly typical are described below.

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

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

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

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

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

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

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

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

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

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

Various prepolymers having an isocyanurate ring, which are obtained by cyclotrimerizing various polyisocyanates as described above;

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

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

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

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

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

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

The compounds include a class of compounds in which isocyanate groups are regenerated by heat, such as compounds having various uretdione structures obtained by cyclodimerization of isocyanate groups.

[0364] Particularly, only typical representative blocking agents used for preparing the blocked polyisocyanate compound are exemplified by methanol,
Various alcohols such as ethanol, benzyl alcohol or lactate;

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

Alternatively, various oximes such as acetone oxime or methyl ethyl ketoxime, and various active methylene compounds such as methyl acetoacetate, ethyl acetoacetate or acetylacetone may be used.

[0367] Only the typical examples of the above-mentioned polyepoxy compounds are exemplified, and ethylene glycol, hexanediol, neopentyl glycol,
Polyglycidyl ethers of various aliphatic or cycloaliphatic polyols, such as trimethylolpropane, trimethylolethane, glycerin, pentaerythritol, sorbitol or hydrogenated bisphenol A;

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

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

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

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

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

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

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

Subsequently, if only typical examples of the above-mentioned amino resin 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, the functional group used for preparing the above-mentioned vinyl polymer (b-2) may be used. As a part of the vinyl monomer (m-4) containing the group (Fu), various vinyl monomers having a primary or secondary amide group as exemplified above alone may be used. Polymer

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.

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

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

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

As the above-mentioned polyhydroxy compounds, only typical ones are exemplified. 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),
As already exemplified, homopolymers of various vinyl monomers having a hydroxyl group bonded to a carbon atom

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

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

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

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 the compound (D) itself is a vinyl polymer, it is also suitable to use it as an emulsion polymer.

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

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

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

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

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

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

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

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

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

The amount of the carboxyl group contained in the compound (D) is in the range of about 0.2 to about 5.0 equivalents, preferably in the range of 0.5 to 3.0 equivalents, more preferably
What is necessary is just to mix the said compound (D) so that it may become in the range of 0.7-2 equivalents.

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

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

The curable clear coating composition (I) further includes:
A curing catalyst, a flow regulator, a dye, a leveling agent, a rheology control agent, an ultraviolet absorber, an antioxidant or a plasticizer, etc., in a form in which various known and commonly used additives are also compounded. Can be used.

Of the above-mentioned additives, only those which are particularly typical as curing catalysts are exemplified, and those which are used for the preparation of the polysiloxane (a-1) as described above are already used. Various catalysts as described above can be used, and in addition to these compounds, tetramethylphosphonium salt, tetraethylphosphonium salt, tetrapropylphosphonium salt, tetrabutylphosphonium salt, trimethyl (2-hydroxyl It is also possible to use various compounds such as propyl) phosphonium salts, triphenylphosphonium salts or benzylphosphonium salts having various anions as a counter anion, such as, for example, fluoride, chloride, bromide or carboxylate. I can do it.

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

When each of the aqueous resins (W-1) to (W-4) has only a nonionic group as a hydrophilic group, crosslinking by condensation of silanol groups is very slow at room temperature. Therefore, in order to crosslink such a resin at room temperature by condensation of silanol groups, it is preferable to add a curing catalyst as described above.

[0404] The curable clear coating composition (I) which contains each of the aqueous resins (W-1) to (W-4) as an essential component and is used when the method of forming a coating film of the present invention is carried out. When a curing catalyst is added, the amount of the curing catalyst to be added is in the range of 0.01 to 15 parts by weight, preferably 0.05 to 15 parts by weight, based on 100 parts by weight of the total amount of the resin solids contained. It is appropriate to set it in the range of 10 to 10 parts by weight, particularly preferably in the range of 0.1 to 5 parts by weight.

[0405] Among such additives, the addition of an ultraviolet absorber and / or an antioxidant is, inter alia,
This is extremely effective in further improving the durability such as gloss retention of the cured coating film.

Examples of the above-mentioned ultraviolet absorbers which are particularly typical ones include various known and commonly used compounds such as benzotriazole-based compounds, hydroxybenzophenone-based compounds and oxalic anilide-based compounds. Of these, any compound can be used.

The UV absorber may be added in an amount of about 0.1 to about 3% by weight of the total solid content of the film-forming components contained in the curable clear coating composition (I). That is, about 0.1 to about 3% may be sufficient based on the total solid weight of the film-forming components contained in each clear paint.

In addition, if only typical representative examples of the above-mentioned antioxidants are given, only 2,2,6,6
Having a tetramethylpiperidine ring, various hindered amine-based compounds, hindered phenol compounds, and the like, various known and commonly used compounds, and any of these compounds may be used. I can do it.

[0409] The amount of the antioxidant added is
It may be about 0.1 to about 3% of the total solid weight of the film-forming components contained in the curable clear coating composition (I). That is,
About 0.1 to about 3% based on the total solid weight of the film-forming components contained in each curable clear coating,
That's what it means.

The curable clear coating material (I) may contain no pigment or may contain, if necessary, about 3% by weight of the total solid content of the film-forming components as long as the clearness of the coating film is not impaired. %, And a so-called color clear paint in a form containing less than 10% of a pigment.

[0411] If only typical pigments are used as examples of the color clear paint used in preparing such a color clear paint, carbon black and the like, and further, phthalocyanine blue, phthalocyanine. Like green or quinacridone red,
Various known and commonly used organic pigments are used.

The curable clear coating composition (I) thus obtained, which is used in carrying out the method for forming a coating film according to the present invention, contains (D) the presence or absence of a component, the presence or absence of a curing catalyst, or the presence or absence of a curing catalyst. The curing conditions vary depending on the type, but are dried at room temperature for 1 to 14 days,
Baking for about 30 seconds to about 3 hours, preferably for about 30 seconds to 1 hour in a temperature range of about 250 ° C. to about 250 ° C., to obtain a highly practical cured coating film. Can be done.

[0413] In the present invention, as the substrate used as the substrate, there are various well-known and commonly used substrates. If only typical ones are exemplified as such substrates, iron, stainless steel or the like can be used. Various metals such as steel or aluminum; polyethylene, polycarbonate, polypropylene, polymethyl methacrylate,
Various plastics such as ABS resin or polystyrene; and various inorganic materials such as glass, slate plate or concrete, silicates such as calcium silicate, gypsum, asbestos or ceramics. Things.

[0414] These various substrates are each in the form of a plate,
Such as spherical, film-like, sheet-like or large structures or complex shaped assemblies or moldings,
It is to be used in various forms depending on various applications, and in particular, the restrictions are

[0415] Here, the substrate on which a film is formed in advance, which is used as one of the objects to be coated, refers to a crosslinked or non-crosslinked organic paint or inorganic paint.
It refers to various substrates such that at least one paint is applied to form a crosslinked film or a thermoplastic film.

[0416] If only typical examples of organic paints used when preparing a substrate on which a film has been formed in advance are mentioned, only the typical ones used in the method of the present invention may be used. Containing resins (W-1) to (W-4) as essential components, or each of these,
Including coatings containing compound (D) as an essential component,

Acrylic-urethane, chlorinated polyolefin-modified acrylic-urethane, acrylic-melamine, acrylic-epoxy, alkyd-melamine, alkyd-urethane, polyester-melamine, polyester-urethane, epoxy-melamine Various cross-linkable paints such as epoxy-based, epoxy-polyamide-based, epoxy-urethane-based or polyurethane-melamine-based paints;

Further, various non-crosslinkable paints such as acrylic lacquer, chlorinated polyolefin lacquer or nitrocellulose-based lacquer, polyurethane lacquer and the like can be used.

[0419] The form of these various paints may be any of various forms such as an organic solvent solution type, an organic solvent dispersion type, an aqueous solution type, an aqueous dispersion type or a powder type. It may be something.

Typical examples of inorganic paints include various paints prepared using inorganic binders such as silicate condensates, water glass, colloidal silica and phosphates.

[0421] Such various paints may be clear paints or any of colored paints containing pigments.

The base coat paint (I) used in carrying out the method for forming a paint film according to the present invention.
I) refers to various paints in the form containing a color pigment, and if only a typical representative paint is used as the base coat paint, as described above, Various organic paints such as those used when preparing a substrate on which a film has been formed in advance can be used.

Further, the base coat paint (I)
Examples of the form I) include an organic solvent solution type, an organic solvent dispersion type, an aqueous solution type, an aqueous dispersion type and a powder type.
Any of various forms may be used.

[0424] These various base coat paints (I
If only particularly typical pigments used in preparing I) are exemplified, the pigments described above may be used.
In addition to various organic pigments, various inorganic pigments such as titanium oxide, iron oxide, aluminum flake, titanium-coated mica and the like can be mentioned.

[0425] The curable clear coating material (I) is applied to the various base materials as described above or various base materials having a film formed thereon in advance to form a cured coating film. To do so, apply air spray method, airless spray method, brush coating or roll coating to various substrates.
With various coating methods known and used, such as a coating method,

Each clear paint is applied, and depending on the curability of each paint or the heat resistance of the base material, and further, depending on the use and the like, at room temperature, from one day (day and night) to about two weeks. Dry and cure, or about 60 to about 250
The baking hardening may be performed for about 30 seconds to about 3 hours in a temperature range of about ° C.

Next, a base coat paint (I) containing a pigment is applied to the base material or the base material on which a film is formed in advance.
I) and a method of forming a cured coating film by sequentially applying the curable clear coating material (I) will be described.

That is, first, a base coat paint (II) is applied to a base material or a base material on which a film is formed in advance by various coating methods as described above. Immediately after the coating operation or after setting for about 5 minutes to about 1 hour, the clear paint (I) is then applied onto the base coat thus obtained, as described above.
The paint is applied by various coating methods.

Subsequently, depending on the curability of each of the curable clear paints, the curability of the base coat paint, the heat resistance of the base material, and the like, and further according to the respective applications, the temperature is set at room temperature. Drying and curing for about two weeks from one day (one day and night), or baking and curing for about 30 seconds to about 3 hours in a temperature range of about 60 to about 250 ° C. It is possible to set a wide range of curing conditions.

That is, paint for base coat (II)
Is a non-crosslinked type, and if the clear coating for the top coat has room-temperature curability, the clear coating is applied and then dried at room temperature or baked to form a base coat. The clear layer may be cured at the same time as drying the layer.

If the base coat paint (II) is of a non-crosslinked type and the clear paint is of a thermosetting type, the clear paint is applied and then baked. Is performed to dry the base coat layer and simultaneously cure the clear layer.

When both the base coat paint (II) and the clear paint have room-temperature curability, the clear paint is applied and then dried at room temperature or baked to obtain a base coat. The coat layer and the clear layer may be cured at the same time.

If either the base coat paint (II) or the clear paint is thermosetting, the clear paint is applied and baked to form a base coat layer. And the clear layer may be simultaneously cured.

The cured coating film obtained by the method for forming a coating film according to the present invention is excellent in so-called durability, such as gloss retention, exposure contamination resistance and acid resistance.
Since it also has extremely high clarity, the method of forming a coating film according to the present invention is particularly suitable for top coats of automobiles, for repairing automobiles, and also for painting exterior walls of buildings or building materials. It is extremely practical for painting.

Also, it can be used very effectively as a method of forming a coating film on a use other than the above-mentioned use, for example, for a building exterior, a building material, or for heavy corrosion protection. It is possible.

The coated product according to the present invention is prepared by coating various substrates by the method for forming a coating film of the present invention as described above. , Respectively, automobiles, motorcycles, trains, bicycles, ships or airplanes or other transportation-related equipment using a metal substrate as a substrate, and a metal substrate or a plastic substrate used therefor. Various components used; TV, radio, refrigerator, washing machine, cooler, cooler outdoor unit or computer or other household appliances using metal base or plastic base as base material; Those various parts;

Various building materials, such as various inorganic tiles, metal roof materials, inorganic outer wall materials, metal wall materials, metal window frames, metal or wooden doors or inner wall materials;
Various outdoor structures, such as roads, road signs, guardrails, bridges, tanks, chimneys or buildings; and various coating films coated on various organic films such as polyester resin films, acrylic resin films, or fluororesin films. However, the coated article according to the present invention can be effectively used for such purposes.

[0438]

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 aqueous resin (W-1)]

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

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

Next, at the same temperature, one of styrene (ST)
00 parts, 300 of methyl methacrylate (MMA)
Parts, 327 parts of n-butyl methacrylate (BMA),
186 parts of n-butyl acrylate (BA), 3-methacryloyloxypropyltrimethoxysilane (MPT
MS) 30 parts and 57 parts of acrylic acid (AA);
450 parts of PA and tert-butyl peroxy-2
A mixture of 50 parts of -ethylhexanoate (TBPO) was added dropwise over 4 hours.

After the completion of the dropwise addition, the mixture was stirred at the same temperature for 16 hours to combine the carboxyl group and the trimethoxysilyl group having a nonvolatile content of 53.5% and a number average molecular weight of 11,900. To obtain a solution of the target polymer. Hereinafter, this is abbreviated as (b-1-1).

In a similar reaction vessel, 467 parts of phenyltrimethoxysilane (PTMS) and 4 parts of IPA were added.
02 parts were charged and the temperature was raised to 80 ° C.

Next, at the same temperature, 4.0 parts of “AP-3” (trade name of isopropyl acid phosphate manufactured by Daihachi Chemical Industry Co., Ltd.) and 127 parts of ion-exchanged water were added to 5 was added dropwise over a period of between min at the same temperature, the mixture was stirred during 4 hours, Te following nuclear magnetic resonance analysis ⁽¹ H-NMR), verify that the hydrolysis of PTMS has proceeded 100% did.

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%.

Next, at the same temperature, “tinuvin-384”
10 parts of [trade name of UV absorber manufactured by Ciba Geigy, Switzerland] and "Tinuvin-123" [Ciba, Switzerland]
Of antioxidants manufactured by Geigy Corporation] and IP
A mixture with 10 parts of A was added over 5 minutes.

Subsequently, at the same temperature, a mixture of 56 parts of triethylamine (TEA) and 1,437 parts of ion-exchanged water was added dropwise over 30 minutes, and then methanol (MEOH) and IPA were distilled under reduced pressure. Excluding the alcohols such as the above, a target aqueous resin having a nonvolatile content of 39.3% was obtained. Hereinafter, this is abbreviated as (W-1-1).

Reference Example 2 (same as above) First, a 92-liter stainless steel autoclave, the inside of which was replaced with nitrogen gas, was filled with IPA 92
0 parts, 68 parts of monobutyl maleate, 120 parts of vinyl acetate, 352 parts of ethyl vinyl ether, 60 parts of vinyl tris (β-methoxyethoxy) silane, and 5 parts of tert-butyl peroxypivalate as a polymerization initiator.
0 parts were charged.

Next, 400 parts of the liquefied and collected chlorotrifluoroethylene was injected into the flask. By continuing the reaction at 60 ° C. for 15 hours with stirring, the non-volatile content is 51.3% and the number average molecular weight is 10,100, which has both a carboxyl group and a trimethoxysilyl group. A solution of the desired fluorocopolymer 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 ion-exchanged water were added dropwise over 5 minutes, and the mixture was stirred at the same temperature for 4 hours. Thereafter, it was confirmed by ¹ H-NMR that hydrolysis of PTMS and MTMS had progressed 100%.

Thereafter, 1,1 of the polymer (b-1-2)
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%.

Next, at the same temperature, “tinuvin-384”
10 parts of "Tinuvin-123" and 1 part of IPA
The mixture with 0 parts was added over 5 minutes.

Subsequently, at the same temperature, a mixture of 26 parts of TEA and 1,424 parts of ion-exchanged water was added dropwise over 30 minutes, and then MEOH and IPA were distilled under reduced pressure.
Excluding the alcohols such as above, a target aqueous resin having a nonvolatile content of 40.0% was obtained. Hereinafter, this is referred to as (W-1-2)
Abbreviated.

Reference Example 3 (Same as above) First, in a reaction vessel similar to Reference Example 1, 1,015 parts of methyltrimethoxysilane (MTMS), 670 parts of methylphenyldimethoxysilane (MPDMS), and I
1,605 parts of PA were charged, and the temperature was raised to 80 ° C. under a flow of nitrogen gas.

Next, at the same temperature, 17.P.
And 9 parts of a 602 parts of ion-exchanged water was added dropwise in about 5 minutes, at the same temperature, the mixture was stirred during 4 hours, ¹ H-
By NMR, the hydrolysis of MTMS and MPDMS is
It was confirmed that the progress was 100%.

Thereafter, at the same temperature, 100 parts of ST, M
300 parts of MA, 304 parts of BMA, 186 parts of BA,
80 parts of AA and 30 parts of MPTMS and 3 parts of IPA
A mixture of 50 parts of TBPO and 50 parts of TBPO was added dropwise over 4 hours, and after completion of the addition, the mixture was stirred at the same temperature for 16 hours to continue the polymerization reaction. Obtained. 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 MPTMS had progressed.

Then, at the same temperature, “tinuvin-384”
20 parts of "Tinuvin-123" and 2 parts of IPA
The mixture with 0 parts was added over 5 minutes.

Subsequently, at the same temperature, a mixture of 112 parts of TEA and 2,700 parts of ion-exchanged water was added dropwise over 30 minutes to neutralize the carboxyl groups. By removing alcohols such as MEOH and IPA, a target aqueous resin having a nonvolatile content of 40.8% was obtained. Hereinafter, this is referred to as (W-1-
Abbreviated as 3).

Reference Example 4 (same as above) First, 272 of PTMS was placed in the same reaction vessel as in Reference Example 1.
Parts, 138 parts of MTMS, 280 parts of cyclohexyltrimethoxysilane (CHTMS) and 1,0 parts of IPA
Then, the mixture was heated to 80 ° C. under nitrogen gas flow.

Next, at the same temperature, 6.0 of “AP-3” was obtained.
Of ST and 1 part of ST
00 parts, 300 parts of MMA, 327 parts of BMA, 186 parts of BA, 57 parts of AA and 30 parts of MPTMS,
A mixture of 350 parts of IPA and 50 parts of TBPO is
Each was added dropwise over 4 hours.

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

Next, at the same temperature, “tinuvin-384”
20 parts of "Tinuvin-123" and 2 parts of IPA
The mixture with 0 parts was added over 5 minutes.

Subsequently, at the same temperature, a mixture of 80 parts of TEA and 2,036 parts of ion-exchanged water was added dropwise over 30 minutes to neutralize the carboxyl groups.
By removing alcohols such as MEOH and IPA by distillation under reduced pressure, a target aqueous resin having a nonvolatile content of 40.0% was obtained. Hereinafter, this is abbreviated as (W-1-4).

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

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

Thereafter, at the same temperature, a mixture consisting of 64 parts of 3-aminopropyltrimethoxysilane and 64 parts of xylene was added dropwise over 10 minutes. The mixture was stirred for a while, and after confirming that the isocyanate group had disappeared by infrared absorption spectrum analysis (IR analysis), 50 parts of xylene and 450 parts of n-butanol were added. A solution of an amino-trimethoxysilyl group-copolymer having 3% and a number average molecular weight of 5,400 was obtained. Hereinafter, this is abbreviated as (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.

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

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

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

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

Then, at the same temperature, “tinuvin-384”
10 parts of "Tinuvin-123" and 1 part of IPA
The mixture with 0 parts was added over 5 minutes.

Subsequently, at the same temperature, a mixture of 19.1 parts of acetic acid and 1,411 parts of ion-exchanged water was added dropwise over 30 minutes, and then distilled under reduced pressure to remove alcohols such as MEOH and IPA. , The non-volatile content becomes 3
9.7% of the target aqueous resin was obtained. Hereinafter, this is referred to as (W
Abbreviated as -1-5).

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

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

First, M was placed in the same reaction vessel as in Reference Example 1.
692 parts of TMS, 140 parts of DMDMS, IPA
And 988 parts of the mixture were charged at 80 ° C. under nitrogen gas flow.
The temperature was raised to.

Then, at the same temperature, the “10.
And 0 parts, and 388 parts of ion-exchanged water was added dropwise in about 5 minutes, at the same temperature, the mixture was stirred during 4 hours, ¹ H-
NMR confirmed that the hydrolysis of MTMS had progressed 100%.

Thereafter, at the same temperature, 100 parts of ST, M
300 parts of MA, 184 parts of BMA, 186 parts of BA,
2-hydroxyethyl methacrylate (HEMA) 5
0 parts, 30 parts of MPTMS and a number average molecular weight of about 1,
Of methoxypolyethylene glycol methacrylate (PEGMA) of 150 parts by weight
A mixture of 350 parts of A and 50 parts of TBPO were each added dropwise over 4 hours, and after completion of the addition, at the same temperature,
By stirring for 16 hours to continue the polymerization reaction, first, a composite resin was obtained.

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

Next, at the same temperature, “tinuvin-384”
20 parts of "Tinuvin-123" and 2 parts of IPA
The mixture with 0 parts was added over 5 minutes.

Subsequently, at the same temperature, 1
969 parts were added dropwise over 30 minutes, and then distilled under reduced pressure to obtain M
By removing alcohols such as EOH and IPA, a target aqueous resin having a nonvolatile content of 35.0% was obtained. Hereinafter, this is abbreviated as (W-2-1).

Reference Example 7 (Same as above) First, 470 parts of IPA was charged into the same reaction vessel as in Reference Example 1, and the temperature was raised to 80 ° C. under nitrogen gas flow.

Next, at the same temperature, 100 parts of ST, MM
A 300 parts, BMA 297 parts, BA 186 parts, H
50 parts of EMA and 67 parts of AA and 450 parts of IPA
Part and tert-butylperoxy-2,2-dimethyl-3-trimethoxysilylpropanoate (TBPO
50 parts of a mixture of TMS) were added dropwise over 4 hours.

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

The polymer (b) was placed in the same reaction vessel as in Reference Example 1.
1,126 parts of -2-1), 467 parts of PTMS, 154 parts of dimethyldimethoxysilane (DMDMS), and 480 parts of IPA were charged, and the temperature was raised to 80 ° C.

Then, at the same temperature, “tinuvin-384”
10 parts of "Tinuvin-123" and 1 part of IPA
The mixture with 0 parts was added over 5 minutes.

Subsequently, at the same temperature, 5.9 parts of “AP-3” and 197 parts of ion-exchanged water were added dropwise over 5 minutes, and after stirring at the same temperature for 4 hours, ,
^{According to 1} H-NMR, trimethoxysilyl group, PTMS and DMDM contained in polymer (b-2-1)
It was confirmed that the hydrolysis of S had progressed 100%.

Thereafter, at the same temperature, 57 parts of TEA and 1,402 parts of ion-exchanged water were added dropwise over 30 minutes, and then vacuum distillation was performed to remove alcohols such as MEOH and IPA. Thus, a target aqueous resin having a nonvolatile content of 40.5% was obtained. Hereinafter, this is abbreviated as (W-2-2).

Reference Example 8 [Preparation example of aqueous resin (W-3)]

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

First, a composite resin (C-3-1) was prepared. In a reaction vessel similar to that of Reference Example 1, 124 parts of propylene glycol-n-propyl ether (PNP) were added.
186 parts of IPA were charged, and 8
The temperature was raised to 0 ° C.

Next, at the same temperature, 100 parts of ST, MM
A 300 parts, BMA 274 parts, BA 186 parts, M
A mixture consisting of 30 parts of PTMS and 110 parts of AA and a mixture of 310 parts of PNP and 50 parts of TBPO were separately added dropwise over 4 hours.

After the completion of the dropwise addition, stirring was carried out at the same temperature for 16 hours to obtain a carboxyl group and a trimethoxysilyl group having a non-volatile content of 55.9% and a number average molecular weight of 12,300. To obtain a solution of the target polymer. Hereinafter, this is abbreviated as (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, the temperature was raised to 80 ° C., and then “AP
A mixture of 2.9 parts of "-3" and 96 parts of ion-exchanged water was added dropwise over 5 minutes, and the mixture was stirred at the same temperature for 4 hours.

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 thereto, and the mixture was stirred at the same temperature for 4 hours, whereby the polysiloxane obtained from PTMS and the polymer ( b-3-1), followed by dropping 62 parts of TEA at the same temperature and under stirring over 5 minutes to obtain a composite resin (C-3-1).
Was prepared.

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%.

Subsequently, polysiloxane (p-1) was prepared. In a reaction vessel similar to that of Reference Example 1, 2,428 parts of MTMS was charged, and the temperature was raised to 80 ° C.
At the same temperature, 0.3 part of “AP-3” and 3 parts of ion-exchanged water
The mixture with 54 parts 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 MEOH was removed by distillation under reduced pressure to obtain a methoxy group content of about 35% and a number average molecular weight of 1,000. The target polysiloxane (M
A partially hydrolyzed condensate of TMS) was obtained. Hereinafter, this is abbreviated as (p-1).

Finally, 1,1 of the composite resin (C-3-1)
89 parts and 505 parts of polysiloxane (p-1)
Mix at room temperature, then at the same temperature,
384 "and 10 parts of" Tinuvin-123 "and I
A mixture with 10 parts of PA was added over 5 minutes, and 1,317 parts of ion-exchanged water was added dropwise over 30 minutes, and then alcohols such as MEOH and IPA were distilled under reduced pressure. And the non-volatile content is 4
0.2% of the target aqueous resin was obtained. Hereinafter, this is referred to as (W
-3-1).

Reference Example 9 (same as above)

First, PT was placed in the same reaction vessel as in Reference Example 1.
Charged 354 parts of MS and 310 parts of PNP,
The temperature was raised to 0 ° C., and then a mixture of 2.9 parts of “AP-3” and 96 parts of ion-exchanged water was added dropwise at the same temperature over 5 minutes. Stirring was performed for 4 hours.

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

Subsequently, 784 parts of the polymer (b-1-2) prepared in Reference Example 2 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 performed, and then 15 parts of TEA was added dropwise at the same temperature under stirring over 5 minutes to prepare a composite resin (C-3-2).

The composite resin thus obtained was analyzed by ¹ H-NMR to find that the polymer (b-1-2)
The hydrolysis of the trimethoxysilyl group contained in it,
It turned out that it was progressing 100%.

Finally, 1,5 of the composite resin (C-3-2)
62 parts and 505 parts of the polysiloxane (p-1) prepared in Reference Example 8 were mixed at room temperature, and then, at the same temperature, 10 parts of "Tinuvin-384" and "Tinuvin-123" A mixture of 10 parts and 10 parts of IPA,
The mixture was added over 5 minutes, and 1,500 parts of ion-exchanged water was added dropwise over 30 minutes. After that, non-volatile components were removed by vacuum distillation to remove alcohols such as MEOH and IPA. 40.1% of the target aqueous resin was obtained. Hereinafter, this is abbreviated as (W-3-2).

Reference Example 10 (same as above) First, 76 MPDMS was placed in the same reaction vessel as in Reference Example 1.
6 parts, 124 parts of PNP and 186 parts of IPA were charged, and the temperature was raised to 80 ° C. under nitrogen gas flow.

Then, at the same temperature, 100 parts of ST, MM
A 300 parts, BMA 274 parts, BA 186 parts, M
A mixture of 30 parts of PTMS and 110 parts of AA,
A mixture of 310 parts of NP and 50 parts of TBPO
Each was separately 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 6.8 parts of “AP-3” and 227 parts of ion-exchanged water was added.
The mixture was added dropwise over a period of minutes, followed by stirring at the same temperature for 18 hours.

Then, at the same temperature, 154 parts of TEA
By dropping over 5 minutes, the composite resin (C-3
-3) was obtained.

Here, this composite resin is represented by ¹ H—N
Analysis by MR confirmed that the hydrolysis reaction of MPDMS and MPTMS had progressed 100%.

Finally, 1,1 of the composite resin (C-3-3)
30 parts and 505 parts of the polysiloxane (p-1) prepared in Reference Example 8 were mixed at room temperature, and then, at the same temperature, 10 parts of “Tinuvin-384” and 10 parts of “Tinuvin-123” A mixture of 10 parts and 10 parts of IPA,
The mixture was added over 5 minutes, and 1,317 parts of ion-exchanged water was added dropwise over 30 minutes, and then methanol and alcohols such as IPA were removed by distillation under reduced pressure. The target aqueous resin having a content of 40.1% was obtained. Hereinafter, this is abbreviated as (W-3-3).

Reference Example 11 (Same as above) First, a composite resin (C-3-4) was prepared. In a reaction vessel similar to that of Reference Example 1, 1,467 parts of CHTMS, P
124 parts of NP and 186 parts of IPA were charged and heated to 80 ° C. under nitrogen gas flow.

Then, at the same temperature, 100 parts of ST, MM
A mixture of 300 parts of A, 279 parts of BMA, 186 parts of BA and 135 parts of AA, and a mixture of 310 parts of PNP and 50 parts of TBPOTMS were separately 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 ion-exchanged water was added. The mixture was added dropwise over a period of minutes, followed by stirring at the same temperature for 18 hours.

Then, at the same temperature, 140 parts of TEA were
By dropping over 5 minutes, the composite resin (C-3
-4) was obtained.

Here, this composite resin is represented by 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.

Subsequently, polysiloxane (p-2) was prepared. The same reaction vessel as in Reference Example 1 was charged with 2,201 parts of MTMS and 475 parts of PTMS, and
The temperature was raised to 0 ° C., and then, at the same temperature, the temperature of “AP-3” was increased to 0.
A mixture of 3 parts and 368 parts of ion-exchanged water was dropped over about 1 hour.

After the completion of the dropwise addition, stirring was carried out at the same temperature for 4 hours, and then the alcohols such as MEOH and IPA were removed by distillation under reduced pressure, whereby the methoxy group content was about 35%, and The desired polysiloxane (partial cohydrolysis condensate of MTMS and PTMS) having a number average molecular weight of 1,200 was obtained. Hereinafter, this is referred to as (p−
Abbreviated as 2).

Lastly, 842 of the composite resin (C-3-4)
Parts and 586 parts of the polysiloxane (p-2) were mixed at room temperature, and then, at the same temperature, "Tinuvin-38" was added.
4 "and 10 parts of" Tinuvin-123 "and IPA
Was added over 5 minutes, and 1,211 parts of ion-exchanged water were added dropwise over 30 minutes, and then methanol and alcohols such as IPA were distilled under reduced pressure. And the non-volatile content is 4
0.2% of the target aqueous resin was obtained. Hereinafter, this is referred to as (W
-3-4).

Reference Example 12 (Same as above) First, a composite resin (C-3-5) was prepared. 1,074 parts of CHMDMS, P
1,131 parts of TMS, 124 parts of PNP and IPA
Was charged, and the temperature was raised to 80 ° C. under nitrogen gas flow.

Then, at the same temperature, 100 parts of ST, MM
300 copies of A, 184 copies of BMA, 186 copies of BA, A
A mixture of 200 parts of A and 30 parts of MPTMS,
A mixture of 310 parts of NP and 50 parts of TBPO
Each was separately 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 18.4 parts of “AP-3” and 617 parts of ion-exchanged 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, 280 parts of TEA
By dropping over 5 minutes, the composite resin (C-3
-5) was obtained.

Here, this composite resin is represented by ¹ H—N
Analysis by MR confirmed that the hydrolysis reaction of CHMDMS, PTMS and MPTMS had progressed 100%.

Subsequently, polysiloxane (p-3) was prepared. MTMS 3 was placed in the same reaction vessel as in Reference Example 1.
643 parts and 1065 parts of DMDMS
The temperature was raised to 0 ° C., and then, at the same temperature, the temperature of “AP-3” was increased to 0.
A mixture of 6 parts and 706 parts of ion-exchanged water was dropped over about 1 hour.

After completion of the dropwise addition, stirring was carried out at the same temperature for 4 hours, and then MEOH was removed by distillation under reduced pressure to obtain a methoxy group content of about 35% and a number average molecular weight of 900%. The desired polysiloxane (partial co-hydrolysis condensate of MTMS and DMDMS) was obtained. Hereinafter, this is abbreviated as (p-3).

Finally, 1 of the composite resin (c-11-3)
186 parts and 852 parts of polysiloxane (p-3) are mixed at room temperature, and then, at the same temperature, 10 parts of "tinuvin-384", 10 parts of "tinuvin-123" and 10 parts of IPA. Parts of the mixture are added over 5 minutes,
Further, after dropping 1,317 parts of ion-exchanged water over 30 minutes, MEOH and IP were distilled off under reduced pressure.
By removing alcohols such as A, a target aqueous resin having a non-volatile content of 39.9% was obtained. Hereinafter, this is abbreviated as (W-3-5).

Reference Example 13 [Preparation of aqueous resin (W-4)]

This example shows one example for preparing the aqueous resin (W-4).

First, PT was placed in the same reaction vessel as in Reference Example 1.
884 parts of MS, 124 parts of PNP and 18 parts of IPA
Six parts 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 and MPTMS 3
0 parts of the mixture, 310 parts of PNP and 5 parts of TBPO
0 parts of the mixture were each separately 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 ion-exchanged water was added.
The mixture was added dropwise over a period of minutes, followed by stirring at the same temperature for 18 hours.

Then, at the same temperature, 154 parts of TEA were
By dropping over 5 minutes, the composite resin (C-4
-1) was obtained.

Here, this composite resin is represented by ¹ H—N
Analysis by MR showed that the hydrolysis of the trimethoxysilyl group from PTMS and MPTMS was 100%.
% Progress was confirmed.

Finally, 1,1 of the composite resin (C-4-1)
82 parts and 505 parts of the polysiloxane (p-1) prepared in Reference Example 8 were mixed at room temperature, and then, at the same temperature, 10 parts of "Tinuvin-384" and "Tinuvin-123" A mixture of 10 parts and 10 parts of IPA,
The mixture was added over 5 minutes, and 1,317 parts of ion-exchanged water was added dropwise thereto over 30 minutes. After that, non-volatile components were removed by distillation under reduced pressure to remove alcohols such as MEOH and IPA. Was 40.2%. Hereinafter, this is abbreviated as (W-4-1).

Reference Example 14 (same as above) First, the MPDMS 37 was placed in the same reaction vessel as in Reference Example 1.
7 parts, CHMDMS 388 parts, PNP 124 parts, I
186 parts of PA and charged with 8
The temperature was raised to 0 ° C.

Next, at the same temperature, 100 parts of ST, MM
200 copies of A, 194 copies of BMA, 186 copies of BA, 2
-Dimethylaminoethyl methacrylate (DMAEM
A mixture of 240 parts of A), 50 parts of HEMA and 30 parts of MPTMS and 310 parts of PNP and 50 parts of azobisisobutyronitrile (AIBN),
Each was separately 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 ion-exchanged 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 give the composite resin (C-4-
2) was obtained.

Here, this composite resin is represented by ¹ H—N
Analysis by MR confirmed that the hydrolysis reaction of the trimethoxysilyl group derived from MPDMS, CHMDMS and MPTMS had progressed 100%.

Finally, 1,1 of the composite resin (C-4-2)
06 parts and 505 parts of the polysiloxane (p-1) prepared in Reference Example 8 were mixed at room temperature, and then, at the same temperature, 10 parts of “Tinuvin-384” and 10 parts of “Tinuvin-123” A mixture of 10 parts and 10 parts of IPA,
The mixture was added over 5 minutes, and 1,324 parts of ion-exchanged water was added dropwise thereto over 30 minutes. After that, non-volatile components were removed by distillation under reduced pressure to remove alcohols such as MEOH and IPA. Was 40.4%. Hereinafter, this is abbreviated as (W-4-2).

Reference Example 15 (same as above) First, PTMS 884 was placed in the same reaction vessel as in Reference Example 1.
, 124 parts of PNP and 186 parts of IPA were charged, and the temperature was raised to 80 ° C. under nitrogen gas ventilation.

Then, at the same temperature, 100 parts of ST, MM
200 copies of A, 204 copies of BMA, 186 copies of BA, A
A mixture of 80 parts of A, 150 parts of PEGMA, 50 parts of HEMA and 30 parts of MPTMS, and 310 parts of PNP
Parts and a mixture of 50 parts of TBPO were each separately 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 ion-exchanged water was added.
The mixture was added dropwise over a period of minutes, followed by stirring at the same temperature for 18 hours.

Then, at the same temperature, 112 parts of TEA were
By dropping over 5 minutes, the composite resin (C-4
-3) was obtained.

Here, this composite resin is represented by ¹ H—N
When analyzed by MR, it was confirmed that the hydrolysis reaction of PTMS and MPTMS had progressed 100%.

Finally, 1,1 of the composite resin (C-4-3) was used.
66 parts and 505 parts of the polysiloxane (p-1) prepared in Reference Example 8 were mixed at room temperature, and then, at the same temperature, 10 parts of “Tinuvin-384” and 10 parts of “Tinuvin-123” A mixture of 10 parts and 10 parts of IPA,
The mixture was added over 5 minutes, and 1,317 parts of ion-exchanged water was added dropwise thereto over 30 minutes. After that, non-volatile components were removed by distillation under reduced pressure to remove alcohols such as MEOH and IPA. Was 40.1%. Hereinafter, this is abbreviated as (W-4-3).

Reference Examples 16 to 18 [Polymer (R-1) to
Preparation Example of (R-4)]

Polymerization was carried out in the same manner as in Reference Example 1 except that the kind and amount of the monomer used and the amount of the polymerization initiator were changed as shown in Table 1, and the polymerization was carried out. Various target polymers (R-1) to (R-
4) was obtained. The polymers are abbreviated as shown in the table.

[0553]

[Table 1]

[0554]

[Table 2]

<< Footnote to Table 1 >>"R-1" obtained in Reference Example 16 is a polymer to be used in preparing Control Resin 1.

“R-2” obtained in Reference Example 17 is a polymer to be used when preparing Control Resin 2.

“R-3” obtained in Reference Example 18 is a polymer to be used when preparing Control Resin 3.

“R-4” obtained in Reference Example 19 is a polymer to be used when preparing Control Resin 4.

Reference Example 20 [Preparation Example of Control Resin 1] In the same reaction vessel as in Reference Example 1, the polymer (R-1)
273 parts were charged. Then, at room temperature and under stirring, a mixture of 7 parts of "Tinuvin-384", 7 parts of "Tinuvin-123" and 7 parts of IPA was added over 5 minutes, and 49 parts of TEA was further added thereto. And 1,00 of ion exchanged water
The mixture with 0 parts was added dropwise over 30 minutes, and then IPA as a solvent was removed by distillation under reduced pressure to obtain a control aqueous resin having a nonvolatile content of 34.5%. Less than,
This is abbreviated as control resin 1.

Reference Example 21 [Preparation Example of Control Resin 2] In the same reaction vessel as Reference Example 1, the polymer (R-2)
289 parts were charged. Then, at room temperature and with stirring, a mixture of 7 parts of "Tinuvin-384", 7 parts of "Tinuvin-123" and 7 parts of IPA was added over 5 minutes, and 29 parts of acetic acid was further added thereto. Parts and ion exchange water 1,000
The mixture was added dropwise over 30 minutes, and then IPA as a solvent was removed by distillation under reduced pressure to obtain a control aqueous resin having a nonvolatile content of 36.1%. Hereinafter, this is abbreviated as Control Resin 2.

Reference Example 22 [Preparation Example of Control Resin 3] In the same reaction vessel as Reference Example 1, the polymer (R-3) 1
252 parts were charged. Next, a mixture of 7 parts of “Tinuvin-384”, 7 parts of “Tinuvin-123” and 7 parts of IPA was added over 5 minutes under stirring at room temperature, and further ion-exchanged water was added thereto. Was dropped over 30 minutes, and IPA as a solvent was removed by distillation under reduced pressure, whereby the non-volatile content was 35.7.
% Of a control aqueous resin was obtained. Hereinafter, this is abbreviated as control resin 3.

Reference Example 23 [Preparation Example of Control Resin 4] In the same reaction vessel as Reference Example 1, the polymer (R-4)
266 parts were charged. Then, a mixture of 7 parts of "Tinuvin-384", 7 parts of "Tinuvin-123" and 7 parts of IPA was added over 5 minutes at room temperature with stirring, and further, 49 parts of TEA was added thereto. Parts and 1,0 of deionized water
Then, 00 parts were added dropwise over 30 minutes, and then IPA as a solvent was removed by distillation under reduced pressure to obtain a control aqueous resin having a nonvolatile content of 35.3%. Hereinafter, this is abbreviated as control resin 4.

Reference Examples 24 to 40 [Preparation of Clear Coating (I)]

Aqueous Resins (W-1), (W-2), (W-
Various clear coatings were prepared by mixing each of 3) or (W-3) with water, PNP or compound (D) as required.

Aqueous Resins (W-1), (W-2), (W-
The use ratio of each of 3) or (W-4), PNP, and compound (D) is as shown in Table 2.

Reference Examples 41 to 44 [Preparation of clear paint using control resin]

Each of the control resins 1 to 4 was mixed with water, PNP or the compound (D), if necessary, to prepare various clear paints for control.

Each of the control resins 1 to 4 and PNP
And the use ratio of the compound (D) and that of the compound (D) are as shown in Table 2.

[0569]

[Table 3]

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

"GPTMS": abbreviation for 3-glycidoxypropyltrimethoxysilane

[0572]

[Table 4]

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

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

[0575]

[Table 5]

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

"EGM-400" is a trade name of a cyclic polysiloxane having a 3-glycidoxypropyl group, manufactured by Dow Corning Toray Silicone Co., Ltd.

[0578]

[Table 6]

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

[0580]

[Table 7]

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

[0582]

[Table 8]

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

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

[0585]

[Table 9]

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

Examples 1 to 3 and Comparative Example 1

An acrylic-melamine-based red paint (below -1) prepared as described below was spray-coated on an untreated mild steel sheet so as to have a dry film thickness of about 40 micrometers (μm). The coated steel sheet was baked at 140 ° C. for 25 minutes to prepare a steel sheet having a film formed thereon in advance.

Next, each of the previously prepared clear paint and control paint was dried to a thickness of about 30 μm.
It was air spray painted so that it became.

[0590] Thereafter, the clear coating material was cured under the conditions shown in Table 3 to obtain various cured coating films. Each of the coating films obtained here and using various clear paints used for carrying out the method of the present invention was particularly excellent in appearance.

The items to be evaluated for various properties of the coating film after drying were weather resistance accelerated by a sunshine weatherometer, stain resistance after two months of outdoor exposure, acid resistance and alkali resistance. is there. The results are summarized in Table 3.

Preparation of White Paint (Lower-1) “Acridic A-418” [trade name of a hydroxyl group-containing acrylic resin manufactured by Dainippon Ink and Chemicals, Inc .; Solvent: mixed solvent of xylene / n-butanol; Non-volatile content = 5
[0%] and 35 parts of "CR-97" (rutile type titanium oxide manufactured by Ishihara Sangyo Co., Ltd.), and the glass beads were added thereto. Dispersion was performed.

[0593] Next, "Super Beckamine L-11"
7-60 ”and then“ Solvesso ”
By diluting with a mixed solvent of 100 "/ n-butanol = 70/30 (parts by weight) so that the viscosity by Ford Cup # 4 becomes 20 seconds,
A target white paint (lower -1) having a PWC (pigment weight concentration) of 35% was prepared.

[0594]

[Table 10]

<< Footnote to Table 3 >>"Weatherresistance" means the 60-degree specular reflectance (%) of the coating film after exposure for 2,000 hours using a sunshine weatherometer.
Is divided by the same gloss value of the coating film when not exposed, and multiplied by 100 (gloss retention:
%).

[0596] The higher the value, the better the weather resistance.

The “stain resistance” indicates the color difference (ΔE) between the unwashed coating film after two months of exposure outdoors and the coating film without exposure. . The closer the value is to zero, the better the stain resistance is.

[0598] "Acid resistance" means that the test was carried out as a substitute test for "acid rain resistance", and 0.1 ml of a 10% sulfuric acid aqueous solution was placed on the surface of each cured coating film. The test plate was placed in a hot air dryer at 60 ° C. for 30 minutes.
After holding for a minute, the coating film surface was washed with water and dried, and the state of the surface was visually evaluated and determined.

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

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

[0601] "Alkali resistance" means that each test plate was immersed in a 5% aqueous sodium hydroxide solution at room temperature for 24 hours, and then the coating film surface was separately washed with water and dried. The surface state is visually evaluated and determined.

The criteria for evaluation evaluation at this time are as follows.

◎: no etching 若干: slight etching was observed △: gloss was reduced ×: etching was remarkable

Examples 4 to 7 and Comparative Example 2 On a steel plate which was previously coated with a polyester-melamine-based gray paint and baked, first a base coat paint (II-1) prepared as described below was prepared. After air spray coating so that the dry film thickness became about 20 μm, the film was left at 25 ° C. for 10 minutes.

Next, each of the clear paints and the control paints prepared as described above were applied by air spraying so that the dry film thickness was about 30 μm.

Thereafter, baking was carried out under the conditions shown in Table 3 to obtain various cured coating films. Each of the coating films obtained here and used in carrying out the method of the present invention, using various clear paints,
In each case, the appearance was particularly excellent.

Items to be evaluated for various properties of the dried coating film include weathering accelerated by a sunshine weatherometer, stain resistance after 2 months of outdoor exposure, acid resistance and alkali resistance. is there. The results are summarized in Table 3.

Preparation of base coat paint (II-1)

A mixture comprising the three components as described below is
Toluene / 2-ethoxyethyl acetate = 90/10
(Parts by weight) was diluted with a mixed solvent having a composition of 13 parts by volume using a Ford cup # 4 to obtain a metallic base coat paint (II).
-1) was prepared.

"Alpaste 1700NL" 10 parts "Acrydic 47-712" 100 parts "Super Beckamine L-117-60" 23.8 parts

Note) "Alpaste 1700NL" ...
...... Aluminum paste manufactured by Toyo Aluminum Co., Ltd .; active ingredient content = 65%

"Acrydic 47-712": A hydroxyl-containing acrylic resin solution manufactured by Dainippon Ink and Chemicals, Incorporated; nonvolatile content = 50%

[0613]

[Table 11]

Examples 8 to 11 and Comparative Example 3 Acrylic-urethane-based white paint (lower-2) prepared as described below was coated on a slate plate with a dry film thickness of about 4
The coated steel sheet was prepared in advance by applying an air spray coating so as to have a thickness of 0 μm and curing it at room temperature for one week.

Next, each of the previously prepared clear paint and control paint was dried with a dry film thickness of about 30 μm.
It was air spray painted so that it became.

Thereafter, the clear coating composition was cured under the conditions shown in Table 3 to obtain various cured coating films. Each of the coating films obtained here and using various clear paints used for carrying out the method of the present invention was particularly excellent in appearance.

The items to be evaluated for various properties of the coating film after drying include weather resistance accelerated by a sunshine weatherometer, stain resistance after 2 months of outdoor exposure, acid resistance and alkali resistance. is there. The results are summarized in Table 3.

Preparation of White Paint (Lower-2) “Acridic A-801P” [trade name of a hydroxyl group-containing acrylic resin manufactured by Dainippon Ink and Chemicals, Inc .; solvent = toluene / n-butyl acetate mixed solvent; Non-volatile content = 5
0%, the hydroxyl value of the solution = 50] and 91 parts of "CR-9
7] was mixed with glass beads, and the mixture was dispersed in a sand mill for 1 hour.

[0619] Next, "Barnock DN-990S"
19.7 of [trade name of non-yellowing type polyisocyanate resin manufactured by Dainippon Ink and Chemicals, Inc .; isocyanate group content = 17.3% by weight, nonvolatile content = 100%]
Parts were added.

Then, xylene / toluene / acetic acid n
-Butyl / 2-ethoxyethyl acetate = 40/30
/ 20/10 (parts by weight) to prepare a white paint (lower-2) with a PWC of 3% by diluting the mixture with a Ford cup # 4 so that the viscosity becomes 20 seconds. did.

[0621]

[Table 12]

Examples 12 to 14 and Comparative Example 4 A polyester-melamine-based gray paint was previously applied and baked on a steel plate. First, an acrylic-urethane-based base coat paint ( II-2), so that the dry film thickness is about 20 μm,
For 20 minutes after air spray painting,
It was left at 25 ° C.

Next, each of the clear paints and the control paints prepared as described above were applied by air spray so that the dry film thickness was about 30 μm.

Then, various kinds of cured coating films were obtained by baking under the conditions shown in Table 3. Each of the coating films obtained here and using various clear paints used for carrying out the method of the present invention was particularly excellent in appearance.

[0625] Items to be evaluated for various properties of the dried coating film include weatherability accelerated by a sunshine weatherometer, stain resistance after 2 months of outdoor exposure, acid resistance and alkali resistance. is there. The results are summarized in Table 3.

Preparation of base coat paint (II-2) A mixture composed of the following three components was mixed with toluene / ethyl acetate / 2-ethoxyethyl acetate = 70 /
A metallic base coat paint (II-2) was prepared by diluting with a mixed solvent having a composition of 20/10 (parts by weight) so that the viscosity by Ford Cup # 4 became 13 seconds.

"Alpaste 1700NL" 11 parts "Acrydic 44-127" 100 parts "Barnock DN-950" 19.5 parts

Note) "Acridic 44-127"
…… A trade name of a hydroxyl group-containing acrylic resin manufactured by Dainippon Ink and Chemicals, Inc .; nonvolatile content = 50%, hydroxyl value of solution = 32.5

"Bernock DN-950": trade name of non-yellowing polyisocyanate resin manufactured by Dainippon Ink and Chemicals, Inc .; nonvolatile content = 75%, isocyanate group content of solution = 12.5 weight%

[0630]

[Table 13]

[0631] In the case of directly coating on a base material, a top coat is separately applied by spraying so as to have a dry film thickness of 40 to 80 µm, and dried and cured under predetermined drying conditions. I tried to make it.

Examples 16 to 19 and Comparative Example 5 First, a base coat paint (II-1) prepared as described above was directly applied to a zinc phosphate-treated steel sheet so that the dry film thickness was about 20 μm. After the air spray coating, it was left at 25 ° C. for 10 minutes.

Next, each of the clear paints and the control paints prepared as described above were applied by air spraying so that the dry film thickness was about 30 μm.

Then, baking was carried out under the conditions shown in Table 3 to obtain various cured coating films. Each of the coating films obtained here and used in carrying out the method of the present invention, using various clear paints,
In each case, the appearance was particularly excellent.

The items to be evaluated for various properties of the dried coating film include weather resistance accelerated by a sunshine weatherometer, stain resistance after two months of outdoor exposure, acid resistance and alkali resistance. is there. The results are summarized in Table 3.

[0636]

[Table 14]

Examples 20 to 21 and Comparative Example 6 Each of the clear paint and the control paint prepared as described above was directly sprayed on a slate plate by air spraying so that the dry film thickness was about 30 μm. I painted it.

Then, baking was carried out under the conditions shown in Table 3 to obtain various cured coating films. Each of the coating films obtained here and used in carrying out the method of the present invention, using various clear paints,
In each case, the appearance was particularly excellent.

[0639] Items to be evaluated for various properties of the dried film include weatherability accelerated by a sunshine weatherometer, stain resistance after 2 months of outdoor exposure, acid resistance and alkali resistance. is there. The results are summarized in Table 3.

[0640]

[Table 15]

[0641]

The method for forming a coating film according to the present invention is excellent in so-called overall durability such as gloss retention, exposure contamination resistance, acid resistance and alkali resistance, and extremely high sharpness. The cured film has a high practicality. And also in the coated product obtained by coating various base materials by the coating film forming method of the present invention, the overcoat coating film has excellent durability, and high durability is required. It can be effectively used for various applications.

Claims (21)

[Claims] An aqueous solution obtained by dispersing or dissolving a composite resin composed of a polysiloxane and a polymer other than the polysiloxane in an aqueous medium on a substrate or on a substrate on which a film has been previously formed. A method for forming a coating film, comprising applying a curable clear coating composition (I) containing a resin (A) as an essential component, and then curing the coating composition. 2. A base coat paint (I) containing a pigment on a substrate or on a substrate on which a film has been previously formed.
I) and a curable clear coating material (I) containing, as an essential component, an aqueous resin (A) obtained by dispersing or dissolving a composite resin comprising a polysiloxane and a polymer other than the polysiloxane in an aqueous medium. A method of forming a coating film characterized by sequentially coating and then simultaneously drying or curing two layers formed from both paints. 3. The curable clear coating composition (I) further comprises, as an essential component, a compound having a functional group that reacts with a functional group contained in the aqueous resin (A). The method for forming a coating film according to the above. 4. The substrate on which a film is formed is a substrate coated with an undercoat paint.
The method for forming a coating film according to the above. 5. The polysiloxane segment (A-1) wherein the aqueous resin (A) has a hydrolyzable group bonded to a silicon atom and / or a hydroxyl group bonded to a silicon atom.
And a composite resin (C-1) composed of a polymer segment (B-1) having at least one kind of hydrophilic group selected from the group consisting of an anionic group, a cationic group and a nonionic group, The method for forming a coating film according to any one of claims 1 to 4, wherein the method is an aqueous resin (W-1) obtained by dispersing or dissolving in an aqueous medium. 6. The polysiloxane segment (A-1) wherein the aqueous resin (A) has a hydrolyzable group bonded to a silicon atom and / or a hydroxyl group bonded to a silicon atom.
And, in addition to at least one hydrophilic group selected from the group consisting of an anionic group, a cationic group and a nonionic group, the hydrophilic group, a hydrolyzable group bonded to a silicon atom, and a silicon atom A polymer segment (B-2) which also has a functional group other than the three types of groups, conveniently with a bonded hydroxyl group.
The coating film according to any one of claims 1 to 4, which is an aqueous resin (W-2) obtained by dispersing or dissolving a composite resin (C-2) formed from an aqueous medium. Formation method. 7. The aqueous resin (A) 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. Selected from the group consisting of a polysiloxane segment (A-2) and an anionic group, a cationic group, and a nonionic group;
A composite resin (C-3) composed of a polymer segment (B-1) having at least one hydrophilic group, and having a hydrolyzable group bonded to a silicon atom and / or a hydroxyl group bonded to a silicon atom The aqueous resin (W-3) obtained by mixing the polysiloxane (p), and further condensing as necessary, and then dispersing or dissolving in an aqueous medium. 4. The method for forming a coating film according to any one of 4. 8. The aqueous resin (A) 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. Selected from the group consisting of a polysiloxane segment (A-2) and an anionic group, a cationic group, and a nonionic group;
In addition to at least one type of hydrophilic group, the compound also has functional groups other than the three types of the 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) 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. An aqueous resin (W-4) obtained by condensing and then dispersing or dissolving in an aqueous medium, if necessary. Forming method. 9. The polysiloxane segment (A-1) and the polymer segment (B-1) constituting the composite resin (C-1) are represented by the following structural formula (SI). ] (However, the carbon atom in the formula is a polymer segment (B-
The silicon atom that forms part of 1) and is bonded only to oxygen atoms forms part of the polysiloxane segment (A-1). 6. The method for forming a coating film according to claim 5, wherein the composite is formed through a bond represented by the following formula: 10. The polysiloxane segment (A-1) and the polymer segment (B-2) constituting the composite resin (C-2) are represented by the following structural formula (SI). ] (However, the carbon atom in the formula is a polymer segment (B-
The silicon atom which forms a part of 2) and is bonded only to an oxygen atom forms a part of the polysiloxane segment (A-1). 7. The method for forming a coating film according to claim 6, wherein the composite is formed through a bond represented by the following formula: 11. A polysiloxane segment (A-2) and a polymer segment (B-1) constituting the above-mentioned composite resin (C-3) are represented by the following structural formula (SI). ] (However, the carbon atom in the formula is a polymer segment (B-
The silicon atom which forms a part of 1) and is bonded only to the oxygen atom forms a part of the polysiloxane segment (A-2). 8. The method for forming a coating film according to claim 7, wherein the composite is formed through a bond represented by the following formula: 12. The polysiloxane segment (A-2) and the polymer segment (B-2) constituting the composite resin (C-4) are represented by the following structural formula (SI). ] (However, the carbon atom in the formula is a polymer segment (B-
The silicon atom which forms a part of 2) and is bonded only to an oxygen atom forms a part of the polysiloxane segment (A-2). 9. The method for forming a coating film according to claim 8, wherein the composite is formed through a bond represented by the following formula: 13. The polysiloxane segment (A-1) has the following structural formula (S-II): (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. The method for forming a coating film according to claim 5, wherein the polysiloxane segment has a structure represented by a monovalent organic group) as an essential unit structure. 8. 14. The polysiloxane (p) has the following structural formula (S-II): (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. 9. The method for forming a coating film according to claim 7, wherein the polysiloxane has a structure represented by a monovalent organic group as an essential unit structure. 15. The polymer segment (B-1) described above.
Is a segment derived from at least one polymer selected from the group consisting of a vinyl polymer, a polyester polymer, an alkyd polymer, and a polyurethane polymer. 3. The method for forming a coating film according to item 1. 16. The polymer segment (B-2) described above.
Is a segment derived from at least one polymer selected from the group consisting of a vinyl polymer, a polyester polymer, an alkyd polymer, and a polyurethane polymer. 3. The method for forming a coating film according to item 1. 17. The method according to claim 5, wherein the hydrolyzable group is an alkoxy group. 18. At least one hydrophilic group selected from the group consisting of an anionic group, a cationic group and a nonionic group, a hydrolyzable group bonded to a silicon atom, and a bond to a silicon atom Functional groups other than the three types described above are preferably a hydroxyl group bonded to a carbon atom, a blocked hydroxyl group, a carboxyl group, a blocked carboxyl group, a carboxylic acid anhydride group, a tertiary amino group, or a cyclocarbonate. Group, epoxy group, primary amide group, secondary amide, carbamate group and the following structural formula (S-II
I) 9. It is at least one kind of functional group selected from the group consisting of functional groups represented by the following:
3. The method for forming a coating film according to item 1. 19. The compound having a functional group that reacts with a functional group contained in the aqueous resin (A) is a compound having a hydroxyl group bonded to a silicon atom and / or a hydrolyzable group bonded to a silicon atom. Compound having both isocyanate group and hydrolyzable group bonded to silicon atom in molecule, compound having both epoxy group and hydrolyzable group bonded to silicon atom in molecule, polyisocyanate compound, blocked polyisocyanate Compounds, polyepoxy compounds,
4. The compound according to claim 3, which is at least one compound (D) selected from the group consisting of a polycyclocarbonate compound, an amino resin, a compound containing a primary or secondary amide group, a polycarboxy compound and a polyhydroxy compound. The method for forming a coating film according to the above. 20. 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. A method for forming a coating film according to any one of claims 4, 5, 8, 9 and 12. 21. A coated article coated by the method for forming a coating film according to any one of claims 1 to 20.