JPH02233181A - Film forming method - Google Patents

Abstract

PURPOSE:To enhance the anticorrosion property of an edge part and to improve weatherability by a method wherein a sharp corner part is painted with cation electrodeposition paint having good film forming properties and subsequently painted with intermediate coat of a specific composition and top coat in succession if desired. CONSTITUTION:A sharp corner part is painted with cation electrodeposition paint having excellent film forming properties and subsequently painted with intermediate coat and top coat in succession if necessary. In this case, paint containing a resin having a hydroxyl group directly bonded to a silicon atom and/or a hydrolyzable group and an epoxy group or a resin composed of a mixture of a resin having a hydroxyl group directly bonded to a silicon atom and/or a hydrolyzable group and a resin having an epoxy group as an essential component is used as either one of or both of the intermediate coat and the top coat.

Description

[Detailed Description of the Invention] Industrial Field of Application The present invention forms a thick coating film even on sharp edges such as corners, protrusions, and cuts, thereby improving the rust prevention properties of the edges. The present invention also relates to a method for forming a coating film with excellent smoothness, sharpness, weather resistance, acid resistance, stain resistance, etc.

BACKGROUND ART Conventional techniques and their problems When painting automobile exterior panels, etc., there is a strong demand for forming coating films with excellent cosmetic properties such as smoothness and sharpness, and excellent corrosion resistance. These coating systems usually consist of a cationic electrodeposition coating, an intermediate coating (sometimes omitted), and a top coating. Furthermore, the outer panel of an automobile, which is the object to be coated, has many sharp corners such as corners, protrusions, and cuts (these may be collectively referred to as "edges" in this specification). are doing.

In this coating system, the electrodeposition coating is designed to melt and flow during baking and hardening, resulting in an excellent coating surface such as smoothness. Since 《 is not formed at all, a defect occurs in that the corrosion resistance (rust prevention) of that part is significantly deteriorated. Proposed methods for improving edge corrosion resistance include, for example, adding a multi-base pigment to the cationic electrodeposition paint, using crosslinking agents with different curing reaction initiation temperatures, and including internally crosslinked gelled fine particles. has been done. Although this method improves the corrosion resistance of the edge portion, it has the drawback of reducing the smoothness of the coated surface.Cationic electrodeposition forms a coating film with excellent both smoothness and edge corrosion resistance. No paint has been found so far.

For intermediate coatings, conventionally, base resins such as polyester resins and acrylic resins are combined with alkyl etherified melamine resins and polyisocyanate compounds (including blocked products).
A combination of crosslinking agents such as the following is generally used.

Not only is it required that the intermediate coating has excellent adhesion with the undercoat (electrodeposition) and topcoat, but in recent years, intermediate coatings have also been required to have excellent adhesion to the undercoat (electrodeposition). etc.) can form an intermediate coated surface with excellent smoothness even if the surface is rough,
Furthermore, there is a strong demand for the top coat to not swell due to the organic solvent contained in the top coat and to contribute to improving the image clarity of the top coat. However, the volume shrinkage of the coating film progresses due to the volatilization of the solvent during the heat curing process of the coating film and the volatilization of condensates and blocking agents produced as by-products due to the curing reaction. It was difficult to form an excellent intermediate coated surface.

Furthermore, the top coat is usually made of polyester resin or a. Thermosetting paints whose main components are a base resin such as Coolyl resin and a crosslinking agent such as alkyl etherified melamine resin are often used, but these have the same problems as explained above for the intermediate coating paint. For some reason, it has drawbacks in the smoothness of the intermediate coated surface and the sharpness of the top coated surface. Moreover,
Systems using melamine resin have insufficient acid resistance, chemical resistance, stain resistance, weather resistance, and gloss retention, are prone to pinholes, and are difficult to thicken (80μ or more). However, it has drawbacks such as insufficient low temperature curing properties (below 120°C).

Means for Solving the Problems The present inventors have solved the above-mentioned defects and improved the finished appearance such as smoothness and sharpness. It is easy to apply even if there are many edges, so it has good corrosion resistance.It also has improved acid resistance, chemical resistance, stain resistance, weather resistance, and gloss retention. The present invention has been completed by successfully developing a coating film forming method that can form a thick top coating film and curing the coating film at a low temperature.

That is, in the present invention, a cationic electrodeposition paint with excellent film-forming properties is applied to sharp corners, and then, if necessary, an intermediate coat is applied, and then a top coat is applied to form a film. In the method of A coating material having sharp corners, characterized in that it is a paint whose essential component is a resin made by mixing a resin having a bonded hydroxyl group and/or a hydrolyzable group with a resin having an epoxy group. Pertains to methods of forming coatings on objects.

The method of the present invention is based on coating an object having an edge portion based on a process consisting of cationic electrodeposition coating, intermediate coating (sometimes omitted), and top coating. Its features are: (1) the corrosion resistance of the edge is improved by using an electrodeposition paint that has excellent film-forming properties on the edge, and (2) a resin having the above-mentioned specific functional groups is used on the surface of the electrodeposition coating. This is where a top coat and/or intermediate coat is applied. As a result, the corrosion resistance of the edges is excellent, and the roughness of the coated surface caused by the electrodeposited coating is eliminated by the intermediate coat and/or top coat whose main component is a resin having the above-mentioned specific functional groups, resulting in smoothness. , it is possible to finish the painted surface with excellent image clarity. Furthermore, this method can provide excellent acid resistance, chemical resistance, stain resistance, weather resistance, gloss retention, etc., and furthermore, it is possible to form a thick intermediate coating film and top coating film. It is possible to cure the coating film at low temperature.

The coating film forming method of the present invention mainly consists of: (1) applying a cationic electrodeposition paint with excellent film-forming properties to the edge portion on the object to be coated, (2) applying an intermediate coat as necessary; After applying the paint, the process consists of ■ applying a top coat, and in both or either of steps ■ and (2), a hydroxyl group and/or a hydrolyzable group directly bonded to a silicon atom and an epoxy group are added to the same resin. It is necessary to use a paint containing as an essential component a resin that has a hydroxyl group and/or a hydrolyzable group directly bonded to a silicon atom, and a resin that is a mixture of a resin that has an epoxy group.

Next, the coating film forming method of the present invention will be explained in detail based on these steps (1) to (2).

Process ■: Surface to be coated with edges The method of the present invention is applicable to areas where it is difficult to form a coating film with normal cationic electrodeposition paints, such as sharp corners and protrusions such as cut surfaces and bent areas. It can also be applied to objects having a shape (“edge portion”).

The material to be coated is preferably a metal product that can be coated by cationic electrodeposition, or a combination of the metal product and another material (such as plastic). Specifically, it is most suitably applied to the outer panels of automobiles (passenger cars, buses, motorcycles, trucks, etc.), but is not limited to these, and is also useful for painting electrical products, prefabricated steel frames, etc. It is preferable that the surfaces of these objects to be coated be degreased and cleaned and subjected to a chemical conversion treatment by a method known per se before coating.

Step (2): A cationic electrodeposition paint having excellent ability to form a coating film on edge portions is applied to the object to be coated by cationic electrodeposition.

Examples of the cationic electrodeposition paint and its coating film forming method include those illustrated in (1) to (10) below.

(1) Apply a cationic electrodeposition paint containing 40 parts by weight or more (preferably 50 to 60 parts by weight) of a pigment per 100 parts by weight of resin solids in the cationic electrodeposition paint (details are in Japanese Patent Publication No. (See Publication No. 124298/1982).

(2) The pigment (B) is composed of at least one type of resin (A) and a pigment (B), of which at least 5% by weight is composed of a pigment with an oil absorption of 100 or more, and the pigment (B) is The total oil absorption amount is 1000 to 10000 per 100g of resin (A).
After performing the first electrodeposition coating using a cationic paint (I) within the range of , using the object to be coated as a cathode, it is left uncured and consists of a resin (c) and a pigment (ii), Minimum deposition current density 0.7mA/cm2 or less and emulsification degree 80
Electrodeposition is carried out for the second time using an emulsion type cationic electrodeposition paint (n) in which the total oil absorption amount of the pigment (2) is smaller than that of the cationic electrodeposition paint (I). The coating is applied and then heated and cured to form a composite cured coating (see JP-A-62-228500).

(3) A resin composition for a cationic electrodeposition coating containing a blocked polyisocyanate compound as a curing agent component, wherein the blocked polyisocyanate compound has a dissociation temperature of the blocking agent in one molecule of about 80 to about 120°. A resin composition for cationic electrodeposition coatings (JP-A No. 62-295972), which is a compound containing one blocked isocyanate group represented by C and one or more blocked isocyanate groups that dissociate at a temperature at least about 40°C higher than the blocked isocyanate group. (see official bulletin)
.

(4) Electrodeposition paint with a coating film curing initiation temperature of less than 130°C is applied without curing, the coating film curing initiation temperature is 130°C or higher, and the minimum electrodeposition current density is 0
．． 7mA/cm2 or less and emulsion degree is 80
After applying a cationic electrodeposition paint with a heavy tooth% or higher,
Both electrodeposited coatings are cured by heating above the coating film curing start temperature of the cationic electrodeposition coating (Japanese Patent Application Laid-Open No. 63-1928).
(See Publication No. 97).

(5) Dispersing in water an acrylic copolymer containing a hydrolyzable alkoxysilane group and a cationic group, and applying a cationic electrodeposition paint containing a cationic electrodepositable gelling fine particle polymer made by intraparticle crosslinking. .

A tertiary amino group is suitable as the cationic group.

Further, as the acrylic copolymer, for example, (a) a polymerizable unsaturated vinyl silane monomer containing a vinyl double bond and a hydrolyzable alkoxysilane group, and (b) a polymerizable unsaturated vinyl silane monomer containing a vinyl double bond and a tertiary amino group. and (c) a polymerizable unsaturated monomer containing a vinyl double bond and a hydroxyl group and/or (d) other polymerizable monomers as an essential monomer component. A copolymer that may contain an unsaturated monomer as an additional monomer component, or (a) a polymerizable unsaturated vinyl silane monomer containing a vinylic double bond and a hydrolyzable alkoxysilane group and an unsaturated vinyl monomer containing a glycidyl group. as an essential monomer component, and if necessary, (C) a polymerizable unsaturated monomer containing a vinyl double bond and a hydroxyl group and/or (d) another polymerizable unsaturated monomer as an additional monomer. An example is an acrylic copolymer obtained by reacting a secondary amine with a glycidyl group of a copolymer that may be contained as a component. In addition, examples of the vinyl silane monomer (a) include vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris-β-methoxyethoxysilane, and γ-acrylicoxypyl(tri)
Preferred are methoxysilane, γ-methacryloxypyltrimethoxysilane, γ-methacryloxypylmethyldimethoxysilane, and the like. Polymerizable unsaturated monomer (
b) is dialkylaminoalkyl (meth)acrylate (all of these alkyls have 1 to 1 carbon atoms);
6 alkyl), dialkylaminoalkyl (meth)
Acrylamide (all of these alkyls have 1 to 6 carbon atoms) and the like are preferred. As the glycidyl group-containing unsaturated vinyl heptanomer, glycidyl acrylate, glycidyl methacrylate, etc. are preferable, and as the polymerizable unsaturated monomer (C), 2-hydroxyethyl (meth)acrylate, hydroxypropyl (meth)
Acrylate and the like are preferred. The composition ratios of these monomers in the copolymer are preferably 1 to 30% by weight of the vinylsilane monomer (a), 5 to 30% by weight of the polymerizable unsaturated monomer (b), and 5 to 30% by weight of the polymerizable unsaturated monomer (b). C) 0
~30% by weight and polymerizable unsaturated monomer (d) 10~
This is 94%. The acrylic copolymer preferably has an amine value of about 10 to about 100, a hydroxyl value of about 200 or less, and a number average molecular weight of about 5,000 to about 100,000.

The intraparticle crosslinking can be achieved, for example, by neutralizing an acrylic copolymer containing a hydrolyzable alkoxysilane group and a cationic group with an acid and dispersing it in water, then heating it to 50°C or higher, or This can be carried out in the presence of a group condensation catalyst. The silanol group condensation catalyst is preferably tin octylate, zinc octylate, zirconium octylate, and dibutyltin laurate.

The content of the gelled polymer fine particles formed by intraparticle crosslinking is preferably 1 to 50% by weight based on the resin solid content in the cationic electrodeposition paint.

(6) Electrodeposit the cationic electrodeposition paint of (5) above onto the uncured electrodeposition coating film at a minimum electrodeposition current density of 0.7 mA/c♂ or less as described in (2) above. A cationic electrodeposition coating composition (I) having a degree of emulsion of 80% by weight or more
I) is applied by electrodeposition and then cured by heating to form an electrodeposited multilayer coating film.

(7) A mixture of the acrylic copolymer described in (5) above and a particulate pigment having an oil absorption of 100 or more and a primary particle diameter of 0.5 μm or less is water-dispersed, and the same procedure as in (5) is carried out. A cationic electrodeposition paint containing gelled polymer microparticles containing a microparticle pigment that is crosslinked within the particles is applied.

(8) (a) Polymerizable unsaturated vinyl silane monomer containing a vinyl double bond and a hydrolyzable alkoxysilane group (b) Polymerizable monomer containing at least two radically polymerizable unsaturated groups in the molecule (C) A polymerizable unsaturated monomer containing a vinyl double bond and a hydroxyl group and (
d) Cation formed by emulsion polymerization of other polymerizable unsaturated monomers using a cationic reactive emulsifier containing an allyl group in the molecule, optionally in the presence of a water-soluble azoamide compound as a polymerization initiator. A cationic electrodeposition paint containing an electrodepositable gelling fine particle polymer is applied.

The vinyl silane monomer (a) above is a compound represented by the following general formula R3SiX. In the formula, X represents a vinyl group such as .gamma.-methacrylicoxypyl, and R represents an acetoxy group or an alkoxy group having 1 to 8 carbon atoms. Examples include vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris(2
-methoxyethoxy) silane, γ-methacryloxypyltrimethoxysilane, vinyltriacetoxysilanes, etc. Among them, γ-methacryloxypyltrimethoxysilane is most preferred. In addition, as the polymerizable monomer containing at least two radically polymerizable unsaturated groups in the molecule of (b), polymerizable unsaturated carboxylic acid esters of polyhydric alcohols, polymerizable unsaturated carboxylic acid esters of polybasic acids, etc. Examples include alcohol esters and aromatic compounds substituted with two or more vinyl groups. The polymerizable unsaturated monomer 7 containing a vinyl double bond and a hydroxyl group (C) is a monomer component that introduces a hydroxyl group into the gelled fine particle polymer, and the hydroxyl group is used when producing the gelled fine particle polymer. It functions as a hydrophilic group or a functional group for a crosslinking reaction between dispersed particles. Examples of the unsaturated monomer include 2-hydroxyethyl (meth)acrylate, hydroxybutyric (meth)acrylate, and the like. In addition, as a typical cationic reactive emulsifier containing an allyl group in the molecule, there is a general formula (wherein R1 has 8 to 2 carbon atoms, which may have a substituent).
2 represents a hydrocarbon group, R2 and R3 represent an alkyl group having 1 to 3 carbon atoms, R4 represents a hydrogen atom or a methyl group, and X0 represents a monovalent anion. ) There is a reactive emulsifier containing a quaternary ammonium salt represented by: This product is publicly known (Japanese Patent Publication No. 6Q-78947), and Latemul K-
It is commercially available under trade names such as 180 (manufactured by Kao Corporation).

As a polymerization initiator, the following general formula Cth CHs (wherein, X represents a linear or branched alkylene group having 2 to 12 carbon atoms) or the general formula (wherein, XI, X2 and A water-soluble azoamide compound represented by the following formula is particularly suitable. These things are publicly known (Japanese Patent Application Laid-Open No. 61-21861
No. 8, JP-A No. 61-63643), and VA series (manufactured by Wako Pure Chemical Industries, Ltd.).

(9) The minimum electrodeposition current density is 0.7 mA/cm2 or less on the uncured electrodeposition coating film obtained by electrodeposition coating the cationic electrodeposition coating composition of (8) above on the object to be coated. The cationic electrodeposition coating composition (II) having a degree of emulsion of 80% or more is applied by electrodeposition, and the uncured electrodeposited multilayer coating film in poor condition is baked and cured.

(10) Applying a cationic electrodeposition paint made by blending an alkyl tin ester compound of an aromatic carboxylic acid to the paint containing the cationic electrodeposition gelling particle polymer in (5) to (9) above. The tin ester compound is a dissociation catalyst for block polyisocyanate, and is a liquid type that can be uniformly mixed into the electrodeposition paint and does not cause abnormalities in the stability of the paint or the condition of the coated surface. The number of carbons is 1
0 or less is preferable, dioctyltin penzoate oxy,
Examples include dibutyltin penzoate oxy, dioctyltin penzoate, dibutyltin dibenzoate, and the like.

Among the cationic electrodeposition paints listed above, (1) and (3)
, (8) and (10) are particularly preferred.

These cationic electrodeposition coatings can be applied and cured by methods and conditions known per se. In the object coated by electrodeposition in step (2), a hardened electrodeposition coating film is formed not only on the flat parts but also on the edge parts, which is thicker than in the past. The thickness of the electrodeposition coating film is not particularly limited, but a thickness of 20 to 30 μm (cured coating film) is suitable for flat areas.

Step ■: Intermediate coating In the method of the present invention, this intermediate coating step is not an essential requirement, but the electrodeposited coating may be used to improve the adhesion between the electrodeposited coating film in Step ■ and the top coating film in Step It is more preferable to apply an intermediate coat because the rough surface of the deposited coating does not adversely affect the top coated surface.

In the present invention, examples of intermediate coating materials include those illustrated below.

■ Conventionally commonly used, for example, a cross-linked curing type made by using polyester resin or acrylic resin as a base resin, and using this in combination with an alkyl etherified melamine resin or polyisocyanate compound (including block compounds) as a cross-linking resin. Intermediate paint.

■As an effective paint to improve chipping resistance,
For example, 1) the glass transition temperature (Tg) of the formed coating is -30
2) A water-based barrier coat whose main component is a modified polyolefin resin having a temperature of 0 to -60°C (see JP-A-61-176602), 2) an aqueous barrier coat whose formed coating has a Tg of 0 to -75°C. 3) organic solvent-based paints capable of forming a coating film having a tensile elongation at break of 150% or more and a stress at break of 20 kg/cm2 or more (see JP-A No. 61-271062); 4) Thermosetting organic solvent-based acrylic resin paint capable of forming a cured coating with a tensile strength elongation of 10% or more and a stress at break of 20 kg/cm2 or more (Japanese Patent Application Laid-Open No. 1983-1999)
15270), 5) A grafted product of an ethylene-propylene non-conjugated diene copolymer having a Tg of -20°C or less and a polymer containing a functional monomer (JP-A-62-27
3271), 6) A composition whose main component is a modified polyolefin resin obtained by adding a monoepoxy compound to a polyolefin resin graft-polymerized with maleic acid or its anhydride (see JP-A-62-246971) ) etc. are used as intermediate coatings. As a result, even if a pebble or the like collides with the surface of the top coat, the energy of the collision is absorbed by the intermediate coat, thereby preventing scratches, peeling, etc. from occurring on the coat.

■ Specific resins (specifically, resin (I) alone or resin (II) and resin (
A paint containing as a main component a mixture of III) and III) can also be used as an intermediate paint. This intermediate coating has a composition similar to that of the top coating described below, but has physical properties in the cured coating, such as flexibility and adhesion to the electrodeposited coating and top coating. It is preferable to select one with excellent properties.

When using ■ among the intermediate coatings in ■ to ■ above, it is possible to finish the intermediate coating with excellent smoothness even if the electrodeposition coating surface is rough, and it can be cured at low temperatures (approximately 80℃ or higher). Since this is possible, particularly favorable results can be obtained.

As the coating and curing methods for these intermediate coatings, methods already known per se can be employed, and the film thickness is preferably 10 to 40 .mu.m based on the cured coating film.

Furthermore, in the present invention, as an application example of the above-mentioned intermediate coating material (■), there may be a layer between a cationic electrodeposited coating film and an intermediate coating material (■) or a coating film of (■), and (or) a coating film of intermediate coating material (■) or (■) and a topcoat. The chipping resistance can also be improved by interposing it between the layers and the film. In that case, the cured film thickness of the intermediate coating material (1) is suitably 1 to 20 microns.

Process ■: Apply top coat paint.

The top coat is applied to the cationic electrodeposition coating surface or the intermediate coating surface, and is a hydroxyl group and/or a hydrolyzable group directly bonded to a silicon atom (hereinafter, these groups are referred to as "
(sometimes abbreviated as "silane group") and an epoxy group in the same resin, or a resin (II) having a hydroxyl group and/or a hydrolyzable group directly bonded to a silicon atom.
) and an epoxy group-containing resin (m) as an essential component.

Below, the resin (I) and resin (II) and resin (III) constituting the mixed resin, which can be used as a top coat, will be explained.

In this specification, a hydrolyzable group directly bonded to a silicon atom is a group that is hydrolyzed by water or moisture to produce a silanol group. Examples of the group include those represented by the following general formula.

-O-R' (I) 10-C-R
' (II) In the formula, R' is C, -4 alkyl group R J - R''' may be the same or different and represents an alkyl group, aryl group, or aralkyl group of 01-8.

In the general formula, examples of the alkyl group 01 to 8 include methyl, ethyl, n-propyl, iso-butopyl, n
-butyl, iso-butyl, see-butyl, tert
-butyl, n-bentyl, iso-pentyl, n-octyl, 1so-octyl, etc.; examples of the aryl group include phenyl, tolyl, xylyl, etc., and examples of the aralkyl group include, for example, benzyl. , phenethyl and the like.

In addition to the above-mentioned hydrolyzable groups bonded to silicon atoms, examples of hydrolyzable groups include Mi-Si-H groups.

In the above resins (I) and (n), the hydrolyzable group is based on the above general formula (I) from the viewpoint of storage stability, curability, etc.
Silane groups represented by and (If) are preferred.

Next, a method of introducing an epoxy group and a silane group into the resin skeleton will be mentioned.

(1) A resin (A) having a functional group is converted into a compound (B) having a functional group and an epoxy group that reacts complementary to the functional group.
and a reactant (D) obtained by reacting with a compound (C) having a functional group that reacts complementary to the functional group of the resin (A) and a silane group (hereinafter referred to as "(1) resin composition"). , (2) a reactant (F) obtained by reacting a resin (E) having a functional group with a compound (B) having a functional group and an epoxy group that reacts complementary to the functional group; A mixture (I) with a reactant (H) obtained by reacting the resin (G) with a compound (C) having a functional group and a silane group that reacts complementary to the functional group, (hereinafter referred to as "(2) Resin Composition"
(3) Epoxy group-containing polymerizable unsaturated monomer (J
), a copolymer (L) containing a silane group-containing polymerizable unsaturated monomer (K) and, if necessary, another polymerizable unsaturated monomer (M) as a monomer component (hereinafter referred to as "( 3) "resin composition"), (4) a homopolymer (N) of the monomer (J) or a copolymer of a resin composition and another polymerizable unsaturated monomer (M) ( N) and a homopolymer (P) of the monomer (K)
Or this and other polymerizable unsaturated monomers (M)
(hereinafter referred to as "(4) resin composition") (5) a mixture consisting of a copolymer (P) with a functional group-containing polymerizable unsaturated monomer (Q) and the epoxy group-containing polymerizable unsaturated monomer Worldly life 0
) as an essential component, and a monomer (Q).
A reaction product (T) with a compound (S) having a silane group and a functional group that reacts complementary to the functional group resulting from the reaction (hereinafter referred to as "(
5) a copolymer containing as essential components a polymerizable unsaturated monomer (U) having a functional group and the above-mentioned silane group-containing polymerizable unsaturated monomer (K). A reaction product (X
), (hereinafter referred to as "(6) resin composition"), (7) the homopolymer (N) or copolymer (N) and the reactant (H
) (hereinafter referred to as "(7) resin composition") (8) A mixture (2) of the homopolymer (P) or copolymer (P) and the reactant (F) ( (hereinafter referred to as "(8) resin composition") In the resin compositions of (1) to (8) above, (1), (
3) (5) and (6) correspond to resin (I), (2),
(4), (7) and (8) are resin (II) and resin (m)
It corresponds to a mixture with

In the resin compositions (1) to (8) above, the complementary reacting groups are groups that can react with each other,
For example, you can select from the table below.

Table 1 Table 1 (Continued) Complementarily reactive groups can be selected and combined as appropriate from the above table, but among them, the following combinations are preferred.

Resin (A)/Compound (B) [or Resin (E)/Compound (
B)] functional group combinations (1)/(5), (2)/(4), (3)/(3)
, (5)/(1) etc.

Resin (A)/Compound (C) [or Resin (G)/Compound (
C)] functional group combinations (1)/(5), (2)/(3), (2)/(4)
, (2)/(5), (3)/(3) , (4)/(2
), (4)/(6), (4)/. (7), (5)/
(1) , (5)/(2) , (5)/(6) , (5
)/(7), (8)/(4), (6)/(8), (
7)/(4), (7)/(8), (7)/(5), etc.

Combinations of functional groups of monomer (Q)/compound (S) (1)/(5), (4)/(2), (4)/(6)
, (4)/(7), (5)/(1) , (5)/(2
), (5)/(3), (5)/(6), (5)/(
7) etc.

Monomer (U)/compound ('W) functional group combinations (1)/(5), (2)/(4), (2)/(5)
, (3)/(L), (5)/(1), (8)/(4
), (8)/(5), (6)/(8), (7)/(
4), (7)/(5), (7)/(8), etc.

(1) Resin Composition The resin (A) can be appropriately selected from conventional resins without any particular limitations as long as it has the above-mentioned functional group. Specifically, resins such as vinyl resin, fluororesin, polyester resin, alkyd resin, silicone resin, urethane resin, and polyether resin can be mentioned.

The resin (A) contains the compound (B) and the compound (
Although the resin has an average of two or more functional groups that react with the functional group of C), the functional groups in the resin may be the same or different from each other.

When the functional groups in the resin (A) are the same, for example, the resin (A) having an average of two or more hydroxyl groups, the compound (B) having an isocyanate group (5), and the compound having an isocyanate group (5) A resin (A
) can be reacted with a compound (B) having a hydroxyl group (1) and a compound (C) having an isocyanate group (5).

In addition, when the functional groups in the resin (A) are different, for example, an average of one or more hydroxyl groups (1) and carboxyl groups (
2), a compound (C) having an isocyanate group (5) and an epoxy group (4). It can be reacted with a compound (B) having two.

The functional group in the compound (B) that reacts with the functional group in the resin (A) may be the same as the epoxy group that the compound (B) has. Similarly, the functional group in the compound (C) that reacts with the functional group in the resin (A) may be the same as the silane group that the compound (C) has.

As the resin (A), resins having functional groups such as a hydroxyl group, a carboxyl group, an isocyanate group, a silane group, and an epoxy group will be explained.

[Hydroxy group-containing resin]

The following items can be mentioned.

■Hydroxyl group-containing vinyl resin As a typical example of the resin, for example, the following hydroxyl group-containing polymerizable unsaturated monomer (a) and, if necessary, other polymerizable unsaturated monomers (b) are used as single components. The following polymers can be mentioned.

Examples of the hydroxyl group-containing polymerizable unsaturated monomer (a) include compounds represented by the following general formulas (1) to (4).

[In the formula, Rl represents a hydrogen atom or a hydroxyalkyl group. ]

[In the formula, R1 is the same as above. ] [In the formula, Z represents a hydrogen atom or a methyl group, and m is 2 to 8
p is an integer of 2 to 18, and q is an integer of 0 to 7. ] [In the formula, Z is the same as above. T1 and T2 are the same or different and represent a divalent hydrocarbon group having 4 to 20 carbon atoms.

S and V each represent an integer of 0 to 10. However, S
The sum of and ■ is 1 to 10. ] In the general formulas (1) and (2), the hydroxyalkyl group is a hydroxyalkyl group in which the alkyl moiety has 1 to 6 carbon atoms. Specifically, for example, -C2H40H,
Examples include -C3H60H, -ε4H80H, and the like.

The divalent hydrocarbon group having 4 to 20 carbon atoms in general formula (4) is, for example, -CH2-(CH2)2
(CH2 ) 3-CH3CH3 CH3 CH2 CH2 C CH2 CH2 (C
Hz) '+o-CH3 (CH2) +2-, (CHz) 18-, K
>, -CH2-{I)-CH2, and the like.

As the monomer component of general formula (2), for example, CH2
=CHCH2 0H CHz =CHCH2 0 CH2 CH2 0HC
I12 = CIlCH2 0(CI12 CI{20
h-HCH2 = CHCH2 0(CH2 C82
0 catty H etc. can be mentioned.

As the monomer component of general formula (3), for example, CH2
=C(CH3) COOC2 Ha OHC}12
=CHCOOC31{s OH, etc. can be mentioned.

As the monomer component of general formula (4), for example, CH2
=C(CH3)COO-(CH2CHCH3 咋r
7THCH2 = CHCOO (CH2 CH2 0 catties τ
TI1CH2 = C(CH3)Coo-(CH2 CH
2 0 loaf τgoHCll2=CHCOO(CH2 CH2
CH2 CH2 0 te "τ] - I {CH2 = C (C
H3 )Coo-(CH2 CHz O)5~6-(
Examples include CH2CH(CH2)3, r7rH, and the like.

Furthermore, in addition to the above, hydroxyl group-containing unsaturated monomers represented by the general formulas (1) to (4) and ε-cabrolactone, γ
-Adducts with lactones such as valerolactone can be used.

Other polymerizable unsaturated monomers (b) include, for example:
The following (b-1) to (b-6) can be mentioned.

(b-1) Olefin compounds: for example, ethylene, propylene, butylene, isoprene, chloroprene, etc.

(b-2) Vinyl ether and allyl ether:
For example, ethyl vinyl ether, probyl vinyl ether, isoprobyl vinyl ether, butyl vinyl ether, tert-butyl vinyl ether, pentyl vinyl ether, hexyl vinyl ether, isohexyl vinyl ether, octyl vinyl ether, 4-methyl-1-
Chain alkyl vinyl ethers such as pentyl vinyl ether, cycloalkyl vinyl ethers such as cyclopentyl vinyl ether, cyclohexyl vinyl ether,
Phenyl vinyl ether, o-, m-, p-
Aryl vinyl ethers such as trivinyl ether, aralkyl vinyl ethers such as penzyl vinyl ether, phenethyl vinyl ether, etc.

(b-3) Vinyl esters and brovenyl esters: for example, vinyl esters such as vinyl acetate, vinyl lactate, vinyl butyrate, vinyl isobutyrate, vinyl caproate, vinyl incaproate, vinyl bivaric acid, vinyl cabrate, and isoacetic acid. Propenyl esters such as isopropenyl propenylpropionate, etc.

(b-4): Acrylic acid or methacrylic acid ester:
For example, methyl acrylate, ethyl acrylate, probyl acrylate, isobrobyl acrylate, butyl acrylate, hexyl acrylate, octyl acrylate, lauryl acrylate, methyl methacrylate, ethyl methacrylate, probyl methacrylate, isoprobyl methacrylate. , butyl methacrylate, hexyl methacrylate, octyl methacrylate, alkyl esters of acrylic acid or methacrylic acid having 1 to 18 carbon atoms such as lauryl methacrylate: methoxybutyl acrylate, methoxybutyl methacrylate, methoxyethyl acrylate, methacrylic acid Alkoxyalkyl esters of acrylic acid or methacrylic acid having 2 to 18 carbon atoms, such as methoxyethyl, ethoxybutyl acrylate, and ethoxybutyl methacrylate.

(b-5) Vinyl aromatic compounds: for example, styrene, α-methylstyrene, vinyltoluene, p-chlorostyrene, etc.

(b-6) Others: acrylonitrile, methacrylonitrile, etc.

■ Hydroxyl group-containing fluororesin Hydroxyl group-containing polymerizable unsaturated monomer (a), fluorine-containing polymerizable unsaturated monomer (c), and other polymerizable unsaturated monomers (b) as necessary Polymer used as a mass component.

Examples of the fluorine-containing polymerizable unsaturated monomer (c) include compounds represented by the following general formulas (5) and (6).

CX2=CX2 (5) [wherein, X
are the same or different and represent H, CQ, Br, F, an alkyl group or a haloalkyl group. However, the formula contains at least one F. ] CH2=CZ C=O (6)0-CnH
2n-R2 [wherein Z is the same as above. R2 represents a fluoroalkyl group, and n represents an integer of 1 to 10. ] The alkyl group in general formula (5) has 1 to 6 carbon atoms, preferably 1 to 4 carbon atoms.

? Specific examples include methyl, ethyl, probyl, isopropyl, butyl, and pentyl groups.

Further, the haloalkyl group is one having 1 to 6 carbon atoms, preferably 1 to 4 carbon atoms. Specifically, for example, CF3,
CHF2, CH2F1CIQ3, CHCQ■, CH2
CQ, CFCQ2 (CF2 )2 CF3, (CF2
)3 CF3, CF2 CH3, CF2 CHF2
, CF2Br,C}{'2Br, etc.

Examples of the monomer represented by general formula (5) include C
F2=CF2, CHF=CF2, CH2=CF2
．． , C}{2 = CHF , CCQ F = CF2,
CHCQ=CF2, CCQ2=CF2, CCQF=
CCQP, CHF = CCQ2, CII2 = CC
QF , CCQ 2 =C(J2 F , CP3
CF=CF2, CF3 CP=CHF SCF3 CH
=CF2, CF3 CF=CH2, CHF2CF
=CHP, CH3CF=CP2, CH3CF
=CH2, CP2 CQ CF=CP2, CP3
CC2 = CF2, CF3CP” CPCQ SCF2
CQ CC (2 = CP2, CF2 CQ CF
=CF-(J'.CFCΩ2CP=CF2,
CF2 CCQ=CCQP, CF3CCQ=CCQ
2, CCQ F 2 CF=CC92 2, CC
Q3 CF=CP2, CP2 CQ CCR=
CCQ2 , CFCR 2 C (12 = CCQ 2
, CF3 CF=CHC(2 ,CC(2
P2 CF=CHCQ,CP3 CCL=CHC
Q , CHF 2 CC12 = CCQ2 , CF2
CQCH=CCI22, CF2 CQCCQ=
CH(J!, CC2 3 CP= CHCI2 S
CF2 1cF = CF2 , CF2 BrCH=C
P2, CF3 CBr=CHBr, CF2
CRCBr=CH2, CH2 BrCF=CCl2
z, CF3 CBr=CHz, CP2 CH=C
HBr, CF2 BrCH=CHF, CF2 Br
CF=CF2, CF3 CF2 CF=CF2, C
F3 CF=CFCF3, CF3 CH=CFCF3
, CP2 = CFCP2 CHP 2 , CF3 C
F2 CFF CH2, CF3 CH=CHCF3,
CF2=CFCF2 CH3, CF2=CFCH
2 CH3, CF3 CH2 CH=CH2, CF
3 CH=CHCH3, CP2=CHCH2C
H3, CH3 CF2 CH=CH2, CFJ{
2 CH=CHCPH 2 , CH3 CP2 CH
=CH3, CH2 =CPCH2 CH3, C
P3 (CF2) 2 CF=CF2, CF3
(CF2) 3 CF=CF2, etc. can be mentioned.

The fluoroalkyl group in general formula (6) has 3 carbon atoms.
~21. Specifically, for example, 04F9,
(CF2)s CF (CF3)2, C8F+7,
C1. F2 1 etc. can be mentioned.

Examples of the monomer represented by general formula (6) include: CH3 CH2 =C-COO- C2 H4 -C4
P9CH2 = C-COO- C2 Ha -CB
FlyCH3 CH2 = C-COO- C2 H4 -CIO
F2 +■ Hydroxyl group-containing polyester resin polybasic acid (e.g. (anhydrous) phthalic acid, isophthalic acid,
Terephthalic acid, (anhydrous) maleic acid, (anhydrous) pyromellitic acid, (anhydrous) succinic acid, sebacic acid, azelaic acid, dodecanedicarboxylic acid, dimethyl isophthalate, dimethyl terephthalate, etc. have 2 to 4 in one molecule. Compounds having a carboxyl group or carboxylic acid methyl ester group)
and polyhydric alcohols (e.g. ethylene glycol, polyethylene glycol, propylene glycol, neopentyl glycol, 1,6-hexanediol, trimethylolpropane, pentaerythritol, glycerin,
, 2 to 6 in one molecule such as tricyclodecane dimethanol, etc.
It can be obtained by ester reaction or ester conversion reaction with an alcohol having 2 hydroxyl groups. In addition to the above, monobasic acids (for example, fatty acids such as castor oil fatty acid, soybean oil fatty acid, tall oil fatty acid, linseed oil fatty acid, benzoic acid, etc.) can be used as necessary.

■ Hydroxyl group-containing polyurethane resin Isocyanate obtained by modifying hydroxyl group-containing vinyl resin, hydroxyl group-containing fluororesin, hydroxyl group-containing polyester resin, etc. with a polyisocyanate compound (for example, tolylene diisocyanate, xylene diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, etc.) Resin without groups.

■Hydroxyl group-containing silicone resin Hydroxyl group-containing vinyl resin, hydroxyl group-containing fluororesin, hydroxyl group-containing polyester resin, etc.
-6018, Z-6188 (all Dow Corning products), SH5050, SH6018, SH6188
A resin that does not have alkoxysilane groups or silanol groups and is obtained by modification with (all products of Toray Silicone Co., Ltd.).

(2) Vinyl alcohol-styrene copolymer [carboxy group-containing resin] Examples (1) to (2) below can be mentioned.

(2) Carboxyl group-containing vinyl resin A polymer containing a carboxyl group-containing polymerizable unsaturated monomer (d) and, if necessary, the other polymerizable unsaturated monomer (b) as monomer components.

Examples of the carboxyl group-containing polymerizable unsaturated monomer (d) include compounds represented by the following general formulas (7) and (8).

[In the formula, R3 represents a hydrogen atom or a lower alkyl group. R
4 represents a hydrogen atom, a lower alkyl group or a carboxyl group. R5 represents a hydrogen atom, a lower alkyl group or a carboxy lower alkyl group. ] Indicates a chill group. ] In the general formula (7), the lower alkyl group is preferably one having 4 or less carbon atoms, particularly a methyl group.

Examples of the compound of general formula (7) include acrylic acid, methacrylic acid, crotonic acid, itaconic acid, maleic acid, maleic anhydride, fumaric acid, and the like.
Ru.

Further, examples of the compound of general formula (8) include 2-carboxyethyl (meth)acrylate, 2-carboxyprobyl (meth)acrylate, and the like.

In addition to the above, hydroxyl group-containing polymerizable unsaturated monomers (
a) 1 mol and polycarboxylic anhydride (e.g. maleic anhydride, itaconic anhydride, succinic anhydride, phthalic anhydride, etc.)
Adducts with 1 mol of the compound can also be used.

■Carboxyl group-containing fluororesin fluorine-containing polymerizable unsaturated monomer (C), carboxyl group-containing polymerizable unsaturated monomer (d), and other polymerizable unsaturated monomers as necessary (b) A copolymer containing as a monomer component. As these monomer components, the same ones as mentioned above can be used.

In addition to the above resins, resins obtained by reacting the fluoropolyol resin and the polycarboxylic anhydride compound can also be used.

(2) Carboxyl group-containing polyester resin Examples include resins obtained by esterifying the polybasic acid and the polyhydric alcohol.

[Isocyanate group-containing resin]

The following items can be mentioned.

(2) Isocyanate group-containing vinyl resin A polymer containing an isocyanate group-containing polymerizable unsaturated monomer (e) and, if necessary, other polymerizable unsaturated monomers (b) as monomer components.

Examples of the isocyanate group-containing polymerizable unsaturated monomer (e) include monomers represented by the following general formulas (9) and (10).

R6 CH2=C-Coo{CnH2n}NCO (9) [wherein R6 and n are the same as above. ] The monomer of the above general formula (9) includes, for example, isocyanate ethyl (meth)acrylate.

[In the formula, R6 and n are the same as above. R7 represents a hydrogen atom or an alkyl group having 5 or less carbon atoms. ]The above general formula (10
) includes, for example, α,α-dimethyl-m-isopropenylbenzyl isocyanate.

In addition to the above, a reaction product of 1 mol of the hydroxyl group-containing polymerizable unsaturated monomer (b) and 1 mol of a polyisocyanate compound can be used. Examples of the polyisocyanate compound include toluene diisocyanate, 1,6-hexamethylene diisocyanate, 4,4'-diphenylmethane diisocyanate, 4,4'-diphenyl ether diisocyanate, phenylene diisocyanate, naphthalene diisocyanate, and biphenylene diisocyanate. Diisocyanate, 3,3'-dimethyl-4,4'-biphenylene diisocyanate, dicyclohexylmethane, 4,4'
-diisocyanate, p-xylene diisocyanate,
m-xylene diisocyanate, bis(4-isocyanate phenyl) sulfone, isobropylidene bis(4-
phenyl isocyanate), lysine isocyanate, isophorone diisocyanate, and their polymers and bullets.

Furthermore, as the isocyanate group-containing fluororesin, in addition to those mentioned above, those obtained by reacting a hydroxyl group-containing fluororesin with, for example, the polyisocyanate compound can also be used.

(2) Inocyanate group-containing fluororesin A resin obtained by adjusting the hydroxyl group-containing fluororesin and the polyisocyanate compound so that the isocyanate component is in excess.

(2) Isocyanate group-containing polyester resin A resin obtained by adjusting the hydroxyl group-containing polyester resin and the polyisocyanate compound so that the isocyanate component is in excess.

(2) Isocyanate group-containing polyurethane resin A resin obtained by preparing the hydroxyl group-containing polyether resin and the polyisocyanate compound so that the isocyanate component is in excess.

[Silane group-containing resin]

Typical examples of the resin include, for example, a resin obtained by reacting the hydroxyl group-containing resin with the isocyanate group-containing silane compound described below, and a resin obtained by reacting the isocyanate group-containing resin with the hydroxyl group-containing silane compound described below. Examples include the silicone resins mentioned above for the hydroxyl group-containing silicone resins.

[Epoxy group-containing resin]

A resin obtained by reacting the hydroxyl group-containing resin with the isocyanate group-containing epoxy compound described below.

The compound (B) used in the resin composition (1) has 1 epoxy group and a functional group that reacts with the functional group in the resin (A).
One or more of each is present in the molecule. The resin (
The functional group that reacts with the functional group in A) may be the same as the epoxy group.

When the functional group is the same as an epoxy group, it is necessary to contain two or more epoxy groups in one molecule.

Next, a representative compound (B) will be explained.

[Epoxy compound containing hydroxyl group]

Examples of the compound include the following general formulas (11) to (2).
Compounds represented by 1) can be mentioned.

Indicates an elementary group. ] In general formulas (11) to (21), 2 having 1 to 8 carbon atoms
The valent hydrocarbon group can be appropriately selected from the above divalent hydrocarbon groups having 1 to 20 carbon atoms. Further, as the divalent hydrocarbon group having 1 to 20 carbon atoms, the same groups as mentioned above can be mentioned.

Specific examples of compounds represented by general formulas (11) to (21) include. For example, [In each of the above formulas, R6 and n are the same as above. R8 is a divalent hydrocarbon group having 1 to 8 carbon atoms, and R9 is the same or different and can be a divalent hydrocarbon group having 1 to 20 carbon atoms.

[Silane group-containing epoxy compound]

For example, compounds represented by the following general formulas (22) to (25) can be mentioned.

As a specific example of \0' Y represented by, for example, Y [wherein R6 and R8 are the same as above, and R8 may be the same or different. Y is the same or different and represents a hydrogen atom, a hydroxyl group, a hydrolyzable group, an alkyl group having 1 to 8 carbon atoms, an aryl group, or an aralkyl group. However, at least one of Y is a hydrogen atom, a hydroxyl group, or a hydrolyzable group. ] In the general formulas (22) to (25), the hydrolyzable group includes the groups of the above general formulas (I) to (VI). Furthermore, the same alkyl groups, aryl groups, and aralkyl groups having 1 to 8 carbon atoms can be exemplified as mentioned above.

Examples include compounds represented by general formulas (22) to (25).

In addition to the above-mentioned compounds, compounds represented by general formulas (22) to (25) may also be used with polysilane compounds described below (for example, general formula (
Compounds obtained by condensation with the compounds represented by 38) to (40) can also be used.Specifically, the following can be mentioned.

[Polyepoxy compound]

Compounds represented by the following general formulas (26) to (33) can be mentioned.

[In the formula, R6 and R8 are the same as above, and R6 and R
8 may be the same or different. RIO is the same or different and represents an alkyl group, phenyl group, aryl group, or aralkyl group having 1 to 8 carbon atoms.

Rl+ is the same or different and has a hydrogen atom or a carbon number of 1 to 4
represents an alkyl group. W represents 0 and an integer from 1 to 10. ] Specific examples of the compounds represented by general formulas (26) to (33) include LC and the like.

In addition to the above, for example, the following can be used.

Adducts with anate compounds (Polyisocyanate compounds that can be used include, for example, aliphatic diisocyanates such as hexamethylene diisocyanate or trimethylhexamethylene diisocyanate; cycloaliphatic diisocyanates such as hydrogenated xylylene diisocyanate or isophorone diisocyanate 1) Diisocyanates; organic diisocyanates themselves such as aromatic diisocyanates such as tolylene diisocyanate or 4,4'-diphenylmethane diisocyanate, or combinations of each of these organic diisocyanates with polyhydric alcohols, low-molecular all-polyester resins, water, etc. Examples include adducts, polymers of each organic diisocyanate as described above, and isocyanate biuret bodies, etc., and a typical commercially available example of these is "Parnock D-750".
, -800, DN-950, -970 or 15-4
55'' [The above are Dainippon Ink & Chemicals ■ products], [Desmodule LSNHL, IL or N3390J
(Manufactured by Bayer, West Germany), "Takene D-"
102, -202, -110N or -123NJ
(Takeda Pharmaceutical ■Product), “Coronate LSHL, E
H or 203J [Nippon Polyurethane Kogyo product], [Duranate 24A-90CXJ [Asahi Kasei Kogyo product], etc.)) (e.g., tetrahydrophthalic anhydride, trimethylolpropane, and 1,4-butanediol) Examples include those obtained by oxidizing an esterified product (with a number average molecular weight of 900) obtained by esterification reaction with peracetic acid or the like.

[Incyanate group-containing epoxy compound] Examples include compounds obtained by reacting the hydroxyl group-containing epoxy compound and the polyisocyanate compound so that epoxy groups and isocyanate groups remain. in particular,
For example, - Reaction product of the compound represented by general formula (11) and hexamethylene diisocyanate - Reaction product of general formula (21) and xylene diisocyanate n diisocyanate - Compound represented by general formula (18) and isophorone diisocyanate Examples include a reaction product of the compound represented by the general formula (20) and isophorone diisocyanate, and the like.

(1) The compound (C) used in the composition has one or more functional groups that react with the functional groups in the resin (A) and one or more silane groups in one molecule.

The functional group that reacts with the functional group in the resin (A) may be the same as the silane group. When the functional group is the same as a silane group, it is necessary to contain two or more silane groups in one molecule.

Next, a representative compound (C) will be explained.

[Hydroxyl group-containing silane compound]

Compounds represented by the following general formulas (34) to (36) can be mentioned.

HO-R8 -Si-Y CHi CH3 Y [In each formula, R9% RIO and Y are the same as above, and R9, R1G and Y may be the same or different.

However, any one of Y is a hydrogen atom, a hydroxyl group, or a hydrolyzable group. ] Specific examples of the compounds represented by general formulas (34) to (36) include OCH3 HO (CH2 ) 3 81-OCH30CH3 and the like.

In addition, in addition to the above, for example, general formulas (34) to (36
) and a polysilane compound described below can also be used. As an example of the condensate, CH3 HO (CH2 ) a ball Si-0 sa' Tr O C
An example is H 3CH3.

[Polysilane compound]

Hydrolyzable groups directly bonded to silicon and Si
A compound having two or more groups selected from OH groups, specifically, for example, the following general formulas (38) to (40)
Compounds represented by can be mentioned.

Y' I Y'-Si-Y'Y' R 1G Y'-31-Y'Y' R IG RIll-81-Y'Y' [In each of the above formulas, RIG is the same as above, and R 10 is They may be the same or different. Y' are the same or different and represent a hydrogen atom, a hydroxyl group, or a hydrolyzable group. ] Specific examples of the compounds represented by the general formulas (38) to (40) include dimethyldimethoxysilane, dibutyldimethoxysilane, diisopropoxysilane, diphenyldibutoxysilane, diphenyldiethoxysilane, and diethyldimethoxysilane. Silanol, dihexyldisilanol methyltrimethoxysilane, methyltriethoxysilane, ethyltriethoxysilane, propyltrimethoxysilane, phenyltriethoxysilane, phenyltributoxysilane, hexyltriacetoxysilane,
Methyltrisilanol, phenyltrisilanol, tetramethoxysilane, tetraethoxysilane, tetrabioxysilane, tetraacetoxysilane, diisopropyloxydibaroxysilane, tetrasilanol,
[Epoxy group-containing silane compound] The above-mentioned silane group-containing epoxy compounds can be mentioned.

[Isocyanate group-containing silane compound] Examples include compounds represented by the following general formulas (40) and (41).

etc. can be mentioned.

In addition to those mentioned above, condensates of the polysilane compounds mentioned above can also be used.

Y 0CN-Si-Y (4 1
)Y [In each of the above formulas, R8 and Y are the same as above, and Y may be the same or different. However, at least one Y represents a hydrogen atom, a hydroxyl group, or a hydrolyzable group. ] Specific examples of compounds represented by general formulas (40) and (41) include, for example, OCNC2 H431 (QC}l 3 ) 3, O
CNC3 H6 81 (OC2 Hs) 3,
OCNC3 Hs St (OC2 Hs) 2
,CH3OCNC2H4Si(OCH3)2,C
H3 OCNCH 2 81 (OC2 Hs) 3, O
CNCH 2 St (OCH 3 ) 3, OCN
CH 2 81 (OC2 H5 ) 2, CH3 OCNCH 2 S1 (OCH 3) 3 , CH
3 CH a 0CN- C3 H6 -Si(OCClh)3
CH 3 I C[{3 l OCN- C3 Hs -SiN-( C2 H5
)2CHI3O0CN-81 (OCCH3)3OCNSi OCC4119 and the like can be mentioned.

In addition to the above, compounds obtained by reacting the hydroxyl group-containing silane compound with the polyisocyanate compound can be used.

Specifically, the following can be mentioned.

Reaction products of general formula (34) and hexamethylene diisocyanate or tolylene diisocyanate, for example, can be mentioned.

Furthermore, a condensate of the epoxy group-containing silane compound and, for example, the polysilane compound can also be used. Examples of the compound include:

[Mercapto group-containing silane compound]

Examples include compounds represented by the following general formula (42).

HS-R8 -St-Y Y [In the formula, R8 and Y are the same as above. Y may be the same or different. However, at least one Y represents a hydrogen atom, a hydroxyl group, or a hydrolyzable group. ] Specific examples of the compound represented by general formula (42) include HS-C3H6 -St (OCCH3 )2C H3 and the like.

In addition to the above, the hydroxyl group-containing silane compound may be added to the polyisocyanate compound and thiocol compound (for example, HS
-C, H2m-OH, m is the same as above. ),
For example, the following can be mentioned.

Furthermore, condensates of the mercaptosilane compounds and, for example, polysilane compounds can also be used.

[NH group- or NH2 group-containing silane compound] The following general formula (
Compounds represented by (43) and (44) can be mentioned.

Y j }{2 N-R8 -81-Y Y Y HN (R8 81 Y)2 Y [In each of the above formulas, R8 and Y are the same as above. Y and R8 may be the same or different. However, at least one Y represents a hydrogen atom, a hydroxyl group, or a hydrolyzable group. ] Specific examples of compounds represented by general formulas (43) and (44) include OCH3 H2 N (CH2 )3 -Si-OCHa0
CH3 OCdlg l O C z H s and the like can be mentioned.

In addition, in addition to the above, general formulas (43) and (44)
) and the above-mentioned polysilane compounds can also be used. Examples of the condensate include the following.

[Unsaturated group-containing silane compound]

The same ones as the silane group-containing polymerizable unsaturated monomer (10) described later can be used.

Resin (A) can have a number average molecular weight of about 3000 to 200000, preferably about 5000 to soooo.

Compound (B) and compound (C) are about 120 to 1000
0, preferably 120 to 3000 number average molecular hills.

The reactant (D) obtained by reacting the resin (A) with the compound (B) and the compound (C) each has an average of 1 or more, preferably an average of 2 to 40 epoxy groups and silane groups in one molecule. and can have.

(2) The resin composition resin (E) has on average one or more functional groups in one molecule that react with the functional groups of the compound (B), and specifically, You can select and use them as appropriate.

Compound (B) has on average one or more functional groups in one molecule that react with the functional groups of resin (E), and also has one or more epoxy groups on average.

The functional group in the compound (B) may be the same as the epoxy group. As the compound (B), the same compounds as those described in (1) resin composition can be used.

The resin (G) has on average one or more functional groups in one molecule that react with the functional groups of the compound (C), and specifically, it is appropriately selected from the resin compositions (1) above. It can be used as

Compound (C) has on average one or more functional groups in one molecule that react with the functional groups of resin (G), and also has one or more silane groups on average. The functional group in the compound (C) may be the same as the silane group. As the compound (C), the same compounds as those described in (1) Resin composition can be used.

Resins (E) and (G) are about 3,000 to 200,000,
Preferably, it can have a number average molecular weight of 5000 to soooo.

The reactant (F) obtained by reacting the resin (E) and the compound (B) has an average of 1 or more per molecule, preferably 2 to 1 per molecule.
It can have 40 or more epoxy groups.

The reactant (H) obtained by reacting the resin (G) and the compound (C) has an average of 1 or more, preferably an average of 2 per molecule.
It can have ~40 silane groups.

Reactant (F) and reactant (H) can be blended so that the ratio of epoxy group/silane group is usually 1/99 to 99/1.

(3) Resin composition The epoxy group-containing polymerizable unsaturated monomer (J) is a compound having an epoxy group and a radically polymerizable unsaturated group in one molecule. The epoxy group may be alicyclic or alicyclic. The radically polymerizable unsaturated group is, for example, the radically polymerizable unsaturated group, and the epoxy group-containing polymerizable unsaturated monomer of R6 CH2=CC00- is, for example, the following general formulas (45) to (57). Compounds represented by can be mentioned.

cH2 = C-CC- CH2 = CHCH20-CH
2=C}{O-, CH2=CI{- [wherein, R6 is the same as above. ] R6 (56) [In each of the above formulas, R", R8, R9 and W are the same as above. R6, R8 and R9 may be the same or different.] Represented by general formulas (45) to (57) Specific examples of compounds containing radically polymerizable unsaturated groups include, for example, monomers containing the following general formulas (58) to (6).
0) can be mentioned.

The radically polymerizable unsaturated group is [In each formula, R6 and R8 are the same as above. R6 and R
8 may be the same or different. ] General formula (58) ~
Specific examples of the compound represented by (60) include the following.

As the monomer, for example, the following general formulas (61) to (6
Compounds represented by 3) can be mentioned.

[In each of the above formulas, R6 and R8 are the same as above. R6 and R
8 may be the same or different. ] General formula (61) ~
Specific examples of the compound represented by (63) include the following.

Examples of the epoxy group-containing u-polymerizable unsaturated monomer in which the radically polymerizable unsaturated group is CH2=C-CN- include compounds represented by the following general formulas (64) to (69). .

[In each formula, R6, R8, R9 and W are the same as above, and R6, R8 and R9 may be the same or different. ] Specific examples of the compounds represented by general formulas (64) to (6) include the following.

For example, the epoxy group-containing polymerizable unsaturated monoplate in which the radically polymerizable unsaturated group is C H2 = C H C H2 0- is represented by the following general formula (
Compounds represented by (70) to (73) can be mentioned.

[In each of the above formulas, R6 and R8 are the same as above, and R6
and R8 may be the same or different. ] General formula (7
Specific examples of compounds represented by 0) to (73) include:
For example, the following can be mentioned.

Examples of the epoxy group-containing unsaturated monomer in which the radically polymerizable unsaturated group is CH2=CHO- include the following general formula (74
) to (76) can be mentioned.

R6 [In each of the above formulas, R6 and R8 are the same as above, and R8
may be the same or different. ] General formula (74) ~ (
Specific examples of the compound represented by 76) include the following.

As the epoxy group-containing unsaturated monomer in which the radically polymerizable unsaturated group is CH2=CH1, for example, the following general formula (77) is used.
Compounds represented by (79) can be mentioned.

[In each of the above formulas, R6 and R8 are the same as above, and R8
may be the same or different. ] General formula (77) ~ (
Specific examples of compounds represented by (7) include, for example.

Examples of R6 radically polymerizable unsaturated groups include compounds represented by the following general formulas (80) to (84).

[In each of the above formulas, R6, R8 and R9 are the same as above, and R6 and R9 may be the same or different. ] Specific examples of the compounds represented by general formulas (80) to (84) include the following.

A compound having at least one silane group and a radically polymerizable unsaturated group in one molecule of the silane group-containing polymerizable unsaturated monomer (K).

As the radically polymerizable unsaturated group, for example, R6 CH2 =CCOO- R6 CH2 = C1 CH2 Thousand CHO- CH2 = CHCH2 01 [In the formula, R6 is the same as above. ] etc. can be mentioned.

Examples of the silane group-containing polymerizable unsaturated monomer in which the R6 radically polymerizable unsaturated group is CH2=CCOO- include a compound represented by the following general formula (85).

Y [wherein R6, R9 and Y are the same as above, and Y may be the same or different. However, at least one Y represents a hydrogen atom, a hydroxyl group, or a hydrolyzable group. ] Specific examples of the compound represented by general formula (85) include:
For example, γ-(meth)acryloxybyltrimethoxysilane, γ-(meth)acryloxypyltriethoxysilane, γ-(meth)acryloxypyltrippoxysilane, γ-(meth)acryloxypylmethyldimethoxysilane, γ- -(meth)acryloxypylmethyldiethoxysilane, γ-(meth)acryloxypylmethyldipropoxysilane, γ-(meth)acryloxybutylphenyldimethoxysilane, γ-(meth)acryloxybutylphenyldiethoxy Silane, γ
1-(meth)acryloxybutyl phenyl dibutoxysilane, γ-1(meth)acryloxypyldimethylmethoxysilane, γ-(meth)acryloxypyldimethylethoxysilane, γ-(meth)acryloxypyl pylphenylmethylmethoxy Silane, γ-(meth)acryloxypyrphenylmethylethoxysilane, γ-(
meth)acryloxypyltrisilanol, γ-(meth)acryloxypylmethyldihydroxysilane, γ-(meth)acryloxybutylphenyldihydooxysilane, γ-(meth)acryloxypyldimethylhydroxysilane, γ- Examples include (meth)acryloxypylphenylmethylhydroxysilane, CI300CCH3CtHs, and the like.

Examples of the silane group-containing polymerizable unsaturated monomer include compounds represented by the following general formulas (86) to (88).

[In the formula, R6, R9 and Y are the same as above, and Y may be the same or different. However, at least one Y represents a hydrogen atom, a hydroxyl group, or a hydrolyzable group. ] Specific examples of the compounds represented by general formulas (86) to (88) include the following.

CH-=CHdC2H<ES゛i(OH)xR6 As a silane group-containing polymerizable unsaturated monomer in which the radically polymerizable unsaturated group is CH2=C1, for example, the following general formula (8
Compounds represented by (9) and (90) can be mentioned.

R6 Y CH2 =CHSi (OCCH3) 3CH2 =
CHCH2Si (OCC}{3) 3CH2 =C
t{SL (CH3) 2 N(CH3 ) 2Y c In the formula, R6, R9 and Y are the same as above, and Y may be the same or different. However, at least one Y represents a hydrogen atom, a hydroxyl group, or a hydrolyzable group. ] Specific examples of compounds represented by the general formulas (8) and (90) include, for example, CH2 = CHSi (OCH 3 ) 3CH2 =
CHSi (OC2 H s ) 3CH2=CHSi
(OCH3)2CH3CH2=CHSi
(CH3) 2 0CH 3CI+2 = CIICI
12 81 (OCII 3 ) 3 Examples of silane group-containing polymerizable unsaturated monomers in which the radically polymerizable unsaturated group is CH, 2 = CHO- include the following general formulas (91) and (
92) can be mentioned.

Y CH3 CH2 =CHO-Si-Y (
92) Y [In the formula, R9 and Y are the same as above, and Y may be the same or different. However, at least one Y represents a hydrogen atom, a hydroxyl group, or a hydrolyzable group. ] Specific examples of compounds represented by general formulas (91) and (92) include: CH3 8 CH3 CH2 = CHO(CH2) 2 Si-OCH
3CH3 CH3 CH3 etc. can be mentioned.

Examples of the silane group-containing polymerizable monomer in which the radically polymerizable unsaturated group is CH2=CHCH20- include compounds represented by the following general formulas (93) and (94).

Y CH2 = CHCH2 0-St-Y (9
3) Y Y CH2 = CHCH2 0-R9 -81-Y
(94)Y [In the formula, R9 and Y are the same as above, and Y may be the same or different. However, at least one of Y represents a hydrogen atom, a hydroxyl group, or a hydrolyzable group. ] Specific examples of the compounds represented by general formulas (93) and (94) include, in addition to the silane group-containing polymerizable unsaturated monomer, the silane group-containing polymerizable unsaturated monomer, For example, a polysiloxane unsaturated monomer having a silane group and a polymerizable unsaturated group obtained by reacting with a polysilane compound (for example, a compound represented by general formulas (38) to (40)) may also be used. Can be done.

Specific examples of the polysiloxane unsaturated monomer include compounds of the general formula (85) and general formulas (38) to
(40) with at least one compound, the former 30 to 0
．． 001 mol% of the latter, 70 to 99.999 mol% of the latter (such as those described in JP-A-62-275132) and the following compounds.

CH”　OCR. etc. can be mentioned.

Ql'' OCR Yu0(;CHs Other polymerizable unsaturated monomers (M) Radical polymerization with the epoxy group of the monomer (J) and the silane group of the monomer (K) without an active group Compounds having sexually unsaturated groups can be used.

Specifically, the hydroxyl group-containing unsaturated monomer (a), the polymerizable unsaturated monomers (b-1) to (b-6), the fluorine-containing unsaturated monomer (C), and the carboxyl group Examples include the polymerizable unsaturated monomer (d) contained therein.

The copolymer (L) obtained by radical polymerization reaction of the monomer (J), the monomer (K), and other monomers (M) as necessary has an average of 1 in each molecule. or more, preferably 2 to 40 on average, of epoxy groups and silane groups.

As the monomer (J), the monomer (K), and the monomer (M), the same monomers as described in the resin composition (3) above can be used.

The copolymer (N) of the monomer (J) and the monomer (M) is 1
The molecule can have an average of 1 or more epoxy groups, preferably 2 to 40 epoxy groups.

Copolymer (P) of monomer (K) and monomer (M) is 1
The molecule can have an average of one or more silane groups, preferably 2 to 40 silane groups.

Homo or copolymer (N) and Homo or copolymer (N)
P) usually has an epoxy group/silane group ratio of 1/99 to
It can be blended so that the ratio is 99/1.

(5) Resin composition polymerizable unsaturated monomer (Q) A compound having in one molecule a radically polymerizable unsaturated group and a functional group that reacts with the functional group of compound (S).

The functional group of the monomer (Q) is a group inert to the epoxy group, and the functional group may be the same as the epoxy group.

Regarding the copolymer (R) obtained using the monomer (Q), the following examples (1) to (2) will be given.

■ Hydroxyl group-containing polymerizable unsaturated monomer (a), epoxy group-containing polymerizable unsaturated monomer 0) and, if necessary, polymerizable unsaturated monomers (for example, monomers (b-1) to ( A copolymer having a hydroxyl group as a functional group, obtained by radical polymerizing b-6) and a fluorine-containing polymerizable unsaturated monomer (C), etc.).

■ Isocyanate group-containing polymerizable unsaturated monomer (e), epoxy group-containing polymerizable unsaturated monomer (J), and optionally a polymerizable unsaturated monomer (for example, monomer (b-1) ~(b
-6) and a fluorine-containing polymerizable unsaturated monomer (C), etc.), and has an isocyanate group as a functional group.

■ Epoxy group-containing polymerizable unsaturated monomer (J) and, if necessary, polymerizable unsaturated monomers (e.g. monomer (b-1) ~
(b-6) and a fluorine-containing polymerizable unsaturated monomer (C), etc.), a copolymer having an epoxy group as a functional group.

The compound (S) is a compound having a functional group that reacts with the functional group in the copolymer (R) and a silane group, and the compound (c
) can be selected as appropriate.

The reactant (T) obtained by the reaction of the copolymer (R) and the compound (S) each has an average of 1 or more, preferably an average of 2 to 40 epoxy groups and silane groups in one molecule. be able to.

(6) Resin composition polymerizable unsaturated monomer (V) A compound having in one molecule a radically polymerizable unsaturated group and a functional group that reacts with the functional group of compound (W).

The functional group of the monomer (V) is a group inert to the silane group, and the functional group may be the same group as the silane group.

Regarding the copolymer (W) obtained using the monomer (V), the following examples 1 to 2 are given.

■ Hydroxyl group-containing polymerizable unsaturated monomer (a), silane group-containing polymerizable unsaturated monomer (K), and if necessary, polymerizable unsaturated monomers (for example, monomers (b-1) to A copolymer having a hydroxyl group as a functional group, obtained by radical polymerization of (b-6) and a fluorine-containing polymerizable unsaturated monomer (c), etc.).

■Isocyanate group-containing polymerizable unsaturated monomer (e), silane group-containing polymerizable unsaturated monomer (K), and optionally a polymerizable unsaturated monomer (for example, monomer (b-1)) ~(b-
A copolymer having an isocyanate group as a functional group obtained by radical polymerizing 6) and a fluorine-containing polymerizable unsaturated monomer (C), etc.).・■ Carboxyl group-containing polymerizable unsaturated monomer (d), silane group-containing polymerizable unsaturated monomer (K), and if necessary, a polymerizable unsaturated monomer (for example, monomer (b-1) ) ~ (b-6
) and a fluorine-containing polymerizable unsaturated monomer (C), etc.), and a copolymer having a carboxyl group as a functional group.

The compound (W) is a compound having an epoxy group and a functional group that reacts with the functional group in the copolymer (V).
You can choose from B) as appropriate.

The reactant (X) obtained by the reaction of the copolymer (V) and the compound (W) each has an average of 1 or more, preferably an average of 2 to 40 epoxy groups and silane groups in one molecule. be able to.

(7) Resin composition homopolymer (N), copolymer (N), and reactant (H) are the same monomers and reactants as described in the above (2) and (4) resin composition. can be used.

The monopolymer or copolymer (N) and the reactant (H) can be blended so that the epoxy group/silane group ratio is usually 1/99 to 99/1.

(8) Resin composition homopolymer (P) or copolymer (P) and reactant (F)
The same monomers and reactants as described in the resin compositions (2) and (4) above can be used.

The homopolymer or copolymer (P) and the reactant (F) can be blended so that the epoxy group/silane group ratio is usually 1/99 to 99/1.

Each of the above-mentioned ingredients can be obtained by conventionally known methods. That is, the reaction between a hydroxyl group and an isocyanate group,
The condensation reaction, copolymerization reaction, etc. of silane groups can be carried out based on conventionally known methods. For example, the reaction between a hydroxyl group and an isocyanate group is sufficient for about 30 to 360 minutes at room temperature to about 130°C. The condensation reaction of silane groups is carried out in the presence of an acid catalyst (e.g. hydrochloric acid, sulfuric acid, formic acid, acetic acid, etc.)
Heating at about 150°C for about 1 to 24 hours is sufficient.

Further, the copolymerization reaction may be carried out using the same method and conditions as those for ordinary synthesis reactions of acrylic resins, vinyl resins, etc., and thereby the desired copolymer can be obtained. As an example of such a synthesis reaction, each monomer component is dissolved or dispersed in an organic solvent, and 60% is added in the presence of a radical polymerization initiator.
A method of heating while stirring at a temperature of about 180° C. can be shown. The reaction time may be about 1 to 10 hours. Further, as the organic solvent, one that is inert to the monomer or compound used, such as an ether solvent, an ester solvent, a hydrocarbon solvent, etc. can be used. When using a hydrocarbon solvent, it is preferable to use other solvents in view of solubility.

As the radical polymerization initiator, any commonly used radical polymerization initiator can be used; examples thereof include peroxides such as benzoyl peroxide, t-butylperoxy-2-ethylhexanoate, and azoisobutylnitrile. and azo compounds such as azobisdimethylbaretnitrile.

(1) to (8) Reactants (D), (F), (
H), (L), (N), (P), (T) and (W) are each about 3,000 to 200,000, preferably about 500
It can have a number average molecular weight ranging from 0 to soooo.

In the resin composition, it is preferable to introduce a carboxyl group and/or a hydroxyl group in addition to the epoxy group and silane group, since this further improves the curability of the film.

The resin composition having a carboxyl group can be dissolved or dispersed in water by neutralizing it with a basic compound.

In the resin composition of the present invention, the above resin or copolymer may be combined with other resins (e.g., vinyl resin, polyester resin, urethane resin, silicone resin, epoxy resin, etc.).
Modified resins chemically bonded with can also be used in the same way.

The resin composition may be used, for example, in a hydrocarbon solvent such as toluene or xylene, a ketone solvent such as methyl ethyl ketone or methyl isobutyl ketone, an ester solvent such as ethyl acetate or butyl acetate, or an ether solvent such as dioxane or ethylene glycol diethyl ether. The resin composition can be used in a dissolved or dispersed form in an alcoholic solvent such as butanol or propanol, water, or the like, or in the form of a non-aqueous dispersion containing the resin composition as a dispersion stabilizer component.

A non-aqueous dispersion of polymer particles can be obtained by polymerizing one or more radically polymerizable unsaturated monomers in an organic solvent in the presence of the dispersion stabilizer. The organic solvent dissolves the dispersion stabilizer and the radically polymerizable unsaturated monomer, but does not dissolve the resulting polymer particles.

All the monomers already described can be used as the monomers used to form the polymer which is the polymer particle component of the non-aqueous dispersion. Preferably, the polymer serving as the particle component is a copolymer containing a large amount of highly polar monomer, since it must not be dissolved in the organic solvent used. Namely, methyl (meth)acrylate, ethyl (meth)acrylate, (meth)acrylonitrile, 2-hydroxy(
Meth)acrylate, Hydroxybutyl (meth)acrylate, (meth)acrylamide, acrylic acid, methacrylic acid, itaconic acid, styrene, vinyltoluene, α
- It is preferable to contain a large amount of monomers such as methylstyrene and N-methylol (meth)acrylamide. In addition, the particles of the non-aqueous dispersion may be crosslinked if necessary.
be able to. Examples of methods for crosslinking the inside of the particles include a method of copolymerizing polyfunctional monomers such as divinylbenzene and ethylene glycol dimethacrylate, and a method of simultaneously using an epoxy group-containing monomer and a carboxy group-containing monomer. Can be done.

The organic solvent used for the non-aqueous dispersion does not substantially dissolve the dispersed polymer particles produced by the polymerization, but is a good solvent for the dispersion stabilizer and radically polymerizable unsaturated monomer. Included. Specific examples of organic solvents that can be used include aliphatic hydrocarbons such as pentane, hexane, heptane, octane, mineral spirits, and naphtha; aromatic hydrocarbons such as benzene, toluene, and xylene;
Alcohol, ether, ester and ketone solvents, such as isopropyl alcohol, n-butyl alcohol, isobutyl alcohol, octyl alcohol, cellosolve, butyl cellosolve, diethylene glycol monobutyl ether, methyl isobutyl ketone, diisobutyl ketone, ethyl acyl ketone, methyl Examples include hexyl ketone, ethyl butyl ketone, ethyl acetate, isobutyl acetate, acyl acetate, 2-ethylhexyl acetate, etc. Each of these can be used alone or in a mixture of two or more, but generally , aliphatic hydrocarbons are preferably used in combination with aromatic hydrocarbons and alcohol-based, ether-based, ester-based, or ketone-based solvents such as those mentioned above. Furthermore, halogenated hydrocarbons such as trichlorotrifluoroethane, metaxylene hexafluoride, tetrafluorobutane, etc. can also be used if necessary.

Polymerization of the above monomers is carried out using a radical polymerization initiator. Usable radical polymerization initiators include, for example, azo initiators such as 2,2-azoisobutyronitrile and 2,2'-azobis(2,4-dimethylvalenitrile), penzoyl peroxide, and lauryl peroxide. Examples include peroxide-based initiators such as oxide and tert-butyl peroctoate, and these polymerization initiators generally contain 100% of the monomer (radically polymerizable unsaturated monomer) to be subjected to polymerization.
It can be used in a range of about 0.2 to 10 parts by weight. The amount of the dispersion stabilizer resin to be present during the above polymerization can be appropriately selected from a wide range depending on the type of resin, but in general, the amount of the radically polymerizable unsaturated monomer is 3 to 100 parts by weight of the resin. About 240 parts by weight, preferably about 10 to 82 parts by weight may be used.

In the above-mentioned non-aqueous dispersion, by combining the dispersion stabilizer resin and the polymer particles, the storage stability of the non-aqueous dispersion is improved, and further excellent curing properties such as transparency, smoothness, and mechanical properties are achieved. A film can be formed. Examples of the method for bonding the dispersion stabilizer resin and the polymer particles include a method of polymerizing a radically polymerizable unsaturated monomer in the presence of a dispersion stabilizer having a polymerizable double bond. can.

The most effective method for introducing polymerizable double bonds is to add α,β monoethylenically unsaturated monocarboxylic acids such as acrylic acid, methacrylic acid, and itaconic acid to a portion of the oxirane groups in the resin. Although convenient, there are other methods, such as adding an isocyanate group-containing monomer such as isocyanoethyl methacrylate to hydroxyl groups that have been incorporated in the resin in advance, and adding glycidyl methacrylate to some of the carboxyl groups in the resin. There are methods such as adding a monomer.

Furthermore, as a method for bonding the dispersion stabilizer and the polymer particles, in addition to the above-mentioned method, as a monomer component forming the polymer particles, for example, γ-methacrylate trimethoxysilane, γ-methacrylate trimethoxysilane, etc. Acryloxybutyltriethoxysilane, γ-acryloxybutyltrimethoxysilane, γ-methacryloxybutyltriethoxysilane, γ-
There is a method using reactive monomers such as acryloxypyltrisilanol.

In the present invention, the resin (I) alone or the resin (II)
The mixture of resin (m) and resin (m) itself can form the coating film targeted by the present invention, but in order to accelerate the curing reaction of the coating film, it is preferable to include a curing catalyst as exemplified below. .

Curing Catalyst: (1) Metal Chelate Compound The metal chelate compound is preferably an aluminum chelate compound, a titanium chelate compound, or a zirconium chelate compound. Among these chelate compounds, chelate compounds containing a compound capable of forming a keto-enol tautomer as a ligand forming a stable chelate ring are preferred.

Compounds that can constitute keto-enol tautomers include β-diketones (acetylacetone, etc.), acetoacetic esters (methyl acetoacetate, etc.), malonic acid esters (ethyl malonate, etc.), and Ketones having a hydroxyl group (such as diacetone alcohol), aldehydes having a hydroxyl group at the β position (such as salicylaldehyde), esters having a hydroxyl group at the β position (methyl salicylate), and the like can be used. In particular, acetoacetic acid esters, β
- Favorable results are obtained using diketones.

The aluminum chelate compound has, for example, the general formula R,10-AROR++ [wherein Rl+ is the same or different and has 1 to 1 carbon atoms]
20 alkyl or alkenyl groups are shown. ] It is suitably prepared by mixing the above-mentioned compound capable of forming the keto enol tautomer at a molar ratio of about 3 moles or less per mole of the aluminum alkoxide represented by the formula, and heating as necessary. be able to.

As the alkyl group having 1 to 20 carbon atoms, the above-mentioned alkyl group having 1 to 20 carbon atoms
In addition to the 10 alkyl groups, examples include undecyl, dodecyl, tridecyl, tetradecyl, octadecyl, etc., and examples of alkenyl groups include vinyl, allyl, etc.

Examples of the aluminum alcoholates represented by the general formula (95) include aluminum trimethoxide, aluminum triethoxide, aluminum tri-n-proboxide, aluminum tri-isopropoxide, aluminum tri-n-butoxide, aluminum triisobutoxide, aluminum tri-s. -butoxide, aluminum tri-tert-butoxide, etc., especially aluminum triisopropoxide, aluminum tri-tert-butoxide, etc.
Preferably, ec-butoxide, aluminum tri-n-butoxide, etc. are used.

The titanium chelate compound has, for example, the general formula [wherein Rl+ has the same meaning as above]. m is 0 to 10
indicates an integer. ] For 1 mole of Ti in titanates represented by
It can constitute the above keto-enol tautomer. It can be suitably prepared by mixing the compounds at a molar ratio of usually about 4 moles or less and heating if necessary.

Titanates represented by the general formula (96) include m
For those with 1, tetramethyl titanate, tetraethyl titanate, tetra n-probyl titanate, tetra isobutyl titanate, tetra n-butyl titanate, tetra isobutyl titanate, tetra tert
-butyl titanate, tetra n-bentyl titanate, tetra n-hexyl titanate, tetraisooctyl titanate, tetra n-lauryl titanate, etc., especially tetraisobutyl titanate, tetra n-
Suitable results are obtained using butyl titanate, tetraisobutyl titanate, tetratert-butyl titanate, and the like. In addition, for those where m is 1 or more, tetraisobutyl titanate, tetra n-butyl titanate, tetra isobutyl titanate, tetra tert
- butyl titanate dimer to 11-mer (general formula (9)
6) where m=1 to 10) gives preferable results.

The zirconium chelate compound has, for example, the general formula [where m and Rl+ have the same meanings as above]. ] Preferably prepared by mixing the above-mentioned compound capable of forming the keto enol tautomer at a molar ratio of about 4 mol or less to the Zrl mole in the zirconate represented by the formula, and heating as necessary. can do.

As the zirconates represented by the general formula (97),
Tetraethyl zirconate, Tetra n-probyl zirconate, Tetra isobyl zirconate, Tetra n-butyl zirconate, Tetra see-butyl zirconate, Tetra tert-butyl zirconate, Tetra n-pentyl zirconate, Tetra tert-
Bentyl zirconate, tetra-tert-hexyl zirconate, tetra-n-heptyl zirconate, tetra-n-octyl zirconate, tetra-n-stearyl zirconate, etc., especially tetra-tert-tert-hexyl zirconate, tetra-n-propyl zirconate. , tetraisobutyl zirconate, tetra n-butyl zirconate, tetra sec-butyl zirconate, tetra tert-butyl zirconate, etc., yielding favorable results. In addition, for those where m is 1 or more, tetraisobutyl zirconate, tetra n-probyl zirconate, tetra n-butyl zirconate, tetra isobutyl zirconate, tetra sec-butyl zirconate, tetra tert-butyl zirconate dimer to 11-mer (m=1 to 10 in general formula (97)
) gives suitable results. Further, it may contain a structural unit in which these zirconates are associated with each other.

Particularly preferred chelate compounds in the present invention include tris(ethylacetoacetate)aluminum, tris(n-propylacetoacetate)aluminum, tris(isopropylacetoacetate)aluminum, and tris(n-butylacetoacetate)aluminum. , isopropoxybis(ethylacetoacetate)aluminum, diisopropoxyethylacetoacetatealuminum, tris(acetylacetonato)aluminum, tris(probionylacetonato)aluminum, tris(ethylacetonato)aluminum, diisopropoxypoxybutionyl aluminum acetonate,
Acetylacetonatosha bis (probionyl acetonato)
Aluminum, monoethylacetoacetate bis(acetylacetonato)aluminum, tris(impropylate)aluminum, tris(see-butyrate)
Aluminum, diisopropoxy birate mono-see-butoxyaluminum, aluminum chelate compounds such as tris(acetonatoacetone)aluminum; diisopropoxy bis(ethylacetoacetonato)titanate,
Diisopropoxy bis(acetylacetonato) titanate, diisopropoxy bis(acetylacetonato)
Titanium chelate compounds such as titanates; tetrakis(acetylacetone) zirconium, tetrakis(n
-propylacetoacetate) zirconium, tetrakis(acetylacetonato)zirconium, tetrakis(
Examples include zirconium chelate compounds such as zirconium (ethyl acetoacetate).

Any one type of the aluminum chelate compound, zirconium chelate compound, and titanium chelate compound may be used, or two or more types may be used in combination as appropriate. The blending amount of the crosslinking reaction curing agent is 100% of the solid content of the resin composition.
It is appropriate that the amount is about 0.01 to 30 parts by weight based on the weight of parts.

If the amount is less than this range, crosslinking curability tends to decrease, and if it is more than this range, it tends to remain in the cured product and reduce water resistance, which is not preferable. The preferred amount is 0.1 to 10 parts by weight, and the more preferred amount is 1 to 5 parts by weight.
Parts by weight.

(2) Lewis acid metal halides, compounds in which the metal shares a halogen and other substituents, and complex salts of these compounds can be mentioned. Specifically, for example, AIC. A7BF
3. AIF. ．． AIEtCI1. AIEt. 2
CI! ．． SncL1, TxCmu. TIB)-4
, TIF4, lrcL. 2rBr<, ZrF<, S
nCI4. FeCmu, SbClx. SbCfg
．． PC1x, pcm, Ga[mu], GaFs, InF
a, BCmu, BBrs, BF. ,BF3: (OC
2Hi1 2, BF4: (OCJsl-, BCmu:
roc2Hs+-, BF. :NH. C2H. , BF
．． :NHICJ. OH. BFs: NHCHzCH-
CHzCHz, PF. S→()), etc. can be mentioned.

(3) Protonic acids The protonic acids include, for example, organic protonic acids such as methanesulfonic acid, ethanesulfonic acid, trifluoroethanesulfonic acid, benzenesulfonic acid, p''-toluenesulfonic acid, phosphoric acid, Phosphite nasphinic acid,
Examples include inorganic protons such as phosphonic acid, sulfuric acid, and perchloric acid.

(4) Metal alkoxides As the metal alkoxides, specifically, the aforementioned aluminum alkoxides, titanium alkoxides, zirconium alkoxides, and the like can be used.

Furthermore, in addition to the above, alkoxides of metals such as iron, calcium, and barium, preferably compounds to which an alkoxy group having 1 to 18 carbon atoms are bonded, can be mentioned. These compounds may be associated.

(5) Organometallic compound Specific examples of the compound include triethylaluminum, diethylzinc, and the like.

(6) Compound having S i -0-Af bond A specific example of this compound is aluminum silicate.

These curing catalysts can be used alone or in combination of two or more. In addition, the blending amount of these resins (I
) It is in the range of about 0.01 to 30 parts by weight, preferably about 0.1 to 5 parts by weight, per 100 parts by weight of the solid content of the resin (II) or a mixture of resin (II) and resin (m).

These paints of the present invention may contain the following, if necessary.

(1) Hydroxyl group-containing resin and hydroxyl group-containing compound. (
2) Carboxyl group-containing resin and carboxyl group-containing compound (3) Silane group-containing resin and silane group-containing compound (4) Epoxy group-containing resin and epoxy group-containing compound (5) Chelating agent (to improve storage stability) 6) Organic solvent and/or water (7) Pigment (8) Additive resin (for example, cellulose acetate butyrate resin) (9) Polyepoxy compound As the above pigment, colored pigments, extender pigments, metallic pigments, etc. can be used. As zinc white, titanium white,
Carbon black, chrome vermilion, red iron, permanent red, perinone orange, chrome yellow, antimony yellow, monoazo, isoindolinone, thren, chrome green, cyanine green, ultramarine blue, cyanine blue, quinacridone red, zinc powder, zinc Monolithic pigments such as chromate include clay, calcium carbonate, white carbon, beryum carbonate, etc. Metallic pigments include aluminum powder, bronze powder, stainless steel powder, nickel powder, iron oxide-coated mica, titanium oxide-coated mica, Examples include titanium oxide-coated mica-like iron oxide and mica-like iron oxide. Among these, colored pigments are used to color the top coat (coloring pigments), and metallic pigments are used to finish the paint film with a metallic tone with a glittering feel (metallic paint).

In the present invention, the top coat is applied to the cationic electrodeposited surface or the intermediate coated surface.

The coating process for the top coat paint includes, for example, (1) painting a colored pigment (one-coat system), (2) painting a colored paint or a metallic paint, and then painting a clear paint (2)
(3) Painting with a colored paint or metallic paint and then painting with a clear paint twice (3-coat system).

It is most preferable that the top coat of these colored paints, metallic paints, clear paints, etc. is a paint containing the resin (I) alone or a mixture of resin (II) and resin (m) as an essential component. , at least one of the colored paint, metallic paint, and clear paint in the above painting steps (2) and (3) may be the paint defined above. ) may be used in combination. Preferably, only the outermost coating film is formed using the above-mentioned specific paint.

First, in the one-coat system (1), the colored paint is applied by air spray, air spray, electrostatic coating, dip coating, etc.
It is suitable to cure the colored coating by heating to 0°C. The film thickness is preferably in the range of 20 to 100 μm based on the cured coating film.

In the two-coat system (2), a colored paint or metallic paint (including water-based paint) is applied, a clear paint is applied without or after curing, and then both or the clear paint is cured. It is a process, 2
It is called a one-coat, two-bake system or a two-coat, two-bake system. In this system, the paint film thickness of colored paint or metallic paint is 10 to 5 mm based on the cured film.
0μ, and the film thickness of the clear paint is preferably 20 to 100μ, respectively. Further, as a method for curing the film thickness in this system, heating at 80 to 200°C is suitable.

The coating method for these paints can be performed in the same manner as in (1) above.

In the three-coat system (3), it is suitable to apply a clear paint after coating with the two-coat system (2) above and cure it in the same manner as above. The thickness of the second clear coat is preferably 20 to 60 microns based on the cured coating.

In the present invention, the above resin CI) alone or the resin (II
) and resin (■) must be used as either or both the intermediate coat and the top coat; colored paints must be used as the top coat. , metallic paint, and clear paint.

Next, examples related to the present invention will be described.

As a general rule, all parts and percentages are based on weight.

Example■. Production Example of Cationic Electrodeposition Paint ■CHD-1 The following components were dispersed in a Pebble Mill for 40 hours and diluted with water to a solid content concentration of 20% to prepare an electrodeposition bath.

Water-soluble epoxy polyamine resin Note) 100 parts (as solid content) Titanium oxide 35 parts Purified kaolin 10 parts 145 parts Resin: Pigment = 100:45 Note) Epoxy polyamine resin with a resin base number of 50 was neutralized with acetic acid. Water-solubilized at .25 CED-2 After dissolving 174 parts of 2.4-tolylene diisocyanate in 78 parts of methyl isobutyl ketona, 87 parts of methyl ethyl ketoxime was added dropwise at 25 to 35°C. The isocyanate value of the reaction product after completion of the dropwise addition was 161.

Furthermore, 130 parts of 2-ethylhexyl alcohol was added dropwise, and after the completion of the dropwise addition, the temperature was raised to 100°C, maintained for 4 hours, and then the isocyanate number was measured and found to be 0. Thus solid content 8
3% and the thermal dissociation temperature of the blocking agent is about 100° C. and about 160° C. in the presence of a catalyst to obtain a curing agent having two different blocked isocyanate groups.

Next, 1900 parts of bisphenol A type epoxy resin (trade name Ebicoat 1004, manufactured by Shell Chemical Co., Ltd.) having an epoxy equivalent of 950 was dissolved in 1012 parts of butyl cellosolve, and 124 parts of diethylamine was heated to 120°C at 80 to 100°C. The mixture is maintained for 2 hours to obtain an epoxy resin-amine adduct having an amine value of 47.

Next, dimer acid type polyamide resin with an amine value of 100 (product name: Persamide 460, Henkel Hakusui Co., Ltd.)
1,000 parts of amide resin are dissolved in 429 parts of methyl isobutyl ketone, heated to reflux at 130 to 150°C, the water produced is distilled off, and the terminal amino group of the amide resin is converted to ketimine. This material is maintained at 150°C for about 3 hours, and after water has stopped distilling off, it is cooled to 60°C. Next, this was added to the epoxy resin monoamine adduct and heated to 100°C,
After holding for 1 hour, the mixture was cooled to room temperature to obtain an epoxy resin-amine-polyamide addition resin having a solid content of 68% and an amine value of 65. 1.5 parts of acetic acid was added to 100 parts of this resin to neutralize it,
Obtain a base resin.

Next, 23 parts of the curing agent and 3 parts of dibutyltin dilaurate were added to 101.5 parts of the above base resin, and 121.4 parts of deionized water was added with sufficient stirring to give a solid content of about 35%.
A clear emulsion for cationic electrodeposition was prepared. Add the following 43% pigment paste (A) to 572 parts of this emulsion.
) 139.4 parts with stirring, and 5 parts of deionized water.
It was diluted with 88.6 parts to obtain an electrodeposition bath with a solid content of 20%.

O pigment paste (A) Quaternary ammonium chloride epoxy resin Titanium pentoxide 14 Purified clay
10 carbon black
1 deionized water 39
．． 7 ■ CED-3 1 equipped with a stirring device, thermometer, cooling tube and heating mantle
3,507.5 parts of deionized water and 80 parts of Latemul K-180 (manufactured by Kao Corporation, 25% aqueous solution) were placed in a flask, and the temperature was raised to 90° C. with stirring. This is a polymerization initiator, VA-086 (manufactured by Wako Pure Chemical Industries, Ltd.)
Twenty percent of an aqueous mixture of 12.5 parts dissolved in 500 parts deionized water was added. After 15 minutes, 5 percent of the following monomer mixture was added.

Styrene 430 parts n-butyl acrylate 440 parts 1,6-hexanediol diac 40 parts Lylate 2-hydroxyethyl acrylate 40 parts KBM-
503' 50 parts 8 γ-methacrylate trimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd.) Next, after further stirring for 30 minutes, dropping of the remaining monomer mixture and aqueous polymerization initiator solution was started. The monomer mixture was fed for 3 hours, and the aqueous polymerization initiator solution was fed for 3 and 5 hours, respectively, and the polymerization temperature was maintained at 90°C. After the dropwise addition of the aqueous polymerization initiator solution was completed, the mixture was heated for 30 minutes and kept at 90°C, then cooled to room temperature, filtered through a cloth, and taken out. Thus 20% solids, pH 3.7, viscosity of 90 cps (
BM type rotational viscometer, No. 2 spindle), average particle size 71 nm (measured with Coal Tar Nanosizer N-4)
A gelled fine particle polymer was obtained.

572 parts of a clear emulsion for cationic electrodeposition with a solid content of 35% (manufactured by Kansai Paint Co., Ltd., trade name, Elekron 9450) consisting of a polyamide-modified epoxy resin and a completely blocked diisocyanate, and 120 parts of the gelled fine particle polymer with a solid content of 20% and the solid. Add 139.4 parts of pigment paste A below at 43% with stirring and add 76 parts of deionized water.
8. A cationic electrodeposition bath was obtained by diluting with 6 parts.

Pigment paste A: Quaternary ammonium chloride epoxy resin/titanium oxide/purified clay/carbon black/deionized water = 5/14/10/1/39. Regarding the blending amount of the above-mentioned fine particle polymer, Examples 4 and 6 and Comparative Example 1 in Table 2 below.
Further electrodeposit C'ED-4 as shown (2
In the coating electrodeposition step, 120 parts of the gelled fine particle polymer was increased to 150 parts.

■CED-4 Hydroxyl group 100, amine value (mgKOH/g solid content)
1.5 parts of acetic acid was added to 133.3 parts of a 75% solids solution of polyamide-modified epoxy resin No. 50 for neutralization, to obtain a neutralized resin solution.

Next, to 134.8 parts of the above neutralized resin solution, 20 parts of 2-ethylhexyl alcohol diblock of 4,4'-diphenylmethane diisocyanate and 1 part of dibutyltin diacetate were added.
35% solids by adding further deionized water with thorough stirring to create an emulsion with a solids content of 35%. This emulsion had a degree of emulsification of 93%. Further, the minimum electrodeposition current density was 0.20 mA/cm2. Pigment paste A1 of the above CED-3 is added to this Emma/l/572 parts.
Add 39.4 parts and add deionized water to make the solids content about 20%.
A cationic electrodeposition paint bath with a pH of 6.7 was obtained.

(2) CHD-5 It was prepared in the same manner as CED-3 except that 1.5 parts by weight of dibutyltin penzoate oxy were added per 100 parts by weight of the total amount of the polyamide-modified epoxy resin of CEDO3 and the completely blocked polyisocyanate.

■Manufacturing example of intermediate coating paint■SE-1 Glycidyl methacrylate 14.2 parts Ethyl acrylate} Molecular weight consisting of 74.22-hydroxyethyl acrylate 11.8 (peak molecular weight by gel permeation chromatography, same below) 20,000 acrylic resin [resin (
23.6 parts of γ-methacryloxypropyl trichloride and 76.4 parts of methoxysilane ethyl acrylate [resin (
100 parts of a 50% solution of xylene (2)] and 1 part of tris(acetylacetonato)aluminum were mixed.

Titanium oxide JR-6 for 20 parts by weight of the solid content of the above resin.
02 (manufactured by Teikoku Kako Co., Ltd.) was blended with 60 parts by weight, and dispersed with a solvent for 1 hour using a paint shaker.
Created a paste. The bulges of this paste were measured with a bulge gauge and were 10 μm or less. The above-mentioned resin was added to this paste and the weight ratio of titanium oxide/resin solid content was adjusted to 60/100 to produce intermediate coating paint SE-1.

This intermediate paint is Swazol 1000 (Cosmo Oil)
Co., Ltd.) / Cellosolve Acetate = 22 seconds with 80/20 weight ratio thinner / Ford Cup NO. It was diluted to 4 and used for painting.

■SE-2 An acrylic resin with a molecular weight of 7000 consisting of 3,4-epoxyhexyl 20.0 parts methyl methacrylate siloxane macromer 20.0 2-hydroxyethyl methacrylate 13.0 parts and 2-ethylhexyl acrylate 47.0. 100 parts of a 60% solution (trol/isobutyl acetate = 1/1), 0.2 part of tetrakis(ethyl acetate) zirconium, and 1 part of ethyl acetoacetate were mixed.

*Methyltrimethoxysilane/γ-methacrylatetrimethoxysilane = 20 molecules/lmol of siloxane macromer [7000 siloxane macromer] Method for manufacturing intermediate coating paint SE-1 using the above resin Intermediate paint SE-2 having a titanium oxide/resin solid content weight ratio of 60/100 was prepared according to the above procedure, and diluted in the same manner as above.

(2) SE-3 In SE-2 above, 20 parts of Ebiko}828 (manufactured by Shell Chemical Co., Ltd.) was blended per 100 parts of acrylic resin.

Intermediate coating SE-3 was produced using the above resin in a titanium oxide/resin solid content ratio of 60/100 by weight according to the method for producing intermediate coating SE-1, and diluted in the same manner as described above.

■SE-4 Trimethylolpropane 40.95 parts Adipic acid 87.6 Neopentyl glycol 73.5 Phthalic anhydride 4
1746 parts of a 75% xylene solution of polyester with oxidation 2.2 consisting of 4.4 was reacted with 131 parts of succinic anhydride, and 313 parts of highly oxidized polyester was added with 1 part of the following compound P.
29 parts were added to carry out an addition reaction in oxidation 6.

Compound P: Per 100 parts of this polyester having an epoxy group at the end, 5 parts of methylphenyl silicone resin (molecular weight 1000) with a methoxy end, 30 parts of the following oligomer, 10 parts of acetylatocene, and 20 parts of fine aluminum hydroxide. Added.

Oligomer: Using the above resin, an intermediate coating material SE-4 having a titanium oxide/resin solid content = 60/100 weight ratio was produced according to the method for producing intermediate coating material SE-1, and diluted in the same manner as above.

■SE-5 Intermediate paint whose main components are polyester resin and amino resin (manufactured by Kansai Paint Co., Ltd.), trade name Amirac N-
2 sealer).

■Manufacturing example of top coating paint■TS-1 (Colored paint) 3,4-epoxycyclohexy 20.0 parts methyl methacrylate siloxane monomer''< 20.02-hydroxyethyl methacrylate 13.0 tons n-butyl methacrylate 100 parts of a 60% solution (trol/isobutyl acetate = 1/1) of an acrylic resin having molecules jl7000 consisting of 47.0, 0.2 part of tetrakis(ethyl acetoacetate) zirconium, and 1 part of ethyl acetoacetate were mixed. .

A siloxane macromer with a molecular weight of 7000 in which 8 methyltrimethoxysilane/γ-methacrylate trimethoxysilane = 20 mol/l mol was hydrolyzed and bonded to 20 parts by weight of the solid content of the above resin, titanium oxide JR-
602 (manufactured by Teikoku Kako Co., Ltd.) was blended and dispersed together with a solvent for 1 hour using a paint shaker to create a paste. The bulges of this paste were measured with a bulge gauge and were 10 μm or less. The above resin was added to this paste and the weight ratio of titanium oxide/resin solid content was adjusted to 60/100 to produce top coat TS-1.

This top coat is Swasol 1000 (Cosmo Oil)
Co., Ltd. / Cellosolve Acetate = 22 seconds with 80/20 weight/total ratio thinner / Ford Cup No. It was diluted to 4 and used for painting.

■TS-2 (Colored paint) Trimethylolpropane 40.95 parts Adipic acid 87.6 Neobentyl glycol 73.5 Phthalic anhydride
75 of polyester with oxidation of 2.2 consisting of 44.4
The following compound 1 was added to 313 parts of highly oxidized polyester prepared by reacting 1746 parts of % xylene solution with 131 parts of succinic anhydride.
29 parts were added to carry out an addition reaction up to oxidation 6.

Compound: O To 100 parts of this polyester having an epoxy group at its terminal, 5 parts of methylphenyl silicone resin (molecular 81,000) having a methoxy terminal group, 10 parts of acetylacetone, and 20 parts of fine aluminum hydroxide were added.

Using the above resin, a top coat TS-2 with a weight ratio of titanium oxide/resin solid content of 60/100 was produced according to the method for producing the top coat TS-1, and diluted in the same manner as above.

(2) TS-3 (Colored paint) 20 parts of the oligomer used in SE-4 was further added to 100 parts of the mixed solution of acrylic resin, tetrakis(ethyl acetate) zirconium, and ethyl acetoacetate in TS-1.

Using the above resin, a top coat TS-3 with a weight ratio of titanium oxide/resin solid content of 60/100 was produced according to the method for producing the top coat TS-1, and diluted in the same manner as above.

■TS-4 (Colored paint) Top coat mainly composed of polyester resin and amino resin (manufactured by Kansai Paint Co., Ltd., product name: Amirac No.
6000 White).

■TM-1 (metallic paint) Glycidyl methacrylate 14.2 parts n-butyl methacrylate 44. 2-hydroxyethyl acrylate 11.6 xylol 50% solution of acrylic resin with molecular weight 20,000 consisting of styrene 30.0 1
00 parts and γ-methacrylate 23.6 parts Rimethoxysilane n-butyl methacrylate 46. ．． 4 Xylene 50% solution 1 of acrylic resin with a molecular weight of 20,000 made of styrene 30.0
00 parts and tris(acetylacetonato)aluminum 1
part was mixed.

Aluminum pigment (Aluminum Paste #55-519, manufactured by Toyo Aluminum Co., Ltd.) was added to a resin liquid containing 95 parts by weight of the solid content of the above resin and 5 parts by weight of Cellosolve Acetate Butyrate resin as an active ingredient of aluminum. A metallic paint was prepared by thoroughly mixing with a stirrer.

This metallic paint was prepared using Ford Cuff No. 1 thinner with a weight ratio of ethyl acetate/toluene/Swazol 1500 (Cosmo Oil) = 40/40/20. 4 to 13 seconds and used for painting.

■TM-2 (Metallic paint) 2-Hydroxyethyl methacrylate 26.0 parts Acrylic acid 7.2 Methyl methacrylate} 15 parts of the following compound Q and the following compound R are added to an acrylic resin (molecule if 40,000) consisting of 66.8. After addition reaction of 10 parts, Troll 50
% solution.

Compound Q: Compound R: CON CH2 CH2 S1 (OC2
Hs)3 1 part of tris(acetylacetonato)aluminum was added to 100 parts of this solution.

Using the above resin, metallic paint TM-2 was manufactured and diluted according to the manufacturing method of metallic paint TM-1.

(2) TM-3 (Metallic paint) 20 parts of the oligomer used in SE-4 was added to 100 parts of the mixed solution of acrylic resin, tetrakis(ethyl acetate) zirconium, and ethyl acetoacetate in TS-1.

Metallic paint TM-3 was manufactured and diluted using the above resin according to the manufacturing method of metallic paint TM-1.

■TM-4 (Metallic paint) Meric paint whose main components are thermosetting acrylic resin, amino resin, and cellosolve acetate butyrate resin (manufactured by Kansai Paint Co., Ltd., trade name: Magikron No. 30)
0 silver).

■TC-1 (Clear paint) 3,4-epoxycyclohexy 20.0 parts Methyl methacrylate Siloxane monomer 'A 20.02-Hydroxyethyl methacrylate 136〇1ton N-Butyl methacrylate 47.0 with a molecular weight of 7000 100 parts of a 60% solution of acrylic resin Trol/isobutyl acetate = 1/1, 0.2 part of tetrakis(ethyl acetoacetate) zirconium, and 1 part of ethyl acetoacetate were mixed.

A siloxane macromer with a molecular weight of 7000 in which X-methyltrimethoxysilane/γ-methacryloxybrobyltrimethoxysilane = 20 mol/l mol is hydrolyzed and bonded to 100 parts by weight of the solid content of the above resin, and an ultraviolet absorber (Tinuvin 900: manufactured by Ciba Geigy) 1.5 parts by weight was blended to prepare clear paint TC-1.

Apply this paint to Swasol #1000 (Cosmo Oil Co., Ltd.)
) using Ford Cup No. 4 to 22 seconds.

@ITc-2 (Clear paint) 20 parts of the oligomer used in SE-4 was further added to 100 parts of the mixed solution of acrylic resin, tetrakis(ethyl acetate) zirconium, and ethyl acetoacetate in TS-1.

Clear paint TC-2 was manufactured using the above resin and diluted according to the manufacturing method of clear paint TC-1.

■TC-3 (Clear paint) A clear paint (manufactured by Kansai Paint Co., Ltd.) whose main components are thermosetting acrylic resin and amino resin.

Product name: Magikron No. 300, clear paint)
.

■ Examples and Comparative Examples The surface of the cationic electrodeposition paint CEDI~5 obtained in the production example was coated with Pearlbond 13030 (Nippon Parkerizing Co., Ltd.).
Co., Ltd., 0.8X300 chemically treated with zinc phosphate type)
A cold-rolled dull steel plate (having a flat part and an acute corner part having an angle of 30 degrees) having a diameter of 90 mm was immersed, and electrodeposition was performed using it as a cathode. Electrodeposition coating conditions are: Electrodeposition paint bath temperature 28℃, T) H6.5, voltage 25℃ for 1 coat electrodeposition.
0V, film thickness (based on the cured film thickness on the flat part) 20~
A 25 μm electrodeposition coating film was formed, the coating film was washed with water after electrodeposition, and 1
The coating film is cured by heating at 70°C for 30 minutes.

On the other hand, in 2-coat electrodeposition, the conditions for the first (first layer) electrodeposition coating are: electrodeposition paint bath temperature: 28°C, pH: 6.5, voltage: 3.
00V, film thickness (based on the cured film thickness on the flat part) 10
An electrodeposition coating film having a thickness of μm was formed, and after electrodeposition, the coating film was washed with water, and a second electrodeposition coating (second layer) was applied to the coated surface without curing. Electrodeposition coating conditions were a bath temperature of 30°C and a pH of 6.
7. The voltage was 300 V, and the thickness of the second layer was 15 μm.

After washing with water, both coatings were cured by baking at 180°C for 30 minutes.

An intermediate coating material was spray-painted on the surface of the cured electrodeposited coating film, and was cured by heating. The coating film thickness, heating conditions, etc. are also listed in Table 2.

In the top coat, the viscosity of the coloring agent and clear paint was adjusted to 20 to 24 seconds (Ford Cup #4/20°C), and the viscosity of the metallic paint was adjusted to 12 to 14 seconds (same as above). The colored paint was used as a topcoat (one-coat, one-baking method), and the metallic paint was a two-coat, two-bake method in which a clear paint was applied to the wet surface and cured by heating. These film thicknesses and heating conditions are also listed in Table 2.

Table 2 describes the coating process using the various paints obtained in the above production examples.

■ Coating film performance test results Using coated plates obtained according to the coating process shown in Table 2, the performance of the overall coating film was investigated.

The results were as shown in Table 3.

Table 3 (continued) The test method is as follows.

■IMAGE CLARITY METE
R: Measured using Suga Test Instruments Co., Ltd.). The numbers in the table are ICM values ranging from 0 to 100%, the higher the number, the better the image clarity (image clarity), and if the ICM value is 80 or higher, the image clarity is extremely excellent. Show that.

■Pencil hardness: Scratch the coating surface with the lead of a Mitsubishi 22 pencil,
The maximum hardness of the core that will not scratch the painted surface is indicated by a symbol.

■Xylol resistance Hold the gauze soaked in xylol with your fingers and rub the painted surface strongly back and forth 10 times. The degree of melting of the painted surface, scratches and swelling is between good (◎) and markedly poor (×): ◎, ○, ■, △,
Measured in 5 stages of ×.

■Create 100 grids by making incisions at 1 mm intervals in each direction on the painted surface to reach the adhesive substrate. A cellophane adhesive tape was pasted on top of this and the condition was evaluated after it was suddenly removed.

Display: Number of peeled eyes/100.

■After immersing in acid-resistant 40% H2S04 at 40℃ for 5 hours, washing with water,
The condition of the painted surface was evaluated. ◎, depending on the degree, between no abnormalities (◎), significant glossy beard, and abnormalities such as soaking (×).
Judgment was made in five stages: O, ■, Δ, and ×.

■Scratch resistance: Use a dyeing rub fastness tester (manufactured by Daiei Kagaku Seiki Seisakusho). Knead polishing powder (Daruma Cleanser) with water, place it on the painted surface, press it with the testing machine terminal, and apply 0.5k.
Apply a load of g and perform 25 reciprocating friction. After washing with water, the degree of scratches was evaluated using a five-point scale of ◎, O, ■, △, and X.

■Water resistance Coated surface evaluation after immersion at 40°C for 10 days.

■Weather Resistance Based on the QUV accelerated weathering test using an accelerated weather resistance tester manufactured by Q Panel.

Test conditions: UV irradiation 16H/60°C water condensation 9H
The coating film was evaluated after being tested for 3,000 hours (125 cycles) with /50°C as one cycle.

■Edge corrosion resistance: 240 by JIS Z 2371 salt spray test
A time test was conducted to check for rust on the 30'' edge.

■Corrosion resistance on flat areas The coating film on non-scratching areas is examined for spot rust and blistering using the JIS Z 2371 salt spray test. 200
The test was carried out for 0 hours, and the presence or absence of spot rust and blistering was examined.

(that's all)

Claims (1)

[Claims] 1. A method in which a cationic electrodeposition paint with excellent film-forming properties is applied to sharp corners, and then, if necessary, an intermediate coat is applied, and then a top coat is applied to form a film. Either one or both of the intermediate coating and the top coating has a hydroxyl group directly bonded to a silicon atom and/or a resin having a hydrolyzable group and an epoxy group in the same resin, or a hydroxyl group and/or a hydroxyl group directly bonded to a silicon atom. Or, a coating film on a coated object having sharp corners, characterized by being a coating whose essential component is a resin made by mixing a resin with a hydrolyzable group and a resin with an epoxy group. Formation method.