JPH09263731A - Low-solvent resin composition, low-solvent coating composition prepared using the same, and method for coating therewith - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a low-solvent coating compsn. which has good chemical and physical properties, a good weatherability, excellent antisagging properties, and a desirable pot life and to provide a method for coating with the same. SOLUTION: This resin compsn. is prepared by using a combination of a first functional group which forms a coating film by curing and is selected from among hydroxyl, blocked hydroxyl, acetoacetyl, hydrolyzable silyl, epoxy, acid anhydride, and vinyl-ether-blocked carboxyl or phosphoryl groups with a second functional group selected from among silyl-blocked sulfo, silyl-blocked carboxyl, and silyl-blocked phosphoryl groups. The first functional group exists in a vinyl polymn. oligomer, and the second one, in the vinyl polymn. oligomer or in a single nonpolymerizable compd. The oligomer has an Mn of 300-1,500, an Mw of 300-3,000, and an Mw/Mn of 1-2.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a low solvent type resin composition useful for various applications such as paints, inks, adhesives, etc., a low solvent type paint composition using the same, and a low solvent type paint thereof. The present invention relates to a coating method for coating a composition. The present invention particularly has a low solvent type resin composition having good chemical and physical performance and weather resistance, excellent anti-sagging property and good pot life, and a low solvent type coating composition using the same. And a method for coating the low solvent type coating composition.

[0002]

2. Description of the Related Art Conventionally, an improvement in anti-sagging at the time of coating has been made by adding a rheology modifier. However, it is difficult to sufficiently improve the anti-sagging property by adding such a rheology modifier in a high solid coating system composed of a low molecular weight resin composition. As a method of improving the anti-sagging property, a method of using an acidic catalyst that starts curing immediately after coating has been proposed. However, it is difficult to achieve both sagging prevention property and pot life simply by using such an acidic catalyst, and it cannot be said to be a sufficient countermeasure from the viewpoint of workability.

[0003]

Accordingly, the present inventor has
For example, at a relatively low temperature such as 0 to 50 ° C., curing starts quickly, so that the anti-sagging property is excellent,
On the other hand, an excellent low-solvent type resin composition capable of ensuring a good pot life, a low-solvent type coating composition using the same, and as a result of diligent studies to develop a coating method therefor, a specific functional group In a low solvent type resin composition or a low solvent type coating composition consisting of a combination of, by using a silyl-blocked acid group having a specific structure in combination,
The present invention has been accomplished by finding that the above object can be achieved with certainty.

[0004]

That is, the present invention relates to the following inventions. 1. A first functional group selected from the group consisting of a hydroxyl group, a blocked hydroxyl group and an acetoacetyl group, and selected from the group consisting of a silyl blocked sulfonic acid group, a silyl blocked carboxylic acid group and a silyl blocked phosphoric acid group. Whether the first functional group is present in the same or different vinyl polymerized oligomer, and the second functional group is present in the vinyl polymerized oligomer. , Or present in separate compounds, and wherein the vinyl polymerized oligomer has a number average molecular weight of 300 to 1500, a weight average molecular weight of 300 to 3000, and a weight average molecular weight / number average molecular weight of 1-2. Solvent type resin composition, 2. A first functional group selected from the group consisting of a hydroxyl group, a blocked hydroxyl group and an acetoacetyl group, and selected from the group consisting of a silyl blocked sulfonic acid group, a silyl blocked carboxylic acid group and a silyl blocked phosphoric acid group. Whether the first functional group is present in the same or different vinyl polymerized oligomer, and the second functional group is present in the vinyl polymerized oligomer. , Or present in separate compounds, and wherein the vinyl polymerized oligomer has a number average molecular weight of 300 to 1500, a weight average molecular weight of 300 to 3000, and a weight average molecular weight / number average molecular weight of 1-2. Solvent type coating composition, 3. A first functional group consisting of a hydrolyzable silyl group and a second functional group selected from the group consisting of a silyl blocked sulfonic acid group, a silyl blocked carboxylic acid group and a silyl blocked phosphoric acid group, The vinyl polymerized oligomers are contained in the same or different vinyl polymerized oligomers, or the second functional group is present in a different compound, and the vinyl polymerized oligomers have a number average molecular weight of 600 to 1500 and a weight average molecular weight of 6
00-3000, and weight average molecular weight / number average molecular weight 1
3. A low-solvent type resin composition, characterized in that A first functional group consisting of a hydrolyzable silyl group and a second functional group selected from the group consisting of a silyl blocked sulfonic acid group, a silyl blocked carboxylic acid group and a silyl blocked phosphoric acid group, The vinyl polymerized oligomers are contained in the same or different vinyl polymerized oligomers, or the second functional group is present in a different compound, and the vinyl polymerized oligomers have a number average molecular weight of 600 to 1500 and a weight average molecular weight of 6
00-3000, and weight average molecular weight / number average molecular weight 1
4. A low-solvent type coating composition, characterized in that A first functional group selected from the group consisting of a hydroxyl group, a blocked hydroxyl group, a hydrolyzable silyl group and an epoxy group,
It contains a second functional group consisting of an acid anhydride group and a third functional group selected from the group consisting of a silyl blocked sulfonic acid group, a silyl blocked carboxylic acid group and a silyl blocked phosphoric acid group. The first functional group and the second functional group are present in the same or different vinyl polymerized oligomers and the third functional group is present in the vinyl polymerized oligomers or, if present, in a separate compound. And the vinyl polymerized oligomer has a number average molecular weight of 600 to 150.
0, a weight average molecular weight of 600 to 3000, and a weight average molecular weight / number average molecular weight of 1 to 2; A first functional group selected from the group consisting of a hydroxyl group, a blocked hydroxyl group, a hydrolyzable silyl group and an epoxy group,
It contains a second functional group consisting of an acid anhydride group and a third functional group selected from the group consisting of a silyl blocked sulfonic acid group, a silyl blocked carboxylic acid group and a silyl blocked phosphoric acid group. The first functional group and the second functional group are present in the same or different vinyl polymerized oligomers and the third functional group is present in the vinyl polymerized oligomers or, if present, in a separate compound. And the vinyl polymerized oligomer has a number average molecular weight of 600 to 150.
6. A low-solvent coating composition having a weight average molecular weight of 600 to 3000 and a weight average molecular weight / number average molecular weight of 1 to 2. A vinyl (thio) ether blocked carboxyl group, a phosphoric acid group or a hydroxyl group, a first functional group, an epoxy group, a second functional group, a silyl blocked sulfonic acid group, a silyl blocked carboxylic acid group, and And a third functional group selected from the group consisting of silyl-blocked phosphate groups, wherein the first functional group and the second functional group are present in the same or different vinyl polymerized oligomers, and the third functional group is Present in the vinyl polymerized oligomer or in a separate compound, and the vinyl polymerized oligomer has a number average molecular weight of 600 to 1500, a weight average molecular weight of 600 to 3000, and a weight average molecular weight of
7. A low-solvent type resin composition having a number average molecular weight of 1 to 2. A vinyl (thio) ether blocked carboxyl group, a phosphoric acid group or a hydroxyl group, a first functional group, an epoxy group, a second functional group, a silyl blocked sulfonic acid group, a silyl blocked carboxylic acid group, and And a third functional group selected from the group consisting of silyl-blocked phosphate groups, wherein the first functional group and the second functional group are present in the same or different vinyl polymerized oligomers, and the third functional group is Present in the vinyl polymerized oligomer or in a separate compound, and the vinyl polymerized oligomer has a number average molecular weight of 600 to 1500, a weight average molecular weight of 600 to 3000, and a weight average molecular weight of
8. A low-solvent type coating composition having a number average molecular weight of 1 to 2. A method for coating the surface of an article to be coated with the low solvent type coating composition according to any one of the above 2, 4, 6 and 8, wherein the article is rotatably supported about a substantially horizontal axis. The coating is applied to the surface of the object in a thickness that causes sagging on the surface that normally extends in the vertical direction, and then the object to be coated is substantially horizontal before the sagging of the paint applied to the surface of the object occurs due to gravity. At the speed at which the surface of the object to be coated shifts from a substantially vertical state to a substantially horizontal state before it starts to rotate about the directional axis and at least before the sag of the applied coating is caused by gravity, and by the centrifugal force due to the rotation. 10. A method for coating a low-solvent type coating composition, which comprises rotating at a speed lower than the speed at which the coating sags. The low solvent type coating composition according to any one of the above 2, 4, 6 and 8 is applied to the surface of an article to be coated and then heat cured to form a coating film on the surface of the article to be coated. A method for coating a characteristic low-solvent type coating composition.

[0005]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in detail. Description of functional group contained in coating resin used in the present invention The hydroxyl group (OH) used in the present invention is a functional group represented by --OH. The blocked hydroxyl group (BOH) used in the present invention is represented by --O--Z, where Z
Is a block group derived from a blocking agent bonded to an oxygen atom of a hydroxyl group, and a silyl block group or a vinyl (thio) ether block group represented by the following formula can be mentioned as a preferable example. [1] Silyl Block Group As the silyl block group, a silyl block group represented by the following formula (1) can be exemplified.

[0006]

Embedded image R ^{1 to} R ³ in the above formula (1) are each independently an alkyl group or an aryl group. Examples of the alkyl group include linear or branched alkyl groups having 1 to 10 carbon atoms, such as methyl group, ethyl group, propyl group, butyl group, s-butyl group, t-butyl group, pentyl group. And lower alkyl groups having 1 to 8 carbon atoms such as hexyl group are particularly preferable. The aryl group includes a phenyl group which may have a substituent, a naphthyl group, an indenyl group and the like, and particularly,
A phenyl group is preferred. Examples of the silyl block group represented by the formula (1) include trimethylsilyl group, diethylmethylsilyl group, ethyldimethylsilyl group, butyldimethylsilyl group, butylmethylethylsilyl group, phenyldimethylsilyl group, phenyldiethylsilyl group, diphenylmethylsilyl group. Group, a diphenylethylsilyl group and the like. In particular, the smaller the molecular weight of R ^{1 to} R ^3, the easier it is for the blocking group to come off, and the more preferable it is. As a blocking agent for forming such a silyl block group, halogenated silane can be preferably used. As the hagen atom contained in the halogenated silane,
Examples thereof include chlorine atom and bromine atom. Specific blocking agents include, for example, trimethylsilyl chloride, diethylmethylsilyl chloride, ethyldimethylsilyl chloride, butyldimethylsilyl bromide,
Butyl methyl ethyl silyl bromide etc. are mentioned. [2] Vinyl (thio) ether block group As the vinyl (thio) ether block group, a vinyl (thio) ether block group represented by the following formula (2) is exemplified.

[0007]

Embedded image R ¹ , R ² and R ³ in the above formula (2) are each independently a hydrogen atom or a hydrocarbon group having 1 to 18 carbon atoms. R
⁴ is a hydrocarbon group having 1 to 18 carbon atoms. Y is
It is an oxygen atom or a sulfur atom. R ³ and R ⁴ may be bonded to each other to form a heterocycle having Y as a hetero atom. Examples of the hydrocarbon group in the above formula include an alkyl group, a cycloalkyl group, an aryl group and the like. As the alkyl group, for example, a lower alkyl group having 1 to 8 carbon atoms such as methyl group, ethyl group, propyl group, butyl group, s-butyl group, t-butyl group, pentyl group and hexyl group is particularly preferable. . As the cycloalkyl group, for example,
Examples include a cyclopentyl group and a cyclohexyl group.
The aryl group includes a phenyl group which may have a substituent, a naphthyl group, an anthracene group and the like, and a phenyl group is particularly preferable. Such vinyl (thio) ether blocking groups can be formed by reacting an aliphatic vinyl ether or thioether or a cyclic vinyl ether or thioether with a hydroxyl group. Examples of the aliphatic vinyl (thio) ether include methyl vinyl ether, ethyl vinyl ether, isopropyl vinyl ether, n-propyl vinyl ether, isobutyl vinyl ether, 2-ethylhexyl vinyl ether, cyclohexyl vinyl ether and the like, or vinyl thioether corresponding thereto. Examples of the cyclic vinyl (thio) ether include 2,3-dihydrofuran,
3,4-dihydrofuran, 2,3-dihydro-2H-pyran, 3,4-dihydro-2H-pyran, 3,4-dihydro-2-methoxy-2H-pyran, 3,4-dihydro-4,4 -Dimethyl-2H-pyran-2-one, 3,4
-Dihydro-2-ethoxy-2H-pyran, sodium 3,4-dihydro-2H-pyran-2-carboxylate and the like and corresponding cyclic vinyl thioethers.

The acetoacetyl group (AA used in the present invention
EM) is a functional group represented by the formula: CH ₃ —CO—CH ₂ CO—. This functional group exists as a keto-enol tautomer in the coating composition. Therefore, the acetoacetyl group has a property as a hydroxyl group as well as a property as a ketone group. In the present invention, based on the property of the acetoacetyl group as a hydroxyl group, a crosslinking reaction is carried out,
It is a functional group used for curing. The hydrolyzable silyl group (Si) used in the present invention is a group that produces a silanol group by hydrolysis, and a group represented by the following formula (3) is preferred.

[0009]

Embedded image In the above formula, R ¹ and R ² may be the same or different,
Hydroxyl group, alkyl group, alkoxy group, -OSi (R ₁ R ₂ R ₃ ) (provided that R ₁ , R ₂ and R ₃ are the same or different alkyl groups or aryl groups), -NR ¹ R ² group ( However, R ¹ and R ² are alkyl groups or aryl groups), —NR ¹ COR ² (provided that R ¹ and R ² are alkyl groups or aryl groups), —COR ¹ group (provided that R ^{1 1} is an alkyl group or an aryl group), -O
COR ¹ group (provided that R ¹ is an alkyl group or aryl group), aryl group, -ONR ¹ R ² group (provided that R ¹ and R ² are an alkyl group or aryl group), -ONCR ¹ R ² groups (however,
R ¹ and R ² are alkyl groups or aryl groups). R ³ is an alkyl group, —NR ¹ R ² group (provided that R ¹ and R ² are
An alkyl group or an aryl group), a -COR ¹ group (however,
R ¹ is an alkyl group or an aryl group), an aryl group, a —NCR ¹ R ² group (provided that R ¹ and R ² are an alkyl group or an aryl group). In the above formula, examples of the alkyl group include linear or branched alkyl groups having 1 to 10 carbon atoms, and examples thereof include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, and s. -
Examples thereof include a butyl group, a t-butyl group and a pentyl group. Examples of the alkoxy group include those having an alkyl group portion similar to the above alkyl group. The aryl group particularly includes a substituted or unsubstituted phenyl group, and examples of the substituent include a halogen atom, an alkyl group, an alkoxy group and the like. Examples of the halogen atom as the substituent include a fluorine atom, a chlorine atom, a bromine atom or an iodine atom. The alkyl group as a substituent includes a linear or branched alkyl group having 1 to 10 carbon atoms, for example, a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, s- Examples thereof include a butyl group, a t-butyl group and a pentyl group. Also,
Examples of the alkoxy group as a substituent include those in which the alkyl group constituting the alkoxy group is the same as the above alkyl group. Examples of preferable substituents include a halogen atom such as a fluorine atom and a lower alkyl group having 1 to 5 carbon atoms.

The epoxy group (Ep) used in the present invention includes a non-alicyclic epoxy group and an alicyclic epoxy group. Examples of the non-alicyclic epoxy group include 1,2-
Examples thereof include those having an epoxy bond formed by an oxygen atom between carbon atoms of an epoxy group or an alkyl group such as a 1,3-epoxy group. 5 or 6 as the alicyclic epoxy group
Examples of the member ring (including bridged hydrocarbon) include those in which an oxygen atom is epoxy-bonded between adjacent carbon atoms of the ring. Of these, it is practically preferable to use a non-alicyclic epoxy group rather than an alicyclic epoxy group. The acid anhydride group (AA) is a functional group represented by -CO-O-CO-. The vinyl (thio) ether-blocked carboxyl group used in the present invention has a hydroxyl group of the carboxyl group,
It is a carboxyl group blocked with the vinyl (thio) ether block group. The vinyl (thio) ether blocked phosphoric acid group used in the present invention is a phosphoric acid group obtained by blocking the hydroxyl group of the phosphoric acid group with the vinyl (thio) ether block group. A silyl-blocked carboxylic acid group used in the present invention,
Silyl-blocked sulfonic acid groups or silyl blocks
Phosphoric acid group used in the present invention as the second functional group or the third functional group, silyl-blocked carboxylic acid group (BCa (s)), silyl-blocked sulfonic acid group (BSu (s)) and silyl group. The blocked phosphoric acid group (BPh (s)) is a functional group obtained by blocking the hydroxyl groups of the carboxylic acid group, the sulfonic acid group and the phosphoric acid group with the silyl block group. These functional groups may be contained as a functional group of the resin (or oligomer) that constitutes the coating resin in the coating resin, or the functional group of a non-polymerizable compound separate from those oligomers. It may be present as a group. These functional groups act as a so-called latent acidic catalyst in the paint and do not accelerate the curing reaction of the paint resin during storage, and the blocking agent dissociates with the humidity in the air after coating. Then, when heated at a relatively low temperature of 0 to 50 ° C., it has the property of promoting the curing reaction.

As the silyl-blocked carboxylic acid group, a functional group represented by --COOZ (Z is the same as the above silyl block group) is exemplified as a preferable functional group. As the silyl-blocked sulfonic acid group, a functional group represented by --SO ₂ OZ (Z is the same as the above silyl block group) is exemplified as a preferable functional group. Examples of the silyl-blocked phosphate group include functional groups represented by the following formula (4).

[0012]

Embedded image (However, Z is the same as the above silyl block group, and n
Is 1 or 2. The functional group represented by) is illustrated as a preferable functional group.

Main functional groups such as hydroxyl group, blocked hydroxyl group, acetoacetyl group, hydrolyzable silyl group, epoxy group, acid anhydride group, vinyl (thio) ether blocked carboxyl group or phosphoric acid group involved in curing reaction Oligomer containing a silyl-blocked acid group acting as a latent catalyst together with a group is used to prepare a monomer containing such a silyl-blocked acid group to prepare a resin having such a main functional group. It can be easily produced by polymerizing with the monomer used. Examples of the silyl-blocked acid group-containing monomer include a monomer having such an acid group and a polymerizable unsaturated group such as a vinyl group in the molecule. As the vinyl group, for example, an acrylic group,
Methacrylic groups are mentioned. Incidentally, between the silyl-blocked acid group and these vinyl groups, an alkylene group, an amide group, an ester group, an ether group, a ureido group,
Functional groups such as urea groups or combinations thereof may be present. As the functional group used for imparting vinyl polymerizability to the monomer having a silyl-blocked acid group, for example, those represented by the following formulas can be preferably cited.

[0014]

Embedded image In the above formula, R ¹ represents a hydrogen atom or a methyl group, and n and m represent an integer of 1 to 10, preferably 2 to 5. Examples of particularly preferable functional groups include (meth) acryloyloxyalkyl groups. Examples of the alkylene group contained in this functional group include an ethylene group and a propylene group. In the silyl-blocked phosphate group, there are two blocked hydroxyl groups,
Preference is given to only one blocked phosphate group. on the other hand,
The silyl-blocked acid group may be present in the oligomer constituting the coating resin as described above, or may be present in a compound other than the oligomer. The compound containing a silyl-blocked acid group is not particularly limited as long as it contains such an acid group. The moiety other than the silyl-blocked acid group contained in such a compound may be an alkyl group or an aryl group, and further an ether group, an ester group, an amide group, a ureido group, a urea group, or the like acid group. It may be connected. The compound containing a silyl-blocked acid group used in the present invention is obtained by blocking a compound containing a carboxylic acid, a sulfonic acid or a phosphoric acid with the above-mentioned silyl blocking agent. Examples of the free acid group-containing compound before blocking include the following compounds.

Carboxylic Acid Group-Containing Compounds Preferred carboxylic acid group-containing compounds include, for example, a reaction of a fatty acid such as caproic acid, capric acid, or caprylic acid, butanol or a monoalcohol such as 2-ethylhexanol with an acid anhydride. Examples thereof include an ester group-containing carboxylic acid obtained by the above, and an ester group-containing carboxylic acid obtained by a reaction of a hydroxyl group-containing (meth) acrylate and an acid anhydride. Examples of acid anhydrides include succinic anhydride and hexahydrophthalic anhydride. Sulfonic Acid Group-Containing Compound Preferred examples of the sulfonic acid group-containing compound include unsubstituted or polysubstituted benzenesulfonic acid such as mono-, di-, and tri-, and naphthalenesulfonic acid. There may be a plurality of sulfonic acid groups. Examples of particularly preferable sulfonic acid group-containing compounds include dinonylsulfonic acid and dinonyldisulfonic acid. Phosphoric acid group-containing compound As a preferable phosphoric acid group-containing compound, for example, mono-
Or a di-alkyl or aryl phosphate is mentioned. As the alkyl group, for example, methyl group, ethyl group, propyl group, butyl group, s-butyl group, t-butyl group,
A lower alkyl group having 1 to 8 carbon atoms such as a pentyl group and a hexyl group is particularly preferable. The aryl group includes a phenyl group which may have a substituent, a naphthyl group, an indenyl group and the like, and a naphthyl group is particularly preferable.

Methods for silyl-blocking free carboxylic acid groups, sulfonic acid groups and phosphoric acid groups are known, and the reaction conditions are obvious to those skilled in the art. For example, a compound having a free carboxylic acid group, a sulfonic acid group or a phosphoric acid group, for example, in a solvent such as tetrahydrofuran, optionally in the presence of a catalyst such as triethylamine, at -20 to 80 ° C, Preferably at 0-50 ° C,
For example, the silyl blocking reaction can be performed by reacting a silyl blocking agent such as trimethylsilyl laloride. Production of Coating Resin or Oligomer The vinyl polymerized oligomer used in the present invention comprises a hydroxyl group, a blocked hydroxyl group, an acetoacetyl group, a hydrolyzable silyl group, or a vinyl (thio) ether blocked carboxyl group or phosphate group. It can be obtained by polymerizing (or copolymerizing) a vinyl group-containing monomer with a functional group selected from the group. In the vinyl polymerized oligomer used in the present invention, the main functional groups may be present in the same vinyl polymerized oligomer or different vinyl polymerized oligomers.

The method of polymerizing these monomers can be carried out by a known conventional means. For example, anionic polymerization,
Polymerization can be performed by ionic polymerization such as cationic polymerization or radical polymerization. In the present invention, radical polymerization is preferred from the viewpoint of ease of polymerization. However, in the present invention, since it is necessary to produce a low-molecular weight vinyl-polymerized oligomer, during the polymerization, a mercaptan such as mercaptoethanol, thioglycerol, lauryl mercaptan or the like, so that the vinyl-polymerized oligomer can be produced at a low molecular weight, It is desirable to employ a method of using a chain transfer agent, a method of reacting at 60 to 180 ° C., a method of reacting at a low monomer concentration, or the like. When a monomer having a carboxyl group or a phosphoric acid group blocked with a vinyl (thio) ether group is polymerized, it is preferable to carry out the polymerization at 60 to 100 ° C. When the polymerization is carried out at a temperature higher than 100 ° C, the block group is easily dissociated. The molecular structure of the vinyl polymerized oligomer is not particularly limited, and various structures such as linear, comb-shaped, block-shaped, star-shaped, star-burst-shaped can be used. Radical polymerization is preferably performed in solution. As a solvent used for such radical solution polymerization, a solvent conventionally used for polymerization of a vinyl polymerizable monomer such as an acrylic monomer can be used without limitation. Such solvents include:
Examples thereof include toluene, xylene, butyl acetate, methyl ethyl ketone, methyl isobutyl ketone, Solvesso (manufactured by Exxon) and the like.

As the radical reaction initiator used in radical solution polymerization, a reaction initiator conventionally used in radical polymerization can be used without limitation. Examples of such a reaction initiator include peroxides such as benzoyl peroxide, lauroyl peroxide, t-butyl hydroperoxide, t-butyl peroxy-2-ethylhexanol, and azobisvaleronitrile (AIVN). , Azobisisobutyronitrile (AIB
N) and azo compounds such as azobis (2-methylpropionitrile). As the hydroxyl group-containing monomer, a monomer having a hydroxyl group and a vinyl polymerizable unsaturated bond group is preferably used. The vinyl-polymerizable unsaturated bond group is a radical-polymerizable vinyl bond (CHR ¹ = CR ²
-(R ¹ and R ² are each a hydrogen atom, an alkyl group or a single bond) is preferably exemplified. Here, the alkyl group includes a linear or branched alkyl group, and for example, a methyl group, an alkyl group having 1 to 20 carbon atoms such as an ethyl group, a propyl group, and a butyl group is preferable. As such a hydroxyl group-containing monomer, a monomer represented by the following formula (6) can be preferably mentioned.

[0019]

[Chemical 6] In the above formula, R ¹ is a hydrogen atom or a methyl group.
R ² is an alkylene group, a cycloalkylene group or an arylene group. Y is -COO-, -CO-, -NHCO-, a single bond or
-O-. X is a hydroxyl group. Where Y is
Acrylic (including methacrylic) monomers that are -COO- are preferred. The alkylene group includes a linear or branched alkylene group having 1 to 18 carbon atoms, and examples thereof include a methylene group, an ethylene group, a propylene group, a butylene group, an isobutylene group, and a hexamethylene group having 1 to 6 carbon atoms.
And lower alkylene groups of Examples of the cycloalkylene group include cycloalkylene groups having 5 to 18 carbon atoms, and preferably cyclopentylene groups and cycloalkylene groups having 5 to 8 carbon atoms such as cyclohexylene groups. As the arylene group, for example, ortho, meta or para-phenylene group, naphthalene group, fluorene group, indolene group, anthracene group, furan group,
A thiophene group etc. are mentioned.

Specific preferred hydroxyl group-containing monomers include hydroxyl group-containing (meth) acrylic monomers, such as 2-hydroxyethyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, and 4
-Hydroxybutyl (meth) acrylate and the like, and those modified with a lactone compound are mentioned. Examples of the lactone include ε-caprolactone, β-propiolactone, γ-butyrolactone, δ-valerolactone and the like. From the viewpoint of ease of synthesis, it is preferable to use ε-caprolactone as the lactone. Specific examples of the lactone-modified vinyl polymerizable monomer (lactone adduct) include Praxel FM- manufactured by Daicel Chemical Industries.
1, FM-2, FM-3, FM-4, FM-5, FA-1, FA-2, FA-3, FA-
4, FA-5, etc. can be mentioned. Here, FM is a methacrylate-based lactone-modified hydroxyl-containing vinyl-polymerizable monomer, and FA is an acrylate-based lactone-modified hydroxyl-containing vinyl-polymerizable monomer. The numbers are the amounts of ε-caprolactone added. For example,
FA-1 indicates that it is an acrylate-based hydroxyl group-containing vinyl polymerizable monomer to which one molecule of ε-caprolactone is added. As the blocked hydroxyl group-containing monomer, a monomer obtained by blocking the hydroxyl group in the above hydroxyl group-containing monomer with the above block group can be mentioned as a preferable example. As the acetoacetyl group-containing monomer,
For example, a monomer represented by the following formula (6) can be mentioned as a preferable example.

[0021]

Embedded image In the above formula, R ¹ and R ³ are a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, R ² is an alkylene group, a cycloalkylene group, an arylene group or a single bond, and Y is —COO. -
, -CO-, -O-, -CONH-, or a single bond, and Z is an acetoacetyl group. Among these, an acrylic monomer in which Y is —COO— is particularly preferable in terms of radical polymerizability. Here, as the alkyl group having 1 to 6 carbon atoms,
For example, a linear or branched alkyl group is included, and examples thereof include methyl group, ethyl group, propyl group, n-butyl group, s-
Butyl group, t-butyl group, n-pentyl group, s-pentyl group,
An alkyl group such as a hexyl group can be mentioned. Preferred alkyl groups include a methyl group and an ethyl group. The alkylene group includes a linear or branched alkylene group having 1 to 18 carbon atoms, preferably 1 to 10 carbon atoms, and examples thereof include a methylene group, an ethylene group, a propylene group, a butylene group, an isobutylene group, and a hexa group. Examples thereof include alkylene groups such as methylene groups. Examples of the cycloalkylene group include cycloalkylene groups having 5 to 18 carbon atoms, and preferably cyclopentylene groups and cycloalkylene groups having 5 to 8 carbon atoms such as cyclohexylene groups. As the arylene group, for example,
Ortho, meta or para-phenylene group, naphthalene group,
Examples thereof include fluorene group, indolene group, anthracene group, furan group and thiophene group.

Specific examples of the acetoacetyl group-containing vinyl polymerizable monomer include acetoacetoxyethyl (meth) acrylate, acetoacetoxypropyl (meth) acrylate, acetoacetoxyethyl crotonate, acetoacetoxypropyl crotonate, and the like. , Allyl acetoacetate, N- (2-acetoacetoxyethyl) (meth) acrylamide, vinyl acetoacetate and the like. As the acetoacetyl group-containing monomer, a (meth) acrylic monomer in which R ³ is a hydrogen atom and Y is —COO— in the above formula is preferable. Specific preferred monomers include, for example, acetoacetoxyalkyl (meth) acrylates such as 2-acetoacetoxyethyl (meth) acrylate, 3-acetoacetoxypropyl (meth) acrylate, and 4-acetoacetoxybutyl (meth) acrylate. Can be mentioned. The synthesis of these acetoacetyl group-containing monomers is a technique known to those skilled in the art. For example, it can be synthesized by acetoacetylating a hydroxyl group-containing α, β-ethylenically unsaturated monomer with acetoacetic acid ester or diketene.

As the hydrolyzable silyl group-containing monomer, a monomer in which X is a hydrolyzable silyl group in the above formula (5) can be preferably used. Particularly, in the above formula (5), a (meth) acrylate-based hydrolyzable silyl group-containing monomer in which Y is —COO— is preferable. Specific examples of such a monomer include, for example, γ
-(Meth) acryloyloxypropyltrimethoxysilane, γ- (meth) acryloyloxypropyltriethoxysilane, γ- (meth) acryloyloxypropyltripropoxysilane, γ- (meth) acryloyloxypropylmethyldimethoxysilane , Γ- (meth) acryloyloxypropylmethyldiethoxysilane, γ- (meth)
Acryloyloxypropylmethyldipropoxysilane,
γ- (meth) acryloyloxybutylphenyldimethoxysilane, γ- (meth) acryloyloxyphenyldiethoxysilane, γ- (meth) acryloyloxyphenyldipropoxysilane, γ- (meth) acryloyloxypropyldimethylmethoxy Silane, γ- (meth) acryloyloxypropyldimethylethoxysilane, γ- (meth) acryloyloxypropylphenylmethylmethoxysilane, γ- (meth) acryloyloxypropylphenylmethylethoxysilane, γ- (meth) acryloyl Roxypropyltrisilanol, γ- (meth) acryloyloxypropylmethyldihydroxysilane, γ- (meth)
Acryloyloxybutylphenyldihydroxysilane,
γ- (meth) acryloyloxypropyldimethylhydroxysilane, γ- (meth) acryloyloxypropylphenylmethylhydroxysilane, γ- (meth) acryloyloxypropylmethoxyditrimethylsiloxysilane, γ- (meth) acryloyloxy Examples include propylethoxytrimethylsiloxysilane.

As the epoxy group-containing monomer, the monomer having an epoxy group as the hydroxyl group in the above (5) can be preferably used. Examples of such an epoxy group-containing vinyl polymerizable monomer include glycidyl (meth) acrylate. As the monomer containing an acid anhydride group, for example, itaconic anhydride,
Monomers forming an acid anhydride group in the molecule such as maleic anhydride and monomers having a radical-polymerizable unsaturated bond and one carboxyl group in one molecule are used in one molecule in one molecule.
A monomer obtained by condensing a compound having one carboxyl group by dehydration or dealcoholization reaction can be mentioned.
The compound having one carboxyl group in one molecule may or may not have a radical polymerizable unsaturated bond in the molecule. Examples of such a monomer include a monomer obtained by condensing a monoester of a divalent polybasic acid such as methacrylic acid anhydride or monoalkyl maleate or monoalkyl itaconate by dealcoholation reaction. As the vinyl polymerizable monomer having a vinyl (thio) ether blocked carboxyl group or phosphoric acid group, the following monomers can be preferably mentioned.

[0025]

Embedded image (In the formula, R ¹ is a hydrogen atom or a methyl group.) Incidentally, other polymerizable monomers that can be used in producing the hydroxyl group-containing vinyl polymerized oligomer used in the present invention, for example, α, β -Examples of the ethylenically unsaturated monomer include the following monomers. (1) Acrylic acid or methacrylic acid ester: For example, methyl acrylate, ethyl acrylate, propyl acrylate, isopropyl acrylate, butyl acrylate, hexyl acrylate, octyl acrylate, lauryl acrylate, methyl methacrylate, methacrylic acid C1-18 alkyl group esters of acrylic acid or methacrylic acid such as ethyl, propyl methacrylate, isopropyl methacrylate, butyl methacrylate, hexyl methacrylate, octyl methacrylate, lauryl methacrylate; methoxybutyl acrylate, methacrylic acid Acid such as methoxybutyl acrylate, methoxyethyl acrylate, methoxyethyl methacrylate, ethoxybutyl acrylate, ethoxybutyl methacrylate, etc., having 2 to 18 carbon atoms. Lucoxyalkyl ester; alkenyl ester of acrylic acid or methacrylic acid such as allyl acrylate or allyl methacrylate having 2 to 8 carbon atoms; acrylic acid or methacrylic acid such as allyloxyethyl acrylate or allyloxyethyl methacrylate having 3 carbon atoms ~ 18 alkenyloxyalkyl esters. (2) Vinyl compounds: for example, vinyl acetate, hexafluoropropylene, tetrafluoropropylene, styrene, α-methylstyrene, vinyltoluene, p-chlorostyrene. (3) Polyolefin compound: For example, butadiene, isoprene, chloroprene. (4) Allyl ethers: hydroxyethyl allyl ether and the like. (5) Others: For example, methacrylamide, acrylamide, diacrylamide, dimethacrylamide, acrylonitrile, methacrylonitrile, methyl isopropenyl ketoin, vinyl acetate, vinyl propionate, vinyl pivalate, acrylic acid, methacrylic acid, N, N -Dialkylaminoalkyl (meth) acrylate, perfluorovinyl ether such as trifluoromethyl vinyl ether, vinyl ether such as hydroxyethyl vinyl ether and hydroxybutyl vinyl ether.

In the vinyl polymerized oligomer of the present invention,
The amount of the first functional group selected from the group consisting of a hydroxyl group, a blocked hydroxyl group, and an acetoacetyl group (mol / Kg resin, means the total weight of the resin contained. The same applies hereinafter) refers to each functional group. Independently, preferably 0.5 to 4.5 mol / Kg resin, and particularly preferably 0.7 to 4.0 mol / Kg.
Resin. The amount of these first functional groups is 0.5 mol / Kg
When the amount is less than that of the resin, the crosslinking is insufficient and the gasoline resistance is likely to be lowered. On the other hand, the amount of the first functional group is 4.5
If the amount is more than the mol / Kg resin, the crosslinking becomes too dense, so that the curing shrinkage becomes large and the appearance is likely to deteriorate. The amount of the first functional group composed of a hydrolyzable silyl group is preferably 0.5 to 3.5 mol / Kg resin, more preferably 1.
0 to 3.0 mol / Kg resin. This amount is 0.5 mol / Kg
If the amount is less than that of the resin, the crosslinking density is lowered and the solvent resistance is lowered, which is not preferable. On the other hand, if this amount exceeds 3.5 mol / Kg resin, the crosslink density becomes too high and cracks are likely to occur, which is not preferable. The amount of the first functional group selected from the group consisting of a hydroxyl group, a blocked hydroxyl group, a hydrolyzable silyl group and an epoxy group is, independently of each functional group, preferably 0.5 to 4.5 mol / Kg resin, further preferably It is 1.0 to 4.0 mol / Kg resin. If this amount is less than 0.5 mol / Kg resin, the crosslink density becomes low and the solvent resistance decreases, which is not preferable. On the other hand, if this amount exceeds 4.5 mol / Kg resin, the crosslinking density becomes too high, which is not preferable.

On the other hand, the amount of the second functional group consisting of the acid anhydride group combined with the first functional group is preferably 0.5 to.
3.5 mol / Kg resin, more preferably 1.0 to 3.0 mol / Kg
Resin. If this amount is less than 0.5 mol / Kg resin, the crosslinking density will be low and the solvent resistance will be reduced, such being undesirable. On the other hand, if this amount exceeds 3.5 mol / Kg resin,
This is not preferable because the glass conversion temperature of the resin becomes high and the solvent content becomes high. Further, the amount of the first functional group selected from the group consisting of vinyl (thio) ether blocked carboxyl group and phosphoric acid group is, independently of each functional group, preferably 0.5 to 4.5 mol / Kg resin, more preferably 1.0
~ 4.0 mol / Kg resin. When this amount is less than 0.5 mol / Kg resin, the crosslinking density is lowered and the solvent resistance is lowered, which is not preferable. On the other hand, if this amount exceeds 4.5 mol / Kg resin, the crosslinking density becomes high and cracks are likely to occur, which is not preferable. On the other hand, the amount of the second functional group consisting of an epoxy group combined with the first functional group is preferably 0.5 to 4.5 mol / Kg resin, more preferably 1.0.
~ 4.0 mol / Kg resin. When this amount is less than 0.5 mol / Kg resin, the crosslinking density is lowered and the solvent resistance is lowered, which is not preferable. On the other hand, if this amount exceeds 4.5 mol / Kg resin, the crosslinking density becomes too high and cracks and the like are likely to occur, which is not preferable.

A first functional group selected from the group consisting of a hydroxyl group, a blocked hydroxyl group and an acetoacetyl group, and a second functional group selected from the group consisting of a silyl blocked sulfonic acid group, a carboxylic acid group and a phosphoric acid group. The number average molecular weight of the vinyl polymerized oligomer composed of a combination with a group is 300 to
It is 1500, preferably 500 to 1400, and particularly preferably 700 to 1300. Number average molecular weight is 3
When it is less than 00, an oligomer having no functional group in one molecule is generated, and the gasoline resistance is likely to decrease. On the other hand, when the number average molecular weight exceeds 1500, the viscosity becomes too high, and it becomes necessary to use a large amount of diluent, and the film thickness tends to be difficult to obtain. The weight average molecular weight of the vinyl polymerized oligomer in this system is 300 to 3,000, preferably 500 to 3,000.
2500, particularly preferably 700 to 2300.
When the weight average molecular weight is less than 300, an oligomer having no functional group in one molecule is generated, and the gasoline resistance is likely to decrease. On the other hand, if the weight average molecular weight exceeds 3,000, the viscosity becomes too high and it becomes necessary to use a large amount of diluent.
It is easy to lose the film thickness. Furthermore, the value of weight average molecular weight / number average molecular weight (Mw / Mn) is 1-2, preferably 1-1.
8, particularly preferably 1 to 1.7. When this value is larger than 2, a problem occurs when an oligomer having a too small molecular weight or an oligomer having a too large molecular weight is caused, which is not preferable.

A system comprising a combination of a first functional group consisting of a hydrolyzable silyl group and a second functional group selected from the group consisting of a silyl blocked carboxylic acid group, a sulfonic acid group and a phosphoric acid group. In, the vinyl polymerized oligomer has a number average molecular weight of 600 to 1500, preferably 7
00 to 1400, particularly preferably 800 to 13
00. When the number average molecular weight is less than 600, an oligomer having no functional group in one molecule is generated, and the gasoline resistance is likely to decrease. On the other hand, when the number average molecular weight exceeds 1500, the viscosity becomes too high, and it becomes necessary to use a large amount of diluent, and the film thickness tends to be difficult to obtain. The weight average molecular weight of the vinyl polymerized oligomer in this system is 600 to
3000, preferably 700 to 2500, particularly preferably 800 to 2300. Weight average molecular weight is 600
When it is less than 1, the oligomer having no functional group in one molecule is generated, and the gasoline resistance is likely to be lowered. On the other hand, if the weight average molecular weight exceeds 1500, the viscosity becomes too high, and it becomes necessary to use a large amount of diluent, and the film thickness tends to be difficult to obtain. Further, the value of weight average molecular weight / number average molecular weight (Mw / Mn) is 1 to 2, preferably 1 to 1.9, particularly preferably 1
~ 1.8. When this value is larger than 2, a problem occurs when an oligomer having a too small molecular weight or an oligomer having a too large molecular weight is caused, which is not preferable.

A first functional group selected from the group consisting of a hydroxyl group, a blocked hydroxyl group, a hydrolyzable silyl group and an epoxy group, a second functional group consisting of an acid anhydride group, and a silyl-blocked carboxylic acid. In a system comprising a combination with a third functional group selected from the group consisting of a group, a sulfonic acid group and a phosphoric acid group, the vinyl polymerized oligomer has a number average molecular weight of 600 to 1500, preferably 700 to 140.
It is 0, and particularly preferably 800 to 1300.
When the number average molecular weight is less than 600, an oligomer having no functional group in one molecule is generated, and the gasoline resistance is likely to decrease. On the other hand, when the number average molecular weight exceeds 1500, the viscosity becomes too high, and it becomes necessary to use a large amount of diluent, and the film thickness tends to be difficult to obtain. The weight average molecular weight of the vinyl polymerized oligomer in this system is 600 to 3000,
Preferably 700 to 2500, particularly preferably 800
~ 2300. When the weight average molecular weight is less than 600,
An oligomer having no functional group in one molecule is generated, and the gasoline resistance is likely to be lowered. On the other hand, the weight average molecular weight is 150
If it exceeds 0, the viscosity becomes too high, and it becomes necessary to use a large amount of diluent, and the film thickness tends to be difficult to obtain. Furthermore, the value of weight average molecular weight / number average molecular weight (Mw / Mn) is 1 to
2, preferably 1 to 1.9, particularly preferably 1 to 1.8. When this value is larger than 2, a problem occurs when an oligomer having a too small molecular weight or an oligomer having a too large molecular weight is caused, which is not preferable.

Further, a first group consisting of a vinyl (thio) ether blocked carboxyl group, phosphoric acid group or hydroxyl group
In a system comprising a combination of a functional group, a second functional group consisting of an epoxy group, and a third functional group selected from the group consisting of a silyl-blocked carboxylic acid group, a sulfonic acid group and a phosphoric acid group, vinyl The number average molecular weight of the polymerized oligomer is 600 to 1500, preferably 700 to 1400, and particularly preferably 800 to 1300. When the number average molecular weight is less than 600, an oligomer having no functional group in one molecule is generated, and the gasoline resistance is likely to decrease. On the other hand, when the number average molecular weight exceeds 1500, the viscosity becomes too high, and it becomes necessary to use a large amount of diluent, and the film thickness tends to be difficult to obtain. The weight average molecular weight of the vinyl polymerized oligomer in this system is 600 to 3000, preferably 700 to 2500, and particularly preferably 800 to 23.
00. When the weight average molecular weight is less than 600, an oligomer having no functional group in one molecule is generated, and the gasoline resistance is likely to decrease. On the other hand, if the weight average molecular weight exceeds 1500, the viscosity becomes too high, and it becomes necessary to use a large amount of diluent, and the film thickness tends to be difficult to obtain. Further, the value of weight average molecular weight / number average molecular weight (Mw / Mn) is 1 to 2, preferably 1 to 1.9, and particularly preferably 1 to 1.8. When this value is larger than 2, a problem occurs when an oligomer having a too small molecular weight or an oligomer having a too large molecular weight is caused, which is not preferable.

In the present invention, a melamine resin or an isocyanate prepolymer is used in combination with a vinyl polymerized oligomer containing a first functional group selected from the group consisting of a hydroxyl group, a blocked hydroxyl group and an acetoacetyl group. The melamine resin is not particularly limited as long as it is produced by polymerization of melamine and formaldehyde and is conventionally used in a coating having a hydroxyl group or the like, and various melamine resins can be used. Also,
The isocyanate prepolymer is not particularly limited as long as it is used in the field of coating materials having a hydroxyl group and the like, and various isocyanate prepolymers can be used. As a preferable melamine resin, for example, a melamine resin containing melamine represented by the following formula (7) is particularly preferable.

[0033]

Embedded image (In the formula, R ^{1 to} R ⁶ are independently a hydrogen atom, a methylol group, or an alkoxy group having 1 to 5 carbon atoms.) When the alkoxy group in the formula (7) has more carbon atoms than 5, The viscosity becomes too high, which is not preferable. The preferred carbon number is 1 to 4. Specific examples of such an alkoxy group include a methoxy group, an ethoxy group, a propoxy group, a butoxy group and an isobutoxy group. Melamine may be a mononuclear body or a polynuclear body in which it self-condenses. An embodiment of melamine is R ^{1 of the} above formula (7).
To R ⁶ are all alkoxy groups, a mixture of hydrogen atoms and a methylol group, a mixture of hydrogen atoms and an alkoxy group, a mixture of a methylol group and an alkoxy group Further, a mixture of a hydrogen atom, a methylol group and an alkoxy group can be mentioned.
Specifically, Cymel 325, Cymel 327, Cymel 370 (above, manufactured by Mitsui Cyanamid, in formula (7),
R ^{1 to} R ⁶ are methylol groups (methylol type), Super Beckamine L-116-70 (Dainippon Ink and Chemicals),
Super Beckamine L-121-60 (Dainippon Ink and Chemicals), Uban 2028 (Mitsui Toatsu), Uban 2
1R (Mitsui Toatsu), Uban 2028 (Mitsui Toatsu) (all above are imino types), and Cymel 303,
Uban 120 (manufactured by Mitsui Toatsu) (in the formula (7), R ^{1 to} R ⁶ are all alkoxy groups (alkoxy type)).

Examples of the isocyanate prepolymer include polymers of polyisocyanate and addition reaction products of polyisocyanate with water or polyhydric alcohol. Examples of the polyisocyanate polymer include a polyisocyanate compound in which a plurality of polyisocyanates are bonded to form a ring. Preferred examples of such a cyclic polyisocyanate include isocyanurates having an isocyanuric ring. Polyisocyanate reacts with water or a polyhydric alcohol to give an addition reactant having a plurality of isocyanate groups. The burette is formed from the reaction of polyisocyanate with water. Examples of the polyhydric alcohol used here include dihydric or trihydric, and further tetrahydric or higher alcohols, such as ethylene glycol, propylene glycol, 1,3-butylene glycol, 2-methylpropanediol, 1 , 4-butyryl glycol, neopentyl glycol, 1,6-hexane glycol, 1,
2-dodecanediol, glycerin, trimethylolpropane, trimethylolethane, pentaerythritol, dipentaerythritol, hydroxypivalic acid neopentyl glycol ester, 1,4-cyclohexanedimethanol, bisphenol A ethylene oxide adduct, bisphenol A propylene oxide Examples thereof include adducts and 1,4-hydroxyhydroquinone.

A preferred specific isocyanate prepolymer is hexamethylene diisocyanate prepolymer which is a cyclic polymer (for example, Pernock 901S).
(Manufactured by Dainippon Ink) and Duranate TPA-100 (manufactured by Asahi Kasei). In the resin composition for coating material, which comprises a vinyl polymerized oligomer containing a first functional group selected from the group consisting of a hydroxyl group, a blocked hydroxyl group and an acetoacetyl group, and a melamine resin or an isocyanate prepolymer, the vinyl polymerized oligomer is 95 to 30% by weight, preferably 90 to 35% by weight, particularly preferably 85 to 40% by weight, based on the weight of the both.
Used in. Within this quantitative range, the coating film performance becomes good, which is preferable. The functional group selected from the group consisting of silyl-blocked carboxylic acid group, sulfonic acid group and phosphoric acid group may be contained in the resin (or oligomer) in a catalytic amount. Specifically, the amount of these functional groups is, independently of each functional group, usually 0.000001 to 0.5 mol / Kg resin, preferably 0.000001 to 0.1 mol / Kg resin, particularly It is preferably 0.001 to 0.05 mol / Kg resin. If this amount is less than 0.000001 mol / Kg resin, curing will be poor, and coating film performance such as solvent resistance will decrease,
Not preferred. On the other hand, if this amount exceeds 0.5 mol / Kg resin, the pot life becomes short, which is not preferable.

Regarding the oligomers containing these functional groups, the number average molecular weight, weight average molecular weight, and weight average molecular weight / number average molecular weight of the oligomers are the same as in the case of oligomers having functional groups in the curing reaction system. It is. When a functional group selected from the group consisting of a silyl-blocked carboxylic acid group, a sulfonic acid group and a phosphoric acid group is contained in a non-polymerizable compound other than an oligomer, the amount of the compound is May be in an amount sufficient to exert a catalytic effect. Generally, depending on the molecular weight of the compound, it is from 0.001 to 10% by weight, preferably from 0.01 to 5% by weight, particularly preferably from 0.1 to 3% by weight, based on the resin. The low-solvent type resin composition of the present invention, as it is, or as the case requires, is a curing catalyst conventionally used in the field of coating materials, various pigments (for example, color pigments, brightening agents), anti-sagging. A low-solvent type coating composition can be prepared by appropriately blending an agent or an anti-settling agent, a revelig agent, a dispersant, a defoaming agent, an ultraviolet absorber, a light stabilizer, an antistatic agent, a thinner and the like. An acid catalyst is used as such a curing catalyst. As the acid catalyst, for example, a strongly acidic catalyst or a weakly acidic catalyst can be used. Examples of the strongly acidic catalyst include inorganic acid esters such as hydrochloric acid, nitric acid and sulfuric acid, salts such as ammonium salts and onium salts, and aromatic sulfonic acid esters.

On the other hand, examples of the weakly acidic catalyst include phosphoric acid monoester, phosphorous acid ester, unsaturated group-containing phosphoric acid ester and the like. As the weakly acidic catalyst, an ester of phosphoric acid is particularly preferable. Examples of such phosphoric acid ester include phosphoric acid mono- or diesters. Examples of the phosphoric acid monoester include monooctyl phosphate, monopropyl phosphate, monolauryl phosphate and the like. Examples of the phosphoric acid diester include dioctyl phosphate, dipropyl phosphate, dilauryl phosphate and the like. Further, phosphonium salts such as tetrabutylphosphonium bromide can also be preferably mentioned. Examples of pigments or glitters include:
Titanium oxide, carbon black, precipitated barium sulfate,
Calcium carbonate, talc, kaolin, silica, mica,
Aluminum, red iron oxide, lead chromate, lead molybdate, chromium oxide, cobalt aluminate, azo pigment, phthalocyanine pigment, anthraquinone pigment and the like can be preferably used. As the anti-sagging agent or the anti-settling agent, for example, bentonite, castor oil wax, amide wax, microgel (for example, MG100S (manufactured by Dainippon Ink and Chemicals)) and the like can be preferably used.

As the leveling agent, for example, KF69, Kp
321 and Kp301 (manufactured by Shin-Etsu Chemical) and other silicon-based materials, Modaflow (manufactured by Mitsubishi Monsanto), BYK358, 30
1 (manufactured by Big Chemie Japan) and Dia-Aid AD9001
(Manufactured by Mitsubishi Rayon) and the like can be preferably used. As the dispersant, for example, Anti-Terra U or Anti-
Terra P, Disperbyk-101 (above, manufactured by Big Chemie Japan) and the like can be preferably used. As the defoaming agent, for example, BYK-O (manufactured by BYK Chemie Japan) or the like can be preferably used. Examples of ultraviolet absorbers include Tinuvin 900, Tinuvin 384, Tinuvin P.
A benzotriazole-based ultraviolet absorber such as (above, manufactured by Ciba-Geigy) or an oxalic anilide-based ultraviolet absorber such as Sandba-3206 (manufactured by Sand) can be preferably used. Examples of the light stabilizer include Sanol LS292.
Hindered amine light stabilizers such as (manufactured by Sankyo) and Sandbar 3058 (manufactured by Sand) can be preferably used.

Examples of the thinner include aromatic compounds such as toluene, xylene and ethylbenzene, alcohols such as methanol, ethanol, propanol, butanol and isobutanol, acetone, methyl isobutyl ketone, methyl amyl ketone, cyclohexanone, isophorone and N-. Ketones such as methylpyrrolidone, ethyl acetate,
An ester compound such as butyl acetate or methyl cellosolve, or a mixture thereof can be used. As the antistatic agent, for example, Esocard C25 (manufactured by Lion Armor) or the like can be preferably used. The low-solvent type coating composition of the present invention can reduce the viscosity of the coating composition although the amount of the organic solvent is small. That is, it is possible to maintain the viscosity suitable for coating, although the solid content of the coating can be significantly reduced as compared with the conventional case. For example, the amount of organic solvent is 40% or less, preferably 3
It can be 5% or less, particularly preferably 30% or less. The lower limit is 5%. Further, by using the above silyl-blocked carboxyl group, sulfonic acid group or phosphoric acid group in combination, it is possible to exhibit the action as a so-called latent catalyst, so that the pot life is excellent and at a predetermined low temperature, For example, the curing reaction can be easily caused by heating at 0 to 50 ° C, preferably 10 to 40 ° C, and particularly preferably 20 to 30 ° C.

The low solvent type coating composition of the present invention is, for example,
It can be used for various applications such as paints, inks and adhesives. The low solvent type coating composition of the present invention is particularly useful as a clear coating, an intermediate coating, a base coating, a solid color coating and the like used for coating automobiles. The low-solvent type coating composition of the present invention is particularly useful as a clear coating. The low solvent type coating composition of the present invention,
It is particularly excellent as a clear coating used for 2 coat 1 bake, 3 coat 2 bake or overcoat. Further, the low solvent type coating composition of the present invention, each of the following,
It can be applied as an intermediate coating composition, a base coating composition and a clear coating composition, or a solid color coating composition and a clear coating composition. Furthermore, the low-solvent type coating composition of the present invention can be used as an intermediate coating, and a base coat coating consisting of a conventionally known organic solvent-based coating or water-based coating can be further applied thereon by wet-on-wet. . It is also possible to use the coating composition of the present invention as a base coat coating and to apply a conventionally known clear coating thereon. Furthermore, a conventionally known base coat paint may be applied, and then a clear paint as the paint composition of the present invention may be applied thereon by wet on wet. In this case, the base coat paint may be an organic solvent type paint or an aqueous paint. As the organic solvent type paint, for example, it is preferable to use a paint composition containing an oligomer having a hydroxyl group and a weight average molecular weight of 6000 or less, and a melamine resin. Further, the base coat coating composition preferably has a coating solid content of 35% by weight or more, particularly 40% by weight or more.

The coating of the paint is generally carried out at a film thickness after drying of 10 to 30 μm, preferably 15 to 25 μm. Further, for application of the low solvent type coating composition of the present invention,
In order to prevent sagging even when applied thickly and to improve the surface smoothness, it is preferable to apply the object while rotating it around a horizontal axis. For example, JP-A-6
As disclosed in Japanese Laid-Open Patent Publication No. 3-178871, for example, an object to be coated such as an automobile body is fixed from the vertical direction, and the low solvent type coating composition of the present invention is applied while rotating the body in the horizontal direction. Even when it is dried, baked, or dried, it can be coated to a thickness equal to or greater than the limit thickness (limit film thickness) at which sagging when stationary occurs. The rotation is preferably continuous rotation and has a large sagging prevention effect. More specifically, it is a method for coating the surface of an article to be coated with the low-solvent type coating composition of the present invention, in which a normal upper and lower surface of the article to be coated rotatably supported about a substantially horizontal axis is provided. On the surface extending in the direction, paint is applied to a film thickness that causes sagging, and then the sagging of the paint applied to the surface of the object is started to rotate about the horizontal axis before the sagging occurs due to gravity. , And the speed at which the surface of the object to be coated transitions from a substantially vertical state to a substantially horizontal state before at least the rotation of the applied coating is caused by gravity, Rotate at a slow speed.

The rotation speed is generally 0.2 to 120 rpm, preferably 5 to 20 rpm. When the rotation speed is less than 0.2 rpm, the effect of preventing sagging is small, which is not preferable. On the other hand, if it is higher than 120 rpm, conversely, sagging tends to occur due to centrifugal force, which is not preferable. Note that, for example, they may be reversed in the order of 90 ° → 135 ° → 160 °. In this way, after coating while rotating the coated object around the horizontal axis, while maintaining the rotation, the paint is set vertically (usually without a heating device) or baked (with a heating device). Meanwhile, a coating film is formed by moving the object to be coated. The set (dry) is
Generally 5 to 30 minutes, preferably 5 to 15 minutes, at room or ambient temperature. The baking is performed at 60 to 180 ° C., preferably 80 to 160 ° C. for 1 to 60 minutes, preferably 1
It is preferable to carry out for 0 to 40 minutes. Furthermore, the low solvent type coating composition of the present invention can be applied with a coating by hot spraying while further reducing the amount of solvent. In such hot spraying, for example, the steps from the tank storing the low solvent type coating composition to immediately before spraying are kept at a predetermined temperature, generally 30 to 80 ° C, preferably 35 to 70 ° C. Can be done by In the low-solvent coating composition of the present invention, the characteristics of the coating film to be formed, for example, chipping resistance, gasoline resistance, scratch resistance, acid resistance, various properties such as water resistance, excellent quality, While having it, the amount of organic solvent can be reduced much more than before. For example, the amount of organic solvent can be reduced to 40% or less, preferably 35% or less, and more preferably 30% or less. Therefore, the problem of environmental pollution due to the release of the organic solvent can be significantly reduced.

[0043]

EXAMPLES The present invention will be described in more detail with reference to Reference Examples and Examples, but the scope of the present invention is not limited to these Reference Examples and Examples.
However, in the following, “%” or “part” means “% by weight” and “part by weight” unless otherwise specified. Reference Example 1 Sily Blocked Blocked Phosphate Ph 1 to Ph 7
In a four-necked flask equipped with a synthetic dropping funnel, a stirrer, an inert gas inlet, and a thermometer, 130 parts of tetrahydrofuran was placed, and the mixture was ice-cooled to 0 ° C., and then phosphoric acid was added in the amount shown in Table 1 below. An ester and a silyl blocking agent were added, and a catalyst mixture consisting of 70 parts of tetrahydrofuran and 11 parts of triethylamine was further added, followed by reaction at 0 ° C. for 10 hours to prepare a silyl blocked phosphoric acid.

[0044]

[Table 1] Table 1 Synthesis of silyl-blocked blocked phosphoric acid Ph1 Ph2 Ph3 Ph4 Ph5 Ph6 Ph7 Monobutyl phosphate 7.7 7.7 7.7 7.7 Monolauryl phosphate 17.5 Dibutyl phosphate 21 Diphenyl phosphate 25 Tetrahydrofuran 130 130 130 130 130 130 130 130 Trimethylsilyl chloride 11 11 11 Lide t-butyldimethylsi 16 16 Ryl chloride triphenylchlorosi 32 Lan octadecyldimethyl 38 Chlorosilane Tetrahydrofuran 70 70 70 70 70 70 70 Triethylamine 11 11 11 11 11 11 11 Obtained silyl blocked phosphorus Acid compounds Ph 1 to Ph 7
Is a compound having the following structure:

[0045]

Embedded image

[0046]

Embedded image

Reference Example 2 Silyl-blocked sulfonic acid and carboxylic acid Su 1 to
Synthesis of Su 3 and Ca 1 to Ca 3 In a four-necked flask equipped with a dropping funnel, a stirrer, an inert gas inlet, and a thermometer, 130 parts of tetrahydrofuran was placed and ice-cooled to 0 ° C. After adding naphthalene sulfonic acid or carboxylic acid and silyl blocking agent in the amounts shown in Table 2 and further adding a catalyst mixture consisting of 70 parts of tetrahydrofuran and 11 parts of triethylamine,
Reaction was carried out at 0 ° C. for 10 hours to prepare a silyl-blocked sulfonic acid or carboxylic acid.

[0048]

[Table 2] Table 2 Synthesis of silyl-blocked sulfonic acids and carboxylic acids Su1 Su2 Su3 Ca1 Ca2 Ca3 p-toluenesulfonic acid 17.8 Sodium dinonylnaphthalene sulfonate 52.4 Dinonylnaphthalene diphosphonate 31 Rufonic acid carboxylic acid 1 ^* 17.4 Carboxylic acid Acid 2 ^** 23 Caproic acid 11.6 Tetrahydrofuran 130 130 130 130 30 130 Trimethylsilylk 11 11 11 11 11 11 Loride tetrahydrofuran 70 70 70 70 70 70 Triethylamine 11 11 11 11 11 11 Note) Carboxylic acid 1 is butanol and succinic anhydride. Carbonic acid obtained by reaction with an acid. On the other hand, carboxylic acid 2 is a carboxylic acid obtained by the reaction of 2-ethylhexanol and succinic anhydride. The structures of the silyl-blocked sulfonic acid and carboxylic acid obtained by the above reaction are as follows.

[0049]

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[0050]

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Reference Example 3 Phosphoric Acid and Carboxylic Acid Monomers Ph Blocked by Silyl
Synthesis of 8 to Ph10 and Ca 4 to Ca 8 In a four-necked flask equipped with a dropping funnel, a stirrer, an inert gas inlet, and a thermometer, 130 parts of tetrahydrofuran was placed, and the mixture was ice-cooled to 0 ° C. In the amounts shown in Table 3 above, a phosphoric acid ester or a carboxylic acid or a carboxylic acid ester and a silyl blocking agent were added, and a catalyst mixture consisting of 70 parts of tetrahydrofuran and 11 parts of triethylamine was added, followed by reaction at 0 ° C. for 10 hours. Then, phosphoric acid and carboxylic acid having a polymerizable unsaturated bond and having a silyl block were prepared.

[0052]

[Table 3] Table 3 Synthesis of silyl-blocked phosphoric acid monomer and carboxylic acid monomer Ph8 Ph9 Ph10 Ca4 Mono (2-acryloylro 9.8 9.8 xyethyl) acid phosphate Mono (2-methacryloyl 21 roxyethyl) acid phosphate Acrylic acid 7.2 Tetrahydrofuran 130 130 130 130 Trimethylsilylchlora 11 11 Id t-butyldimethylsilyl 16 16 Lucloride tetrahydrofuran 70 70 70 70 Triethylamine 11 11 11 11

[0053]

[Table 4] Table 3 (continued) Synthesis of silyl-blocked carboxylic acid Ca5 Ca6 Ca7 Ca8 Acrylic acid 7.2 2-methacryloyloxy 28.3 28.3 Ethyl hexahydrophthalic acid 2-methacryloyloxy 27.8 Ethylphthalic acid tetrahydrofuran 130 130 130 130 Trimethylsilylchlora 11 Id triphenylchlorosilane 32 Octadecyldimethyl chloride 38 Rollosilane N-trimethylsilyla 14.3 Cetoamide tetrahydrofuran 70 70 70 70 triethylamine 11 11 11 11 The phosphoric acid or carboxylic acid monomer obtained by the above reaction is represented by the following structure.

[0054]

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[0055]

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[0056]

Embedded image Reference Example 4 Preparation of Oligomer for Coating Material 674 parts of xylene was placed in a four-necked flask equipped with a dropping funnel, a stirrer, an inert gas inlet, and a thermometer.
Reaction temperature of 40 ° C (however, vinyl polymerized oligomer Q-
In the case of synthesizing 1-2, R-1 and 2 and S-1, the reaction temperature was raised to 80 ° C., and the amount was determined according to the amount shown in Table 4 (“Monomer blending” item) below. And a predetermined amount of perbutyl O.
A catalyst mixture of (peroxide catalyst, manufactured by NOF CORPORATION) and xylene was added dropwise. Further, at the reaction temperature, the reaction was continued, the solid content was confirmed to be 26%, the synthesis was stopped, and xylene was distilled off under reduced pressure to obtain the characteristics and the amount of functional groups shown in Table 4. A vinyl polymerized oligomer having was prepared.

[0057]

[Table 5] Table 4 Preparation of vinyl polymerized oligomer containing hydrolyzable silyl group (Si), blocked hydroxyl group (BOH), acid anhydride group (AA) and epoxy group (Ep) (synthesized at 140 ° C) A- 1 A-2 A-3 A-4 Number average molecular weight (Mn) 850 1450 670 860 Weight average molecular weight (Mw) 1360 2610 1005 1390 Mw / Mn 1.6 1.8 1.5 1.6 Functional group amount (mol / Kg resin ) Si 1 1 1 1 Ep 1 1 1.5 1 AA 1 1 1.5 1 BOH 1 1 1 1 1 BPh (s) * 0.043 Reflux solvent xylene 674 674 674 674 Monomer blend γ-methacryloyloxypro 62 62 62 62 Pyrtrimethoxysilane Glycidyl methacrylate 35.5 35.5 53.3 35.5 Itaconic anhydride 28 28 42 28 Trimethylsiloxyethyl methy 46.5 46.5 46.5 46.5 Tacrylate Styrene 25 25 25 25 n-Butyl acrylate 15.5 15.5 3.7 15.5 2-Ethylhexylmethacrylate 37.5 37.5 17.5 37.5 Rate Ph8 (monomer) 4 Polymerization initiator Perbutyl-O (PO) 24 18 26 24 Xylene 26 24 24 26 Additional catalyst P-O 1 1 1 1 Xylene 1 1 1 1 Note) BPh (s) is a silyl-blocked phosphate group. Indicates.

[0058]

Table 4 (continued) Preparation of vinyl polymerized oligomer containing blocked hydroxyl group (BOH), acid anhydride group (AA) and epoxy group (Ep) ( synthesized at 140 ° C) B-1 B-2 Mn 765 780 Mw 1065 1090 Mw / Mn 1.4 1.4 functional group content (mol / Kg resin) Ep 1 1 AA 1 1 BOH 1.5 1.5 BPh (s) 0.043 reflux solvent xylene 674 674 monomer blend glycidyl methacrylate 35.5 35.5 itaconic anhydride 28 28 trimethyl Siloxyethyl meth 68.5 68.5 Styrene 75 75 n-Butyl acrylate 4.3 4.3 2-Ethylhexyl methacylate 37.5 37.5 Rate Ph8 (monomer) 4 Polymerization initiator P-O 24 24 Xylene 26 26 Additional catalyst P-O 1 1 Xylene 1 1

[0059]

[Table 7] Table 4 (continued) Preparation of vinyl polymerized oligomer containing blocked hydroxyl group (BOH), acid anhydride group (AA) and hydrolyzable silyl group (Si) (synthesized at 140 ° C ) C-1 C- 2 Mn 879 900 Mw 1406 1350 Mw / Mn 1.6 1.6 Functional group amount (mol / Kg resin ) Si 1.5 1.5 AA 11 BOH 2 2 BPh (s) 0.04 Reflux solvent xylene 674 674 Monomer-containing γ-methacryloyloxy pro 93 93 Pyrtrimethoxysilane Itaconic anhydride 28 28 Trimethylsiloxyethylmetha 93 93 Taacrylate Styrene 17.5 17.5 2-Ethylhexylmethacrylate 18.5 18.5 Rate Ph10 (monomer) 4 Polymerization initiator P-O 24 24 Xylene 26 26 Additional catalyst P-O 1 1 Xylene 1 1

[0060]

Table 4 (continued) Preparation of vinyl polymerized oligomer containing blocked hydroxyl group (BOH), epoxy group (Ep) and hydrolyzable silyl group (Si) (synthesized at 140 ° C) D-1 D-2 Mn 888 850 Mw 1243 1160 Mw / Mn 1.4 1.4 Functional group amount (mol / Kg resin ) Si 1.5 1.5 Ep 11 BOH 2 2 BCa (s) * 0.074 Reflux solvent xylene 674 674 Monomer-containing γ-methacryloyloxypro 93 93 pill Trimethoxysilane Glycidyl Methacrylate 35.5 35.5 Trimethylsiloxyethyl Meth 93 93 Tacrylate Styrene 17.5 17.5 n-Butyl Acrylate 2-Ethylhexyl Methacrylate 28.5 28.5 Rate Ca4 (Monomer) 4 Polymerization Initiator P-O 24 24 Xylene 26 26 Additional Catalyst P-O 1 1 Xylene 11 Note) BCa (s) represents a silyl-blocked carboxylic acid group.

[0061]

[Table 9] Table 4 (continued) Preparation of vinyl polymerized oligomer containing blocked hydroxyl group (BOH) and acid anhydride group (AA) ( synthesis at 140 ° C) E-1 E-2 Mn 1045 960 Mw 1672 1530 Mw / Mn 1.6 1.6 Functional group amount (mol / Kg resin ) AA 1.5 1.5 BOH 2 2 BCa (s) 0.044 Refluxing solvent xylene 674 674 Monomer-containing itaconic anhydride 42 42 Trimethylsiloxyethylme 93 93 Tacrylate Styrene 50 50 n-Butyl acrylate 25 25 2-Ethylhexyl Methacrylate 40 40 Rate Ca 5 (Monomer) 4 Polymerization Initiator P-O 22 22 Xylene 28 28 Additional Catalyst P-O 11 Xylene 11

[0062]

[Table 10] Table 4 (continued) Preparation of vinyl polymerized oligomer containing blocked hydroxyl group (BOH) and epoxy group (Ep) ( synthesis at 140 ° C) F-1 F-2 Mn 1020 1180 Mw 1632 1540 Mw / Mn 1.6 1.6 Functional group amount (mol / Kg resin ) Ep 1.5 1.5 BOH 1.5 1.5 BCa (s) 0.03 Reflux solvent Xylene 674 674 Monomer-containing glycidyl methacrylate 53.3 53.3 Trimethylsiloxyethylmethacrylate 69.8 69.8 Tacrylate Styrene 50 50 n-Butyl acrylate 39.5 39.5 2- Ethylhexyl methacrylate 37.5 37.5 Rate Ca6 (monomer) 4 Polymerization initiator P-O 22 22 Xylene 28 8 Additional catalyst P-O 11 Xylene 11

[0063]

[Table 11] Table 4 (continued) Preparation of vinyl polymerized oligomer containing hydrolyzable silyl group (Si), acid anhydride group (AA) and epoxy group (Ep) ( synthesized at 140 ° C) G-1 G-2 Mn 890 920 Mw 1424 1400 Mw / Mn 1.6 1.6 Functional group amount (mol / Kg resin ) Si 11 Ep 11 AA 11 BCa (s) 0.006 Reflux solvent xylene 674 674 Monomer-containing γ-methacryloyloxy pro 62 62 pill Trimethoxysilane Glycidyl Methacrylate 35.5 35.5 Itaconic Anhydride 28 28 Styrene 45 45 n-Butyl Acrylate 42 42 2-Ethylhexyl Methacrylate 37.5 37.5 Rate Ca7 (Monomer) 4 Polymerization Initiator P-O 24 24 Xylene 26 26 Additional Catalyst P-O 1 1 xylene 1 1

[0064]

Table 12 (Continued) Preparation of vinyl polymerized oligomer containing blocked hydroxyl group (BOH) and hydrolyzable silyl group (Si) ( synthesized at 140 ° C.) H-1 H-2 Mn 860 900 Mw 1204 1130 Mw / Mn 1.4 1.4 Functional group amount (mol / Kg resin ) Si 0.5 0.5 BOH 2 2 BCa (s) 0.004 Reflux solvent xylene 674 674 Monomer-containing γ-methacryloyloxypro 31 31 pyrtrimethoxysilane trimethylsiloxyethylmethy 93 93 Tacrylate Styrene 50 50 n-Butyl acrylate 26 26 2-Ethylhexyl Methacrylate 50 50 rate Ca 8 (monomer) 4 Polymerization initiator P-O 24 24 Xylene 26 26 Additional catalyst P-O 1 1 Xylene 11

[0065]

Table 13 Table 4 (Continued) Preparation of vinyl polymer oligo mers containing an epoxy group (Ep) and an acid anhydride group (AA) (synthesized at 140 ℃) I-1 I- 2 Mn 890 920 Mw 1424 1450 Mw / Mn 1.6 1.6 Functional group amount (mol / Kg resin ) Ep 1.5 1.5 AA 1.5 1.5 BPh (s) 0.004 Reflux solvent xylene 674 674 Monomer-containing glycidyl methacrylate 53.3 53.3 Itaconic anhydride 42 42 Styrene 50 50 n-Butyl acrylate 62.5 62.5 2- Ethylhexyl methacryl 43 43 rate Ph10 (monomer) 4 Polymerization initiator P-O 24 24 Xylene 26 26 Additional catalyst P-O 11 Xylene 11

[0066]

Table 4 (continued) Preparation of vinyl polymerized oligomer containing hydrolyzable silyl group (Si) and acid anhydride group (AA) ( synthesized at 140 ° C.) J-1 J-2 Mn 890 930 Mw 1424 1490 Mw / Mn 1.6 1.6 Functional group amount (mol / Kg resin ) Si 2 2 AA 1.5 1.5 BCa (s) 0.133 Reflux solvent xylene 674 674 Monomer blend γ-methacryloyloxypro 12.3 12.3 Pyrtrimethoxysilane Itaconic anhydride 42 42 Styrene 50 50 n-Butyl acrylate 2-Ethylhexyl methacrylate 35.5 35.5 Rate Ca4 (monomer) 4 Polymerization initiator P-O 20 20 Xylene 30 30 Additional catalyst P-O 11 Xylene 11

[0067]

[Table 15] Table 4 (continued) Preparation of vinyl polymerized oligomer containing epoxy group (EP) and hydrolyzable silyl group (Si) ( synthesized at 140 ° C) K-1 K-2 Mn 1065 970 Mw 1597 1460 Mw / Mn 1.5 1.5 Functional group amount (mol / Kg resin ) Si 2 2 Ep 1.5 1.5 BPh (s) 0.043 Refluxing solvent xylene 674 674 Monomer blend γ-methacryloyloxypro 124 124 Pyrtrimethoxysilane glycidyl methacrylate 53.3 53.3 Styrene 35.3 35.3 n -Butyl acrylate 2-Ethylhexyl methacrylate 37.5 37.5 Rate Ph8 (monomer) 4 Polymerization initiator P-O 22 23 Xylene 28 27 Additional catalyst P-O 11 Xylene 11

[0068]

[Table 16] Table 4 (continued) Preparation of vinyl polymerized oligomer containing hydrolyzable silyl group (Si) ( synthesized at 140 ° C) L-1 L-2 Mn 1325 1240 Mw 2120 2200 Mw / Mn 1.6 1.7 Functional group amount (Mole / Kg resin ) Si 2.5 2.5 BPh (s) 0.041 Reflux solvent xylene 674 674 Monomer blend γ-methacryloyloxypro 155 155 Pyrtrimethoxysilane Styrene 64 64 n-Butyl acrylate 2-Ethylhexyl methacrylate 31 31 Rate Ph 8 (Monomer) ) 4 polymerization initiator P-O 20 20 xylene 30 30 additional catalyst P-O 11 xylene 11

[0069]

[Table 17] Table 4 (continued) Preparation of vinyl polymerized oligomer containing acid anhydride group (AA) (synthesized at 140 ° C) M-1 M-2 Mn 1035 1100 Mw 1656 1580 Mw / Mn 1.6 1.4 Functional group amount ( Mol / Kg resin ) AA 33 BCa (s) 0.043 Reflux solvent Xylene 674 674 Monomer blended itaconic anhydride 84 84 Styrene 75 75 n-Butyl acrylate 41 41 2-Ethylhexyl methacrylate 50 50 rate Ca 6 (monomer) 4 Polymerization initiator P -O 22 22 xylene 28 28 additional catalyst P-O 11 xylene 11

[0070]

[Table 18] Table 4 (continued) Preparation of vinyl polymerized oligomer containing epoxy group (Ep) (synthesized at 140 ° C) N-1 N-2 Mn 865 900 Mw 1384 1400 Mw / Mn 1.6 1.6 Functional group amount (mol / mol Kg resin ) Ep 4 4 BPh (s) 0.043 Refluxing solvent Xylene 674 674 Monomer-blended glycidyl methacrylate 142 142 Styrene 25 25 n-Butyl acrylate 45 45 2-Ethylhexyl methacrylate 38 38 rate Ph 8 (monomer) 4 Polymerization initiator P-O 23 23 xylene 27 27 additional catalyst P-O 11 xylene 11

[0071]

[Table 19] Table 4 (continued) Preparation of vinyl polymerized oligomer containing blocked hydroxyl group (BOH) ( synthesized at 140 ° C) O-1 O-2 Mn 1065 970 Mw 1597 1480 Mw / Mn 1.5 1.5 Functional group amount (mol / Kg resin ) BOH 33 BPh (s) 0.004 Reflux solvent xylene 674 674 Monomer blend trimethylsiloxyethyl methacryl 137 137 late Styrene 50 50 n-Butyl acrylate 50 50 2-Ethylhexyl methacrylate 13 13 Ph 10 (monomer) 4 Polymerization initiator P -O 22 22 xylene 28 28 additional catalyst P-O 11 xylene 11

[0072]

[Table 20] Table 4 (continued) Preparation of vinyl polymerized oligomer containing vinyl ether blocked carboxyl group (BCa (v)) (synthesized at 80 ° C) P-1 P-2 Mn 1025 1000 Mw 1640 1543 Mw / Mn 1.6 1.5 Amount of functional group (mol / kg resin ) BCa (v) * 33 BCA (s) 0.022 Reflux solvent Xylene 674 674 Monomer containing monomer A ** 107 107 Styrene 50 50 n-Butyl acrylate 50 50 2-Ethylhexyl methacrylate 43 43 Ca4 (monomer) 4 polymerization initiator AIVN 11 11 AIBN 11 11 xylene 28 28 additional catalyst AIBN 1 1 xylene 1 1 (Note) BCa (v) shows a vinyl ether blocked carboxyl group.

Monomer A is methylethoxymethyl acrylate (a monomer containing a vinyl ether blocked carboxyl group).

[0074]

[Table 21] Table 4 (continued) Preparation of vinyl polymerized oligomer containing vinyl ether blocked carboxyl group (BCa (v)) and epoxy group (EP) (synthesized at 80 ° C) Q-1 Q-2 Mn 865 963 Mw 1384 1423 Mw / Mn 1.6 Functional group amount (mol / Kg resin ) Ep 2 1.5 BCa (v) 2 1.5 BPh (s) 0.032 Reflux solvent xylene 674 674 Monomer-containing glycidyl methacrylate 49 49 Monomer B ^* 59 59 Styrene 50 50 n-butyl Acrylate 50 50 2-Ethylhexyl methacrylate 42 42 Ph8 (monomer) 3 Polymerization initiator AIBN 13 13 AIBN 13 13 Xylene 24 24 Additional catalyst AIBN 11 Xylene 11 Note) Monomer B is a vinyl ether blocked carboxyl represented by the following formula. It is a group (BCa (v))-containing monomer.

[0075]

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[0076]

Table 4 (continued) Preparation of vinyl polymerized oligomer containing vinyl ether blocked carboxyl group (BCa (v)) and hydrolyzable silyl group (Si) (synthesized at 80 ° C) R-1 R-2 Mn 1112 1030 Mw 1779 1683 Mw / Mn 1.6 Functional group amount (mol / Kg resin ) Si 11 BCa (v) 3 3 BCa (s) 0.048 Reflux solvent xylene 674 674 Monomer-containing γ-methacryloyloxypropylate 62 62 Remethoxysilane monomer A 107 107 styrene 30 30 n-butyl acrylate 30 30 2-ethylhexyl methacrylate 21 21 Ca5 (monomers) 4 polymerization initiator AIVN 11 11 AIBN 11 11 xylene 28 28 additional catalyst AIBN 1 1 xylene 1 1

[0077]

[Table 23] Table 4 (continued) Preparation of vinyl polymerized oligomer containing hydrolyzable silyl group (Si) and epoxy group (Ep) ( synthesized at 140 ° C) S-1 Mn 890 Mw 1424 Mw / Mn 1.6 Functional group amount (Mol / Kg resin ) Si 2 Ep 1 BCa (s) 0.048 reflux solvent xylene 674 monomer blend γ-methacryloyloxypropylto 124 remethoxysilane glycidyl methacrylate 36 styrene 30 2-ethylhexyl methacrylate 24 Ca 9 * 4 polymerization initiator AIBN 13 AIVN 13 xylene 34 additional catalyst AIBN 1 xylene 1 Note) Ca9 is a silyl-blocked carboxyl group-containing monomer and is represented by the following formula.

[0078]

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[0079]

[Table 24] Table 4 (continued) Preparation of vinyl polymerized oligomer containing hydroxyl group (OH) (synthesis at 140 ° C) T-1 T-2 Mn 920 950 Mw 1472 1530 Mw / Mn 1.6 1.6 Functional group amount (mol / Kg Resin ) OH 33 BPh (s) 0.032 Reflux solvent Xylene 674 674 Monomer blend 2-hydroxyethyl methacrylate 98 98 Styrene 50 50 n-Butyl acrylate 50 50 2-Ethylhexyl methacrylate 52 52 Ph 8 (monomer) 4 Polymerization initiator P-O 22 22 Xylene 28 28 Additional catalyst P-O 1 1 Xylene 1 1

[0080]

[Table 25] Table 4 (continued) Preparation of vinyl polymerized oligomer containing hydroxyl group (OH) and epoxy group (Ep) ( synthesized at 140 ° C) U-1 U-2 Mn 912 900 Mw 1459 1400 Mw / Mn 1.6 1.6 functional group Base amount (mol / Kg resin ) Ep 2 2 OH 2 2 BPh (s) 0.036 Refluxing solvent Xylene 674 674 Monomer-containing glycidyl methacrylate 71 71 2-Hydroxyethyl methacrylate 65 65 Styrene 40 40 n-Butyl acrylate 40 40 2-Ethylhexyl methacrylate 34 34 Ph9 (monomer) 4 Polymerization initiator P-O 22 22 Xylene 28 28 Additional catalyst P-O 11 Xylene 11

[0081]

[Table 26] Table 4 (continued) Preparation of vinyl polymerized oligomer containing hydroxyl group (OH) and hydrolyzable silyl group (Si) ( synthesized at 140 ° C) V-1 V-2 Mn 856 850 Mw 1198 1200 Mw / Mn 1.4 1.4 Functional group amount (mol / Kg resin ) Si 2 2 OH 2 2 BPh (s) 0.032 Reflux solvent xylene 674 674 Monomer blend γ-metalloylyloxypropyl trime 124 124 Toxysilane 2-hydroxyethyl methacrylate 65 65 Styrene 20 20 n -Butyl acrylate 21 21 2-Ethylhexyl methacrylate 20 20 Ph8 (monomer) 4 Polymerization initiator P-O 22 22 Xylene 28 28 Additional catalyst P-O 11 Xylene 11

[0082]

[Table 27] Table 4 (continued) Preparation of vinyl polymerized oligomer containing hydrolyzable silyl group (Si), hydroxyl group (OH) and epoxy group (Ep) ( synthesized at 140 ° C) W-1 W-2 Mn 893 930 Mw 1428 1420 Mw / Mn 1.6 1.5 Functional group amount (mol / Kg resin ) Si 11 Ep 11 OH 11 BPh (s) 0.032 Reflux solvent xylene 674 674 Monomer blend γ-methacryloylpropyltri 62 62 methoxysilane glycidyl methacrylate 53 53 2-Hydroxyethyl Methacrylate 33 33 Rate Styrene 60 60 2-Ethylhexyl Methacrylate 42 42 Ph 8 (Monomer) 4 Polymerization Initiator P-O 22 22 Xylene 28 28 Additional Catalyst P-O 1 1 Xylene 1 1

[0083]

[Table 28] Table 4 (continued)Functional group selected from the group consisting of hydroxyl group, blocked hydroxyl group and acetoacetyl group Preparation of vinyl-polymerized oligomers containing (synthesized at 140 ° C) X-1 X-2 Y-1 Y-2 Z-1 Z-2 Mn 900 860 890 920 850 920 MW 1450 1370 1390 1430 1380 1400Mw / Mn 1.6 1.6 1.6 1.6 1.6 1.5 Amount of functional groups (mol / Kg resin ) OH 1 1 1 1 BOH 2 2 AAEM^* 3 3 2 2 BPh (s) 0.032 0.016 BCa (s) 0.078 0.039 Reflux solvent Xylene 674 674 674 674 674 674 Monomer combination 2-Hydroxyethyl 33 33 33 33 Methacrylate trimethylsiloxyethyl 91 91 Methacrylate acetoacetoxyethyl 149 149 99 99 99 Methacrylate n-butyl acrylate 50 50 35 35 40 40 Styrene 50 50 35 35 40 40 2-Ethylhexyl meta 26 26 31 31 38 38 Acrylate Ph8 (monomer) 42Ca4 (monomer) 4 2 Polymerization initiator P-O 22 22 22 22 22 22Xylene 28 28 28 28 28 28 Additional catalyst P-O 1 1 1 1 1 1 1Xylene 1 1 1 1 1 1 Note) AAEM means acetoacetyl group.

[0084]

[Table 29] Table 4 (continued) hydroxyl, blocked hydroxyl, acetoacetyl group, in the preparation of vinyl polymer sediment Goma containing a functional group selected from epoxy groups and the group consisting of vinyl ether-blocked phosphoric acid group (80 ° C. Synthesis) AA-1 BB-1 CC-1 CC-2 DD-1 Mn 830 850 850 870 810 MW 1360 1360 1400 1360 1410 Mw / Mn 1.6 1.6 1.6 1.6 1.7 Amount of functional groups (mol / Kg resin ) BOH 11 OH 0.9 AAEM 21 BPh (v) * 3 3 1.5 Ep 1.5 BPh (s) 0.032 Refluxing solvent xylene 674 674 674 674 674 674 Monomer-containing trimethylsiloxyethyl meta 46 46 acrylate acetoacetoxymethacry 99 46 rate Monomer D ^** 128 128 64 Glycidyl methacrylate 54 n-Butyl acrylate 35 50 40 40 50 Styrene 35 50 60 60 50 2-Ethylhexyl methacrylate 35 58 22 22 32 Relate 2-hydroxyethyl Taakuri 33 Rate pH 8 (monomers) 4 polymerization initiator P-O 22 22 22 22 22 Xylene 28 28 28 28 28 Additional catalyst P-O 1 1 1 1 1 Xylene 1 1 1 1 1 Note) Monomer D is the following formula Shown are the monomers with vinyl ether blocked phosphate groups shown.

[0085]

Embedded image Application Example 1 A. Preparation of clear paint A clear paint (coating raw material) was prepared based on the composition shown in Table 5 below, and then this clear paint was prepared.
A clear coating composition was prepared by diluting with a mixture of Solvesso 150 / Solvesso 100 of 8/2 at 25 ° C. to be 100 cps.

[0086]

[Table 30] Table 5 Formulation of clear coating C1 C2 C3 C4 C5 Functional group present in oligomer Si ○ ○ ○ ○ ○ BOH ○ ○ ○ ○ ○ AA ○ ○ ○ ○ ○ Ep ○ ○ ○ ○ ○ A1 100 A2 100 A3 100 B1 80 L1 20 C1 80 N1 20 Ph1 2 2 2 Ph2 2 Ph3 2 Sandbar 3206 2 2 2 2 2 Tinuvin 123 1 1 1 1 1 KP321 0.1 0.1 0.1 0.1 0.1 0.1 Acetone 3 3 3 3 3 Tetrabutylphosphonium 3 3 3 3 3 Bromide MG100S 2 2 2 2 2

[0087]

[Table 31] Table 5 (continued) Clear paint formulation C6 C7 C8 C9 C10 C11 Functional group present in oligomer Si ○ ○ ○ ○ ○ ○ BOH ○ ○ ○ ○ ○ ○ AA ○ ○ ○ ○ ○ ○ Ep ○ ○ ○ ○ ○ ○ L1 20 C1 N1 30 D1 90 M1 30 40 G1 90 O1 30 20 E1 50 K1 50 F1 50 J1 50 H1 30 I1 70 Ph3 2 Ph 4 2 2 Ph 5 2 2 Ph 6 2 Sandbar 3206 2 2 2 2 2 2 2 2 2 2 2 Chinubin 123 1 1 1 1 1 1 KP321 0.1 0.1 0.1 0.1 0.1 0.1 Acetone 3 3 3 3 3 3 Tetrabutylphosphonium 3 3 3 3 3 3 Bromide MG100S 2 2 2 2 2 2

[0088]

[Table 32] Table 5 (continued) Compounding of clear coating C12 C13 C14 C15 C16 C17 C18 Functional group present in oligomer BOH ○ ○ ○ ○ ○ AA ○ ○ ○ ○ ○ Ep ○ ○ ○ ○ ○ ○ ○ BCa (v ) ○ ○ P1 50 N1 50 22.5 30 Q1 100 B1 100 E1 60 F1 60 M1 30 40 I1 80 O1 20 30 Ph1 2 2 2 Ph7 2 Ca1 2 2 Ca2 2 Sandbar 3206 2 2 2 2 2 2 2 Chinubin 123 1 1 1 1 1 1 1 KP321 0.1 0.1 0.1 0.1 0.1 0.1 0.1 Acetone 3 3 3 3 3 3 3 3 Tetrabutylphosphonium 3 3 3 3 3 3 3 Bromide MG100S 2 2 2 2 2 2 2

[0089]

[Table 33] Table 5 (continued) Formulation of clear coating C19 C20 C21 C22 C23 C24 Functional group present in oligomer Si ○ ○ ○ ○ ○ ○ BOH ○ AA ○ ○ ○ ○ ○ ○ Ep ○ ○ ○ ○ ○ ○ M1 40 30 40 N1 30 30 30 O1 20 L1 10 30 G1 100 I1 80 L1 20 K1 60 J1 80 Ca3 3 Ph1 2 2 2 2 2 Ph3 2 Sandbar 3206 2 2 2 2 2 2 Tinubin 123 1 1 1 1 1 1 KP321 0.1 0.1 0.1 0.1 0.1 0.1 Acetone 3 3 3 3 3 3 Tetrabutylphosphonium 3 3 3 3 3 3 Bromide MG100S 2 2 2 2 2 2

[0090]

[Table 34] Table 5 (continued) Formulation of clear paint C25 C26 C27 C28 C29 Functional group present in oligomer Si ○ ○ ○ ○ Ep ○ ○ ○ BCa (v) ○ ○ ○ ○ BOH ○ N1 30 40 O1 100 L1 20 20 S1 100 R1 60 Q1 80 P1 40 Ca3 2 Ph1 2 2 Ph3 2 Su3 4 Cymel 303 40 Sandbar 3206 2 2 2 2 2 Tinuvin 123 1 1 1 1 1 KP321 0.1 0.1 0.1 0.1 0.1 0.1 Acetone 3 3 3 3 Tetrabutylphosphonium 3 3 3 3 Bromide MG100S 2 2 2 2 2

[0091]

[Table 35] Table 5 (continued) Formulation of clear coating C30 C31 C32 C33 C34 C35 Functional group present in oligomer BOH ○ ○ ○ OH ○ ○ ○ O1 100 100 100 T1 100 100 100 Ph1 3 2 2 2 Su1 4 4 Parnock 901 S 54 54 Cymel 303 40 40 Cymel 370 40 40 Sandbar 3206 2 2 2 2 2 2 Tinuvin 123 1 1 1 1 1 1 1 KP321 0.1 0.1 0.1 0.1 0.1 0.1 Acetone 3 3 3 3 3 3 3 Tetrabutylphosphonium 3 3 3 3 3 3 Bromide MG100S 2 2 2 2 2 2

[0092]

[Table 36] Table 5 (Continued) Formulation of clear coating C36 C37 C38 C39 C40 Functional group present in oligomer Si ○ ○ ○ ○ ○ BOH ○ OH ○ ○ ○ O1 30 T1 30 L1 100 70 70 V1 100 H1 100 Ph1 2 2 2 2 2 Sandbar 3206 2 2 2 2 2 Tinuvin 123 1 1 1 1 1 KP321 0.1 0.1 0.1 0.1 0.1 Acetone 3 3 3 3 3 Tetrabutylphosphonium 3 3 3 3 3 Bromide MG100S 2 2 2 2 2

[0093]

[Table 37] Table 5 (continued) Formulation of clear paint C41 C42 C43 C44 C45 Functional group Si present in oligomer ○ ○ ○ ○ ○ AA ○ ○ ○ ○ ○ Ep ○ ○ ○ ○ BOH ○ ○ ○ ○ ○ BPh ( s) ○ ○ ○ BCa (s) ○ ○ A2 100 B2 80 L1 20 C2 80 N1 20 D2 90 M1 30 G2 90 O1 30 Sand bar 3206 2 2 2 2 2 Tinuvin 123 1 1 1 1 1 KP321 0.1 0.1 0.1 0.1 0.1 Acetone 3 3 3 3 3 Tetrabutylphosphonium 3 3 3 3 3 Bromide MG100S 2 2 2 2 2

[0094]

[Table 38] Table 5 (continued) Compounding of clear coating C46 C47 C48 C49 Functional group Si present in oligomer ○ ○ ○ ○ ○ AA ○ ○ ○ ○ Ep ○ ○ ○ ○ BOH ○ ○ ○ ○ BPh (s) ○ ○ BCa (s) ○ ○ C2 20 N2 30 M2 40 O2 20 E2 50 K1 50 F2 50 J1 50 H1 30 I2 70 Sandbar 3206 2 2 2 2 Tinuvin 123 1 1 1 1 KP321 0.1 0.1 0.1 0.1 Acetone 3 3 3 3 Tetrabutyl Phosphonium 3 3 3 3 Bromide MG100S 2 2 2 2

[0095]

[Table 39] Table 5 (continued) formulation of clear paint C50 C51 C52 C53 C54 functional groups present in the oligomer AA ○ ○ ○ ○ ○ Ep ○ ○ ○ ○ ○ BOH ○ ○ ○ ○ ○ BPh (s) ○ ○ ○ ○ BCa (s) ○ ○ ○ N2 22.5 30 B2 100 E2 60 F2 60 M2 30 40 I2 80 O1 20 30 Sand bar 3206 2 2 2 2 2 Tinuvin 123 1 1 1 1 1 KP321 0.1 0.1 0.1 0.1 0.1 0.1 Acetone 3 3 3 3 3 3 Tetrabutylphosphonium 3 3 3 3 3 Bromide MG100S 2 2 2 2 2

[0096]

[Table 40] Table 5 (continued) Formulation of clear coating C55 C56 C57 C58 C59 C60 Functional group present in oligomer Si ○ ○ ○ ○ ○ ○ AA ○ ○ ○ ○ ○ ○ Ep ○ ○ ○ ○ ○ ○ BOH ○ BPh (s) ○ ○ ○ ○ ○ BCa (s) ○ ○ ○ ○ ○ M2 40 30 40 N2 30 30 30 O1 20 L1 10 30 G2 100 I2 80 L1 20 K2 60 J2 80 Ca3 3 Ph1 2 2 2 2 Ph3 2 Sand bar 3206 2 2 2 2 2 2 Tinuvin 123 1 1 1 1 1 1 KP321 0.1 0.1 0.1 0.1 0.1 0.1 0.1 Acetone 3 3 3 3 3 3 Tetrabutylphosphonium 3 3 3 3 3 3 Bromide MG100S 2 2 2 2 2 2 2

[0097]

[Table 41] Table 5 (continued) Compounding of clear paint C61 C62 C63 C64 C65 Functional group present in oligomer Si ○ AA ○ Ep ○ BOH ○ ○ ○ OH ○ ○ BPh (s) ○ ○ ○ ○ ○ O2 100 100 T2 100 100 C2 100 Ph1 3 2 2 2 Pernock 901 S 54 54 Cymel 370 40 40 Sandbar 3206 2 2 2 2 2 Tinuvin 123 1 1 1 1 1 KP321 0.1 0.1 0.1 0.1 0.1 Acetone 3 3 3 3 3 Tetrabutylphosphonium 3 3 3 3 3 3 Bromide MG100S 2 2 2 2 2

[0098]

[Table 42] Table 5 (continued) Compounding of clear paint C66 C67 C68 C69 Functional group present in oligomer Si ○ ○ ○ ○ AA ○ ○ BOH ○ ○ ○ OH ○ ○ BPh (s) ○ ○ ○ BCa (s) ○ T2 30 C2 70 70 V2 100 H2 30 100 Ph1 2 2 2 2 Sand bar 3206 2 2 2 2 Tinuvin 123 1 1 1 1 KP321 0.1 0.1 0.1 0.1 Acetone 3 3 3 3 Tetrabutylphosphonium 3 3 3 3 Bromide MG100S 2 2 2 2 2

[0099]

[Table 43] Table 5 (continued) Clear paint formulation C70 C71 C72 C73 C74 C75 C76 Functional group present in oligomer BOH ○ ○ ○ ○ ○ OH ○ ○ ○ ○ ○ ○ AAEM ○ ○ ○ ○ ○ ○ ○ BPh ( s) ○ ○ BCa (s) ○ ○ X1 50 50 Y1 50 50 50 33 X2 50 Y2 50 50 Z1 50 Z2 50 O1 50 33 T1 50 33 Ph1 3 3 3 3 3 Sand bar 3206 2 2 2 2 2 2 2 Chinubin 123 1 1 1 1 1 1 1 KP321 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 MG100S 2 Cymel 370 30 30 30 30 30 30 30

[0100]

[Table 44] Table 5 (continued) Clear paint formulation C77 C78 C79 C80 C81 C82 Functional group present in oligomer BOH ○ ○ OH ○ ○ AAEM ○ ○ ○ Ep ○ ○ ○ BPh (v) ○ ○ ○ Y1 33 O1 33 AA1 100 33 BB1 100 CC1 60 CC2 60 N1 45 45 DD1 100 Ph1 3 3 3 3 3 3 Sandbar 3206 2 2 2 2 2 2 Tinuvin 123 1 1 1 1 1 1 KP321 0.1 0.1 0.1 0.1 0.1 0.1 0.1 Acetone 3 3 3 Tetra Butylphospho 3 3 3nium bromide

[0101]

[Table 45] Table 5 (continued) Clear paint comparative example HC1 HC2 HC3 Functional group present in oligomer Si ○ ○ ○ BOH ○ ○ ○ AA ○ ○ ○ Ep ○ ○ ○ A1 100 B1 80 L1 20 20 N1 30 M1 40 O1 20 Sand bar 3206 2 2 2 Tinuvin 123 1 1 1 KP321 0.1 0.1 0.1 Acetone 3 3 3 Tetrabutylphosphonium 3 3 3 Bromide Monooctyl phosphate 3 MG100S 2 2 2

[0102]

[Table 46] Table 5 (continued) Comparative example of clear paint HC4 HC5 HC6 HC7 Functional group present in oligomer BOH ○ ○ ○ ○ AA ○ ○ ○ ○ Ep ○ ○ ○ ○ N1 22.5 30 B1 100 E1 60 M1 40 I1 80 O1 20 30 Tinuvin 384 2 2 2 2 Sanol LS292 1 1 1 1 KP321 0.1 0.1 0.1 0.1 Acetone 3 3 3 3 Tetrabutylphosphonium 3 3 3 3 Bromide San-Aid SI400 4 4 Monooctyl Phosphate 4 MG100S 2 2 2 2

[0103]

[Table 47] Table 5 (continued)Clear paint comparative example HC8 HC9 HC10 In the oligomer Functional groups present BOH ○ ○ ○BPh (v) ○ ○ O1 100 100 100 Ph11 ^* 4 4 Purnock 901S 54 Cymel 303 40Cymel 370 40 Tinuvin 384 2 2 2 Sanol LS292 1 1 1 KP321 0.1 0.1 0.1 Acetone 3 3 3 Tetrabutylphosphonium 3 3 3 Bromide San-Aid SI400 4MG100S 2 2 2 Note) Ph11 represents vinyl ether-blocked phosphoric acid represented by the following formula, obtained by reacting 7.7 parts of monopentyl phosphoric acid with 15 parts of ethyl vinyl ether at room temperature for 40 hours.B. Clear paint performance evaluation The clear coating composition obtained as described above was
Apply it to the surface of the test piece prepared in
After being formed, the coating film performance was measured in the following manner. 1. Creating a painted board OTO850 (Nippon Paint Co., Ltd. intermediate coating on the electrodeposition plate)
Material) and baked at 140 ° C. for 30 minutes. Then O
TO520 (Nippon Paint Co., Ltd. base coat paint)
And baking for 10 minutes at 140 ° C.
Clear paints (C1-82) shown in Table 6 or comparative clear
-Apply paint (HC1-10) and bake at 140 ° C for 30 minutes
I attached.2. Performance evaluation method (1) Solvent content: Sol so that the paint becomes 100 cps at 25 ℃ and 60 ℃.
Dilute with a mixed solution of Vesso 100 / xylene = 1/1,
Bake at 140 ° C. for 30 minutes and measure the volatile content of the paint. (2) Pot life 25 ° C., viscosity after 4 hours.

Less than 200 cps: ○ 200 cps or more: × (3) Storage stability Increase in viscosity (cps) after standing for 10 days at 40 ° C. Less than 30: ○ 30 or more: × (4) Gasoline resistance The coated plate was tilted at 45 °, 1 ml of gasoline (Nisseki Silver) was poured into it, and left to dry. This was set as one cycle, and after 10 cycles, changes in the coating film state were visually observed. Here, those that did not change were evaluated as ◯, and those that caused discoloration and cracks were evaluated as x. (5) Anti-sagging property A clear coat is obliquely applied to a coated plate on which the base coat has been applied, set for 10 minutes, and then baked at 140 ° C for 30 minutes.
Measure the critical film thickness where sagging occurs.

Less than 30 μ: × 30 to 40: ◯ 40 or more: ◎ Table 6 below shows the results of these tests together.

[0106]

[Table 48] Table 6 Pot storage anti- dripping life stability stability gasoline resistance C1 ○ − * ◎ ○ C2 ○ − ◎ ○ C3 ○ − ◎ ○ C4 ○ − ◎ ○ C5 ○ − ◎ ○ C6 ○ − ◎ ○ C7 ○ − ◎ ○ C8 ○ − ◎ ○ C9 ○ − ◎ ○ C10 ○ − ◎ ○ C11 ○ − ◎ ○ C12 ○ ○ ◎ ○ C13 ○ ○ ◎ ○ C14 ○ − ◎ ○ C15 ○ − ◎ ○ C16 ○ − ◎ ○ C17 ○ − ◎ ○ C18 ○ − ◎ ○ C19 ○ − ◎ ○ C20 ○ ○ ○ ○ C21 ○ ○ ◎ ○ C22 ○ ○ ○ ○ C23 ○ ○ ○ ○ C24 ○ ○ ○ ○ C25 ○ ○ ○ ○ C26 ○ ○ ○ ○ * Since the reaction was quick and it was difficult to liquefy it, it was not measured. Therefore, when storing, it should be stored as a two-part solution.

[0107]

[Table 49] Table 6 (continued) Pot storage Anti- dripping life Stability Stability Gasoline resistance C27 ○ ○ ○ ○ C28 ○ ○ ○ ○ C29 ○ ○ ○ ○ C30 ○ ○ ○ ○ C31 ○ ○ ○ ○ C32 ○ − ◎ ○ C33 ○ ○ ○ ○ C34 ○ ○ ○ ○ C35 ○ − ◎ ○ C36 ○ ○ ○ ○ C37 ○ ○ ○ ○ C38 ○ ○ ◎ ○ C39 ○ ○ ◎ ○ C40 ○ ○ ○ ○ C41 ○ − ◎ ○ C42 ○ − ◎ ○ C43 ○ − ○ ○ C44 ○ − ◎ ○ C45 ○ − ◎ ○ C46 ○ − ◎ ○ C47 ○ − ◎ ○ C48 ○ − ◎ ○ C49 ○ − ◎ ○ C50 ○ − ◎ ○ C51 ○ − ◎ ○ C52 ○ − ◎ ○

[0108]

[Table 50] Table 6 (continued) Pot storage anti- dripping life Stability Stability Gasoline resistance C53 ○ − ◎ ○ C54 ○ − ◎ ○ C55 ○ ○ ○ ○ C56 ○ − ◎ ○ C57 ○ ○ ○ ○ C58 ○ ○ ○ ○ C59 ○ ○ ○ ○ C60 ○ ○ ○ ○ C61 ○ ○ ○ ○ C62 ○ − ◎ ○ C63 ○ ○ ○ ○ C64 ○ − ◎ ○ C65 ○ ○ ○ ○ C66 ○ ○ ◎ ○ C67 ○ ○ ◎ ○ C68 ○ ○ ○ ○ C69 ○ ○ ◎ ○ C70 ○ ○ ○ ○ C71 ○ ○ ○ ○ C72 ○ ○ ○ ○ C73 ○ ○ ○ ○ C74 ○ ○ ◎ ○ C75 ○ ○ ◎ ○ C76 ○ ○ ○ ○ C77 ○ ○ ◎ ○ C78 ○ ○ ◎ ○ C79 ○ ○ ◎ ○ C80 ○ ○ ◎ ○ C81 ○ ○ ◎ ○ C82 ○ ○ ○ ○ * Not measured because the reaction was quick and one liquefaction was difficult.

[0109]

[Table 51] Table 6 (continued) Pot storage Anti- dripping life Stability Stability Gasoline resistance HC1 ○ − × ○ HC2 × − ◎ ○ HC3 ○ − × ○ HC4 ○ − × ○ HC5 ○ − × ○ HC6 ○ − × ○ HC7 × − ◎ ○ HC8 ○ × × ○ HC9 ○ × × ○ HC10 ○ − × ○

[0110]

According to the present invention, a paint having excellent pot life and sagging prevention property can be obtained. The coating composition of the present invention has an organic solvent content of 30% or less and has good coating workability, and is very useful in preventing pollution.

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Hiroyuki Uemura No. 3 Shinchi, Fuchu-cho, Aki-gun, Hiroshima Prefecture Mazda Co., Ltd. (72) Inventor Kazuyo Koga No. 3 Shinchi, Fuchu-cho, Aki-gun, Hiroshima Prefecture Mazda Corporation (72) Inventor Mika Osawa 3-1, Shinchi, Fuchu-cho, Aki-gun, Hiroshima Mazda Motor Corporation

Claims (10)

[Claims] 1. A first functional group selected from the group consisting of a hydroxyl group, a blocked hydroxyl group and an acetoacetyl group, a silyl-blocked sulfonic acid group, a silyl-blocked carboxylic acid group and a silyl-blocked phosphoric acid group. Containing a second functional group selected from the group consisting of a melamine resin and an isocyanate prepolymer, wherein the first functional group is present in the same or different vinyl polymerized oligomer, and the second functional group is the vinyl polymerized Is it present in the oligomer,
Alternatively, a low solvent which is present in a separate compound and in which the vinyl polymerized oligomer has a number average molecular weight of 300 to 1500, a weight average molecular weight of 300 to 3000, and a weight average molecular weight / number average molecular weight of 1 to 2. Type resin composition. 2. A first functional group selected from the group consisting of a hydroxyl group, a blocked hydroxyl group and an acetoacetyl group, a silyl blocked sulfonic acid group, a silyl blocked carboxylic acid group and a silyl blocked phosphoric acid group. Containing a second functional group selected from the group consisting of a melamine resin and an isocyanate prepolymer, wherein the first functional group is present in the same or different vinyl polymerized oligomer, and the second functional group is the vinyl polymerized Is it present in the oligomer,
Alternatively, a low solvent which is present in a separate compound and in which the vinyl polymerized oligomer has a number average molecular weight of 300 to 1500, a weight average molecular weight of 300 to 3000, and a weight average molecular weight / number average molecular weight of 1 to 2. Type coating composition. 3. A second functional group selected from the group consisting of a hydrolyzable silyl group and a silyl-blocked sulfonic acid group, a silyl-blocked carboxylic acid group and a silyl-blocked phosphoric acid group. The functional group and the vinyl functional oligomer are contained in the same or different vinyl polymerized oligomers, or the second functional group is present in a different compound, and the vinyl polymerized oligomers have a number average molecular weight of 600 to 1500 and a weight average molecular weight of 600 to A low solvent type resin composition having a weight average molecular weight of 3000 and a number average molecular weight of 1 to 2. 4. A second functional group selected from the group consisting of a hydrolyzable silyl group, a silyl-blocked sulfonic acid group, a silyl-blocked carboxylic acid group and a silyl-blocked phosphoric acid group. The functional group and the vinyl functional oligomer are contained in the same or different vinyl polymerized oligomers, or the second functional group is present in a different compound, and the vinyl polymerized oligomers have a number average molecular weight of 600 to 1500 and a weight average molecular weight of 600 to 3000, and a weight average molecular weight / number average molecular weight 1-2, The low solvent type coating composition characterized by the above-mentioned. 5. A first selected from the group consisting of a hydroxyl group, a blocked hydroxyl group, a hydrolyzable silyl group and an epoxy group.
A second functional group consisting of a functional group and an acid anhydride group, and a third functional group selected from the group consisting of a silyl blocked sulfonic acid group, a silyl blocked carboxylic acid group and a silyl blocked phosphoric acid group. The first functional group and the second functional group are present in the same or different vinyl polymerized oligomers, and the third functional group is present in the vinyl polymerized oligomers or in a separate compound. And the vinyl polymerized oligomer has a number average molecular weight of 600 to
A low-solvent type resin composition having 1500, a weight average molecular weight of 600 to 3000, and a weight average molecular weight / number average molecular weight of 1 to 2. 6. A first selected from the group consisting of a hydroxyl group, a blocked hydroxyl group, a hydrolyzable silyl group and an epoxy group.
A second functional group consisting of a functional group and an acid anhydride group, and a third functional group selected from the group consisting of a silyl blocked sulfonic acid group, a silyl blocked carboxylic acid group and a silyl blocked phosphoric acid group. The first functional group and the second functional group are present in the same or different vinyl polymerized oligomers, and the third functional group is present in the vinyl polymerized oligomers or in a separate compound. And the vinyl polymerized oligomer has a number average molecular weight of 600 to
A low-solvent type coating composition having 1500, a weight average molecular weight of 600 to 3000, and a weight average molecular weight / number average molecular weight of 1 to 2. 7. A vinyl (thio) ether-blocked carboxyl group, phosphoric acid group, or hydroxyl group-containing first functional group, an epoxy group-containing second functional group, a silyl-blocked sulfonic acid group, or a silyl-blocked group. And a third functional group selected from the group consisting of a carboxylic acid group and a silyl blocked phosphoric acid group, wherein the first functional group and the second functional group are present in the same or different vinyl polymerized oligomers, The third functional group is present in the vinyl polymerized oligomer or in a separate compound, and the vinyl polymerized oligomer has a number average molecular weight of 600 to 15
00, weight average molecular weight 600-3000, and weight average molecular weight / number average molecular weight 1-2, The low solvent type resin composition characterized by the above-mentioned. 8. A vinyl (thio) ether blocked first functional group consisting of a carboxyl group, a phosphoric acid group or a hydroxyl group, a second functional group consisting of an epoxy group, a silyl blocked sulfonic acid group and a silyl blocked group. And a third functional group selected from the group consisting of a carboxylic acid group and a silyl blocked phosphoric acid group, wherein the first functional group and the second functional group are present in the same or different vinyl polymerized oligomers, The third functional group is present in the vinyl polymerized oligomer or in a separate compound, and the vinyl polymerized oligomer has a number average molecular weight of 600 to 15
00, weight average molecular weight 600-3000, and weight average molecular weight / number average molecular weight 1-2, The low solvent type coating composition characterized by the above-mentioned. 9. A method for coating the surface of an article to be coated with the low-solvent type coating composition according to claim 2, wherein the composition is rotatable about a substantially horizontal axis. On the surface of the supported object to be coated, the coating is applied to a thickness that causes sagging on the surface extending in the normal vertical direction, and then the sagging of the coating applied to the surface of the object to be coated is caused by gravity. At a speed such that the object to be coated starts to rotate about a substantially horizontal axis, and the surface of the object to be coated transitions from a substantially vertical state to a substantially horizontal state at least before the rotation causes sagging of the applied coating due to gravity. Moreover, a method for coating a low solvent type coating composition, characterized in that the coating composition is rotated at a speed slower than the speed at which the coating sags due to the centrifugal force caused by the rotation. 10. The low-solvent type coating composition according to any one of claims 2, 4, 6 and 8 is applied to the surface of an object to be coated and then heat-cured to be applied to the surface of the object to be coated. A method for coating a low-solvent type coating composition, which comprises forming a film.