JP3369274B2 - High solid content resin composition and paint finishing method using the same - Google Patents

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a novel and useful high solid content resin composition and a coating method using the same. More specifically, the present invention relates to a specific acrylic oligomer having, in part, a blocked hydroxyl group and also having one or more functional groups such as an acid anhydride group and / or an epoxy group, A compound having a decomposable silyl group and further having one or more functional groups such as an epoxy group, a blocked hydroxyl group and / or an acid anhydride group, a dissociation catalyst and / or a curing catalyst, and a reactive diluent. A novel high-solids resin composition containing as an essential component a fine particle polymer;

Secondly, a resin composition having a high solid content and a high solid content coating composition, which are mainly composed of a low-viscosity acrylic oligomer in a form in which a hydroxyl group is blocked with a specific compound, thus obtained. 1 coat 1 bake (hereinafter,
It is abbreviated as 1C-1B. ) 2 coats 1 bake (hereinafter,
It is abbreviated as 2C-1B. ) 2 coat 2 bake (hereinafter,
2C-2B is abbreviated. ) 3 coat 2 bake (hereinafter,
It is abbreviated as 3C-2B. ) And a method for applying a resin composition and a paint in an overcoat system.

[0003]

2. Description of the Related Art In recent years, in the exterior coating of automobiles, line coating with a 2C-1B finish is carried out in the form of a combination of acrylic polyol and melamine resin. A large amount of solvent is released into the atmosphere from the painting line, and burning the discharged solvent also accelerates the global warming phenomenon due to the generation of a large amount of carbon dioxide. There is a social problem.

[0004] Of course, a study of making the composition water-based, centering on the base coat, has been widely made. The clear coat is required to have high appearance and high coating performance such as durability.

Although water-based paints, powder paints, UV-curable paints and the like have been widely studied, it can be said that the reduction of solvent in conventional resins is the shortest route.

When a conventional acrylic polyol-melamine resin combination is used to reduce the molecular weight in order to achieve high solidification, the hydroxyl group content must be increased to compensate for insufficient curing. .

However, with such means, it is not always possible to achieve a low viscosity, and a coating film in which a resin having a high hydroxyl value is cured with a melamine resin is extremely resistant to acid. This results in a decrease in sex.

In addition, at the time of coating, there is a problem that the sagging of the vertical surface is remarkable due to the decrease in viscosity.

[0009]

Therefore, the object of the present invention is to solve various problems in the prior art as described above.
It is to provide a resin composition that can be reduced in viscosity by greasing, eliminating and solving it, improving acid resistance and scratch resistance, and not causing armpits or sagging. At the same time, it is an object of the present invention to provide an extremely highly practical coating method and baking method with these various performances improved.

[0010]

Therefore, the inventors of the present invention have conducted intensive studies mainly for the purpose of the present invention as described above, and as a result, have achieved a reduction in viscosity and a low molecular weight. At the same time as the conversion, it was learned that it is done by a method such as lowering the glass transition temperature.

Further, in the present system, a fine particle dispersion technique for obtaining a coating film having a so-called beautiful appearance, which is free from cracks and sagging while maintaining a high solid content, and which is extremely practical. Well, not a little, I learned.

That is, the present inventors have a hydroxyl group blocked in one molecule as an essential functional group in order to reduce the polarity of the low molecular weight acrylic resin, and further include an acid anhydride group and / or an epoxy group. And a specific acrylic oligomer (A) having one or more functional groups and having a number average molecular weight of 1,500 or less,

Having a hydrolyzable silyl group as an essential functional group in one molecule, and further having at least one functional group such as an epoxy group, a blocked hydroxyl group and / or an acid anhydride group, and A specific compound (B) having a number average molecular weight of 1,500 or less,

Dissociation catalyst and / or curing catalyst (C)
And a reactive diluent (D) and fine particle polymers (E) as essential film-forming components.
Specific high solid content resin composition,

Further, by using a high solid content type coating composition using the high solid content resin composition as a binder, a sufficiently low viscosity is achieved, and a coating film free from cracks and sagging. The present invention has been completed here by discovering that the above can be completed.

That is, the present invention basically has a hydroxyl group blocked in one molecule as an essential functional group,
Furthermore, an acrylic oligomer (A) having at least one functional group selected from the group consisting of acid anhydride groups and epoxy groups, and having a number average molecular weight of 1,500 or less,

It has a hydrolyzable silyl group as an essential functional group in one molecule, and also has at least one functional group selected from the group consisting of an epoxy group, a blocked hydroxyl group and an acid anhydride group. And has a number average molecular weight of 1,500
The following compound (B),

Dissociation catalyst and / or curing catalyst (C)
And a reactive diluent (D) and a fine particle polymer (E) as essential film-forming components. Particularly, it is possible to reduce the viscosity, and
In particular, it is an object of the present invention to provide a highly solid resin composition having extremely high practicality, in which acid resistance and scratch resistance can be improved, and in addition, cracking or sagging does not occur.

The present invention also provides 1C-1B,
2C-1B, 2C-2B, 3C-2B or an overcoat system, so-called,
A method of coating paint by laminated coating, in which first, a colored film is applied on a base material to form a base coat,

Next, the base coat has a hydroxyl group blocked in one molecule as an essential functional group, and further has at least one functional group selected from the group consisting of an acid anhydride group and an epoxy group. Specific acrylic oligomer (A) having a number average molecular weight of 1,500 or less
When,

It has a hydrolyzable silyl group as an essential functional group in one molecule, and further has at least one functional group selected from the group consisting of an epoxy group, a blocked hydroxyl group and an acid anhydride group. And has a number average molecular weight of 1,500
The following compound (B),

Dissociation catalyst and / or curing catalyst (C)
And a reactive diluent (D), and further fine particle polymers (E) as essential film-forming components, a specific high solid content resin composition, an essential component of the binder An object of the present invention is to provide a novel coating method for coating a coating material (base material) with a high solid content coating composition, which is substantially free from sagging.

In particular, when such fine particle polymers are added to the above mixture, it is important to disperse them while maintaining the primary particle diameter without causing aggregation or fusion of particles. .

As a method of dispersing the fine particle polymers (E), only representative ones are exemplified, and the fine particle polymer powder is added to the above mixture and subjected to high shear by a sand mill or the like. After the method and dispersion in highly polar solvents such as alcohols and ketones,
There are various methods such as a method of adding it to the resin, but there are various problems such as workability and low coating solid content.

Therefore, in the present invention, a reactive diluent having an acid anhydride group is used in place of the above-mentioned highly polar solvent, so that the resin solid content can be extremely easily reduced. That is, they have found that they can disperse the fine particle polymers, and have completed the present invention.

The present invention will be described in detail below. First, the first component in the high-solids resin composition of the present invention, which has the above-mentioned blocked hydroxyl group in one molecule as an essential functional group, and further has an acid anhydride group and / or an epoxy group. The acrylic oligomer (A) having and having a number average molecular weight of 1,500 or less is

A compound having any one of the structures represented by the following general formulas (I), (II) and (III) is referred to. That is,

[0028]

[Chemical 7]

(However, R ₁ and R ₂ in the formulas respectively represent an alkyl group having 1 to 18 carbon atoms, a phenyl group or an aryl group, or a hydrogen atom, a chlorine atom or a fluorine atom. , it is assumed that may be the same or different R1 and R2. the, R ₃ denote the alkyl group, a phenyl group or an aryl group having a carbon number becomes 1-18.)

[0030]

[Chemical 8]

(Wherein R ₄ represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, and R ₅ represents a cycloalkyl group, an aralkyl group, an aryl group, an alkoxyl group or an alkanoyloxy group. A group, substituted with at least one atomic group selected from the group consisting of an alkyl group having 1 to 18 carbon atoms and a halogen atom,
It represents an alkyl group having 1 to 22 carbon atoms. )

[0032]

[Chemical 9]

(However, X in the formula is at least one selected from the group consisting of an alkoxyl group, an aralkyl group, an aryl group, an aryloxy group, an alkanoyloxy group, an alkyl group having 1 to 10 carbon atoms and a halogen atom. Represents an alkyl group having 1 to 18 carbon atoms, which may or may not be substituted by the atomic group.

The one having any one of the structures shown by is referred to.

And, only by exemplifying the typical ones as the above-mentioned monomers represented by the general formula (I), trimethylsiloxyethyl (meth) acrylate and trimethylsiloxypropyl (meth) acrylate are given. , Trimethylsiloxybutyl (meth) acrylate,
Starting with triethylsiloxyethyl (meth) acrylate or tributylsiloxypropyl (meth) acrylate,

Furthermore, various triphenylsiloxyalkyl (meth) acrylates or various dimethyl-
and tert-butylsiloxyalkyl (meth) acrylates.

That is, the hydrogen atom forming the hydroxyl group in the hydroxyl group-containing polymerizable unsaturated monomer is blocked by a so-called silylating agent (that is,
Hydroxyl block group-containing unsaturated monomers), but is not limited to the above-listed monomers.

That is, N-methylolated (meth) acrylamide or β-hydroxyethyl (meth) acrylate in the form of addition reaction of ε-caprolactone, or (meth) acrylates of polyoxyalkylene glycols. It is also possible to use a silylated form.

Next, only the representative monomers of the above-mentioned general formula (II) will be given. 1-methoxy-ethoxyethyl (meth) acrylate, 1-ethoxy-ethoxyethyl (Meth) acrylate, 1-butoxy-ethoxyethyl (meth) acrylate, 1- (2-ethylhexanoxy) -ethoxyethyl (meth) acrylate, 1-isobutoxy-ethoxyethyl (meth) acrylate or 1-cyclohexyloxy- Such as ethoxyethyl (meth) acrylate,

Various 1-alkoxy-ethoxyethyl (meth) acrylates, ie, hydroxyl groups in the hydroxyl group-containing polymerizable unsaturated monomers, are subjected to an addition reaction with alkyl vinyl ethers to hydrogen atoms constituting the hydroxyl groups. However, it is by no means limited to the above-listed monomers.

That is, N-methylolated (meth) acrylamide or β-hydroxyethyl (meth) acrylate in the form of addition reaction of ε-caprolactone, or various (meth) acrylates of polyoxyalkylene glycols. In addition, it is possible to use a form obtained by addition-reacting various vinyl ethers.

Further, only the typical monomers as the above-mentioned monomers represented by the general formula (III) will be mentioned, the following general formulas (III-1) to (III) will be given.
-4) and the like. That is,

[0043]

[Chemical 10]

[0044]

[Chemical 11]

[0045]

[Chemical 12]

Or

[0047]

[Chemical 13]

And so on.

The number of carbon atoms of "X" in the general formula (III) is usually appropriate within the range of 1-18.
Preferably, the range of 2 to 6 is suitable.

The amount of these various hydroxyl group-blocked monomers used is 1.5 to 3 mol / mol.
A range of 1,000 g is suitable. 1.5 mol / 1
If it is less than 000 g, the effect of lowering the viscosity tends to be small, while if it exceeds 3 mol / 1,000 g and is too large, the effect of the blocking agent is more important than the effect of decreasing the viscosity. In any case, it is not preferable because it also causes an increase in volatile components.

If only representative examples of unsaturated monomers having an acid anhydride group, which can be introduced by copolymerization with the above-mentioned unsaturated monomer containing a hydroxyl group, are given, It is in a form represented by itaconic anhydride, maleic anhydride or methacrylic anhydride.

Further, various monocarboxylic acid copolymers represented by monoalkyl maleic acid or monoalkyl itaconic acid can also be obtained by a ring-closing reaction by dealcoholation reaction. Of course.

The appropriate amount of these used is within the range of 1.5 to 3 mol / 1,000. This means that it is desirable to use it in such a proportion that it becomes equimolar so that it can easily react with the regenerated hydroxyl group.

Next, when a hydroxyl block group and an acid anhydride group are simultaneously introduced, an epoxy group is required as a functional group capable of obtaining a highly cured coating film without increasing the viscosity. Become.

As a method for introducing such an epoxy group, for example, a polymerizable unsaturated monomer containing an epoxy group is copolymerized with the unsaturated monomer containing a hydroxyl block group and an unsaturated monomer containing an acid anhydride group. The method of burrowing is especially recommended, but

As the epoxy group-containing polymerizable unsaturated monomer, only typical ones will be given. Reaction products of glycidyl (meth) acrylate, isocyanate ethyl (meth) acrylate and glycidol;

Or (meth) acryloyloxymethyl-3,4-epoxycyclohexane, vinylcyclohexene monoepoxide, etc., and these epoxy group-containing polymerizable unsaturated monomers and various copolymerizable unsaturated monomers. It is in the form obtained by copolymerizing with the body.

As only other typical monomers copolymerizable with the above-mentioned monomers, only monovalent alcohols having 1 to 22 carbon atoms, Including various alkyl (meth) acrylates that are esterification products with (meth) acrylic acid,

Styrene, vinyltoluene, tert-butylstyrene, glycidyl (meth) acrylate, 2-
Various (meth) acrylic acid esters such as ethoxyethyl (meth) acrylate, (meth) acrylonitrile, cyclohexyl (meth) acrylate;

Diesters of maleic acid or fumaric acid with monohydric alcohols having 1 to 22 carbon atoms; various acrylamides such as (meth) acrylamide and (meth) dimethylacrylamide;

Vinyl acetate, "Veova" (various vinyl esters such as vinyl ester of branched aliphatic monocarboxylic acid manufactured by Shell, Switzerland; haloolefins such as hexafluoropropylene and tetrafluoroethylene;

Or perfluoroalkyl perfluorovinyl ethers such as trifluoromethyl trifluorovinyl ether and pentafluoroethyl trifluorovinyl ether, and

(Per) fluorovinyl ethers, perfluoroalkyl vinyl ethers (provided that the number of carbon atoms in the alkyl group is in the range of 1 to 18), etc. Of course, the monomers may be used alone or in combination of two or more, depending on the desired coating film performance.

The number average molecular weight of the acrylic oligomer (A) obtained by copolymerizing the various components listed above is preferably 1,500 or less, and preferably 700 to 1,200. The range of is appropriate.

If it exceeds 1,500 and becomes too high, the solubility or viscosity in the solvent-free state will inevitably increase, and the amount of the diluting solvent will increase extremely accordingly. Not preferable.

The polymerization of these various monomers can be carried out by a known and conventional method. Preferably,
It can be easily carried out by the radical solution polymerization method.
Regarding the method of obtaining a low molecular weight polymer, a method using various chain transfer agents, including various mercaptan compounds such as mercaptoethanol, thioglycerol or lauryl mercaptan, and high temperature (usually 140 ~ It can be easily obtained by carrying out the reaction at a low monomer concentration.

Here, only typical solvents are listed, and xylene, "Solvesso" (manufactured by Exxon Co.), butyl acetate, methyl ethyl ketone, methyl amyl ketone, butyl acetate, excluding alcohol solvents. Alternatively, any solvent that is commonly used in the production of acrylic polymers, such as ethyl acetate, is used.

As the radical polymerization initiator, any one may be used as long as it is usually used, but of these, benzoyl peroxide can be mentioned as only representative ones. , Lauroyl peroxide, tert-butyl hydroperoxide, tert-butylperoxy-2-ethylhexanoate, tert-amylperoxy-2-ethylhexanoate, tert-amylperoxybenzoate. Oxides; or various azo compounds such as azobisisobutyronitrile and azobis (2-methylpropionitrile).

The so-called ionic polymerization method such as anionic polymerization or cationic polymerization can be particularly advantageously used for the copolymerization of monomers having a blocked hydroxyl group.

Moreover, the acrylic oligomer (A) thus obtained, which has both a blocked hydroxyl group and an acid anhydride group and / or an epoxy group, is the high solid resin composition of the present invention, or the present invention. As a component of the high solids type paint of, without regenerating the hydroxyl group,
It can be used stably as it is.

Then, it should be called the second component of the present invention.
It has a hydrolyzable silyl group as an essential functional group in one molecule, and further has one or more functional groups selected from the group consisting of an epoxy group, a blocked hydroxyl group and an acid anhydride group. And, regarding the compound (B) having a number average molecular weight of 1,500 or less,

The compound (B) having one or more hydrolyzable silyl groups in one molecule and also having an epoxy group, a blocked hydroxyl group and / or an acid anhydride group is as follows. Is mentioned.

That is, for example, the following general formula (IV)

[0074]

[Chemical 14]

An alicyclic epoxy group represented by the following general formula (V)

[0076]

[Chemical 15]

(In the formula, R ₆ represents a hydrogen atom or a monovalent organic group such as an alkyl group, an aryl group or an aralkyl group. R ₇ represents a halogen atom, an alkoxyl group, an acyloxy group, Phenoxy group,
It represents an iminooxy group or an alkenyloxy group. In addition, a is assumed to be a natural number of 0, 1 or 2. )

A compound having a hydrolyzable silyl group as shown by is particularly representative.

Specifically, β-3,4-epoxycyclohexylethyltrimethoxysilane, β-3,4-epoxycyclohexylethyltriethoxysilane, γ-isocyanatopropyltrimethoxysilane and the like, γ-isocyanatopropyltrimethoxysilane, etc. An adduct of isopropenyloxysilane and β-3,4-epoxycyclohexylethanol and the like are particularly representative.

Γ- (meth) acryloyloxypropyltrimethoxysilane, γ- (meth) acryloyloxypropylmethyldimethoxysilane, γ- (meth)
Such as acryloyloxypropyltriisopropenyloxysilane, γ- (meth) acryloyloxypropyltriiminooxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, vinyl (tris-β-methoxyethoxy) silane or vinyltriacetoxysilane,

Vinyl monomers having various hydrolyzable silyl groups, β-3,4-epoxycyclohexylmethanol, an esterified product of (meth) acrylic acid, and a hydroxyl group-containing unsaturated monomer. , Vinyl system containing hydrolyzable silyl group as an essential functional group by copolymerization with epoxy group-containing unsaturated monomer, acid anhydride group-containing unsaturated monomer and other copolymerizable monomers A copolymer can be obtained.

As only typical compounds having a glycidyl group as an epoxy group and a hydrolyzable silyl group, γ-glycidoxypropyltrimethoxysilane and γ-glycid will be mentioned. With xypropyltriethoxysilane, γ-glycidoxypropylmethyldiethoxysilane, γ-glycidoxypropyltriisopropenyloxysilane, γ-glycidoxypropyltriiminooxysilane or γ-isocyanatopropyltrimethoxysilane, and the like, An adduct with glycidol; or an adduct with γ-aminopropyltrimethoxysilane and a diepoxy compound.

The above-mentioned vinyl copolymer having a hydrolyzable silyl group includes a polymerizable monomer having a glycidyl group, an acid anhydride group-containing polymerizable monomer or a hydroxyl block group-containing polymerizable monomer. It can also be obtained by copolymerizing the above-mentioned polymerizable monomers having a hydrolyzable silyl group, and further other copolymerizable monomers.

Glycidyl (meth) acrylate, 1-methylglycidyl (meth) acrylate and the like are particularly representative as the monomers having a glycidyl group, but the monomers are by no means limited to these. Not a thing.

The number average molecular weight of the compound (B) obtained by copolymerizing the various components listed above is preferably 1,500 or less, and preferably 700 to 1,200. Within the range is appropriate.

If it exceeds 1,500 and becomes too high, the solubility or the viscosity in the solvent-free state will extremely increase, and the amount of the diluting solvent will increase extremely accordingly. Not preferable.

Further, it should be called the third component of the present invention,
The above-mentioned dissociation and / or curing catalyst (C) is hydrolyzed by the reaction with moisture in the air to regenerate the hydroxyl group, and further promotes the reaction between the regenerated hydroxyl group and the acid anhydride group to generate. A compound that promotes the reaction between the carboxyl group and the epoxy group is referred to.

Needless to say, it is necessary to use a catalyst in order to accelerate the hydrolysis, but only the typical catalysts for promoting the reaction with the acid anhydride group can be mentioned. For example, phosphoric acid, phosphoric acid ester, phosphorous acid ester, unsaturated group-containing phosphoric acid ester,

Further, various acidic catalysts such as p-toluenesulfonic acid or an amine salt thereof; benzoic acid, trichloroacetic acid, naphthalene disulphonic acid or an amine salt thereof, or tetraethylammonium fluoride. ,

Furthermore, compounds which generate halogen ions such as tetraethylammonium chloride are effective. The addition amount of these catalysts is 0.001 to 10% with respect to the acrylic oligomer (A).
The range is appropriately, and preferably 0.005
The range of 6% is suitable.

As only specific examples of the catalyst for promoting the reaction between the epoxy group and the carboxyl group, tetramethylammonium fluoride, tetramethylammonium bromide, trimethylbenzylammonium hydroxide, 2-hydroxypyridine, trimethylammonium methoxide, phenyltrimethylammonium chloride, phenyltrimethylammonium bromide, phenyltrimethylammonium hydroxide, phenyltrimethylammonium iodide, phenyltrimethylammonium bromide, phosphocholine chloride sodium salt,

Stearyl ammonium bromide, tetra-n-butylammonium hydroxide, tetra-n-butylammonium phosphate, tetra-n
-Dodecyl ammonium trichloride, tetraethyl ammonium hydroxide, tetraethyl ammonium tetrafluoroborate, acetylcholine bromide, alkyldimethylbenzyl ammonium chloride, benzyl choline bromide, benzyl-n-butyl ammonium bromide, betaine, butyryl chloride, bis (tetra Various quaternary ammonium salts, such as -n-butylammonium) dichromate or trimethylvinylammonium bromide;

Allyltriphenylphosphonium chloride, n-amyltriphenylphosphonium bromide, benzyltriphenylphosphonium chloride,
Bromomethyltriphenylphosphonium bromide,
2-dimethylaminoethyltriphenylphosphonium bromide, ethoxycarbonylphosphonium bromide, n-heptyltriphenylphosphonium bromide, methyltriphenylphosphonium bromide,
Various phosphonium salts such as tetrakis (hydroxymethyl) phosphonium sulphate or tetraphenylphosphonium bromide;

Various acid catalysts such as phosphoric acid, p-toluenesulfonic acid or dimethylsulfate; 1,8-diazabicyclo (5,4,0) undecene-7 or 1,4-
Various basic catalysts such as diazabicyclo (2,2,2) octane; various carbonates such as calcium carbonate.

The amount of the dissociation and / or curing catalyst (C) used is 100 parts by weight of the solid content of the acrylic oligomer (A) and the compound (B).
The range of 0.01 to 10 parts by weight is suitable, and the range of 0.1 to 5 parts by weight is suitable.

The amount of the dissociation and / or curing catalyst (C) used has a major effect on the baking temperature when the high-solids resin composition of the present invention forms a coating film. If the amount is less than 0.01 parts by weight, the crosslinking reaction tends to be difficult to proceed sufficiently, and on the other hand, 1
If the amount exceeds 0 parts by weight and becomes too large, the storage stability of the thermosetting resin composition, the water resistance of the coating film, and the like will inevitably decrease, which is not preferable in any case.

Further, if necessary, the high solid content resin composition or the high solid content type coating composition (hereinafter, both of them may be represented as the resin composition, or vice versa).
Sometimes represented as a paint. ) Includes various resins, solvents, colorants such as various pigments and dyes,

It is needless to say that various known and conventional additives such as flow regulators, antioxidants, ultraviolet absorbers, light stabilizers or silane coupling agents can be added. Is.

In particular, as the solvents in this case,
Use of dipolar aprotic solvents with high water absorption is effective.

Further, the above-mentioned reactive diluent (D) is for wetting the fine-particle polymers described below to make them in a solvent-dispersed state, and further for having a specific functional group, By itself, it is possible to make the resin into a high solid state by reacting at the baking stage.

If only representative examples of such reactive diluents having a specific functional group, especially an acid anhydride group, are given, trimellitic acid, tetrahydrophthalic anhydride, methylhexahexyl Hydrophthalic anhydride, hettic anhydride, and hymic acid anhydride ["Himic acid" is a registered trademark of Hitachi Chemical Co., Ltd.]. ], Various acid anhydride group-containing low-molecular compounds such as maleic anhydride, itaconic anhydride, pyromellitic anhydride, and glycerol tris (trimellitate).

The number average molecular weight of the above-mentioned low molecular weight compound containing an acid anhydride group is appropriately 1,000 or less, preferably 700 or less. If it exceeds 1,000 and becomes too high, the dispersibility of the highly gelled fine particle polymers (microgel) is inevitably lowered, which is not preferable.

At this time, the amount of the reactive diluent (E), particularly the acid anhydride-containing reactive diluent, used is 0.1% or more and 50% by weight or less based on the solid content of the coating material. Preferably, 1% by weight or more and 10% by weight or less is suitable.

When the amount is less than 1%, the dispersion of the fine particle polymers is apt to occur, and when the amount exceeds 50%, the amount is too large.
Inevitably, unreacted acid anhydride groups are left behind, and the weather resistance and the like are likely to decrease. In either case, this is not preferable.

Furthermore, the above-mentioned fine particle polymers (E) are the above-mentioned acrylic oligomers (A), respectively.
And a compound (B), a catalyst (C) and a reactive diluent (D) are not miscible with the system and can be stably dispersed. The purpose thereof is to add to each of the mixture of (A), (B) and (C) constituting the coating material so as to impart so-called pseudoplastic viscosity behavior.

All of these above mixtures exhibit substantially Newtonian flow properties and either have no yield value due to low molecular weight, or have very low yield values, so that the substrate When performing painting work vertically,
Various coating film defects occur such that sagging easily occurs and cissing easily occurs with an increase in temperature during baking performed after such coating.

However, for these above mixtures,
When the fine particle polymers as shown below are added, the apparent viscosity during standing becomes large, but when high shear stress is applied such as during spraying, the viscosity is sufficiently high. Becomes smaller, and you can perform spraying work without any difficulty.

In addition, after a few seconds or a few minutes have passed after the coating on the substrate, the structural viscosity has already been developed and the coating defects such as cissing are not generated. The preventive effect such as will work sufficiently.

As a matter of course, the fine particle polymer (E) component to be present in the clear coat preferably has such a composition that the cured coating film after baking becomes completely transparent.

Typical examples of the fine particle polymers (E) are inorganic ones represented by powdered silica, low molecular weight polyolefin polymers, non-aqueous dispersion type polymers or aqueous emulsions. Or, there is an organic type such as highly gelled fine particle polymers having an intramolecular cross-linking structure obtained by an aqueous suspension polymerization method. Among them, in terms of effects, an aqueous emulsion or a suspension polymerization method is particularly preferable. Highly gelled fine particle polymers (microgel) in a form obtained by the method are preferable.

Such highly gelled fine particle polymers are substantially non-swellable in a solvent having a high polymer dissolving power such as toluene and ethyl acetate, and
When it is added to a resin solution or dispersion (binder resin) containing a solvent that is non-fusing and has a high dissolving power, it does not increase the viscosity of the resin (solution) dispersion and contains the resin. High rate,

That is, it is possible to obtain a high-solid dispersion liquid, and after drying, it is possible to form a solid resin composition together with the added resin solution or dispersion liquid. It can be defined as fine particle polymers having a crosslinking density of.

Examples of the method for preparing the highly gelled fine particle polymers are as follows. That is, 2 to 100% by weight of a polyfunctional monomer and a monomer having one unsaturated bond in one molecule, that is, 98 to 0% by weight of a monofunctional monomer are halved at a temperature lower than 100 ° C. There is a method of polymerizing in an aqueous emulsion or aqueous suspension state at a temperature of 20 ° C. or higher and lower than 100 ° C. using an organic and / or inorganic radical polymerization initiator having a period of 3 hours or less.

Here, if only representative examples of the polyfunctional monomer are given as examples, ethylene glycol di (meth) acrylate having a total carbon number of 10 to 10
28 oligoethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate,
Of various polyhydric alcohols such as neopentyl glycol di (meth) acrylate, trimethylolethane tri (meth) acrylate, trimethylolpropane tri (meth) acrylate, glycerin tri (meth) acrylate, pentaerythritol tetra (meth) acrylate Poly (meth) acrylates;

Various esters of allyl alcohol, such as diallyl succinate, sialyl phthalate, triallyl isocyanurate; or divinylbenzene, dicyclopentenyl (meth) acrylate, butadiene,
Examples include pentadiene, isoprene or chloroprene.

As the monofunctional monomer, various monomers that are used when preparing the above-mentioned acrylic oligomer (A) can be applied as they are.

On the other hand, as the low temperature decomposition type initiator, various inorganic compounds such as potassium persulfate, ammonium persulfate or hydrogen peroxide, or acetyl peroxide, propionyl peroxide, iso-butyryl peroxide, benzoyl peroxide are used. Oxide, ter
t-butyl peroxyoctoate, azobis-iso
-Butyronitrile or azobiscyanovaleric acid,
Each of the various organic compounds is particularly representative.

In the polymerization reaction, various known emulsifiers and dispersion stabilizers can be appropriately used.

Thus, the highly gelled fine particle polymer in the aqueous emulsion or the aqueous suspension obtained after the polymerization of various modes is subjected to the evaporation or azeotropy of water or the precipitation or aggregation of the polymer (particles). It can be separated in the form of a solid by physical or chemical means,

Alternatively, when such a physical or chemical means is applied, resins and / or organic solvents other than the various polymers used in the respective paints, which are used in carrying out the method of the present invention, are present. In this state, the medium of the objective highly gelled fine particle polymers may be directly replaced with water from the resin and / or the organic solvent.

The appropriate amount of the fine particle polymers as described above is 0.1 to 50 parts by weight based on the acrylic oligomer (A).

Subsequently, the high solid content resin composition of the present invention or the high solid content type coating composition in which the high solid content resin composition is used as a binder,
C-1B, 2C-1B, 2C-2B, 3C-2B or a coating method (including a resin composition in some cases) and a baking method in an overcoat system will be described below.

The resin composition of the present invention is
It is used in the state of being diluted with the minimum necessary solvent or in the state of no solvent.However, in any case of coating, the blocking agent is in the atomized state during this coating. Is to be dissociated, and when it is applied to the object to be coated, the hydroxyl groups are already regenerated and the viscosity is rapidly increased.

Therefore, as compared with the conventional type in which the viscosity is reduced only by using the solvent, sagging is less likely to occur.

That is, in the case of a coating material containing a large amount of solvents as in the prior art, the rapid increase in viscosity accompanying the volatilization of such solvents causes
You can prevent so-called primary sagging,

On the other hand, as in the case of the present invention, a high solid content resin composition having no solvent or low solvent content or a high solid content type coating composition using this high solid content resin composition as a binder is used. Immediately after coating, of the object to be coated (base material),

The risk of sagging on the vertically extending surface, that is, on the so-called vertical surface, and eventually causing the appearance of the coating film (poor appearance), is always at risk.

In that respect, in the coating method of the present invention, by adding fine particle polymers to the resin composition to impart a pseudoplastic viscosity behavior, it is possible to prevent primary sagging from occurring. It has true characteristics.

Therefore, in order to prevent so-called secondary sagging in the baking step, it is absolutely necessary to continuously maintain such characteristics of the coating method of the present invention.

1C-1B system of the present invention, 2C-1
B system, 2C-2B system or 3C-2
As a base coat for B-system, especially 2C-1B
The effect of the present invention can be further improved by using an aqueous paint as the base coat of the system or 3C-2B system.

The water-based paint used here is not particularly limited as long as it is water-soluble or water-dispersible, but it is desirable to use a system having a smaller organic solvent content.

[0132] To exemplify only typical water-based paints, water-soluble resin compositions are those containing a carboxyl group in the resin composition and are organic or inorganic. So-called water-soluble polyester resins or water-soluble vinyl-based copolymers in a form neutralized with a base;

Alternatively, so-called water-soluble vinyl copolymers in a water-solubilized form neutralized with various basic nitrogen compounds such as aminoalkyl esters of (meth) acrylic acid or N-aminoalkylamides. Such as polymers.

As the water-dispersible resin composition, an anionic surfactant, a cationic surfactant, a zwitterionic surfactant and / or a nonionic surfactant are used as emulsifiers, Water dispersibility obtained by dispersing vinyl monomers in an aqueous phase and polymerizing them with Iwayu R water-soluble polymerization initiators such as potassium persulfate, hydrogen peroxide or cumene hydroperoxide. Vinyl-based copolymers;

Alternatively, various surfactants such as those mentioned above are added to polyester resins, vinyl copolymers, epoxy resins or polyurethane resins obtained by using an organic solvent, and then, Water-dispersible polyester resins, water-dispersible vinyl-based copolymers, water-dispersible epoxy resins or water-dispersible polyurethane resins obtained by a so-called post-emulsification method of inversion of a solvent from an organic solvent to water. Kind;

Further, in the post-emulsification method, the resin composition is allowed to react with a surface-active component in advance to impart self-emulsification property to the post-emulsification to obtain various water dispersibility described above. The resin composition and the like are particularly representative examples, but needless to say, these are not the only examples.

The water-soluble or water-dispersible resin composition obtained as described above is used as it is, as a lacquer type, or as a crosslinking agent having reactivity with the functional group contained in each resin composition. You may use it in the form mixed.

As the cross-linking agents here, for example, when the resin composition contains a hydroxyl group, it is desirable to use a block polyisocyanate compound or an amino resin, and when it contains an epoxy group. , It is desirable to use carboxyl group-containing resins or polycarboxylic acids,

Alternatively, when it contains a carboxyl group, it is desirable to use resins having at least two epoxy groups in one molecule.

The conditions for coating are also such that the resin composition or the coating composition of the present invention is heated, and the acrylic oligomer (A), the compound (B) and the dissociation catalyst are contained in the resin composition of the present invention, respectively. And / or a curing catalyst (C),

Immediately before use, it can be blended and coated by various methods such as air atomization coating and airless coating. The degree to which the resin composition or paint here is heated is preferably 100 ° C. or lower.

The high solids resin composition or high solids type coating material of the present invention, and the coating method and baking method of the coating material of the present invention are respectively the so-called metal materials or metal products such as automobiles and building materials. It can be applied to other types.

[0143]

EXAMPLES Next, the present invention will be explained more specifically by reference examples, examples, application examples and comparative application examples. In the following, parts and% are as long as there is no notice. All are based on weight.

Reference Example 1 (Preparation example of acrylic oligomer having blocked hydroxyl group, acid anhydride group and epoxy group)

A 4-necked flask equipped with a stirrer, an inert gas inlet, a thermometer and a condenser was charged with 1,0 of xylene.
After charging 00 parts and heating up to 140 ° C., 150 parts of trimethylsiloxyethyl methacrylate, 150 parts of styrene, 70 parts of maleic anhydride, 50 parts of glycidyl methacrylate, 3 parts of n-butyl acrylate.
A mixture of 0 parts,

A mixture of 500 parts of xylene, 30 parts of azobisisobutyronitrile and 50 parts of tert-butylperoxy-2-ethylhexanoate was added dropwise over 7 hours.

Further, the reaction was carried out at the same temperature for 5 hours to obtain a resin solution having a nonvolatile content of 25%, and then xylene was distilled off under reduced pressure. 25 of this resin solution
The viscosity at 0 ° C. was 1,950 centipoise (cps), and the number average molecular weight of this resin was 980. Hereinafter, this resin solution is abbreviated as resin (A-1).

Reference Example 2 (Preparation example of acrylic oligomer having blocked hydroxyl group and acid anhydride group)

1,000 parts of methyl amyl ketone were used, together with 100 parts of styrene, 200 parts of trimethylsiloxybutyl acrylate, 65 parts of itaconic anhydride and 1 part of 2-ethylhexyl acrylate.
A resin solution was obtained in the same manner as in Reference Example 1 except that the monomer mixture consisting of 35 parts was used.

The resin solution obtained here has a nonvolatile content of 2
7.8%, and the viscosity of the resin obtained by distilling off the solvent is 2,
It was 200 cps and the molecular weight was 880. Hereinafter, this resin solution fat is abbreviated as resin (A-2).

Reference Example 3 (Preparation Example of Acrylic Oligomer Having Blocked Hydroxyl Group and Epoxy Group)

After charging 1,000 g of xylene into a 3 liter autoclave, the mixture was set so as not to leak, and the temperature was raised to 160 ° C.
Part, 300 parts of n-butyl methacrylate, 400 parts of trimethylsiloxyethyl methacrylate and 200 parts of glycidyl methacrylate, and 100 parts of di-tert-butyl peroxide are pressed in over 5 hours,

Further, after reacting for 4 hours, xylene was distilled off, and 2,300 cp without solvent.
An acrylic oligomer having a viscosity of s and a molecular weight of 1,100 was obtained. Hereinafter, this is a resin (A-
It is abbreviated as 3).

Reference Example 4 (Preparation Example of Compound Having Hydrolyzable Silyl Group and Epoxy Group) 700 parts of xylene was used, 100 parts of styrene, and n-
Using a monomer mixture consisting of 60 parts of butyl acrylate, 200 parts of γ-methacryloyloxypropylmethoxysilane and 140 parts of glycidyl methacrylate,

Furthermore, tert-butylperoxy-
Reaction was carried out in the same manner as in Reference Example 1 except that 75 parts of 2-ethylhexanoate was used, and the mixture was desolvated to have a viscosity of 40 poise (ps) and a number average molecular weight of The compound of 1,120 was obtained. Hereinafter, this compound is abbreviated as (B-1).

Reference Example 5 (Preparation Example of Compound Having Hydrolyzable Silyl Group and Acid Anhydride Group) Using the same apparatus as in Reference Example 1, 50 parts of n-butyl acetate was used.
Charge 0 parts and 500 parts of xylene, raise the temperature to 120 ° C., and then add 200 parts of xylene,

A mixture of 170 parts of maleic anhydride, 130 parts of 2-ethylhexyl acrylate and 200 parts of γ-methacryloyloxypropylmethoxysilane, 200 parts of n-butyl acetate and tert-butylperoxy-2. A mixture of 100 parts of ethylhexanoate and 10 parts of azobisisobutyronitrile was added dropwise over 7 hours,

Further, the reaction was carried out for 3 hours, and the solvent was removed under reduced pressure to give a nonvolatile content of 99% and a viscosity of 1,50.
A compound having a number average molecular weight of 1,500 at 0 cps was obtained. Hereinafter, this is abbreviated as compound (B-2).

Reference Example 6 (Preparation Example of Fine Particle Polymers) In a reactor equipped with a stirrer, a thermometer, a cooling pipe and a nitrogen introducing pipe, a mixture (a) was prepared according to the raw material charging composition shown in Table 1. ) In a reactor and heated to 75 ° C,
1/20 of the mixture (b) was added, and 30 minutes after that, 19/20 of the mixture (b) and 3/5 of the mixture (c) were added.
Dropwise over 3 hours.

After the completion of the dropping, 1/5 of the mixture (c) was added, and the mixture was maintained at 80 ° C. for 1 hour while stirring, and then the temperature was raised to 160 ° C. in a sealed state, and at the same temperature, 3 The number average particle size is about 50 nanometers (nm) by continuing the stirring for a period of time to terminate the crosslinking reaction.
A monodisperse crosslinked fine particle emulsion was obtained.

The emulsion was then cooled to 30 ° C and filtered through a 200 mesh oven cloth to 100 ° C.
It was dried with heating and stirring. Then, the agglomerates of the generated polymerized fine particles are pulverized with a supersonic jet mill manufactured by Nippon Pneumatic Mfg. Co., Ltd., and the particle size is 10 microns (μm) or more, and the particle distribution is 0.1% or less. A fine powder of fine particle polymers (E) having a weight average particle diameter of 3.9 μm was obtained. Hereinafter, this is abbreviated as fine particle polymers (E-1).

[0162]

[Table 1]

<< Footnote in Table 1 >>
It is the number of parts by weight.

"Emulgen 950" ... Polyoxyethylene nonyl phenyl ether manufactured by Kao Corporation

"Hitenol N-08" ... Polyoxyethylene dodecyl phenyl ether sulfate ammonium salt manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd.

[Lebenol WZ] ……………… Kao Corporation's sodium polyoxyethylene dodecyl phenyl ether sulfate

Examples 1 to 8 Using the respective resins obtained in Reference Examples 1 to 6,
Various high solid content resin compositions of the present invention were obtained according to the compounding composition ratios shown in Table 2 below.

[0168]

[Table 2]

<< Footnote in Table 1 >> γ-glycidoxypropyltrimethoxysilane was used as the compound (B-3).

Dissociation catalyst (C-1): Monoisopropyl ester of phosphoric acid Dissociation catalyst (C-2): Trifluoromethanesulfonic acid curing catalyst (C-3): Tetrabutylphosphonium bromide curing catalyst (C-4) ... 1-Methylimidazole

Reactive Diluent (D-1) ... Methylhexahydrophthalic Anhydride Reactive Diluent (D-2) ... Tetrahydrophthalic Anhydride Reactive Diluent (D-3) ... Methacrylic Anhydride

[0172]

[Table 3]

Comparative Examples 1 to 4 Each of the resins obtained in Reference Example 1 and Reference Examples 3 to 6 was used to prepare various control compositions according to the compounding composition ratios shown in Table 2 below. A resin composition was obtained.

[0174]

[Table 4]

Application Examples 1 to 8 and Comparative Application Examples 1 to 4 The various resin compositions obtained in the respective Examples and Comparative Examples were treated with xylene /
The viscosity was adjusted with a mixed solvent of n-butyl acetate = 60/40 (part by weight ratio), and the coating non-volatile content of each composition was measured. The results are collectively shown in Table 3 below.

[0176]

[Table 5]

[0177]

[Table 6]

[0178]

[Table 7]

A coating was applied to a stationary vertical surface using the above diluted composition. Then, after 10 minutes of natural drying, similarly, baking was performed in a dryer in a vertical state under the condition of 140 ° C. for 20 minutes.

[0180] At this time, the occurrence of cracks in the coating film and the condition of sagging were comprehensively observed and evaluated, and the results are summarized in Tables 6 and 7 below. Show.
With respect to the coating film that was cured and baked, a comparative study of various properties was further conducted. The results are summarized and shown in Table 3 below.

By the way, as a coating method at this time, a metallic base paint is applied to a coated plate after a predetermined treatment, and then a top clear coating of the present resin composition is applied on a wet-on-wet basis. A two-coat, one-bake system was adopted in which a coating film was applied and then baked at a predetermined temperature for a predetermined time to obtain a cured coating film.

The coated plate used in this case was an electrodeposition coated plate,
"Beckolite CF-542" [hydroxyl group-containing polyester resin manufactured by Dainippon Ink and Chemicals, Inc.], "Super Beckamine L-117-60" and a so-called intermediate coating consisting of carbon black are applied and baked. It was prepared by performing.

The base paint is "Acridic
47-712 "[hydroxyl group-containing acrylic resin manufactured by Dainippon Ink and Chemicals, Inc.]," Super Beckamine L-1 "
17-60 "and" Aluminum paste 7160NS "
It is a metallic base paint containing [Aluminum paste manufactured by Toyo Aluminum Co., Ltd.].

[0184]

[Table 8]

<< Footnote in Table 3 >> Limiting film thickness of armpits ... Limiting film thickness without causing armpits when coated on a stationary vertical surface

Sagging limit film thickness: The limit film thickness without sagging when coated on a stationary vertical surface

Appearance: An index showing the sharpness or smoothness of the coating film evaluated by the image brightness measuring instrument manufactured by Suga Test Instruments Co., Ltd. The larger this value is, the better the sharpness is. It means that the property or smoothness is good.

Storage stability ... Viscosity immediately after preparation of the resin composition (or paint) (that is, initial viscosity), and 50
It is based on the viscosity after being held at 0 ° C for 2 days, and the values in the table are for Ford
It represents the "seconds" of cup # 4.

Mitsuzawa ………… Displayed as 60 degree specular reflectance (%)

Impact resistance: ............ Performed with 1/2 inch notch and displayed at 500 g / cm

Xylene rubbing test: After rubbing 10 times (that is, the surface condition of the coating film was visually judged at the time when the rubbing number was 10 times).

Acid resistance: 5% at 60 ° C
After dropping 0.5 ml of sulfuric acid aqueous solution,
Visually judge the coating surface condition

Alkali resistance: Visual judgment of the coated surface state after immersion in a 5% aqueous solution of sodium hydroxide for 24 hours at room temperature

Weather resistance: Displayed by the gloss retention rate (%) after accelerated weather resistance test for 2,000 hours using a QUV panel.

[0195]

[Table 9]

[0196]

[Table 10]

As described in detail above, in the present invention, the thermosetting resin composition has, as an active ingredient, a blocked hydroxyl group as an essential functional group, and further has an epoxy group and / or an acid anhydride. Acrylic oligomer having a group as a functional group, a hydrolyzable silyl group as an essential functional group, and one or more functional groups selected from the group consisting of an epoxy group, a blocked hydroxyl group and an acid anhydride group. And a dissociation catalyst or a curing catalyst (curing accelerator).

The high solid content resin composition of the present invention having such a constitution, and the high solid content type coating composition using this high solid content resin composition as a binder are extremely soluble in an organic solvent. In addition, since a hydroxyl group is generated at the time of coating, a drastic increase in viscosity is unlikely to cause sagging during coating or baking, and when such sagging occurs. Also, in the above, there is a number of advantages that such an armpit that occurs in the sagging portion is extremely unlikely to occur.

In addition, the coating and baking method of the coating composition of the present invention uses a high solid content resin composition having such a constitution, or a high solid content type coating composition using this high solid content resin composition as a binder. It can be said that it is extremely effective in improving the smoothness of the coating film by adding the reactive diluent and the fine-particle polymers during the coating and baking.

Further, the baked coating film obtained according to the present invention is useful as a top coat for automobiles, and is particularly excellent in acid resistance, solvent resistance, weather resistance and scratch resistance. is there.

[0201]

As described in detail above, the high solid content resin composition of the present invention and the high solid content coating composition of the present invention are extremely excellent in solubility in organic solvents. In addition, since a hydroxyl group is generated at the time of coating, a drastic increase in viscosity is unlikely to cause sagging during coating or baking, and therefore, if such sagging occurs Also, in the case of "," an armpit or the like that occurs in the sagging portion is also extremely unlikely to occur.

Further, the baked coating films obtained by using the high solid content resin composition and the high solid content type coating material of the present invention are, in particular, acid resistance and resistance which are useful as top coats for automobiles. It is extremely practical in terms of solvent resistance, weather resistance and scratch resistance.

─────────────────────────────────────────────────── ─── Continuation of front page (51) Int.Cl. ⁷ identification code FI C09D 201/02 C09D 201/02 (58) Fields investigated (Int.Cl. ⁷ , DB name) C08L 1/00-101/16 C09D 4/00-201/10 B05D 1/36 B05D 7/14-7/24

Claims (10)

(57) [Claims] 1. Having a blocked hydroxyl group in one molecule as an essential functional group, and further having at least one functional group selected from the group consisting of an acid anhydride group and an epoxy group, and A group consisting of an acrylic oligomer (A) having a number average molecular weight of 1,500 or less, a hydrolyzable silyl group as an essential functional group in one molecule, and an epoxy group, a blocked hydroxyl group and an acid anhydride group. A compound (B) which also has one or more functional groups selected from the group and has a number average molecular weight of 1,500 or less, a dissociation catalyst and / or a curing catalyst (C), and a reactive diluent ( A high-solids resin composition comprising D) and a fine particle polymer (E) as essential film-forming components. 2. One coat and one bake, two coat and one bake,
A method for applying a paint in a two-coat, two-bake, three-coat, two-bake or overcoat system, which comprises applying a colored film-forming composition onto a substrate to form a base coat, and then forming a base film on the base coat as a clear film. , Having a blocked hydroxyl group in one molecule as an essential functional group, and further having one or more functional groups selected from the group consisting of an acid anhydride group and an epoxy group, and having a number average molecular weight of An acrylic oligomer (A) having 1,500 or less and a hydrolyzable silyl group as an essential functional group in one molecule, and further selected from the group consisting of an epoxy group, a blocked hydroxyl group and an acid anhydride group, It also has one or more functional groups and has a number average molecular weight of 1,50.
A high solid content containing a compound (B) of 0 or less, a dissociation catalyst and / or a curing catalyst (C), a reactive diluent (D), and fine particle polymers (E) as essential film-forming components. A method for coating and finishing a high solids-type paint, which comprises using a resin composition as a binder. 3. The above-mentioned one having a blocked hydroxyl group in one molecule as an essential functional group, and further having at least one functional group selected from the group consisting of an acid anhydride group and an epoxy group. And the acrylic oligomer (A) having a number average molecular weight of 1,500 or less is represented by the following general formula (I) to
The high solid content resin composition according to claim 1, which has any one structure represented by (III). [Chemical 1] (Wherein, R ₁ and R ₂ in the formula respectively 18 becomes an alkyl group carbon atoms, a phenyl group or an aryl group or a hydrogen atom, and represents a chlorine atom or a fluorine atom. However, R ₁ And R ₂ may be the same or different, and R ₃ has 1 to 1 carbon atoms.
8 represents an alkyl group, a phenyl group or an aryl group. ) [Chemical 2] (However, R ₄ in the formula is a hydrogen atom or a carbon atom of 1 to
It represents an alkyl group of 10. R ₅ is substituted with at least one atomic group selected from the group consisting of a cycloalkyl group, an aralkyl group, an aryl group, an alkoxyl group, an alkanoyloxy group, an alkyl group having 1 to 18 carbon atoms and a halogen atom. Also, carbon number is 1
Represents an alkyl group represented by .about.22. ) [Chemical 3] (However, X in the formula is at least one atom selected from the group consisting of an alkoxyl group, an aralkyl group, an aryl group, an aryloxy group, an alkanoyloxy group, an alkyl group having 1 to 10 carbon atoms and a halogen atom. Represents an alkyl group having 1 to 18 carbon atoms, which may or may not be substituted with a group.) 4. The above-mentioned one having a blocked hydroxyl group in one molecule as an essential functional group, and further having at least one functional group selected from the group consisting of an acid anhydride group and an epoxy group. And the acrylic oligomer (A) having a number average molecular weight of 1,500 or less is represented by the following general formulas (I) to (I
The coating finishing method according to claim 2, which has any one structure shown by II). [Chemical 4] (Wherein, R ₁ and R ₂ in the formula respectively 18 becomes an alkyl group carbon atoms, a phenyl group or an aryl group or a hydrogen atom, and represents a chlorine atom or a fluorine atom. However, R ₁ And R ₂ may be the same or different, and R ₃ has 1 to 1 carbon atoms.
8 represents an alkyl group, a phenyl group or an aryl group. ) [Chemical 5] (However, R ₄ in the formula is a hydrogen atom or a carbon atom of 1 to
It represents an alkyl group of 10. R ₅ is substituted with at least one atomic group selected from the group consisting of a cycloalkyl group, an aralkyl group, an aryl group, an alkoxyl group, an alkanoyloxy group, an alkyl group having 1 to 18 carbon atoms and a halogen atom. Also, carbon number is 1
Represents an alkyl group represented by .about.22. ) [Chemical 6] (However, X in the formula is at least one atom selected from the group consisting of an alkoxyl group, an aralkyl group, an aryl group, an aryloxy group, an alkanoyloxy group, an alkyl group having 1 to 10 carbon atoms and a halogen atom. Represents an alkyl group having 1 to 18 carbon atoms, which may or may not be substituted with a group.) 5. The high solids resin composition according to claim 1, wherein the reactive diluent (D) is a compound having an acid anhydride group. 6. The coating finishing method according to claim 2, wherein the reactive diluent (D) is a compound having an acid anhydride group. 7. The high solid content resin composition according to claim 1, wherein the fine particle polymers (E) have an intramolecular crosslinked structure. 8. The coating finishing method according to claim 2, wherein the fine particle polymers (E) have an intramolecular crosslinked structure. 9. The coating finishing method according to claim 2, wherein an aqueous paint is used as the base coat in the above-mentioned 2 coat 1 bake system or 3 coat 2 bake system. 10. The two-coat one-bake system or the three-coat two-bake system described above, wherein the high solid content resin composition is applied to an object to be coated while being heated to 100 ° C. or lower. The coating finishing method according to claim 2, wherein