JPS60229961A - Coating composition having high solid content - Google Patents

Abstract

PURPOSE:To obtain the titled composition having improved paintability, by compounding an OH-containing polymer with a specific hardening resin, fine powder of a polymer, and a solvent at specific ratios. CONSTITUTION:The objective composition contains (A) 90-30pts.(wt.) of an OH- containing polymer composed of preferably a mixture of (i) a vinyl resin having an average molecular weight (Mn) of 500-8,000 and a hydroxyl value of 40- 250, (ii) an alkyd resin, an oil-free alkyd resin and/or an urethane resin having an Mn of 200-3,000 and a hydroxyl value of 40-600 and (iii) a mixture of the component (i) and the component (ii), (B) 10-70pts. of an amino plast of the aminoaldehyde resin etherified preferably with a 1-4C alcohol or blocked or unblocked polyisocyanate, (C) 0.1-100pts. (based on 100pts. of the components A+B) of a non-aqueous dispersion of fine polymer powder preferably having a segment soluble in an aliphatic or alicyclic hydrocarbon solvent and a segment insoluble in said solvent, at the same time, and (D) a proper amount of a solvent.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a novel and useful high solids coverage composition, and more particularly, to a composition comprising a hydroxyl group-containing polymer, a specific curing resin, and a particulate car body. and the essential base resin components,
In other words, it is referred to as a coating film forming component. In particular, it relates to a coating composition with improved coating workability.

One of the recent trends in the growth of the coating industry is the trend toward low-pollution coating threads.

The move toward this type of low-pollution coating system is to completely reduce the amount of common agents that volatilize and diffuse during loading and become the cause of environmental pollution. Progress is being made in the development of high-solids separable paint compositions and in the use of water-based paints to replace solvent-based paint threads.

However, such methods still have many drawbacks; for example, in the case of high solids fraction coating compositions, the bath agent K in the system is significantly lower than in conventional coatings, which causes Since the content of the applied film-forming component (film-forming component) is extremely high, the smoothness (leveling) of the film surface, which in conventional paints was controlled by the evaporation rate of diluted thinner, is now possible. In addition, maintenance may deteriorate.

Particularly in the case of baking-type paint systems, there is a drawback that the film-forming component applied to the substrate during baking causes a decrease in viscosity and tends to cause "sagging".

To explain these drawbacks in detail, methods for obtaining high solidity separation coating compositions include using low molecular weight polymers for film-forming polymers, or employing non-aqueous dispersion polymerization. However, in the case of the former method, the lower molecular weight of the film-forming polymers leads to even more sagging during baking, which is also accompanied by ``easiness to sag''. In particular, when vinyl polymers are used, there is a drawback that functional groups that can react with the curing agent cannot be efficiently introduced. On the other hand, when condensation polymers are used, functional groups that can react with Although it is easy to introduce it, it has disadvantages such as poor weather resistance compared to vinyl polymers.

In the case of the latter method, which involves the use of non-aqueous dispersible polymers, these polymers have the form of particles.
Since the polymer particles are dispersed in a solvent, it is necessary to achieve a high degree of solidification by exceeding the closest packing of these particles. K if there is a lack of storage stability or if the coating is cured.

This can lead to poor coating performance such as acid resistance and gasoline resistance.

Furthermore, when using water-based paints, the dispersion medium is water, which has low volatility, so spraying operations are difficult.
Or, when the water is applied to the base material, the water evaporates.
, it has the disadvantage of being highly dependent on the humidity of the atmosphere,
Moreover, when forming a multilayer film, it has the disadvantage that it may cause coating film defects such as "wax".

For the reasons mentioned above, there are still many problems with low-pollution paints that need to be solved, and the current situation is that they have not yet reached the stage of being widely put into practical use.

However, in view of the various shortcomings in the prior art as described above, the present inventors have attempted to improve the various shortcomings, especially in high solids content m coating compositions containing low-molecular needle-shaped polymers as a main component. As a result of intensive research, we discovered that hydroxyl group-containing polymers.

The combination of curing resins and fine particle polymers is effective in preventing "repelling" and "sag" when painting on substrates, and in addition, it is a coating with excellent curing properties and weather resistance. The present invention was completed based on the discovery that the membrane provides the following properties: water, an m group-containing polymer (90 to 30 parts of Al), aminoblast, or Blocked or unblocked polyisocyanates) (total amount of 100 To with 10 to 70 parts of Bl).

Each contains 0.1 to 100 parts by weight of a fine particle polymer (C1) and additional solvents (DI).Provides a high solids coating composition with improved diagnostic workability and various coatings. Here, first, what is the above-mentioned hydroxyl group-containing polymer (Al)?

(condensation) polymers having at least one, preferably at least two hydroxyl groups per molecule, and which are used to differentiate high solids coating compositions, which are the object compositions of the present invention. refers to those within the necessary and sufficient molecular weight range.

Therefore, any resin that meets these conditions can be applied, but it is preferable to use specific resins that meet the following conditions. Vinyl thread resins having a hydroxyl value (oi-tv) of 40 to 250.

■ KrDFm with Mn of 200 to 5.0 [JO, alkyd lateral force a with ohv of 40 to 600, at least one type selected from the group consisting of oil-free alkyd resins and urethane resins! fats, and ■
To prepare a mixture of the above-mentioned resins 0) and resins ①, among these, resin ②, hydroxyl group-containing monomers and other monomers having co-N attachment properties are mixed in a conventional manner. Typical hydroxyl group-containing monomers that can be copolymerized include 2-hydroxyethyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate% 3-hydroxoglobyl ( meth)acrylate, 2-hydroxybutyl(meth)acrylate, 3-hydroxybutyl(meth)acrylate%4-hydroxybutyl(meth)acrylate, 3-chloro-2
-Hydroxyalkyl esters of (meth)acrylic acid such as hydroxypropyl (meth)acrylate and polyethylene glycol mono(,meth)acrylate; monomers containing acid anhydride groups such as maleic anhydride and itaconic anhydride and glycols such as ethylene glycol unsaturated bond-containing hydroquinoalkyl ester monocarboxylic esters, such as adducts with unsaturated bond-containing hydroquinoalkyl esters; Esters: Examples include hydroxydialkyl vinyl ethers such as hydroxyethyl vinyl ether.

! On the other hand, other typical copolymerizable heptamers include methyl (meth)acrylate, ethyl (meth)acrylate, butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, and cyclohexyl (meth)acrylate.
Meth)acrylate, benzyl (meth)acrylate @ (meth)acrylic furnace esters; dimethyl maleate, diethyl fumarate, dibutyl itaconate @1
Diesters of unsaturated dicarbons WI and monohydric alcohols: vinyl acetate, vinyl esters such as "Beova" (product of Shell, Netherlands); [Visco] 8F, 8FM.

3F or 3FMJ (fluorine-containing product manufactured by Osaka Organic Chemical Co., Ltd.)
(meth)acrylic monomers) or perfluorocyclohexyl (meth)acrylate, Jeeperfluorozochlorohexyl (meth)acrylate or N-1so-
Propyl perfluorooctane sulfonamidoethyl (
Perfluoroalkyl group-containing vinyl esters such as meth)acrylates: Vinyl halides such as vinyl chloride, vinylidene chloride, vinylbutylene fluoride, and vinylidene fluoride.
α-olefins such as ethylene and propylene; styrene.

α-methylstyrene, p-tart7'thylstyrene,
Aromatic vinyl monomer furnace such as 0-methylstyrene, p-methylstyrene; (meth)acrylic #, crotonic acid,
Maleic e1 Fumar P1 Carboxyl group-containing monomers such as itaconic acid and citraconic acid ψ (unsaturated mono- or dicarboxylic acid); Fermentation anhydride group-containing monomers such as maleic anhydride and itaconic anhydride; (meth)acrylamide , N, N-dimethyl (meth)acrylamide, N
- Alcoquine methylated (meth)acrylamide, diacetone (meth)acrylamide, N-methylol (meth)
Carboxylic acid amide group-containing monomer AI' such as acrylamide; p-styrenesulfonamide, N-methyl-p
-Styrenesulfonamide%N,N-dimethyl-sulfonic acid amide group-containing monomers such as p-styrenesulfonamide; such as N,N-dimethylamine ethyl (meth)acrylate@N,N-dialkylaminoalkyl (
Meth)acrylates: adducts of the above @anhydride group-containing monomers and compounds having both an active hydrogen group and a tertiary amine group that can react with iME water groups, such as N,N-dimethylamino norobylamine. Tertiary amino group-containing monomers; monomers having an ano group such as (meth)acrylonitrile; hydroxyalkyl esters of α,β-ethylenically unsaturated carboxylic acids such as the hydroxyalkyl esters of (meth)acrylic acid mentioned above; Monomers having a phosphate ester bond, which are condensation products of phosphoric acid or phosphoric acid esters: Monomers containing sulfonic acid groups, such as monomers or 2-acrylamido-2-methyl-propanesulfonic acid, or similar amines etc.

Among the above monomers, the amount of hydroxyl group-containing monomers used varies depending on the molecular weight of the vinyl resin obtained, but it is desirable that they account for approximately 10 to 50% of the total monomers. , so the remaining 90-50
1% can be freely selected from among the above-mentioned copolymerizable monomers, taking into consideration other desired factors such as the physical properties of the finally obtained cured coating film and pigment dispersibility. good.

1, among other copolymerizable monomers such as those listed above.

Carphocyle group-containing monomers that also serve as latent catalysts for the crosslinking reaction between the vinyl resin and the aminoplast or (block) polyisocyanate as the curing resin.

Because of the existence of acidic group-containing monomers, such as sulfonic acid group-containing monomers, it is desirable to use these specific monomers.

In order to prepare such a hydroxyl group-containing vinyl resin, known and commonly used methods such as a broth polymerization method, a liquid pressure polymerization method, a bulk polymerization method, an emulsion polymerization method, and a suspension polymerization method can be applied. However, solution radical polymerization is the simplest method.

Typical bath additives used for this purpose are:
Toluene, xylene, cyclohexane, n-hexane,
Hydrocarbon threads such as octane; methanol, ethanol,
is.

-Alcohols such as glopanol, n-butanol, 1so-butanol, 5cc-butanol, ethylene glycol monomethyl ether; esters such as methyl acetate, ethyl acetate, 1vn-butyl acid, amyl acetate; acetone, methyl ethyl ketone, methyl-1so- Examples include ketone types such as butyl ketone, methyl amyl ketone, and cyclohexanone; and amide types such as dimethylforamide and dimethyl acetamide. Of course, any mixtures thereof may also be used.

Polymerization may be carried out by a conventional method using the solvent and a radical polymerization initiator such as an azo or peroxide type, and if necessary, a molecular flame regulator. Lauryl mercaptan, octyl mercaptan.

2-Mercaptoethanol or α-methylstyrene
Chain transfer agents such as dimers can also be used. In particular, when using a hydroxyl group-containing chain transfer agent such as 2-mercaptoethanol, it is possible to efficiently introduce hydroxyl groups into the following fractions of the average molecule of the resulting resin, but the weather resistance Since it has the disadvantage of being inferior in quality, it should be used for limited purposes.

In addition, as a method for producing such hydroxyl group-containing vinyl resin,
In addition to the above-mentioned liquid radical polymerization method, there is also an ionic polymerization method, and the resin obtained by this ionic polymerization method is also a primary polymerization method.
It can be used without any problem in the present invention.

In this ionic polymerization method, MO is performed using an ionic polymerization initiator whose functional groups have been blocked in advance, and then the blocking agent at the end of the resulting resin is released, resulting in an extremely narrow molecular weight distribution. Furthermore, it is possible to obtain a resin having at least one functional group in the molecule. The glass transition point of the obtained hydroxyl group-functionalized vinyl thread resin is suitably within the range of -20 to +50°C.

Next, the above-mentioned alkyd resin, oil-free alkyd resin and/or urethane resin (2) are all distinctive in that the raw material components and onv are limited, and 6D,
As the so-called synthesis conditions such as esterification method, well-known and commonly used means can be applied up to the first stage.

Here, urethane resin refers to resins having one or more urethane bonds in the molecule, such as isocyanate-modified acrylic resins, incyanate-modified alkyd resins, and incyanate-modified polyester resins, or synthetically It is preferable to use incyanate-modified alkyd resins and/or straddle polyester resins from the viewpoints of simplicity and relatively low risk of gelation.1. It is preferable to elongate the molecular chain by reacting the polyester oligomer with an organic diisocyanate compound in the alkyd oligomer having one or more hydroxyl groups therein.

As a representative example of usable organic diisocyanate compounds! Aliphatic diisocyanates such as hexamethylene diicanate and trimethylhexamethylene diisocyanate; alicyclic diisocyanates such as xylylene diisocyanate and isophorone diisocyanate;
or tolylene diincyanate), and aromatic diincyanates such as 4,4'-diphenylmethanediyne heptaanate.

Of course, these may be used in combination, but from the viewpoint of the weather resistance of the coating film, it is preferable to use aliphatic diisocyanate.

1. Typical polybasic acid components used in synthesizing the polyester component of the resin (1) are terephthalic acid, isophthalic acid, orthophthalic acid, 2.6-naphthalene dicarboxylic acid, and 4.4' - diphenyldicarboxylic acid, tetrahydrophthalic acid, methyltetrahydrophthalic acid, hexahydrophthalic acid, methylhexahydrophthalic acid, endomethylenetetrahydrophthalic acid, methylendomethylenetetrahydrophthalic acid, maleic acid, fumaric acid, itaconic acid, succinic acid, Glutaric acid, adipic acid, azelaic acid, pimelic acid, superric acid, sebacic acid or dimeric fatty acids (dimer acids), or trimellitic acid, trimesic acid, pyromellitic acid or cyclopenkune tetracarboxylic acid.

Examples include reactive derivatives thereof such as alkyl esters or anhydrides, but preferred are hexahydrophthalic acid, methyl hexahydrophthal #, hexahydroterephthal #'E, or various thereof. 1 of reactive derivatives
50 mol% of the total polybasic acid components
If used in the above manner, the composition of the present invention will have less occurrence of "1 repellency" on the cured film, and will have excellent curability and weather resistance of the coating film, as well as solubility and low viscosity. will be obtained.

In this way, the polybasic acid components mentioned above should be appropriately selected in consideration of the physical properties of the coating film, economic efficiency, and the like.

On the other hand, typical alcohol components used in synthesizing the polyester component of the oil class (2) are as follows.

Ethylene glycol, propylene glycol, trimethylene glycol & 1.4-butanediol, 1.3-
Butanediol, 1,5-bentanediol, 1,6-
Alkylene glycols such as hexanediol and neopentyl glycol: 1,4-cyclohexanedimethanol, bis-hydroxyethyl terephthalate, water &j
Aromatic or alicyclic glycogen compounds such as alkylene oxide of bisphenol A% or hydrogenated bisphenol A can be used, and monoepoxy 7 compounds can also be used in combination as the alcohol component, glycerin, trimethylolethane, trimethylolpropane, etc. , pentaerythritol, dipentaerythritol, mannitol, ゛ or each glycol component listed above and ε-
Polyester compounds such as caprolactone can also be used, or neopentyl glycol is added to the total alcohol component from the viewpoint of less "repellency" in the cured coating film and the weather resistance of the coating film. If used in an amount of 60 mol% or more, good results can be obtained.

Therefore, each of the above-mentioned alcohol components should be appropriately selected depending on the stability performance of the finally obtained cured coating film.

Typical fatty acids used to obtain alkyd resins include octylic acid, palmitic acid,
Stearic acid, persatic acid, olein r! 1. Including linoleic acid, Riluin P, coconut oil fatty acid, hydrogenated coconut oil fatty acid, tall oil fat #, castor oil fatty acid, dehydrated castor oil fatty acid, rice bran oil fatty acid, melon oil fatty acid, soybean oil Examples include long-chain saturated or unsaturated basic acids of 08 or higher, such as fatty acids and safflower oil fatty acids. should be selected accordingly.

In this way, the polyester components used to prepare the alkyd resins, oil-free alkyd resins and/or urethane resins are obtained. and 40~ for the total of all alcohol components
It is also possible to use a polyester component obtained by adding ε-caprolactone in an amount of 90 mol %, and in this case, the occurrence of "1" in the cured coating film is reduced.

Moreover, the cured coating film of the composition of the present invention has excellent flexibility.

In this way, the above-mentioned hydroxyl group-containing resins (Ai) used in the present invention are obtained, but the alkyd resin, oil-free alkyd resin and/or urethane resin can also be used as 1tJi or a mixture of two or more,
It goes without saying that the composition of the present invention can also be used as a mixture of the above-mentioned vinyl fibre, alkyd #J, oil-free alkyd resin and/or urethane resin. When trying to obtain the composition of the present invention, a large amount of vinyl resin is used, and when trying to obtain the composition of the present invention with good stopability, alkyd resin, oil-free alkyd alJJ1 and/or urethane resin are used. By increasing the amount of K used, the coating film performance can be adjusted as desired.

Next, the above-mentioned aminoplast or (block) polyincyanate (Bl is 1) and the curing agent (B1) of the composition of the present invention.
Among them, aminoplasts include compounds with amino groups such as melamine, urea, acetoguanamine, benzoguanamine, steroguanamine, or spiroguanamine, formaldehyde, paraformaldehyde, acetaldehyde, and others. Typical examples include condensation products obtained by reacting aldehyde compounds such as glyoxal with known and commonly used methods, and modified products obtained by etherifying each of these condensation products with m alcohols. However, any known and commonly used paints can be applied.

Preferably, those partially or completely etherified with C1 to C4 monohydric alkyl alcohols are suitable, specifically methyl etherified melamine, n-
Examples include butyl etherified melamine and 1so-butyl etherified melamine, but among these, butyl etherified melamine is preferable from the viewpoint of high solid differentiation.

Next, as the blocked polyisocyanate, a polyisocyanate obtained by blocking a so-called non-yellowing polyisocyanate using a known and commonly used blocking agent is used. , [Takene] BaI2-NJ (Takeda Pharmaceutical ■product)% or [Azoitol (ADD I T
OL) VXL/-80J [Hoechst synthetic product] is a typical example.

Typical polyinsyanates include:

Various organic diisocyanate compounds as listed above,
Addition-1 with polyhydric alcohols, low molecular weight polyesters, or water, etc., or polymers of the organic silicanates, and even inquanate biuret bodies.51 Particularly representative examples of these include "Burnock D -750,800ON-950,970 or 15-455J (same company product), [Desmodur N, L,) 1L A or ILJ (West German Bayer product), "Takene" D-102,202,11ON or 123N
J (same company product), [Coronate L, BL, E!
H or 203J (Nippon Polyurethane Kogyo ■ product) or [Duranate 24-90CXJ (Asahi Kasei Kogyo ■ product)].

And, the aminoplast or (block) polyisocyanate (Bl and the hydroxyl group-containing N group @ are
(A) For the 90 to 30 weight portion of the component (1 of the Bl component)
It may be used in a proportion of 0 to 70 parts by weight.

Further, the above-mentioned fine particle polymers (Cl) are added in order to completely impart pseudoplastic viscosity behavior to the mixture of the At component and the Bl component detailed above.

Such (Al) (the mixture of B11 components exhibits the property of substantially Newtonian flow to Teutonian flow) and has no yield value or has a small yield value, so for example, it is difficult to move the base material vertically. In cases where gambling work is carried out at high temperatures, or when the temperature rises during baking, 'talley' is likely to occur. Since these compounds have relatively low molecular weights, they have the disadvantage that they tend to cause "cracking" during loading and baking.

However, as in the present invention, IAIh(B
By adding and blending the fine particle polymers (C) into the mixture of 11 components, static! Although the apparent viscosity increases when a high shear force is applied to such a system, the viscosity becomes sufficiently low during spraying, and as a result, spraying becomes easier, and fC8: As a result of the structural viscosity developed within a short period of time, from a few seconds to a few minutes after the coating is applied to the material, coating film defects such as sagging and sagging do not occur.

By the way, the fine particle polymer @C1 is the above-mentioned (A
A mixture of the t component and the (Bl component) has the shape of a particle.
In this case, the term "can be stably dispersed in the form of particles" refers to the difference in polarity or affinity between the polymer and the medium in which the polymer is present. Even if the shape of the particles is maintained due to the difference in V.

Rarely when the polymer and the medium are easily VC# compatible, i.e. have a strong affinity between the two, it is possible to form a more obvious chemical bond in such a medium that can lead to the formation of particulate particles. It may also be a shadow.

Specific examples of the fine particle polymers (q include inorganic ones represented by fine powder silica, and organic ones represented by low molecular weight polyolefin polymers or non-aqueous dispersible polymers). Among these, particularly preferred are non-aqueous dispersible polymers.

Such non-aqueous dispersible polymers and ilt, as is known in the art, contain segments that can be disintegrated in bath agents such as aliphatic or alicyclic hydrocarbons, and on the other hand, segments that can be dissolved in these bath agents. With unpopular or bloated segments? In the presence of a dispersion stabilizer, monomers (hereinafter abbreviated as core monomers) that are soluble in the acid agent, but are insoluble in 7If and coalescence, are always added. A polymeric metal having a particle shape that can be stably dispersed in the bath agent, which is obtained by chemically or physically bonding to a dispersion stabilizer as described above by polymerization by a method. They are synonymous.

A specific method for preparing such non-aqueous dispersible polymers is as follows.

That is, first, the solvent to be used is non-polar and has a relatively small dissolving power, and although it does not dissolve the polymer produced from the core monomers (hereinafter abbreviated as core polymer), it stabilizes the dispersion. Any acid can be used as long as it can completely dissolve or swell the acid, but typical examples include aliphatic hydrocarbons such as hexane, hegetane, and octane; petroleum benzene, and ligroin. , mineral spirits, petroleum naphtha, and hydrocarbon mixtures with boiling points in the range of 30 to 300τ, such as mineral spirits, petroleum naphtha, and chlorine;
Alicyclic hydrocarbons such as cyclohexane, methylcyclohexane, ethylfucrosan, or mixtures thereof can be mentioned.

In some cases, in addition to these aliphatic hydrocarbons, hydrocarbon mixtures, and/or alicyclic hydrocarbons, up to about 70% of the total acidic agents may contain aromatic hydrocarbons, ester threads, Alcohol-based, ketone-based, or ether-based compounds including polar compounds may also be used.

The amount of the solvent used is such that the solid content of the resulting non-aqueous dispersible polymer is 30 to 70*ir%, preferably 40 to 6
It is appropriate to set the value within a range where the weighted view% is 0.

Next, typical examples of the dispersion stabilizer include: (1) unsaturated bond-containing polymers such as polybutadiene and polyinclune; (1) one or more of the following monomers: A graft copolymer obtained by polymerization, or the above-mentioned non-1. In addition to the graft copolymerization obtained by combining the nuclear monomers and (meth)acrylic ff [as described later in the 1-coalescence class, the carboxyl in this latter graft copolymer is An unsaturated bond-functionalized graft copolymer obtained by total addition reaction of an unsaturated bond-containing epoxy compound such as glycidyl (meth)acrylate to
An alkyl etherified melamine antilipid condensate etherified with an alkyl alcohol of Φ12 and soluble in each of the above-mentioned glazing agents; Φ12 ~ self-condensation of hydroxyl group-containing saturated fatty acids such as hydroxstearic acid A terminal unsaturated bond-containing graft copolymer obtained by adding the above-mentioned unsaturated bond-combining epoxy compound to the carboxyl group at the terminal position of a polyester is then polymerized with the following core monomers. kraft copolymer,
Alternatively, the terminal unsaturated bond-containing polyester is copolymerized with (meth)acrylic acid and the core monomer listed below, and then the carboxyl group is subjected to a gold addition reaction with the unsaturated bond-containing epoxy compound. unsaturated bond-containing graft copolymer; or @n-butyl (meth)acrylate), is.

~Butyl (meth)acrylate, 2-ethylhexyl (
meth)acrylate, lauryl(meth)acrylate,
(Co)polymers obtained by copolymerizing (meth)acrylic acid esters of alkyl alcohols of 04 or higher, such as stearyl (meth)acrylate, with other vinyl monomers as necessary; The main component is (meth)acrylic acid ester of C4 or higher alkyl alcohol.

The above-mentioned unsaturated bond-poor epoxy compound is added to the carboxyl group in the copolymer obtained by co-merging the lint, (meth)acrylic acid, and other vinyl monomers as necessary. 12! of the core monomers listed below in the unsaturated bond-functionalized copolymers obtained by J or a graft copolymer obtained by copolymerizing two or more types, a copolymer obtained by copolymerizing the unsaturated bond-functionalized copolymers, the nuclear monomers listed below, and (meth)acrylic acid. Examples include unsaturated bond-containing graft comonomers obtained by subjecting carboxyl groups in a polymer to an addition reaction of the above-mentioned unsaturated bond-containing epoxy compound.

Among these, each of the above-mentioned dispersion stabilizers of group ① and 0, and the dispersion stabilizer of group 0 mentioned above
Esterified with a C4 or higher alkyl alcohol, (
(meth)〒 The main component is alkyl esters of acrylic acid (co-)
When unsaturated bond-functionalized copolymers derived from polymerization or (co)polymers are used as dispersion stabilizers, all of these dispersion stabilizers are subject to penalty t. Although such solvents do not have a wide range of segments, it is possible to use a dispersion stabilizer in such a part to create a segment on the core that is carried out in the preparation of a non-aqueous dispersion polymerization process. At the initial stage of polymerization, segments that are not bathable in the above-mentioned solvent are formed, and the desired non-aqueous dispersion type polymer ρ is obtained.

Here, as the core monomers, the above-mentioned hydroxyl group-containing polymers or the monomers of each type used in obtaining Al't- can be used as they are, and (meth)acrylic Hydroxydialkyl ester of acid 1
1*, unsaturated bond-containing hydroxyalkyl ester monocarboxylic acids, unsaturated bond-containing polyhydroxyalkyl esters, (meth)acrylic alkyl esters of alcohols from C+ to C8, or cyano group-containing monomers, etc. On the other hand, typical monomers that can be combined with the core monomers include (meth)acrylic acetic acid alkyl esters of C4 or higher alcohols; dialkyl of unsaturated dicarbonate groups; Esters: Perfluoroalkyl group-containing vinyl ester 2i
α-Olefins: aromatic nR vinyl monomers; vinyl halides (vinyritine); acid anhydride group-containing monomers; carboxylic acid amide group-containing monomers; sulfonic acid amide group-containing monomers; tertiary amino Group-containing monomers: phosphoric acid ester bonds, monomers containing monomers, or sulfonic group-containing monomers or organic amine salts thereof.

In addition to the above-mentioned dispersion stabilizers, dispersion stabilizers with a hydrolyzable silyl group, and the dispersion stabilizers mentioned above have a dispersion stabilizer with a hydrolyzable silyl group, and a dispersion stabilizer with a hydrolyzable silyl group, and A dispersion stabilizer, etc., in which the bond is formed by a reaction between a hydrolyzable silyl group and a group capable of reacting with the silyl group,
Is it possible to create a stable non-aqueous dispersion polymer?
! -'R1, and the present inventors have confirmed that this class of non-aqueous dispersion type polymers is extremely useful as the particulate polymers (C1) used in the present invention.

These dispersion stabilizers having a hydrolyzable zolyl group are
The membrane can be split by the following method.

That is, the main component is an alkyl ester of (meth)acrylic acid esterified with a C4 or higher alkyl alcohol as shown in (1) above, and a hydrolyzable silyl group-containing monomer such as γ-(meth). ) acryloyloxy7glopyrtrimethoxy7rane, γ-(
meth)acryloyloxypropyltriethoxypuran, γ-(meth)acryloyloxypropylmethyldimethoxy7norane, vinyltrimethoxysilane, vinyltriethoxysilane, vinyltriethoxysilane, vinylmethyldiethoquinocrane, vinyltris(β- methoxyethoxy) silane or allyltrimethoxy 7-rane 1
The seed material is a method of copolymerizing two or more polymers with a monomer that can be combined with the other materials, or a polymer obtained by such a method (stem polymer) has a hydrolyzable property as described above. A method of graft copolymerizing a monomer having a group capable of reacting with a silyl group, such as a hydroxyl group and/or a carboxyl group, with a known nuclear monomer 1a+ or 2 or more as listed above can be applied.

Among these methods, in the case of the former method, a monomer 0'l' having a group (carboxyl group, hydroxyl group, etc.) that can react with the silyl group in the hydrolyzable solyl group-containing monomer as mentioned above is used. It is necessary to use it as a nuclear monomer.1 By doing this, a nuclear monomer reactor having a group capable of reacting with a silyl group participates in the bonding of the grafting point.

By the way, if the obtained non-aqueous dispersion polymer is dissolved in a mixture of the above-mentioned AAl component and (BljM component), it can be directly used in the enemy particle army coalescing reactor (C1) of the present invention. It can be used as f8W, but conversely f8W
l! In such cases, it is necessary to form a structure (for example, the formation of an insoluble part) that can maintain the particles of the non-aqueous dispersion polymer, and for this purpose, it is necessary to It is necessary to bridge the whole part of the nucleus that is to become a water-dispersed N fragment within the molecule.

Methods for achieving such intramolecular cross-securing include a method of using a pair of monomers having 2 and y functional groups that can react with each other together with core monomers, a method of using a polyfunctional vinyl monomer, Examples include a method in which a vinyl monomer having at least two unsaturated bonds is used in combination with a nucleating monomer.

Among these intramolecular crosslinking methods, typical examples of pairs of monomers containing two functional groups that can react with each other used in the former method include an example of an epoxy group and a carboxyl group. Examples of acid anhydride groups and hydroxyl groups in (β-n:thyl)glycidyl (meth)acrylate and (meth)acrylic acid include maleic anhydride and β-hydroxyethyl (
Examples of incyanate groups and hydroxyl groups with meth)acrylate include β-isocyanate ethyl (meth)acrylate and β-hydroxyethyl (meth)acrylate.
It'll also include the hydroxyl group and methylol group of β-isocyanate ethyl (meth)acrylate and allylamine, and the example of the alkyl etherified methylol group will include β-hydroxyethyl (
Examples of the hydrolyzable 7lyl group and hydroxyl group in the n-butyl etherified product of meth)acrylate and N-methylol(meth)acrylamide include γ-(meth)acryloylox7probyltrimethocycrunane and I-hydroxyl group. Examples of hydrolyzable acrylic groups and carboxyl groups with quetyl (meth)acrylate include combinations of γ-(meth)acryloyloxypropyltrimethoxy 7rane and (meth)acrylic acid, and Examples of decomposable 7lyl groups include using γ-(meth)acryloylox7probyltrimethoxycunlan alone, or appropriately selecting one or more of the various hydrolyzable silyl group-containing monomers listed above. Then you can do that.

Either these two persimmon monomers forming a pair are reacted simultaneously with the non-aqueous dispersion polymerization as part of the core monomers, or they are reacted by raising the temperature at the end of the non-aqueous dispersion polymerization.
Furthermore, in order to promote such a reaction, intramolecular crosslinking may be carried out by allowing the reaction to occur in the presence of a known and commonly used molecule.

On the other hand, even in the case of the latter intramolecular crosslinking method in which a polyfunctional vinyl monomer is used in combination with a core monomer, the following polyfunctional vinyl monomer is used in combination with a core monomer, as in the former method. By polymerizing it as a part of the non-aqueous dispersion type polymer, a crosslinked structure can be imparted to the non-aqueous dispersible polymer. ) acrylate or trimethylolpropane tri(meth)acrylate.

The fine particle polymer @C1 used in the present invention contains both the dispersion stabilizer and the core monomers (
It is particularly preferable to use a non-aqueous dispersion type polymerization furnace into which the same type of M0 group, ie, a hydroxyl group, which can react with the Bl component is introduced.

This is because when the composition of the present invention becomes a cured coating film, both the dispersion stabilizer part and the core part of the non-aqueous dispersion type polymer react with the curing agent (curing resin). This is because a uniform and highly transparent coating film can be obtained.

As mentioned above, in order to prepare such a non-aqueous association dispersion, the dispersion stabilizer and the core monomers may be polymerized in the presence of the bath agents listed above. In this case, it is possible to use radical N-group initiators, such as those mentioned above, and, if necessary, chain transfer agents, as mentioned above.

As for the use of the fine particle polymers (C1) as described above, the total of the (Al component and (Bl component) is 1i10
A suitable range is 0.1 to 100 close-up parts to 0P amount parts.

Furthermore, as the above-mentioned solvent [Dl, the solvents already used in the evaluation of the (Al component or (C1 component) can be used alone or in combination, and the types and combinations of the solvents can be used as is. Needless to say, the composition in each case should be determined depending on the type of coating method, baking conditions, etc.

In addition, when polyiso7anate is used as the former 1QBl component, it is a matter of course that the 68 agents (Dl) should be selected from those that do not react with this polyisocyanate.

The thus obtained composition for high@@now coating of the present invention includes:
Furthermore, if necessary, pigments, various resins, known and commonly used flow regulators, color separation inhibitors, antioxidants or ultraviolet absorbers, 7-run coupling agents, and curing catalysts can be added.

Typical pigments include inorganic pigments such as titanium oxide and carbon black, organic pigments such as quinacridone, azo, and phthalocyanine, and various types such as aluminum powder, copper powder, and zinc powder. Typical resins include nitrocellulose, cellulose acetate butyrate, fibrous resins, ketone resins, petroleum resins, and 7-run coupling agents. Typical examples include γ-aminopropyltrimethoxysilane, r-gridquinglobilmethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, and γ-mercaptoglobiltrimethoxysilane.

In addition, typical curing catalysts include bαB
When (block) polyisocyanate is used as one component, diptyltin diacetate, diptyltin dilaurate, triethylamine, jetanolamine, etc. are used, and when using aminoglass If as the component αB), para Toluenesulfonic acid, or "Beccamin P-198J [Dainichi Fu Ink Chemical Industry ■ product]," Naicure 155, 2500X,
49-110.5225 or 6525'' (product of King Company, USA). The amount of the skeleton catalysts to be used may be appropriately selected depending on the degree of baking and baking time.

The punching composition of the present invention is applied by a conventional method such as coating, spray coating, brush coating, or roll coating, and then heated from room temperature to 100"C (if polyisocyanate is used as the Bl component) If a substance other than the above-mentioned polyisocyanate is used as the flB+ component, brittle hardened coating can be obtained by baking at a temperature range of <50°C to 180°C for 10 to 40 minutes.

Thus, the solid-coated a resin composition of the present invention can be applied particularly to general baking products such as home appliances, or for automobiles, but more specifically, it can be used as an enamel paint for automobiles, as a metallic base paint. It can be used as a paint or as a clear paint.

Next, the present invention will be specifically explained using Reference Examples, Examples, and Comparative Examples. In the following, all parts and percentages are based on weight base yarn unless otherwise specified.

Reference Example 1 [Hydroxyl group-containing 1 coalescence (preparation example of Al)] 160 parts of xylene and 160 parts of n-butyl acetate were charged into a reactor equipped with a stirring device, a hygrometer, a nitrogen inlet pipe, and a reflux condenser. , the temperature was raised to 125°C under a nitrogen atmosphere, and 120 parts of styrene and 18 parts of n-butyl acrylate were added.
0s.

120 parts of n-butyl methacrylate, 108 parts of β-hydroxyglobyl acrylate, 66 parts of β-hydroxyglobyl methacrylate and 6 parts of acrylic acid, 80 parts of n-butanol, tert-butyl peroxyoctate. 48 parts, 3 parts of di-tart-butyl peroxide and 1 part of azobisisobutyronitrile
The mixture consisting of 2 parts was added dropwise over a total of 8 hours, and even after the addition was completed, the mixture was kept at the same temperature for 15 hours to remove the non-volatile content (NY).
is 60%, Gardner color (G, C9) is 1 or less, 2
Hydroxyl group-containing vinyl polymers (Al
A vinegar solution was obtained. Hereinafter, this will be abbreviated as total polymers (A-1), but the solid content of this product is OHMij109.
Met.

Reference Example 2 (Same as above) 215 parts of adipic acid, corresponding to 63.8 mol% of the total polybasic acid components, was put into a reactor equipped with a stirring device, a hygrometer, a crab inlet tube, and a reaction product water distiller. 400 parts of hexahydrophthalic anhydride, 446 parts of trimethylolpropane, 50 parts of ethylene glycol and 7 parts of the total alcohol content.
390.2 of neopentyl glycol corresponding to 67 mol%
After preparing all parts, gradually boiling for 23 hours in a desirable atmosphere for 5 hours.
The mixture was heated in a 0°C trench and maintained at the same temperature until the acid value reached 10, to obtain an oil-free alkyd resin with an OHV of 111 and an Mn of 1.010.

Next, this resin was cooled to 100° C. or lower, and 250 parts of xylene was added to obtain an oil-free alkyd resin solution containing 80% NY. Hereinafter, this will be abbreviated as 'klF coalescence class (body furnace 2).

Reference Example 3 (Same as above) 83.2 parts of adipic acid, 400 parts of hexahydrophthalic anhydride corresponding to 82 mol% of the total polybasic acid component, 61.1 parts of trimethylolpropane, and 90 parts of the total alcohol component 423 of neopentyl glycol in mole%
An oil-free alkyd product was obtained by reacting Reference Example 2 and persimmon until the acid value reached 10, except that the preparation was changed to i (ii).

Next, this resin was cooled to below 100°C, 250 parts of xylene and 0.1 part of diptyltin dilaurate were added, and the temperature was raised to 65°C, and while maintaining the same temperature, 100 parts of hexamethylene diisocyanate was added for 2 hours. The temperature was gradually lowered over the course of the heat generation process, and even after painting was completed, the temperature was maintained at the same temperature for 2 hours, and then the temperature was raised to 80°C and held for 1 hour, resulting in a partially urethanized oil-free product with an NV of 80%. A solution of alkyd resin was obtained. Hereinafter, this will be referred to as polymer 15'1 (A
-3) is abbreviated as 0H regarding the solid content of this product.
-V was 118, and Mn was i, o 7o.

Reference example 4 (same as above) 1574 parts of adipic acid, 64.4 parts of the total polybasic acid component
300 parts of hexahydrophthalic anhydride, 203.8 parts of trimethylolpropane, and 23 parts of neopentyl glycol, representing 59 mol% of the total alcohol component.
Except that 0 parts and 200 parts of coconut oil fatty acid were charged, the reaction was carried out in the same manner as Example 2 until the acid value reached 10 to obtain an 80% solution of alkyd resin. below,
This is abbreviated as polymers (A-4), and the OHV of the solid content of this is 125, and 6 is 1.140.
Met.

Reference Example 5 (Same as above) In a reactor similar to Reference Example 1, 134 parts (1 mol) of trimethylolpropane and 684 parts of ε-caprolactone were added.
(6 mol) and 0.04 part of tetrabutyl titanate were charged, the temperature was raised to 180°C, and the same temperature was maintained at VC for 10 hours to obtain a lactone-added polyester resin. Hereinafter, this is abbreviated as total polymers (A-5), and this product has an NV of 100%, a Gardner viscosity of X, and 0) IV
was 206, and the response was 820.

Reference example 6 (same as above) Instead of xylene and butyl acetate, jLAWsJ
The procedure was the same as in Reference Example 1, except that 320 parts of the product was used (product of Shell, Netherlands), and the NV was 60%.
, G, C, were 1 or less and a Gardner viscosity of F was obtained. Hereinafter, this will be abbreviated as Polymer D (A-6), and the ORV of this solid content is 109, and the crime rate is 3,100.
Met.

Reference Example 7 [Example of Preparation of Particulate Polymers (C)] In a reactor similar to Reference Example 1, [Isopar El (aliphatic hydrocarbon mixture manufactured by Ekun, USA; b, p = 115 to 14) was added.
2°C] and 70 parts of n-butanol, the temperature was raised to 100°C under nitrogen% lff1, and then at the same temperature, 465 parts of 2-ethylhexyl acrylate,
10 parts of β-hydroxyglobil acrylate and r
- 25 parts of methacryloyloxypropyltrimethoxysilane and 51 L of tart-butylperoxyoctoate 2 parts of tert-butylperoxybenzoate
．． A mixture consisting of 5 parts and 100 parts of Isopar EJ was boiled down over 4 hours, and after the sieving was finished, it was kept at the same temperature for 10 minutes.
A dispersion stabilizer in the form of a polymer bath liquid having an NV of 60%, G and C of 1 or less, and a Gardner viscosity of 81 was obtained by holding the mixture for a period of time. Hereinafter, this will be abbreviated as a dispersion stabilizer (11).

Separately, this dispersion stabilizer (1
) and 400 parts of "Isopar E" were heated to 90°C under a nitrogen atmosphere, and while maintaining the same temperature, 360 parts of methyl methacrylate, 560 parts of ethyl acrylate, and β-hydroxy 1531L of quetyl acrylate.

9 parts of glycidyl methacrylate, 18 parts of acrylic acid, 3 parts of tetrabutyl titanate, 1 part of 2-methylimidazole, 200 parts of "Isopar E" and ter
A mixture consisting of 13.5 parts of t-butyl peroxyoctoate was added to the mixture over a period of 4 hours, and after the addition was completed, the reaction was continued at the same temperature for 10 hours to obtain a white target fine particle polymer containing 60% NY. A dispersion was obtained. Hereinafter, this will be abbreviated as polymer (c-1), and its Gardner viscosity was A3.

Reference Example 8 (Same as above) In a reactor similar to Reference Example 1, 1667 parts of the dispersion resin obtained in Reference Example 7 was added to the chemical agent il+ and "Aitunoku-E".
400 parts of methyl methacrylate, 560 parts of ethyl acrylate, 162 parts of β-hydroxyethyl acrylate, and the temperature was raised to 90°C under a nitrogen atmosphere. 3 parts of tetrabutyl titanate, [200 parts of Isopar El and t
A mixture consisting of 16.5 parts of ert-butyl-oxydioctoate was added dropwise over a total of 4 hours, and after the addition was completed, the reaction was continued at the same temperature for 10 hours to obtain the desired white particulate polymer containing 60% NY. A similar dispersion was obtained. Hereinafter, this will be abbreviated as all polymers (C-2), and its Gardner viscosity was A4.

Examples 1 to 14 (As the Al component, the hydroxyl group-containing polymers (A-1) to (A-6) of Reference Examples 1 to 6 were used as the Bl component. Hexamethoxomethyl melami (NY = 10 parts %) and l Burnock D-550J [blocked product of non-yellowing type polyisocyanate resin manufactured by Dainippon Ink Chemical Industry Co., Ltd.: NV =
55%], the fine particle polymers (C-1) and (C-2) of Reference Examples 7 and 8 were used as component (C), and if necessary, a pigment and/or a curing catalyst was added to the first A mixed paint was prepared using the blending ratio as shown in the table, and further, in the case of Example 9, "Isopar El
/ethyl acetate/cellosolve acetate)/n-butanol = 60/10/10/2 (similar weight ratio)
[Aromatic hydrocarbon mixture manufactured by Ekun ■]/n-butanol/cellosolve acetate = 60/20/20 (grained ratio) A paint solution was obtained by adjusting the spray viscosity with a diluting thinner.

Next, add 0.0% of each of the ingredients. Coating was applied to a mild steel plate of f3 am thickness so that the dry film thickness was approximately 65 μrIL, and setting was performed for 30 minutes. [When Burnock D-55DJ was used, it was incubated at 160°C for 20 minutes.

Regarding each cured coating film obtained in this way, mainly 1).
Presexual evaluation was performed by observing the state of the painted surface, such as "Jiki".

The results are summarized in the same table.

Comparative Examples 1 to B (Example 1 except that no C1 component was added)
．． 8.9.10.11.12.13 and 14, prepare a coating, paint, set, and then bake each cured coating, and then measure the performance of the cured coating. Table 1 summarizes the locations where this was done.

As is clear from the results in Table 1, the high solids coating composition of the present invention has the advantage that coating work can be performed while maintaining a high solids content, and moreover, It is known that the resulting cured coating film has the advantage of having a beautiful appearance without "repelling".

Attorney: Patent Attorney Takahashi Victory Procedure Amendment ν1 June 7, 1980 Director of the Patent Office Kazuo Wakasugi 1, Indication of the case 1982 Patent Application No. 86706 2, Name of the invention: High solid content coating composition 6 , Relationship to the case of the person making the amendment Patent applicant 3-35-58 Sakashita, Itabashi-ku, Tokyo (288) Dainippon Ink Chemical Industry Co., Ltd. Representative Shigekuni Yomura 4, Agent Address: 103 Nihonbashi, Chuo-ku, Tokyo No. 3-7-20 Dainippon Ink & Chemicals Co., Ltd. Tel: Tokyo (O3) 272-4511 (Main Representative) Voluntary 6, Detailed Description of the Invention J of the Specification Subject to the Amendment Contents of the Amendment (1) ) The statement "The membrane has been improved" on page 9, line 8 of the specification is corrected to "The membrane performance has been improved."

(2) The statement in page 16, line 12 (■) is corrected as follows.

"Amides such as methylformamide and dimethylacetamide" (3) The statement in W, page 27, line 11, is corrected as follows.

jD-750,800, DN-950,970 or 15-" (4) The statement in the first line of page 64 of the same is corrected as follows.

(5) The statement on page 48, line 15 of the same is corrected as follows.

"Contains a hydroxyl group in which (the same applies hereafter) is E, 9 is 3,000, and the glass transition temperature is 0°C" (6) "70 parts of n-butanol" described on page 53, line 6 of the same, is [n -67.5 parts of phthanol”.

(7) "Table 1, page 59 of the same" is corrected as follows.

Procedural amendment June 27, 1980 Mr. Kazuo Wakasugi, Commissioner of the Japan Patent Office■, Indication of the case, Patent Application No. 86706 of 1986 2, Name of the invention: High solids coating composition 3, Person making the amendment Related Patent applicant: 35-58 Sakashita, Itabashi-ku, Tokyo 174 (28
8) Dainippon Ink & Chemicals Co., Ltd. Representative: Shigeru Kuni Mura 4, Agent Address: 3-7-20 Nihonbashi, Chuo-ku, Tokyo 103 Dainippon Ink & Chemicals Co., Ltd. Tel: Tokyo (03) 272-4511 (Dainippon Ink & Chemicals Co., Ltd.) (Representative) Voluntary Issue 6, "Detailed Description of the Invention" column 7 of the specification to be amended, Contents of the amendment (1) The statement on page 12, line 12 of the specification is corrected as follows.

“Silfumarate or N 1so-propyruva J (
2) The statement on page 14, line 14 is corrected as follows.

``There are Min salts, etc.'' (3) The statement on page 16, line 12 of the same is corrected as follows.

"Amides such as methylformamide and dimethylacetamide" (4) The statement on page 44, line 11 of the same is corrected as follows.

``Shi can be applied as is in combination form, and its PIR
The above procedural amendments August 1, 1980 + Date Mr. Manabu Shiga, Commissioner of the Patent Office ■, Indication of the case, Patent Application No. 86706, filed in 1982, 2, Title of the invention: High solid content coating composition 3, Amendments are made. Relationship with the patent applicant 3-35-58 Sakashita, Itabashi-ku, Tokyo 174 (28
B) Dainippon Ink and Chemicals Co., Ltd. Representative: Shigeru Kuni Mura 4, Agent: Dainippon Ink and Chemicals Co., Ltd., 3-7-20 Nihonbashi, Chuo-ku, Tokyo 1-1, 1, 103; Sponsored by 6 , correction target 7, correction content T1. l The statement on page 37, line 9 of the specification is corrected as follows.

"Acid ester-bonded gold-containing heptamers; or sulfonic acid group-containing J or more" -

Claims (1)

[Claims] 1. (90 to 30 parts by weight of Al hydroxyl group-containing polymers,
(Bl 10-703 of aminoplast or blocked, if unblocked polyinyanate)
Part ii, (cl above (total amount of both Al and IBI components 100
A high solids coating composition comprising, based on parts by weight, 0.1 to 100 parts by weight of particle-free polymers and an appropriate amount of (Di) solvents as all essential components. 2. Hydroxyl group-containing polymer IXAl is 500 to 8,0
The composition according to claim 1, characterized in that it is a vinyl resin having a number average molecular weight of 0.00 and a hydroxyl value of 40 to 250. & The above hydroxyl group-containing polymers, 200 to 3,000
At least one selected from the group consisting of alkyd resins, oil-free alkyd resins, and urethane resins having a number average molecular weight of 40 to 600 and a hydroxyl value of 40 to 600.
2. The material according to claim 1, which is a resin for a rod. 4. The aforementioned hydroxyl group-containing polymers (AI is hexahydrophthalic acid, methyl hexahydrophthalic acid, hexahydroterephthalic acid, and one or more polybasic acid components of these reactive derivatives) At least 50 mol% of the floor components
The composition according to claim 1 or 3, which contains an alkyd resin, an oil-free alkyd resin, and/or a urethane resin. 5. The hydroxyl group-containing polymer furnace part has a molecular weight of 500 to 8,000
A vinyl resin having a number average molecular weight of 40 to 250 and a hydroxyl value of 40 to 250%! It has a number average molecular weight of 1.000 and is a mixture with at least one type of oil-resistant resin selected from the group consisting of alkyd resins, oil-free alkyd resins and urethane resins of 40 to 600. A composition according to claim 1. &The composition according to claim 1, wherein the aminoblast is an aminoaldehyde resin etherified with an alcohol having a concentration of % CI to C4. l A patent claim characterized in that the fine particle polymer (cl) is a non-aqueous dispersion type polymer having both a segment soluble in an aliphatic or alicyclic hydrocarbon soap agent and a segment insoluble. Range 1: The composition according to lJ. In 8, the fine particle N fic+ is a soluble segment and an insoluble segment in an aliphatic or alicyclic hydrocarbon bath agent. In each segment, The aminogellast or the blocked or unblocked polyisocyanate (a non-aqueous dispersible polymer having a hydroxyl group that reacts with Bl), Composition.9 The fine particle polymers (Cl is a hydrolyzable silyl group and the solyl group as a bond between a segment soluble in a fat liquid or an alicyclic swelling hydrogen solvent and a segment insoluble) The composition according to claim 1, characterized in that it is a non-aqueous dispersion type polymer having a bond formed by a reaction with a group capable of reacting with a group capable of reacting with the fine particles 1. 10. The fine particle 1 aggregate C) is a non-aqueous dispersion type polymer having an intramolecular cross-linked structure in the segment as a segment insoluble in an aliphatic or aliphatic hydrocarbon static agent. Composition according to paragraph 1fJ1.