JPS60241970A - Process for forming double-coated colored film - Google Patents

Abstract

PURPOSE:To improve the workability for coating, and curability and weather resistance of coated film by coating a colored paint consisting of a film forming component, pigments, solvents, fine particles of polymers and solvents on a substrate, then coating a top coating paint and then baking. CONSTITUTION:A color paint consisting of a film forming component consisting of 30-90pts.wt. OH-contg. vinyl polymer having 500-8,000 number average mol.wt. and 40-250 OH value and 70-10pts.wt. aminoplast, and pigemtns, solvents, and fine particles of polymers (e.g. powdery silica, low mol.wt. polyolefine, etc.), is coated on a substrate. Then, a top coating paint consisting of a component for forming a coating layer consisting of a polymer (such as alkyd resin, oil-free alkyl resin, urethane resin, etc.) and aminoplast, is coated thereon. The coated layer is baked thereafter at 60-180 deg.C.

Description

[Detailed Description of the Invention] The present invention provides a novel two-coat colored coating film.
7. Concerning useful formation methods, more specifically, colored paints or metallic paste paints and top coats each require specific film-forming components (base resin components), particulate polymers, and solvents. A two-coat colored coating with a high solids content is achieved by applying both types of paints as components, first a colored paint, then a top coat, and then baking. The present invention relates to an improved method of forming a coating film by which a film can be obtained.

One of the trends in the coating industry in recent years is toward so-called low-pollution coating systems.

Conventionally, the approach to increasing such low-pollution coating systems has been to reduce the amount of solvents used, which can be said to be the cause of environmental pollution because they volatilize and diffuse during coating. Progress is being made in the form of developing mold compositions or using water-based paints to replace these solvent-based paint systems.

However, all of the conventional paint/painting methods described above require a so-called two-coat colored finish, in which metallic paint or colored paint is applied to the base material, and then a top coat is applied, as in the case of car body painting. The method of forming such a multilayer film has considerable drawbacks.

In other words, in the case of film formation using the former high solid content type composition, the amount of solvent (amount of diluting thinner) in the system is significantly reduced, so that during one spray coating, less paint is applied to the substrate. As a result of the extremely high content of film-forming components, the smoothness of the painted surface, which had been controlled by varying the evaporation rate of the diluted thinner, deteriorated.
Alternatively, in baking-type paint systems, the film-forming component applied to the base material decreases in viscosity during baking, resulting in the drawback that it tends to ``sag'' and crack.

Furthermore, when using a film-forming polymer with a low molecular weight as a high solids composition, it is possible to
This tends to cause coating film defects such as pinholes and craters, and also results in poor readability of the cured coating film.

On the other hand, when using the latter type of water-based paint, the dispersion medium is water with low volatility, resulting in poor spray workability, or the volatilization of water when applied to the base material may be affected by atmospheric humidity. It has the disadvantage that it is highly dependent on the color of the paint, and furthermore, when a two-coat colored paint film is formed, paint film defects such as 'flanks' are induced.

As mentioned above, there are many problems that need to be solved with conventional low-pollution paints, and the current situation is that they have not been widely put into practical use, particularly for two-coat color finishing of automobiles and the like.

However, in view of the various shortcomings and deficiencies in the prior art as described above, the inventors of the present invention have made repeated efforts to apply high solid content type paints to two-coat color coating systems for automobiles and the like. As a result, when using a coating film forming method that involves sequentially applying a colored paint and a top coat containing fine particle polymers as film-forming components, followed by a baking process, a high solids content is required. The inventors have discovered that it is possible to prevent coating film defects such as 1 sliver 1 in the top coat film while maintaining the same, and to obtain a coating film with excellent curability and weather resistance, and have completed the present invention. Ta.

That is, in the present invention, 100% of the film-forming component (A-1)
and pigments (B) in a proportion of 4 to 470 parts by weight based on 100 parts by weight of this component (A-1).
-1), 0.1 to 100]i parts of the above component (A-1), the ingredients (B-1) and the following solvents (D-1) in a different system. A fine particle polymer that is immiscible and can be stably dispersed [
A colored paint comprising C) and an appropriate amount of solvents (D-1) as essential components is applied onto a substrate, and then a film-forming component (A-2) is applied thereon as an essential component.
The above component (A,-2) and the following solvents (D-2) in a proportion of 0.1 to 100 parts by weight, respectively, based on 100 parts by weight of this component (A-2) and 100 parts by weight of this component (A-2). ) and a fine particle polymer M (including El and an appropriate amount of solvents (D-2)) that is immiscible in other systems and can be stably dispersed in other systems, and further contains the above components (A, -2) 10
Painting consisting of applying a top coat comprising pigments (B-2) in a ratio of at most 22 parts by weight to 0 parts by weight, and then baking at a temperature in the range of 60 to 180°C. A new and useful coating film formation method that can obtain a two-coat colored coating film with excellent performance such as curability and weather resistance while maintaining a high solids content without any loss in workability. It provides:

Here, first of all, the film-forming component (A-1) or (A-2) is preferably within the range shown below, and b(A-1) component and (A-2) component are , may be the same or have the same composition as long as they are within the following range, and the number average molecular weight (Mn
), hydroxyl value (OHV) and/or glass transition point (
They may be different in terms of Tg) or the like.

■ Mn is 500-8,000 and OHV is 40-40
250 hydroxyl group-containing vinyl polymers from 30 to 90M
A mixture having a ratio of 70 to 10 parts by weight of aminoplast,
600, a ratio of 30 to 90 parts by weight of at least one hydroxyl group-containing polymer selected from the group consisting of alkyd resins, oil-free alkyd resins and urethane resins and 70 to 10 parts by weight of aminoplast. A mixture of ■
30 to 90 polymers of at least one hydroxyl group-containing polymer selected from the group consisting of hydroxyl group-containing polymers belonging to Group 0 and hydroxyl group-containing polymers belonging to Group 0 above and 70 to 70 b of aminoplast. (1) hydroxyl group-containing polymers belonging to the above group 0 and the above 0 group;
A cocondensate obtained by reacting 30 to 90 parts by weight of at least one hydroxyl group-containing polymer selected from the group consisting of hydroxyl group-containing polymers and 70 to 10 parts by weight of aminoplast. .

Among the film-forming components (A-1) or (A-2), in order to prepare a hydroxyl group-containing vinyl polymer, a hydroxyl group-containing monomer and another monomer copolymerizable with the monomer are usually mixed. Typical examples of such hydroxyl group-containing monomers include 2-hydroxyethyl (meth)acrylate, 2-hydroxylpropyl (meth)acrylate, and 6-hydroxypropyl (meth)acrylate. -Hydroxybutyl (meth)acrylate, 3-hydroxybutyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate,
Hydroxyalkyl esters of (meth)acrylic acid such as 3-chloro-2-hydroxypropyl (meth)acrylate and polyethylene glycol mono(meth)acrylate; monomers containing acid anhydride groups such as maleic anhydride and itacone anhydride, and ethylene Unsaturated 17-bond-containing hydroxyalkyl ester monocarboxylic acids such as adducts with polyhydric alcohols such as glycols, and dihydroxyalkyl esters of polycarboxylic acids such as maleic acid, fumaric acid, and itaconic acid. Saturated bond-containing polyhydroxyalkyl esters; or hydroxyalkyl vinyl ethers such as hydroxyethyl vinyl ether.

On the other hand, typical monomers copolymerizable with such hydroxyl group-containing monomers include methyl (meth)acrylate, ethyl (meth)acrylate, n-butyl (meth)acrylate, and l5o-butyl (meth)acrylate. (meth)acrylic acid esters such as acrylate, 2-ethylhexyl (meth)acrylate, cyclohexyl (meth)acrylate, and benzyl (meth)acrylate; dimethyl maleate.

Diesters of the above-mentioned polyhydric carboxylic acids and monohydric alcohols such as diethyl fumarate and di-n-butyl itaconate; Quivinyl esters; [Viscoat 8F, 8FM, 3F or 3FMJ (Osaka Organic Chemicals surplus fluorine-containing (meth)acrylic monomer), perfluorocyclohexyl (meth)acrylate, di-
perfluorocyclohexyl fumaley), N-1go-
Propyl perfluorooctane sulfonamidoethyl (
Perfluoroalkyl group-containing vinyl esters such as meth)acrylates; vinyl halides (vinylidene) such as vinyl chloride, vinylidene chloride, vinyl butylene, vinylidene butyrate, and chlorotrifluoroethylene; Olefins; styrene,
α-methylstyrene, p-tertbutylstyrene, 0
- Aromatic vinyl monomers such as methylstyrene and p-methylstyrene; (meth)acrylic acid, Riff)-4
unsaturated mono- or dicarboxylic acids such as , maleic acid, fumaric acid, itaconic acid; monomers containing the above acid anhydride groups; (meth)acrylamide, N,N-dimethyl (meth)
Acrylamide% N-alkoxymethylated (meth)acrylamide, diacetone (meth)acrylamide, N-
Carboxylic acid amide group-containing monomers such as methylol(meth)acrylamide; p-styrenesulfonamide, N-methyl-p-styrenesulfonamide, N,N-
Sulfonic acid amide group-containing monomers such as dimethyl-p-styrenesulfonamide; N,N-dialkylaminoalkyl (meth)acrylate such as N,N-dimethylaminoethyl (meth)acrylate; ) Additives of acrylates and the above-mentioned acid anhydride group-containing monomers with a compound having both an active hydrogen group and a tertiary amino group that can react with the acid anhydride group of N,N-dimethylaminopropylamine. Tertiary amino group-containing monomers such as (meth)acrylonitrile; cyano group-containing monomer rods such as (meth)acrylic acid (α,β-
Monomers having a phosphoric acid ester bond obtained by a condensation reaction between an ethylenically unsaturated carboxylic acid and phosphoric acid or a phosphoric ester; monomers having a sulfonic acid group such as 2-acrylamido-2-)thyl-propanesulfonic acid or its organic amine salts.

and K for preparing the hydroxyl group-containing vinyl polymers.
The amount of the above-mentioned hydroxyl group-containing monomer to be used varies depending on the molecular weight of the vinyl polymer to be obtained, but it is generally appropriate to be within the range of 10 to 50% by weight based on the total amount of monomers. , 90 to 50% of the residue may be appropriately selected from other copolymerizable monomers, and the other copolymerizable monomers are suitable for the physical properties of the final cured coating film and the pigment dispersion. Decisions should be made taking into account factors such as gender.

Among other copolymerizable monomers, monomers with acid groups such as carboxyl group-containing monomers and sulfo/acid-containing monomers can be used.
Since these monomers are useful as latent catalysts for the crosslinking reaction between the hydroxyl group-containing vinyl polymers and aminoplasts as described below, it is also advisable to copolymerize these types of monomers.

To obtain the hydroxyl group-containing vinyl polymers, known and commonly used methods such as solution polymerization, bulk polymerization, emulsion polymerization, suspension polymerization, and solution pressure polymerization can be applied as is. Among them, the solution radical method is the simplest.

Typical solvents used in this process include:
Toluene, xylene, cyclohexane, n-hexane,
Hydrocarbons such as heptane and octane; methanol, I
RQ-22- propatool, n-butanol, 1so-butanol,
Alcohols such as Bee-butanol and ethylene glycol monomethyl ether; Ester systems such as methyl acetate, ethyl acetate, n-butyl acetate, and amyl acetate; Ketones such as acetone, methyl ethyl ketone, methyl-1ao-butyl ketone, methyl amyl ketone, and cyclohexanone. or amide systems such as dimethylformamide and dimethylacetamide; of course, any mixtures thereof may also be used.

Polymerization may be carried out by a conventional method using these solvents and various polymerization initiators such as azo type or A oxide type. Various known and commonly used chain transfer agents such as lauryl mercaptan, octyl mercaptan, 2-mercaptoethanol, or α-methylstyrene dimer can also be used.

In particular, when a chain transfer agent containing Hiko hydroxyl groups such as 2-mercaptoethanol is used, it is possible to efficiently introduce Kagaro hydroxyl groups even into a fraction of the obtained polymers having a molecular weight below the average molecular weight. However, it has the disadvantage of poor weather resistance, so it should be used for limited purposes.

In addition to the above-mentioned solution radical vehicle method, there is also an ionic polymerization method as a method for preparing the above-mentioned hydroxyl group-containing vinyl polymers, and the polymers obtained by such an ionic polymerization method are also suitable for use in the present invention. It can be used without any problem.

According to this ionic polymerization method, polymerization is carried out using an ionic polymerization initiator whose functional groups have been blocked in advance, and then the blocking agent present at the ends of the obtained polymer is removed, so that the molecular weight distribution is extremely controlled. It is possible to obtain a polymer having a narrow, yet one or more functional group in the molecule, and such an ionic polymerization method is described in Japanese Patent Application Laid-open No. 5
The details detailed in Japanese Patent No. 8-13608 can be applied as is.

The Tg of the hydroxyl group-containing vinyl polymers thus obtained is suitably within the range of -20°C to +50°C.

Next, the above-mentioned aminoplasts include melamine, urea,
Various amino group-containing compound components such as acetoguanamine, benzoguanamine, steroguanamine or spiroguanamine, formaldehyde, paraformaldehyde,
A condensate obtained by reacting an aldehyde compound component such as acetaldehyde or glyoxal by a conventional method, or a partially or completely K-condensed condensate obtained by reacting these condensates with an aldehyde compound component such as acetaldehyde or glyoxal. Specifically, methyl etherified melamine, ]-butyl etherified melamine or Is.

- Butyl etherified melamine, etc., but among these, methyl etherified melamine is desirable from the viewpoint of high solidification.

A mixture having a ratio of 60 to 90 parts of the hydroxyl group-containing vinyl polymer as described above and 70 to 10 parts of the aminoplast as described above can be used to form a satisfactory film. It is used as a component of the formative component (A-1) or (A-2).

In addition, the film-forming component (A-1) and the film-forming component (A-2
), we will discuss the preparation method for (condensation) polymers such as alkyd resins, oil-free alkyd resins, and urethane resins. It is characteristic in that it is limited, and well-known and commonly used means can be applied as is as so-called synthesis conditions such as esterification method.

Here, urethane resins include isocyanate-modified ar26=acrylic resins, isocyanate-modified alkyd resins, isocyanate-modified oil-free alkyd resins, etc.
It refers to resins that have one or more urethane bonds in the molecule, but incyanate-modified alkyd resins and/or oil-free resins are used because of their ease of synthesis and relatively low risk of gelation. Preference is given to using alkyd resins.

First, such a urethane resin can be prepared by reacting an alkyd oligomer or oil oligomer having one or more hydroxyl groups in the molecule with an organic diisocyanate compound to elongate the molecular chain.

Typical organic diisocyanate compounds that can be used include aliphatic diisocyanates such as hexamethylene diisocyanate and trimethylhexamethylene diisocyanate; cycloaliphatic diisocyanates such as xylylene diisocyanate and inphorone diisocyanate; and tolylene diisocyanate. , 4.4'-diphenylmethane diisocyanate, and other aromatic diisocyanates, and it is of course possible to use these in combination, but from the viewpoint of yellowing resistance of the coating film, aliphatic diisocyanates are preferably used. It is better.

In addition, typical polybasic acid components used in synthesizing the polyester component of the alkyd resin, oil-free alkyd resin, or urethane resin include:
Terephthalic acid, isophthalic acid, orthophthalic acid, 2,6
- Naphthalenedicarboxylic acid, 4,4'-diphenyldicarboxylic acid, tetrahydrophthalic acid, methyltetrahydrophthalic acid, hexahydrophthalic acid, hexahydroterephthalic acid, methylhexahydrophthalic acid, endomethylenetetrahydrophthalic acid, methylendomethylenetetrahydro Futar I'#! , maleic acid, fumaric acid, itaconic acid, succinic acid, glutaric acid, adipic acid, azelaic acid, pimelic acid, superic acid, sebacic acid, or dimer fatty acids (dimer acids), or trimellitic acid, trimellitic acid, Examples include pyromellitic acid or cyclopentanetetracarboxylic acid, or reactive derivatives thereof such as their alkyl esters or anhydrides, but preferably hexahydrophthalic acid, methylhexahydrophthalic acid, hexahydroterephthalic acid or their alkyl esters or anhydrides. If one or more of various reactive derivatives are used in an amount of 50 mol% or more of the total polybasic acid component, the curability and weather resistance of the coating film, as well as solubility and viscosity reduction, etc. can be improved. This results in a paint that is excellent in terms of.

As described above, these polybasic acid components should be appropriately selected taking into consideration the physical properties of the coating film, economic efficiency, and the like.

On the other hand, typical polyhydric alcohol components used in synthesizing the polyester component of the alkyd resin, oil-free alkyd resin and/or urethane resin include KFi, ethylene glycol, propylene glycol, trimethylene glycol, Alkylene glycols such as 1,4-butanediol, 1,3-butanediol, 1,5-bentanediol, 1,6-hexanediol, neopentyl glycol: 1,4-cyclohexane dimetatool, bis-hydroxyethyl Aromatic or alicyclic glycols such as terephthalate, hydrogenated bisphenol A1 or alkylene oxide adducts of hydrogenated bisphenol A, monoepoxy compounds can also be used in combination as the alcohol component, and glycerin, triglyceride, etc. Polyester compounds such as methylolethane, trimethylolpropane, pentaerythritol, dipentaerythritol, mannitol, or adducts of various glycol components listed above with ε-caprolactone can also be used. However, from the viewpoint of weather resistance of the coating film, good results can be obtained if neopentyl glycol is used in an amount of 30 mol % or more based on the total alcohol component.

Therefore, the above-mentioned alcohol components should be appropriately selected depending on the required performance of the final cured coating film.

In addition, alkyd resin 1. ! Typical fatty acids used in 1&l are octylic acid, palmitic acid, stearic acid, persatic acid, oleic acid, linoleic acid, lylunic acid, coconut oil fatty acid,
Hydrogenated coconut oil fatty acids, tall oil fatty acids, castor oil fatty acids,
Examples include long chain saturated or unsaturated basic acids of C6 or higher, such as dehydrated castor oil fatty acids, rice bran oil fatty acids, linseed oil fatty acids, soybean oil fatty acids, safflower oil fatty acids, etc., which are soluble in solvents. should be selected appropriately, taking into consideration the weather resistance and economic efficiency of the coating film.

In this way, the hydroxyl group-containing (alkyd resin, oil-free alkyd resin and/or urethane resin)
The polyester component used to prepare the condensation) polymers is used, but in addition to the above, polyester-forming components, each in the range of 40 to 90 mol % with respect to the total iK of the polybasic acid component and the total alcohol component, are used. So ε−
It is also possible to use a polyester component obtained by adding caprolactone, and in this case, a coating with excellent flexibility in the cured coating film can be obtained.

30 to 90 parts by weight of at least one selected from alkyd resins obtained by oxidation, oil-free alkyd resins, and urethane resins, and 70 parts by weight of the above aminoplast.
A mixture in a proportion of ~10 parts by weight can also be used as one of the film-forming components (A-1) or (A-2) to give satisfactory results.

In addition, the film-forming component containing the specific hydroxyl group-containing vinyl polymer listed above and the film-forming component consisting of the specific alkyd resin, oil-free alkyd resin, and/or urethane resin may be in any ratio. Mixture, that is, 9 is 500 to 8,000 and OHV is 40 to 250
A group consisting of at least one hydroxyl group-containing polymer of Nara hydroxyl group-containing vinyl polymers, an alkyd resin, an oil-free alkyd resin, and a urethane resin having a Ma of 200 to 3,000 and an OHV of 40 to 600. 30 to 9 of at least one hydroxyl group-containing polymer selected from
0 parts by weight and 70 to 70 parts of at least one aminoplast
A mixture in a proportion of 10 parts by weight can also be used as one of the film-forming components (A-1) or (A-2) to give satisfactory results.

63- Furthermore, 30 to 90 parts by weight of at least one hydroxyl group-containing polymer selected from the group consisting of hydroxyl group-containing vinyl polymers, alkyd resins, oil-free alkyd resins, and urethane resins listed above; A cocondensate obtained by combining aminoplus as mentioned above can also be used as a kind of film-forming component (A-1) or (A-2) to give satisfactory results.

Among the cocondensates obtained in this way at arbitrary ratios, the weight average molecular weight (Mw) measured by gas chromatography (GPC) is that of the mixture of reaction ingredients before the reaction, the hydroxyl group-containing It is desirable to use a cocondensate which exhibits an increase of 120 to 300%, preferably 150 to 250%, compared to a mixture of polymers and aminoplast.

Furthermore, such a cocondensate, at least one hydroxyl group-containing polymer selected from the group consisting of the above-mentioned hydroxyl group-containing vinyl polymers, algide resins, oil-free alkyd resins, and urethane resins, and aminoplast. A mixture of 1 nuclear film-forming component (A-1)
Alternatively, it can be used as (A-2) to give satisfactory results.

Next, as the above-mentioned pigments (B-1) or (B-2), any pigment that is normally used for paints can be used, but among them, the representative ones are: Examples include inorganic pigments such as titanium oxide and carbon black; organic pigments such as quinacridone, azo, and phthalocyanine; and metal powders such as aluminum powder, copper powder, and zinc powder.

These pigments can be used alone or as a mixture of two or more, and if the dispersibility of the pigment is poor, the pigment can be dispersed in advance using a suitable resin for pigment dispersion using a conventional method. It can be used in various forms such as serving.

Among them, the above-mentioned pigment stool (1) is used for colored paints.
'1-1) is used as the film-forming component (A
-1) It is appropriate to use the ratio of 4 to 470 heavy bone parts per 100 heavy bone parts.

On the other hand, since the top coat is usually used in the form of a clear paint, the use of these pigments is essential, but there is no problem in using the various pigments listed above as necessary. Instead, the pigment Q at that time (
The amount of B-2) used is as follows:
For 100 parts by weight of 2), the amount is at most 221 ridges.

In this way, in particular, using metal powders such as those mentioned above, 1.
In this case, the coating film obtained by the method of the present invention can be obtained as a so-called two-coat metallic coating film, and when inorganic and/or organic pigments are used, the coating film obtained by the method of the present invention can be obtained as a two-coat metallic coating film. A two-coat colored coating film with a beautiful appearance can be obtained.

Next, the above-mentioned fine particle polymers C) or (g))
are immiscible in the system consisting of the film-forming component (A-1), the pigments (B-1), and the solvents (D-1) as listed below, and are stable. It is not miscible with the dispersible polymers or the film-forming component (A-2) and the solvent Mi(1)-2) listed below, and cannot be stably dispersed. It is a synonym for polymers that can be used to make colored paints.
Pseudoplastic viscosity behavior is applied to each of the mixtures consisting of components A-1), (B-1) and (D-1), or the mixture consisting of (A-2) and (B-2) constituting the top coat. There is K added to give it.

37- Both of these above-mentioned mixtures exhibit substantially Newtonian (Eutonian) flow properties and have no yield value or a very small yield value, so that K
.

For example, when painting is carried out with the substrate vertical, or when baking is performed after such painting, sagging is likely to occur as the temperature rises over time, or the formation of each film in each mixture. sexual component (A-
Since the molecular weight of each (condensation) polymer in 1) or (A-2) is relatively small, various coating film defects such as 'repellent 1' tend to occur.

However, when the above-mentioned fine particle polymers (fc) or (scent) as shown below are added to each of the above two types of mixtures, the apparent viscosity when left still is Although it becomes larger, in cases where high shear stress is applied, such as during spraying, the viscosity becomes sufficiently small that spraying can be performed without the difficulty of installing separately. Moreover, structural viscosity is already developed several seconds or minutes after application to the base material, and coating film defects such as scratches 7 do not occur; therefore, the effect of preventing such coating film defects is sufficient. I will be working in

For the reasons mentioned above, the fine particle polymers (C1 and (El) may be the same thing or the same type, respectively, and can also be used to form a colored coating film obtained from a colored paint as a pace coat and a clear coat. Different types may be used depending on the required performance with respect to the clear coating film obtained by the top coating.

That is, the above (
It goes without saying that component E) preferably has a composition such that the cured coating film after baking becomes completely transparent.

Here, the fine particle polymers are as mentioned above.
Retained particle morphology in the seed mixture! , refers to polymers that can be stably dispersed, but this ``can be stably dispersed while retaining the shape of particles'' means that the polymer can be stably dispersed in the medium in which it is present. , the shape of the particles may be maintained due to the difference in polarity or affinity between the medium and the polymers, or the medium and the polymers may retain their shape due to the affinity between them. If the particles are easily soluble, such as in the case of strong particles, they may be chemically bonded to form a particle structure in such a medium through some chemical means.

Typical examples of the fine particle polymer [C1 or (g)) include inorganic ones such as powdered silica, low molecular weight polyolefin polymers, non-aqueous dispersible polymers, and aqueous polymers. There are organic types such as highly gelled fine particle polymers obtained by emulsion or aqueous suspension polymerization, but first of all, a representative example of powdered silica, which can also be called fine particle silica powder, is “Mizukasil P”.
-527Jll: Mizusawa Kagaku Kogyo ■Products], and as low molecular weight polyolefin polymers, those commonly known as paraffin waxes can be used without any particular problems, but among them, Examples include "Evolen C-16 Wax" (product of Eastman Co., Ltd., USA), "Hoechst Wax PE520 or PE130J (product of Hoechst Co., Ltd., West Germany),""Viscol 330-P, 550-P, 660-P, etc." T
Examples include "S-200" [Sanyo Chemical Industries ■ product].

Among these, non-aqueous dispersion type polymers and highly gelled fine particle polymers obtained by aqueous emulsion or suspension polymerization are particularly preferred in terms of effectiveness.

Here, non-aqueous dispersion type polymers include, for example, in an aliphatic group and/or alicyclic hydrocarbon solvent, a segment that is soluble in the solvent and an insoluble segment that is swellable. The polymer is insoluble in the solvent, but the monomer is soluble in the presence of a dispersion stabilizer (hereinafter, these are abbreviated as core monomers), and , by chemically or physically bonding to the dispersion stabilizer as described above,
This refers to polymers having a particle shape that can be stably dispersed in the solvent, and the preparation of such non-aqueous dispersible polymers is
The analogy is made as follows.

First, suitable solvents are those that are non-polar or have relatively low dissolving power, and do not dissolve the polymer produced from the core monomers, but dissolve or swell the dispersion stabilizer.

Typical such solvents include hexane, heptane,
42- Aliphatic hydrocarbons such as octane; alicyclic hydrocarbons such as petroleum benzene, ligroin, mineral spirits, petroleum naphtha, kerosene, boiling points of 30 to 30 b, methylcyclohexane, ethylcyclohexane; and There are various mixtures.

In some cases, the aliphatic hydrocarbons listed herein,
Hydrocarbon mixtures and/or alicyclic hydrocarbons, aromatic hydrocarbons, esters, alcohols, ethers or ketones, up to about 70% of the total solvent amount. It is best to use a system that includes polar compounds.

The amount of such solvents used is such that the solid content of the resulting non-aqueous dispersion type resin is 30 to 70% by weight, preferably 40 to 6% by weight.
A suitable range is such that the content is 0% by weight.

Furthermore, typical dispersion stabilizers include those listed below.

■ Graft copolymers obtained by polymerizing unsaturated bond-containing polymers such as polybutadiene and polyisoprene with one or more of the core monomers listed below, and such unsaturated bond-containing polymers. Unsaturated bond-containing graft copolymers obtained by graft copolymerizing nuclear monomers and (meth)acrylic acid to the copolymer, and then adding glycidyl (meth)acrylate to the carboxyl group of this copolymer, ■ Alkyd resins, alkyl etherified melamine resin condensates etherified with alkyl alcohols of 0 C4 to CI2 and soluble in the solvents listed above, ■ such as 12-hydroxystearic acid. An epoxy compound containing an unsaturated bond such as glycidyl (meth)acrylate is added to the carboxyl group at the end of a self-condensed polyester resin of a hydroxyl group-containing saturated fatty acid, and then nuclear monomers are added to the resulting polyester resin containing a terminal unsaturated bond. Graft copolymers obtained by polymerizing one or more types, and graft copolymers obtained by copolymerizing this terminal unsaturated bond-containing polyester resin, core monomers, and (meth)acrylic acid. Unsaturated bond-containing graft copolymers obtained by addition-reacting an unsaturated bond-containing epoxy compound to the combined carboxyl group, or ■
n-butyl (meth)acrylate, 1so-butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, lauryl (meth)acrylate, stearyl (
The main component is an alkyl ester ester of (meth)acrylic acid esterified with an alkyl alcohol of C3 or higher, such as meth)acrylate, and 1-1 (co)polymerization of other vinyl monomers as necessary. Obtained (co)polymers;
Mainly composed of an alkyl ester of (meth)acrylic acid esterified with the alkyl alcohol of C4 or higher listed above, copolymerized with (meth)acrylic acid and other vinyl monomers as necessary, and then obtained. Unsaturated bond-containing copolymers obtained by adding an unsaturated bond-containing epoxy compound to the carboxyl group of a copolymer; this unsaturated bond-containing copolymer and one or more core monomers; Graft copolymers obtained by copolymerizing the above-mentioned unsaturated bond-containing copolymers, supranuclear Tsumers, and (meth)acrylic acid, and then carboxyl of the obtained graft copolymer. These include unsaturated bond-containing graft copolymers obtained by addition-reacting an unsaturated bond-containing epoxy compound to a base.

46- Among these, each of the dispersion stabilizers in the ■ and 0 groups, and the alkyl esters of (meth)acrylic acid esterified with an alkyl alcohol of s C4 or higher in the dispersion stabilizers of the 0 group, respectively. When using a (co)polymer as the main component or an unsaturated bond-containing copolymer derived from the (co)polymer as a dispersion stabilizer, these dispersion stabilizers Although none of them have segments that are insoluble in the solvents mentioned above, the core monomers that are used in the subsequent preparation of non-aqueous dispersion type polymers using these types of dispersion stabilizers At the initial stage of polymerization, segments insoluble in solvents as mentioned above are formed, and the desired non-aqueous dispersible polymers are obtained.

Here, typical nuclear monomers include:
Hydroxyalkyl esters of (meth)acrylic acid, unsaturated bond-containing hydroxyalkyl ester monocarboxes, as described above, used in preparing the film-forming component (A-1) or (A-2). Acids, unsaturated bond-containing polyhydroxyalkyl esters, C1
-C8 (meth)acrylic acid alkyl esters of alcohols include cyano group-containing monomers, while other typical monomers copolymerizable with such core monomers include , (meth)acrylic acid alkyl esters of alcohols of 04 or more, unsaturated dicarbonate, etc. used in preparing the film-forming component (A-1> or (A-2)). Acid dialkyl esters, perfluoroalkyl group-containing vinyl esters, α-olefins, aromatic vinyl monomers, vinyl halides (vinylidene), acid anhydride group-containing monomers, carboxylic acid amide group-containing monomers, sulfones Examples thereof include acid amide group-containing monomers, tertiary amino group-containing monomers, phosphoric acid ester bond-containing monomers, sulfonic acid group-containing monomers, and organic amine salts thereof.

In carrying out the method of the present invention, the fine particle polymers (
C) or (El is used as an essential component of colored paints or top coats, respectively, but dispersion stabilizers used in the preparation of non-aqueous dispersible polymers among the fine particle polymers (C1 or CFJl) In addition to various dispersion stabilizers such as ■, ■, [stock] and ■, which have been promoted as above, we also introduce hydrolyzable silyl groups into these various dispersion stabilizers ■～■. , or the bonds between the segments soluble and insoluble in the above-mentioned solvents in the various dispersion stabilizers named ■, [stock] and Those caused by reaction with reactive groups, etc.
When carrying out the method of the present invention, the fine particle polymers (C
The present inventors have discovered that 1a49- or (E) and 1- are extremely effective, thereby further expanding the usefulness of the present invention.

Such a hydrolyzable silyl group-containing dispersion stabilizer can be prepared, for example, from 1 to 1 as follows.

That is, the main component is an alkyl ester of (meth)acrylic acid esterified with a C4 alkyl alcohol indicated by a final square, and this and r-(meth)acryloyloxypropyltrimethoxysilane, r-(
Meta)acryloyloxypropyltriethoxysilane, rCmeth)acryloyloxyglovylmethyldimethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, vinyltripropoxysilane, vinylmethyljethoxysilane, vinyl (β-methoxyethoxy)silane or It is a method of copolymerizing one or more hydrolyzable silyl group-containing monomers such as allyltrimethoxysilane with other copolymerizable monomers, or The obtained copolymer is copolymerized with a monomer having a group capable of reacting with a hydrolyzable silyl group, such as a hydroxyl group or a carboxyl group, and one or more of the above-mentioned core monomers to obtain a graft copolymer. There are various methods for making polymers, and there are also various variations based on the method (2) of deterioration.

Among these methods, when preparing a dispersion stabilizer by the former method, a monomer having a group capable of reacting with a hydrolyzable silyl group, such as a carboxyl group or a hydroxyl group, participates in the bonding of the grafting point. In this sense, it is essential to use, as core monomers, monomers having groups that can react with such hydrolyzable silyl groups.

In addition, the non-aqueous dispersion type polymers obtained in this manner can be mixed with film-forming components (A-1') and pigments (B-1') as mentioned above.
1) and solvents (D-1) or in the mixture of film-forming component (A-2) and solvents (D-2), such non-aqueous dispersible heavy The polymers can be used as they are as the particulate polymers, but if they are dissolved in the respective mixtures of the upper rudders,
It is necessary to provide a structure that can maintain the particles of these non-aqueous dispersible polymers, and to do so, it is necessary to intramolecularly crosslink the core portion of these non-aqueous dispersible polymers. It is.

K, which performs intramolecular crosslinking, can be obtained by using a monomer pair ' having two types of functional groups that can react with each other in combination with the above-mentioned nuclear monomers, or by using two or more (α,
A method can be adopted in which a vinyl monomer having a β-ethylenically unsaturated bond, that is, a polyfunctional vinyl monomer, is used in combination with nuclear monomers. Typical examples of pairs of monomers with two types of functional groups that can react include glycidyl (meth), an example of an epoxy group and a carboxyl group.
An example of an acrylate and (meth)acrylic acid, an acid anhydride group and a hydroxyl group is maleic anhydride and β-hydroxyethyl (meth)acrylate, and an example of an isocyanate group and a hydroxyl group is β-isocyanateethyl (meth)acrylate. ) Examples of isocyanate groups and amino groups in acrylate and β-hydroxyethyl (meth)acrylate include hydroxyl groups and methylol groups in β-incyanate ethyl (meth)acrylate and allylamine; Examples include β-hydroxyethyl (meth)acrylate and n-butyl etherified N-methylol (meth)acrylamide, and examples of hydrolyzable silyl groups and hydroxyl groups include r-(meth)acryloyloxypropyltrimethoxy. Silane and β-hydroxyethyl (meth)
Examples of combinations of hydrolyzable silyl groups and carboxyl groups with acrylates include shrinkage combinations of γ-(meth)acryloyloxypropyltrimethoxysilane and (meth)acrylic acid; As examples of the groups, two types may be appropriately selected from among the various hydrolyzable silyl group-containing monomers listed above.

These two types of monomers can be reacted with some of the above-mentioned core monomers at the same time as the non-aqueous dispersion polymerization, or they can be reacted by raising the temperature at the end of the non-aqueous dispersion polymerization. Intra-molecular cross-linking may be carried out by reacting in the presence of known and commonly used catalysts to promote the reaction.

On the other hand, in the case of the latter intramolecular crosslinking method in which a polyfunctional vinyl monomer is used in combination with core monomers, K, as in the former method, is used in combination with a polyfunctional vinyl monomer as one of the core monomers. By polymerizing as a part,
Non-water ~54- A crosslinked structure can be provided in the dispersed polymers.

In carrying out the method of the present invention, the fine particle polymer uf
cl or (g)) includes the film-forming component (A-1) described above in both the dispersion stabilizer and the core monomers.
It is particularly preferable to use non-aqueous dispersible polymers into which the same kind of functional group, ie, hydroxyl group, that can react with the aminoplast used in the preparation of 1) or (A-2) is introduced.

This means that when the colored paint or top coat used for carrying out the method of the present invention is applied to form a cured film, the dispersion stabilizer portion also becomes a non-aqueous dispersible polymer. The core part also contains a curing agent (curing resin)
This is because a uniform and highly transparent coating film can be obtained by reacting with.

As mentioned above, in order to prepare such non-aqueous dispersible polymers, the dispersion stabilizer and the core monomers may be polymerized in the presence of the solvents listed above. In this case, a polymerization initiator such as those mentioned above and, if necessary, a linkage transfer agent can be used.

In carrying out the method of the present invention, highly gelling fine particulate polymers such as those obtained by aqueous emulsion or aqueous suspension polymerization can be used as the particulate polymers (C1 or (El).

Even in solvents with high polymer dissolving power such as toluene and ethyl acetate, such highly gelled fine particle polymers can be dissolved.
A resin solution or dispersion containing a solvent that is substantially non-swellable, non-fusing, and has a high dissolving power (
binder resin) K is added, without increasing the viscosity of such a resin (solution) dispersion, with a high resin content,
It is possible to obtain a solid dispersion, and after drying, the added resin solution together with the dispersion (binder resin) forms a solid resin composition. It can be defined as particulate polymers with a high degree of crosslinking density, capable of

Examples of methods for preparing such highly gelled fine particle polymers include the following.

That is, 5 to 100% by weight of polyfunctional monomers and 95 to 100% of monofunctional monomers, i.e., monomers having one (α,β-ethylenically) unsaturated bond in the molecule, one or more organic and/or inorganic radical polymerization initiators having a half-life of 3 hours or less at a temperature of less than 100°C, that is, a low-temperature decomposition type initiator;
Using an organic radical polymerization initiator with a half-life of 3 hours at a temperature of 0"C, that is, one or more types of high-temperature decomposition type initiators, an aqueous emulsion or Polymerization is carried out in a suspension state, preferably 60 to 99 mol % of the unsaturated 57-bonds are reacted, and then 10
There is a method of carrying out additional polymerization at a temperature of 0 to 250 DEG C. and then polymerizing the remaining seven polymers, that is, accelerating the polymerization and improving the polymerization rate.

Here, typical polyfunctional monomers include ethylene glycol di(meth)acrylate, oligoethylene glycol di(meth)acrylate having a total carbon number of 10 to 28, brobylene glycol di(vine) acrylate, and Poly(meth)acrylates of polyhydric alcohols such as methylolethane tri(meth)acrylate, trimethylolpropane tri(meth)acrylate, glycerin tri(meth)acrylate, and pentaerythritol tetra(meth)acrylate; diallyl succinate, diallyl phthalate , triallyl isocyanurate; divinylbenzene, dicyclopentenyl (meth)acrylate, butadiene, pentagene, isoprene or chloroprene, among others divinylbenzene, dicyclopentenyl (
Suitable are meth)acrylates, triallylisocyanurate or poly(meth)acrylates of polyhydric alcohols.

Further, as the monofunctional monomer, monomers used in preparing the above-mentioned hydroxyl group-containing polymers can be used as they are.

On the other hand, low-temperature decomposition type initiators include inorganic compounds such as potassium persulfate, ammonium persulfate or hydrogen peroxide, or acetyl peroxide, propionyl peroxide, lIO-butyryl peroxide, benzoyl peroxide, tert-butyl peroxide. Typical examples of octoatemata are organic compounds such as azobis-IIIO-butyronitrile, and examples of high-temperature decomposition type initiators include tart-butyl hydroperoxide, tart-butylcumyl peroxide, and tert-butyl peroxide. benzoate, gite
Typical examples include organic compounds such as rt-butyl peroxide, dicumyl peroxide, and cumene hydroperoxide.

If the method as proposed for the preparation of the highly gelled fine particle polymers is followed, the polymerization reaction in the first step will be 2
Since the process is carried out under relatively mild conditions at a temperature of 0° C. or more and less than 100° C., an aqueous emulsion or aqueous suspension can be prepared in good yield even if a large amount of the above-mentioned polyfunctional monomer is used.

In the first-stage polymerization reaction, various known and commonly used emulsifiers and dispersing agents can be used as appropriate.

The second stage reaction following the first stage reaction is 100 to 25
It is a continuation of the polymerization reaction in the first stage, and it is an acceleration of the first stage polymerization. or under pressure, or in air or inert gas,
For example, the reaction may be carried out in either nitrogen gas or carbon dioxide gas, but in order to carry out the reaction in such air or inert gas, instead of the second stage reaction, after the first stage reaction is completed, The resulting aqueous emulsion or suspension may be separated, if necessary, in the form of a solid by known and customary physical or chemical means, in addition to drying the solid in a subsequent drying step. The polymerization reaction in the second stage may be completed integrally with the polymerization reaction in the second stage, and by doing so, the same reaction as in the case where the reaction in the second stage is carried out subsequent to the reaction in the first stage is achieved. Get results.

Since particles of the highly gelled fine particle polymers thus obtained have already been formed in the first stage polymerization reaction, the second stage polymerization reaction or alternative method such as the one described above can be used. In any case of the polymerization reaction in the drying step carried out in an inert gas, agglomeration (block formation) due to reaction between fine particles does not occur.

Thus, highly gelled particulate aggregates in aqueous emulsions or suspensions obtained after various modes of polymerization can be produced by physical or chemical processes such as evaporation or azeotropy of water, or precipitation or agglomeration of polymers (particles). Alternatively, the various weights in the respective paints used in carrying out the method of the present invention can be separated by physical or chemical means. In the presence of resins and/or organic solvents other than the polymers, the medium for the desired high-gelling fine-particle polymers is directly mixed with water to form the resins and/or the polymers. It can also be replaced with organic solvents.

62- The highly gelled fine particulate polymers obtained in this manner may be separated from the solids from the aqueous emulsion or suspension as described above, or treated with other resins, organic solvents, or water. The presence rate of particles with a particle size of 30 μm or more is 1% by weight or less in a medium such as
Moreover, the weight average particle diameter is 20 μm or less, preferably 10 μm or less.
It is extremely easy to pulverize the particles to a size of μm or less.

When the particle distribution of the highly gelling fine particle polymers is adjusted so that the abundance of particles having particles of 30 μm or more is 1% by weight or more, or the weight average particle size is 20 μm or more. It is no longer possible to prepare a paint that gives a smooth painted surface.

In addition, the refractive index (nA') of the fine particle polymers [)β or (El) at 25°C is 1.45 to 165.
Between the fine particle polymers and another resin to be used in combination with the polymers,
When such refractive indices are mutually equal, a transparent coating can be provided.

The amount of the above-mentioned fine particle polymers or odor used is 0.1 to 1.0% per 100 parts by weight of the film-forming component (A-1) or (A-2).
A ratio of 001ti parts is appropriate.

Next, as the solvent #1 (D-1) or (D-2), the film-forming component (A-1) and the pigment Th (B-
1) or the film-forming component (A, -
2) as long as it can be dissolved or stably dispersed,
Any of these may be used; for example, solvents such as those used in preparing P]ff coating film cedar coating forming component 1) or (A-2) can be used, and one or more such solvents may be used. It can be used as a mixture of

Depending on the amount of the solvent (D-1) or (D-2) used or the mixed composition ratio as a mixed bath agent, depending on the method of application such as spraying, etc., and the temperature of the paint at the time of spraying, baking will occur. It should be determined appropriately according to the baking conditions such as temperature and time.

Colored paints or top coats can be prepared by mixing the components described above in a conventional manner.These colored paints or top coats used in carrying out the method of the present invention In addition to the above-mentioned essential components, K also contains curing catalysts, various resins, fluidity regulators,
Conventional amounts of known and commonly used additives commonly used for paints, such as color separation inhibitors, antioxidants, ultraviolet absorbers, and/or silane coupling agents, can be added.

Among them, representative resins include nitrocellulose, cellulose acetate phthalate resin, petroleum resin, and ketone resin, and representative silane coupling agents include r -Aminopropyltrimethoxysilane, r-glycidoxyglobiltrimethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane or r-mercaptoglobiltrimethoxysilane, etc., and typical curing catalysts K is 1 Beckamin P-198J [Dainippon Ink & Chemicals Product] or [Nicure 155.2500X
, X49-110.3525 or 5225J (product of King Company, USA).

The amounts of these various additive components to be used should be appropriately determined depending on the baking temperature and baking time when a colored paint or top coat is used when carrying out the method of the present invention.

Thus, by mixing each of the above-mentioned essential components and the above-mentioned various additive components added as necessary by a conventional method, and further adding or subtracting the solvent a (D-1) or (D-2), the desired composition can be obtained. The colored paint or top coat used in carrying out the method of the present invention can be obtained by adjusting the coating viscosity to .

Next, the colored paint is applied onto the base material, and after a setting time of several minutes if necessary, a top coat is applied.

66- Thereafter, if necessary, setting may be performed for a further several minutes to several tens of minutes to bake and harden.

The baking conditions at this time are 60-180℃ and 10-100℃.
A period of 40 minutes is appropriate, and in this way a cured coating film as a two-coat colored coating film, which is the object of the present invention, can be obtained.

The thickness of the colored coating film at this time should be the minimum required to completely hide the base material, and is usually 15 to 20 mm thick.
The minimum required film-forming lid is 10 μm or less, and preferably 10 μm or less.
~12 μm or less is appropriate, and on the other hand, the final cured film thickness of the top coat is usually 30 μm or less.
A suitable thickness is at least .mu.m, preferably about 40 to 60 .mu.m.

Thus, the method of the present invention can be applied to various types of coatings, typified by automobile coatings, and can therefore be applied to a wide range of substrates to be coated, from general metals to plastics.

Next, the present invention will be specifically explained using reference examples, working examples, and comparative examples. ill standard.

Reference Example 1 (Example of Preparation of Polymers Containing Hydroxyl Groups) In a reactor equipped with a stirring device, a thermometer, a nitrogen inlet tube, and a reflux condenser,
160 parts of xylene and 160 parts of n-furinol were charged, and the temperature was raised to 125°C in a nitrogen atmosphere.
(120 parts of styrene, 18 parts of n-butyl acrylate)
0 parts, 120 parts of n-butyl methacrylate, 108 parts of β-hydroxypropyl acrylate, 66 parts of β-hydroxypropyl methacrylate and 6 parts of acrylic acid, 80 parts of n-butanol, tart-butylbaroxyoc A mixture consisting of 48BIS of Tate, 3 parts of di-tert-butyl peroxide, and 12 parts of azobis-1go-butyronitrile was added dropwise over 8 hours, and the reaction was continued by maintaining the same temperature for 15 hours after the dropwise addition was completed. The non-volatile content (NN/) is 60%, Gardner color (G, C,) less than 1, 25℃ 1711
J, -Kel cartoner viscosity (G, Vl s,) KaE
A solution of the desired polymer having an Mn of 3,000 and a T7 of 0° C. was obtained, but the OHV per solid content was 109. Hereinafter, this will be referred to as polymer fA(a
It is abbreviated as the solution of -1).

Reference Example 2 (same as above) Monomer composition: 120 parts of styrene, 9 parts of methyl methacrylate, 120 parts of n-butyl methacrylate, 114 parts of n-butyl acrylate, 90 parts of β-hydroxyglobyl acrylate, β- A solution of the desired polymer was obtained in the same manner as in Reference Example 1, except that 60 parts of hydroxypropyl methacrylate and 6 parts of acrylic acid were used. NY of this is 60%, G, C9 is less than 1, G
, Via,) If, Mo was 5,000, and T was 20°C. Moreover, the OHV per solid content of this product was 94. Hereinafter, this will be referred to as polymers (a-2
) solution.

-69= Reference Example 3 (both) 215 parts of adipic acid and 638 mol% of the total polybasic acid components were added to a reactor equipped with a stirring device, a thermometer, a 9-element introduction tube, and a reaction product water distillation tube. 400 parts of hegisahydrophthalic anhydride and 4 tsil of trimethylolpropane
+, 39 parts of neopentyl glycol corresponding to 50 parts of ethylene glycol and 767 mol% of the total alcohol content
The temperature was gradually raised in a trench at 230°C over 5 hours in a stream of 9 elements, and the temperature was maintained until the acid value reached 10, resulting in an OHV of 111 and a Mn of 1. ．． f']1
0 oil-free alkyd resin? :Obtained.

Next, this resin is heated to below 100℃? Then, 250 parts of xylene was added to obtain an oil-free alkyd resin solution containing 80% NY. Hereinafter, this will be referred to as polymers (a-3
) solution.

70- Reference Example 4 (same as above) In a polyester reactor similar to Reference Example 3, 83.2 parts of adipic acid and 400 parts of hexahydrophthalic anhydride corresponding to 82 mol% of the total polybasic acid components, and trimethylolpropane were added. 61.1 parts of and 90 parts of total alcohol content
426 parts of neopentyl glycol corresponding to mol% was charged, the temperature was gradually raised to 230°C over 5 hours in a nitrogen atmosphere, and the temperature was maintained until the acid value reached 10 to obtain an oil-free alkyd resin. I got it.

Next, this resin was cooled to below 100°C, 250 parts of xylene and 0.1 part of dibutyltin dilaurate were added, the temperature was raised to 65°C, and while maintaining the same temperature, 100 parts of hexamethylene diisocyanate was added. , while being careful of fever 2
It was dripped gradually over time.

After completion of the dropwise addition, the solution was kept at the same temperature for 2 hours and then at 80° C. for 1 hour to obtain a partially urethanized oil-free alkyd resin solution with an NV of 80%. The OHV of this item is 1
18, and Mn was 1.070. Hereinafter, this will be abbreviated as a solution of polymers (a-4).

Reference Example 5 (same as above) Adipine f was added to the same polyester reaction apparatus as Reference Example 3.
157.4 parts of jl and 300 parts of hexahydrophthalic anhydride representing 64.4 mol% of the total polybasic acid component, and 203.8 parts of trimethylolpropane and neopentyl glycol representing 59 mol% of the total alcohol component. 2
30 parts of coconut oil and 200 parts of coconut oil fatty acid were charged, and the temperature was gradually raised at 2300 G over a period of 5 hours in a nitrogen atmosphere.
An alkyd resin was obtained by holding the reaction at the same temperature until the acid value reached 10.
Cool to below ℃, add 250 parts of xylene until the NV is 80
% alkyd resin solution.

The solid content of this product is C) HV of 125, and Mn is 1.
,140. Hereinafter, this will be abbreviated as a solution of polymers (a-5).

Reference Example 6 (same as above) In a reactor similar to Reference Example 1, 134ffli (1 mol) of trimethylolpropane and 68% of ε-caprolactone were added.
4 parts (6 mol) and 0.04 part of tetrabutyl titanate were charged, the temperature was raised to 180°C, and the temperature was maintained for 10 hours to obtain a lactone-added polyester resin.

This product had a NY of 100%, a GVis of X, an OHV of 206, and a VIN of 820. Hereinafter, these will be abbreviated as polymers (a-6).

Reference Example 7 [Example of Preparation of Film-Forming Component (A-1)] In a reactor similar to Reference Example 1, the polymers obtained in Reference Example 2 (a
-2) 100 parts of the solution and [Sumi? -Le M-100CJ
73- [Hexamethquine methylmelamine manufactured by Sumitomo Chemical Industries;
NV=100%] and 60 copies of “Herakami 7P-198
0.2 part of J [reaction accelerator manufactured by Inu Nippon Ink Chemical Industry ■; active ingredient - 100%] was added and mixed well.
At this time, the viW between the resin solid contents was 3,600.

Next, the mixture was heated to 100°C and maintained at the same temperature for 2 hours to form a 75% solution of a cocondensate of hexamethoxymethylmelamine and monomer fi(a-2), that is, a hydroxyl group-containing vinyl polymer. I got it. Hereinafter, this will be referred to as the film-forming component (A-1-1), and this is M
w was 6,600.

Reference Example 8 [Preparation of film-forming component (A-2)] Except that the same amount of polymers (a-1) was used instead of polymers (a-2). A film-forming component (A-1-2) was obtained in the same manner as in Example 7.

74- The NV of this product was 75%, and the change in molecular weight before and after the cocondensation reaction in this example was that the Mw at the time of mixing, that is, before the reaction, was 3,000, but 1 Mw in the reaction was 5,800. It became.

Reference Example 9 (Example of Preparation of Particulate Polymers) 1.800 parts of 12-hydroxystearic acid was charged into a reactor equipped with a stirrer, a thermometer, a cooling tube, and a nitrogen introduction tube, and the mixture was heated at 220° C. Esterification was carried out by heating.

During this temperature rise, 12-hydrostearic acid begins to melt when the temperature reaches 72°C or higher, so stirring is started at the same time as melting.

At about 190°C, water began to flow out, and esterification proceeded until the acid value reached about 38. After reacting for about 7 hours, it was cooled and taken out.

The self-condensed polyester of 12-hydroxystearic acid obtained here has an NV of 100% and a G and Vis of 2. And G and C9 were 16. Hereinafter, this will be abbreviated as intermediate (b-1).

Next, this intermediate (b-
1), 330.5 parts of n-butyl acetate, 46 parts of glycidyl methacrylate equivalent to the carboxyl group in this intermediate (b-1), 1 part of 2-methylimidazole, and hydroquinone. Prepare 1 part of 13
Glycidyl methacrylate-1-intermediate (b-
1), but this reaction may be carried out by monitoring the acid value.

The terminal unsaturated bond-containing polyester thus obtained is N
V is 60%, G, Vis, is A1, G, C, is 16,
and a solution with an acid value of 1 or less. Hereinafter, this will be abbreviated as intermediate (b-2).

Separately, in a reactor similar to Reference Example 1, “Aitsuno (-E)”
The temperature was raised to 105°C, and at the same temperature, 167 parts of intermediate (b-2) and 4 parts of methyl methacrylate were charged.
75 parts, 25 parts of acrylic acid, 305 parts of toluene, t
45 parts of ert -butyl peroxyoctoate, t
A mixture consisting of 0.8 parts of ert-butylperoxybenzoate and 0.9 parts of azobis-1so-butyronitrile was added dropwise over a total of 4 hours. Immediately after the addition was completed, the temperature was raised to 110°C, and the temperature was kept at the same temperature for 10 minutes. After holding for a period of time, a 35% solution of the dispersion stabilizer was obtained.

In this case, G, Vi m, is A, and G, C, is 1
The solution was 1.

Separately, in a reactor similar to Reference Example 1, [iso/<
- 200.2 parts of E J was charged and the temperature was raised to 100°C,
At the same temperature, 1677 parts of methyl methacrylate, 104.8 parts of ethyl acrylate, 77-699 parts of β-hydroxyethyl methacrylate, 3'5 parts of glycidyl methacrylate, 37 parts of methacrylic acid, 34 parts of azobis-1so-butyronitrile, and 695 parts of the above dispersion stabilizer and 2-
A mixture consisting of 0.7 parts of methylimidazole and 331.7 parts of "Isopar E" was added dropwise over 8 hours.
- Subsequently, the mixture was reacted at the same temperature for 10 hours to obtain a desired dispersion of polymer fine particles.

This dispersion has an NV of 45%, G, Vi [1, and A
It had a white color. Hereinafter, this will be abbreviated as fine particle polymers (E/C-1).

Reference Example 10 (same as above) Into a reactor similar to Reference Example 1, 170 parts of Isopar EJ (an aliphatic hydrocarbon mixture manufactured by Exxon, USA) and 67.5 parts of n-butanol were charged and heated to 110°C. The temperature was raised, and at the same temperature, 46 of 2-ethylhexyl acrylate was added.
5 parts of β78-hydroxypropyl acrylate and 10 parts of γ-
Methacryloyloxypropyltrimethoxysilane 2
5 parts and 5 parts of tert-butyl peroxyoctoate.
parts, 2.5 parts of tart-butyl peroxybenzoate
and 100 parts of "Aitzuba-E" were added dropwise over a period of 4 hours, and even after the addition was completed, the same temperature was maintained for 10 hours to cause a reaction, thereby obtaining a 60% solution of the dispersion stabilizer. This one is G, Vi a, is A, and G, C0
was less than 1.

Separately, 166.7 parts of this dispersion stabilizer solution and 400 parts of "Isopar E" were charged into the same reactor as in Reference Example 1, and the temperature was raised to 90°C in a nitrogen atmosphere and maintained at the same temperature. 360 parts of methyl methacrylate, 360 parts of ethyl acrylate, 153 parts of β-hydroxyethyl acrylate, 9 parts of glycidyl methacrylate, 18 parts of acrylic acid, 3 parts of tetrabutyl titanate, 2
- 1 part of methylimidazole, 20 parts of "Isopar E"
A mixture of 0 part and 135 parts of tert-butylperoxyoctoate was added dropwise over 4 hours, and the same temperature was maintained for 10 hours after the dropwise addition was completed to react, resulting in a dispersion of polymer particles with an NV of 60%. I got it. Hereinafter, this will be abbreviated as fine particle polymer a (C/E-2'), and this was a white dispersion with G, Vill, and A.

Reference Example 11 (same as above) According to the raw material composition shown in Table 1, mixture (a) was stirred in a reactor, heated to 75°C, and 60 minutes after adding 1/20 of mixture (b). After 60 minutes, 19720% of mixture (c) and 5% of mixture (c) were added dropwise over a total of 3 hours.

Immediately after dropping, add 1A of the mixture (・→) and heat to 80°C.
After stirring and maintaining for an hour, the temperature was raised to 160° C. in a closed state, and stirring was continued at the same temperature for 6 hours to terminate the crosslinking reaction.

Next, the emulsion thus obtained was cooled to 30°C, passed through a 200-mesh P cloth, and dried at 100°C with stirring.

After that, the aggregates of the produced polymer particles were pulverized using a supersonic jet mill manufactured by Nippon Pneumatics Industries, Ltd., until the particle size was 1.
The distribution of particles larger than 0 μm is 0.1% or less, and the LEEDs & N0
The weight average particle diameter measured using [Microtrac STD type 7991-[]J manufactured by RTHRUP) is 6.9 μm, and n25 measured using an Atsabe refractometer type ■ manufactured by Atago. was 1.51, and a crosslinking point density of 1.5 x 10-' mol/I was obtained by measuring the absorbance of vinyl groups using an infrared spectrophotometer. Hereinafter, this will be referred to as fine particle polymers (C
/E-3) was obtained.

81- Table 1 * Polyoxyethylene nonylphenyl ether manufactured by Kao Soap ■ ** Polyoxyethylene dodecylphenyl ether @tie ester ammonium manufactured by Daiichi Kogyo Seiyaku ■ *** Polyoxyethylene dodecylphenyl ether manufactured by Kao Soap ■ Sodium sulfate ester 82- Examples 1 to 16 and Comparative Examples 1 to 9 Polymers (a-1) to (a-6) obtained in Reference Examples 1 to 6
) and “Sumimar M-100” as an aminoplast.
The co-condensate obtained in Reference Example 7 or 8 [film-forming component (A -1-1) or (A to 1-2)) as a film-forming component, while the fine particle polymers (C/E-1) to (C/E-3) obtained in Reference Examples 9 to 11 were used as film-forming components. ) and a curing catalyst, and if necessary pigments, these components are made into a paint in the proportions shown in Tables 2 and 3 to form a colored paint stock solution and a curing catalyst, respectively. A top coat stock solution was obtained.

However, in the case of the comparative example, no particulate polymers were used.

After that, the solvents (D-1) and (D-2) were combined with the solvent FL, and a) Luene/xylene/ethyl acetate/cellosolve acetate = 40/2 [1/20/20 (weighted) and Relpetsuso 100J (Aromatic hydrocarbon mixing power manufactured by Exxon, USA)/n-Furinol-70730 (
Both paints were obtained by adjusting the spray viscosity with diluted thinner (mold ratio).

Next, one of the colored paints was spray-painted on a mild steel plate with a thickness of 88 mm to a dry film thickness of about 10 μm, allowed to set for 5 minutes, and then the other top coat was applied to a mild steel plate with a dry film thickness of about 10 μm. Spray paint so that the thickness is about 55 μm, let it set for 30 minutes, and then apply 140 μm.
Bake at ℃ for 30 minutes.

The finished state of the coating film surface of each cured coating thus obtained was evaluated and the results are shown in the same table.

JP-A-Sho GO-241970 (25) →←

Claims (1)

[Claims] 1. 100 parts by weight of (A-1) film-forming component as an essential component on the substrate. (B-1) 4 to 470 ff&' parts of pigments, (C) a system consisting of the above film-forming component (A-1), pigments (B-1), and the following solvents (D-1); A colored paint comprising 01 to 100 parts by weight of immiscible and stably dispersible particulate polymers and an appropriate amount of (D-1) solvents is applied, and then (A-2)
100 parts by weight of the film-forming component, (El) A fine particle polymer that is immiscible in the system consisting of the above film-forming component (A-2) and the following solvents (D-2) and can be stably dispersed. 0.1 to 100 parts by weight of the above-mentioned compounds and an appropriate amount of (D-2) solvents as essential components, and further contains at most 22 parts by weight of (B-2) pigments based on the required pressure. A method for forming a two-coat colored coating film, characterized by applying a top coat and then baking at a temperature range of 60 to 180°C. 2. The film-forming component (A-1) is ,500~a,o
30 to 9 of hydroxyl group-containing vinyl polymers having a number average molecular weight of oo and a hydroxyl value of 40 to 250
2. The method according to claim 1, wherein the mixture comprises 70 to 10 parts by weight of aminoplast and 70 to 10 parts by weight of aminoplast. 3. The film-forming component (A-1) is 200 to 3.0
At least one hydroxyl group-containing polymer selected from the group consisting of alkyd resins, oil-free alkyd resins and urethane resins, having a number average molecular weight of 0.00 and a hydroxyl value of 40 to 600. 2. A method according to claim 1, characterized in that the mixture is comprised of ~90 parts in bulk and 70 to 10 parts in bulk of aminoplast. 4 The film-forming component (A-1) is 500 to 8,0
Hydroxyl group-containing vinyl polymers having a number average molecular weight of 0.00 and a hydroxyl value of 40 to 250;
30 to 90 parts by weight of a mixture of at least one hydroxyl group-containing polymer selected from the group consisting of alkyd resins, oil-free alkyd resins, and urethane resins having a hydroxyl value of 0 to 60; and 70 to 90 parts by weight of aminoplast. 10
The method according to claim 1, characterized in that it is a mixture consisting of parts by weight. 5. The film-forming component (A-1) is 500 to 8,0
Hydroxyl group-containing vinyl polymer m having a number average molecular weight of 00 and a hydroxyl value of 40 to 250, 200-
has a number average molecular weight of 3,000 and 40 to 600
A cocondensate of 30 to 9 OHi parts of at least one hydroxyl group-containing polymer selected from the group consisting of alkyd resins, oil-free alkyd resins, and urethane resins having a hydroxyl value of 70 to 10 parts by weight of aminoplast. The method according to claim 1, characterized in that: 6. Above; Film-forming component (A-2), 500-8
．． 30 of hydroxyl group-containing vinyl thread polymers having a number average molecular weight of 000 and a hydroxyl value of 40 to 250
90 parts by weight of aminoplast and 70 to 10 parts by weight of aminoplast. Z @ period film-forming component (A-2) is 200 to 6. O
It has a number average molecular weight of DD and a water M value of 40 to 600. It is a mixture consisting of 30 to 90 parts by weight of at least one hydroxyl group-containing polymer selected from the group consisting of alkyd resins, oil 7-ly alkyd resins, and urethane resins and 70 to 10 parts by weight of aminoplast. do. 1. The method according to claim 1. 8. The film-forming component (A-2) is 500 to 8,0
Hydroxyl group-containing vinyl polymers having a number average molecular weight of 00 and a hydroxyl value of 40 to 250, and a number average molecular weight t' of 200 to 3,000, and 4
30 to 90 parts by weight of a mixture of at least one hydroxyl group-containing polymer selected from the group consisting of alkyd resins, oil-free alkyd resins, and urethane resins having a hydroxyl value of 0 to 600, and 70 to 10 parts by weight of aminoplast. The method according to claim 1, characterized in that it is a mixture consisting of parts by weight. 9 The film-forming component (A-2) is 500 to 8,0
Hydroxyl group-containing polymers having a number average molecular weight of 5-00 and a hydroxyl value of 40 to 250, alkyds having a number average molecular weight of 200 to 3,000 and a hydroxyl value of 40 to 600. It is a co-condensate of 60 to 90 parts by weight of at least one hydroxyl group-containing polymer selected from the group consisting of resins, oil-free alkyd resins and urethane resins, and 70 to 10 parts by weight of aminoplast. A method according to claim 1, characterized in: 10. The method according to claim 1, wherein the pigment (B-1) is at least one metal powder selected from the group consisting of aluminum powder, copper powder, and zinc powder. 11. The method according to claim 1, wherein the fine particle polymer @(C) is a polymer that is substantially non-swellable in solvents and is prepared by an emulsion polymerization method. . 6-12 The fine particle polymers (C1 are non-aqueous dispersible polymers having both segments that are soluble and segments that are insoluble in aliphatic hydrocarbon solvents or alicyclic hydrocarbon solvents) 13. The method according to claim 1, characterized in that: The method according to claim 1 or 12, wherein the fine particle polymer is a non-aqueous dispersion type polymer having a hydroxyl group that reacts with aminoblast in each segment.14. (CI is a hydrolyzable silyl group and a group capable of reacting with the silyl group as a bond between a segment that is soluble in an aliphatic hydrocarbon solvent or an alicyclic hydrocarbon solvent and a segment that is insoluble) 15. The method according to claim 1, characterized in that the polymer is a non-aqueous dispersible polymer having multiple bonds formed by the reaction of Claim 1 is characterized in that the segment insoluble in hydrocarbon solvents or alicyclic hydrocarbon solvents is a non-aqueous dispersion type polymer having an intramolecular crosslinked structure in the segment. The method according to claim 16, wherein the fine particle polymer (E) is a polymer prepared by an emulsion polymerization method and is substantially non-swellable in solvents. The method according to item 1. 1Z The fine particle polymer (El is characterized in that it is a non-aqueous dispersion type polymer having both segments that are soluble in an aliphatic hydrocarbon solvent and segments that are insoluble in an aliphatic hydrocarbon solvent. 18. The method according to claim 1. 18. The fine particle polymers (El is soluble in an aliphatic hydrocarbon solvent or an alicyclic hydrocarbon solvent and as an insoluble segment, respectively) Claim 1 characterized in that there is an amitsubu in the segment.
or the method according to paragraph 17. 19 The fine particle polymer (E) has a hydrolyzable silyl group and the silyl group as a bond between a segment soluble in an aliphatic hydrocarbon solvent or an alicyclic hydrocarbon solvent and a segment insoluble in an aliphatic hydrocarbon solvent or an alicyclic hydrocarbon solvent. 2. A method according to claim 1, characterized in that the polymers are non-aqueous dispersible polymers having bonds formed by reaction with a group capable of reacting with the polymer. 20. The fine particle polymer fE) is a non-aqueous dispersion type polymer having an intramolecular crosslinked structure in the segment as a segment that is insoluble in an aliphatic hydrocarbon solvent or an alicyclic hydrocarbon solvent. A method according to claim 1, characterized in that: 9-