JPS6142579A - Topcoating composition - Google Patents

Abstract

PURPOSE:A topcoating which has an improved appearance of a finished coating film and is capable of being combined with a wide range of microgels, comprising a film-forming polymer containing functional groups, an organic liquid diluent, a crosslinking agent, fine particles of a crosslinked polymer, and pigments in specified proportions. CONSTITUTION:A coating composition comprising a film-forming polymer (a) having functional groups capable of reacting with a crosslinking agent; a volatile organic liquid diluent (b) carrying this polymer; a crosslinking agent (c) dissolved in this diluent; fine particles of a crosslinked polymer (e) mentioned below which has a particle diameter of 0.01-10mum and is insoluble and dispersed stably in a mixture of polymer (a), diluent (b), and crosslinking agent (c); and pigments (e). The aforementioned particle (d) comprises 0.2-30wt% of the total solids of polymer (a), crosslinking agent (c), fine particles (d), and pigments (e), and is obtained by the emulsion polymerization of an ethylenically unsaturated monomer and a crosslinkable comonomer whose kinds and amounts to be used have been selected to satisfy the relation: the refractive index of polymer (d) minus the refractive index of polymer (a) is less than or equal to 0.05.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a solid color or one-coat metallic color paint composition for use as a top coat, for example as a knob coat for painting automobile bodies.

1-P'! and. For example, solid color paints containing colored pigments and metallic paints containing metallic pigments are painted and baked as a tofu coat as protective and decorative coatings for automobile bodies. Coatings for this purpose must be durable and aesthetically pleasing.

Recently, durability has reached a level that almost satisfies market requirements, but there is still a desire for a significant improvement in aesthetics. As one means of improving aesthetics, it is also considered to form a high-finish appearance coating film by thick film coating. However, conventional paint compositions have poor sagging performance, with a film thickness of 30 to 35μ at most in one coating;
Even with two coats, the limit is 40-45μ. If you increase the number of lengths, it will be 1'! 7. Coating is possible, but it not only increases the number of steps and lowers productivity, but also requires modification of the existing line.

Therefore, in recent years, paints in which crosslinked polymer fine particles (hereinafter referred to as "microgel") are added for the purpose of imparting structural viscosity to a system consisting of a film-forming polymer, a crosslinking agent, a diluent, and a pigment have been improved in sagging performance. In addition, it has attracted attention as a paint that can be applied thickly with a small number of coats. For example, see JP-A-49-97026 and JP-A-58-129065.

In the paint containing microgel, it is essential for the microgel to be insoluble in its dispersion medium (generally consisting of a film-forming polymer, a crosslinking agent, a pigment, and a solvent) in order to exhibit its characteristics. Naturally, the particles are dispersed in a non-uniformly dispersed state within the coating film formed from the coating material. At this time, it is easy to understand that if the optical refractive index of the microgel is different from that of the surrounding film-forming polymer, diffuse reflection will occur at the interface, resulting in a decrease in the gloss of 'Iin'A as a whole. Of course, micro-tsuku colors, but solid colors, when painted, form an extremely thin clear layer on the surface, which suppresses the exposure of the pigment layer and exhibits high gloss, so the transparency of this surface layer is In particular, it becomes a factor of ff15 for the finished appearance. Therefore, if the optical refractive index of the microgel differs from that of the surrounding film-forming polymer in this surface layer, even if thick coating is possible for the purpose of obtaining a high-finished appearance, it will be reversed due to diffuse reflection in the surface layer. This will reduce the finished appearance.

According to the findings of the present inventors, the film-forming resin.

If the refractive index and the refractive index of the microgel are too different, when a color paint containing them is applied to the body of a car, for example, approximately 20 μ thicker than before, a glossy sink phenomenon may be observed, especially on the vertical surfaces of the body (e.g., door areas). The finished appearance deteriorated. Gloss and sink marks can also be seen on horizontal surfaces (such as bonnets and roofs), but the phenomenon of gloss and sink marks on vertical surfaces is even more remarkable.

This is why JP-A-49-97026 cited above requires that the optical refractive index of the microgel be substantially the same as that of the main film-forming polymer. However, the microgel used therein was manufactured by a method called the NAD method. In other words, the NAD method is a method in which an ethylenically unsaturated monomer and a crosslinkable copolymer are copolymerized in the presence of a stabilizer in a non-aqueous organic solvent that dissolves monomers such as aliphatic hydrocarbons but does not dissolve the polymer. However, in order to prevent the polymer from dissolving, the monomers constituting the microgel must have a solubility parameter that is relatively different from the solubility parameter of the nonaqueous organic solvent used.

Therefore, the fluctuation width of the refractive index is also within a relatively narrow range, and the type of film-forming polymer that can be used in combination with this is also limited.

The object of the present invention is to overcome these drawbacks of the prior art and
An object of the present invention is to provide solid color and metallic color coating compositions for top coating containing microgels that improve the finished appearance of the formed coating film and allow a wide range of combinations.

Yuta Fumoto The clear top coating composition of the present invention comprises (a) a film-forming polymer having a functional group capable of reacting with a crosslinking agent; (bl) a volatile organic liquid diluent supporting the polymer; , (c) a crosslinking agent dissolved in the organic liquid diluent, and (d) insoluble in the mixed system of the polymer (al), diluent (b), and crosslinking agent (c1); (e) a pigment; and (e) a pigment.

The crosslinked polymer fine particles Tdl, ie, the microgel, account for 0.2 to 30% by weight of the total solid weight of the polymer (al), the crosslinking agent (c1), the microgel (dl), and the pigment (e).

The present invention provides that the microgel (d) has a light refractive index nD
The type and amount of ethylenically unsaturated compounds 1'! are selected in advance so that d satisfies the relationship: 111)d-nDa |≦0.05 in relation to the optical refractive index nDa of the polymer (al). , a microgel obtained by emulsion polymerization of a polymer and a crosslinkable comonomer.

The microgel (d) contained in the composition of the present invention is produced by emulsion polymerizing an ethylenically unsaturated monobase with a crosslinkable comonomer in an aqueous medium to create a fine particle copolymer, and then removing water. Manufactured. Unlike the aliphatic hydrocarbons used in the NAD method, water has a high solubility parameter of about 23, which is significantly different from the solubility parameter of ordinary organic polymers, so it does not dissolve most organic polymers. Therefore, even microgels that cannot be produced by the NAD method because they are dissolved or swelled in a non-aqueous organic solvent can be produced by emulsion polymerization, and therefore microgels with different refractive indexes over a relatively wide range can be obtained. Therefore, according to the present invention, it is possible to combine a wide range of film-forming polymers and microgels without impairing transparency, and it is possible to combine a wide range of film-forming polymers and microgels without impairing transparency.
j-dazu composition can be provided.

Furthermore, in recent years, attention has been paid to the use of high solid paints that reduce the amount of solvent gold used in paints due to requests for resource conservation and anti-pollution measures. It can be applied thickly and the finished appearance can be improved.

The film-forming polymer (al) having a functional group capable of reacting with a crosslinking agent used in the present invention is generally known. These include acrylic copolymers, polyesters, alkyds, etc. It has, for example, a hydroxyl group or a carboxyl group as a functional group that can react with a crosslinking agent, and has protective properties necessary for solid color and metallic color coatings, such as weather resistance against gloss reduction, solvent resistance, chemical resistance,
It must exhibit impact resistance and have excellent decorative functions. Therefore, the acid value is usually 0.5 to 40°, preferably 2 to 30, and the hydroxyl value is 40 to 2.
00. It is preferably 50 to 150. If the acid value or hydroxyl value is too low, the crosslinking density will be low, resulting in insufficient coating strength and solvent resistance.On the other hand, if the acid value or hydroxyl value is too high, water resistance will be insufficient, causing blistering.

The polyester resin provided in the present invention is one known to those skilled in the art for use in surface coating compositions, and is essentially a condensation product of a polyhydric alcohol and a polycarboxylic acid. shall mean any resin.

The term includes alkyd resins obtained by adding to such starting materials components that provide fatty acid residues derived from natural drying or semi-drying oils or, in some cases, oils that do not have calm drying properties. shall be included.

Furthermore, the term also includes polyester resins that do not bind any natural ura residues. All these resins contain a proportion of free hydroxyl and/or carboxyl groups which are available for reaction with conventional crosslinking agents.

Polyhydric alcohols suitable for the production of polyester resins include ethylene glycol, propylene glycol, butylene gelicol, 1,6-hexanetriol, neopentyl glycol, glycerol, trimethylolpropane,
oligomers of trimethylolethane, pentaerythritol, dipentaerydrift, tripentaerydrift, hexanetriol, styrene and allyl alcohol (such as those marketed by Monsando, Chemical, Company under the name HJloo) and trimethylolpropane; Condensation products with ethylene oxide or propylene oxide (e.g. “Niax”)
) ”commercially known as triols)
includes. Suitable polycarboxylic acids are succinic acid (or its anhydride), adipic acid, azelaic acid, sebacic acid, maleic acid (or its anhydride), fumaric acid, muconic acid, iconic acid, phthalic acid (or its anhydride) , isophthalic acid, terephthalic acid, trimellidic acid (or its anhydride) and pyromellitic acid (or its anhydride). Those derived from oil include linseed oil, soybean oil,
It incorporates fatty acids derived from tall oil, dehydrated castor oil, fish oil and tung oil, fatty acids derived from safflower oil, sunflower oil and cottonseed oil.

Generally, it is preferred that the oil length of the alkyd resin does not exceed 50%. For the purpose of imparting plasticity to the polyester, a monofunctional saturated carboxylic acid may be further blended. Examples of such acids may include the 04-C20 saturated aliphatic acids, benzoic acid, p-tert-butylbenzoic acid and abietic acid.

The acrylic copolymer that can be used in the present invention comprises an alkyl ester of allylic acid or methacrylic acid, optionally other ethylenically unsaturated monomers that can be copolymerized therewith, and a functional group that can react with a crosslinking agent. It can be obtained by copolymerizing a monomer having a group by a conventional method.

Examples of suitable (meth)acrylic acid alkyl esters include:
Includes methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, butyl (meth)acrylate, and 2-ethylhexyl (meth)acrylate.

Examples of other ethylenically unsaturated monomers include vinyl acetate, acrylonitrile, styrene and vinyltoluene.

Examples of small molecules having functional groups that react with crosslinking agents include acrylic acid, methacrylic acid, and (meth)acrylic acid 2-
Examples include hydroxyethyl, (meth)acrylic #, 2-hydroxypropyl, N-(butoxymethyl)-(meth)acrylamide, and glycidyl (meth)acrylate.

Furthermore, a monomer that can act as a catalyst for the crosslinking reaction between the polymer (a) and the crosslinking agent can be incorporated into the acrylic polymer; for example, acrylic acid and methacrylic acid are commonly used, but sulfonate Acid groups can be introduced into the polymer using group-containing monomers such as 2-sulfoethyl methacrylate and acidic butyl maleate.

The film-forming polymer (a) used in the present invention is dissolved in a mixed system of a liquid diluent (bl) and a crosslinking agent (c1):
or even if it is stably dispersed without dissolving.
A portion may be dissolved and the remainder may be dispersed.

As the polymerization method, known solution polymerization, non-aqueous dispersion polymerization, bulk polymerization, etc. can be used, and solvent replacement from emulsion polymerization can also be used.

Examples of crosslinking agents that can be used in the present invention include known polyisocyanates, formaldehyde condensates of nitrogen-containing compounds such as aminoplast resin 1, urea, thiourea, melamine, and benzoguanamine, and lower alkyl ethers of these condensates ( If the number of carbon atoms in the alkyl group is 1 to 4), etc.

The composition of the crosslinking agent is as follows: film-forming polymer (a)
The total solid content of the crosslinking agent and crosslinking agent (b) is suitably 5 to 50% by weight, preferably 1 to 40% by weight.

The microgel (d) used in the present invention is produced by emulsion polymerization of an ethylenically unsaturated carmer and a crosslinkable comonomer in an aqueous medium by a known method to form an elmudgeon containing crosslinked polymer fine particles. (It is obtained by removing water by solvent displacement, azeotropy, centrifugation, filtration, drying, etc.) Emulsion polymerization may be carried out using known emulsifiers and/or dispersants, but zwitterionic It is preferable to use an emulsifier having a zwitterionic group.Since the structural viscosity of the exposed microgel differs depending on the particle size when added to a coating composition, it is important to obtain a uniform particle size. This is because microgels with uniform particle size can be easily obtained by use.

Ethylenically unsaturated monomers that can be used for the production of microgels include methyl (meth)acrylate, ethyl (meth)acrylate, n-butyl (meth)acrylate,
Isobutyl (meth)acrylate, (meth)acrylic acid 2
- Alkyl esters of acrylic acid or methacrylic acid such as ethylhexyl, and other compounds having an ethylenically unsaturated bond that can be copolymerized with this, such as styrene, α-
Examples include methylstyrene, vinyltoluene, L-butylstyrene, ethylene, propylene, vinyl acetate, vinyl propionate, acrylonitrile, methacrylatrile, dimethylaminoethyl (meth)acrylate, and the like. Two or more types of these monomers may be used.

As a crosslinkable co-metallic 1χmer, ff has two or more radically polymerizable ethylenically unsaturated bonds in the molecule.
11 and/or two types of ethylenically unsaturated group-containing monomers each carrying a group capable of reacting with each other.

Monomers having two or more radically polymerizable ethylenically unsaturated groups in the molecule include polymerizable unsaturated monocarboxylic acid esters of polyhydric alcohols, polymerizable unsaturated alcohol esters of polybasic acids, and There are aromatic compounds substituted with one or more vinyl groups, examples of which include the following compounds.

Ethylene glycol diacrylate, ethylene glycol dimethacrylate, triethylene glycol dimethacrylate, tetraethylene glycol dimethacrylate, 1,3-butylene glycol dimethacrylate-1, trimethylolpropane triacrylate, trimethylolpropane trimethacrylate, 1,4 -Butanediol diacrylate, neopentyl glycol diacrylate, 1,6-hexanediol diacrylate, pentaerythritol diacrylate, pentaerythritol-
tosidimethacrylate, 1.1.1-1-lishydroxymethyl Ethanediacrylate, Ll, 1-trishydroxymethylethanetriacrylate, 1,1
．． 1-trishydroxymethylethane dimethacrylate, 1.1.1-1-lishydroxymethylethane trimethacrylate, 1,1.1-)lishydroxymethylpropane diacrylate, 1,1.1-1-lishydroxymethylpropane Triacrylate, 1.1.1-trishydroxymethylpropane dimethacrylate, 1,1
．． 1-Trishydroxymethylpropane trimethacrylate, triallyl cyanurate, triallyl isocyanurate, triallyl trimellitate, diallyl terephthalate, diallyl phthalate and divinylbenzene.

Furthermore, in place of the monomer having two or more radically polymerizable ethylenically unsaturated groups in the molecule as a monomer for crosslinking purposes, or optionally together with them, each carries a group capable of reacting with each other. It is also possible to use monomers with some ethylenically unsaturated groups. For example, glycidyl group-containing ethylenically unsaturated metal bodies such as glycidyl methacrylate and glycidyl acrylate-1, and carboxyl group-containing ethylenically unsaturated monomers such as acrylic acid, methacrylic acid, and crotonic acid; 2-hydroxy Hydroxyl group-containing ethylenically unsaturated carmers such as ethyl acrylate, hydroxypropyl acrylate, 2-hydroxyethyl methacrylate, hydroxypropyl methacrylate, hydroxythyl acrylate, hydroxyethyl acrylate, allyl alcohol, methalyl alcohol, vinyl nesocyanate, Examples include ethylenically unsaturated monomers having an isocyanate group such as isopropenyl isocyanate. However, in addition to these, any combination of two types of ethylenically unsaturated carmers each carrying a group that can react with each other can be used.

The monomer constituting the microgel may include a monomer having a functional group that can react with a crosslinking agent, such as a carboxyl group-containing monomer such as acrylic acid,
Methacrylic acid, crotonic acid, itaconic acid, maleic acid,
fumaric acid, hydroxyl group-containing monomers such as 2-hydroxyethyl acrylate, hydroxypropyl acrylate, 2-hydroxyethyl methacrylate, hydroxypropyl methacrylate, hydroxybutyl acrylate, hydroxybutyl methacrylate-1.
, allyl alcohol, methacrylic alcohol, and nitrogen-containing compounds such as acrylic acid amide and methacrylic acid amide.

The optical refractive index (nDd) of the crosslinked polymer fine particles is |nDd − with respect to the optical refractive index (nDa) of the film-forming resin.
nDa | ≦0.05, preferably ≦0.0
Must be within the range of 3. If it exceeds this range, blurring occurs especially on the vertical surface, a decrease in gloss is observed, and the finished appearance becomes poor. The optical refractive index of the film-forming resin is determined by forming the film-forming resin into a clear film with a thickness of 30 to 50 μm.
The measurement was carried out using α-bromonaphthalene as a medium at 20°C with R (ATAGO Co., Ltd. Kan).

The optical refractive index nDd of crosslinked polymer fine particles (microgel) is determined by the following formula.

nDd = ΣC1rl, Cznz ・---Cmnm
However, C1, C2...buttons indicate the weight fraction of each monomer constituting the microgel (c1+Cz+...Cn=1)
where nl, nz...nm are the refractive indexes at 20''C of the single polymer of each HLfif body.

The microgel used in the present invention may have a uniform structure or
Alternatively, the particle may have a multilayer structure with a layer structure within the particle.

In the case of a multilayer structure, the final surface layer is prepared so that the difference in refractive index of the microgel as a whole with the surrounding film-forming polymer in the coating is in the range of |nDd −nDa |≦0.05, and the inner The layer can be a so-called microgel with other functions, such as a layer that provides structural viscosity.

The particle size of the microgel is then in the colloid size range of 0.01-10μ, preferably 0.02-5μ.

The formulation of this microgel is a film-forming polymer (a
1, a crosslinking agent (c), a microgel (dl), a pigment (e
) in the total solid content of 0.2 to 30% by weight, preferably 1
It accounts for ~20% by weight. If the amount of microgel is too small, the coating composition will easily sag (J! 7. The intended purpose of obtaining a high finished appearance by coating will not be achieved. On the other hand, if the amount of microgel is too large, the smoothness of the film will be deteriorated. harm, rg-
Even if painted, a high finished appearance cannot be obtained.

The organic liquid diluent (bl) used in the present invention is any organic liquid or liquid mixture commonly used as a solvent for polymers in conventional coating compositions, such as hexano,
Aliphatic hydrocarbons such as heptane, aromatic hydrocarbons such as toluene or xylene, various /! consisting primarily of aliphatic hydrocarbons but containing some aromatic hydrocarbons. Il
i point range petroleum fractions, esters such as butyl acetate, ethylene glycol diacetate, 2-ditoxyethyl acetate, ketones such as acetone and methyl isobutyl ketone, and alcohols such as butyl alcohol. It goes without saying that these should be appropriately selected depending on the type of film-forming polymer (al) or the form in which the polymer (a) is supported in the diluent Fbl, that is, whether it is in the form of a solution or a dispersion. Furthermore, when a polyisocyanate compound is used as the crosslinking agent (c), it is a matter of course that it must not have an active hydrogen group that reacts with the polyisocyanate compound.

In addition to the above-mentioned (a) or el components, the composition of the present invention may contain other commonly used components, such as viscosity modifiers such as organic montmorillonite, polyamide, and polyethylene wax,
It can contain silicone or organic polymer surface conditioners, curing catalysts such as para-toluenesulfonic acid, ultraviolet absorbers, hindered amines, hindered phenols, and the like.

Although the method for preparing the coating composition of the present invention is arbitrary, the coating composition containing resin (Al and diluent (b)) is usually prepared in advance by S.
ms, add the pigment (e) and disperse it, then add the cross-linking agent (c) and microgel (dl) and mix well. If necessary, adjust the viscosity to an appropriate level with a diluent.
You can do EM. If polyisocyanate is used as a crosslinking agent, store it in a separate container and mix it before use.

Pigments that can be used in the present invention include any commonly used in surface coating compositions, such as inorganic pigments such as titanium dioxide, iron oxide, chromium oxide, lead chromate, carbon black, phthalocyanine blue, phthalocyanine green, carbazole, etc. Organic pigments such as violet, anthrapyrimidine yellow, flavanthrone yellow, isoindoline yellow, indanthrone blue, quinacridone red and violet, perylene red may be used. As used herein, "pigment" refers to conventional fillers and spreading agents (extender pigments) such as talc and kaolin.
The purpose is to include the following.

In particular, metallic colors contain metal flake pigments in addition to the above pigments. Suitable metal pigments include aluminum powder, copper powder, and the like.

The amount of the pigment may be such that it accounts for 5 to 50% by weight of the total solid content of the paint consisting of the film-forming polymer (al), the crosslinking agent (c), the microgel (dl), and the pigment (e). .

The coating composition of the present invention can be applied to an object to be coated by a conventional method and cured at room temperature or by heating to produce a high-thick film with an excellent finished appearance, and a metallic and Can form solid color coatings.

Examples of the present invention are shown below, in which "parts" and "%" are by weight unless otherwise specified.

Example ■ Bishydroxyethyl taurine 1 was added to a 21-kolben equipped with a micronol (1'de 1 (a) I ion O Ru- pick-up stirrer, nitrogen inlet tube, temperature control device, condenser, and decanter).
34 parts, neopentyl glycol 130 parts, azelaic acid 236 parts, phthalic anhydride 186 parts and xylene 27 parts
Prepare the ingredients and raise the temperature. Water produced by the reaction is azeotroped with xylene and removed.

After about 2 hours from the start of reflux, the temperature was brought to 190°C.
Stirring and dehydration are continued until the acid value equivalent to carboxylic acid reaches 145, and then the mixture is cooled to 140°C.

The temperature was then maintained at 140°C and the "Cardura E10"
314 parts of persatic acid glycidyl ester (manufactured by Shell) were added dropwise over 30 minutes, and stirring was continued for 2 hours to complete the reaction. The resulting polyester resin has an acid value of 59. The hydroxyl number was 90 and the M5 was 1,054.

1-1 Micro slow flow dish (1-hour powder) stirrer,
232 parts of deionized water, 10 parts of the polyester resin obtained in (a) above, and 0.75 parts of dimethylethanolamine were placed in a reaction vessel equipped with a cooler and a temperature control device, and the temperature was adjusted to 80°C while stirring. While holding the volume at 1'l
To this, a solution prepared by dissolving 4.5 parts of azobiscyanovaleric acid in 45 parts of deionized water and 4.3 parts of dimethylethanolamine is added. Then methyl methacrylate 70.
7 parts, n-butyl acrylate 94.2 parts, methylene 7
A mixed solution consisting of 0.7 parts of 2-hydroxyethyl acrylate, 30 parts of 2-hydroxyethyl acrylate, and 4.5 parts of ethylene glycol dimethacrylate was mixed for 60 minutes. After dropping, add 1.5 parts of azobiscyanovaleric acid to 15 parts of deionized water.
1.4 parts of dimethylethanolamine were added thereto and stirring was continued for 60 minutes at 80°C to obtain an emulsion with a non-volatile content of 45%, a pH of 7.2, and a viscosity of 92 cps (25°C). This emulsion was spray dried to obtain a microgel. The particle size was 0.8μ.

The refractive index of the microgel was determined using the above formula, and was found to be 1
．． 51 (+) However, the following values were used for the refractive index of the single polymer of each polymer.

Polymethyl methacrylate = 1.489 Polystyrene = 1.591 Ethylene glycol dimethacrylate - 1,506 Poly n-
Butyl acrylate -1,4662-hydroxyethyl methacrylate = 1.5121-2 Microl P12 (single-layer powder) Same formulation and same conditions as I-1 except for the polymerized monomer. A microgel was produced. The monomer composition was 189 parts of methyl methacrylate, 54 parts of n-butyl acrylate, and 27 parts of ethylene glycol dimethacrylate.

The refractive index of the microgel was determined in the same manner as I-1 and was found to be 1.486. The powder particle size was 1.2 Met.

I-3 Microgel 1 Pa13 (Single-layer powder) A microgel was produced in the same manner as I-1 using the same formulation and under the same conditions except for the polymerized monomer. The monomer composition was 243 parts of n-butyl acrylate and 27 parts of ethylene glycol dimethacrylate.

The refractive index was 1.470. The powder particle size was 1.0μ.

I-4 microgel) name structure] column '4 (1 layer solvent replacement) I
In the same manner as in -1, except for the polymerizable monomer, all the components except the polymerizable monomer were used until the emulsion polymerization was completed (the same formulation and the same conditions were used. However, after that, the azeotrope was used to replace the quijirole solution, and the microgels in the solution were removed. Particle size 0.2μ, microgel-containing ff140f
A kijirole dispersion with a fi amount of % was obtained. Polymerizability R at this time
The m-body composition was 216 parts of styrene, 27 parts of n-butyl acrylate, and 27 parts of ethylene glycol dimethacrylate, and the refractive index was 1.571.

I-5 microl 11jJ row”-(2-layer solvent replacement) I
Using the same apparatus as in 1, add 23 mL of deionized water to the reaction vessel.
2 parts, 10 parts of the polyester resin obtained above (al) and 0.75 parts of dimethylethanolamine were charged and dissolved while stirring while maintaining the temperature at 80°C. A solution dissolved in 20 parts of ionized water and 0.260 parts of dimethylethanolamine is added. Next, a mixed solution consisting of 108 parts of methyl methacrylate and 27 parts of ethylene glycol dimethacrylate is added dropwise over a period of 60 minutes. After that, for 60 minutes The first stage reaction was completed by maintaining the temperature at 80°C, and azobiscyanovalerina M0.
5 parts with 25 parts of deionized water and 0 parts of dimethylethanolamine.
．． Add 3 parts of the solution. Continue with styrene 9.5
A mixed solution consisting of 20 parts of methyl methacrylate, 14 parts of n-butyl acrylate, and 6 parts of ethylene glycol dimethacrylate was added dropwise over a period of 60 minutes. After lowering the temperature, add 1.5 parts of azobiscyanovaleric acid to 15 parts of deionized water.
When the two-step reaction was completed by adding 1.4 parts of dimethylethanolamine and 1.4 parts of dimethylethanolamine and stirring at 80°C for 60 minutes, the nonvolatile content was 45%, the pH was 7.2, and the viscosity was 1.
An emulsion with a particle diameter of 0.2μ is obtained at 0.5cps (25°C).

This emulsion was subjected to solvent substitution for Qysilol in the same manner as in Production Example 1-4 to obtain a Qysilol dispersion containing microgel at 140% by weight. The microgel particle size in this solution is 0.
．． It was 25μ. The refractive index of the microgel as a whole is 1.527, but the refractive index of the inner part (core) made in the first stage reaction is 1.492, and the refractive index of the outer part (shell) made in the second stage is 1.492. The rate was 1.559.

The following raw materials were charged into a container equipped with a stirrer, a temperature controller, and a decanter, heated in a nitrogen stream, and transesterified at 220°C for 20 minutes.

Coconut oil 130 parts Trimethylolpropane 117 parts Dibutyltin oxide 0.12 parts After cooling, add 173 parts of phthalic anhydride
Add 53 parts and raise the temperature to reflux conditions to approximately 180°C.
), and from here the temperature was gradually increased to 230°C over 3 hours.

Then, the water produced as the reaction progresses is d1 along with xylene.
The reaction was carried out until the acid value reached 8 (in solid content) while removing the solution at a temperature of 1. After cooling, 77 parts of Kijiroll and 77 parts of Tsurupetz 100 (manufactured by Shell) were added to obtain a polyester varnish. Non-Jm content 60%, hydroxyl value 80. The number average molecular weight was 2400 (polystyrene gel equivalent), and the refractive index of the resin solid film was 1.532.

11-2-doacrylic preparation ¥u1 80 parts of xylene and 10 parts of methyl isobutyl ketone were charged into a container equipped with a stirrer, a temperature control device, and a reflux condenser. Next, a solution of the following composition: methacrylic acid 1.8 parts methyl methacrylate 39.4 parts ethyl acrylate 43.6 parts inbutyl methacrylate 3.2 parts 2-hydroxyethyl acrylate 12.0 parts azobisisobutyronitrile 1.
20 parts of the 5 parts were added and heated with stirring to raise the temperature. While refluxing, the remaining 81.5% of the above mixed solution
1 part was added dropwise over 3 hours, and then a solution consisting of 0.3 parts of azobisisobutyronitrile and 10 parts of quidylol was added dropwise over 30 minutes. The reaction solution was further stirred and refluxed for 2 hours to increase the conversion rate to resin, and then the reaction was terminated to obtain an acrylic resin varnish with a nonvolatile content of 50% and a number average molecular weight of 18,000.

An acrylic resin film with a thickness of 35μ was made from this varnish, and the refractive index was determined using the Abbe refractive index measuring device, and the refractive index was 1.
It was 479.

I [-2-2 Acrylic MU to Kukakari■ Using the same equipment as in Production Example n-1, 57 parts of xylene, n
- 6 parts of butanol was charged, and then a solution of the following composition: styrene 30.0 parts ethylhexyl methacrylate 45.2 parts ethylhexyl acrylate 5.5 parts 2-hydroxyethyl methacrylate 16.2 parts methacrylic acid 3.1 parts azo Add 20 parts of 4.0 parts of bisisobutyronitrile,
Heat with stirring to increase temperature. While refluxing, the remaining 84 parts of the mixed solution was added dropwise over 2 hours, and then a solution consisting of 0.5 parts of azobisisobutyronitrile, 23 parts of xylene, and 14 parts of n-butanol was added dropwise over 20 minutes.

The reaction solution was further stirred and refluxed for 2 hours to complete the reaction,
An acrylic resin varnish with a nonvolatile content of 50% and a number average molecular weight ffl' of 3400 was obtained.

The refractive index was measured and found to be 1.521.

Production example n-1 Polyester face 100 parts Titanium oxide R-5N (manufactured by Sakai Chemical Co., Ltd.) 90 parts Kijiroru 30 parts were weighed into a dispersion container, an appropriate amount of glass peas was added, mixed and dispersed using a paint conditioner, and further Microgel I - 15 parts Microgel ■ - 35 parts - were added and mixed and dissolved in a paint conditioner for 2 to 3 minutes to obtain paints I[-1-1 and I[l-1-2].

nl-2 acrylic sled...'force---Δrat remainsllll-
A paint having the following formulation was produced in the same manner as in Example 1.

T [-2-1111-2-2 II-2-1 Acrylic FES 140 parts 14
0 parts Titanium oxide R-5N 40 parts 4
0 parts Kijiroru 30 parts 30 parts Microgel I-2-15 parts I and produced paint.

II[-3-1 Plate Two Moxibustion Production Example n-2-2 Acrylic Fes 100 copies 100
Part Kijirole 12 parts 12 parts Microgel I-32 parts □ Microgel I-5-4, 4 parts m-4 Urenso 1-'Car's 11"i" Production Example l
In the same manner as in 11-1, III-4-I III-4-2■-1 polyester resin 100 parts 100 parts Titanium oxide R-
5N 90 parts 90 parts Kiji roll
30 parts 30 parts Toray Silicone 5H-2
90.1 part 0.1 part Microgel I-1-5 parts Microgel I-35 parts
A paint was prepared by adding 27 parts of -75 (a polyisocyanate manufactured by Bayer AG).

The paints from m-1 to lll-71 were mixed with Kijirol/Tsurubenz 100/butyl acetate/methyl ethyl ketone = 40
/30/15/20 seconds for non-metallic paints with thinner at a ratio of 15/NCL4 Ford Cup/
The metallic paint was diluted to 16 seconds and applied at 20°C. For each paint, two iron plates each were treated with cationic electrodeposition and intermediate coating, one was applied vertically, vertically set, and vertically baked, and one was applied horizontally.
Performed horizontal setting and horizontal baking. The number of coatings was performed twice in succession, and the dry film was set to 35 to 40 μm. Set up at room temperature (20-25°C) for 10 minutes.
Baking was performed at 140°C for 30 minutes. However, only the urethane paint system of m-4 was forced to dry at 80°C for 30 minutes.

(Comparative Example 1. Example 1) The coating film of Comparative Example 1, which uses a microgel whose refractive index is significantly different from that of the polyester resin used for the solid color, has low gloss, and especially on the vertical side, it does not have what is known in the industry as blurring. Occurrence was observed. In comparison, the appearance of the coating film of Example 1 using microgel with a refractive index close to that of the coating film was smooth and had good gloss both when prepared horizontally and vertically. The results are shown in the table.

(Comparative Example 2. Example 2) Similarly to the acrylic solid color, a coating film using a microgel having a refractive index significantly different from that of the acrylic resin had poor gloss windows and vertical blurring.

(Comparative Example 3. Example 3) When a microgel with a refractive index similar to that of acrylic resin was used in the metallic coating film, the gloss and metallic feel were good, but in Comparative Example 3, it had a cloudy feel. There was no metallic feel and there was no glossy window. The results are shown in the table.

(Comparative Example 4. Example 4) The same results as in the above Examples and Comparative Examples were obtained with the isocyanate-cured paint system. The results are shown in the table.

Procedural amendment filed on May 3, 1981, Patent Application No. 7t/y+091, filed in 1982, 2, Title of invention: Top coating composition 3, Relationship with the person making the amendment: Patent applicant name: Nippon Paint Co., Ltd. 4 , Agent Address: Koei Building, 2-40-4, Awaji-cho, Higashi-ku, Osaka Name (6036) Patent Attorney Taku Akaoka 1. Pa'・
Husband', "j5, Date of amendment order spontaneous 6, Number of inventions increased by amendment None 7, Detailed explanation of Neil's original subject invention Contents of amendment 1, "Allyr" on page 12, line 13 of the specification "acid"
Acrylic acid”, corrected.

2, rCnJ on page 20, lines 14 and 15 is “
Correct as CmJ.

3. In the last line of page 23, "Perylene Red" is corrected to "Perylene Red."

4. On page 30, line 16, "53 copies" is corrected to "57 copies."

5. In the third line of page 31, "(manufactured by Shell)" is corrected to "(manufactured by Esso)".

6. Replace r2400J on page 31, lines 5 and 6 with “2
Corrected to 900J.

Claims (7)

[Claims] (1) (a) a film-forming polymer having a functional group capable of reacting with a crosslinking agent; (b) a volatile organic liquid diluent supporting the polymer; and (c) in the organic liquid diluent. A crosslinking agent dissolved in (
d) Cross-linked particles having a particle size of 0.01 to 10 μ that are insoluble in the mixed system of the polymer (a), diluent (b), and cross-linking agent (c) and are stably dispersed in the system. and (e) a pigment, and the crosslinked polymer fine particles (d) contain the polymer (a), a crosslinking agent (c), the crosslinked polymer fine particles (d), and a pigment (e).
) accounts for 0.2 to 30% by weight of the total solid weight of
The crosslinked polymer fine particles (d) have a light refractive index nDd in relation to a light refractive index nDa of the polymer (a),
It is obtained by emulsion polymerization of an ethylenically unsaturated monomer and a crosslinkable comonomer, the type and amount of which are selected in advance so as to satisfy the relationship |nDd-nDa|≦0.05. A top coating composition characterized by: (2) The composition according to claim 1, wherein the film-forming polymer (a) is selected from acrylic copolymers, polyesters, and alkyds having hydroxyl groups and/or carboxyl groups. (3) The film-forming polymer (a) is a diluent (b).
) and a crosslinking agent (c) dissolved in a mixed system according to claim 1 or 2. (4) The film-forming polymer (a) is a diluent (b).
2. The composition according to claim 1 or 2, which is insoluble and stably dispersed in a mixed system of (c) and a crosslinking agent (c). (5) A part of the film-forming polymer (a) is insoluble and stably dispersed in the mixed system of the diluent (b) and the crosslinking agent (c), and the remaining part is dissolved. A composition according to claim 1 or 2. (6) The composition according to any one of claims 1 to 5, wherein the crosslinking agent (c) is an aminoplast resin. (7) The composition according to any one of claims 1 to 5, wherein the crosslinking agent (c) is a polyisocyanate.