JPH03220274A - High-solid coating composition, article coated therewith, and method for coating - Google Patents

Abstract

PURPOSE:To improve both the flow-controlling action of a coating film and an excellent appearance by compounding a mixture of a polyol resin with a hydroxyl-reactive curing agent with a specific powdered crosslinked polymer. CONSTITUTION:30-90wt.% polyol resin, pref. an acrylic resin, and 10-70wt.% hydroxyl-reactive curing agent, pref. an alkyl-etherified melamine resin having 8C or lower alkyl groups and a number-average mol.wt. of 1000 or lower, are mixed, if necessary with a reactive diluent, a curing accelerator, etc. 100 pts.wt. (based on the solid content) resulting mixture is compounded with 1-100 pts.wt. powdered crosslinked polymer having a mean particle diameter of 0.001-1.0mum and a hydroxyl value (OHV)g, which is in a relation shown by the formula with the hydroxyl value of the polyol resin, (OHV)r.

Description

Detailed Description of the Invention (Field of Industrial Application) The present invention relates to a high solid coating composition applicable to steel plates or plastic materials, coated objects using the same, and coating methods. 1 of crosslinked polymer fine particles that are very fine in diameter and have a hydroxyl value that is in a certain relationship with the hydroxyl value of the polyol resin in the coating film-forming resin.
The present invention relates to a high-appearance high-solid coating composition containing a specific amount of one species or a combination of two or more species, a coated article using the same, and a coating method.

(Prior Art) In recent years, the need for high solid paints has been increasing in fields such as automobile paints with the aim of reducing organic solvent emissions.

Generally, in order to make paints highly solid, it is known to use low viscosity base materials, curing agents, or crosslinked polymer fine particles.

Here, the addition of cross-linked polymer fine particles is used not only for the purpose of high solids, but also for the purpose of controlling the flow of the paint, such as preventing sagging in vertical coating areas and adjusting the orientation of metals such as aluminum and inorganic flat pigments. It is also known that
-129065, JP-A-60-250067, JP-A-61-42579). In addition, uniform orientation of aluminum pigments and the like leads to a smoother surface of the paint film, and the anti-sagging effect allows for thick film coating, resulting in a paint film with high quality appearance.

At this time, in order to give the crosslinked polymer fine particles a flow regulating effect and achieve a high appearance, it is necessary to control the interparticle interaction, which is thought to be based on the interparticle hydrogen bonding force, and to adjust the interaction between the coating film-forming resin and the particles. It is necessary to highly control the degree of particle aggregation based on the polarity difference.

From this point of view, for example, Japanese Patent Application Laid-Open No. 1-17246
In Publication No. 4, the quality of the appearance of the coating film is improved by defining the relationship between the hydroxyl value of the crosslinked polymer fine particles and the hydroxyl value of the coating film forming resin.

On the other hand, a low-viscosity polyol is generally used as a base material, and a low-molecular-weight alkyl etherified melamine resin or an isocyanate compound is generally used as a curing agent.

In order to lower the viscosity of a polyol resin, it is usually necessary to lower the molecular weight and glass transition temperature (hereinafter abbreviated as Tg), but if these are lowered indefinitely, it will naturally affect the physical properties of the coating after curing. It will come. Therefore, for example, in U.S. Pat. No. 4,276,212 and U.S. Pat. No. 4,291,137, the molecular weight, Tg, and hydroxyl group concentration of the polyol resin are specified, and the blending amount of the alkyl etherified melamine resin as a curing agent is specified. Performs adjustment.

(Problem to be solved by the invention) However, in conventional crosslinked polymer fine particles (hereinafter sometimes simply referred to as particles), there are coarse particles with a particle size of several tens of micrometers, and there are ionic groups on the particle surface. Because of its presence, there are drawbacks such as difficulty in freely controlling the polarity relationship with the coating film-forming resin, and it is still insufficient to achieve both flow control and high appearance properties of the coating film.

That is, if coarse particles are present in the paint, the surface of the paint film will be rough and the sharpness of the image will be reduced. In particular, if it is present in base coats containing flat pigments, such as metallic 2-coat, 1-bake paint films, the smoothness of the paint film will be impaired, and if it is present in clear coats, minute irregularities on the paint film surface will become noticeable. This results in a decrease in the gloss of the paint film. In addition, in this case, when used for hair coats and when used for clear coats, the desired flow adjustment effect is the orientation adjustment of metal pigments in the former case, and is different from the sagging effect in the latter case, so the form of each coating film is different. The hydrogen bonding force between particles and the degree of aggregation must be controlled in a well-balanced manner according to the However, if there are ionic groups on the particle surface or non-polar dispersion stabilizer components, etc., it is difficult to exert the highly balanced flow regulating effect as described above. there were.

Furthermore, in cases where the viscosity decreases markedly during baking and melting, such as high-solid paints, a greater flow control effect is required; Merely increasing the fluidity regulating effect by increasing the amount has a limit due to rough skin, decreased gloss, decreased compatibility, etc., and there is also a small degree of freedom in terms of interparticle hydrogen bonding force.

Therefore, controlling the polarity difference between particles is an extremely important factor in obtaining a coating film with high appearance.

For example, in the method of JP-A-53-133234,
Due to constraints on synthesis, a nonpolar dispersion stabilizer component is present on the particle surface, so the polarity relationship with the coating film-forming resin cannot be controlled. Further, since there are particles having a large particle size of 0.01 to 10 μm, problems such as rough skin and decreased gloss arise.

In addition, even in the method of JP-A-58-129065, there are amphoteric ionic groups on the particle surface, and there is no mention of the polarity of the particle constituent material itself, so the relationship between the coating film-forming resin and the particles is Because the polarity difference is not taken into account and there are particles with large particle sizes of 0.02 to 40 μm,
This also causes problems such as rough skin and decreased gloss.

Furthermore, JP-A-60-250067, JP-A-61
In the method of Publication No. 42579, the glossiness of the coating film is improved by matching the refractive index of the particles and the coating film-forming resin. Since the difference in polarity between the particles was not taken into consideration and there were particles with large particle diameters of 0.01 to 10 μm, rough skin and deterioration of gloss were unavoidable in this case as well.

On the other hand, in the method disclosed in JP-A-1-172464, the particle size is reduced to 0.001 to 0.1 μm, and the relationship between the hydroxyl value of the particles and the hydroxyl value of the coating film-forming resin is regulated, and the polarity difference between the two is controlled. However, since surfactants and polymerization initiator fragments are supported on the outermost surface of the particles and ionic groups exist, the polarity of the particle surface is determined by these ionic groups. Therefore, strictly speaking, it could not be said that the polarity difference between the coating film-forming resin and the particles was controlled. Therefore, it is still insufficient in cases such as two-coat, one-bake metallic paints, high solid type paints, etc., which require a highly balanced flow control effect.

On the other hand, regarding polyol resins, conventional high solid coating compositions are mainly aimed at one-coat, one-hake systems, and are disclosed in U.S. Pat.
In the method of No. 291137, when applied to a base coat/clear coat system that has recently become mainstream especially in the field of automobile paints, the adhesion at the base coat/clear coat interface may be insufficient.

(Means for Solving the Problems) As a result of intensive research into methods for solving these problems, the present inventors reduced the particle size of the crosslinked polymer fine particles contained in the coating composition, and Only hydroxyl groups are allowed to exist as reactive functional groups on the surface, and the hydroxyl value of the particles is specified to have a certain relationship with the hydroxyl value of the polyol resin in the coating film-forming resin, and two or more types of particles are used. In some cases, it has been found that by specifying the hydroxyl values of each particle in a certain relationship, it is possible to achieve both a high degree of flow control and high appearance of the coating film. In addition, in the base coat/clear coat system, we have found that by lowering the glass transition temperature of the polyol resin used for the hair coat than the glass transition temperature of the polyol resin used for the clear coat, it is possible to improve the adhesion at the base coat/clear coat interface, The present invention has now been completed.

That is, in the present invention, the polyol resin is 30 to 90% by weight.
and 10 to 70% by weight of a curing agent capable of reacting with hydroxyl groups.
It has an average particle size of 01 to 1.0 μm, and its hydroxyl value (O
HV)g is the hydroxyl value (O)Iν)r of the polyol resin and O≦l (OHV) r-(OHV)g≦1
A high solid coating composition containing 1 to 100 parts by weight of crosslinked polymer fine particles having a relationship of 60, a coated article using the same, and a coating method.

The crosslinked polymer fine particles used in the present invention are extremely small particles with an average particle size of 1.0 μm or less at maximum, so the particle surface area is large and interparticle interactions, which are thought to be based on hydrogen bonding forces, work effectively ( In addition, since the reactive functional groups present on the particle surface are reduced to only hydroxyl groups by subjecting the particles to the treatment described below, the polarity of the particle surface can be uniquely expressed using the hydroxyl value as a parameter. Then, by specifying the relationship between the hydroxyl value of the particles and the hydroxyl value of the polyol resin, and when using two or more types of particles, also identifying the relationship between the hydroxyl values of each particle, the polarity difference of the rain particles can be determined. Therefore, for example, in the case of a metallic 2-coat, 1-hake coating, with Heath Coat, flat pigments such as aluminum are oriented uniformly by the synergistic effect of particle aggregation due to interparticle hydrogen bonding force and polarity difference. By suppressing particle aggregation due to polarity differences, clear coats can eliminate minute irregularities on the surface of the coating film, and also have excellent anti-sagging effects due to interaction through hydrogen bonds. For high-solid paints that require fluidity adjustment, a large particle aggregation effect can be provided without causing roughness or loss of gloss of the paint film.

Therefore, the high-solid paint composition of the present invention has an excellent flow control function, allows thick film coating, and also does not cause roughness or minute irregularities on the surface of the paint film, resulting in a high-quality paint film. Obtainable.

As the polyol resin used in the present invention, acrylic resin is particularly preferred in order to utilize the present invention more effectively, but other examples include polyester resin, alkyd resin, epoxy resin, polyurethane resin, fluororesin, Silicone resins, polycarbonate resins, polyether resins, and the like may be used alone or as a mixture of two or more within the range of compatibility.

When using an acrylic resin as a polyol resin in a base coat/clear coat system paint, the properties of the acrylic resin are preferably within the following ranges.

The important point here is that the Tg of the acrylic resin used for the base coat is lower than the Tg of the acrylic resin used for the clear coat. By maintaining this relationship, excellent adhesion can be achieved at the base coat/clear coat interface.

Therefore, if the Tg of the acrylic resin in the base coat exceeds 20°C, or if the Tg of the acrylic resin in the clear coat exceeds 20°C,
If g is less than 20°C, the adhesion at the base coat/clear coat interface may decrease.

On the other hand, if the Tg of the acrylic resin in the base coat is less than 10°C, the solvent resistance of the cured film will decrease, and if the Tg of the acrylic resin in the clear coat exceeds 50°C, the bending resistance of the cured film will decrease. This is not preferable because it lowers the temperature.

If the weight average molecular weight of the acrylic resin for the base coat and clear coat is less than 3,000, the weather resistance of the cured coating film will be lowered, and if it exceeds 15,000, it will be difficult to achieve high solubility, which is not preferred. When the hydroxyl value of the acrylic resin is less than 50, the solvent resistance of the cured coating film decreases, and
If it exceeds 50, it is not preferable because the bending resistance of the cured coating film decreases. If the acid value of the acrylic resin exceeds 30, it is not preferable because the moisture resistance of the cured coating may decrease.

Furthermore, when using an acrylic resin as a polyol resin in a base coat/clear coat system for flexible plastic materials such as polypropylene resin and polyurethane resin, it is desirable that the properties of the acrylic resin fall within the following ranges. .

In the second case as well, it is important that the Tg of the acrylic resin used for the base coat is lower than the Tg of the acrylic resin used for the clear coat. By maintaining this relationship, excellent adhesion can be achieved at the base coat/clear coat interface.

Here, the Tg of the acrylic resin of the base coat exceeds 11°C, or the Tg of the acrylic resin of the clear coat
If the temperature is less than 120°C, the adhesion at the base coat/clear coat interface will decrease, which is not preferable. Furthermore, if the Tg of the acrylic resin in the base coat is less than 160°C, the solvent resistance of the cured film will decrease, and if the Tg of the acrylic resin in the clear coat exceeds 19°C, the flexibility of the cured film will decrease. It is not desirable because

If the weight average molecular weight of the acrylic resin for the base coat and clear coat is less than 4,000, the weather resistance of the cured coating film will be reduced, and if it exceeds 40,000, the coating workability will be reduced, which is not preferred. When the hydroxyl value of the acrylic resin is less than 30, the solvent resistance of the cured coating film decreases;
If it exceeds 0, it is not preferable because the flexibility of the cured coating film decreases. If the acid value of the acrylic resin exceeds 30, it is not preferable because the moisture resistance of the cured coating may decrease.

Acrylic resin has a hydroxyl group-containing α, β-ethylenically unsaturated monomer as an essential component, and is mixed with other α, β-ethylenically unsaturated monomers in a normal radical solution within a range that satisfies the above-mentioned hydroxyl value. It can be easily synthesized by polymerization. Here, as the hydroxyl group-containing α,β-ethylenically unsaturated monomer, for example, 2-hydroxyethyl (meth)
Acrylate, 2-hydroxypropyl (meth)acrylate, 3-hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, 3-hydroxybutyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, di Pentaerythritol hexa(meth)acrylate, 2-hydroxyethyl (
Examples include a ring-opened adduct of ε-caprolactone (1 to 10 mol) to meth)acrylate, a ring-opened adduct of ε-caprolactone (1 to 10 mol) to 2-hydroxypropyl (meth)acrylate, and the like. In addition, other α,β-ethylenically unsaturated monomers include, for example, methyl (meth)
Acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, isopropyl (meth)acrylate, n-butyl (meth)acrylate, isobutyl (meth)acrylate, 5ec-butyl (meth)acrylate, t-butyl (meth)acrylate , n-hexyl (meth)acrylate, cyclohexyl (meth)acrylate, hensyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, lauryl (meth)acrylate, stearyl (meth)acrylate, glycidyl (meth)acrylate, styrene, α -methylstyrene, p-vinyltoluene, (meth)acrylonitrile,
(Meth)acrylic acid, (meth)acrylamide, vinyl acetate, vinyl propionate, vinyl butyrate, vinyl caproate, itaconic acid, crotonic acid, fumaric acid, maleic acid, butadiene, vinyl chloride, vinylidene chloride, diptyl fumarate, anhydrous Examples include maleic acid, allyl glycidyl ether, and allyl alcohol, which are used for the purpose of satisfying the above-mentioned glass transition temperature and acid value ranges and adjusting compatibility.

On the other hand, in the case of the high solid coating composition of the present invention, the following reactive diluent can be contained as a polyol resin component. That is, (1) polyether polyols polyethylene glycol 200, 300, 400,
600, 1000, 1500, 1540, 2000 (all number average molecular weights of polyethylene glycol), Uniol D400, 0700, 010
00, D1200, 02000, TG 400
, TG1000, TG2000 (all product names, polypropylene glycol manufactured by NOF ■) (2) Caprolactone polyols Plaxel 205, 208, 212, 220, 230, 303, 305, 308 (products) Polycaprolactone manufactured by Daicel Chemical Industries, Ltd.) (3) Ester polyols Flexoret 188, 148, XP-171-9
0 (trade name, ester diol manufactured by King Co., Ltd.) (4) Urethane polyols Flexolets [1O-320 (trade name, manufactured by King Co., Ltd.)
urethanediol), urethanediol UP-144 (
(trade name, manufactured by Auto Kagaku Kogyo ■, urethane diol) (5) Silicone polyols such as KR-213, KR-217, KR-218 (trade name, manufactured by Shin-Etsu Chemical ■, methoxy group-containing silicone compound), ethylene glycol, propylene glycol ,1,3-
Butanediol, 1,4-butanediol, 1,5-butanediol, 1,6-hexanediol, diethylene glycol, dipropylene glycol, neopentyl glycol, triethylene glycol, hydrogenated bisphenol A1 bisphenol dihydroxypropylethyl,
These include condensates with diols such as cyclohequine dimethanol at a mixing ratio of methoxy groups/hydroxyl groups of -172 (molar ratio).

In addition, examples of curing agents that can react with hydroxyl groups include:
Examples include aminomethylol resins such as melamine resins, urea resins, henzoguanamine resins, and glycolyl resins, polyisocyanate compounds, and blocked isocyanate compounds. Among these, in the case of the high solid paint of the present invention, an alkyl etherified melamine resin with an alkyl group having 8 or less carbon atoms and a number average molecular weight of 1000 or less, a polyisocyanate compound or a blocked isocyanate with a number average molecular weight of 1000 or less Compounds etc. are particularly preferred. Here, if the number of carbon atoms in the alkyl group of the alkyl etherified melamine resin exceeds 8, it is not preferable because the water resistance of the resulting coating film decreases.

In addition, when the number average molecular weight of the polyisocyanate compound and the blocked isocyanate compound in the alkyl etherified melamine resin exceeds 1000, it becomes difficult to achieve high solidification.

Such alkyl etherified melamine resins are commercially available products such as Cymel 300, Cymel 301, Cymel 303, Cymel 350, Cymel 1116, Cymel 1130, Cymel 1168 (all manufactured by American Cyanamid Company, trade names), Nikalac. IIW-
30, Nikalak MW-22A, Nikalak MX-40
, Nikalac MX-45 (all manufactured by Sanwa Chemical Co., Ltd., trade names), Remin 730, Remin 731, Remin 735, Remin 745, Remin 746, Remin 747, Remin 753, Remin 755, Remin 764 (all manufactured by Monsando) (manufactured by Mitsui Toatsu Co., Ltd., trade name), and Kneepan 120 (manufactured by Mitsui Toatsu Co., Ltd., trade name).

In this case, aromatic or aliphatic sulfonic acid compounds can be used as the curing catalyst, but aliphatic sulfonic acid compounds are preferable in terms of storage stability of the paint, appearance of the coating film, etc. In addition, the polyisocyanate compound is an aromatic or aliphatic compound having two or more isocyanate groups in one molecule, such as 2,4-tolylene diisocyanate, 4,4'-diphenylmethane diisocyanate, 1,6- Polyisocyanate compounds such as xamethylene diisocyanate and cyclohexane 1,4-diisocyanate, alcohols such as ethanol and hexanol, compounds having phenolic hydroxyl groups such as phenol and cresol, and oximes such as acetoxime and methyl ethyl ketoxime. Examples include blocked isocyanate compounds blocked with blocking agents such as lactams such as , ε-caprolactam, and T-caprolactam.

Here, the mixing ratio of the polyol resin and the curing agent is used in the range of 10 to 70% by weight of the curing agent to 30 to 90% by weight of the polyol resin. At this time, the polyol resin
If it is less than 0% by weight, the chemical resistance of the resulting coating film will decrease, and if it exceeds 90% by weight, the water resistance of the resulting coating film will decrease, which is not preferable.

The crosslinked polymer fine particles used in the present invention have an average particle size of 0.0
01 to 1.0 am, the total amount of crosslinked polymer fine particles is 1 to 100 parts by weight per 100 parts by weight of a resin solid mixture consisting of 30 to 90% by weight of a polyol resin and 10 to 70% by weight of a curing agent capable of reacting with hydroxyl groups. Contains parts by weight.

However, in clear coat paint compositions used for 2-coat paints and 3-coat paints, it is necessary to smooth even minute surface irregularities, so the total content of crosslinked polymer fine particles is 1 to 60 parts by weight. It is preferable. At this time, if the average particle size is less than 0.001 μm, the crosslinked polymer fine particles become unstable and aggregate violently in the paint, making it impossible to improve the appearance of the paint film. Since the particles themselves have a large particle size and the reactivity of the hydroxyl groups on the particle surface decreases, the surface of the coating film becomes uneven, which is not preferable. Here, the particles are preferably adjusted to have a refractive index difference of 0.005 or less with respect to the coating film-forming resin, as in the known technique ("ABS Resin" p. 53, published by the Society of Polymer Science, 1970, Maruzen Co., Ltd.). If the content of the crosslinked polymer fine particles is less than 1 part by weight, the flow control effect of the coating film will be insufficient and metal unevenness in the base coat will occur. If the amount exceeds 100 parts by weight, the fluidity regulating effect becomes too large and the leveling property may deteriorate.

On the other hand, the hydroxyl value (OHV) g of the crosslinked polymer fine particles is
In relation to the hydroxyl value (OHV) r of the polyol resin, 0≦](OHV)r −(OHV)g |≦160
By satisfying the following conditions, an excellent flow regulating effect can be exhibited. However, in high solid paint compositions for clear coats used in two-coat and three-coat paints, it is necessary to smooth out even minute irregularities caused by particle aggregation, so the hydroxyl value of the crosslinked polymer fine particles (
The relationship between OHV)g and the hydroxyl value (OHV)r of the polyol resin preferably satisfies 0≦|(OHV)r−(OHV)g|≦100.

Here, the hydroxyl value (OHV) r of the polyol resin is
When it is a mixture of two or more types or contains the above-mentioned reactive diluent, the value can be taken as the arithmetic average of the weight ratios of all polyol components.

In addition, the hydroxyl value (OHV) g of crosslinked polymer fine particles is the hydroxyl value of the entire particle in the case of particles obtained by normal emulsion polymerization method, and the hydroxyl value of the shell part in the case of particles obtained by core/shell type emulsion polymerization. The hydroxyl value is In particular, when using particles obtained by core/shell type emulsion polymerization or when containing a reactive diluent in the polyol resin, excellent coating properties can be achieved even in systems where (OHV)g is higher than (OHV)r. A good film appearance can be obtained. l (OHV)r
If -(OHV) g l exceeds 160, particle aggregation due to polarity differences becomes too large, which is undesirable because it tends to cause rough skin in the hair coat and minute irregularities in the clear coat.

On the other hand, when two or more types of crosslinked polymer fine particles are used, a more highly balanced flow regulating effect can be exhibited. At this time, the hydroxyl value (OHV) g of each particle is O≦| in relation to the hydroxyl value (OHV) r of the polyol resin.
(OHV)r-(OHV)g ｜≦160,
Furthermore, the difference between the maximum and minimum values of (OHV)g for each particle
must satisfy O<x≦120. However, in high solid paint compositions for clear coats used in 2-coat paints and 3-coat paints, it is necessary to smooth out even minute irregularities caused by particle aggregation, so X is 10≦x.
It is preferable that ≦60. If X exceeds 120, particle aggregation due to polarity differences becomes too large, which is undesirable because roughness in the hair coat and fine irregularities in the clear coat tend to occur.

Furthermore, when two or more types of crosslinked polymer fine particles are used, the content of each crosslinked polymer fine particle is preferably 10% by weight or more based on the total amount of crosslinked polymer fine particles. The ungrooved crosslinked polymer fine particles are 10% by weight of the total amount of particles,
This is not preferable because it may not be able to contribute to a highly balanced flow regulating effect.

The crosslinked polymer fine particles used in the present invention have the following components (a) hydroxyl group-containing α, β-ethylenically unsaturated monomer (b) polyfunctional α, β-ethylenically unsaturated monomer (c) (a ) and β-ethylenically unsaturated monomers other than (b) are subjected to emulsion polymerization or core/shell type polymerization using a water-soluble polymerization initiator in the presence of a soap-free or ester group-containing surfactant. It can be synthesized by emulsion polymerization. Among these, component (a) is used to adjust the hydroxyl value (OHV) g of the crosslinked polymer fine particles, and is used to adjust the hydroxyl value (OHV) g of the polyol resin.
) is used to satisfy the above relationship with r. It takes (
As the component a), for example, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 3-hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, 3
- ε-caprolactone (1 to 10
mole) ring-opening adduct, ε-cabrolactone (1 to 10 mole) ring-opening adduct of 2-hydroxypropyl (meth)acrylate (e.g., manufactured by Daicel Chemical Industries, trade name: Praxel FM1, Praxel FM2, Praxel FM3, Praxel FM3, FM?, FMI
O), 2-hydroxyethyl (meth)acrylate, or 2-hydroxypropyl (meth)acrylate, other lactones such as β-propiolactone, β-butyrolactone, γ-butyrolactone, pivalolactone,
1 to 10 such as T-valerolactone, δ-valerolactone, etc.
molar ring-opening adducts of ethylene oxide and/or propylene oxide of (meth)acrylic acid;
10 molar ring-opening adduct (e.g., manufactured by NOF ■, trade name,
Blenmar PP500, PP800, PP100
0, PE90, PE200, PE350, PE
P350B) or a monomer R represented by the following formula.

υ Lltl υ(
Here, R1 is either a hydrogen atom or a methyl group, R
2 is an alkylene group having 1 to 17 carbon atoms, and n is an integer of 1 to 10. ) etc. can be used singly or as a mixture of two or more.

In addition, component (b) three-dimensionally crosslinks the inside of the polymer fine particles,
It is used to maintain a stable particle form without dissolving in paints, and is usually used in the range of 0.5 to 80% by weight of components (a), (b), and (c). Examples of the component (b) include divinylhenzene, diallyl phthalate, diallyl terephthalate, ethylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, and polyethylene glycol di(meth)acrylate. meth)acrylate, 1,4-butanediol di(meth)acrylate, 1.3-butylene glycol di(meth)acrylate, 1.6-hexanethiol di(
meth)acrylate, neobentyl glycol di(meth)acrylate, 2-hydroxy 1,3-di(meth)acryloxypropane, 22-bis[:4-((meth)acryloxyethoxy)phenyl]propane, trimethylol Propane tri(meth)acrylate, tetramethylolmethanetri(meth)acrylate, pentaerythritol tri(meth)acrylate, dipentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol tetra(meth)acrylate, Examples include dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate, tetramethylolmethanetetra(meth)acrylate, epoxy prepolymer, and urethane(meth)acrylate, used as a type or as a mixture of two or more types. It will be done.

If 0.5% by weight of component (b) in the fine particles is ungrooved, the crosslinking density within the particles is too low, so when used in a non-aqueous paint, the particles will swell with the solvent and the viscosity will increase. It ends up. Moreover, if it exceeds 80% by weight, the unreacted crosslinking agent within the particles will react between the particles, resulting in agglomeration of the particles, which is not preferable.

Furthermore, the α,β-ethylenically unsaturated monomer of component (c) is a monomer that does not contain any reactive functional groups other than unsaturated groups, such as methyl (meth)acrylate, ethyl (meth)acrylate, etc. ) acrylate, lowpropyl (meth)acrylate, isopropyl (meth)acrylate, n-butyl (meth)acrylate, isobutyl (meth)acrylate, 5ec-butyl (meth)acrylate, t-butyl (meth)acrylate, n-hexyl ( meth)acrylate, cyclohexyl(meth)acrylate, Hensyl(meth)acrylate, 2-ethylhexyl(meth)acrylate, lauryl(meth)acrylate, stearyl(meth)acrylate, styrene, α-methylstyrene, p-vinyltoluene, (meth)acrylate ) acrylonitrile,
Vinyl acetate, vinyl propionate, vinyl butyrate, vinyl caproate, vinyl 2-ethylhexanoate, vinyl laurate, vinyl stearate, vinyl chloride, vinylidene chloride, dibutyl fumarate, etc. depending on the coating used. The compatibility of the crosslinked polymer fine particles, the glass transition temperature,
It is used singly or as a mixture of two or more for the purpose of adjusting acid value and the like.

On the other hand, ester group-containing surfactants used in emulsion polymerization include anionic surfactants such as alkyl sulfate ester salts, monoalkyl sulfosuccinates, dialkyl sulfosuccinates, alkyl ether sulfates, and polyoxyethylene alkylphenyl ether sulfates. Salts, alkyl phosphate ester salts, alkyl ether phosphate ester salts, and Na salts, salts, or amine salts of sulfonic acid compounds represented by the following formulas can be used alone or as a mixture of two or more.

1 R3-0-C-CH2SO31 ((Here, R3 is an alkyl group having 12 to 18 carbon atoms.) Here, as the alkyl sulfate salt, for example,
Sodium lauryl sulfosuccinate, sodium 2-ethylhexyl sulfate; monoalkyl sulfosuccinate salts such as sodium hexyl sulfosuccinate; dialkyl sulfosuccinate salts such as sodium dihexyl sulfosuccinate, sodium di-2-ethylhexyl sulfosuccinate; alkyl Examples of ether sulfates include sodium polyoxyethylene lauryl ether sulfate; examples of polyoxyethylene alkylphenyl ether sulfates include sodium polyoxyethylene octylphenyl ether sulfate; examples of alkyl phosphate ester salts include potassium lauryl phosphate; Examples of alkyl ether phosphate salts include potassium polyoxyethylene lauryl phosphate, which can be used alone or as a mixture of two or more.

Examples of cationic surfactants include compounds represented by the following formula.

L-0-C-C1,N■ (cH3)3C1○ (where,
R4 is an alkyl group having 12 to 18 carbon atoms. ) When carrying out emulsion polymerization, the amount of the surfactant used is preferably 7% by weight or less relative to water. If the surfactant concentration exceeds 7% by weight, the ionic compound generated by hydrolyzing the surfactant tends to remain in the non-aqueous polymer dispersion, reducing the water resistance of the coating film. It is not desirable because

Through such emulsion polymerization, the average particle size is 0°001 to 1.0 μm.
crosslinked polymer fine particles can be obtained.

In addition, examples of water-soluble polymerization initiators used in emulsion polymerization or core/shell type emulsion polymerization include potassium persulfate,
Persulfates such as sodium persulfate and ammonium persulfate are particularly preferred, and are used singly or as a mixture of two or more. Of course, at this time, ferrous salt, acidic sodium sulfite, and N.

N-dimethylaniline or the like can also be used in combination with a persulfate as a redox polymerization system.

Here, the amount of water-soluble polymerization initiator used is 1 to 10% by weight based on the total amount of α,β-ethylenically unsaturated monomers in the case of a soap-free system, and in the presence of a surfactant, the amount used is 0. .1
It is used within the range of ~2% by weight. In the case of soap-free systems, if the water-soluble polymerization initiator is less than 1% by weight, the polymer particles will aggregate due to poor emulsification, and if it exceeds 10% by weight, the polymer particles will aggregate due to salting out, which is undesirable. .

In the presence of a surfactant, if it is less than 0.1% by weight, the polymerization conversion rate will be insufficient and it will be difficult to form polymer particles, and if it exceeds 2% by weight, the polymer particles will agglomerate due to salting out. Therefore, it is undesirable.

The cross-linked polymer fine particles obtained as described above are treated with the ester group-containing surfactant and water-soluble polymerization initiator fragments (hereinafter referred to as ionic groups) supported on the particle surface by performing the following steps. (sometimes abbreviated) can be decomposed and removed, leaving only hydroxyl groups as the reactive functional groups present on the particle surface. By carrying out this step, particles can be obtained as a non-aqueous dispersion.

That is, first, an organic solvent that does not cause dissolution or aggregation of the particles and does not cause water separation is added to an aqueous dispersion of crosslinked polymer fine particles produced by emulsion polymerization. Such organic solvents include organic solvents that have hydroxyl groups on the particle surface and amphiphilic properties.
It is desirable to contain 0 to 100% by weight. Examples of amphipathic organic solvents include alcohols, ketones,
Ethers or glycol ethers are suitable, and can prevent aggregation between particles by forming hydrogen bonds with hydroxyl groups on the particle surface. Here, if the amount of the amphipathic organic solvent is less than 20% by weight, this is not preferable because particle aggregation and water separation will occur.

Examples of such organic solvents having amphiphilic properties with the hydroxyl groups on the particle surface include the following, which can be used alone or in a mixture of two or more.

Alcohols: 2-ethyl-1-butyl alcohol, 3
-heptyl alcohol, ■-octyl alcohol, 2-
Octyl alcohol, 2-ethylhexyl alcohol,
1-nonyl alcohol, 3.5.5-trimethyl-1-
Hexyl alcohol, 1-decyl alcohol, 1-undecyl alcohol, ■-dodecyl alcohol, n-butyl alcohol, n-pentyl alcohol, n-hexyl alcohol, nibutyl alcohol, isobutyl alcohol, 2-pentyl alcohol, 4-methyl -2-pentyl alcohol, 3-pentyl alcohol, 2-methyl-1-butyl alcohol, ketone cheeks: methyl n-propyl ketone, methyl isopropyl ketone, diethyl ketone, methyl n-butyl ketone, methyl isobutyl ketone, methyl n-pentyl ketone , diropropyl ketone, diisobutyl ketone, ethyl n-butyl ketone, methyl ethyl ketone ethers diethyl ether, dipropyl ether,
Diisopropyl ether, dibutyl ether, dibutyl ether, dioxane, tetrahydrofuran, tetrahydropyran, 1. 2-Jetoxyethane glycol ethers = 2-isopentyloxyethanol, 2-hexyloxyethanol, 2-phenoxyethanol Organic solvents other than the above, that is, organic solvents that do not have hydroxyl groups on the particle surface and amphiphilic properties, It is used in an amount of 0 to 80% by weight for the purpose of simplifying the step of removing residual water after conversion to a non-aqueous system, and is preferably added to and mixed with the organic solvent until the solubility of water at 20°C becomes 5% by weight or less. Examples of such organic solvents include the following, which can be used alone or as a mixture of two or more, but the present invention is not limited thereto.

Aliphatic solvents: n-pentane, n-hexane, n-hebutane, cyclohexane, methylcyclohexane, ethylcyclohexane Aromatic? g Agent: benzene, toluene, xylene, ethylbenzene ester solvent: ethyl acetate, n-propyl acetate, isopropyl acetate, n-butyl acetate, isobutyl acetate, nibutyl acetate Also added to the aqueous dispersion of crosslinked polymer fine particles The amount of organic solvent used is in the range of 5 to 90% by weight, preferably 10 to 90% by weight of the total weight of the aqueous dispersion of crosslinked polymer fine particles and the organic solvent.
It is mixed in a range of 70% by weight. Here, if the organic solvent is less than 5% by weight, the crosslinked polymer fine particles will aggregate,
This is not preferable because the viscosity of the system becomes high and stirring cannot be carried out efficiently.

If it exceeds 90% by weight, the aqueous layer and organic layer will separate, and the hydrolysis reaction on the surface of the polymer particles in the next step will be insufficient, and the reactive functional groups on the particle surface may be other than hydroxyl groups. Therefore, it is undesirable.

After adding an organic solvent to the aqueous dispersion of crosslinked polymer fine particles, a hydrolysis step is then performed. The purpose of the hydrolysis reaction is to divide and remove the ionic groups on the particle surface, reduce the reactive functional groups on the particle surface to only hydroxyl groups, and then completely transfer the particles to the organic layer without agglomeration. ,95℃
At the following temperature, preferably 70 to 95°C, a basic compound catalyst is used when an anionic surfactant is used, an acidic compound catalyst is used when a cationic surfactant is used, and soap-free emulsion polymerization is carried out at a temperature of 70 to 95°C. is reacted with a basic compound catalyst or an acidic compound catalyst. Here, if the reaction temperature exceeds 95°C, not only the ionic groups on the particle surface but also other ester groups are hydrolyzed to form carboxyl groups, and reactive functional groups other than hydroxyl groups are formed on the particle surface. Undesirable.

Moreover, when the reaction temperature is less than 70°C, it is not preferable because it takes a long time to complete the hydrolysis reaction.

In addition, the amount of the basic compound catalyst or acidic compound catalyst added is 1% to the stoichiometric amount of the ester group to be hydrolyzed.
It is desirable that the amount be 3 to 3 times the amount; if the amount added is less than the same amount, the hydrolysis rate will be insufficient and the ionic group will tend to remain on the particle surface, which is not preferable. Moreover, if the amount added exceeds 3 times the amount, the acrylic ester constituting the particles begins to be hydrolyzed and carboxyl groups are formed on the particle surface, which is not preferable. Here, the ester group to be hydrolyzed means the sum of twice the amount of persulfate and the total amount of ester groups of the surfactant. Examples of basic compound catalysts include sodium hydroxide, potassium hydroxide, lithium hydroxide, tetramethylammonium hydroxide, and tetraethylammonium hydroxide, and examples of acidic compound catalysts include sulfuric acid, hydrochloric acid, p-)
Examples include luenesulfonic acid, methanesulfonic acid, and benzenesulfonic acid. The degree of progress of hydrolysis can be monitored by neutralization titration of the consumption amount of the added basic compound catalyst or acidic compound catalyst, and the end point of the reaction can be easily determined.

After the hydrolysis reaction is completed, in a system using a basic compound catalyst, use the same acidic compound as the above acidic compound catalyst, or in a system using an acidic compound catalyst, use the same basic compound as the above basic compound catalyst. A neutralization reaction is carried out according to a conventional method, and then 10 to 200 parts by weight of a dispersion stabilizing resin is added to 100 parts by weight of the crosslinked polymer fine particles in terms of resin solid content to stabilize the dispersion of the particles. The dispersion stabilizing resin used here is preferably one that is compatible with the binder of the coating film, and includes at least hydroxyl group-containing acrylic resin, alkyd resin, polyester resin, or a mixture of two or more of them, melamine resin, henzoguanamine, etc. One or a mixture of two or more of amino resins such as resins, urea resins and glycolyl resins are preferred.

In addition, if the dispersion stabilizing resin is less than 10 parts by weight based on 100 parts by weight of the particles in solid resin content, the dispersion stabilization of the particles will be insufficient and the particles will fuse at the gas-liquid interface in the reaction device. There are things to do. Moreover, if it exceeds 200 parts by weight, it is not preferable because the efficiency of separation into two layers consisting of an organic layer containing polymer particles and an aqueous layer decreases.

After adding the dispersion stabilizing resin, add the organic acid amine salt, stop stirring, and let the system stand to separate into two layers: a resin solution layer (organic layer) containing particles and an aqueous layer containing inorganic ionic substances. urge The inorganic ionic substances mentioned here include surfactants, hydrolysis reaction products of water-soluble polymerization initiator fragments, and basic compound catalysts and acidic compound catalysts added during hydrolysis reactions and neutralization reactions. Alternatively, it includes salts produced by neutralization reactions. Here, it is preferable to heat the system in order to promote water separation, and the temperature of the system is set at 50 to 80°C.
Water separation efficiency can be increased by maintaining the temperature within the range of 0°C.

Examples of organic acids used in the organic acid amine salt added here include carboxylic acids such as formic acid, acetic acid, propionic acid, oxalic acid, and malonic acid, sulfonic acids such as methanesulfonic acid and ethanesulfonic acid, and monomethyl phosphoric acid. acid,
It includes organic phosphoric acids such as monoethyl phosphoric acid, dimethyl phosphoric acid, and diethyl phosphoric acid. On the other hand, as the amine, those having a boiling point of 150°C or less are particularly preferable, such as monoethylamine, propylamine, isopropylamine, n-
butylamine, isobutylamine, nibutylamine,
Primary amines such as t-butylamine and pentylamine,
Dimethylamine, diethylamine, dipropylamine,
Examples include secondary amines such as diisopropylamine, diisobutylamine, and dipentylamine, and tertiary amines such as trimethylamine, triethylamine, tripropylamine, tributylamine, and pyridine, but the present invention is not limited to these. Here, the boiling point is 150
If the temperature exceeds 0.degree. C., the amine may remain in the non-aqueous dispersion of crosslinked polymer fine particles, resulting in a decrease in coating film properties such as water resistance.

The organic acid amine salt consisting of the above combination of organic acid and amine can be easily produced by mixing predetermined amounts of the organic acid and amine at room temperature in the presence of water.

Further, the amount of organic acid amine salt added is suitably in the range of 0.1 to 10% by weight, preferably 1 to 5% by weight, based on the water present in the system. Since the separation efficiency between the layer and the organic layer decreases, and if the amount exceeds 10% by weight, the organic acid amine salt tends to remain in the non-aqueous dispersion of crosslinked polymer fine particles, resulting in a decrease in coating film performance such as water resistance. Therefore, it is undesirable.

Next, after removing the aqueous layer, the inorganic ionic substance remaining in the organic layer is washed with water, and the above organic acid amine salt is added and allowed to stand to separate and remove the washing water. The water washing process is repeated until the pH of the aqueous layer to be separated and removed becomes 5 to 8, and the amount of inorganic ionic substances remaining in the organic layer becomes 50 ppm or less. Here, the pH of the aqueous layer to be separated and removed is 5.
If it is less than or exceeds 8, or if the inorganic ionic substance remaining in the organic layer exceeds 50 ppm,
This is not preferred because the coating film performance such as water resistance deteriorates.

In addition, the residual moisture in the organic layer after washing with water is 5% by weight.
If the amount of water is lowered to 100%, it is possible to simplify the removal of residual water in the next step.

Residual moisture in the organic layer can be removed by the following method.

(a) Water distillation under reduced pressure b) Decomposition removal by reaction with a compound (c) Water absorption treatment with a water absorbing material (d) Water removal by azeotropic and spray drying (a) Method As it is a solvent-based product that does not make
This is a method in which only water is distilled off under reduced pressure of less than 760 mm) at 50 to 100°C. Method (b) involves adding orthocarboxylic acid esters such as methyl orthoformate, ethyl orthoformate, methyl orthoacetate, and ethyl orthoacetate, or diketene, or formamide, or dicyclohexylcarbodiimide, etc., at 30 to 90°C. This method decomposes residual moisture by reacting at a temperature of . If the decomposition temperature is less than 30"C, it will take a long time to decompose water, and if it exceeds 90"C, water droplets will adhere to the voids in the reactor, making moisture removal insufficient. do not have.

In the above water removal method, when orthocarboxylic acid esters are used, methyl alcohol, ethyl alcohol, methyl formate, ethyl formate, methyl acetate, ethyl acetate, etc. are produced as decomposition products, and when diketene is used, acetone and other decomposition products are produced. Since a boiling point solvent is produced as a by-product, it is preferable to distill off the low boiling point solvent under reduced pressure after the water decomposition reaction in order to prevent the coating film from flaking. Furthermore, when formamide is used, ammonium formate is used, and when dicyclohexylcarbodiimide is used, dicyclohexylurea is produced as a by-product, so it is necessary to filter out the decomposition products after the respective water splitting reactions. Method (c) uses polymeric water-absorbing materials such as Sumikagel 5-50, Sumikagel 5P-520, Sumikagel N-100, Sumikagel NP-
1020, F-03, F-51, F-75 (all product names, manufactured by Sumitomo Chemical), Aqua Keep 4S,
The organic layer is passed through a column packed with 10SH (both trade names, manufactured by Seitetsu Kagaku Kogyo ■) or molecular sieve, or the above-mentioned polymeric water absorbing material, molecular sieve, or sodium sulfate, calcium chloride,
Either or 2 dehydrated inorganic salts such as calcium oxide
This is a method in which a mixture of more than one species is mixed into an organic layer, stirred, and then filtered. (d) The law is e.g. UK Patent No. 967051
As cited on page 5 of the issue, this is a water removal method that is generally used to obtain dry particles after emulsion polymerization.
Water is azeotropically distilled off at 00°C. Alternatively, the organic layer is sprayed from a nozzle at 20 to 100°C, water is dried together with the organic solvent, and the dried residue is dispersed again in the organic solvent.

In order to form the high solids coating composition of the present invention into a paint, these components are mixed using a usual addition method using a dispersion device used for normal paint production, such as a ball mill, sand mill, attritor, etc. I can do it. At this time, in addition to colorants such as pigments, dyes, glass flakes, aluminum flakes, and mica flakes, additives commonly used in paints, such as pigment dispersants, viscosity modifiers, leveling agents, curing catalysts, gels, etc. Antioxidants, ultraviolet absorbers, radical scavengers, etc. can also be added.

The paint obtained in the above manner can be applied to ordinary objects to be coated, such as metals, other inorganic materials, plastics and Coating other organic materials using a system such as 1 coat 1 bake, 2 coats 2 bake, 2 coats 1 bake, 3 coats 3 bake, 3 coats 2 hakes, etc., and drying at a temperature of 60 to 180 degrees Celsius for 20 to 60 minutes. A superior coating film can be obtained.

The hair coat of the present invention referred to herein means pigments, dyes,
A clear coat is a coating with a high solid paint composition that is made of a coloring agent such as glass flakes, aluminum flakes, or mica flakes, and a clear coat is a high solid paint composition that is transparent or colored with a small amount of the above colorant. It is to paint.

(Effects of the Invention) As described above, the high solids coating composition of the present invention, the coated object using the same, and the coating method contain crosslinked polymer fine particles with extremely small particle diameters, and the surface of the particles has no reactive properties. Only hydroxyl groups are allowed to exist as functional groups, and the hydroxyl value of the particles is specified to have a certain relationship with the polyol resin in the coating film-forming resin, and when two or more types of particles are used, each particle has a certain relationship with the other. Because the hydroxyl value of the paint is also specified in a certain relationship, it is possible to exhibit an extremely well-balanced flow regulating effect, exhibit excellent anti-sagging effects, and enable thick film coating. A high-appearance coating film with a smooth surface and excellent gloss can be obtained.

Furthermore, in the base coat/clear coat system, by specifying the glass transition temperatures of the polyol resins used for the base coat and clear coat, a coating film with excellent adhesion at the base coat/clear coat interface can be obtained.

(Example) Next, the present invention will be explained in more detail with reference to Examples and Comparative Examples. In addition, in the examples, parts are parts by weight, and % is weight %.

Production of acrylic resin ■ 4 equipped with a reflux condenser, stirrer, and dropping funnel thermometer
61.8 parts of methyl amyl ketone was placed in a double flask, and the temperature was raised to 150° C. while stirring. Next, a mixture 100 of the monomer components and polymerization initiator shown in Table 1 was prepared.
The mixture was added dropwise at a constant addition rate over 2 hours at 150°C. After the completion of the dropwise addition, the reaction was terminated by maintaining the temperature at 150''C for an additional 2 hours to obtain acrylic resin solutions I to ①, each having the characteristic values shown in Table 1.

Production of Polyester Resin 100 parts of the monomer composition listed in Table 2 was charged into a four-bottle flask equipped with a water metering receiver equipped with a reflux condenser, a stirrer, and a nitrogen gas inlet tube, and the mixture was stirred. The temperature was raised to 230"C over 4 hours to carry out a dehydration condensation reaction, and then
The dehydration condensation reaction was continued by keeping the temperature at 30°C for 3 hours. Thereafter, 5.0 parts of xylene was added into the flask, and the reaction was continued by switching to a condensation reaction in the presence of a solvent. Resin acid value is 5
The reaction was terminated when the temperature decreased to 100%, and the reaction was cooled. After cooling,
In production example ■, xylene was 55.9 parts, and in production example ■, it was 5 parts.
Add 6.5 parts, stir until uniform, and add 2.
Polyester resin solutions (1) and (2) having the characteristic values shown in the table were obtained.

Table 2 Note 1) Previously, Table 1 Footnote 1) Note 2) JIS-K 54004.2.2 Production of cross-linked polymer fine particles using a bubble viscometer (a) Aqueous system of cross-linked polymer fine particles Manufacture of dispersion liquid deionized water Rapizole B90 (Note 1) 380.0 parts 5.5 parts Electron, ?・'-1 Deionized water 10.0 parts Sodium persulfate 0.3 parts α, -Ethylene 2-hydroxyethyl methacrylate 2.3 parts 1.
4-butanediol dimethacrylate) 50.0 parts Styrene 10.0 parts n-butyl methacrylate 37.7 parts Electric sweat water 10.0 parts Deionized water 10.0 parts Sodium persulfate 0.3 parts (Note) 1
) Ravisol B90 (manufactured by NOF ■, trade name of sodium di-2-ethylhexylsulfosuccinate, active ingredient 90%) Flask equipped with a stirring device, reflux condenser, dropping funnel (2), nitrogen inlet tube and thermometer A surfactant aqueous solution was added to the solution, and the temperature was raised to 80°C under a nitrogen stream to form a polymerization initiator aqueous solution.
1 was added. After raising the temperature to 80 DEG C. again, 80 parts of the mixture in the flask were added dropwise over 3 hours while keeping the temperature at 2 DEG C. During the dropwise addition of the monomer mixture, the polymerization initiator aqueous solution was added 1 hour after the start of the dropwise addition.
2 was added dropwise over 2 hours. After the addition of the α, β-ethylenically unsaturated monomer mixture and the aqueous polymerization initiator solution-2, polymerization was further carried out at 80°C for 2 hours to form an aqueous system of crosslinked polymer fine particles having the characteristic values shown in Table 3. Dispersion liquid AA
I got I.

(b) Production of non-aqueous dispersion of crosslinked polymer fine particles Aqueous dispersion of crosslinked polymer fine particles obtained in (a) AA 1.50
0 parts, 200 parts of methyl isobutyl ketone and 3N
22.7 parts of a0)1 aqueous solution was charged, the temperature was raised to 85°C, and 85 parts were subjected to a hydrolysis reaction at 2°C for 3 hours.

Next, the temperature was lowered to 80°C, and a 3N hydrochloric acid aqueous solution was added at 22°C.
．． After adding 7 parts and neutralizing, 71.4 parts of the solution of acrylic resin I obtained in Acrylic Resin Production Example I was added as a particle dispersion stabilizing resin, and after stirring for 10 minutes, a 20% aqueous solution of triethylamine acetate was added. (Described later) Immediately after adding 25 parts, stirring was stopped and the mixture was allowed to stand. An organic layer in which crosslinked polymer fine particles were dispersed was separated into an upper layer, and an aqueous layer was separated below, so the lower aqueous layer was removed.

200 parts of deionized water was added to the remaining organic layer containing dispersed crosslinked polymer particles, and the temperature was raised to 70°C with stirring. When the temperature reached 70°C, 1 part of a 20% aqueous solution of triethylamine acetate was added.
2.5 parts were added, stirring was immediately stopped, and the mixture was allowed to stand still. Once again, the organic layer in which the crosslinked polymer fine particles were dispersed was separated into two layers: the upper layer was the aqueous layer, and the lower aqueous layer was removed. The remaining organic layer contained 266% by weight as measured by a Karl Fischer moisture meter.
of water remained.

Next, the temperature of the organic layer was cooled to 50'C, 70 parts of methyl orthoformate was added dropwise from the dropping funnel over 30 minutes, and the reaction was continued at 50C for 30 minutes to decompose the remaining water. After that, 120 parts of xylene was added, a new Dean-Stark trap was installed between the reflux condenser and the flask, the upper part of the reflux condenser was connected to the aspirator, and the inside of the flask was reduced to a pressure of 300±1100 mm1 (, 80±
A non-aqueous dispersion AA2 of crosslinked polymer fine particles was obtained by distilling off the solvent at 10° C. until the nonvolatile content of the dispersion became 50%. Table 3 shows the characteristic values of the obtained non-aqueous dispersion.

(Production of 20% aqueous solution of triethylamine acetate salt) 7.5 parts of acetic acid was dissolved in 80 parts of deionized water, and 12.5 parts of triethylamine was added thereto over 30 minutes with stirring at room temperature.

11 Notice IAB-AK, 86-8M (a) Production of aqueous dispersion of crosslinked polymer fine particles Table 3 AB-AK and B
Production Example AA (a
), aqueous dispersions ABI to AKI of crosslinked polymer fine particles having the characteristic values shown in Table 3 were obtained.
and BAI to BMI were obtained, respectively.

(b) Production of non-aqueous dispersion of crosslinked polymer fine particles aB (a
) ~aK(a) and B A (a) ~B M (
Aqueous dispersion ABI of crosslinked polymer fine particles obtained in a)
AKI and BA1 to BMI were used, and the resins shown in Table 3 were used as particle dispersion stabilizing resins, and for BA to BM, the final heating residue was 40%.
By using the same method as in Production Example AA(b) except that
2 were obtained respectively.

Example 1 - Production of non-aqueous dispersion of crosslinked polymer fine particles B E Ca)
Aqueous dispersion of crosslinked polymer fine particles obtained in BEI, 50
Add 200 parts of methyl isobutyl ketone to 0 parts and make 80'
The temperature was raised to C. Next, 71.4 parts of the solution of acrylic resin V obtained in Acrylic Resin Production Example V was added as a particle dispersion stabilizing resin, and the mixture was stirred for 10 minutes while maintaining the temperature at 80°C. Next, 25 parts of a 20% aqueous solution of acetic acid triethylamine salt (previously described) was added, and stirring was immediately stopped and the mixture was allowed to stand still.
An organic layer in which crosslinked polymer fine particles were dispersed was separated into an upper layer and an aqueous layer below, so the lower aqueous layer was removed.

Next, the temperature of the organic layer was cooled to 50°C, and 70 parts of methyl orthoformate was added dropwise from the dropping funnel over 30 minutes.
The reaction was continued at 50'C for 30 minutes to decompose the remaining water. After that, 200 parts of xylene was added, a new Dean-Stark trap was installed between the reflux condenser and the flask, the upper part of the reflux condenser was connected to the aspirator, and the pressure inside the flask was reduced to 300 ± 100 mmHg while stirring with heating. 80±
A non-aqueous dispersion N2 of crosslinked polymer fine particles was obtained by distilling off the solvent at 10° C. until the heating residue of the dispersion became 40%. Table 3 shows the characteristic values of the obtained non-aqueous dispersion.

Production of non-aqueous dispersion of cross-linked polymer fine particles B P (a)
, BJ The same procedure as in Production Example N was carried out, except that the aqueous dispersions BFI and BJI of the crosslinked polymer fine particles obtained in (a) were used, and the resins shown in Table 3 were used as the particle dispersion stabilizing resins. By using the method, a non-aqueous dispersion of crosslinked polymer fine particles having the characteristic values shown in Table 3 was prepared. P2 were obtained respectively.

Note 1) Surfactant aqueous solution Ravisol B90: Syntrex L100: manufactured by Nippon Oil & Fats ■, trade name of sodium lauryl sulfate, active ingredient 100% Aerosol MA80: manufactured by American Cyanamid Company,
Trade name of sodium dihexyl sulfosuccinate, active ingredient 80% Note 2) α, β-ethylenically unsaturated monomer mixture Hydroxyl group-containing α, β-ethylenically unsaturated monomer HEM^: 2-hydroxyethyl methacrylate HEA: 2-Hydroxyethyl acrylate HPMA: 2-hydroxypropyl methacrylate polyfunctional α,β-ethylenically unsaturated monomer 1.4-B
DDM: 1.4-butanediol dimethacrylate 1.6-HDDM: L6-hexanediol dimethacrylate DVB Nidivinylbenzene (60% active ingredient, remaining 40% ethylvinylbenzene) EGDM: Ethylene glycol dimethacrylate and others α,β-Ethylenically unsaturated monomer St: Styrene BMA: n-butyl methacrylate MMA: Methyl methacrylate EHMA: 2-ethylhexyl methacrylate Note 3
) Various resin solutions obtained in acrylic resin production examples I to ■ and polyester resin production examples ■ and ■ Note 4) Based on JIS-K 5400 8.2 heating residue Note 5) Using a Brunkfield viscometer Measurement, 60r
pm, 20°C Note 6) Measured with “Naicomp, Model 370” (trade name) manufactured by Pacific Science Inc. Note 7) Measured with KF-05 moisture meter manufactured by Mitsubishi Chemical Corporation. a) Production of aqueous dispersion of cross-linked polymer fine particles (core/shell type emulsion polymerization) Deionized water 3B 0.0 part Syntrex L100 (see above, to production example E) 7.0 5 units in the division J Ushio? -1 Deionized water 10.0 parts Sodium persulfate 0.3 parts Core α,
2-hydroxyethyl methacrylate containing β-ethylene 2.8 parts Ethylene glycol dimethacrylate 12.0 parts Styrene
30.0 parts n-butyl methacrylate
15.2 parts shell α, -ethylene
16.
4 parts 1.4-butanediol dimethacrylate 14
゜0 parts Methyl methacrylate 9.6
Deionized water 10.0 parts Sodium persulfate 0.3 parts Production example AA (
An aqueous surfactant solution was placed in the same flask as in a), the temperature was raised to 80°C under a nitrogen stream, and an aqueous polymerization initiator solution-1 was added. After raising the temperature to 80°C again, the mixture in the flask was heated to 80°C.
The core-forming α,β-ethylenically unsaturated monomer mixture was added dropwise over 108 minutes while maintaining the temperature at ±2°C, followed by the shell-forming α,β-ethylenically unsaturated monomer mixture over 72 minutes. .

During the dropping of the core and shell-forming α, β-ethylenically unsaturated monomers, 1 hour after the start of the dropping of the core-forming α, β-ethylenically unsaturated monomer mixture, 2 ml of polymerization initiator aqueous solution-2 was added.
It dripped over time. α.

After completing the dropping of the β-ethylenically unsaturated monomer mixture and the aqueous polymerization initiator solution-2, polymerization is further carried out at 80°C for 2 hours to obtain an aqueous dispersion of crosslinked polymer fine particles having the characteristic values shown in Table 4. Obtained BQI.

(b) Production of a non-aqueous dispersion of crosslinked polymer fine particles Using the aqueous dispersion BQ1 of crosslinked polymer fine particles obtained in (a),
Production example AA(b) was used, except that 18.5 parts of the solution of acrylic resin V obtained in production example (2) of acrylic resin was used as the particle dispersion stabilizing resin, and the final heating residue was 40%.
By using the same method as above, a non-aqueous dispersion BQ2 of crosslinked polymer fine particles having the characteristic values shown in Table 4 was obtained.

Table 4 BR
By using the emulsion polymerization composition shown in -BU and performing the same operation as in Production Example BQ(a), aqueous dispersions BRI to BUI of crosslinked polymer fine particles having the characteristic values shown in Table 4 were obtained, respectively. However, the total dropping time of the core and shell-forming α,β-ethylenically unsaturated monomer mixture was 3 hours, and each dropping time was made equal to the weight proportion of the entire monomer mixture.

(b) Production of non-aqueous dispersion of crosslinked polymer fine particles BR (
a) to B U Aqueous dispersions BRI to BUI of crosslinked polymer fine particles obtained in (a) were used, respectively, and the resins shown in Table 4 were used as particle dispersion stabilizing resins, and the final heating residue was Production example AA [
A non-aqueous dispersion BR2~ of crosslinked polymer fine particles having the characteristic values shown in Table 4 was prepared by using the same method as
BU2 was obtained respectively.

Table 4 Footnote 1) Above, Table 3 Footnote 1 Note 2) Above, Table 3 Footnote 2 Note 3) Above, Table 3 Footnote 3 Note 4) Above, Table 3 Footnote 4 Note 5 ) Above, Table 3, footnote 5 Note 6) Above, Table 3, footnote 6 Note 7) Above, Table 3, footnote 7 Comparative production example V (a) Production of unsaturated ester Stirrer, thermometer, reflux Dean-Stark trap with condenser, 1 in a four-loaf flask with nitrogen gas inlet tube
2-Hydroxystearic acid 1501 was added, heated while blowing nitrogen gas, stirred at a temperature of 200°C, and the reaction was terminated when the acid value reached 39. After cooling, 159 parts of xylene was added and the heated residue was heated. A 90% 5 molar 12-hydroxystearic acid condensate solution was obtained. In addition, 72 parts of water was eliminated in this reaction. Next, using this 12-hydroxystearic acid 5 molar condensate solution, a mixture having the following composition was stirred at a temperature of 120°C in a four-hole flask equipped with a stirrer, a temperature needle, a reflux condenser, and a nitrogen gas inlet tube. Then, the esterification reaction was carried out until the acid value of the heated residue became 1.0 or less to obtain an unsaturated ester solution with a heated residue of 80%.

12-hydroxystearic acid 5 molar condensate solution 158
6.67 parts glycidyl methacrylate 142.00 parts N
, N-dimethylbenzylamine 3.93 parts Hydroquinone 1.96 parts Xylene 227.94 parts (b) Preparation of amphiphilic dispersion stabilizer Next, a 405.0 parts of ethyl acetate and 203.4 parts of n-butyl acetate were placed in a two-cylinder flask and refluxed with stirring. Next, a mixture having the following composition was added at a constant addition rate over 3 hours under reflux, and the mixture was further refluxed for 2 hours to obtain an amphiphilic dispersion stabilizer solution with a heating residue of 33%.

Unsaturated ester solution of (a) 275.0 parts Methyl methacrylate 104.5 parts Acrylic acid 5.5 parts Abdiisobutyronitrile 6.6 parts (c) Production of non-aqueous polymer dispersion Stirrer, reflux condenser A four-loaf flask equipped with a liquid feed and a device for adding liquid feed to the recycle condensate was charged with a mixture of the following composition.

Mineral spirit 1588.0 parts Hexane 389.0 parts Hebutane 2080.2 parts Methyl methacrylate 236.4 parts Azodiisobutyronitrile 18.7 parts Amphiphilic dispersion stabilizer solution (b) above 88.1 parts Above contents 100'
The temperature was raised to 30°C and kept under reflux for 1 hour. Next, the following components were premixed and added to the hydrocarbons returned from the condenser at a constant addition rate over 6 hours.

Methyl methacrylate) 4491.8 parts Methacrylic acid 45.8 parts Glycidyl methacrylate 45.8 parts Azodiisobutyronitrile 60.2 parts Amphiphilic dispersion stabilizer solution of (b) above 945.3 parts However, at the end of addition 3.3 parts of triethylenediamine was additionally mixed into the above addition mixture for 1 hour. After the addition is complete, the reaction mixture is held under reflux for 3 hours to reduce the average particle size to 0.
A non-aqueous polymer dispersion containing 48.2% of 2 μm polymer particles and a heating residue of 52% was obtained.

(d) Modification of particles with auxiliary polymer A fourth flask equipped with the apparatus of step (c) above was charged with the following ingredients and heated to reflux temperature (115°C).

Polymer non-aqueous dispersion of (c) above 4747.1 parts Ethylcyclohexane 1638.2 parts Next, after premixing the following components, the hydrocarbons returned from the condenser were added at a constant rate for 3 hours. Added.

Methyl methacrylate 313.2 parts 2-
Hydroxyethyl methacrylate) 527.1 parts Methacrylic acid 14° 6 parts Butyl methacrylate) 369.7 parts 2-Ethylhexyl acrylate 101.8 parts Styrene
568.8 parts t-butyl peroxybenzoate 90.6 parts octyl mercaptan
84.7 parts 149.5 parts of the above amphipathic dispersion stabilizer solution (c) After the addition was completed, the reaction mixture was refluxed for 2 hours, and then the following solvent mixture was added to heat the solution containing 25% polymer particles. A non-aqueous polymer dispersion (2) with a residual content of 45% was obtained.

n-Butyl alcohol: 559.0 parts Xylene: 372.3 parts Butyl acetate: 462.7 parts Obtained acrylic resin solution 1
76.2 parts Methylated melamine resin (98% heating residue, Cymel 303, manufactured by American Cyanamid, trade name)
20.4 parts Non-aqueous dispersion A^2 obtained in the production of crosslinked polymer fine particles 227.2
Aluminum pigment (65% heating residue, aluminum paste 716ON, manufactured by Toyo Aluminum ■, product name)
15.4 parts sulfonic acid catalyst (
(described later) 1.6 parts 10% xylene solution of ultraviolet absorber (Tinuvin 900, manufactured by Ciba Geigy, trade name) 10.0 parts n~butyl alcohol 1.0 parts Paint with the above composition was treated with thinner (toluene/xylene/ n-butyl alcohol=
5/3/21CI ratio) and coating viscosity (Ford Cup Nα
A base coat paint was prepared by diluting the base coat at 20° C. for 14 seconds.

(Production method of sulfonic acid catalyst) A mixture having the following composition was placed in a three-necked flask equipped with a stirrer, and 98.1 parts of 37.2% hydrochloric acid was added while stirring at room temperature to desodiumize the mixture. At this time, the desodification reaction proceeded immediately after the addition of hydrochloric acid, and 58.5 parts of NaC
fl was precipitated. After separating the precipitated NaCf by suction filtration, 79.0 parts of pyridine was added to the filtrate to obtain an aliphatic sulfonic acid compound solution with an active ingredient concentration (aliphatic sulfonic acid) of 25% blocked with equimolar pyridine. Ta.

C+ eHs7sOJa 35
6.0 parts n-butyl alcohol 861.4
Part (2) Preparation of clear coat paint Acrylic resin solution I obtained in acrylic resin production example ■
I 134.5 parts Methylated melamine resin (heating residue 98%, Cymel 303, American Cyanamid Company, trade name)
15. Example of production of 3-part crosslinked polymer fine particles Non-aqueous dispersion obtained by AP2 2
8.6 parts Tinuvin 900 in 10% xylene solution (supra,
(1)) 10.0 parts hindered amine light stabilizer (Sanol LS-CIO-
440, manufactured by Sankyo Co., Ltd., trade name) 10% xylene solution 10.0 parts Sulfonic acid catalyst (mentioned above, (1)) 1.6 parts n-butyl alcohol 1.0 parts Modaflow (manufactured by Monsando, trade name) ) 0.5 parts Paint with the above composition was mixed with thinner (toluene/xylene/n-butyl alcohol = 4/4/2f)
A clear coat paint was prepared by diluting the resulting material to a coating viscosity (Ford cup Nα of 4.25 seconds at 20° C.).

(3) Preparation of coating film A cationic electrodeposition paint (trade name Aqua No. 4200, manufactured by Nippon Oil & Fats Co., Ltd.) was electrodeposited on a zinc phosphate-treated soft control board to a dry film thickness of 20 μm, and heated at 175°C. Bake for 25 minutes, then apply an intermediate coat (product name: Ebico Nα1500).
CP sealer (manufactured by NOF Corporation) to a dry film thickness of 40μ
Air spray paint so that it becomes m, and 30 at 140℃
A test board was prepared which was baked for a minute. On this test plate, the above (
1) Apply the base coat paint at intervals of 1 minute and 30 seconds.
Air spray painting was performed in two stages to a dry film thickness of 20 μm. After being set vertically for 3 minutes, the clear coat paint described in (2) above was air-sprayed and baked at a temperature of 140°C for 30 minutes while standing vertically. A coating film with excellent appearance, smooth and high gloss was obtained. Furthermore, as shown in Table 9, excellent coating film appearance data and coating film performance were obtained.

(1) Preparation of paint for base coat Each paint for base coat was prepared by carrying out the same operation as in Example 1 (1) using a mixture having the raw material composition shown in Table 5. did.

Note 1) Resin solution properties obtained in acrylic resin production examples and polyester resin production examples 2) Cymel 1130: Methyl butyl mixed alkyl etherified melamine resin, heating residue 100%, manufactured by American Cyanamid Company, trade name Cymel 1168: Methyl butyl mixed alkyl etherified melamine resin, heating residue 98%, manufactured by American Cyanamid Company, trade name RESIMIN 755: Methyl butyl mixed alkyl etherified melamine resin, heating residue 100%, manufactured by Monsanto Company, trade name Note 3) Crosslinked Non-aqueous dispersion obtained in the production example of polymer fine particles Note 4) Above, Example 1 Note 5) Above, Example 1 Note 6) Above, Example 1 (2) Preparation of paint for clear coat Each clear coat paint was produced by performing the same operation as in Example 1 (2) using a mixture having the raw material composition shown in Table 6.

Note 1) Above, Table 4, footnote 1 Note 2) Above, Table 4, footnote 2 Note 3) Above, Table 4, footnote 3 Note 4) Above, Example 1 Note 5) Above, Example 1 Note 6) Above, Example 1 Note 7) Above, Example 1 (3) Preparation of coating film Using each of the obtained paints (1) and (2), Example 1 (
By performing the same operation as in 3), in all of Examples 2 to 6, high-appearance coating films with excellent aluminum orientation and anti-sagging effects, smooth and high gloss were obtained. Furthermore, as shown in Table 9, excellent coating film appearance data and coating film performance were obtained.

Back support 1 (11 Preparation of paint for base coat Polyester resin production example 85.7 parts obtained in ■) Aluminum paste 716ON (previously mentioned, Example 1) 15
．． 4 parts Tinuvin 900 in 10x xylene 10.
0 parts (mentioned above, Example 1) Hexamethylene diisocyanate trimer (heating residue 100χ, isocyanate group content 20χ, Coronate EH, manufactured by Nippon Polyurethane Kogyo ■, trade name) was added to the mixture of the above composition before coating. Add 40.0 parts of paint thinner (toluene/xylene/n-7" ethyl acetate = 4/4/2 weight ratio) to reduce the coating viscosity (Ford Cup Nα4.1 at 20°C).
A base coat paint was prepared by diluting the base coat to 4 seconds).

(2) Preparation of paint for clear coat 101.2 parts of acrylic resin solution ■ obtained in acrylic resin production example ■ 28.6 parts of non-aqueous dispersion obtained in crosslinked polymer fine particle production example AI ^I2 Tinuvin 900 10xylene solution 10.0 parts (
Above, Example 1) 10χ 10 of Sanol LS-C10-440
．． 0 parts xylene solution (supra, Example 1) 35.0 parts of Coronate EH (supra, (1)) was added to the mixture having the above composition before coating, and thinner (xylene/n-butyl acetate) was added. 575 weight ratio) to a coating viscosity (Ford cup Nα of 4.25 seconds at 20° C.) to prepare a clear coat paint.

(3) Preparation of coating film Using each of the obtained coatings (1) and (2), Example 1 (
By performing the same operation as in 3), a high-appearance coating film with excellent aluminum orientation and anti-sagging effect, smooth and high gloss was obtained. Furthermore, as shown in Table 9, excellent coating film appearance data and coating film performance were obtained.

(1) Preparation of paint for base coat Each paint for base coat was prepared by performing the same operation as in Example 1 (1) using a mixture having the raw material composition shown in Table 7.

(2) Preparation of clear coat paints Clear coat paints were prepared by using the mixtures having the raw material compositions shown in Table 8 in the same manner as in Example 1 (2).

supra, supra, supra, supra, supra, supra, Table 5 footnote 1 Table 5 footnote 2 Table 5 footnote 3 Example 1 Example 1 Example 1 Table 8, supra, 5 Table footnote 1, supra, Table 5, footnote 2, supra, Table 5, footnote 3, supra, Example 1, supra, Example 1, supra, Example 1. Preparation of unit two-part (3) coating film obtained. Example 1 (
The same operation as in 3) was carried out, but as shown in Table 9, a coating film satisfying both the coating appearance and coating performance could not be obtained. That is, in Comparative Example 1, the aluminum orientation and anti-sagging effect were both poor, and the gloss and smoothness were insufficient, resulting in a coating film with poor coating performance. This is because the amount of cross-linked polymer fine particles added to both the base coat and clear coat was less than 1 part by weight, resulting in insufficient fluidity adjustment effect of the paint, and also because the amount of polyol resin was too much than 90% by weight. This is thought to be due to a decrease in the water resistance of the paint film. In Comparative Example 2, although the anti-sagging effect was sufficient, the resulting coating film was insufficient in aluminum orientation, gloss, smoothness, and coating performance. This is because the amount of cross-linked polymer fine particles added to both the base coat and clear coat was too much, 100 parts by weight for the base coat and 30 parts by weight for the clear coat, and the difference in hydroxyl value from the polyol resin was too large to 160. The leveling properties of both the base coat and clear coat deteriorated, causing roughness and minute irregularities in the coating film, resulting in a coating film with insufficient aluminum orientation, gloss, and smoothness.

Furthermore, since the amount of polyol resin in both the base coat and the clear coat was less than 30% by weight, the acid resistance was also poor. Further, in Comparative Example 3, although the coating film performance was sufficient, the coating film was insufficient in aluminum orientation, glossiness, and smoothness.

This is because the crosslinked polymer fine particles used are
This is a method based on Japanese Patent No. 133234, and it is thought that the coating film appearance was insufficient because the polarity difference with the polyol resin could not be controlled due to the synthesis method.

Note 1) Polyol resin; supra, Table 5 footnote 1 (OHV
) r: Hydroxyl value of polyol resin, parts in the table are solid content weight Note 2) Curing agent: Above, Example 1, Table 5 footnote 2 (mo):
Number average molecular weight of curing agent Note 3): Crosslinked polymer fine particles: mentioned above, Table 5 footnote 3 (OH
V) g: Hydroxyl value of crosslinked polymer fine particles, the part in the table is particle charge distribution Note 4) Polyol resin V(d): Crosslinked polymer fine particles ■
An auxiliary polymer created to modify particles during production.

Note 5) Good: No unevenness is observed in the orientation of the Nialuminum pigment.

Slightly poor; Some unevenness is observed in the orientation of the aluminum pigment.

Significant unevenness is observed in the orientation of the defective NiAluminum pigment.

Note 6) Film thickness just before clear sagging occurs7)2
0 degree - 20 degree specular gloss Note 8) A value indicating the image clarity of a coating film (measured using a Hunter Co., Ltd. Dorigon variable angle gloss meter D47R-6F) A coating film with a high D/I value has excellent image clarity.

Note 9) Value representing the degree of unevenness on the surface of the paint film (Tokyo Seimitsu ■
Cutoff value 2.5 m by Surfcom 554A
m, center line average roughness when measuring a clear film thickness of 40 um) The coating film with a small value has a smooth surfaceNote 10) Visual observation of the coating film condition after immersing the test piece in boiling water for 3 hours did.

Good: No change in color or gloss is observed in the paint film. Defective: Changes in color and gloss are observed in the paint film.

Note: 0.4 normal) 1cI solution was applied onto the coating film in a thickness of 0.2, and after being held at a temperature of 85° C. for 15 minutes, the condition of the spot marks when washed off with tap water was visually observed.

Good: There is no change in color or gloss of the coating film, and no defects such as blisters are observed.

Defective: Defects such as changes in color, gloss, or blistering are observed in the paint film.

(B) Implemented when two or more types of crosslinked polymer fine particles are used (1) Preparation of base coat paint
) Each base coat paint was produced by performing the same operation as described above.

(2) Preparation of paint for clear coat A mixture having the raw material composition shown in Table 11 was mixed with (2
) Each clear coat paint was produced by performing the same operation as described above.

(3) Preparation of coating films Using the obtained paints (1) and (2), the same procedure as in (3) of Example 1 was carried out to prepare the coatings of Examples 8 to 1.
In all cases of Example No. 6, high-performance coating films were obtained which exhibited excellent aluminum orientation and anti-sagging effects, and exhibited a smooth, high-gloss appearance and the highest level of coating film appearance listed in Table 15.

Fruit 1 Close (1) Preparation of paint for base coat 7” “J 71/Kikuji 0 Manufacturer iVI? i″−9□,
2 parts acrylic resin solution ■ 27.8 parts of the non-aqueous dispersion BA2 obtained in Production Example BA of Cross-linked Polymer Fine Particles 13.9 parts of the non-aqueous dispersion BG2 obtained in Production Example BG of Cross-Linked Polymer Fine Particles Above composition 40.0 parts of hexamethylene diisocyanate trimer (heating residue: 100x, isocyanate group content: 21x, Coronate EH1 manufactured by Nippon Polyurethane Industries, trade name) was added to the paint before painting, and thinner (toluene/ xylene/n-butyl acetate = 4/4/2 weight ratio) and coating viscosity (Ford Cup No. 4. 14 seconds at 20°C)
A base coat paint was prepared by diluting it to .

(2) Preparation of clear coat paint Acrylic resin solution obtained in acrylic resin production example ■9B, 5 parts IJB! ! ! ZKIP+r18" 3.6m Non-aqueous dispersion BL2 obtained in Production Example BL of crosslinked polymer fine particles 3.5 parts Modaflow (mentioned above, Example 1) 0.5 parts A mixture of the above composition was coated with coronet before coating. ) El (supra, (1)
) to convert 40.0 parts of thinner (xylene/acetic acid n
Butyl-515 weight ratio) and coating viscosity (Ford Cup N
A clear coat paint was prepared by diluting the solution at 4.20° C. for 25 seconds.

(3) Preparation of coating film Using each of the obtained coatings (1) and (2), Example 1 (
By performing the same operation as in 3), a high-performance coating film was obtained that had excellent aluminum orientation and anti-sagging effect, was smooth and had a high gloss, and had the highest level of coating appearance listed in Table 15. .

Futabi■J Yuhi (1) Preparation of paint for base coat A mixture with the raw material composition shown in Table 12 was charged into a paint shaker excluding the melamine resin in the formulation, and the particle size was 10.
It was dispersed until it became less than μm. Next, the melamine resin shown in Table 12 was added, and the same operation as in Example 1 (1) was performed to prepare diluted paints for each base coat.

(2) Preparation of clear coat paint In Example 18, the clear coat paint of Example 8 (2) was used as is, and in Example 19, the clear coat paint of Example 11 (2) was used as is.

(3) Preparation of coating film Example 18.
In all cases of No. 19, coating films with high appearance and high performance as shown in Table 15 were obtained, which had an excellent anti-sagging effect, were smooth and had a high gloss.

Note 1) Rubicron Red 500RG (manufactured by Tosoh ■,
(Trade name of Quinacridone) Note 2) Red Garla KN-R (manufactured by Toda Kogyo ■, Trade name of Red Gara) 11" u also has two needles (1) Preparation of paint In the raw material composition shown in Table 13, excluding melamine resin The mixture was placed in a sand mill and dispersed for 30 minutes to reduce the particle size to 10 μm or less. Next, the melamine resin shown in Table 13 was added to prepare each paint. Next, it was diluted with thinner (xylene/n-butyl alcohol = 9/1 filtration ratio) to a coating viscosity (Ford Cup No., 4.25 seconds at 20° C.).

(2) Preparation of coating film The above coating was air sprayed onto the test plate on which the electrodeposited coating film and the intermediate coating film were prepared in the same manner as in (3) of Example I, and the coating was applied vertically for 30 minutes at a temperature of 140°C. When the coating was baked while standing upright, a high-performance coating film with excellent appearance and excellent anti-sagging effect, smoothness, and high gloss as shown in Table 15 was obtained.

Table 13 Note 1) Teika titanium oxide JR-602゜ manufactured by Teikoku Kako ■, trade name Konoka U (1) Preparation of base coat paint
) Each base coat paint was produced by performing the same operation as described above.

(2) Preparation of paint for clear coat A mixture having the raw material composition shown in Table 14 was mixed with
) Each clear coat paint was produced by performing the same operation as described above.

(3) Preparation of coating film Using the obtained coatings (1) and (2), the same operation as in (3) of Example 1 was performed, but as shown in Table 15, the appearance of the coating film was A coating film satisfying both properties and coating performance could not be obtained.

That is, in Comparative Example 4, the coating film was inferior in both aluminum conformation and anti-sagging effect, and furthermore, the gloss and smoothness were insufficient, and the coating film performance was also insufficient.

This is because the amount of crosslinked polymer fine particles added to both the base coat and clear coat was less than 1 part by weight, which resulted in insufficient flow control of the coating (poor aluminum coordinating properties and thin film thickness at the sag limit). The difference in hydroxyl value between the polyol resin and crosslinked polymer fine particles in the base coat is 160
, and the difference in hydroxyl value between the crosslinked polymer fine particles in the base coat exceeded 120.
I value) and smoothness (surface roughness). Furthermore, since the amount of polyol resin in both the base coat and the clear coat is less than 30% by weight, acid resistance is also poor.

Moreover, in Comparative Example 5 using the method of JP-A-1-172464, the coating film was insufficient in gloss (20 degree specular gloss, D/I value) and smoothness (surface roughness). This is because the crosslinked polymer fine particles used are N2.02. It is thought that due to the presence of ionic groups other than hydroxyl groups on the particle surface of P2, it was difficult to strictly control the polarity difference with the polyol resin, resulting in poor coating film appearance.

Production Examples 1 to 2 were carried out to the production base of acrylic resin, except that the components listed in Table 16 were used.
By performing the same operations as above, acrylic resin solutions A to F having the characteristic values shown in Table 16 were obtained.

Note 1) Plaxel FM3: Manufactured by Daicel Chemical Industries, Ltd.
Product name: Monomer with 3 moles of ε-caprolactone added to 2-hydroxyethyl methacrylate Note 2) Based on gel permeation chromatography in terms of styrene Note 3) Calculated value using the following formula 1/Tg('K)・- A/TgA+Wn/Tgl+-
- 10N/TgN1: Weight fraction of each monomer TgN: Glass transition temperature of homopolymer of each monomer Production of crosslinked polymer fine particles 1.1 Production example of crosslinked polymer fine particles BH The characteristic values shown in Table 17 were obtained by performing all the same operations except that acrylic resin solutions A, B, C, D, E, and F were used instead of acrylic resin solution V as the particle dispersion stabilizing resin. Non-aqueous dispersion C of crosslinked polymer fine particles having
E2~) IF5 was obtained.

In Example BP of producing crosslinked polymer fine particles, acrylic resin solutions A, B, C, D, E, and F were used instead of acrylic resin solution V as the particle dispersion stabilizing resin, respectively. , by performing all the same operations, a non-aqueous dispersion C of crosslinked polymer fine particles having the characteristic values shown in Table 18 was obtained.
F2-HF2 was obtained.

In production example BJ of cross-linked polymer fine particles with two-length cross-linked polymer particles, acrylic resin solutions ^, B, C, D, E, and F were used instead of acrylic resin solution V as the particle dispersion stabilizing resin. By performing all the same operations, a non-aqueous dispersion C of crosslinked polymer fine particles having the characteristic values shown in Table 19 was obtained.
J-1 (obtained J.

22-25. '+6 (1) Preparation of paint for base coat Each paint for base coat was produced by performing the same operation as (1) of Example 1 using the mixture of raw materials shown in Table 20.

(2) Preparation of clear coat paints Each clear coat paint was prepared by performing the same operation as in Example 1 (2) using the mixture of raw materials shown in Table 21.

(3) Preparation of coating films Using the obtained paints (1) and (2), the same operations as in (3) of Example 1 were carried out in Examples 22 to 22.
In both Comparative Example 25 and Comparative Example 6, appropriate amounts of cross-linked polymer fine particles were used, so in both cases, the high-appearance coating film described in Table 22 with excellent aluminum orientation and anti-sagging effect, and having a smooth and glossy appearance was obtained. Obtained.

On the other hand, the adhesion of the base coat/clear coat interface is
In Examples 22 to 25, acrylic resins with appropriate glass transition temperatures were used for both the base coat and the clear coat, and thus excellent coating film adhesion was exhibited. On the other hand, in Comparative Example 6, the glass transition temperature of the acrylic resin used for the base coat was made higher than that of the acrylic resin for the clear coat within the scope of the method of U.S. Patent No. 4,276,212, so the film adhesion was poor. Ta.

Table 22 Footnotes Notes 1) to 9) Same as Table 9 Footnotes Note 10) Evaluation of adhesion Cut the coating film to the substrate using a cutter knife in the vertical and horizontal directions 11
Draw parallel lines for each book at intervals of 1- or 2 (goods) to create a square base. Apply cellophane tape with a width of 30 mm to this area, peel it upward, and observe the peeling condition of the paint film.

Good: No peeling is observed in all squares.

Peeling is observed at the base coat/clear coat interface in more than half of the squares that are defective.

Claims (1)

[Scope of Claims] 1. 0.001 to 1.0 μm based on 100 parts by weight of a resin solid mixture consisting of 30 to 90% by weight of a polyol resin and 10 to 70% by weight of a curing agent capable of reacting with hydroxyl groups.
It has an average particle size of 0≦|(OHV)r-(O
HV) A high solid coating composition containing 1 to 100 parts by weight of crosslinked polymer fine particles having the relationship of g|≦160. 2. Contains 1 to 60 parts by weight of crosslinked polymer fine particles whose hydroxyl value (OHV) g has a relationship of 0≦|(OHV)r−(OHV)g|≦100 with the hydroxyl value (OHV)r of the polyol resin. The high solids coating composition according to claim 1, which is used for a clear coat. 3. The crosslinked polymer fine particles are composed of two or more types of crosslinked polymer fine particles, and their hydroxyl value (OHV)
The high solid coating composition according to claim 1, wherein the difference x between the maximum value and the minimum value of g is 0<x≦120. 4. The high solids coating composition according to claim 3, wherein the crosslinked polymer fine particles have only hydroxyl groups as reactive functional groups on their particle surfaces. 5. The crosslinked polymer fine particles are composed of two or more types of crosslinked polymer fine particles, each amounting to at least 10% by weight based on the total amount of the crosslinked polymer fine particles, and their hydroxyl value (OH
The high solid coating composition according to claim 4, wherein the difference x between the maximum value and the minimum value of V)g is 10≦x≦120. 6. Difference x between the maximum and minimum values of the hydroxyl value (OHV) g
6. The high solid coating composition according to claim 5, wherein x is 10≦x≦60 and the total content of the crosslinked polymer fine particles is 1 to 60 parts by weight, and is used for clear coating. 7. The crosslinked polymer fine particles [1] each of the following components (a) a hydroxyl group-containing α,β-ethylenically unsaturated monomer, (b) a polyfunctional α,β-ethylenically unsaturated monomer, and ( c) Emulsion polymerization of α,β-ethylenically unsaturated monomers other than the above (a) and (b) using a water-soluble polymerization initiator in the presence of a soap-free or ester group-containing surfactant. Alternatively, core/shell type emulsion polymerization is performed, and an organic solvent is added to the resulting aqueous polymer dispersion, and then a basic compound catalyst or an acidic compound catalyst is added, and the ester group is a step of completely hydrolyzing the contained surfactant and water-soluble polymerization initiator; [2] adding an acidic compound or a basic compound to the suspension to neutralize the basic compound catalyst or the acidic compound catalyst; Next, after adding a dispersion stabilizing resin, an organic acid amine salt was added and left to stand to separate the system into two layers, an organic layer and an aqueous layer. After removing the aqueous layer, water was added to separate the organic layer. Any one of claims 1 to 6 obtained by performing the steps of washing, adding an organic acid amine salt, leaving to stand, and separating and removing the aqueous layer, and [3] removing residual moisture in the organic layer. The high solids paint composition described in . 8. The high solid coating composition according to claim 7, wherein the crosslinked polymer fine particles are obtained by emulsion polymerization in the step [1], and the hydroxyl value (OHV) g thereof is the hydroxyl value of the entire particle. 9. The crosslinked polymer fine particles form the core/
It is obtained by shell-type emulsion polymerization, and its hydroxyl value (OHV
8. The high solid coating composition according to claim 7, wherein g is the hydroxyl value of the shell portion of the particles. 10. The polyol resin has a weight average molecular weight of 3,000 to
The high solid coating composition according to any one of claims 1 to 9, comprising an acrylic resin having characteristic values in the range of 40,000°C, a hydroxyl value of 30 to 250, an acid value of 30 or less, and a glass transition temperature of -60 to 50°C. . 11. The weight average molecular weight is 3,000 to 15,000
, a hydroxyl value of 50 to 250, and a glass transition temperature of 2
10. The temperature is 0 to 50°C, and the material is for clear coating.
The high solids coating composition described. 12. The weight average molecular weight is 4,000 to 40,000
, hydroxyl value is 30-200 and glass transition temperature is -2
10. The temperature is 0 to 19°C, and the material is for clear coating.
The high solids coating composition described. 13. The weight average molecular weight is 3,000 to 15,000
, hydroxyl value is 50-250 and glass transition temperature is -1
11. The high solid coating composition according to claim 10, which has a temperature of 0 to 20°C and is used as a base coat. 14. The weight average molecular weight is 4,000 to 40,000
, hydroxyl value is 30-200 and glass transition temperature is -6
10. The temperature is 0 to -11°C, and it is for base coat.
The high solids coating composition described. 15. In a coated article consisting of an article to be coated and a coating film of a coating composition covering the surface thereof, the coating composition contains 30 to 90% by weight of a polyol resin and 10 to 70% by weight of a curing agent capable of reacting with hydroxyl groups. A resin solid content mixture 100 consisting of
It has an average particle diameter of 0.001 to 1.0 μm based on the weight part, and the hydroxyl value (OHV) g is equal to the hydroxyl value (OHV) r of the polyol resin, and 0≦|(OHV)r−(OHV)g ｜
1 to 100 crosslinked polymer fine particles with a relationship of ≦160
parts by weight, and the crosslinked polymer fine particles are composed of two or more types of crosslinked polymer fine particles, and their hydroxyl value (
A coated article that is a high solid paint composition in which the difference x between the maximum value and the minimum value of OHV) g is in the range of 0<x≦120. 16. The coated product according to claim 15, wherein the crosslinked polymer fine particles have only hydroxyl groups as reactive functional groups on their particle surfaces. 17. A coated article consisting of a base coat covering the surface of the coated article and a clear coat further laminated thereon, wherein the base coat is made of a polyol resin 30-30.
90% by weight and a curing agent capable of reacting with hydroxyl groups 10-70
The hydroxyl value (OHV) g of the polyol resin has an average particle diameter of 0.001 to 1.0 μm, and the hydroxyl value (OHV) r
and 0≦|(OHV)r-(OHV)g|≦160. OHV)g is the hydroxyl value (OHV)r of the polyol resin
A coated article which is the above-mentioned high solid coating composition, containing 1 to 60 parts by weight of crosslinked polymer fine particles having the relationship: 0≦|(OHV)r-(OHV)g|≦100. 18. In a method of coating a coating composition on an object to be coated,
The coating composition contains 0.001 parts by weight based on 100 parts by weight of a resin solid content mixture consisting of 30 to 90% by weight of a polyol resin and 10 to 70% by weight of a curing agent capable of reacting with hydroxyl groups.
A crosslinked polymer having an average particle size of ~1.0 μm and having a hydroxyl value (OHV) g in a relationship with the hydroxyl value (OHV) r of the polyol resin such that 0≦|(OHV)r−(OHV)g|≦160 The crosslinked polymer fine particles contain 1 to 100 parts by weight of fine particles, and the crosslinked polymer fine particles are composed of two or more types of crosslinked polymer fine particles, and the difference x between the maximum value and the minimum value of their hydroxyl value (OHV) g is 0< A coating method using a high solid coating composition in the range of x≦120. 19. The coating method according to claim 18, wherein the crosslinked polymer fine particles have only hydroxyl groups as reactive functional groups on their particle surfaces. 20. On the object to be coated, as a base coat, 30 to 90% by weight of polyol resin and curing agent 1 that can react with hydroxyl groups.
The average particle diameter is 0.001 to 1.0 μm, and the hydroxyl value (OHV) g is the same as the hydroxyl value (OHV) of the polyol resin.
After applying a high solid coating composition containing 1 to 100 parts by weight of crosslinked polymer fine particles having a relationship of HV)r and 0≦|(OHV)r−(OHV)g|≦160, a clear coat is further applied. contains 1 to 60 parts by weight of crosslinked polymer fine particles whose hydroxyl value (OHV) g has a relationship of 0≦|(OHV)r−(OHV)g|≦100 with the hydroxyl value (OHV)r of the polyol resin. A coating method comprising repeatedly applying the above-mentioned high solid coating composition, and then baking a base coat and a clear coat at once.