JP2667821B2 - Top coating method - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION INDUSTRIAL APPLICATION The present invention applies a solid coat containing a pigment,
Next, after applying the transparent top clear paint repeatedly, heating
So-called two-coat one-bake method to cure and face
After coating the solid coat containing the filler, heat and cure
After that, after applying a transparent top clear paint again,
In addition, so-called two-coat two-bake method for curing by heating
The solid color finishing method
However, gloss reduction of the coating film by the conventional two-coat method,
Improve the so-called weather resistance of cracks, discoloration, fading, blisters, etc.
And there. Conventional technology and its problems Solid color finish is applied to the top coat finish of automobiles.
Finish and metallic color finish.
Color finish, apply metallic coat after coating
Paint clear with wet on, 2 coats 1 bake
The method of baking and hardening has been generalized. However,
For lid color finish, use for solid color
Amino alkyd resin paint is glossy, and
As it has an excellent texture, clear it to improve gloss.
The need for painting was relatively small. However,
Recent variety of paint colors, further improvement of finish, weather resistance
The demand for the above has increased, and
Clear coating on the board began to take place. That is,
Acid resistance and alkali resistance by clearing
Can not be used for conventional 1 coat solid
Pigments can be used, and the choice of pigments expands.
It is now possible to cover a wide variety of color gamuts. Add an ultraviolet absorber to the clear coat
Can improve the weather resistance of the clear coat itself
On the other hand, UV degradation of solid coats and pigments
Pigments that previously could not be used due to poor weather resistance
From among the available pigments come out,
The color gamut that can be used has expanded. In addition, by giving a clear coat more,
Finished appearance with excellent feeling (double layer feeling)
Was. In addition, the clear coat contains an organic solvent-soluble
By using copolymers, 2-coat solid coating
Weather resistance can be further improved
Was. That is, the fluorine-containing polymer generally has another organic polymer.
Compared to coalescence, the intermolecular cohesion is extremely small, and
When coated, water repellent, oil repellent, stain resistant,
It shows tackiness, and more importantly, good weatherability.
It has the feature of Such practically excellent features
Soluble in organic solvents at room temperature
Fluoropolymers are the properties of the fluorinated polymers described above.
It has excellent workability and painting workability.
Has features. However, the fluoropolymer is soluble in organic solvents at room temperature
Heat that must be provided as a coating film
In some cases, the mechanical and mechanical properties may decrease. Furthermore, including
Fluoropolymers are commonly used in clearcoats.
Compared to organic polymers such as acrylic resins and alkyd resins
Costly and with the minimum necessary fluorine atom content.
It is essential that they work. Means for Solving the Problems The present invention has two types of solid coat and clear coat.
The purpose is to solve the above drawbacks in the coating method
It was done. That is, the present invention provides a solid coat containing a color pigment.
And then apply a transparent top clear paint to the painted surface.
In the top coat coating method, the top clear coat
Material contains fluoroolefin as an essential component,
Weight average molecular weight 5000-120,000 and fluorine atom content 1-60
Weight percent of an organic solvent-soluble fluoropolymer containing
The dispersion stabilizer and the radical polymerizable monomer in the presence of a stabilizer
Soluble in the body (not containing fluorine atoms) and the radical
Yes, insoluble in the polymer formed by the polymerizable monomer
Polymerizing the radical polymerizable monomer in an organic solvent
The polymer particles are dispersed in an organic solvent solution of a dispersion stabilizer.
Non-aqueous dispersion liquid (hereinafter abbreviated as "F-NAD")
Characterized by the use of a curable coating mainly composed of
It relates to the topcoat coating method. Further, in the present invention, the F-NAD is
Contains olefin as an essential component, weight average molecular weight 50
00 to 120,000 and a fluorine atom content of 1 to 60% by weight, and 1
Having at least 0.1 polymerizable double bond in the molecule
Stabilizer Consisting of Different Organic Solvent-Soluble Fluoro-Containing Polymers
The dispersion stabilizer and the radical polymerizable monomer in the presence of
(Not containing a fluorine atom) and the radical
Organics that are insoluble in polymers formed by compatible monomers
The fluoropolymerization of the radical polymerizable monomer in a solvent
A non-aqueous dispersion obtained by graft-polymerizing a polymer is also included. The feature of the present invention is that
-As a paint, the fluoroolefin is an essential component.
Non-aqueous dispersion (F-NA) using a fluoropolymer as a dispersant
D) to use a curable paint whose main component is
As a result, the above object can be achieved. According to the method of the present invention, the performance that should originally be possessed as a coating film
That simultaneously have the properties based on
A coating film may be formed. That is, it is chemically stable,
Excellent weather resistance, water repellency, oil repellency, stain resistance, non-adhesion
Fluorine-containing resin that has a low refractive index
Performance, heat resistance, alkali resistance, base coat coating
Originally possesses adhesion, hardness, gloss, sharpness, impact resistance, etc.
Selected software that has both thermal, chemical and mechanical properties
A lid coat film can be formed. Moreover, the said
The coating also significantly improved long-term outdoor exposure. The top coat film formed by the method of the present invention is
Excellent performance as described above is the film formation from F-NAD
The continuous phase of the finished clear coating is primarily a dispersion stabilizer (ie,
And the surface layer of the coating film
Are primarily based on fluorine atoms, such as weather resistance,
Excellent water-based, oil-repellent, stain-resistant, non-adhesive,
Characteristics that can form a coating film with low refractive index
Will be. On the other hand, it must have
Poor thermal, chemical or mechanical properties are dispersed in the dispersion.
Reinforced by polymer particles (not including fluorine)
Because That is, by the reinforcing hardening of the polymer particles,
Increases the strength of the coating film and reduces the stress in the coating film generated over time.
Absorption at the interface between
The entire coating will be cracked and damaged by rubbing.
Can be dispersed without increasing energy.
Furthermore, this fluorine atom is present in the continuous phase (dispersion stabilizer).
It is sufficient if it exists inside the polymer particles of the dispersion.
It is not necessary to use
Compared to the fluoropolymer solution, the amount of the fluoromonomer used is
At least, it has the same characteristics based on fluorine atoms.
Can be volatilized. In other words, a significant price advantage
It also has the advantage that a good coating film can be obtained. Therefore, the top clear paint of the present invention is coated in two coats.
The light of top coat after long-term exposure
It is possible to prevent the occurrence of erosion, cracks, peeling, blisters, etc.
Weatherability can be significantly improved, and the water repellency of the top coat surface
Can be maintained over a long period of time, so that water
Can be prevented, and a layer of a top coat film and a coat film.
Water drops between layers of space, coat film, intermediate coat film, and undercoat film
The generation of blisters can also be prevented. In addition, top chestnut
By blending the above-mentioned F-NAD into the paint,
The finished appearance such as gloss and clarity of the coating film
Can be improved significantly, and it can be maintained for a long time,
In addition, the interlayer coating between the topcoat coating and the basecoat coating has
It is possible to almost completely prevent the occurrence of scrapes and blisters.
You. Hereinafter, the method of the present invention will be described more specifically. <Solid coat> The solid coat paint used in the present invention is conventionally known.
Widely used, curable resin composition and coloring pigment
A coating that is colored to cover the base material containing
It forms a film. The curable resin composition is specifically
Specifically, for example, acrylic resin, polyester resin, aluminum
Kid resin, epoxy resin, fluorine-containing resin, urethane resin, etc.
Base resin and crosslinking agent (amino resin, blocked polyiso
Or a thermosetting resin composition comprising
A curing agent such as a polyisocyanate compound is added to the base resin.
By heating at room temperature or low temperature (about 140 ° C or less)
Examples thereof include resin compositions that crosslink. These resin compositions
A resin that does not undergo a cross-linking and curing reaction, such as cellulose acetate
Tate butyrate resin or the like may be further added. The paint
If the color pigment used in the
Any pigment may be used. In other words, relatively hiding power
Low blue, red, green, yellow organic or inorganic pigments (eg,
Phthalocyanine blue, azo red pigment)
Hiding properties such as white, black and red inorganic pigments (for example,
(Titanium oxide, carbon black, red iron) etc.
Coloring pigments. These pigments can be used alone
Or two or more of them may be used in combination. The amount used depends on the pigment type
A proper amount is selected. <Top clear paint> Painted on the solid coat paint film surface to form a transparent paint film
Paint which is a curable coating mainly composed of F-NAD.
Fees. Fluorine-containing polymerization used as dispersion stabilizer for F-NAD
The body specifically has a fluoroolefin as an essential component,
Alkyl vinyl ether, alicyclic
c) vinyl ether, hydroxy vinyl ether, ole
Fins, haloolefins, unsaturated carboxylic acids and
1 selected from steal and carboxylic acid vinyl ester
Species or two or more unsaturated monomers are used as copolymerization components
Weight average molecular weight 5,000-120,000 (number average molecular weight is about 1,00
0-60,000) and fluorine atom content 1-60% by weight at room temperature
Is a polymer soluble in an organic solvent. The fluorinated polymer
As the fluoroolefin of the copolymer component in
Trafluoroethylene, chlorotrifluoroethylene,
Vinyl fluoride, vinylidene fluoride, etc. are used. Alkyl vinyl ether, another copolymer component,
Examples include ethyl vinyl ether and isobutyl vinyl ether.
Ether, n-butyl vinyl ether, etc .; Alicyclic
Cycloaliphatic vinyl ethers
Syl vinyl ether and its derivatives; hydroxy vinyl
As the ether, hydroxybutyl vinyl ether
Etc .; as olefins and haloolefins, ethylene
, Propylene, isobutylene, vinyl chloride, vinyl chloride
Lidene, etc .;
Nyl, n-vinyl butyrate, etc .;
And its esters include acrylic acid, methacrylic acid,
Unsaturated carboxylic acids such as crotonic acid; and methyl acrylate
Le, ethyl acrylate, propyl acrylate, acrylic
Isopropyl acrylate, butyl acrylate, hexyl acrylate
, Octyl acrylate, lauryl acrylate, methac
Methyl phosphate, ethyl methacrylate, methacrylic acid pro
Pill, isopropyl methacrylate, butyrate methacrylate
Hexyl methacrylate, octyl methacrylate,
Of acrylic acid or methacrylic acid such as lauryl acrylate
C ₁ ~ ₁₈ Alkyl ester; hydroxyethyl acrylate
Hydroxyethyl methacrylate, hydroxypropy
Acrylate, hydroxypropyl methacrylate, etc.
Acrylic acid or methacrylic acid C _Two ~ ₈ Hydroxyal
Kill ester; N, N-dimethylaminoethyl (meth) ac
Relate, N, N-diethylaminoethyl (meth) acryl
Esters of unsaturated carboxylic acids such as
You. These radical polymerizable monomers are used alone.
Or may be used in combination of two or more.
If necessary, part of the monomer may be converted to another radical polymerizable
Monomers such as styrene, α-methylstyrene, vinyl
Vinyl, such as toluene and (meth) acrylonitrile
It may be replaced with an aromatic compound. In addition to the monomers exemplified above, derivatives of the above monomers
For example, carboxylic acid group-containing fluoroolefin, glycidi
A vinyl ether having a hydroxyl group can also be used. The fluorine-containing polymer had a fluorine atom content of 1%.
Below, the characteristics of the fluoropolymer are not sufficiently exhibited, and
%, The solubility in organic solvents will decrease.
Come. In addition, a polymerizable double bond is added to such a fluoropolymer.
May be introduced to achieve grafting with the core of the dispersed particles.
No. The introduction of the polymerizable double bond is carried out, for example, using a fluorine-containing copolymer.
A carboxylic acid group-containing monomer is used as a copolymerization component
Unsaturated monomer containing glycidyl group in the carboxyl group
(Eg glycidyl methacrylate, glycidyl acrylate
Reactant, allyl glycidyl ether, etc.)
Can be done by doing
Glycidyl group-containing acrylic copolymer and carboxyl group-containing
Also performed by reacting with unsaturated monomers
be able to. Such combinations include, in addition to acid anhydride groups and hydroxyl groups,
Hydrate group and mercapto group, isocyanate group and hydroxyl group etc.
Conceivable. Addition reactions between combinations of such reactive groups
The general conditions under which reactions occur are well known and their reactions take place.
This temperature depends on the combination of individual selected reactive groups.
That can be modified by the use of catalysts
Needless to say. By the above reaction, the dispersion stabilizer resin
On average at least 0.1 polymerizable double bond in the
You can have. Of course, in the present invention, a polymerizable secondary resin is added to the dispersion stabilizer resin.
It is not necessary to have a heavy bond, but the introduction of a polymerizable double bond
The covalent bond between the polymer forming the particles and the dispersion stabilizer
Is formed to improve the storage stability and mechanical stability of the dispersion.
Further improvement can be achieved. As a specific example of the above-mentioned fluoropolymer, for example, hydroxyl
"Lumiflon" series of organic solvent-soluble forms containing group
Lumiflon LF200, weight average molecular weight about 50,000, Asahi Glass
Subsidiary), Daikin Industries, Ltd.
Organic from Central Glass Co., Ltd. and Penwalt
Solvent-soluble fluoropolymers are on the market. The molecular weight of the fluoropolymer as a dispersion stabilizer is
Average molecular weight 5,000-120,000 (Number average molecular weight is about 1,000-6
0,000) but the molecular weight is less than about 5,000
Insufficient stabilization of dispersed particles causes aggregation and sedimentation
When the molecular weight exceeds 120,000, the
Decrease in solubility of fluoropolymer in organic solvent, viscosity of dispersion
Cause a significant increase in the degree. To produce the fluoropolymer,
It is usually carried out using a radical polymerization initiator. Available
As a radical polymerization initiator, for example, 2,2'-azobi
Isobutyronitrile, 2,2'-azobis (2,4-dimethyl
Azo initiators such as ruvaleronitrile, benzoyl par
Oxide, lauryl peroxide, tert-butyl peroxide
-Peroxide initiators such as octoate
These polymerization initiators are generally 100% by weight of monomers used for polymerization.
0.2 to 10 parts by weight, preferably 0.5 to 5 parts by weight per part
Can be used within. The reaction format is generally in an aqueous medium.
And emulsion polymerization in an organic solvent.
However, as a dispersion stabilizer, it is in a state of being dissolved in an organic solvent.
Use in Various solvents can be used as the organic solvent.
Aromatic hydrocarbons, alcohols, esters,
Tons, glycol ethers, etc.
Nanna can be used. These may be used alone or in combination of two or more.
You may mix and use in various ratios. Reaction temperature, reaction pressure
The force depends on the type of polymerization initiator, solvent type and reaction type
Selected. The dispersion stabilizer resin used in the present invention is a simple one.
Different copolymer compositions and molecular weights can be used alone
May be used in combination of two or more.
Dispersion stabilizers such as butyl etherified melamine-form
Aldehyde resin, alkyd resin, general acrylic resin, etc.
It is also possible to use together with a small amount of. According to the present invention, in the presence of a dispersion stabilizer resin as described above
At least one radical polymerizable monomer in an organic liquid
The body is polymerized. The organic liquid used for the polymerization contains
Although the dispersed polymer particles do not substantially dissolve,
In combination with the organic solvent of the stabilizer resin solution, the fluorine-containing resin and
And a good solvent for the radical polymerizable monomer.
Liquids are included. Specific examples of such an organic liquid include hexane and hepta.
Aliphatic hydrocarbons such as benzene and octane; benzene, toluene
Aromatic hydrocarbons such as alcohols and xylenes;
Ter, ester and ketone solvents such as isopro
Pill alcohol, n-butyl alcohol, i-butyl alcohol
Alcohol, octyl alcohol, cellosolve, butylcelle
Lososolve, diethylene glycol monobutyl ether,
Methyl isobutyl ketone, diisobutyl ketone, ethyl
Acyl ketone, methylhexyl ketone, ethyl butyl ketone
Ton, ethyl acetate, isobutyl acetate, acyl acetate, 2-
Ethylhexyl acetate and the like.
Each may be used alone, or two or more types may be mixed and used.
Although it can be done, in general, mainly aliphatic hydrocarbons,
In addition to this, aromatic hydrocarbons and alcohols as described above,
Combines ether, ester or ketone solvents
Are preferably used. In addition, trichlorotrif
Luoroethane, meta-xylene hexafluoride, tet
If necessary, use lachlorohexafluorobutane.
Wear. In the presence of the dispersion stabilizer resin and organic liquid described above,
As monomers to be combined, radically polymerizable unsaturated
There is no particular limitation as long as it is a sum monomer, and various types are used.
The following are typical examples.
It is as follows. (A) Acrylic acid or methacrylic acid ester;
For example, methyl acrylate, ethyl acrylate, acrylic acid
Propyl, isopropyl acrylate, butyl acrylate
Hexyl acrylate, octyl acrylate, acrylic
Lauryl acrylate, methyl methacrylate, ethyl methacrylate
, Propyl methacrylate, isopropyl methacrylate
, Butyl methacrylate, hexyl methacrylate, meta
Acrylics such as octyl acrylate and lauryl methacrylate
Acid or methacrylic acid C ₁ ~ ₁₈ Alkyl ester;
Sidyl acrylate, glycidyl methacrylate; ant
Acrylic acid such as acrylate and allyl methacrylate
Or C in methacrylic acid _Two ~ ₈ Alkenyl ester;
Roxyethyl acrylate, hydroxyethyl methacrylate
Rate, hydroxypropyl acrylate, hydroxy
Acrylic acid or methacrylic acid such as propyl methacrylate
Lulic acid C _Two ~ ₈ Hydroxyalkyl ester; allyloxy
Ciethyl acrylate, allyloxy methacrylate, etc.
Acrylic acid or methacrylic acid C _Three ~ ₁₈ Alkenylo
Xyalkyl esters. (B) vinyl aromatic compound: for example, styrene, α-meth
Cylstyrene, vinyltoluene, p-chlorostyrene vinyl
Nilpyridine. (C) α, β-ethylenically unsaturated acid: for example, acrylic
Acid, methacrylic acid, itaconic acid. (D) Others: acrylonitrile, methacrylonitrile
, Methyl isopropenyl ketone; vinyl acetate, veova
Monomer (shell chemical products), vinyl propionate,
Vinyl pivalate and the like. Acrylic acid is particularly preferable among these monomers.
Or at least 40% by weight of methacrylic acid ester
It is a monomer or mixture of monomers. The polymerization of the above monomers is carried out using a radical polymerization initiator.
Will be Examples of radical polymerization initiators that can be used include
For example, 2,2-azoisobutyronitrile, 2,2'-azobis (2,2
Azo-based initiators such as 4-dimethylvaleronitrile;
Zoyl peroxide, lauryl peroxide, tert-butane
Peroxide initiators such as tilper octoate
These polymerization initiators are generally used as monomers for polymerization.
0.2 to 10 parts by weight, preferably 0.5 to 5 parts by weight per 100 parts by weight
It can be used within the range of parts. The amount of the dispersion stabilizer resin used depends on the type of the resin.
Can be changed over a wide range by
Is based on the total amount of the monomer to be polymerized and the dispersion stabilizer.
5 to 80% by weight, preferably about 10 to about 60% by weight.
It is convenient. Furthermore, the radically polymerizable monomer in the above organic solvent
And the total concentration of the dispersion stabilizer is generally about 30 to 70% by weight,
It is preferably about 30 to 60% by weight. The polymerization can be carried out in a manner known per se,
The reaction temperature is generally in the range of about 60 to about 160 ° C.
Temperature can be used and the reaction is usually performed in about 1 to about 15 hours.
You can end it. The F-NAD manufactured by the above described method is extremely
Excellent dispersion stability. The top clear paint in the present invention is the above F-NAD.
Can be used as is, but different copolymerization
Two or more compositions and molecular weights may be used in combination,
Further, if necessary, another dispersion stabilizer such as an alkyl ether may be used.
-Melamine-formaldehyde resin, alkyd tree
It can be used in combination with a small amount of fat, acrylic resin, etc.
You. Add colorant, plasticizer, curing agent, etc. as necessary
You can also. Colorants include dyes, organic pigments, and inorganic
Pigments and the like, known plasticizers, for example,
Small molecules such as dimethyl phthalate and dioctyl phthalate
Plasticizer, vinyl polymer plasticizer, polyester plasticizer
Polymeric plasticizers such as dispersants, and these are reserved for F-NAD.
Can be used by mixing, or when manufacturing F-NAD
In, for example, dissolved in a radical polymerizable monomer,
The resulting dispersion may be distributed in the dispersed polymer particles.
it can. In addition, the curing agent is a dispersion stabilizer or dispersion of F-NAD.
Particles that crosslink and cure, such as amino resins and
Uses a cross-linking agent such as oxy resin and polyisocyanate resin
Can be In the present invention, a solid paint and / or a topcoat
UV absorbers and light stabilizers may be added to the rear coating.
No. The surface layer of the topcoat coating film in the present invention contains
Extremely weather resistance due to the main component of fluoropolymer
It is excellent, but the ultraviolet rays in sunlight are such a transparent target.
Permeate the coating film and deteriorate the solid coating film.
Sometimes. Therefore solid paint and / or topk
Including UV absorber and light stabilizer in rear coating
And not only the top coat but also the solid coat
It also improves the weather resistance of the
2 coat solid core
The purpose of improving the weather resistance of the
You. As the ultraviolet absorbent used in the present invention,
Absorbs energy, and solid resin
Compatible or uniform with fluoropolymer for rear coating
Can be dispersed and easily decomposed at the paint baking temperature
Widely known as long as they do not lose efficacy
Can be used, for example, benzophenone type, triazole type,
Phenyl salicylate type, diphenyl acrylate type,
An acetophenone type is preferred. These UV absorbers
By using a light stabilizer in combination with the absorbent,
Further improve the weather resistance of the paint film and top clear paint film
Can be done. Solid paint as a light stabilizer
Compatible with fluoropolymers for resins and top clear coatings
Or baking of paint which can be dispersed evenly
As long as it does not decompose easily at temperature
Known ones can be widely used, for example, screws (2,2,6,6-
Tetramethyl-4-piperidyl) sebacate, bis (1,
2,2,6,6-pentamethyl-4-piperidyl)
, 2- (3,5-di-tert-butyl-4-hydroxybe
Bis (1,2,2,6-pe)
N-methyl-4-piperidyl), tetrakis (2,2,6,6)
-Tetramethyl-4-piperidyl) -1,2,3,4-butane
Tetracarboxylate, tetrakis (1,2,2,6,6-pe
(N-methyl-4-piperidyl) -1,2,3,4-butanetate
Lacarboxylate and the like. These are one kind alone
Or a mixture of two or more. The blending amount of the above UV absorber is
0.1 to 10% by weight based on the solid resin content of the clear paint,
Preferably, the content is 1 to 5% by weight. In addition,
The amount of the stabilizer is based on the base paint or top clear paint.
0.1 to 10% by weight, preferably 1 to 5%, based on resin solids
% By weight. Examples Hereinafter, the present invention will be described further with reference to Examples and Comparative Examples.
Make it easy. Note that “parts” and “%” are in principle
The shift is also based on weight. 1. Production example of solid coat paint (S-1) 50% alkyd resin solution (* 1) 140 parts 60% Uban 20SE (* 2) 50 parts titanium oxide (* 3) 100 xylol / n-butanol (1/1) ) The composition consisting of 17 was subjected to a viscosity of 25 sec.
Cup # 4/20 ° C). PVC is 19.5
Met. (Note 1) 1 mol of phthalic anhydride, trimethylolpropane
Hydroxyl value of 1 mole of coconut oil and 0.5 mole of coconut oil fatty acid 8
5, 50% alkyd resin solution with 31% oil length and 7.3 acid value. (Note 2) Butanol-modified mela manufactured by Mitsui Toatsu Chemicals, Inc.
Min resin (Note 3) Sakai Chemical Industry Co., Ltd. TITONE R-650 (S-2) 50% acrylic resin solution (Note 7) 140 parts 60% Uban 20SE (Note 2) 50 parts Titanium oxide (Note 3) 4.2 parts Carbon black (Note 4) 1.6 parts Oxide yellow (Note 5) 3.0 parts Organic red pigment (Note 6) 0.5 parts Cyanine blue (Note 8) 6.2 parts (Note 4) Mitsubishi Kasei Kogyo Co., Ltd., carbon black MA-
100B (Note 5) Titanium Industry Co., Ltd., Mapico Yellow XLO (Note 6) Dainichi Seika Industry Co., Ltd., Corofine Red 68
20 (Note 7) Styrene 15 parts, normal butyl acrylate
42 parts, 2-ethylhexyl methacrylate 23 parts, hydro
50% consisting of 18 parts of xymethacrylate and 2 parts of acrylic acid
Acrylic resin solution (* 8) Dainichi Seika Industry Co., Ltd., phthalocyanine blue
5240K 2. Production Example of Top Clear Coating (T-1): Synthesis of Dispersion Polymer Liquid A Heptane 102 parts n-butyl acetate 8 parts Dispersion stabilizer (Lumiflon LF4006 manufactured by Asahi Glass Co., Ltd.)
(A molecular weight of about 19,000, a fluorine atom content of 30% by weight) 108 parts were charged into a flask and heated to reflux, and the following monomers and weight
The initiator was added dropwise over 3 hours, and after aging for 2 hours,
26 parts of n-butyl acetate were added. Styrene 15 parts Methyl methacrylate 40 parts Acrylonitrile 30 parts 2-hydroxyethyl methacrylate 15 parts Tertiary butyl peroxy 2-ethylhexanoate 1.5 parts The liquid thus obtained has a nonvolatile content of 47%. Viscosity A, particle size of polymer particles (measured by electron microscope,
The same applies hereinafter) 0.15 μm milky white stable low-viscosity polymer dispersion
It was a liquid. Precipitates and coarse particles even after standing at room temperature for 3 months
No outbreak was observed. (T-2): Synthesis of Dispersion Polymer Liquid B Heptane 102 parts n-butyl acetate 8 parts 108 parts of the dispersion stabilizer of Example 1 was charged into a flask and heated to reflux, and the following monomers and weight
The initiator was added dropwise over 3 hours, and after aging for 2 hours,
26 parts of n-butyl acetate were added. Styrene 15 parts Methyl methacrylate 17 parts Acrylonitrile 30 parts 2-hydroxyethyl methacrylate 15 parts Glycidyl methacrylate 20 parts Methacrylic acid 3 parts Tertiary butyl peroxy 2-ethylhexanoate 1.5 parts B, particle size 0.12μm
Was a milky white stable low-viscosity polymer dispersion. At room temperature
No sedimentation or coarse particles were observed even after standing for 3 months
Was. (T-3): Introduction of a double bond into a dispersion stabilizer "Lumiflon LF400" (nonvolatile content 50%, acid value 5, weight
200 parts, average molecular weight about 50,000, fluorine atom content about 27%)
Glycidyl methacrylate 0.8 part 4-tert-butylpyrocatechol 0.02 part dimethylaminoethanol 0.1 part was added and reflux reaction was carried out for 5 hours to obtain a copolymerizable double bond.
Was introduced into the molecular chain of the dispersion stabilizer. Resin acid value reduction is kept within 0.02 and one molecular chain
The number of introduced double bonds was limited to one or less. 80 parts of synthetic heptane of dispersion polymer liquid (C) 8 parts of n-butyl acetate 130 parts of the above dispersion stabilizer 130 parts were charged into a flask, heated and refluxed, and the following monomers and
And, the polymerization initiator is added dropwise over 3 hours, and further 2 hours.
After aging, 26 parts of n-butyl acetate was added. Styrene 15 parts Methyl methacrylate 40 parts Acrylonitrile 30 parts 2-hydroxyethyl methacrylate 15 parts Tertiary butyl peroxy 2-ethylhexanoate 1.5 parts The nonvolatile content of the obtained liquid is 47%, viscosity D, particle size 0.18 μm.
Was a milky white stable low-viscosity polymer dispersion. At room temperature
No sedimentation or coarse particles are observed even after standing for 3 months
Was. (T-4): styrene 15 parts, n-butyl methacrylate 42 parts, 2-
23 parts of ethylhexyl methacrylate, hydroxyethyl
18 parts of methacrylate and 2 parts of acrylic acid
Copolymerization in xylol using zobisisobutyronitrile
Combined, heating residue 50%, solution acid value 9.0, solution viscosity H,
An acrylic resin solution having a weight average molecular weight of about 16,000 was obtained. (T-5): Production of dispersion stabilizer 40 parts of isobutyl acetate and 40 parts of toluene were heated to reflux.
And the following monomer and polymerization initiator were added dropwise over 3 hours.
After aging, aging was performed for 2 hours. Styrene 10 parts Isobutyl methacrylate 69 parts 2-ethylhexyl methacrylate 10 parts 2-hydroxyethyl methacrylate 10 parts Methacrylic acid 1 part 2,2'-azobisisobutyronitrile 2 parts The obtained acrylic resin varnish has a nonvolatile content of 55%, viscosity
H and the weight average molecular weight were about 16,000. Production of non-aqueous dispersion 93 parts of heptane and 98 parts of the dispersion stabilizer obtained above
Charge into Lasco, heat to reflux, and polymerize the following monomers and
The initiator was added dropwise over 3 hours and aged for 2 hours. Styrene 15 parts Methyl methacrylate 40 parts Acrylonitrile 30 parts 2-hydroxyethyl methacrylate 15 parts tert-butylperoxy 2-ethylhexanoate 1.5 parts The obtained dispersion has a nonvolatile content of 53%, a viscosity B and a polymer particle.
Milky white stable low-viscosity polymer with a particle size of 0.2 to 0.3 μm
It was a sprinkle. Leave this dispersion at room temperature for 3 months
No generation of precipitates or coarse particles was observed. (T-6): Dispersion stabilizer solution used in T-1 The dispersion or solution obtained in (T-1) to (T-6) above
15 parts of amino resin (Note 2) per 85 parts of solid resin content
(Solid content), and 10% per 100 parts of both resins.
10 parts of UV absorber solution (Note 9) and light stabilizer (Note 10)
5 parts blend, viscosity 20-40 seconds with Swazole # 1000 (Ford
Cup # 4/20 ℃) adjust viscosity to get clear paint
Was. Further, the dispersions obtained in the above (T-1) to (T-6) or
Isocyanate per mole of hydroxyl groups in the resin contained in the solution
The polyisocyanate compound is added at a ratio of 1 mol
(Note 11) and 10 parts of 10% UV absorber solution
0.5 parts of light stabilizer (Note 12) per 100 parts of resin solids
And then with cellosolve acetate for a viscosity of 20 to 40 seconds
Cup # 4/20 ° C) and apply top clear paint.
Obtained. Of the top clear paint thus obtained,
Each of the top clear paints blended with resin
1-AM) to (T-6-AM), isocyanate compound
Each combined top clear paint (T-1-NCO)
-(T-6-NCO). (Note 9): Ciba Geigy's Tinuvin 900 xylose
Dissolving in water (Note 10): Ciba-Geigy Co., Ltd.
Roll solution (Note 11): Non-yellowing block I made by Nippon Polyurethanes
Socyanate DC-2725 (Note 12): Sankyo LS292 manufactured by Sankyo Co., Ltd.
Epoxy amide-based cationic electrodeposition primer and intermediate coater
Prepare a painted plate with painted facer, and place it on the
Apply lid paint (15μ film based on the film to the cured coating)
Thick), apply top clear paint wet-on-wet
(30μ film thickness based on the cured coating) and heated at 140 ℃ for 30 minutes
Heating cured both coatings simultaneously. Painting of these solid paints and top clear paints
Table 1 shows the process and the performance test results of the obtained coating film.
It was shown to. The performance test method of the coating film is as follows. <Accelerated weather resistance> QUV accelerated exposure test: Q Panal accelerated weather resistance tester Test conditions UV irradiation 16 hours / 60 ° C Water coagulation 8 hours / 50 ° C 1 cycle, 5000 hours (208 cycles) test
The coating film after the test was tested. <Mitsuzawa> The gloss before and after the accelerated weathering test
Measurements were made at ° and 20 °. <Surface tension> It was measured by a contact angle using water and paraffin. <Coating state> Determined visually. ◎: No abnormalities ○: Meat stains are observed △: Cracks, blisters, etc. slightly occur ×: Cracks, blisters, discoloration, etc. occur frequently <Visibility> PGD (Portable Gloss Disrinctness) Image clarity tester <Interlayer Adhesiveness> Cross-cut the painted surface to reach the base
After gluing the adhesive cellophane tape to the
Was visually observed. ◎: Almost no peeling of the coating △: A little peeling of the coating ×: A lot of peeling of the coating <Hardness> Pencil for scratch resistance test pencil (Mitsubishi Uni) <Impact resistance> DuPont impact tester At 20 ° C, with the painted surface on the 1/2 inch radius
Place the painted plate, drop 500 g of falling weight on the surface,
Maximum height (cm) without abnormalities such as scratches <Gazoline resistance> Immerse in Nisseki Super Gasoline (20 ° C) for 24 hours. <Alkali resistance> 3 cc of 0.1 N sodium hydroxide (reagent) is dropped on the coated surface
Then, the coated surface after standing at 55 ° C. for 4 hours was observed.

──────────────────────────────────────────────────の Continued on the front page (51) Int.Cl. ⁶ Identification code Agency reference number FI Technical indication location // C09D 133/10 PGF C09D 133/10 PGF 133/20 PFW 133/20 PFW (72) Inventor Nobushige Numa 4-171-1, Higashi-Hachiman, Hiratsuka-shi Kansai Paints Co., Ltd. Document JP-A-61-247750 (JP, A) JP-A-61-115967 (JP, A) JP-A-62-10101 (JP, A) JP-A-61-46283 (JP, A)

Claims (1)

(57) [Claims] In a topcoat coating method in which a solid coat containing a coloring pigment is applied, and then a transparent top clear paint is applied to the coated surface, the top clear paint contains a fluoroolefin as an essential component, and has a weight average molecular weight of 50.
In the presence of a dispersion stabilizer comprising an organic solvent-soluble fluorinated polymer having a content of 00 to 120,000 and a fluorine atom content of 1 to 60% by weight,
The radical polymerizable monomer is dissolved in an organic solvent that is soluble in the dispersion stabilizer and the radical polymerizable monomer (containing no fluorine atom) and insoluble in the polymer formed by the radical polymerizable monomer. A topcoat coating method, characterized in that the polymer particles are a curable coating mainly composed of a non-aqueous dispersion in which the polymer particles are dispersed in an organic solvent solution of a dispersion stabilizer. 2. The non-aqueous dispersion contains a fluoroolefin as an essential component, has a weight average molecular weight of 5,000 to 120,000 and a fluorine atom content of 1 to 60% by weight, and has at least 0.1 polymerizable double bond in one molecule. In the presence of a dispersion stabilizer comprising an organic solvent-soluble fluorinated polymer, which is soluble in the dispersion stabilizer and a radical polymerizable monomer (not containing a fluorine atom) and formed by the radical polymerizable monomer The radical polymerizable monomer is graft-polymerized to the fluoropolymer in an organic solvent that is insoluble in the polymer to be obtained, wherein the polymer particles are dispersed in an organic solvent solution of a dispersion stabilizer. 2. The method according to claim 1, wherein the method is an aqueous dispersion.