JP2003275672A - Method for recovering performance of low-polluting coating film, and low-polluting coating film - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a method for recovering the performance of a low-polluting coating film which, when an automobile body or the like on which a clear coating film containing a functional ladder silicone compound and being excellent in pollution resistance is formed as an outermost surface layer coating film is stored outdoors and a bird dropping or the like is stuck thereto, can easily remove the bird dropping and prevent the coating film surface from being damaged by wiping the coating film surface beforehand with a prescribed stain-proofing restorer, and a low polluting coating film treated by the above method. <P>SOLUTION: In this method for recovering the performance of a low-polluting coating film, the outermost surface layer coating film formed on a substrate by a low-polluting clear coating film containing the functional ladder silicone compound is wiped by using the stain-proofing restorer containing 40 mass% or more of at least one of organic solvent selected from a group consisting of isopropyl alcohol, isobutyl alcohol, and n-propyl alcohol. <P>COPYRIGHT: (C)2003,JPO

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a method for recovering performance of a low-staining coating film, and a low-staining coating film treated by the method for recovering performance of a low-staining coating film.

[0002]

2. Description of the Related Art A coating film formed on an outer panel of an automobile body or the like is waxed after cleaning the surface of the coating film in order to maintain / recover outdoor pollution. Immediately after waxing, gloss was imparted, but removal of bird feces and the like when attached was not easy enough.

In the conventional coating film, the water repellency of the coating film cannot be said to be sufficient, and the problem that outdoor contaminants easily adhere to the coating film was not sufficient. Further, even with a coating film which is said to have low stain resistance, the change in the surface layer of the coating film upon exposure makes the coating film low stain resistance, particularly when bird droppings adhere, becomes insufficient.

[0004]

SUMMARY OF THE INVENTION Therefore, an object of the present invention is to store outdoors an automobile body or the like on which a clear coating film having a good stain resistance containing a functional ladder silicone compound as an outermost surface coating film is formed. Even if bird droppings adhere,
By wiping the coating film surface with a predetermined antifouling recovery agent in advance, bird droppings can be easily removed, and a good surface condition that does not damage the coating film surface (referred to as "contamination removing property" in the present invention). )
The present invention provides a method for recovering performance of a low-staining coating film that provides the above, and a low-staining coating film treated by this method.

[0005]

Means for Solving the Problems The present inventors have accomplished the present invention as a result of intensive studies in view of the above problems. 1. Using the antifouling recovery agent containing at least 40% by mass of at least one organic solvent selected from the group consisting of isopropyl alcohol, isobutyl alcohol and n-propyl alcohol, a low contamination containing a functional ladder silicone compound on the substrate A method for recovering performance of a low-staining coating film, which comprises wiping an outermost surface coating film formed by a transparent clear coating film.

2. The method for recovering the performance of the above low-staining coating film, wherein the base material is an automobile body outer panel or an automobile part.

3. The coating material for forming the outermost coating film is (A) (a-1) based on 100 parts by mass of the solid content of the vehicle.
A ladder silicone oligomer containing a (meth) acryloxyalkyl group, (a-2) an ethylenically unsaturated monomer containing a crosslinkable functional group, and optionally (a
-3) The above low-staining coating film which is a clear coating material containing 0.01 to 2% by mass of a functional ladder silicone copolymer obtained by copolymerizing with another copolymerizable ethylenically unsaturated monomer. Performance recovery method.

4. The coating material for forming the outermost layer coating film is (B) acrylic resin, polyester resin, or
At least one crosslinkable coating film-forming resin selected from the group consisting of alkyd resins, fluororesins, polyurethane resins and polyether resins, and at least one crosslinker selected from the group consisting of amino resins and block polyisocyanate compounds. The method for recovering the performance of the above-mentioned low-staining coating film which is a clear coating material contained.

5. The coating material for forming the outermost layer coating film is (C) (c-1) 15-40% by mass of an acid anhydride group-containing ethylenically unsaturated monomer as a vehicle, and (c-2) another copolymerizable ethylene. Acid anhydride group-containing polymer obtained by copolymerizing 60 to 85% by mass of a water-unsaturated monomer, and (c-3) a monoalcohol containing 1 to 12 carbon atoms, an acid anhydride group And a hydroxyl group are obtained by reacting them in an amount of 1/10 to 1/1 in a molar ratio, and a polymer having a carboxyl group and a carboxylic acid ester group (mass% of the polymer is the total solid content of the resin composition). Based on mass, the same hereinafter); 20 to 60 mass%, (D) (d-1) formula (1)

[Chemical 3] [Wherein, R is a hydrogen atom or a methyl group, X is a linear or branched alkyl or hydroxyalkyl, m is an integer of 2 to 8, n is an integer of 3 to 7, and q is 0.
Is an integer of 4 to 5] 5 to 60% by mass of a hydroxyl group-containing ethylenically unsaturated monomer having a structure represented by (d-2)
Glycidyl group-containing ethylenically unsaturated monomer 10-6
Polymer containing a hydroxyl group and a glycidyl group, obtained by copolymerizing 0% by mass, and optionally 0 to 85% by mass of another copolymerizable ethylenically unsaturated monomer (d-3) 1-60 mass% and (E)
(E-1) 5 to 60% by mass of the hydroxyl group-containing ethylenically unsaturated monomer of (d-1), (e-2) the above (d-2)
Glycidyl group-containing ethylenically unsaturated monomers 10 to 6
0% by mass, 1 to 30% by mass of (e-3) (meth) acryloxyalkyl group-containing ladder silicone oligomer, and (e-4) optionally other copolymerizable ethylenically unsaturated monomer 0 The above low-staining coating film is a clear paint containing 0.01 to 60% by mass of a polymer containing a hydroxyl group, a glycidyl group and a functional ladder silicone, which is obtained by copolymerizing Performance recovery method.

6. A clear coating composition further comprising (F) a polyethylene oxide- or polypropylene oxide-modified poly-silicone compound in an amount of 0.02 to 1 solid part by mass per 100 parts by mass of the total amount of the vehicle in the vehicle of the paint forming the outermost surface coating film. A method for recovering performance of a coating film having low stain resistance as described above.

7. In addition to (G) (g-1) formula (2), which is used as the vehicle for forming the outermost coating film,

[Chemical 4] [Wherein, R is a hydrogen atom or a methyl group, X'is a linear or branched alkyl or hydroxyalkyl, m
′ Is an integer of 2 to 8, n ′ is an integer of 3 to 7,
q ′ is an integer of 0 to 4] and a hydroxyl group-containing ethylenically unsaturated monomer having a structure shown by the formula and an acid anhydride group-containing compound in which the hydroxyl group and the acid anhydride group are 1 / 0.9 to 1 /
20 to 100 mass of a monomer mixture of a carboxyl group-containing ethylenically unsaturated monomer and (g-2) hydroxyalkyl (meth) acrylate compound obtained by mixing and reacting in an amount of 0.5 molar ratio %, And optionally (g-3) 0 to 80 mass% of a copolymerizable ethylenically unsaturated monomer, and 5 to 50 mass% of a polymer having a hydroxyl group and a carboxyl group. The method for recovering the performance of the above-mentioned low-staining coating film which is a clear coating material contained.

8. In addition to (H) (h-1) trifluoromonochloroolefin and / or tetrafluoroolefin 5 to 60% by mass, (h-2) hydroxyalkyl vinyl ether 5 to 20% by mass in the coating vehicle forming the outermost layer coating film. %, (H-3) cyclohexyl vinyl ether 5-40% by mass, (h-4) alkyl vinyl ether 5-20% by mass, (h-5) glycidyl-containing radically polymerizable monomer and / or carboxyl group or acid anhydride group Fluoropolymer 2 obtained by copolymerizing 0 to 40% by mass of a polymerizable monomer
The method for recovering the performance of the above low-staining coating film, which is a clear coating material containing 50% by mass.

9. A low-staining coating film treated by the method for recovering the performance of a low-staining coating film as described above.

[0014]

BEST MODE FOR CARRYING OUT THE INVENTION The constitution of the present invention will be described in detail below.

[Method of recovering performance of low-staining coating film] In the method of recovering performance of a low-staining coating film of the present invention, at least one organic solvent of isopropyl alcohol, isobutyl alcohol and n-propyl alcohol is used as an antifouling recovery agent. A method of recovering performance by wiping an outermost surface coating film formed by a low-staining clear coating film containing a functional ladder silicone compound on a substrate using the antifouling recovery agent.

The low-staining clear coating film forms a metallic base coating film or a solid base coating film on the above-mentioned substrate directly or through the undercoating film, and then, without curing the above-mentioned base coating film, It is preferable that a low-staining clear coating film containing a functional ladder silicone compound is formed as the outermost coating film, and the base coating film and the clear coating film are simultaneously baked and dried. .

The method of recovering the performance of the low-staining coating film of the present invention comprises:
It is carried out by wiping the surface of the low-staining clear coating film containing the functional ladder silicone compound with an antifouling recovery agent and drying the antifouling recovery agent. Wiping is performed by impregnating the antifouling recovery agent on the waste cloth or sponge and wiping the coating film surface with the above-mentioned waste cloth or sponge, or by attaching the antifouling recovery agent to the low-staining clear coating film surface by spraying or the like. After this, it is preferable to wipe off with a dry waste cloth or the like. It is preferable to wipe as uniformly as possible. Prior to wiping, stains on the coating film surface are preferably washed with water or the like. By treating this wipe treatment as a finish at the time of car washing, for example, the contact angle of water on the surface of the low-staining clear coating film becomes large,
The removal properties of bird droppings and various external contaminants attached thereafter are improved, and a good surface condition can be provided. The interval at which the wiping process is performed varies depending on the exposure conditions, but is preferably once to once every several months.

[Antifouling Recovery Agent] The antifouling recovery agent of the present invention is isopropyl alcohol, isobutyl alcohol and n-.
40 mass% or more of at least one organic solvent selected from the group consisting of propyl alcohol is contained. The above antifouling recovery agent is effective even if it contains less than 60 mass% of other organic solvent or water. Preferably, an antifouling recovery is performed on an organic solvent containing at least 60% by mass of an organic solvent selected from the group consisting of isopropyl alcohol, isobutyl alcohol and n-propyl alcohol, relative to 100% by mass of the organic solvent in the composition. 80 mass% or more is contained in 100 mass% of the agent.

[Substrate] The above-mentioned substrate can be applied to various substrates, and specific substrates include, for example, metals such as iron, aluminum, copper or alloys thereof, inorganics such as glass, cement and concrete. Material, polyethylene resin, polypropylene resin, ethylene-vinyl acetate copolymer resin, polyamide resin, acrylic resin, vinylidene chloride resin, polycarbonate resin, polyurethane resin, epoxy resin and other plastic materials, and various FRP and other plastic materials, etc. Examples thereof include natural and synthetic materials such as wood and fiber materials (paper, cloth, etc.). In the case where the base material is a car body outer panel and parts, after the chemical conversion treatment is performed on the base material in advance,
It is preferable to form a base coating film formed by undercoat coating such as electrodeposition coating or intermediate coating. The intermediate coating is carried out for concealing the base, imparting chipping resistance, and ensuring adhesion with the topcoat. The above-mentioned intermediate coating is performed with a commonly used intermediate coating, but an organic solvent type, water-based or powder coating can be used as the intermediate coating. In addition, in the text, a base material may be a base material on which a base coating film formed by chemical conversion treatment, undercoating, intermediate coating or the like is formed.

[Method for forming low-staining clear coating film] A base coating film is formed by coating a base coating material on the above base material. For forming this base coating film, a metallic base coating material containing a bright pigment or a solid base coating material containing a coloring pigment, which is generally used for base coating, can be used. The crosslinkable coating film-forming resin as a vehicle for the base coating material, the crosslinking agent that can be used if necessary, and the compounding amounts thereof are the same as those for the clear coating material. The above base coating film is formed by a conventional topcoat base paint, but an organic solvent type, water-based or powder coating can be used as the topcoat base paint.

Further, the metallic base paint contains various bright pigments. Examples of the bright pigment,
Aluminum flake pigment, colored aluminum flake pigment, metal oxide coated alumina flake pigment, interference mica pigment, colored mica pigment, metal oxide coated glass flake, metal plated glass flake, metal oxide coated glass flake, metal oxide coated silica flake. Examples thereof include pigments, metallic titanium flakes, graphite, stainless flakes, plate-shaped iron oxide, phthalocyanine flakes and hologram pigments.

Further, even with a metallic base paint,
If necessary, the color pigment used in the solid base paint can be used in combination with the bright pigment. As the coloring pigment, an azo lake pigment, a phthalocyanine pigment, an indigo pigment, a perylene pigment, a quinophthalone pigment,
Examples include organic pigments such as dioxazine pigments, quinacridone pigments, isoindolinone pigments, metal complex pigments, and inorganic pigments such as yellow lead, yellow iron oxide, red iron oxide, titanium dioxide, and carbon black. The addition amount of the bright pigment and the coloring pigment can be arbitrarily set in accordance with the development of a desired hue. Further, various extender pigments can be used in combination.

When the bright pigment and / or the coloring pigment are used in combination, the total content (PW
C) is preferably less than 50%, more preferably less than 30%. If it exceeds 50%, the appearance of the coating film deteriorates.

In addition to the above components, various additives used in the above clear coating composition can be added to the above base coating composition.

In the case where the base material is an undercoat, an intermediate coating, or the like, the base coating is a wet-on-wet (W / W) method or a wet-on-dry method on the base coating. It can be applied by the (W / D) method. The W / W method is a method of applying an undercoat and then drying it by air drying or the like to apply it to an uncured or semi-cured undercoat, whereas the W / D method is a method of baking to cure. This is a method of coating the underlying coating film later.

The method for forming the above base coating film on the substrate is not particularly limited, but a spray method, a roll coater method and the like are preferable, and it is also possible to apply a plurality of times.
The dry film thickness of the above base coating film is a lower limit of 5μ per coat.
m, and the upper limit is preferably 50 μm, the lower limit is more preferably 10 μm, and the upper limit is more preferably 30 μm.

At least one low-staining clear coating film is formed on the base coating film thus formed. The method for forming the clear coating film is not particularly limited, but a spray method, a roll coater method and the like are preferable. Further, the dry film thickness of the clear coating film is preferably in the range of the lower limit of 20 μm and the upper limit of 50 μm per coat, more preferably the lower limit of 25 μm and more preferably the upper limit of 40 μm.

The low stain resistant clear coating film may be formed after the base coating film is cured or before it is cured. Before curing, the base coating film and the clear coating film are simultaneously cured by the W / W method.
When the low stain resistant clear coating film is applied a plurality of times, it may be baked at the same time after the final clear coating film is applied, or may be baked for each layer. The baking temperature is preferably 120 to 160 ° C. The multilayer coating film of the present invention can be obtained by the above forming method.

[Clear coating for forming the low stain resistant clear coating film] The clear coating used for forming the low stain resistant coating film to which the antifouling restorer is applied is based on 100 mass% of the vehicle solid content. A) A ladder silicone oligomer containing (a-1) (meth) acryloxyalkyl group, (a-2) an ethylenically unsaturated monomer containing a crosslinkable functional group, and (a-3) other as necessary. The lower limit of the ladder silicone copolymer obtained by copolymerizing the copolymerizable ethylenically unsaturated monomer is 0.0
It is preferably contained within the range of 1 part by mass and the upper limit of 2 parts by mass. When the content of the ladder silicone copolymer (A) is less than 0.01 parts by mass, good repelling property of coating film cannot be obtained, and when it exceeds 2 parts by mass, good non-sanding recoating property cannot be obtained. The lower limit is preferably 0.05 parts by mass and the upper limit is preferably 1 part by mass.

The ladder silicone oligomer containing a (meth) acryloxyalkyl group (a-1) contains a (meth) acryloxyalkyl group as a side chain group and a substituent other than a (meth) acryloxyalkyl group. An alkyl group having 1 to 18 carbon atoms, a substituted alkyl group, a phenyl group, or a substituted phenyl group is used as. It is also possible to add a small amount of glycidyl group or amino group to the side chain group.

The (a-2) ethylenically unsaturated monomer containing a crosslinkable functional group may be any one as long as the crosslinkable functional group is a functional group contained in the crosslinkable coating film-forming resin, and preferably a hydroxyl group. , Carboxyl group, acid anhydride group,
It is one or more ethylenically unsaturated monomers containing a functional group such as a glycidyl group or an amine group.

Examples of the hydroxyl group-containing monomer include hydroxyethyl acrylate, hydroxypropyl acrylate, hydroxyethyl methacrylate, hydroxypropyl methacrylate, and the like. Examples of the carboxyl group-containing monomer include acrylic acid, methacrylic acid, and itaconic acid. , Fumaric acid and the like, examples of the monomer having an acid anhydride group include maleic anhydride and itaconic anhydride, and examples of the monomer having a glycidyl group include glycidyl acrylate and glycidyl methacrylate. As the monomer having an amine group, a primary amine,
Aliphatic, cycloaliphatic, aromatic or cyclic amines having secondary amines and tertiary amines are mentioned, for example acrylamide, methacrylamide, methylol acrylamide,
Methylol methacrylamide, alkoxy methylol acrylamide, alkoxy methylol methacrylamide, dimethylaminopropyl methacrylamide, dimethylaminoethyl methacrylamide, tributylaminoethyl methacrylamide, oxazolidinoethyl methacrylate, 3-aminopropyl methacrylate, 2-isopropenyl-2- Examples include oxazoline and dimethylaminoethyl methacrylate. Further, examples of the monomer having an amine group also include a monomer having an isocyanate group, and examples thereof include aromatic diisocyanates such as tolylene diisocyanate, phenylene diisocyanate, and naphthalene diisocyanate; , Araliphatic diisocyanates such as xylene diisocyanate and tetramethyl xylene diisocyanate, isophorone diisocyanate,
Examples thereof include alicyclic diisocyanates such as hydrogenated tolylene diisocyanate. Preferred are monomers having a hydroxyl group or a glycidyl group.

The other copolymerizable ethylenically unsaturated monomer (a-3) is used, if necessary, and as the monomer, acrylic acid or methacrylic acid methyl, ethyl, propyl, n-butyl, i -Butyl, t-
Butyl, 2-ethylhexyl, lauryl, phenyl, benzyl, styrene, α-methylstyrene, vinyl acetate,
One or more such as divinylbenzene.

The compounding amount of the component (a-1) in the component (A), the component (a-2), and the component (a-3), which is optionally used, is 1 component (a-1). ~ 30% by mass,
It is preferable that the ratio of the component (a-2) is 1 to 50 mass% and the ratio of the component (a-3) is 0 to 90 mass%. (A
If the component (-1) is less than 1% by mass and the component (a-2) is less than 1% by mass, the cross-linking reaction of the coating film is insufficient and the coating film may be dissolved when the coating film is wiped with an organic solvent. ,
When the amount of the component (a-1) exceeds 30% by mass and the amount of the component (a-2) exceeds 50% by mass, the formed coating film may have insufficient gloss. In the present specification, the blending ratio of the monomers represents the ratio of each monomer when the total amount of the monomers is 100% by mass.

The number average molecular weight of the resulting ladder silicone copolymer (A) is preferably within the range of 500 as the lower limit and 8000 as the upper limit. The lower limit is more preferably 1500 and the upper limit is more preferably 5000.

The coating material for forming the outermost surface coating film is at least one crosslinkable coating material selected from the group consisting of (B) acrylic resin, polyester resin, alkyd resin, fluororesin, polyurethane resin and polyether resin as a vehicle. A clear coating material containing a film-forming resin and at least one crosslinking agent selected from the group consisting of amino resins and blocked polyisocyanate compounds is preferable.

Examples of the acrylic resin include a copolymer of an acrylic monomer and another ethylenically unsaturated monomer. Acrylic monomers that can be used for the copolymerization include methyl, ethyl, propyl, n-butyl, i-butyl and t- of acrylic acid or methacrylic acid.
Butyl, 2-ethylhexyl, lauryl, phenyl, benzyl, 2-hydroxyethyl, 2-hydroxypropyl, and other esterified products, 2-hydroxyethyl acrylate or 2-hydroxyethyl methacrylate, caprolactone ring-opening adducts, glycidyl acrylate, methacryl Glycidyl acid,
There are acrylamide, methacrylamide and N-methylol acrylamide, and (meth) acrylic acid esters of polyhydric alcohols. Other ethylenically unsaturated monomers copolymerizable with these include styrene, α-methylstyrene, itaconic acid, maleic acid, vinyl acetate and the like.

Examples of the polyester resin include saturated polyester resin and unsaturated polyester resin, which can be obtained, for example, by heating and condensing a polybasic acid and a polyhydric alcohol. Polybasic acids include saturated polybasic acids and unsaturated polybasic acids, examples of saturated polybasic acids include phthalic anhydride, terephthalic acid, and succinic acid, and examples of unsaturated polybasic acids include , Maleic acid, maleic anhydride,
Examples include fumaric acid. Also, as polyhydric alcohol,
Dihydric alcohols and trihydric alcohols can be used, and examples of dihydric alcohols include ethylene glycol and
Examples include diethylene glycol, and examples of the trihydric alcohol include glycerin and trimethylolpropane.

Examples of the alkyd resin include polybasic acids and polyhydric alcohols as described above, and further fats and oils and fatty acids (soybean oil, linseed oil, coconut oil, stearic acid, etc.), natural resins (rosin, amber, etc.) and the like. An alkyd resin obtained by reacting a modifier can be used.

The above-mentioned fluororesin comprises vinylidene fluoride resin, tetrafluoroethylene resin or a mixture thereof, a fluoroolefin and a hydroxy group-containing polymerizable compound, and other copolymerizable vinyl compounds. Resins made of various fluorine-based copolymers obtained by copolymerizing monomers can be used.

Examples of the epoxy resin include resins obtained by the reaction of bisphenol and epichlorohydrin. Examples of bisphenols include bisphenol A and bisphenol F. Examples of such a bisphenol type epoxy resin include Epicoat 828, Epicoat 1001,
Examples include Epicoat 1004, Epicoat 1007, and Epicoat 1009 (all manufactured by Shell Chemical Co., Ltd.), and those obtained by chain extension of these with an appropriate chain extender can also be used.

Examples of the polyurethane resin include resins having a urethane bond obtained from various polyol components such as acrylic, polyester, polyether and polycarbonate and a polyisocyanate compound. As the polyisocyanate compound,
2,4-Tolylene diisocyanate (2,4-TD
I), 2,6-tolylene diisocyanate (2,6-T
DI) and mixtures thereof (TDI), diphenylmethane-4,4'-diisocyanate (4,4'-MD
I), diphenylmethane-2,4'-diisocyanate (2,4'-MDI), and mixtures thereof (MDI),
Naphthalene-1,5-diisocyanate (NDI),
3,3'-dimethyl-4,4'-biphenylene diisocyanate, xylylene diisocyanate (XDI), dicyclohexylmethane diisocyanate (hydrogenated HD
I), isophorone diisocyanate (IPDI), hexamethylene diisocyanate (HDI), hydrogenated xylylene diisocyanate (HXDI) and the like can be mentioned.

The above-mentioned polyether resin is a polymer or copolymer having an ether bond, and is a polyoxyethylene-based polyether, polyoxypropylene-based polyether, polyoxybutylene-based polyether, bisphenol A or bisphenol F. And polyether resins having at least two hydroxyl groups per molecule, such as polyethers derived from aromatic polyhydroxy compounds. Further, the above-mentioned polyether resin is reacted with a polycarboxylic acid such as succinic acid, adipic acid, sebacic acid, phthalic acid, isophthalic acid, terephthalic acid or trimellitic acid, or a reactive derivative such as an acid anhydride thereof. The carboxyl group-containing polyether resin thus obtained can also be used.

Further, a clear coating composition containing a carboxyl group-containing polymer and a glycidyl group-containing polymer described in Japanese Patent Publication No. 8-19315 has a measure against acid rain and a wet-on-wet (W / W) method. A large difference in solubility from the metallic base coating film is preferably used from the viewpoint of not disturbing the orientation of the glittering agent in the metallic base coating film when coated.

A preferred ratio of the crosslinkable coating film-forming resin and the crosslinking agent is 100 parts by weight of the total amount, and the crosslinkable coating film-forming resin is 90 to 50 parts by weight in terms of solid content. The crosslinking agent is 10 to 50 parts by mass, and more preferably the crosslinking agent is 15 to 40 parts by mass with respect to 85 to 60 parts by mass. 1 crosslinker
If it is less than 0 parts by mass, the crosslinking in the coating film may not be sufficient. On the other hand, when the amount of the crosslinking agent exceeds 50 parts by mass, the storage stability of the coating composition decreases and the curing rate increases, so that the appearance of the coating film may deteriorate. In the first aspect of the present invention, the crosslinkable coating film forming resin and the crosslinker (B) do not include the above ladder silicone copolymer (A).

The coating material for forming the outermost surface coating film comprises (C) (c-1) 15-40% by mass of an ethylenically unsaturated monomer containing an acid anhydride group as a vehicle, and (c-2) another copolymer. An acid anhydride group-containing polymer obtained by copolymerizing 60 to 85% by mass of a possible ethylenically unsaturated monomer, and (c-3) a monoalcohol containing 1 to 12 carbon atoms are treated with an acid. A polymer having a carboxyl group and a carboxylic acid ester group obtained by reacting an anhydride group and a hydroxyl group in a molar ratio of 1/10 to 1/1 (mass% of the polymer is the resin composition). Based on the total solid mass, the same applies hereinafter); 20 to 60 mass%,
(D) (d-1) Formula (1)

[Chemical 5] [Wherein, R is a hydrogen atom or a methyl group, X is a linear or branched alkyl or hydroxyalkyl, m is an integer of 2 to 8, n is an integer of 3 to 7, and q is 0.
Is an integer of 4 to 5] 5 to 60% by mass of a hydroxyl group-containing ethylenically unsaturated monomer having a structure represented by (d-2)
Glycidyl group-containing ethylenically unsaturated monomer 10-6
Polymer containing a hydroxyl group and a glycidyl group, obtained by copolymerizing 0% by mass, and optionally 0 to 85% by mass of another copolymerizable ethylenically unsaturated monomer (d-3) 1-60 mass% and (E)
(E-1) 5 to 60% by mass of the hydroxyl group-containing ethylenically unsaturated monomer of (d-1), (e-2) the (d-2)
Glycidyl group-containing ethylenically unsaturated monomers 10 to 6
0% by mass, 1 to 30% by mass of (e-3) (meth) acryloxyalkyl group-containing ladder silicone oligomer, and (e-4) optionally other copolymerizable ethylenically unsaturated monomer 0 It is also preferable that it is a clear paint containing 0.01 to 60% by mass of a polymer containing a hydroxyl group, a glycidyl group, and a functional ladder silicone, which is obtained by copolymerizing about 85 to 85% by mass.

The acid anhydride group-containing polymer is the acid anhydride group-containing ethylenically unsaturated monomer (c-1) 15-40.
It is obtained by copolymerizing 60% by mass, preferably 15% by mass to 30% by mass, with another copolymerizable ethylenically unsaturated monomer (c-2) of 60% by mass to 85% by mass, preferably 70% by mass to 85% by mass. If the amount of the acid anhydride group-containing ethylenically unsaturated monomer (c-1) is less than 15% by mass, the curability is insufficient, and if it exceeds 40% by mass, the obtained coating film is too hard and brittle and the weather resistance is insufficient. Is not preferred.

Examples of the acid anhydride group-containing ethylenically unsaturated monomer (c-1) include itaconic anhydride, maleic anhydride and citraconic anhydride. The other copolymerizable ethylenically unsaturated monomer (c-2) is not particularly limited as long as it does not adversely affect the acid anhydride group, and has 3 to 1 carbon atoms having one ethylenically unsaturated bond.
It is preferable that the number of monomers is 5, especially 2 to 12.

Examples of the other copolymerizable ethylenically unsaturated monomer (c-2) include styrene derivatives such as styrene, α-methylstyrene and pt-butylstyrene as ethylenically unsaturated monomers, (Meth) acrylic acid ester (for example, methyl (meth) acrylate, (meth)
Ethyl acrylate, propyl (meth) acrylate, (meth) acrylic acid-n, i, and t-butyl, (meth)
2-ethylhexyl acrylate and lauryl (meth) acrylate, cyclohexyl (meth) acrylate, etc.,
Isomethanyl (meth) acrylate, Veo from Shell
Va-9, VeoVa-10, etc. are mentioned. It is also possible to use monomers having a carboxyl group such as acrylic acid and methacrylic acid. When styrene or a derivative thereof is used as the other copolymerizable ethylenically unsaturated monomer, it is particularly preferably used in an amount of 5 to 40% by mass.

The copolymerization of the acid anhydride group-containing polymer is
The polymerization can be carried out by a known method such as solution polymerization such as radical polymerization, and can be carried out, for example, at a polymerization temperature of 100 to 150 ° C. and a polymerization time of 3 to 8 hours. As the initiator, an azo type or peroxide type initiator is preferably used. Other additives such as chain transfer agents can also be used. The number average molecular weight of the obtained acid anhydride group-containing polymer is preferably 1500 to 8000, and particularly preferably 2000 to 5000. When the number average molecular weight exceeds 8,000, the viscosity of the polymer becomes high, so that it becomes difficult to prepare a clear coating composition having a high solid content. If the number average molecular weight is less than 1500, the curability of the clear coating composition will be insufficient.
The molecular weight of the polymer used in the present invention is determined by the GPC method.

The acid anhydride group-containing polymer has an average of at least 2, preferably 2 to 15 acid anhydride groups in one molecule. If the number of acid anhydride groups contained in one molecule is less than 2, the curability of the clear coating composition will be insufficient. If it exceeds 15, it becomes too hard and brittle, and the weather resistance is insufficient.

Next, the obtained acid anhydride group-containing polymer is added to the acid anhydride group and the hydroxyl group in a molar ratio of 1/10 to 1: 1.
/ 1, preferably 1/8 to 1 / 1.1, and more preferably 1 / 1.5 to 1 / 1.3, with a carboxyl group by reacting with the monoalcohol (c-3). A polymer (C) having a carboxylic acid ester group is prepared. If this ratio is less than 1/10, the excess alcohol is too much and causes cracking at the time of curing, and if it exceeds 1/1, unreacted acid anhydride groups remain and storage stability deteriorates.

The above monoalcohol (c-3) is 1 to
It is a low molecular weight compound having 12 and preferably 1 to 8 carbon atoms. This is because the alcohol volatilizes when heated and is good for regenerating the acid anhydride group. The monoalcohol includes methanol, ethanol, n-propanol, i-propanol, n-butanol, i-butanol, t-butanol, methyl cellosolve, ethyl cellosolve, dimethylaminoethanol, diethylaminoethanol, acetol, allyl alcohol and propargyl alcohol. Etc. Particularly preferred are acetol, allyl alcohol, propargyl alcohol and methanol.

When the polymer (C) is blended, the content is 20 to 60% by mass based on the total mass of the solid content of the resin composition. If the content of the polymer (C) is less than 20% by mass, curing will be insufficient and the hardness of the formed coating film will be insufficient, and if it exceeds 60% by mass, the water resistance will decrease. Preferably, it is 25 to 50% by mass.

The polymer (D) having a hydroxyl group and an epoxy group which can be used in the clear coating composition has an average of preferably 2 to 10 epoxy groups in a molecule, more preferably 3 to 8 epoxy groups, and The average number of hydroxyl groups is preferably 2 to 12, more preferably 4 to 10. Also,
The epoxy equivalent is preferably 100 to 800, more preferably 200 to 700, and the hydroxy equivalent is preferably 200 to 1200, more preferably 400 to 1000.
Is. If the epoxy equivalent is larger than the upper limit, the curability of the clear coating composition becomes insufficient. On the other hand, if it is less than the above lower limit, the coating becomes too hard and the coating becomes brittle, which is not preferable. When the hydroxy equivalent is less than 200, the water resistance of the cured coating film is insufficient, and when it exceeds 1200, the curability is insufficient, which is not preferable.

The polymer (D) has, for example, the formula (1)

[Chemical 6] [In the formula, R is a hydrogen atom or a methyl group, X is a linear or branched alkylene group or a hydroxyalkylene group,
m is an integer of 2 to 8, n is an integer of 3 to 7, and q
Is an integer of 0 to 4] 5 to 60% by mass, preferably 15 to 30% by mass, of a hydroxyl group-containing ethylenically unsaturated monomer (d-1) having a structure represented by an epoxy group-containing ethylenically unsaturated monomer ( d-2) 10 to 60% by mass, preferably 15 to 50% by mass, and optionally other copolymerizable ethylenically unsaturated monomer (d-3) 0 to 8
It can be obtained by copolymerizing 5% by mass, preferably 10 to 60% by mass. If the hydroxyl group-containing ethylenically unsaturated monomer (d-1) is less than 5% by mass, curability is insufficient, and if it exceeds 60% by mass, compatibility is insufficient and the reaction does not proceed sufficiently, which is not preferable. If the amount of the epoxy group-containing ethylenically unsaturated monomer (d-2) is less than 10% by mass, the curability will be insufficient, and if it exceeds 60% by mass, it will be too hard and the weather resistance will be insufficient, such being undesirable.

A hydroxyl group-containing alkyl chain of the hydroxyl group-containing ethylenically unsaturated monomer (d-1) which can be used for preparing the above polymer (D), that is,-(X) m- [in the formula (1). When the chain length of the group represented by OCO (CH ₂ ) n] q-OH is too short, the flexibility in the vicinity of the cross-linking point is lost and the group becomes too hard. When it is too long, the molecular weight between cross-linking points tends to be too large. It is in. Therefore, the hydroxyl group-containing alkyl chain preferably has 4 to 20 carbon atoms, and more preferably 4 to 10 carbon atoms. Specifically, (meth) acrylic acid-4-hydroxybutyl, (meth) acrylic acid-6-hydroxyhexyl and their reaction products with ε-caprolactone, and ε of (meth) acrylic acid-2-hydroxyethyl -Compounds such as the reaction products with caprolactone. Alternatively, such a compound is commercially available, and examples thereof include "Plaxel FM1" and "Plaxel FA1" manufactured by Daicel Chemical Industries, Ltd. Alternatively, such a compound esterifies (meth) acrylic acid with a large excess (for example, 1.5 times (mol) or more) of a diol (for example, 1,4-butanediol, 1,6-hexanediol). It can be prepared by

Examples of the epoxy group-containing ethylenically unsaturated monomer (d-2) include glycidyl (meth) acrylate and 3,4-epoxycyclohexanylmethyl (meth) acrylate.

Examples of the other copolymerizable ethylenically unsaturated monomer (d-3) include "other copolymerizable ethylenically unsaturated monomer (c- 2) ”described above.

The copolymerization of the above polymer (D) can be carried out in the same manner as in the above polymer (C). The resulting polymer (D) preferably has a number average molecular weight of 500 to 8,000, and particularly preferably 1500 to 5000.

The content of the polymer (D) is 0.1 to 60% by mass based on the total mass of the solid content of the resin composition. If the content of the polymer (D) is less than 0.1% by mass, the coating film performance may not be sufficiently obtained, and if it exceeds 60% by mass, the water resistance is lowered. Preferably 5 to 50
It is% by mass.

The polymer (E) having a hydroxyl group, an epoxy group and a ladder silicone is obtained by reacting a part of the polymer (D) with a ladder silicone oligomer (e-3) containing a (meth) acryloxyalkyl group. Obtained. The above (e-1) is the same as the above (d-1) and the above (e-1).
-2) is the above (d-2), and the above (e-4) is the above (c).
The same thing as -2) can be mentioned.

The ladder silicone oligomer containing a (meth) acryloxyalkyl group of the above (e-3) contains a (meth) acryloxyalkyl group in a side chain group and has a substituent other than a (meth) acryloxyalkyl group. As the group, an alkyl group having 1 to 18 carbon atoms, a substituted alkyl group, a phenyl group or a substituted phenyl group is used. It is also possible to add a small amount of glycidyl group or amino group to the side chain group.

The amount of the above-mentioned component (e-1) of the polymer (E) to be blended with the above-mentioned component (e-2), the above-mentioned component (e-3) and, if necessary, the above-mentioned component (e-4) is , (E
-1) component is 5 to 60 mass%, and (e-2) component is 10 to
60% by mass, 1 to 30% by mass of (e-3) and (e-
4) The ratio of the components is 0 to 85% by mass. Above (e-
If the component (1) is less than 5% by mass, the curability will be insufficient, and if it exceeds 60% by mass, the compatibility will be insufficient and the reaction will not proceed sufficiently, which is not preferable. The component (e-2) is
If it is less than 10% by mass, the curability is insufficient, and if it exceeds 60% by mass, it becomes too hard and the weather resistance becomes insufficient, which is not preferable. If the content of the component (e-3) is less than 1% by mass, the stain resistance becomes insufficient, and if it exceeds 30% by mass, the reaction becomes nonuniform and the formed coating film becomes cloudy.

The copolymerization of the polymer (E) can be carried out in the same manner as the polymer (C). The number average molecular weight of the obtained polymer is preferably in the range of lower limit 500 to upper limit 8000. More preferably, the lower limit is 1500 and the upper limit is 5000.

The content of the polymer (E) in the case of being compounded is a lower limit of 0.0 based on the total mass of the solid content of the resin composition.
The upper limit is 1% by mass, and the upper limit is 60% by mass. If the content of the polymer (E) is less than 0.01% by mass, the stain resistance decreases, and if it exceeds 60% by mass, the surface of the formed coating film becomes non-uniform and the coating film appearance deteriorates. The lower limit is preferably 0.1% by mass and the upper limit is preferably 50% by mass.

The polymer (G) having a hydroxyl group and a carboxyl group, which can be optionally used in the vehicle of the paint for forming the outermost layer coating film, is (g-1) and (g-2). Monomer mixture, optionally (g-
It is a copolymer of at least two types of ethylenically unsaturated monomers having a hydroxyl group and a carboxyl group, which is obtained by copolymerizing 3).

A mixture of (g-1) a carboxyl group-containing ethylenically unsaturated monomer and (g-2) a hydroxyl group-containing ethylenically unsaturated monomer has the formula (2)

[Chemical 7] [In the formula, R represents a hydrogen atom or a methyl group, X ′ represents a linear or branched alkylene group or a hydroxyalkylene group, m ′ represents an integer of 2 to 8, preferably 2 to 6, and n
′ Is an integer of 3 to 7, preferably 3 to 5, and q ′ is 0.
-4, preferably an integer of 0-2] is obtained by half-esterifying a hydroxyl group-containing ethylenically unsaturated monomer having a structure represented by the formula and an acid anhydride group-containing compound. The monomer (g-1) is
It is used to introduce a carboxyl group in the polymer (G).

(G-2) The hydroxyl group-containing alkyl chain of the hydroxyl group-containing ethylenically unsaturated monomer becomes too hard because the flexibility in the vicinity of the crosslinking point is lost if the chain length is too short, and the molecular weight between the crosslinking points is too long. Is too large, which is not preferable. Therefore, the hydroxyl group-containing alkyl chain preferably has a carbon number lower limit of 4 and an upper limit of 20, and more preferably the upper limit of 10. Specifically, the compound and preparation method described above as (d-1) can be used.

The acid anhydride group-containing compound has a room temperature to 12
There is no particular limitation as long as it is a compound having carboxy functionality by reacting with a hydroxyl group under normal reaction conditions such as 0 ° C. and normal pressure. Here, it is preferable to use an acid anhydride group-containing compound having a cyclic (unsaturated or saturated) group having a lower limit of 8 carbon atoms and an upper limit of 12 carbon atoms because the compatibility of the resin is good. The upper limit of the number of carbon atoms is more preferably 10. Specific examples of preferable acid anhydrides include hexahydrophthalic anhydride, phthalic anhydride, 4-methylhexahydrophthalic anhydride, tetrahydrophthalic anhydride and trimellitic anhydride.

The half-esterification reaction of the above-mentioned hydroxyl group-containing ethylenically unsaturated monomer and acid anhydride group-containing compound can be carried out by a conventional method, for example, at a temperature of room temperature to 120 ° C. At this time, it is preferable to use the above-mentioned hydroxyl group-containing ethylenically unsaturated monomer in an excessive amount in order to prevent unreacted acid anhydride groups from remaining.

The other copolymerizable ethylenically unsaturated monomer (g-3) may be the same as the above-mentioned (c-2). As a preferred monomer, the number of carbon atoms having one ethylenically unsaturated bond is lower limit 3 and upper limit 15
Monomers within the range of More preferably, the upper limit is 12. Furthermore, (g-1) and (g
Other than -2), a hydroxyl group-containing ethylenically unsaturated monomer and a carboxyl group-containing ethylenically unsaturated monomer may be used.

Further, by adding the hydroxyl group-containing ethylenically unsaturated monomer to the amount required for half-esterification and adding the amount required for copolymerization in an excess amount to half-esterify with the acid anhydride group-containing compound, A monomer mixture of a carboxyl group-containing ethylenically unsaturated monomer (g-1) and a hydroxyl group-containing ethylenically unsaturated monomer (g-2) can be obtained. In this case, the hydroxyl group-containing ethylenically unsaturated monomer and the acid anhydride group-containing compound generally have a hydroxyl group and an acid anhydride group of 1 / 0.9 to 1/1 /.
It is preferable to mix and react at a molar ratio of 0.5, particularly at a ratio of 1 / 0.8 to 1 / 0.5.
If this molar ratio is less than 1 / 0.9, half-esterification may take a long time, and the monomer may gel.
If the molar ratio exceeds 1 / 0.5, the amount of carboxyl groups becomes too small and the curability becomes insufficient, which is not preferable.

The above-mentioned polymer (G) is used in a proportion within the range of the lower limit of 20% by weight of the monomer mixture and the upper limit of 100% by weight. The lower limit is preferably 40% by mass and the upper limit is preferably 80% by mass. The other copolymerizable ethylenically unsaturated monomer (g-3) is used in the monomer mixture in a proportion within the range of the lower limit of addition 0% by weight and the upper limit of 80% by weight. The lower limit is preferably 20% by mass and the upper limit is preferably 60% by mass.

If the amount of the above monomer mixture is less than 20% by mass, the curability may be insufficient, which is not preferable.

The copolymerization of the polymer (G) can be carried out in the same manner as in the polymer (C). The number average molecular weight of the obtained polymer is preferably in the range of lower limit 500 to upper limit 8000. The lower limit is more preferably 1500 and the upper limit is preferably 5000.

The polymer (H) which can be optionally used in the above clear coating composition is (h-1) trifluoromonochloroolefin and / or tetrafluoroolefin in an amount of 5 to 60% by mass, (h-2). Hydroxyalkyl vinyl ether 5 to 20% by mass, (h-3)
Cyclohexyl vinyl ether 5-40% by mass, (h-
4) 5 to 20 mass% of alkyl vinyl ether, (h-
5) Radical polymerizable monomer containing glycidyl group and /
Alternatively, it is a fluoropolymer obtained by copolymerizing 0 to 40 mass% of a polymerizable monomer containing a carboxyl group or an acid anhydride group.

The number average molecular weight of the polymer (H) is preferably in the range of lower limit 3000 and upper limit 10,000. The content of (h-1) trifluoromonochloroolefin and / or tetrafluoroolefin in the copolymer is usually preferably 40 mol% as the lower limit and 60 mol% as the upper limit. When the content is less than 40 mol%, not only is it unfavorable from the viewpoint of weather resistance and water repellency, but also inconvenience occurs in manufacturing. On the other hand, if it exceeds 60 mol%, there is a problem in production, which is not preferable.

Next, the content of the (h-2) hydroxyalkyl vinyl ether in the above copolymer is usually 3 to 15 mol%. When the content of the (h-2) hydroxylalkyl vinyl ether exceeds 15 mol%, the solubility of the copolymer is changed, and only specific substances such as alcohols are dissolved, and the pot life is reduced,
The workability of the paint is significantly impaired. When the content of (h-2) hydroxyalkyl vinyl ether in the copolymer is less than 3 mol%, the curability becomes insufficient, the curing time increases, the solvent resistance of the cured coating film, and the stain resistance. This leads to a decrease in sex.

The content of (h-3) cyclohexyl vinyl ether in the above copolymer is usually 3 to 15 mol%.
Is. When the content of the (h-3) cyclohexyl vinyl ether is less than 3 mol%, the hardness when formed into a coating film decreases, and when it exceeds 15 mol%, the weather resistance decreases and cracks occur. It is not preferable because it becomes easier.

The above-mentioned (h-4) alkyl vinyl ether has a lower limit of 2 carbon atoms such as ethyl vinyl ether, isobutyl vinyl ether and n-butyl vinyl ether.
An alkyl vinyl ether having a linear or branched alkyl group having an upper limit of 8 is preferable from the viewpoint of imparting flexibility. The upper limit is preferably 4.

The content of the (h-4) alkyl vinyl ether in the above copolymer is usually 3 mol% as the lower limit and 15 mol% as the upper limit.
Within the range of. When the content of the (h-4) alkyl vinyl ether is less than 3 mol%, flexibility is lowered,
On the other hand, if it exceeds 15 mol%, the hardness of the coating film decreases, which is not preferable.

As the glycidyl group-containing polymerizable monomer in the above optional components, glycidyl methacrylate, glycidyl acrylate, allyl glycidyl ether, etc., and as the polymerizable monomer containing a carboxyl group or an acid anhydride group, the above-mentioned (a) -2), the monomers exemplified in the above (c-1), and the like. The content of the glycidyl group-containing polymerizable monomer and / or the carboxyl group- or acid anhydride group-containing polymerizable monomer in the copolymer is usually in the range of lower limit of 5 mol% and upper limit of 40 mol%. The content of the glycidyl group-containing polymerizable monomer or acid anhydride group-containing polymerizable monomer is 5
If it is less than mol%, the curability is not sufficient, and if it exceeds 40 mol%, the coating film becomes too hard and the weather resistance deteriorates, which is not preferable.

[Low-Staining Coating Film] The low-staining coating film of the present invention is a coating film processed by the method for recovering the performance of the above-mentioned low-staining coating film. The above low-staining coating film has a stain-removing property that can easily remove bird droppings and the like even if bird droppings and the like adhere to the coating film and maintain a good coating film surface.

[0085]

EXAMPLES Next, the present invention will be described more specifically with reference to Examples and Comparative Examples, but the present invention is not limited to these Examples. In addition, the compounding amount represents a mass part unless otherwise specified.

[Preparation of base material] Dull steel plate (length 300 m
m, width 100 mm, and thickness 0.8 mm) was degreased, and a chemical conversion treatment was performed using a zinc phosphate treatment agent (“Surfdyne SD2000”, manufactured by Nippon Paint Co., Ltd.), followed by cationic electrodeposition coating (“Power Top U- 50 ", made by Nippon Paint Co., Ltd.)
Was electrodeposited to a dry film thickness of 25 μm. Then, after baking at 160 ° C. for 30 minutes, a polyester resin / melamine resin-based intermediate coating composition is air-spray coated to a dry film thickness of 40 μm, and baked at 140 ° C. for 30 minutes to form an intermediate coating film. It was made of wood.

[Preparation of Ladder Silicone Compound: Copolymer (A)] LS1 (functionality): "Sunflule LS190" (manufactured by Showa Denko KK) is 10 to 15 parts by mass of a ladder silicone oligomer containing a (meth) acryloxyalkyl group. % And a copolymer of other acrylic monomers, the hydroxyl value (as solid content) is 100, and the solid content is 50%.

LS2 (functionality): 400 parts of butyl acetate was charged into a 2 liter reaction vessel equipped with a thermometer, a stirrer, a cooling tube, a nitrogen introducing tube and a dropping funnel, and the temperature was raised to 125 ° C. In a dropping funnel, 100 parts of styrene, 200 parts of glycidyl methacrylate, 200 parts of 4-hydroxybutyl acrylate, 400 parts of n-butyl methacrylate, ladder silicone oligomer "Sanflule LS112" containing an acryloxyalkyl group (Showa Denko KK) 2)
3 parts of a monomer consisting of 00 parts and 70 parts of t-butylperoxy 2-ethylhexanoate, and an initiator solution.
Dropped over time. After the dropping was completed, the temperature was maintained at 125 ° C. for 30 minutes, and then a solution containing 10 parts of t-butylperoxy 2-ethylhexanoate and 250 parts of xylene was added dropwise for 30 minutes. After the dropping was completed, the reaction was continued at 125 ° C. for an additional 2 hours to give a nonvolatile content of 59% and a number average molecular weight of 4500.
To obtain a ladder silicone polymer LS2 containing glycidyl group.

LS3 (non-functional; for comparative example): thermometer,
400 parts of butyl acetate was charged into a 2 liter reaction vessel equipped with a stirrer, a cooling pipe, a nitrogen introducing pipe and a dropping funnel,
The temperature was raised to 125 ° C. Add styrene 300 to the dropping funnel.
, N-butylmethacrylate 600 parts, acryloxyalkyl group-containing ladder silicone oligomer "Sanflule LS112" (manufactured by Showa Denko KK) 200 parts and t-butylperoxy 2-ethylhexanoate 250 parts , And the initiator solution were added dropwise over 3 hours. After keeping the temperature at 125 ° C. for 30 minutes after completion of dropping, t-butylperoxy 2-ethylhexanoate 1
A solution consisting of 0 part and 250 parts of xylene was added dropwise over 30 minutes. After the dropping was completed, the reaction was continued at 125 ° C. for 2 hours to obtain a ladder silicon polymer LS3 having a non-volatile content of 59% and a number average molecular weight of 4,300 and containing no functional group.

[Preparation of Polymer Containing Carboxyl Group and Carboxylic Acid Ester Group: Polymer (C)] Xylene was added to a 3 liter reaction tank equipped with a thermometer, a stirrer, a cooling tube, a nitrogen introducing tube and a dropping funnel. 150 parts and 400 parts of Solvesso 100 (aromatic hydrocarbon solvent, manufactured by Shell Chemical Co., Ltd.) were charged, and the temperature was raised to 130 ° C. In the above container,
Using a dropping funnel, 300 parts of styrene monomer, 109 parts of 2-ethylhexyl methacrylate, 325 parts of isobutyl acrylate, 25.7 parts of acrylic acid, 240 parts of maleic anhydride, 300 parts of propylene glycol monomethyl ether acetate. , 60 parts of t-butylperoxy-2-ethylhexanoate and 150 parts of xylene were added dropwise over 3 hours. After the dropping, the temperature was kept at 130 ° C. for 30 minutes, and then t-
A solution consisting of 10 parts of butylperoxy-2-ethylhexanoate and 20 parts of xylene was added dropwise for 30 minutes. After completion of this dropping, the reaction was continued at 130 ° C. for an additional hour, the nonvolatile content was 60%, and the number average molecular weight was 45.
A polymer solution (c-1) containing a carboxyl group of 00 and a carboxylic acid anhydride group was obtained. This polymer solution (c
-1) To 1590 parts, add 125 parts of methanol to obtain 70
Reaction for 23 hours at ℃, acid value 157 (mgKOH / g)
A solution-like polymer (C) containing a carboxyl group and a carboxylic acid ester group was obtained. The infrared absorption spectrum of this polymer (C) was measured, and the absorption of the acid anhydride group (1
785 cm ^-1 ) was confirmed to disappear.

[Preparation of Polymer Containing Hydroxyl Group and Glycidyl Group: Polymer (D)] 150 parts of xylene was added to a 3 liter reaction vessel equipped with a thermometer, a stirrer, a cooling tube, a nitrogen introducing tube and a dropping funnel. Charge 400 parts of propylene glycol monomethyl ether acetate, 130 ℃
The temperature was raised to. Using a dropping funnel, Veova-9 (Shell Chemical Co., Ltd., vinyl ester of synthetic saturated monocarboxylic acid having a branched structure with 9 carbon atoms) was added to the above container.
Part, 229 parts of glycidyl methacrylate, acrylic acid 4
-A solution of 231 parts of hydroxybutyl, 340 parts of cyclohexyl methacrylate, 60 parts of t-butylperoxy-2-ethylhexanoate, 6 and 150 parts of xylene was added dropwise over 3 hours. 30 after dropping
After maintaining at 130 ° C. for a minute, a solution containing 10 parts of t-butylperoxy-2-ethylhexanoate and 20 parts of xylene was added dropwise for 30 minutes. After completion of this dropping, the reaction is continued at 130 ° C. for another hour,
A solution-like polymer (D) containing a hydroxyl group and an epoxy group having a nonvolatile content of 60%, a number average molecular weight of 4,600, an epoxy group equivalent of 625 and a hydroxyl group equivalent of 623 was obtained.

[Preparation of Polymer Containing Hydroxyl Group, Glycidyl Group and Functional Ladder Silicone: Polymer (E)] In a 3 liter reaction vessel equipped with a thermometer, a stirrer, a cooling tube, a nitrogen introducing tube and a dropping funnel, 50 xylene
Parts, 400 parts of propylene glycol monomethyl ether acetate were charged, and the temperature was raised to 130 ° C. Using a dropping funnel, 200 parts of VEOVA-9, 229 parts of glycidyl methacrylate, 231 parts of 4-hydroxybutyl acrylate and 2 parts of cyclohexyl methacrylate were placed in the above container.
A solution consisting of 40 parts, 200 parts of a ladder silicone oligomer containing an acryloxyalkyl group "Sanflule LS112" (manufactured by Showa Denko KK), 120 parts of t-butylperoxy-2-ethylhexanoate and 150 parts of xylene. Was added dropwise over 3 hours. After the dropping was completed, the temperature was maintained at 130 ° C. for 30 minutes, and then a solution containing 10 parts of t-butylperoxy-2-ethylhexanoate and 20 parts of xylene was added dropwise for 30 minutes. After completion of this dropping, the reaction is continued at 130 ° C. for another hour, and a solution containing a hydroxyl group having a nonvolatile content of 60%, a number average molecular weight of 4700, an epoxy group equivalent of 625 and a hydroxyl equivalent of 623, an epoxy group and a ladder silicone. A polymer (E) in the form of a solid was obtained.

[Preparation of Polymer Containing Hydroxyl Group and Carboxyl Group: Polymer (G)] Arcosolv PMA (Kyowa Oil Co., Ltd.) was placed in a 2 liter reaction vessel equipped with a thermometer, a stirrer, a cooling tube, a nitrogen introducing tube and a dropping funnel. Chemical Co., Ltd.)
Solvent 360 parts, 4-hydroxybutyl acrylate 777
Part, 665 parts of hexahydrophthalic anhydride and 0.48 part of hydroquinone monomethyl ether were charged, and 145 ° C.
The temperature was raised to and held for 20 minutes. Then, it cooled and taken out from the reaction container, and the carboxyl group-containing ethylenically unsaturated monomer (g-1) was obtained. Next, 300 parts of xylene and 200 parts of Arcosolv PMA solvent were charged into another 3 liter reaction vessel equipped with a thermometer, a stirrer, a cooling tube, a nitrogen introducing tube and a dropping funnel, and the temperature was raised to 130 ° C. Then, 1300 parts of the above-mentioned carboxyl group-containing ethylenically unsaturated monomer (g-1) and 100 parts of t-butylperoxy-2-ethylhexyl hexanoate were added dropwise over 3 hours. After maintaining at 130 ° C. for 30 minutes, a mixed solution of 10 parts of t-butylperoxy-2-ethylhexanoate and 100 parts of xylene was added dropwise over 30 minutes. After maintaining at 130 ° C for 30 minutes, cool down,
Take out from the container, nonvolatile content 54%, number average molecular weight 20
00, an acid value of 168 and a hydroxyl value of 42 in terms of solid content,
A solution polymer (G) having a hydroxyl group and a carboxyl group was obtained.

[Preparation of Fluoropolymer: Polymer (H)] In a stainless steel autoclave with an inner volume of 200 ml equipped with a stirrer, 116 parts of t-butanol, 11.7 parts of cyclohexyl vinyl ether, 11.1 parts of ethyl vinyl ether and hydroxybutyl were added. 7.17 parts of vinyl ether, 5.72 parts of glycidyl vinyl ether, 0.69 part of calcium carbonate and 0.06 part of azobisisobutyronitrile were charged, and the dissolved air was removed by solidification with liquid nitrogen and deaeration. Next, 36 parts of chlorotrifluoroethylene was introduced into the autoclave, and the temperature was gradually raised to cause a reaction to obtain a polymer (H).

[Manufacture of clear coating for forming top coating film] (Preparation of top coating top clear coating 1) Acrylic resin containing a hydroxyl group and melamine resin clear coating ("Superlac 130 clear NO", manufactured by Nippon Paint Co., Ltd.) It was prepared by adding 1 part of the functional ladder silicone copolymer LS1 to 100 parts of the component and diluting with a thinner (1 part of the functional ladder silicone copolymer to 100 parts of the resin and the crosslinking agent in terms of solid content).

(Preparation of Topcoat Top Clear Coating 2) Acrylic resin containing hydroxyl group and polyisocyanate compound type clear coating (“nax Mightylac GII240
2 Coat Clear "(manufactured by Nippon Paint Co., Ltd.) and 100 parts of a mixture of a crosslinking agent and a functional ladder silicone copolymer LS.
It was prepared by adding 0.8 part of 1 and diluting it with a thinner (1 part of the functional ladder silicone copolymer with respect to 100 parts of the resin and the cross-linking agent in terms of solid content).

(Preparation of Top Clear Top Clear Coating 3) A clear coating in which a glycidyl group and a carboxyl group mainly undergo a curing reaction (“Macflow O-590-1 clear N
O ", manufactured by Nippon Paint Co., Ltd.) was prepared by adding 0.8 part of the functional ladder silicone copolymer LS2 to 100 parts of solid content and diluting with a thinner (functional ladder silicone to 100 parts of resin in terms of solid content). 1 part of copolymer).

(Preparation of top clear top clear paint 4) Polymer C 39 parts, polymer D 37 parts, polymer E 1 part,
Tetrabutylammonium bromide as a curing catalyst
Prepared by dissolving 35 parts, 0.7 part of TINUVIN 900 (manufactured by Ciba Specialty Chemicals) as an ultraviolet absorber, and 0.35 part of SANOL LS292 (manufactured by Sankyo Co.) as a light stabilizer (100 parts of resin in terms of solid content). To 1.3 parts of a functional ladder silicone copolymer).

(Preparation of top clear top clear paint 5) Polymer C 31 parts, polymer D 37 parts, polymer E 1 part,
Polymer G 8 parts, tetrabutylammonium bromide 0.35 parts as a curing catalyst, Tinuvin 900 (manufactured by Ciba Specialty Chemicals) as an ultraviolet absorber 0.3.
7 parts, Sanol LS292 (manufactured by Sankyosha) as a light stabilizer
0.35 part was dissolved to prepare (1.3 parts of functional ladder silicone copolymer per 100 parts of resin in terms of solid content).

(Preparation of Top Clear Top Clear Coating 6) Polymer C 39 parts, Polymer D 60 parts, Polymer E 1 part,
18 parts of polymer H, 0.35 part of tetrabutylammonium bromide as a curing catalyst, Tinuvin 900 as an ultraviolet absorber (manufactured by Ciba Specialty Chemicals)
0.7 parts and 0.35 parts of Sanol LS292 (manufactured by Sankyosha Co., Ltd.) as a light stabilizer were prepared by dissolving (resin 100 in terms of solid content).
To 1 part functional silicone ladder copolymer. )did.

(Preparation of top clear top clear coating composition 7) Polymer C 31 parts, polymer D 63.5 parts, polymer E1
Parts, polymer G 8 parts, polymer H 9 parts, tetrabutylammonium bromide 0.35 parts as a curing catalyst, tinuvin 900 (manufactured by Ciba Specialty Chemicals) as an ultraviolet absorber 0.7 parts, and Sanol L as a light stabilizer.
0.32 part of S292 (manufactured by Sankyo Co., Ltd.) was dissolved to prepare (1 part of functional ladder silicone copolymer based on 100 parts of resin in terms of solid content).

(Preparation of top clear top clear coating composition 8) Polymer C 39 parts, polymer D 55 parts, polymer E 1.8
Part, Polymer G 8 parts, Polyethylene oxide modified polysilicone compound 0.2 part, Tetrabutylammonium bromide 0.35 part as a curing catalyst, Tinuvin 900 (manufactured by Ciba Specialty Chemicals) as an ultraviolet absorber 0.7 part, light Sanol LS292 as stabilizer
(Sankyo Co., Ltd.) 0.35 part was dissolved and prepared (2 parts of functional ladder silicone copolymer with respect to 100 parts of resin in terms of solid content).

(Preparation of top clear top coating 9) Prepared by diluting an acrylic resin containing a hydroxyl group and a melamine resin clear coating ("Superlac 130 clear NO", manufactured by Nippon Paint Co., Ltd.) with a thinner (functional ladder silicone copolymer). None.)

(Preparation of top clear top coating 10)
A clear coating in which the glycidyl group and the carboxyl group mainly undergo a curing reaction (“Macflow O-590-1, Clear N
O ", manufactured by Nippon Paint Co., Ltd.), 0.8 parts of non-functional ladder silicone copolymer LS3 was added to 100 parts of solid content and diluted with thinner to prepare (100 parts of resin and crosslinking agent in terms of solid content). 1 part of non-functional ladder silicone copolymer).

(Preparation of top clear top coat paint 11) Polymer C 39 parts, polymer D 38 parts, tetrabutylammonium bromide 0.35 parts as a curing catalyst, and tinuvin 900 (manufactured by Ciba Specialty Chemicals) as an ultraviolet absorber 0 It was prepared by dissolving 0.7 part and 0.35 part of SANOL LS292 (manufactured by Sankyosha Co., Ltd.) as a light stabilizer (not including a functional ladder silicone copolymer).

(Topcoat top clear coating film 1, 3 to 11)
Formation of a hydroxyl group-containing acrylic resin and melamine resin-based metallic base coating (“Superlac M-180BKLO NO”, manufactured by Nippon Paint Co., Ltd.)
Spray coating was performed so that the dry film thickness was 15 μm. Painting is electrostatic coating machine ("Auto REA", AB
B Industry Co., Ltd.), atomization pressure 2.8 kg / c
It was carried out in m ^2. After coating, set for 3 minutes, apply the above top clear topcoat paint with the same coating machine as the base paint to form a dry film thickness of 35 μm, set at room temperature for 10 minutes, set at 140 ° C. for 30 minutes, Two coating layers were baked at the same time.

(Formation of Topcoat Top Clear Coating Film 2) Further, the topcoat top clear coating film 2 is formed on the above substrate.
Is a hydroxyl group-containing acrylic resin and polyisocyanate compound-based metallic base coating (“nax Superior 2K3
044 Snow Metallic Rough "manufactured by Nippon Paint Co., Ltd.), and spray-coated to a dry film thickness of 15 μm. Painting is electrostatic coating machine ("Auto REA", ABB
(Industry), atomization pressure 2.8kg / cm
I went to ² . After coating, set for 3 minutes, then apply top clear top clear coating 2 with the same coating machine as the base coating to form a dry film thickness of 35 μm, set at room temperature for 10 minutes, set at 80 ° C. for 60 minutes, Two coating layers were baked at the same time.

[Evaluation Method and Evaluation Criteria] Regarding the top coating film 6 containing the functional ladder silicone compound and the top coating film 11 not containing the functional ladder silicone compound, before the exposure, and the top coating film containing the functional ladder silicone compound. The coating film 6 was wiped with isopropyl alcohol (Example 1), ethyl acetate (Comparative Example 1), and toluene (Comparative Example 2) after exposure for 2 weeks. Wiping was performed with a gauze containing the above-mentioned solvents. For each of the above samples, the water contact angle before and after wiping and the oleic acid contact angle were measured using a contact angle meter (“CA-D”, manufactured by Kyowa Interface Science Co., Ltd.). The results are shown in Table 1.

Further, the multilayer coating films 1 to 11 obtained by the above method were exposed outdoors for 2 weeks and used for the test. The test plate was washed with water to remove dust, and each wiping solution shown in Table 2 was dipped in gauze to wipe the coating film surface 6 times. The stain resistance after drying was evaluated by the following evaluation methods, and the results are shown in Table 2.
It was shown to.

Anti-staining resistance: An egg albumin 3% aqueous solution was prepared, 0.2 ml of water droplets of this aqueous solution was dropped, and after contacting at 50 ° C. and humidity of 30% for 1 hour, the water droplets of the solution were removed with tap water. The surface of the multilayer coating film was wiped off and after 24 hours, visually evaluated. ⊚ No trace of albumin drying is observed. O ... Trace of albumin drying is slightly observed. △ ... Trace of albumin drying is slightly observed. X ... Trace of albumin drying is clearly observed.

[0111]

[Table 1]

[0112]

[Table 2]

From the above results, 40% by mass of at least one organic solvent selected from isopropyl alcohol, isobutyl alcohol and n-propyl alcohol is used.
By wiping with the antifouling recovery agent included above,
It is clear that the performance of the low-staining coating is restored. Further, it is clear that the above-mentioned recovery effect does not occur in the topcoat coating films 9 to 11 in which the coating film is not low in stain resistance, and it is clear that this is a particularly effective method for the low stain resistance coating film.

[0114]

INDUSTRIAL APPLICABILITY In the present invention, an antifouling recovery agent containing at least 40% by mass of at least one organic solvent of isopropyl alcohol, isobutyl alcohol and n-propyl alcohol is used, and a functional ladder silicone compound is contained on the substrate. By wiping the outermost coating film formed by a low-staining clear coating film with the antifouling recovery agent, the automobile body etc. is stored outdoors, and bird droppings etc. adhere to the coating film. Also, by previously wiping the coating film surface with the antifouling treatment agent, it has become possible to provide a surface state in which bird droppings and the like can be easily removed.

When the outermost surface coating film formed by the low-staining clear coating film after exposure is wiped with an antifouling recovery agent, the mechanism of recovering the stain resistance is simply to remove the contaminants on the surface of the coating film. Not only that, the clear coating surface characteristics including the functional ladder silicone compound increase the contact angle of oleic acid and improve the resistance to oily contamination. That is, looking at the example of wiping the clear coating film surface containing a functional ladder silicone compound with various solvents after exposure, the contact angle of oleic acid was the highest when wiped with the antifouling recovery agent of the present invention. It is estimated that

1. Due to changes in temperature and exposure to rainwater during exposure, the side chains of the functional ladder silicone compound in the clear resin are covered with the main resin, and the surface content is reduced. 2. When the antifouling recovery agent is wiped, the antifouling recovery agent penetrates around the side chains of the functional ladder silicone compound and the main chain of the main resin. 3. The permeation antifouling agent facilitates the movement of the polymer network and side chains, and the side chains of the functional ladder silicone compound are again oriented on the surface of the clear coating film. Since the low-staining coating film obtained by the present invention has the above-mentioned good stain-removing property, it can be used as a vehicle skin for automobiles, motorcycles, etc.
It is preferably used in fields such as the outer surface of a container, coil coating, and the home appliance industry.

─────────────────────────────────────────────────── ─── Continuation of front page (51) Int.Cl. ⁷ Identification code FI theme code (reference) C09D 135/00 C09D 135/00 157/00 157/00 157/10 157/10 161/20 161/20 163 / 00 163/00 175/04 175/04 183/10 183/10 183/12 183/12 201/00 201/00 // C09D 9/00 9/00 (72) Inventor Tatsuya Ishihara Kanagawa Yokohama, Kanagawa 2 Takara-cho, Tokyo Within Nissan Motor Co., Ltd. (72) Takashi Moribu 4-1-115 Minami-Shinagawa, Shinagawa-ku, Tokyo Within Japan Paint Co., Ltd. (72) Goro Nagao 4-chome, Minami-Shinagawa, Shinagawa-ku, Tokyo Ban No. 15 Nippon paint Co., Ltd. in the F-term (reference) 4D075 BB65Z BB69Z CA34 CB06 DA06 DB02 DB06 DB07 DB12 DB13 DB18 DB20 DB36 DB38 DB40 DB43 DB47 DB48 DB50 DB53 DB61 DC12 DC13 EA07 EA43 EB14 EB16 EB20 EB22 EB32 EB33 EB35 EB36 EB37 EB38 EB43 EB45 EB56 EC30 EC54 4J038 CC02 1 CC022 CD091 CD122 CF031 CF032 CG001 CG141 CH031 CH032 CH041 CH042 CH121 CH161 CH171 CH172 DA132 DD001 DG001 DG302 DL132 GA02 GA03 GA06 GA07 GA12 GA15 KA03 NA05 PB07 PC02

Claims (9)

[Claims] 1. A functional ladder silicone compound is applied on a substrate by using an antifouling restorer containing 40% by mass or more of at least one organic solvent selected from the group consisting of isopropyl alcohol, isobutyl alcohol and n-propyl alcohol. A method for recovering the performance of a low-staining coating film, comprising: wiping an outermost surface coating film formed by a low-staining clear coating film containing. 2. The method for recovering the performance of a low-staining coating film according to claim 1, wherein the base material is an automobile body skin or an automobile part. 3. A ladder silicone oligomer containing (A) (a-1) (meth) acryloxyalkyl groups, based on 100 parts by weight of solid content of vehicle, wherein the coating material for forming the outermost surface coating film is (a). -2) Ethylenically unsaturated monomer containing a crosslinkable functional group, and optionally (a-
3) A low-contamination paint according to claim 1 or 2, which is a clear coating containing 0.01 to 2% by mass of a functional ladder silicone copolymer obtained by copolymerizing with another copolymerizable ethylenically unsaturated monomer. Method for recovering the performance of a transparent coating. 4. A coating material for forming the outermost layer coating comprises, as a vehicle, at least one type of crosslinking selected from the group consisting of (B) acrylic resin, polyester resin, alkyd resin, fluororesin, polyurethane resin and polyether resin. A low-staining coating film according to any one of claims 1 to 3, which is a clear coating material containing at least one cross-linking agent selected from the group consisting of an organic coating film-forming resin, an amino resin and a blocked polyisocyanate compound. Performance recovery method. 5. A coating material for forming the outermost surface coating film comprises (C) (c-1) an acid anhydride group-containing ethylenically unsaturated monomer of 15 to 40% by mass as a vehicle, and (c-2) another An acid anhydride group-containing polymer obtained by copolymerizing 60 to 85 mass% of a copolymerizable ethylenically unsaturated monomer, and (c-3) a monoalcohol containing 1 to 12 carbon atoms. , A polymer having a carboxyl group and a carboxylic acid ester group obtained by reacting an acid anhydride group and a hydroxyl group in a molar ratio of 1/10 to 1/1 (mass% of the polymer is a resin composition. The same based on the total solid mass of the product); 20 to 60 mass%,
(D) (d-1) Formula (1) [Wherein, R is a hydrogen atom or a methyl group, X is a linear or branched alkyl or hydroxyalkyl, m is an integer of 2 to 8, n is an integer of 3 to 7, and q is 0.
Is an integer of 4 to 5] 5 to 60% by mass of a hydroxyl group-containing ethylenically unsaturated monomer having a structure represented by (d-2)
Glycidyl group-containing ethylenically unsaturated monomer 10-6
Polymer containing a hydroxyl group and a glycidyl group, obtained by copolymerizing 0% by mass, and optionally 0 to 85% by mass of another copolymerizable ethylenically unsaturated monomer (d-3) 1-60 mass% and (E)
(E-1) 5 to 60% by mass of the hydroxyl group-containing ethylenically unsaturated monomer of (d-1), (e-2) the (d-2)
Glycidyl group-containing ethylenically unsaturated monomers 10 to 6
0% by mass, 1 to 30% by mass of (e-3) (meth) acryloxyalkyl group-containing ladder silicone oligomer, and (e-4) optionally other copolymerizable ethylenically unsaturated monomer 0 5. A clear coating composition containing 0.01 to 60% by mass of a polymer containing a hydroxyl group, a glycidyl group and a functional ladder silicone, which is obtained by copolymerization with ˜85% by mass. The method for recovering performance of a low-staining coating film according to item 1. 6. The (F) polyethylene oxide or polypropylene oxide-modified polysilicone compound is further added to the vehicle of the paint for forming the outermost surface coating film in an amount of 0.02 to 1 solid part by mass per 100 parts by mass of the total vehicle. The method for recovering performance of a low-staining coating film according to any one of claims 1 to 5, wherein the method is a clear coating material. 7. A paint vehicle for forming the outermost coating film, further comprising (G) (g-1) formula (2): [Wherein, R is a hydrogen atom or a methyl group, X'is a linear or branched alkyl or hydroxyalkyl, m
′ Is an integer of 2 to 8, n ′ is an integer of 3 to 7,
q ′ is an integer of 0 to 4] and a hydroxyl group-containing ethylenically unsaturated monomer having a structure shown by the formula and an acid anhydride group-containing compound in which the hydroxyl group and the acid anhydride group are 1 / 0.9 to 1 /
20 to 100 mass of a monomer mixture of a carboxyl group-containing ethylenically unsaturated monomer and (g-2) hydroxyalkyl (meth) acrylate compound obtained by mixing and reacting in an amount of 0.5 molar ratio %, And optionally (g-3) 0 to 80 mass% of a copolymerizable ethylenically unsaturated monomer, and 5 to 50 mass% of a polymer having a hydroxyl group and a carboxyl group. The method for recovering performance of a low-staining coating film according to claim 5 or 6, which is a clear coating material. 8. The (H) (h-1) trifluoromonochloroolefin and / or tetrafluoroolefin 5 to 5 is added to the vehicle of the paint forming the outermost layer coating film.
60% by mass, (h-2) hydroxyalkyl vinyl ether 5 to 20% by mass, (h-3) cyclohexyl vinyl ether 5 to 40% by mass, (h-4) alkyl vinyl ether 5 to 20% by mass, (h-5) glycidyl Fluoropolymer 2 to 50 obtained by copolymerizing the radical-containing polymerizable monomer and / or the carboxyl group- or acid anhydride group-containing polymerizable monomer 0 to 40% by mass
8. A clear paint containing 5% by mass and 8.
The method for recovering the performance of a low-staining coating film according to any one of claims 1. 9. A low-staining coating film treated by the method for recovering the performance of a low-staining coating film according to any one of claims 1 to 8.