JP2010138328A - Polymer for metallic coating material, metallic coating material composition and coated article - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a polymer for a metallic coating material and a metallic coating material composition that have good wear resistance and can form a coating film having high luminance and to provide a coated article that has good wear resistance and has a coating film having high luminance. <P>SOLUTION: The polymer for a metallic coating material (A) has a structural unit derived from (a1) a polyether-modified silicone compound having a vinyl group and a structural unit derived from (a2) other unsaturated monomer. The metallic coating material composition includes the polymer for a metallic coating material (A) and a photoluminescent pigment. The coated article has a coating film formed from the metallic coating material composition. <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

  The present invention relates to a polymer for metallic paint, a metallic paint composition, and a coated product.

  Vinyl polymers are widely used in applications such as paints, inks, adhesives, and synthetic leather because they are excellent in weather resistance, flexibility, strength, adhesiveness, and the like. In particular, in the application of paints, coating compositions containing various vinyl polymers suitable for the required performance are provided for coating on various materials in the fields of automobiles, home appliances, building materials and the like. Yes.

  In recent years, a metallic paint composition containing a luster pigment has been used in many cases in order to impart a metallic or pearly design to the appearance of the coating. The coating film obtained from the metallic coating composition expresses a feeling of brightness by efficiently orienting the bright pigment in the coating film.

  The characteristic of the vinyl polymer is that various properties such as gloss and weather resistance can be imparted to the coating film by changing the type and molecular weight of the monomer. However, when a coating film containing a vinyl polymer is formed on the outermost layer, it must have a high crosslinking density from the viewpoint of scratch resistance and abrasion resistance, but it may be difficult depending on the coating form.

The following are proposed as coating compositions that can form a coating film with improved scratch resistance and abrasion resistance.
A coating composition containing a vinyl polymer obtained by polymerizing an epoxy group-containing vinyl monomer and a vinyl monomer having an organosiloxane side chain (Patent Document 1).

The coating film obtained from the composition has improved scratch resistance due to the slip property imparted by the silicone component (organosiloxane side chain). However, since the silicone component is poorly compatible with the acrylic component (the structural unit derived from the epoxy group-containing vinyl monomer), the fluidity of the vinyl polymer is lowered, and it is difficult to atomize when spraying the paint. Along with this, in the case of a paint containing a bright pigment, the orientation of the bright pigment is lowered, and the desired brightness feeling cannot be obtained.
JP-A-2005-290360

  The present invention relates to a polymer for metallic paints and a metallic paint composition capable of forming a coating film having good wear resistance and high brightness, and a coated article having good wear resistance and having a coating film having high brightness. provide.

  The metallic paint polymer of the present invention is characterized by having a structural unit derived from a polyether-modified silicone compound (a1) having a vinyl group and a structural unit derived from another unsaturated monomer (a2). .

The polyether is preferably a polyalkylene oxide.
The other unsaturated monomer (a2) preferably satisfies the following condition (i) and condition (ii).
(I) The glass transition temperature (Tg) of the polymer of another unsaturated monomer (a2) is 70-130 degreeC.
(Ii) The solubility parameter (δ) of the polymer of the other unsaturated monomer (a2) is 19.7 to 20.4 (J / cm ³ ) ^1/2 .

In the method for producing the polymer for metallic paint (A) of the present invention, a polyether-modified silicone compound (a1) having a vinyl group and another unsaturated monomer (a2) are added in an organic solvent (B). Radical polymerization is performed in the presence of a radical polymerization initiator (C).
In the method for producing the polymer for metallic paint (A) of the present invention, the above-mentioned other unsaturated monomer (into the mixture containing the polyether-modified silicone compound (a1) having a vinyl group and the organic solvent (B) is used. It is preferable to add a2) and the radical polymerization initiator (C) continuously or intermittently.

The metallic paint composition of the present invention comprises the polymer for metallic paint (A) of the present invention and a bright pigment.
The coated article of the present invention is characterized by having a coating film obtained from the metallic coating composition of the present invention.

The polymer for metallic paints and the metallic paint composition of the present invention have good wear resistance and can form a coating film with high brightness.
The coated product of the present invention has good wear resistance and a high-brightness coating film.

<Polymer for metallic paint (A)>
The polymer for metallic paints of the present invention is derived from a structural unit derived from a polyether-modified silicone compound (a1) having a vinyl group (hereinafter referred to as compound (a1)) and another unsaturated monomer (a2). It is a polymer (A) for metallic paints which has these structural units.

  The weight average molecular weight of the polymer for metallic paint (A) is preferably 20,000 to 200,000, more preferably 30,000 to 100,000. If the mass average molecular weight of the polymer for metallic paints (A) is 20,000 or more, the hardness, abrasion resistance and solvent resistance of the coating film will be good. If the mass average molecular weight of the polymer for metallic paints (A) is 200,000 or less, the smoothness of the coating film will be good.

(Compound (a1))
The compound (a1) is a silicone compound having at least one vinyl group and modified with a polyether. The compound (a1) is preferably a silicone compound having at least one vinyl group and modified with polyalkylene oxide. Among them, polyorganosiloxanes such as polydimethylsiloxane and polyphenylmethylsiloxane having a terminal (meth) acryloyl group and having a polyalkylene oxide segment in the molecule are preferable.
Examples of the polyalkylene oxide include polyethylene oxide, polypropylene oxide, polybutylene oxide and the like.

Compound (a1) can be obtained, for example, by modifying a silicone compound having a vinyl group with a polyether such as polyalkylene oxide by a known method.
Commercially available products of the compound (a1) include a terminal modified acryloyl group polyether-modified silicone, Ecacryl 350 (trade name) manufactured by Daicel UCB, BYK-UV3500 (trade name) manufactured by Big Chemie Japan, and a product manufactured by Momentive. COATOSIL 3503 (trade name) and the like.
As the compound (a1), one type may be used alone, or two or more types may be used in combination.

(Other unsaturated monomer (a2))
The other unsaturated monomer (a2) is an unsaturated monomer excluding the compound (a1) and is an unsaturated monomer copolymerizable with the compound (a1).

Other unsaturated monomers (a2) include (meth) acrylic acid ester monomers (methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, i-propyl (meth) acrylate) , N-butyl (meth) acrylate, i-butyl (meth) acrylate, sec-butyl (meth) acrylate, t-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, n-octyl (meth) acrylate, n -Lauryl (meth) acrylate, n-tridecyl (meth) acrylate, n-stearyl (meth) acrylate, cyclohexyl (meth) acrylate, phenyl (meth) acrylate, benzyl (meth) acrylate, isobornyl (meth) acrylate, 2-methoxy Ethyl (meth) acryl 2-ethoxyethyl (meth) acrylate, phenoxyethyl (meth) acrylate, 2- (2-ethylhexaoxy) ethyl (meth) acrylate, 1-methyl-2-methoxyethyl (meth) acrylate, 3-methoxy Butyl (meth) acrylate, 3-methyl-3-methoxybutyl (meth) acrylate, o-methoxyphenyl (meth) acrylate, m-methoxyphenyl (meth) acrylate, p-methoxyphenyl (meth) acrylate, o-methoxyphenyl Ethyl (meth) acrylate, m-methoxyphenylethyl (meth) acrylate, p-methoxyphenylethyl (meth) acrylate, etc.); carboxyl group-containing vinyl monomer ((meth) acrylic acid, 2- (meth) acryloyl) Oxyethylhexahydro Taric acid, 2- (meth) acryloyloxypropylhexahydrophthalic acid, 2- (meth) acryloyloxyethyltetrahydrophthalic acid, 2- (meth) acryloyloxypropyltetrahydrophthalic acid, 5-methyl-2- (meth) acryloyl Oxyethylhexahydrophthalic acid, 2- (meth) acryloyloxyethylphthalic acid, 2- (meth) acryloyloxypropylphthalic acid, 2- (meth) acryloyloxyethylmaleic acid, 2- (meth) acryloyloxypropylmaleic acid 2- (meth) acryloyloxyethyl succinic acid, 2- (meth) acryloyloxypropyl succinic acid, 2- (meth) acryloyloxyethyl oxalic acid, 2- (meth) acryloyloxypropyl oxalic acid, crotonic acid, fumaric acid , Malein Acids, itaconic acid, sorbic acid, monomethyl maleate, monomethyl itaconic acid and the like. ); Acid anhydride group-containing vinyl monomers (maleic anhydride, itaconic anhydride, etc.): epoxy group-containing vinyl monomers ((meth) glycidyl acrylate, α-ethyl acrylate glycidyl, α-n-) Glycidyl propyl acrylate, glycidyl α-n-butyl acrylate, 3,4-epoxybutyl (meth) acrylate, 6,7-epoxyheptyl (meth) acrylate, α-ethyl acrylate 6,7-epoxy Butyl, o-vinyl benzyl glycidyl ether, m-vinyl benzyl glycidyl ether, p-vinyl benzyl glycidyl ether, etc.); hydroxyl group-containing (meth) acrylic acid ester monomer (2-hydroxyethyl (meth) acrylate, 2-hydroxy Propyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 2-H Roxybutyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, glycerol (meth) acrylate, etc.); 2-hydroxyethyl (meth) acrylate and ethylene oxide, propylene oxide, γ-butyrolactone, ε-caprolactone, etc. Adducts; dimers or trimers such as 2-hydroxyethyl (meth) acrylate and 2-hydroxypropyl (meth) acrylate; vinyl monomers (styrene, α-methylstyrene, vinyltoluene, (meth) acrylonitrile , Vinyl acetate, vinyl propionate, etc.); polymerizable unsaturated organic silane compounds (3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropyltriethoxysilane, vinyltrimethoxysilane, etc.).
Among these, the glass transition temperature (Tg) of homopolymers such as isobornyl (meth) acrylate and t-butyl methacrylate is high, and the solubility parameter ( Monomers with a low δ) are preferred. Moreover, the monomer with high solubility parameter ((delta)) of homopolymers, such as methyl (meth) acrylate and ethyl (meth) acrylate, is preferable at the point which can exhibit adhesiveness with a base material.
As the other unsaturated monomer (a2), one type may be used alone, or two or more types may be used in combination.

The other unsaturated monomer (a2) preferably satisfies the following condition (i) and condition (ii).
(I) The glass transition temperature (Tg) of the polymer of another unsaturated monomer (a2) is 70-130 degreeC.
(Ii) The solubility parameter (hereinafter referred to as SP value) (δ) of the polymer of the other unsaturated monomer (a2) is 19.7 to 20.4 (J / cm ³ ) ^1/2 It is.

When the glass transition temperature (Tg) of the polymer of the other unsaturated monomer (a2) is 70 ° C. or higher, the hardness, abrasion resistance, and solvent resistance of the coating film are good. If the glass transition temperature (Tg) of the polymer of another unsaturated monomer (a2) is 130 ° C. or less, the smoothness of the coating film will be good.
If the SP value (δ) of the polymer of the other unsaturated monomer (a2) is 19.7 (J / cm ³ ) ^1/2 or more, adhesion to a plastic substrate such as ABS resin is good. It becomes. If the SP value (δ) of the polymer of the other unsaturated monomer (a2) is 20.4 (J / cm ³ ) ^1/2 or less, the solubility in the solvent is good and the resin solution has a low viscosity. Thus, the smoothness of the coating film is improved.
The SP value (δ) of the polymer of the other unsaturated monomer (a2) is more preferably 19.7 to 20.0 (J / cm ³ ) ^1/2 . If the SP value (δ) of the polymer of the other unsaturated monomer (a2) is 20.0 or less, the smoothness of the coating film is further improved and the appearance of the coating film is remarkably improved.

The glass transition temperature (Tg) of the polymer of the other unsaturated monomer (a2) is the same as that of the other unsaturated monomer (a2) when there is one kind of the other unsaturated monomer (a2). The homopolymer Tg (document value) is adopted as it is. When two or more types of other unsaturated monomers (a2) exist, it calculates | requires from following formula (1).
1 / Tg = Σ (wi / Tgi) (1).
In formula (1), wi represents the mass fraction of unsaturated monomer i, and Tgi represents Tg (document value) of a homopolymer of unsaturated monomer i. The Tg (document value) of the homopolymer is a value described in “POLYMER HANDBOOK, FOURTH EDITION, VI / 193 to VI / 253”.

The SP value (δ) of the polymer of the other unsaturated monomer (a2) is the same as that of the other unsaturated monomer (a2) when the other unsaturated monomer (a2) is one kind. The δ of the polymer is determined from the following formula (2) described in the following document.
δi = {Σ (njEj) / Σ (njVj)} ^1/2 (2).
In the formula (2), nj represents the number of atomic groups j constituting the monomer i, Ej represents the cohesive energy (J / mol) of the atomic group j, and Vj represents the molar volume (cm ³ ) of the atomic group j. / Mol). Ej and Vj are values described in the following documents.
R. F. Fedors, “Polym. Eng. Sci.”, (1974), 14 (2), p. 147, p. 472.

The SP value (δ) of the polymer of the other unsaturated monomer (a2) is obtained from the following formula (3) when there are two or more kinds of other unsaturated monomers (a2).
δ = Σ (miδi) (3).
In formula (2), mi represents the molar fraction of monomer i, and δi represents δ of the homopolymer of monomer i. Δi of the homopolymer of monomer i is obtained from the above formula (2).

  The other unsaturated monomer (a2) is 40 to 85% by mass of methyl methacrylate and 10 to 10% of t-butyl methacrylate in a total of 100% by mass of the compound (a1) and the other unsaturated monomer (a2). More preferably, it is 30 mass%, isobornyl methacrylate is 1-30 mass%, and methacrylic acid is 0.1-1 mass%.

Since the polymer (A) for metallic paint of the present invention described above has a structural unit derived from the compound (a1) which is a silicone component, it can impart good slip properties to the coating film. As a result, a coating film with good wear resistance can be formed.
Moreover, the structural unit (silicone component) derived from the compound (a1) modified with a polyether such as polyalkylene oxide has compatibility with the structural unit (acrylic component) derived from the other unsaturated monomer (a2). Since it is favorable, the fluidity | liquidity of the polymer (A) for metallic paints improves, and it becomes easy to atomize at the time of paint spraying. Accordingly, the orientation of the bright pigment is improved, and a high-brightness coating film is obtained.

<Method for Producing Metallic Paint Polymer (A)>
As a polymerization method of the compound (a1) and the other unsaturated monomer (a2), a known polymerization method may be mentioned. When considering use as a coating material, the compound (a1) and other unsaturated monomer are used. The so-called solution polymerization method in which the body (a2) is radically polymerized in the presence of the radical polymerization initiator (C) in the organic solvent (B) is preferable.

As the solution polymerization method, the following method (I) or method (II) is preferable. In the method (I), it is considered that the compound (a1) is phase-separated in the surface layer of the mixture and may not be efficiently copolymerized in the polymer. Therefore, in the present invention, the method (II) is Particularly preferred.
(I) In the organic solvent (B), the compound (a1), the other unsaturated monomer (a2), the radical polymerization initiator (C) and, if necessary, the organic solvent (B) are continuously added for a predetermined time. A method of polymerizing the compound (a1) and the other unsaturated monomer (a2) by periodically or intermittently adding (for example, dropping).
(II) A mixture containing the compound (a1) and the organic solvent (B), another unsaturated monomer (a2), a radical polymerization initiator (C), and, if necessary, a mixture containing the organic solvent (B) Is added continuously (for example, dropwise) over a predetermined time to polymerize the compound (a1) and the other unsaturated monomer (a2).
In either method (I) or method (II), the compound (a1), the other unsaturated monomer (a2), and the radical polymerization initiator (C) are preferably mixed and added.

  The amount of the compound (a1) used is preferably from 0.1 to 1% by mass, preferably from 0.15 to 0.5% by mass, out of a total of 100% by mass of the compound (a1) and the other unsaturated monomer (a2). % Is more preferable. If the amount of the compound (a1) used is 0.1% by mass or more, the slip property is exhibited. If the usage-amount of a compound (a1) is 1 mass% or less, the adhesiveness of the coating film containing the polymer (A) for metallic paints and other coating films, and the polymer (A) for metallic paints are included. Adhesion of ink when printing or the like is performed on the surface of the coating film is improved.

Examples of the organic solvent (B) include aromatic solvents (toluene, xylene, other high boiling point aromatic compounds, etc.); ester solvents (ethyl acetate, butyl acetate, cellosolve acetate, etc.); ketone solvents (methyl ethyl ketone, Alcohol solvents (methyl alcohol, ethyl alcohol, isopropyl alcohol, n-butyl alcohol, isobutyl alcohol, etc.); hydrocarbon solvents (Supersol 100 (manufactured by Nippon Oil Corporation, product name), Cyclohexane, etc.), and the like, and solvents other than aromatic solvents are preferred from the viewpoint of environmental problems such as concentration restrictions in the interior of buildings and automobiles.
An organic solvent (B) may be used individually by 1 type, and may use 2 or more types together.

Examples of the radical polymerization initiator (C) include known radical polymerization initiators such as organic peroxides and azo compounds.
Examples of the organic peroxide include t-butyl peroxy 2-ethylhexanoate, benzoyl peroxide, dicumyl peroxide, dibutyl peroxide and the like.
Examples of the azo compound include 2,2′-azobisisobutyronitrile, 2,2′-azobis (2-methylbutyronitrile), 2,2′-azobis (2,4-dimethylvaleronitrile), and the like. Can be mentioned.
A radical polymerization initiator (C) may be used individually by 1 type, and may use 2 or more types together.

  The amount of the radical polymerization initiator (C) used is determined by the target molecular weight, but is usually 0 with respect to 100 parts by mass in total of the compound (a1) and the other unsaturated monomer (a2). .1 to 10 parts by mass is preferable.

  When performing polymerization at normal pressure, the polymerization temperature is not higher than the boiling point of the organic solvent (B) previously charged in the reaction vessel in the initial stage, and is usually 70 to 160 ° C. When polymerization is carried out under pressure, the polymerization can be carried out at a temperature higher than this, so the high temperature pressure polymerization method is aimed at reducing the radical polymerization initiator (C), shortening the polymerization time, lowering the molecular weight, etc. Can also be used. 70-120 degreeC is preferable from the point which obtains the polymer (A) for metallic paints of appropriate molecular weight.

  In the method for producing the polymer (A) for metallic paint according to the present invention described above, the compound (a1) and the other unsaturated monomer (a2) are radically polymerized in the organic solvent (B). Since the radical polymerization is carried out in the presence of the initiator (C), the polymer for metallic paint (A) that can form a coating film with good wear resistance and high brightness can be easily produced.

<Metallic paint composition>
The metallic paint composition of this invention contains the polymer (A) for metallic paints of this invention, and a luster pigment.
The metallic paint composition of the present invention is suitable as a so-called thermoplastic paint that does not undergo post-crosslinking by heat or light energy after coating.

(Bright pigment)
Examples of the luster pigment include aluminum flake, pearl, mica and the like.
The blending amount of the luster pigment is preferably 2 to 30 parts by mass with respect to 100 parts by mass of the polymer for metallic paint (A).

(Compound (a1 ′))
The metallic coating composition of the present invention may contain a polyether-modified silicone compound (a1 ′) having no vinyl group (hereinafter referred to as compound (a1 ′)).
Examples of the method for adding the compound (a1 ′) include a method of blending with a metallic coating composition, a method of polymerizing the compound (a1) and another unsaturated monomer (a2) in the presence of the compound (a1 ′), and the like. Is mentioned.

As the compound (a1 ′), L-77, L-720, L-722, L-7001, L-7002, L-7602, L-7604, L-7605, L-7607N manufactured by Toray Dow Corning Y-7006, FZ-2104, FZ-2110, FZ-2161, FZ-2162, FZ-2163, FZ-2164, FZ-2165, FZ-2166 and FZ-2171, Paintad 29, 32, 54, 57, 8142, 8417, 8388A, 8353 and 8336, BYK-302, 306, 307, 320, 325, 330, 331, 337, 344 and 377 (all are trade names) manufactured by Big Chemie Japan, etc. are preferable.
As the compound (a1 ′), one type may be used alone, or two or more types may be used in combination.

(Other ingredients)
If necessary, the metallic coating composition of the present invention may contain other resins (cellulosic resins, etc.), pigments (excluding bright pigments), paint additives (fillers, plasticizers, pigment dispersants, additives). Sticking agent, antifoaming agent, leveling agent, etc.), softness imparting agent (polyurethane, etc.), adhesion imparting agent (chlorinated polyolefin, maleic anhydride modified chlorinated polyolefin, etc.) for the purpose of improving adhesion to polyolefin substrates Etc.) may be included. Among them, cellulose resins (nitrocellulose, cellulose acetate butyrate, etc.) are effective in improving pigment dispersibility, metallic orientation, etc. in addition to being able to express high surface strength and surface hardness when blended in paints. This is preferable. Although the usage-amount of a cellulose resin does not have a restriction | limiting in particular, 10-200 mass parts is preferable with respect to 100 mass parts of polymers (A) (solid content) for metallic paints.
Examples of the pigment include organic pigments and inorganic pigments (titanium oxide, iron oxide, titanium coat, etc.).

(Preparation method of metallic coating composition)
The metallic paint composition of the present invention may be prepared by adding, for example, a bright pigment, and, if necessary, other pigments to the solution of the metallic paint polymer (A) obtained by the method for producing the metallic paint polymer (A) of the present invention. It can be prepared by adding the components and adjusting to the desired viscosity by adding a diluent as necessary.
As a diluent, the thing similar to the organic solvent (B) quoted by the manufacturing method of the polymer (A) for metallic paints is mentioned.

  Since the metallic paint composition of the present invention described above includes the polymer (A) for metallic paint of the present invention, a coating film with good wear resistance and high brightness can be formed.

<Painted object>
The coated product of the present invention has a coating film obtained from the metallic coating composition of the present invention.
The coated product of the present invention can be produced by applying the metallic coating composition of the present invention to the surface of a substrate and drying it to form a coating film.

Examples of the material for the substrate include plastic, metal, inorganic material, wood, paper, fiber, FRP, and the like. In the present invention, plastic or metal is preferable.
Examples of the plastic include polycarbonate, acrylic resin (polymethyl methacrylate, etc.), ABS resin, olefin resin (polypropylene, polyethylene, etc.) and the like.
Examples of the metal include iron, stainless steel, and aluminum.
Examples of the inorganic material include glass, slate plate, concrete, calcium silicate, gypsum, asbestos, and ceramic.

Examples of the coating method include a spray coating method, a brush coating method, a dip coating method, a roll coating method, and a flow coating method.
What is necessary is just to set drying conditions suitably with the kind of metallic coating composition of this invention, the kind of organic solvent, content, etc. The drying temperature is usually from room temperature to 200 ° C., and in the case of a plastic substrate, it is preferably below the heat resistance temperature of the plastic. The drying time is preferably 1 to 120 minutes, and may be appropriately set according to the evaporation rate of the organic solvent, the drying temperature, and the like.

The coating film may be a single layer or two or more layers.
As the two-layer coating film, a base layer excellent in designability obtained from the metallic coating composition of the present invention, and a topcoat layer excellent in gloss, smoothness and abrasion resistance obtained from a clear coating material. A two-layer coating film is mentioned. However, since the coating film obtained from the metallic coating composition of the present invention can achieve both design and wear resistance with only one layer, it is not necessarily required to have two layers.

  Since the coated article of the present invention described above has a coating film obtained from the metallic coating composition of the present invention, the coated article has good wear resistance and high brightness.

  Hereinafter, the present invention will be described by way of examples. “Part” and “%” indicate “part by mass” and “% by mass”, respectively.

(Remaining heating)
The polymer solution was dried at 105 ° C., and the heating residue (solid content) contained in the polymer solution was determined.

(Mass average molecular weight)
After adding tetrahydrofuran to the polymer solution and adjusting the solution concentration to 0.4%, 100 μL of the sample was placed on a Tosoh gel permeation chromatography apparatus equipped with Tosoh columns (GE4000HXL and G2000HXL). The mass average molecular weight of the polymer was measured based on polystyrene by gel permeation chromatogram method at a flow rate of 1 mL / min (eluent: tetrahydrofuran) and a column temperature of 40 ° C.

(Glass transition temperature (Tg))
The glass transition temperature (Tg) of the polymer of the other unsaturated monomer (a2) was determined using the above formula (1).

(SP value (δ))
The SP value (δ) of the polymer of the other unsaturated monomer (a2) was determined using the above formula (3).

(Surface smoothness)
The surface of the coating film was visually observed and evaluated according to the following criteria.
○: Smooth.
Δ: Slightly uneven, but usable level.
X: There is unevenness and it cannot be used.

(Luminance)
The surface of the coating film was visually observed and evaluated according to the following criteria.
○: Aluminum flake particles are not confirmed, and brightness is good.
X: The presence of aluminum flake particles was confirmed, and the luminance was poor.

(Abrasion resistance)
Copy paper (Mitsubishi Paper Co., Ltd., Mitsubishi Recycled PPC paper) cut into a 2cm square is placed on the surface of the coating, and attached to the Gakushin type dyeing friction fastness tester so that a load of 500g is applied on the copy paper. After operating 50 times, the degree of scratches on the surface of the coating film was evaluated according to the following criteria.
A: No scratches are seen at all.
○: Slight scratches are observed.
Δ: Scratches are seen, but usable level.
X: Obvious scratches are seen and it cannot be used.

(Adhesiveness)
Using a razor, make 11 scratches on the coating film vertically and horizontally, reaching the substrate at 1.5 mm intervals to make 100 squares, and use cellophane tape (made by Nichiban Co., width: 25 mm). Crimping was applied to the squares, and then rapidly peeled upward, and the number of squares remaining on the substrate was counted.
○: The number of remaining squares is 100.
X: The number of remaining squares is 0 to 99.

(Cohesive failure)
In the evaluation of adhesion, the degree of adhesion of the aluminum flakes in the coating film to the cellophane tape (manufactured by Nichiban Co., Ltd.) was evaluated.
○: No adhesion.
Δ: Slight adhesion but usable level.
X: There is adhesion and it cannot endure use.

(Unsaturated monomer)
Compound (a1), Compound (a1 ′), Compound (a1 ″) (silicone compound having a vinyl group not modified with polyether), other unsaturated monomers (a2), radicals used in Examples The polymerization initiator (C) is shown in Table 1.

[Example 1]
A four-necked flask equipped with a condenser, thermometer, dropping funnel and stirrer was charged with 16 parts of butyl acetate and 45 parts of isobutanol as the organic solvent (B), and the internal temperature of the flask was raised to 100 ° C. Warm up. Next, a mixture obtained by mixing 43 parts of the compound (a1), other unsaturated monomer (a2), radical polymerization initiator (C), and butyl acetate in the amounts shown in Table 2 was added to the flask. While maintaining the internal temperature at 100 ° C., it was dropped into the flask over 240 minutes. After completion of dropping, the internal temperature of the flask was kept at 100 ° C. for 1 hour. Subsequently, a mixed solution of 0.5 part of perbutyl O and 16 parts of butyl acetate was added over 1 hour, and the internal temperature of the flask was further maintained at 100 ° C. for 2 hours. Subsequently, 30 parts of butyl acetate was added so that solid content might be 40%, it cooled, and the polymer (A-1) solution was obtained. The properties of the obtained polymer are shown in Table 2.

  The polymer (A-1) solution and nitrocellulose (manufactured by SNPE Japan, HIG1 / 4) were dissolved in a mixed solvent of butyl acetate / ethyl acetate = 50/50 (mass ratio) so that the solid content was 33%. A nitrocellulose solution and a bright pigment (manufactured by Toyo Aluminum Co., Ltd., Alpaste 1700NL, aluminum solid content: 64%) were blended in the amounts shown in Table 3 to obtain a metallic coating composition before being diluted with a diluent. Ford was added with a diluent consisting of ethyl acetate / propylene glycol monomethyl ether acetate / supersol 100 (manufactured by Nippon Oil Co., Ltd., hydrocarbon-based high-boiling solvent) / butyl acetate = 10/30/40/20 (mass ratio). It diluted and prepared so that it might become 11 seconds with cup # 4, and the metallic coating composition (B-1) was obtained.

  The metallic coating composition (B-1) was spray-coated on the surface of the ABS resin substrate so that the dry film thickness was about 15 μm. Then, after being left for 20 minutes, it was heated and dried at 80 ° C. for 30 minutes to form a coating film to obtain a coated product. Table 4 shows the evaluation results of the obtained coated product.

[Examples 2 to 7]
Polymer (A-2) to (A-7) solutions were obtained in the same manner as in Example 1 except that the charged raw materials and amounts were changed as shown in Table 2. The properties of the obtained polymer are shown in Table 2.
The metallic paint compositions (B-2) to (B-) were the same as in Example 1 except that the polymer (A-1) solution was changed to the polymer (A-2) to (A-7) solution. 7) was obtained.
The coated materials of Examples 2 to 7 were evaluated in the same manner as Example 1 except that the metallic coating composition (B-1) was changed to metallic coating compositions (B-2) to (B-7). . Table 4 shows the evaluation results of the obtained coated product.

Example 8
In a four-necked flask equipped with a cooler, a thermometer, a dropping funnel and a stirrer, 16 parts of butyl acetate, 45 parts of isobutanol and the amount of the compound (a1) shown in Table 2 are used as the organic solvent (B). The temperature inside the flask was raised to 100 ° C. Next, a mixture obtained by mixing 43 parts of other unsaturated monomer (a2), radical polymerization initiator (C), and butyl acetate in the amounts shown in Table 2 was used. The flask was dropped into the flask over 240 minutes. After completion of dropping, the internal temperature of the flask was kept at 100 ° C. for 1 hour. Subsequently, a mixed solution of 0.5 part of perbutyl O and 16 parts of butyl acetate was added over 1 hour, and the internal temperature of the flask was further maintained at 100 ° C. for 2 hours. Subsequently, 30 parts of butyl acetate was added so that solid content might be 40%, it cooled, and the polymer (A-8) solution was obtained. The properties of the obtained polymer are shown in Table 3.

A metallic coating composition (B-8) was obtained in the same manner as in Example 1 except that the polymer (A-1) solution was changed to the polymer (A-8) solution.
The coated material of Example 8 was evaluated in the same manner as in Example 1 except that the metallic coating composition (B-1) was changed to the metallic coating composition (B-8). Table 5 shows the evaluation results of the obtained coated product.

[Examples 9 and 10]
Polymer (A-9) and (A-10) solutions were obtained in the same manner as in Example 8, except that the charged raw materials and amounts were changed as shown in Table 2. The properties of the obtained polymer are shown in Table 3.
The metallic paint composition (B-9), (B-) is the same as in Example 1 except that the polymer (A-1) solution is changed to the polymer (A-9) and (A-10) solution. 10) was obtained.
The coated materials of Examples 9 and 10 were evaluated in the same manner as in Example 1 except that the metallic coating composition (B-1) was changed to the metallic coating compositions (B-9) and (B-10). . Table 5 shows the evaluation results of the obtained coated product.

[Comparative Examples 1-3]
Polymer (A′-1) to (A′-3) solutions were obtained in the same manner as in Example 1 except that the charged raw materials and amounts were changed as shown in Table 2. The properties of the obtained polymer are shown in Table 3.
The metallic paint composition (B′-1) is the same as in Example 1 except that the polymer (A-1) solution is changed to the polymer (A′-1) to (A′-3) solution. (B′-3) was obtained.
The coated products of Comparative Examples 1 to 3 were prepared in the same manner as in Example 1 except that the metallic coating composition (B-1) was changed to metallic coating compositions (B′-1) to (B′-3). evaluated. Table 5 shows the evaluation results of the obtained coated product.

As is clear from Tables 4 and 5, the coating film formed using the metallic paint composition of the present invention is excellent in smoothness, adhesion, brightness, and abrasion resistance. In particular, in Examples 8 to 9, the SP value (δ) of the polymer of the other unsaturated monomer (a2) is in the range of 19.7 to 20.0 (J / cm ³ ) ^1/2. Therefore, the smoothness is particularly excellent, and it is suitable for coatings for applications requiring a high design.
In Comparative Example 1, since the polymer for metallic paint did not contain a silicone component, the wear resistance was low, and further, cohesive failure occurred in the adhesion test.
In Comparative Example 2, since the metallic paint polymer contains a silicone component that is not modified with a polyether, the compatibility with the acrylic component is low, and the brightness is low.
In Comparative Example 3, since the polyether-modified silicone having no vinyl group was used, the compatibility with the acrylic component was low, and the brightness was low.

  The metallic paint polymer and metallic paint composition of the present invention are used for automobile exterior parts (bumpers, wheel caps, mud guards, lamp housings, etc.), automobile interior parts (instrument panels, console boxes, etc.), household appliances, and the like. It is suitable for applications and greatly contributes to the expansion of applications for high-design paints.

Claims (7)

A structural unit derived from a polyether-modified silicone compound (a1) having a vinyl group;
A polymer for metallic paint (A) having a structural unit derived from another unsaturated monomer (a2).   The polymer for metallic paints (A) according to claim 1, wherein the polyether is a polyalkylene oxide. The polymer (A) for metallic paint according to claim 1 or 2, wherein the other unsaturated monomer (a2) satisfies the following condition (i) and condition (ii).
(I) The glass transition temperature (Tg) of the polymer of another unsaturated monomer (a2) is 70-130 degreeC.
(Ii) The solubility parameter (δ) of the polymer of the other unsaturated monomer (a2) is 19.7 to 20.4 (J / cm ³ ) ^1/2 .   Metallic, wherein a polyether-modified silicone compound (a1) having a vinyl group and other unsaturated monomer (a2) are radically polymerized in an organic solvent (B) in the presence of a radical polymerization initiator (C). The manufacturing method of the polymer (A) for coating materials.   The other unsaturated monomer (a2) and the radical polymerization initiator (C) are continuously or intermittently added to the mixture containing the polyether-modified silicone compound (a1) having a vinyl group and the organic solvent (B). The manufacturing method of the polymer (A) for metallic paints of Claim 4 added. The polymer for metallic paints (A) according to any one of claims 1 to 3,
A metallic paint composition comprising a luster pigment.   A coated article having a coating film obtained from the metallic paint composition according to claim 6.