JPH0261514B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention is low-temperature curable, has excellent drying properties, texture and film performance, especially weather resistance, has high application solidity, and when used as a metallic base, has excellent metallic feel. The present invention relates to a resin composition for automatic repair paint that does not cause metal unevenness and does not cause existing paint films to be attacked by organic solvents. Non-aqueous polymer dispersions are disclosed in Japanese Patent Publication No. 45-19011,
No. 46-9708, No. 46-25011, No. 47-355531, 52-
As seen in publications such as No. 49519 and No. 57-26284, it has been well known for a long time, and is now used in combination with amino resins and (block) isocyanate compounds as thermosetting paints for home appliances and other applications. Although it is commonly used for industrial paints, there are no examples yet of it being used for automotive refinish paints. By the way, this type of automotive refinishing paint can be roughly divided into topcoat and undercoat, and further divided into lacquer-based paints and urethane-based paints, among which urethane-based paints are particularly Due to its good curing properties and excellent performance, urethane-based products are increasingly being used as both top coats and undercoats, but depending on the solvent used, urethane-based products are already It may attack the existing paint film (hereinafter also referred to as the old paint film) being painted or the Lutzker primer surfer when a top coat and undercoat are used in a certain combination, causing stiffness and lifting. As this often happens, identifying what type of old paint film was used is a know-how when refinishing automobiles to avoid failures. Therefore, those skilled in the art are eagerly awaiting the development of an automobile refinishing paint that does not cause distortion or lifting of the old paint film or primer surfacer. In addition, conventional automotive refinish paints generally have low application solids, and therefore require multiple coats to achieve a solid feel. is also desired. One such improvement method is to increase the application solidity by lowering the molecular weight of the resin itself, but in this case it is true that the feeling of texture is improved and the coating work is easier. On the other hand, the drying properties become extremely poor, and the consequent disadvantages are that it is easy to get scratches and dust.Moreover, when used as a top coat, the molecular weight becomes lower. As a result, a decrease in weather resistance and crack resistance is also observed. Furthermore, when the currently used acrylic urethane paints are used for metallic base coats in the 2-coat, 1-bake (hereinafter abbreviated as 2C1B) type, they may give off a metallic feel unless careful application is applied. In order to improve the "metallic appearance" of the paint, we had no choice but to apply a top coat. By lowering the molecular weight of the polyol used for the base coat, by using a polyol with a high molecular weight to make the base coat dry quickly, and by using cellulose compounds such as cellulose, acetate, butyrate, and melamine resin in combination. This can be done by improving the painting technique or skill of a skilled painter, such as by improving the painting itself, by lengthening the painting time or setting time, or by using more quick-drying diluted thinner. At present, people are trying to avoid troubles, and therefore, solving the above-mentioned troubles is difficult.
The 2C1B type is also highly desired from the aspect of painting workability. On the other hand, in the case of non-aqueous polymer dispersions,
Although its viscosity is low, the molecular weight of the dispersed polymer is high, and therefore, when it is made into a coating film, it has excellent drying properties, hardness, and texture. In the so-called 2C1B system, when this non-aqueous polymer dispersion is used for the metallic base coat, there is no metal unevenness when the top clear is applied on top, and because aluminum particles tend to stand up, it is extremely metallic. Excellent sensibility,
A coating film with a metallic finish can be obtained, and even when this non-aqueous polymer dispersion is used as a top clear coat over an acrylic urethane-based metallic base coat, it has a solid feel and finished appearance with no metallic unevenness. Because it provides an excellent coating film, even when used as a top coat or undercoat, the old paint film and Lutzker Primer Surfacer will not be attacked by the solvent used and will dry easily. There is currently a strong demand in the industry for an automobile refinishing paint that has excellent texture, texture, and coating performance, has less metal unevenness, and has a good metallic feel. On the other hand, durability is particularly required as an important performance for outdoor paints, and one way to improve the durability of such paint films is to improve the resin composition itself for paints. In addition, it is known that the use of ultraviolet absorbers is particularly effective. However, when applying a UV absorber to the non-aqueous polymer dispersion, adopting the conventional method of mixing it after the dispersion is prepared has various problems as shown below. It's inconvenient. That is, for example, (i) the ultraviolet absorber is difficult to dissolve in the non-polar organic liquid that is the main component of the organic liquid used in the non-aqueous polymer dispersion, so it precipitates in the liquid and does not reach a sufficient amount. (ii) In addition, in the non-aqueous polymer dispersion, the polymer, which is the main component of the film-forming property, exists as particles; Even if an ultraviolet absorber is mixed into the particles, it cannot be easily diffused into the interior of the particles, and therefore the protective effect of the absorber can hardly be expected. However, in view of the various drawbacks of these conventional methods, the inventors of the present invention have made extensive studies and have developed a coating film that has an excellent metallic feel, is free of metallic unevenness, has a strong feeling of texture, and has an excellent finished appearance. A coating film with excellent performance, especially weather resistance, can be obtained, and by mixing the UV absorber into a vinyl monomer that easily dissolves the UV absorber, it can be used in the desired amount; The present inventors have now completed the present invention by discovering that the absorbent has a great protective effect against oxidants and significantly improves the durability of the coating film. That is, in the present invention, 0.1 to 10% by weight of an ultraviolet absorber is added to 100% by weight of the vinyl monomer in a nonpolar organic solvent or an organic solvent with relatively low solubility and in the presence of a dispersion stabilizer. A non-aqueous dispersion (A) of a vinyl copolymer having a functional group that is reactive with isocyanate groups is obtained by adding and mixing the vinyl monomer containing the ultraviolet absorber and dispersion polymerizing the vinyl monomer. , OH/NCO=1/0.5~1/
A polyisocyanate (B) is blended at an equivalent ratio of 1.5, or if necessary, a reaction accelerator (C) for the urethanization reaction is also blended. The purpose of the present invention is to provide a resin composition for automobile refinish paints that does not require any prior art. In other words, if such a composition of the present invention is used,
In particular, although it dissolves vinyl monomers,
The polymer derived from the monomer, that is, the vinyl copolymer, is not dissolved in an organic liquid that does not polymerize itself, that is, a non-polar or relatively low-solubility organic liquid (hereinafter also referred to as the parent monomer liquid). ) and in the presence of a vinyl copolymer (dispersion stabilizer) dissolved in this parent monomer liquid, in order to polymerize the vinyl monomer,
Firstly, it does not attack the old paint film or Lutzker Primer Surfacer when used as either a top coat or an undercoat, and it is also possible to obtain a paint film with good drying properties. Prior to dispersion polymerization using a monomer liquid, a specific amount of an ultraviolet absorber is added and mixed into a vinyl monomer and polymerized to produce a non-aqueous polymer in which this ultraviolet absorber is contained in a vinyl polymer. Dispersions can also be obtained. When the resin composition for paint of the present invention is used as a paint for automobile refinishing, no matter what old paint film or primer surfer is coated,
There are no problems such as stiffness or lifting that occur in the past, and as mentioned above,
It has excellent durability, texture, drying properties, and coating performance, especially weather resistance, and features such as application solidity, metal unevenness, and metallic feel. As described above, the present invention can be said to be an epoch-making product that improves and eliminates all the defects and shortcomings of conventional paints for automobile refinishing. The non-aqueous polymer dispersion (A), which is one of the constituent components of the composition of the present invention, can be prepared by any known and commonly used method. It is appropriate to use a method in which a monomer having a different polarity from the organic liquid is polymerized using a block polymer or a graft polymer consisting of a combined portion and a polymer portion that is not solvated by the liquid as a dispersion stabilizer. Well-known compounds that can be used as such dispersion stabilizers include natural rubber, butadiene copolymers, drying oil-modified unsaturated polyester resins, oil-modified alkyd resins, acrylic resins with monomers added, and long-chain fatty acids. Polyesters made from alcohol and alcohol with monomers added to them, vinyl copolymers or amino resins modified with fatty acids or glycidyl esters of fatty acids, etc.
Of course, in the present invention, all non-aqueous polymer dispersions obtained using such well-known dispersion stabilizers can be used as they are, but vinyl copolymers are particularly preferred, and among them, fatty acids or fatty acid-based copolymers are preferred. Glycidyl esters are particularly preferred, or oil-modified and/or fatty acid-modified alkyd resins are also particularly preferred, since the crosslinking reaction points with the polyisocyanate (B) are distributed almost uniformly in these polymers or resins. This is because defects in coating properties due to nonuniform crosslinking points can be avoided. The amount of dispersion stabilizer used is as follows:
First, if the dispersion stabilizer is a vinyl copolymer that has not been modified with fatty acids (glycidyl esters), etc., then If the dispersion stabilizer is a vinyl copolymer modified with a fatty acid or a glycidyl ester of a fatty acid, then in the presence of the dispersion stabilizer. A suitable range is 2 to 400% by weight, preferably 20 to 300% by weight, based on 100% by weight of the vinyl monomer to be polymerized, and the dispersion stabilizer is an oil-modified and/or fatty acid-modified alkyd resin. in case of,
The appropriate amount is 5 to 400% by weight, preferably 10 to 300% by weight, based on 100% by weight of the vinyl monomer to be polymerized in the presence of the dispersion stabilizer.
Of course, when a well-known compound other than those mentioned above is used as a dispersion stabilizer, a conventional amount may be used. Here, first, as the above-mentioned unmodified vinyl copolymer which is a preferable dispersion stabilizer in the present invention, at least 25% by weight, preferably 40% by weight or more of (meth)acrylic esters in the copolymer are used. , preferably the side chain alkyl group is C ₃
A copolymer obtained using the following (meth)acrylic esters, having one unsaturated bond per n1000 to 100,000, and at least 3% by weight, preferably 5 to 30% by weight. % is a monomer containing a functional group capable of reacting with the isocyanate group in the polyisocyanate (B), such as a hydroxyl group, a carboxyl group, an amide group, or a methylol group, and if necessary, a monomer other than a monovinyl compound such as dihydrodicyclopentadiene. Suitable examples include monomers having two or more unsaturated group bonds and/or other vinyl monomers. Typical examples of the above functional group-containing monomers include 2-hydroxyethyl (meth)acrylate,
2-hydroxypropyl (meth)acrylate,
3-hydroxypropyl (meth)acrylate,
2-Hydroxybutyl (meth)acrylate, 3
-Hydroxybutyl (meth)acrylate, 4-
Such as hydroxybutyl (meth)acrylate, 3-chloro-2-hydroxypropyl (meth)acrylate, di-2-hydroxyethyl fumarate, mono-2-hydroxyethyl-monobutyl fumarate or polyethylene glycol mono(meth)acrylate Hydroxyalkyl esters of α,β-ethylenically unsaturated carboxylic acids; (meth)
unsaturated mono- or dicarboxylic acids such as acrylic acid, crotonic acid, maleic acid, fumaric acid, itaconic acid or citraconic acid, as well as α,β-ethylenic unsaturated acids such as monoesters of these dicarboxylic acids with monohydric alcohols; Saturated carboxylic acids; the above α,β-unsaturated carboxylic acid hydroalkyl esters, maleic acid, succinic acid, phthalic acid, hexahydrophthalic acid, tetrahydrophthalic acid, benzenetricarboxylic acid, benzenetetracarboxylic acid, “hymic acid” [ products of Hitachi Chemical Co., Ltd.], adducts of polycarboxylic acid anhydrides such as tetrachlorophthalic acid or dodecynylsuccinic acid, and glycidyl esters of branched synthetic fatty acids such as "Cardilla E" (manufactured by Siel in the Netherlands). ),
Monoglycidyl esters of monovalent carboxylic acids such as coconut oil fatty acid glycidyl esters or octylic acid glycidyl esters or adducts with monoepoxy compounds such as butyl glycidyl ether, ethylene oxide or propylene oxide; N
- A methylol group-containing compound of an amide group-containing vinyl monomer such as methylolated acrylamide; or a polyester resin having a polymerizable unsaturated bond and a hydroxyl group (containing other functional groups such as a carboxyl group in addition to the hydroxyl group); Also good.)
Hydroxyl group-containing vinyl monomers such as
- Ethylenically unsaturated carboxylic acids, α, β above -
Adducts of ethylenically unsaturated carboxylic acid hydroxyalkyl esters and the above polycarboxylic acid anhydrides, or polyester resins having a polymerizable unsaturated bond and a carboxyl group (in addition to carboxyl groups, other functional groups such as hydroxyl groups) ), and amide group-containing vinyl monomers such as (meth)acrylamide or diacetone acrylamide. Typical functional group-free vinyl monomers include methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, i-propyl (meth)acrylate, and n-butyl (meth)acrylate. , i-butyl (meth)acrylate, t-butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, lauryl (meth)acrylate, cyclohexyl (meth)acrylate, benzyl (meth)acrylate, dibromopropyl (meth)acrylate, (meth)acrylates such as tribromophenyl (meth)acrylate or alkoxyalkyl (meth)acrylate; diesters of unsaturated dicarboxylic acids and monohydric alcohols such as maleic acid, fumaric acid or itaconic acid;
Nitrogen-containing vinyl compounds such as N-vinyllactam, N-vinylpyrrolidone or N-vinylimidazole; aromatic vinyl compounds such as styrene or vinyltoluene; vinyl acetate, vinyl benzoate, "Beoba" (vinyl ester manufactured by Ciel) ) Vinyl esters such as “Viscoat 8F, 8FM,
3F or 3FM” [fluorine-containing acrylic monomer manufactured by Osaka Organic Chemical Co., Ltd.], perfluorocyclohexyl (meth)acrylate, diperfluorocyclohexyl fumarate or N-i-propyl perfluorooctane sulfonamidoethyl (meth) ) Fluorine-containing compounds such as (per)fluoroalkyl group-containing vinyl esters, vinyl ethers, (meth)acrylates, or unsaturated polycarboxylic acid esters such as acrylate; or (meth)acrylonitrile, vinyl chloride, vinylidene chloride, There are olefins such as vinyl fluoride and vinylidene fluoride. Furthermore, other typical vinyl monomers include N,N-dialkylaminoalkyl (meth)acrylates such as dimethylaminoethyl (meth)acrylate, and phosphoric acid groups such as β-acid phosphooxy (meth)acrylate. Containing (meth)acrylates, glycidyl (meth)acrylate, (β-methyl)glycidyl (meth)acrylate, (meth)allyl glycidyl ether or the above α,β-ethylenically unsaturated carboxylic acids or mono-2-(meth)acrylates, ) "Epicron 200, 400, 441, 850 or 1050" [Dainippon Ink Kagaku Kogyo Co., Ltd. epoxy resin], "Epicoat 828, 1001 or 1004" (Ciel epoxy resin), "Araldite 6071 or 6084" (Switzerland Ciba Geigy epoxy resin), "Titsonox 221" [ Various polyepoxy compounds having at least two epoxy groups in one molecule, such as "epoxy compound manufactured by Chitsuso Co., Ltd." or "Denacol EX-611" [epoxy compound manufactured by Nagase Sangyo Co., Ltd.], in equimolar ratios. Examples thereof include epoxy group-containing polymerizable compounds obtained by addition reaction, dimethyl (meth)acrylamide, and N-alkoxymethylated (meth)acrylamide. Vinyl monomers having two or more unsaturated bonds are used to introduce unsaturated bonds into vinyl copolymers, and typical examples include butadiene or isoprene or (β-methyl)glycidyl (meth). ) acrylate and (meta)
Esters with acrylic acid, esters with a molar ratio of ethylene glycol and (meth)acrylic acid of 1:2, adducts with a molar ratio of 2-hydroxyethyl (meth)acrylate and hexamethylene diisocyanate of 1:2, or ( Examples include esters of β-methyl)glycidyl (meth)acrylate and dicarboxylic acids such as phthalic acid and succinic acid in a molar ratio of 2:1. By the way, (β-methyl)glycidyl (meth)
Of course, compounds having both a functional group and two or more unsaturated bonds, such as an ester with a molar ratio of acrylate and phthalic acid of 1:1, can be used as a monomer for introducing unsaturated bonds, but at the same time, the above-mentioned functional Since it is a group-containing vinyl monomer, care should be taken. Thus, in preparing the vinyl copolymer serving as the dispersion stabilizer, a so-called one-stage method may be used in which copolymerization is carried out by batch charging, or a two-stage method in which the reaction is carried out in two stages. A two-stage method is advantageous in controlling the reaction. Regardless of the one-step method or the two-step method, the vinyl copolymer finally obtained must contain not only unsaturated bonds but also functional groups as specified above. Next, the fatty acid (glycidyl ester) modified vinyl copolymer which is a preferable dispersion stabilizer in the present invention is obtained from 10 to 880% by weight of a fatty acid or glycidyl ester of a fatty acid and 90 to 20% by weight of a vinyl monomer. things are appropriate,
As such vinyl monomers, various monomers such as those listed above can be used, but as mentioned above, monomers that dissolve or swell in organic liquids that do not dissolve the final vinyl copolymer from the vinyl monomers can be used. Of course it should be used. Here, representative fatty acids include saturated fatty acids such as octylic acid, lauric acid, stearic acid, or "versateic acid" (synthetic fatty acids manufactured by Shell); oleic acid, linoleic acid, linoleic acid, and eleostearic acid. acid or unsaturated fatty acids such as ricinoleic acid;
or 300” (synthetic drying oil fatty acid manufactured by Hercules in the United States), Chinese tung oil fatty acid, linseed oil fatty acid,
drying oil fatty acids such as dehydrated castor oil fatty acids, tall oil fatty acids or cottonseed fatty acids; semi-drying oil fatty acids such as soybean oil fatty acids, olive oil fatty acids, safflower oil fatty acids, castor oil fatty acids or rice bran oil fatty acids; or hydrogenated coconut oil fatty acids, There are non-drying oil fatty acids such as coconut oil fatty acids or palm oil fatty acids, and on the other hand, typical examples of the above-mentioned fatty acid glycidyl esters include glycidyl esters derived from various fatty acids as listed above. These fatty acids (glycidyl esters) can of course be used alone or in combination, and in the case of using saturated fatty acids, they may be used in combination with unsaturated fatty acids and vinyl monomers containing functional groups such as carboxyl groups. Needless to say. To explain more specifically, the fatty acid (glycidyl ester) modified vinyl copolymer is:
(1) Those synthesized by the reaction of mutual unsaturated bonds between the above (semi-)drying oil fatty acids (glycidyl esters) and vinyl monomers, (2) 2-hydroxyethyl (meth)acrylate or 2-hydroxypropyl (meth) ) acrylate, and hydroxyl group-containing vinyl monomers such as (β-methyl)glycidyl (meth)acrylate or di(β-methyl)glycidyl fumarate.
or one synthesized from a (β-methyl)glycidyl group-containing copolymer obtained using a (β-methyl)glycidyl group-containing vinyl monomer and a fatty acid, or (3) (meth)acrylic acid as described above, Examples include those synthesized from fatty acid glycidyl esters and carboxyl group-containing copolymers obtained as essential comonomer components of unsaturated carboxylic acids such as maleic acid or mono(meth)acryloyloxyethyl phthalate. The content of fatty acid or fatty acid glycidyl ester in the modified vinyl copolymer is 10 to 10% by weight based on the total of 100% by weight of the fatty acid (glycidyl ester) and vinyl monomer that are the constituent components of the modified copolymer. 80% by weight, preferably 20 to 70% by weight; less than 10% by weight will cause coating defects such as gloss, shine, leveling, or transparency; conversely, if it exceeds 80% by weight, defects will occur. The acid resistance and solvent resistance of the coating film will decrease. Further, the amount of the carboxyl group-containing monomer or (β-methyl)glycidyl group-containing monomer used is preferably within a range of 0.8 equivalent or more per equivalent of fatty acid (glycidyl ester). Furthermore, the modified copolymer is then copolymerized with a vinyl monomer such that the resulting final vinyl-based copolymer is not soluble in an organic liquid to form a block or graft copolymer of the modified copolymer. For this reason, it is preferable that the molecule contains an appropriate amount of unsaturated bonds, and the suitable content is one per n150 to 1,000,000 of the modified copolymer. In order to introduce an unsaturated bond into the modified copolymer, various vinyl monomers and reaction compounds such as those already mentioned in the vinyl copolymer for dispersion stabilizer can be used as they are. In this case, vinyl monomers such as butadiene and (meth)
Acrylic acid and (β-methyl)glycidyl (meth)
It can also be produced by a one-step process in which a reactive compound such as an esterified product having a molar ratio of 2:1 with acrylate is copolymerized with other vinyl monomers in a conventional manner, or one component of the above-mentioned reactive compound After copolymerizing a vinyl monomer such as (meth)acrylic acid with another vinyl monomer, the other component compound, a vinyl monomer such as (β-methyl)glycidyl (meth)acrylate, is added or condensed. Although it can be produced by a two-step method, the two-step method is preferable from the viewpoint of reaction control, especially when a reactive compound is incorporated into the modified copolymer. Regardless of the one-stage method or the two-stage method, unsaturated bonds are contained in the final vinyl copolymer. Thus, the modified copolymer preferably contains unsaturated bonds and is modified with 10 to 80% by weight of fatty acid (glycidyl ester). The modified copolymer can be prepared by any known polymerization method, but solution polymerization is particularly preferred, and the modification with a fatty acid (glycidyl ester) is carried out using a carboxyl group-containing vinyl monomer and a glycidyl group, respectively. This can be easily carried out by known addition or condensation reactions with vinyl monomers contained therein. For these addition or condensation reactions,
Well known catalysts such as BF ₃ complexes, tertiary amines or imidazoles can be used. Further, such modification can be carried out by reacting it with a functional group-containing vinyl monomer in advance, by carrying it out simultaneously with the polymerization reaction of the vinyl copolymer, or by carrying out it after the completion of the polymerization reaction, and any of these methods may be used. Further, as the oil-modified and/or fatty acid-modified alkyd resin which is a preferred dispersion stabilizer in the present invention, the above-mentioned drying oil, semi-drying oil or non-drying oil or their various fatty acids, or the above-mentioned saturated fatty acid or unsaturated One type or a mixture of two or more selected from fatty acids can be mixed with ethylene glycol, propylene glycol, glycerin, trimethylolethane, trimethylolpropane, neopentyl glycol, 1,6-hexanediol, 1,2,6-hexanethritol. ,
One or more polyhydric alcohols such as pentaerythritol or sorbitol, benzoic acid, pt-butylbenzoic acid, phthalic acid (anhydride),
Hexahydrophthalic acid (anhydride), Tetrahydrophthalic acid (anhydride), Tetrachlorophthalic acid (anhydride), Hexachlorophthalic acid (anhydride), Tetrabromophthalic acid (anhydride), Trimellitic acid, ``Himitsic acid'' (Anhydrous) succinic acid, ( maleic anhydride,
One or more carboxylic acids such as fumaric acid, itaconic acid (anhydride), adipic acid, sebacic acid or oxalic acid are added in a conventional manner, and if necessary, a glycidyl fatty acid such as "Cardilla E" is added. Monoepoxy compounds such as esters, ``Epicron 200 or 400'', ``Epicort 828 or
1001, or diisocyanates such as tolylene diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, or 4,4'-methylenebis(cyclohexyl isocyanate), and addition of these diisocyanates with the above polyhydric alcohols or water. A part of the polyhydric alcohol or carboxylic acid is replaced with one or more polyisocyanates obtained by reaction or polyisocyanates having an isocyanuric ring obtained by (co)polymerization of diisocyanates. Those obtained by reaction using a method are suitable. The above-mentioned ultraviolet absorber absorbs ultraviolet energy and is compatible with the vinyl monomer and the polymer obtained from the vinyl monomer,
It refers to substances that can be dispersed uniformly, and the representative ones are benzophenone, 2,
4-dihydrobenzophenone, 2,2',4,4'-
Tetrahydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2,2'-dihydroxy-4,4'-dimethoxybenzophenone,
2,2'-dihydroxy-benzophenone, 2-hydroxy-4-octoxybenzophenone, 2-
hydroxy-4-dodecyloxybenzophenone,
2-Hydroxy-4-methoxy-5-sulfobenzophenone, 5-chloro-2-hydroxybenzophenone, 2,2'-dihydroxy-4,4'-dimethoxy-5-sulfobenzophenone, 2 -Hydroxy-4-methoxy-2'-carboxybenzophenone, 2-hydroxy-4-(2-hydroxy-3-methyl-acryloxyisopropoxybenzophenone; 2-(2'-hydroxy-5'-methyl -phenyl)-benzotriazole, 2-(2-
Hydroxy-3,5-di-tert-amyl-phenyl)-2H-benzotriazole, 2-(2-hydroxy-3,5-di-tert-amyl-phenyl)-
2H-benzotriazole, 2-(2'-hydroxy-3',5'-di-tert-butyl-phenyl)benzotriazole, 2-(2'-hydroxy-3',5'-di
tert-butyl-5'-methyl-phenyl)benzotriazole, 2-(2'-hydroxy-3',5'-di
tert-butyl-phenyl)-5-chloro-benzotriazole, 2-(2'-hydroxy-3',5'-di
tert-isoamyl-phenyl)benzotriazole, 2-(hydroxy-5-tert-butyl-phenyl)benzotriazole; phenyl salicylate, 4-tert-butyl-phenyl salicylate,
p-octyl-phenyl salicylate; ethyl-
2-cyano-3,3'-diphenyl-acrylate, 2-ethylhexyl-2-cyano-3,3'-
Diphenyl acrylate; hydroxy-5-methoxy-acetophenone, 2-hydroxy-naphthophenone; 2-ethoxyethyl-p-methoxycinnamate or nickel-bisoctylphenyl sulfide, 4-benzoyloxy-
Examples include 2,2,6,6-tetramethylpiperidine, bis-(2,2,6,6-tetramethyl-4-piperidyl)-sebacate or "Tinuvin 292" (product of Ciba Geigy, Switzerland). These may be used alone or in combination of two or more. In order to further increase the effectiveness, "Sumilizer BHT" [Sumitomo Chemical Co., Ltd. product], "Sinox BCS" [Shiraishi Calcium Co., Ltd. product], "Irganox 1010 or 1076" [Ciba Geigy product], Well-known and commonly used antioxidants such as "Noclyzer TNP" (manufactured by Ouchi Shinko Co., Ltd.) or "Antioxidant KB" (manufactured by Bayer, West Germany) can also be used together. The above-mentioned ultraviolet absorber may be added and mixed with these vinyl monomers prior to dispersion polymerization of the vinyl monomers, and the amount used at this time is 0.1 to 10% by weight based on 100% by weight of the vinyl monomers. Preferably within the range 0.1% by weight
If the amount is less than 10% by weight, it is difficult to see any effect, whereas if it exceeds 10% by weight, the effectiveness of its use will be great, but the water resistance will be poor and it will often be disadvantageous in terms of cost. In order to prepare the non-aqueous polymer dispersion (A) using the raw materials listed above, first, a dispersion stabilizer, preferably a copolymer for each dispersion stabilizer as described above, is added to an organic liquid. The polymer is dissolved, and then vinyl monomer and ultraviolet absorber are added to this solution.
The vinyl monomer is preferably polymerized by dropping it together with a polymerization initiator, and any known and commonly used means can be used as is. At this time, it is of course possible to freely change the solid content concentration and viscosity by appropriately selecting various manufacturing conditions. Thus, in the present invention, since the ultraviolet absorber is directly added and mixed with the vinyl monomer, the absorber is present in the polymer particles of the vinyl monomer itself, and the ultraviolet absorber is added to the vinyl monomer. Needless to say, the protective effect of the ultraviolet absorber on the combined particle portion is also extremely large. Here, as mentioned above, the organic liquid is non-polar or has a relatively low dissolving power, and does not dissolve the final vinyl copolymer, but dissolves or swells the dispersion stabilizer copolymer. Yes, it is non-polymerizable. Typical examples of such organic liquids (parent monomer liquids) include aliphatic hydrocarbons such as heptane, hexane or octane; petroleum benzine, ligroin, mineral spirits, petroleum naphtha or kerosene having a boiling point of 30 to 300. C.; cycloaliphatic hydrocarbons such as cyclohexane, methylcyclohexane or ethylcyclohexane; or mixtures thereof. Depending on the case, it may contain up to about 50% by weight or more of a polar solvent such as alcohol, ester, ether or ketone. The amount of these parent monomer liquids used is such that the solid content of the obtained dispersion (A) is 30 to 70% by weight, preferably 40% by weight.
It is appropriate to select the amount within the range of ~60% by weight. The vinyl monomer polymerized in these parent monomer liquids produces a final vinyl copolymer (dispersion polymer) that does not dissolve in the liquid, and also forms a block or graft polymer with the above-mentioned various dispersion stabilizers as the solvation part. It produces a polymer. Here, "does not dissolve" means that a polymer with an average molecular weight or more is not dissolved, and does not mean that a polymer with an average molecular weight or less that is irreversibly produced as a by-product in a polymerization reaction is not dissolved. do not have. Typical examples of the above polymerization initiators include azo compounds such as azobisisobutyronitrile and peroxides such as benzoyl peroxide, but any well-known and commonly used initiators can be used. The amount of the polymerization initiator used is 0.1 to 10 parts by weight per 100 parts by weight of the vinyl monomer to be polymerized.
A range of parts by weight is appropriate. Further, if necessary, well-known chain transfer agents such as mercaptans such as lauryl mercaptan, α-methylstyrene, and the like can be used to adjust the molecular weight. The temperature conditions for the polymerization reaction are suitably in the range of 50 to 150°C, preferably 60 to 110°C, and the reaction time is suitably in the range of 2 to 40 hours, preferably 4 to 25 hours. Furthermore, as mentioned above, the vinyl monomer used in preparing the non-aqueous polymer dispersion (A) is dissolved in the parent monomer liquid before polymerization,
As long as the product after polymerization does not dissolve in the liquid, the vinyl monomers already described in detail in the section regarding the dispersion stabilizer can in principle be used as they are. However, some of these vinyl monomers dissolve in the parent monomer liquid if they are homopolymers, but such monomers should be used in combination with other vinyl monomers. Also, (meth)acrylonitrile; (meth)acrylamides such as (meth)acrylamide, dimethyl (meth)acrylamide, N-alkoxymethylated (meth)acrylamide or diacetone acrylamide; N-vinyl lactam, - Nitrogen-containing vinyl compounds such as vinylpyrrolidone or N-methylimidazole; or nitrogen-containing vinyl monomers such as N,N-dialkylaminoalkyl (meth)acrylates such as dimethylaminoethyl (meth)acrylate are used in resins and coatings. 25% by weight or less, preferably 15
It should be used at less than % by weight. In addition, the dispersion stabilizer may be an unmodified vinyl copolymer or a fatty acid (glycidyl ester).
The same applies to vinyl copolymers modified with , so care must be taken. The thus obtained non-aqueous polymer dispersion (A) contains a dispersion stabilizer, preferably the above-mentioned unmodified vinyl copolymer, fatty acid (glycidyl ester) modified vinyl copolymer, or oil-modified and/or The resulting vinyl copolymer is dispersed in the parent monomer liquid in the presence of any of the fatty acid-modified alkyd resins, and the following polyisocyanate (B) is added to the non-aqueous polymer dispersion. (A)
The composition of the present invention can be obtained by blending OH/NCO with an equivalent ratio of 1/0.5 to 1/1.5. In this equivalent ratio, per equivalent of OH group
If the NCO group is less than 0.5 equivalent, it is difficult to obtain a composition with the desired physical properties of the coating film, and conversely, if the NCO group is more than 1.5 equivalent, the coating film may become brittle or
Both are unfavorable because they tend to foam easily. Here, typical examples of the polyisocyanate (B) include aromatic diisocyanates such as tolylene diisocyanate, xylylene diisocyanate or diphenylmethadiisocyanate; tetramethylene diisocyanate;
Aliphatic diisocyanates such as hexamethylene diisocyanate or trimethylhexane diisocyanate; isophorone diisocyanate, methylcyclohexane-2,4-(or -2,
6-) diisocyanate, 4,4'-methylenebis(cyclohexyl isocyanate) or 1,
Alicyclic diisocyanate such as 3-di(isocyanatomethyl)cyclohexane; or each of these diisocyanates and the polyhydric alcohols,
These are low molecular weight polyester resins (including oil-modified products) that are reactive with isocyanate groups, adducts with water, or biuret forms, and polymers (including oligomers) of the above-mentioned diisocyanates. ) etc. However, in the present invention, in particular, polyisocyanates other than aromatic diisocyanates and various derivatives thereof are used so that the cured coating film does not crack or yellow due to ultraviolet rays in terms of weather resistance. is preferable. It is also used in automotive refinish painting.
It goes without saying that if block bodies of the above-mentioned polyisocyanates that can be easily digested under temperature conditions of about 50 to 90°C are developed, such blocks can also be used. Furthermore, in the present invention, if necessary, a reaction accelerator for urethanization reaction can be used in a conventional amount to improve the curability of the coating film. Examples include organometallic compounds such as tin octylate, dibutyltin dilaurate or cobalt naphthenate; amine compounds such as triethylenediamine, N-methylmorpholine or diazabicycloundecane; or acidic compounds such as monobutyl phosphate or monobutyl phthalate. and so on. By the way, in the present invention, the vinyl copolymer (finally produced copolymer) itself can have such a function, not only by blending the urethanization reaction accelerator (C). A method of directly introducing it into such copolymer molecules may also be used. In such cases, among the vinyl monomers already mentioned, unsaturated carboxylic acids such as (meth)acrylic acid, phosphoric acid-containing vinyl monomers such as mono[β-hydroxyethyl (meth)acrylate] acid phosphate, etc. It is best to use basic nitrogen-containing vinyl monomers, such as dimethylaminoethyl (meth)acrylate, for coloring resins and coatings, improving adhesion to substrates and substrates, weather resistance, pot life, solubility, etc. From this point of view, depending on the properties of each of the above monomers, the amount may be within a range of 0.1 to 10% by weight, preferably 0.2 to 5% by weight, based on the total 100% by weight of all vinyl monomers used. The resin composition for paint of the present invention obtained in this manner may or may not contain a coloring pigment depending on whether it is used as a top coat or an undercoat when it is made into a paint. Therefore, since the above-mentioned ultraviolet absorber is used, so-called clear paints with a low pigment content or no pigment at all exhibit the most remarkable effect due to the ultraviolet absorber. Therefore, taking these points into consideration, the amount of pigment used should be kept as small as possible. Typical examples of such coloring pigments include metal materials mainly composed of powder or foil of aluminum, copper, or brass, titanium oxide, iron oxide, phthalocyanine blue, quinacridin, or carbon black. Any known and commonly used one can be used. In addition, the composition of the present invention may contain nitrocellulose or cellulose acetate butyrate to further increase the level of thinner resistance, gasoline resistance, corrosion resistance, flexibility, texture, and dryness. Cellulose compounds, various plasticizers such as dibutyl phthalate, polyester resins (including oil-modified types), other acrylic resins,
Resins such as epoxy resin or epoxy ester can also be used, and in addition,
Known and commonly used paint additives such as leveling agents, pigment dispersants, and antifoaming agents can be used in conventional amounts. In addition, the most common painting methods are brush painting and spray painting, and the curing conditions for the paint can be any of the conditions currently used for this type of automotive repair painting, but they can be applied at room temperature. Dry drying or forced drying at about 50 to 90°C is common. Next, the present invention will be specifically explained using reference examples, examples, and comparative examples. Unless otherwise specified, all parts and percentages are based on weight.
Also, "acid value" or "hydroxyl value" means
All of these are in the form of solutions or dispersions. Reference Example 1 (Preparation example of dispersion stabilizer) In a reactor equipped with a thermometer, stirrer, and reflux condenser, 83 parts of 2-ethylhexyl methacrylate (EHM) and 15 parts of 2-hydroxyethyl methacrylate (2-HEMA) were added. part, 2 parts of glycidyl methacrylate (GMA), di-t-
1.5 parts of butyl peroxide (DTBPO) and 400 parts of butyl acetate were charged and heated to 120°C while blowing nitrogen gas, and then EHM332
A mixture of 60 parts of 2-HEMA, 8 parts of GMA, 3.5 parts of azobisisobutyronitrile (AIBN), and 100 parts of butyl acetate was added dropwise over 3 hours, and the reaction was maintained at the same temperature for 7 hours. let it continue,
Thereafter, 5 parts of acrylic acid (AA), 0.2 parts of hydroquinone monomethyl ether (HQMME), and 0.1 part of BF ₃ -ethyl etherate are added and kept at the same temperature until the acid value becomes 1 or less to remove the nonvolatile content ( A dispersion stabilizer having a hydroxyl group as a functional group and an unsaturated bond from acrylic acid was obtained, which had a NV) of 51.5% and a viscosity (Gardner viscosity at 25° C.; hereinafter the same) of L to M. Hereinafter, this will be abbreviated as a powder stabilizer (SS-1). Reference Example 2 (Example of Preparation of Dispersion Stabilizer) 400 parts of butyl acetate was charged into the same reactor as in Reference Example 1, heated to 100°C while blowing nitrogen gas, and 415 parts of EHM, 75 parts of 2-HEMA, and 2-HEMA were added.
- A mixture consisting of 8 parts of methacryloyloxymonobutyl phthalate (MABP), 2 parts of AA, 3 parts of t-butyl peroctoate (TBPO), 2 parts of AIBN, and 100 parts of butyl acetate was added dropwise over 4 hours, and then the same temperature was added. hold for 1 hour, then
Add 2 parts of AIBN and keep at same temperature for 7 hours.
A dispersion stabilizer having a hydroxyl group as a functional group and an unsaturated bond from MMBP and having an NV of 49.7% and a viscosity of H to I was obtained. Hereinafter, this will be abbreviated as a dispersion stabilizer (SS-2). Reference Example 3 (Example of Preparation of Dispersion Stabilizer) Into the same reactor as in Reference Example 1, 2 parts of t-butyl perbenzoate (TBPB) and 200 parts of butyl acetate were charged, and the mixture was heated to 120 parts while blowing nitrogen gas.
Heat to 20 parts of styrene (ST), GMA
A mixture consisting of 169 parts and 5 parts of AIBN was added dropwise over a period of 6 hours and maintained at the same temperature for 6 hours.
Next, 311 parts of soybean oil fatty acid, 0.2 parts of HQMME and 0.1 part of triethylamine were added, and the temperature was maintained for another 12 hours.
&P naphtha” (low aromatic hydrocarbon manufactured by Ciel)
A dispersion stabilizer having a hydroxyl group as a functional group, a hydroxyl group, and an unsaturated bond from a soybean oil fatty acid was obtained by adding 300 parts of NV of 49.8% and a viscosity of M to N. Hereinafter, this will be abbreviated as a dispersion stabilizer (SS-3). Reference Example 4 (Example of Preparation of Dispersion Stabilizer) 3 parts of TBPB and 300 parts of butyl acetate were placed in the same reactor as in Reference Example 1, heated to 120°C while blowing nitrogen gas, and 94 parts of ST, 90 parts of EHM,
6 parts of a mixture consisting of 114 parts GMA and 8 parts AIBN
It was added dropwise over a period of time and maintained at the same temperature for 6 hours, then 196 parts of dehydrated castor oil fatty acid, 6 parts of mono-n-butyl fumarate, 0.2 parts of HQME and 0.1 part of 2-methylimidazole were added, and the temperature was further maintained at the same temperature.
Hold for 12 hours, then add 200 parts of "Super VM&P Naphtha" to obtain a solution with NV of 51.0% and viscosity of L~
A dispersion stabilizer named M having a hydroxyl group as a functional group and an unsaturated bond from dehydrated castor oil fatty acid and mono-t-butyl fumarate was obtained. Hereinafter, this will be abbreviated as a dispersion stabilizer (SS-4). Reference Example 5 (Example of Preparation of Dispersion Stabilizer) As a mixture for dropping, a mixture consisting of 80 parts of ST, 34 parts of t-butyl methacrylate (TBM), 86 parts of methacrylic acid (MA), and 5 parts of TBPO was used. After obtaining a base polymer in the same manner as in Reference Example 3, glycidyl oleate was added.
300 parts, 0.2 parts of hydroquinone and 0.1 parts of BF ₃ -ethyl etherate were added and the mixture was further heated to the same temperature.
The mixture was held for 12 hours, and then 300 parts of "Super VM&P Naphtha" was added to obtain a dispersion stabilizer having a hydroxyl group as a functional group and an unsaturated bond from glycidyl oleate, with an NV of 49.5% and a viscosity of K. Ta. Hereinafter, this will be abbreviated as a dispersion stabilizer (SS-5). Reference Example 6 (Preparation Example of Dispersion Stabilizer) 470 parts of soybean oil fatty acid and phthalic anhydride (PA) were placed in the same reactor as Reference Example 1 except that a decanter was used instead of the reflux condenser.
250 parts of trimethylolpropane (TMP)
300 parts of pentaerythritol, 27 parts of pentaerythritol, and 35 parts of xylene were reacted at 220°C for 10 hours by a solvent method using reflux dehydration of xylene to obtain an acid value of 5, a hydroxyl value of 70, and an oil length of 50. %, a medium oil alkyd resin that can be infinitely diluted with mineral spirits was obtained. Next, use mineral spirits to raise the NV to 50.
%, a dispersion stabilizer having a viscosity of T and having a hydroxyl group and an unsaturated bond from soybean oil fatty acid was obtained. This will be referred to as a dispersion stabilizer (SS-6) below.
It is abbreviated as Reference Example 7 (Preparation example of dispersion stabilizer) Same as Reference Example 1 except that 19.3 parts of monomethacryloyloxyethyl methacrylate was used instead of AA, with NV of 51.5% and viscosity of K.
A dispersion stabilizer having a hydroxyl group as a functional group and an unsaturated bond from monomethacryloyloxyethyl methacrylate was obtained. Hereinafter, this will be abbreviated as a dispersion stabilizer (SS-7). Reference Example 8 (Example of Preparation of Dispersion Stabilizer) In a reactor similar to Reference Example 1, 504 parts of butyl formaldehyde [formaldehyde/water/n-butanol = 40/10/50 (weight ratio)] and 144 parts of melamine were added.
parts, 112 parts of n-butanol, 40 parts of xylene,
Add 0.24 parts of PA and 1.36 parts of formic acid and heat to 100°C.
After heating to azeotropic distillation for about 3 hours to remove reaction product water, the NV was 70.0% and the viscosity was Z ₄ ~
A resin solution called _Z5 was obtained, which had a mineral spirit tolerance of over 2000%.
Methanol tolerance was 150%. below,
This is abbreviated as a dispersion stabilizer (SS-8). Reference Example 9 [Preparation example of non-aqueous polymer dispersion (A)] Dispersion stabilizer (SS-1) was added to a reactor equipped with a thermometer, a stirrer, and a reflux condenser.
200 parts of ST and 300 parts of an aliphatic hydrocarbon mixture with a boiling point of 115 to 142°C were heated to 80°C while blowing nitrogen gas, and then 120 parts of ST
parts, 120 parts of methyl methacrylate (MMA),
100 parts of n-butyl acrylate (n-BA),
2-A mixture consisting of 60 parts of HEMA, 2 parts of benzoyl peroxide (BTO), 8 parts of TBPO, and 100 parts of the above aliphatic hydrocarbon mixture was added dropwise over 3 hours, and then kept at the same temperature for 6 hours. A milky white non-aqueous polymer dispersion having an NV of 51.9%, a viscosity of T, an acid value of 1.2, and a hydroxyl value of 35 was obtained. Hereinafter, this will be abbreviated as polymer dispersion (A-1). Reference example 10 (Preparation example of non-aqueous polymer dispersion (A)) Using the same amount of (SS-2) instead of (SS-1) as a dispersion stabilizer, as a mixture to be added dropwise.
180 copies of ST, 60 copies of MMA, 80 copies of n-BA, 2
-75 parts of HEMA, 5 parts of MA, 5 parts of BPO,
Using a mixture consisting of 3 parts of TBPO and 100 parts of an aliphatic hydrocarbon mixture with a boiling point of 115 to 142 °C,
NV was 50.3%, viscosity was Q-
A milky white non-aqueous polymer dispersion having an R ² value of 3.9 and a hydroxyl value of 40 was obtained. Hereinafter, this will be abbreviated as polymer dispersion (A-2). Reference Example 11 (Preparation example of non-aqueous polymer dispersion (A)) In a reactor similar to Reference Example 9, a dispersion stabilizer (SS
-6) 400 copies, 50 copies of “Super VM&P Naphtha”
and 150 parts of isobutyl acetate, heated to 80°C while blowing nitrogen gas, and heated to 2-
54 parts of HEMA, 50 parts of ethylene oxide adduct of monomethacryloyloxyethyl hexahydrophthalate (molar ratio = 1:1), 96 parts of ST, 50 parts of isobutyl methacrylate, 40 parts of MMA,
10 parts of MA, 100 parts of "Super VM & P Naphtha"
A mixture consisting of 1 part, 8 parts of BPO, and 3 parts of AIBN was added dropwise over 4 hours and kept at the same temperature for 12 hours, resulting in a NV of 51.3%, a viscosity of N to O, an acid value of 6.5, and a hydroxyl value of 60. A milky white non-aqueous polymer dispersion was obtained. Hereinafter, this will be abbreviated as polymer dispersion (A-3). Example 12 Dispersion stabilizer (SS-1) was added to a reactor equipped with a thermometer, stirrer and reflux codenser.
200 parts and 300 parts of an aliphatic hydrocarbon mixture with a boiling point of 115 to 142°C were charged and heated to 80°C while blowing nitrogen gas, and then 120 parts of ST,
120 parts of methyl methacrylate (MMA), n-
100 parts of butyl acrylate (n-BA), 2-
60 parts of HEMA, 2 parts of benzoyl peroxide (BPO), 8 parts of TBPO, 5 parts of butyl acetate
110 parts of an aliphatic hydrocarbon mixture having a boiling point of 115 to 142°C and 2-(2-hydroxy-3,5-di-tert-amyl phenyl) as an ultraviolet absorber.
A mixture consisting of 15 parts of -2H-benzotriazole was added dropwise over a period of 3 hours, and the mixture was kept at the same temperature for 6 hours, resulting in an NV of 50.9%, a viscosity of S to T, and an acid value of
A milky white non-aqueous polymer dispersion having a hydroxyl value of 1.3 and a hydroxyl value of 35 was obtained. Hereinafter, this polymer dispersion (A-
4). Reference Example 13 (Preparation example of non-aqueous polymer dispersion (A)) In a reactor similar to Reference Example 9, a dispersion stabilizer (SS
-3) 500 copies and “Super VM & Naphtha”
Add 200 parts of
Heat to 175 parts of MMA, 15 parts of n-BMA,
40 copies of EA, 20 copies of MMBP, 5 copies of BPO, 1 copy of AIBN
part, 60 parts of "Super VM &Naphtha", 5 parts of butyl acetate, and 2 parts as ultraviolet absorber.
15 parts of 2'-dihydroxy-4,4'-dimethoxy-benzophenone and ethyl-2-cyano-3,
A mixture consisting of 10 parts of 3-diphenyl acrylate was added dropwise over 3 hours and kept at the same temperature for 12 hours to produce a milky white product with an NV of 51.9%, a viscosity of J to K, an acid value of 4.3, and a hydroxyl value of 35. A non-aqueous polymer dispersion was obtained. Hereinafter, this will be abbreviated as polymer dispersion (A-5). Reference Example 14 (Preparation example of non-aqueous polymer dispersion (A)) In a reactor similar to Reference Example 9, a dispersion stabilizer (SS
-5) 600 copies, “Super VM & Naphtha” 100 copies
1 part and 80 parts of isobutyl acetate were heated to 80°C while blowing nitrogen gas, and 2-
43 copies of HEMA, 10 copies of "Carduura E", 2 copies of AA, 100 copies of MMA, 45 copies of n-BMA, TBPO
8 parts of AIBN, 3 parts of AIBN, 10 parts of butyl acetate, 100 parts of "Super VM &Naphtha", 15 parts of toluene,
and bis(2,2,
5 parts of 6,6-tetramethyl-4-piperidyl) sebacate and 2-(2-hydroxy-3,5
-di-tert-amylphenyl)-2H-benzotriazole was added dropwise over 3 hours and kept at the same temperature for 12 hours until the NV was 50.0%.
A milky white non-aqueous polymer dispersion having a viscosity of G, an acid value of 2.3, and a hydroxyl value of 50 was obtained. Hereinafter, this will be abbreviated as polymer dispersion (A-6). Reference Example 15 (Preparation example of non-aqueous polymer dispersion (A)) In a reactor similar to Reference Example 9, a dispersion stabilizer (SS
-6), 50 parts of "Super VM &Naphtha" and 150 parts of isobutyl acetate, heated to 80℃ while blowing nitrogen gas, and heated to 80℃ while blowing nitrogen gas.
54 parts of HEMA, 50 parts of ethylene oxide adduct of monomethacryloyl oxethyl hexahydrophthalate (molar ratio = 1:1), 96 parts of ST, 50 parts of isobutyl methacrylate, 40 parts of MMA,
10 copies of MA, 100 copies of "Super VM &Naphtha",
8 parts of BPO, 3 parts of AIBN, 5 parts of toluene and 2-hydroxy-4- as UV absorber
A mixture consisting of 5 parts of n-dodecyloxybenzophenone was added dropwise over time and kept at the same temperature for 12 hours, resulting in an NV of 50.5%, a viscosity of ^N2 -O, and an acid value of 7.0.
A milky white non-aqueous polymer dispersion having a hydroxyl value of 60 was obtained. Hereinafter, this will be referred to as polymer dispersion (A-7).
It is abbreviated as Reference Example 21 [Preparation example of polyisocyanate (B)] 134 parts of TMP and 205 parts of coconut oil fatty acid were charged into a reactor equipped with a thermometer, a stirrer, and a cooler, and heated to 200°C. After reacting until the acid value becomes 5 or less while removing the water produced by the reaction,
After cooling to 120°C, 148 parts of PA was gradually added at the same temperature, then the reaction was continued by keeping at the same temperature until the acid number reached about 120, and then the reaction was continued at 150°C.
250 parts of Cardulla E was added dropwise over 1 hour, being careful not to generate heat, and the reaction was continued by maintaining the same temperature until the acid value became 5 or less.
℃, 340 parts of butyl acetate was added thereto, 329 parts of 1,3-bis(isocyanatemethyl)cyclohexane and 400 parts of butyl acetate were added over 1 hour, and then the mixture was heated at the same temperature. 2
After 2 hours of reaction at 90°C, NV was confirmed.
An alkyd-modified polyisocyanate prepolymer with an NCO group content of 60.5% and 11% was obtained. Hereinafter, this will be abbreviated as polyisocyanate (B-1). Examples 1 to 12 and Comparative Examples 1 to 17 With the paint formulation ratios shown in Table 1 (white enamel paint) and Table 2 (2C1B type paint), Examples 1 to 4 and Comparative Examples 1 to 8 were White enamel paint, on the other hand, Examples 5 to 12 and Comparative Examples 9 to
17 prepared the 2C1B type paint, but first, Examples 1 to 2C1B were prepared.
4 and Comparative Examples 1 to 8, Examples 1 to 4
Now, each polymer dispersion (base resin) obtained in Reference Examples 12 to 15, the polyisocyanate obtained in Reference Example 16, and each commercially available curing agent (all are non-yellowing type polyisocyanates). Comparative Example 1
In ~3, each commercially available acrylic polyol for automotive refinish paint and each commercially available curing agent (same as above) were used as the main ingredients, and in Comparative Examples 4 to 7, each commercially available acrylic urethane automotive refinish paint () to () was used, and then ,
In the case of Examples 5 to 12 and Comparative Examples 9 to 17, in Examples 5 to 12, both the top clear coat and the metallic base coat were applied to Reference Examples 9, 10, 11,
Each polymer dispersion obtained in 13 and 14 or each acrylic polyol for commercially available automobile refinish paints was used as the main agent, and in Comparative Examples 9 to 14, each acrylic polyol for automobile refinish paints was used as the main agent for both the top clear coat and metallic base coat. , Examples 5 to 12 and Comparative Example 8 were used as curing agents.
In Comparative Examples 14 to 16, a commercially available non-yellowing type polyisocyanate called "Bernok DN-950" (product of Dainippon Ink and Chemicals Co., Ltd.) was used. and metallic-based coats were used. In Examples 1 to 4 and Comparative Examples 1 to 3, the base agent, solvent, and pigment were mixed in the proportions shown in Table 1, and then ground in a sand mill for 90 minutes to form a white enamel base. Although it was prepared,
In any case, the urethane repair paint is obtained by adding a hardening agent to the white enamel base before painting, and when painting, the viscosity of the paint is adjusted to a certain level with diluting thinner.
In the case of Examples 1 to 4, "Super VM&P naphtha"/
In the case of Comparative Examples 1 to 3, a mixed solvent of "LAWS" (product of Ciel)/butyl acetate/cellosolve acetate = 35/30/25/10 (weight ratio) was used; National Etsuso Standard Co., Ltd. product) / Ethyl acetate / Butyl acetate / Cellosolve acetate = 40 / 20 / 10 /
A mixed solvent of 10/100 (weight ratio) was used. On the other hand, in the coatings in Examples 5 to 12 and Comparative Examples 8 to 13, the composition ratios shown in Table 2 were used,
In the case of a top clear coat, only the main agent is mixed, and in the case of a metallic base coat, the main agent and aluminum paste are mixed so that the PWC is 10%, and in either case, a hardening agent is further added before painting. Both coats are prepared, and the amount of curing agent used for both coats is OH/
The equivalence ratio is NCO=1:1. In addition, during painting, the coating viscosity is adjusted to a constant level using diluting thinner, and the diluting thinner used is the polymer dispersion obtained in Reference Examples 9, 10, 11, 13, and 14 as the main ingredient. When used, "Super VM & P naphtha" / "LAWS" /
Butyl acetate/cellosolve acetate = 35/30/
In other cases, a mixed solution of 25/10 ((weight ratio):
A mixed solvent of 40/20/10/10/10/10 (weight ratio) was used. Next, painting was carried out using Bonderite 144 treated dull steel plate as the base material in both Examples and Comparative Examples.
This was done by air spraying and then cured, but in both Examples and Comparative Examples, they were force-dried at 60° C. for 40 minutes and left for 3 days before being used for testing. A brief explanation of each commercial product listed in Tables 1 and 2 is as follows: "Acridik A-800 and A-801-P" are both manufactured by Dainippon Ink and Chemicals Co., Ltd. ( This is an acrylic polyol for automobile refinish paint manufactured by DIC (hereinafter abbreviated as DIC), with an NV of 50% and a hydroxyl value of 50, using toluene and butyl acetate as solvents.
In addition, DIC's ``Acrydik 54-270'' is an acrylic polyol for automotive refinish paints.
(NV = 50%, OHV = 35, solvent = toluene/xylene/butyl acetate), "Acridik 54-480"
(NV = 50%, OHV = 44, solvent = xylene/isobutyl acetate), "Acridik 44-198" (NV =
50%, OHV = 20, solvent = toluene/butyl acetate), "Acridik 47-567" (NV = 50%,
OHV = 30, solvent = same as above) and "Acridik A-852" (NV = 70%, OHV = 50, solvent = same as above).
70” (NV=70%, OHV=95, solvent=xylene/
methyl isobutyl ketone), and the company's alkyd polyol "Betucosol 57-
1347" [NV = 65%, OHV = 70, solvent = "Swazol 100" (product of Maruzen Sekiyu Co., Ltd.)] was used. In addition, “Bernock DM-970” (DIC product),
"Takenate D-140N" [Takeda Pharmaceutical Co., Ltd. product],
“Desmodeur N-75 and Z-4273” [products of Sumitomo Bayer Co., Ltd.], “IPDI T-1980” products of Hyuls, USA) and “Coronate EH” [products of Nippon Polyurethane Industries Co., Ltd.] are non-yellowing. type of polyisocyanate. Various performance tests were conducted on each paint obtained in each Example and Comparative Example. The results are shown in Tables 3 and 4. In Table 3, "Gloss" refers to 60 degree gloss, "Hardness" refers to the hardness of scratches caused by a pencil, and "Adhesiveness" refers to the number of remaining marks after drawing gongs and peeling them off with cellophane tape. "Impact resistance" with 1/2 inch notch,
The "bending" test means the case of a concave shape with a load of 500g, the "bending" test means the case of 2 mmφ x 180 degrees, and the "chemical resistance"
The presence or absence of whitening or blisters was visually determined after spot testing in 5% caustic soda aqueous solution and 5% sulfuric acid at room temperature for 24 hours, and "gasoline resistance" was determined by immersing the product in high-octane gasoline for 2 hours and removing it. The pencil hardness immediately after pulling and the returned hardness after another 2 hours (same as above) are both judged and evaluated. Therefore, the higher the hardness, and the smaller the difference between the hardness immediately after pulling and the returned hardness. , gasoline resistance is judged to be good. In addition, "weather resistance" is Sunshine, Weathero,
The evaluation was based on the gloss retention rate (%) after a 1,500-hour exposure test using a meter and after two years of outdoor exposure in Miyazaki City. Yes, “dryness”
The evaluation criteria are as follows. be. ◎...No gauze marks 〇...Some gauze marks △...Significant gauze marks ×...Severe gauze marks ××...Significant gauze marks In addition, "lifting property" is particularly important for the following It has been tested and evaluated according to the method. In other words, the mold test method is to first apply a commercially available Lutzker type primer/Surfacer to an old crosslinked coating such as urethane, thermosetting acrylic, or thermosetting polyester that has already been applied to a Bonderite 144-treated dull steel plate. Apply "New One Coat" manufactured by Isamu Paint Co., Ltd., force dry it at 60℃ for 40 minutes, leave it for a day and night, polish it with #400 waterproof paper, dry it, and then degrease it. Each of the paints of Examples 1 to 4 and Comparative Examples 1 to 7 was applied, and in this case, lifting appeared in the primer/Surfacer coating. Next, the mold test method is to apply commercially available urethane lacquer to the old lacquer film, such as nitrocellulose lacquer, modified acrylic lacquer, straight acrylic lacquer, or high-solid lacquer, that has already been painted on the above-mentioned treated steel plate. Apply a Surf Acer primer (Hipura Surf 2C, manufactured by the same company), force dry it at 60℃ for 40 minutes, leave it for a day and night, polish it with #400 waterproof paper, dry it, and then degrease it. Further, each of the paints of Examples 1 to 4 and Comparative Examples 1 to 7 is applied, and in this case lifting appears in the old paint film. On the other hand, "gloss", "hardness", "Erichsen", "impact resistance", "gasoline resistance" and "weather resistance" in Table 4 are as described above, but "adhesion"
A cross cut is inserted and peeled off with cellophane tape to check the releasability (interlayer peeling) between the top coat and base coat.Also, for ``metal unevenness'', a metallic base coat is applied and set for 30 minutes. Then, a top clear coat diluted to a spray viscosity was applied over the top clear coat and left to air dry overnight, and the "unevenness of return" of the metal was visually judged and evaluated, and the "finished appearance of the metallic" is an overall judgment based on visual inspection of metal unevenness, surface gloss, watermarks, and texture.

[Table] A mixed solvent was used.

【table】

【table】

【table】

【table】

【table】

【table】

Claims (1)

[Claims] 1. 0.1 to 10% by weight based on 100% by weight of the vinyl monomer in a non-polar organic liquid or an organic liquid with relatively low solubility and in the presence of a dispersion stabilizer.
A non-aqueous dispersion of a vinyl copolymer having a functional group that is reactive with isocyanate groups, obtained by adding and mixing a UV absorber and dispersing a vinyl monomer containing the UV absorber. Liquid (A)
At an equivalent ratio of OH/NCO=1/0.5 to 1/1.5,
A resin composition for automotive refinish paints that does not attack existing paint films, which is blended with polyisocyanate (B) or, if necessary, with a reaction accelerator (C) for urethanization reaction. . 2. The composition according to claim 1, wherein the dispersion stabilizer of the non-aqueous dispersion is a vinyl copolymer. 3. The composition according to claim 1 or 2, wherein the dispersion stabilizer of the non-aqueous dispersion is a vinyl copolymer modified with a fatty acid or a glycidyl ester of a fatty acid. thing. 4. The composition according to claim 1, wherein the dispersion stabilizer of the non-aqueous dispersion is a fatty acid and/or an oil-modified alkyd resin.