JP2007231081A - Method for producing modified vinyl resin and method for producing one-part crosslinkable coating composition - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a method for producing a modified vinyl resin giving a one-part crosslinkable coating composition that is good in workability such as initial dryability, slight in affecting prime coating film, excellent in the weatherability and chemical resistance of the resulting coating film, and also good in adhesivity to a base material such as coating film formed using an epoxy coating, and to provide a method for producing such a one-part crosslinkable coating composition using the modofied vinyl resin. <P>SOLUTION: The method for producing the modified vinyl resin comprises conducting a reaction in an aliphatic hydrocarbon solvent between (A) an epoxy group-containing vinyl resin modified with an unsaturated fatty acid, for example, obtained by reaction between (a1) an epoxy group-containing vinyl resin and (a2) an unsaturated fatty acid under such a condition that the epoxy groups are excess to the carboxy groups, (B) an alkyl acid phosphate and (C) an acetoacetoxyalkyl ester. The method for producing the one-part crosslinkable coating composition comprises mixing the thus obtained modified vinyl resin and a metallic dryer together. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

  The present invention relates to a method for producing a modified vinyl resin from which a one-component cross-linking coating composition excellent in initial drying property, recoating property, chemical resistance, weather resistance and adhesion, and one component using this modified vinyl resin. The present invention relates to a method for producing a crosslinked coating composition. More specifically, a one-component cross-linking top coating composition suitable for repairing any old coating film for interior and exterior of a building, particularly a one-component cross-linking top coating composition suitable for top coating when the undercoat is an epoxy coating. The present invention relates to a method for producing a modified vinyl resin that can be obtained, and a method for producing a one-component crosslinking coating composition using the modified vinyl resin. The present invention also relates to a modified vinyl resin from which a one-liquid cross-linking coating composition suitable for top coating or undercoating on various substrates such as concrete, siding board, extrusion molding plate, metal, glass, magnetic tile, plastic and the like can be obtained. And a method for producing a one-component crosslinking coating composition using this modified vinyl resin.

  Organic solvent-based vinyl resins having excellent coating performance have been widely used as paint binders. However, in recent years, so-called weak solvent-based paints mainly composed of aliphatic hydrocarbons that are optically inert in terms of air pollution and environmental load have been widely used. Especially in the field of repair coatings such as buildings that are rapidly increasing, it is possible to work at low temperatures in winter, which was difficult with conventional emulsion paints, and it has better resistance to resistance than conventional alkyd paints. Weakly solvent-based vinyl paint because it has both alkalinity, weather resistance and quick-drying properties, and it has good workability in painting methods such as sprays, brushes, and rollers, which are usually used for repairs, and is less toxic. Is mainly used.

  Among these weak solvent-based vinyl paints, the conventional non-crosslinked one-pack type weak solvent-based paints were good in terms of ease of use, but because of their inherently poor solvent resistance, There was a serious drawback that the base paint was dissolved and the appearance was remarkably deteriorated at the time of recoating during repair. Furthermore, since the water resistance, solvent resistance, weather resistance and the like are lower than those of the cross-linking paint, the range of use is limited.

  In order to improve this, an oxidation polymerization type one-pack crosslinked coating using a fatty acid-modified vinyl resin having excellent performance in terms of weather resistance, water resistance and solvent resistance is used. However, for metal substrates, particularly when an epoxy paint is provided as an undercoat layer for the purpose of ensuring corrosion resistance, adhesion to a coating film formed using such an epoxy paint is not always sufficient. In addition, problems such as lifting are likely to occur, and the range of use is still limited.

  As a technique for avoiding such problems, a so-called weak solvent type two-component acrylic urethane coating, in which a hydroxyl group is introduced into a vinyl resin composition and cured with polyisocyanate, is applied to a coating film having poor solvent resistance. However, the cured coating film has good coating performance such as weather resistance, water resistance, chemical resistance, etc., and good solvent resistance. In recent years, the demand for repair coatings has been greatly increased in the repair market because it has the performance required for repair coatings so that no coating defects will occur even if it is repaired with any coating material (for example, (See Patent Document 1).

  However, although weak solvent-based two-component acrylic urethane paints have good performance such as recognizability and weather resistance, they are two-component types that are cumbersome to handle. Since there is only half a day from the time, there is a big problem on the work surface, such as the paint remaining after compounding cannot be used the next day.

  Furthermore, weak solvent two-component acrylic urethane paints are generally dilutable with weak solvent paint thinners mainly composed of aliphatic hydrocarbons used as diluents for paints for interior and exterior of buildings. It is bad, and there is a problem that the viscosity of the paint becomes too high especially when used at low temperatures such as in winter.

  Under such circumstances, it has excellent workability and dilutability, and has coating properties such as weather resistance, water resistance and chemical resistance comparable to weak solvent type two-component acrylic urethane paints. One-component cross-linkable weak solvent paint with excellent adhesion to the undercoat layer made of paint is highly desired in the market and contains a specific acetoacetyl group-containing acrylic resin and a metal chelate compound as a cross-linking component A resin composition has been proposed (see, for example, Patent Document 2), but the coating performance such as solvent resistance and water resistance and adhesion to an undercoat made of an epoxy coating are not always sufficient.

Japanese Patent Laid-Open No. 03-188170 Japanese Patent Laid-Open No. 08-231810

  That is, the problem to be solved by the present invention is a one-component cross-linking type that is excellent in workability such as initial drying property, has little influence on the base coating film, and has weather resistance and chemical resistance ( A modified vinyl resin that provides a coating composition that is particularly excellent in alkali resistance at a level that can be used for inorganic substrates, and that also has excellent adhesion to substrates such as coatings formed using epoxy coatings. And a method for producing a one-component crosslinking coating composition using the modified vinyl resin.

  As a result of intensive studies to solve the above problems, the present inventors react an epoxy group-containing vinyl resin modified with an unsaturated fatty acid with a compound having a specific functional group in an aliphatic hydrocarbon solvent. It has been found that the use of an oxidation-polymerized modified vinyl resin obtained by the production method makes it possible to easily produce a one-component cross-linking coating composition that achieves the above object, and the present invention has been completed.

  That is, the present invention reacts an epoxy group-containing vinyl resin (A) modified with an unsaturated fatty acid, an acidic phosphate ester (B), and an acetoacetoxyalkyl ester (C) in an aliphatic hydrocarbon solvent. A method for producing a modified vinyl resin is provided.

  The present invention also provides a method for producing a one-component cross-linking coating composition characterized by mixing a modified vinyl resin obtained by the method for producing a modified vinyl resin and a metal dryer.

  According to the present invention, the conventional one-component acrylic non-aqueous dispersion-based white paint level has initial drying properties, recoating properties, chemical resistance (alkali resistance), and weather resistance, and is an epoxy which is a conventional problem. A one-component cross-linking type coating composition having excellent adhesion to a coating film or the like can be obtained.

Hereinafter, the present invention will be described in detail based on the embodiments.
The solvent used in the present invention is an aliphatic hydrocarbon solvent mainly composed of aliphatic hydrocarbons, preferably having an aliphatic hydrocarbon content of 50% by weight or more, more preferably aliphatic hydrocarbons. The thing of 60 weight% or more of content rate is mentioned. Here, the expression “aliphatic hydrocarbon” includes not only a linear or branched aliphatic hydrocarbon but also a cyclic aliphatic hydrocarbon (that is, an alicyclic hydrocarbon).

  Examples of the aliphatic hydrocarbon solvent include “AF Solvent” (manufactured by Nippon Oil Co., Ltd.), “IP Solvent 1016, 1020 or 1620” (manufactured by Idemitsu Kosan Co., Ltd.), “Exol D-30, D -40, D-60 or D-70 "," Isopar C, E, G or H "[Exxon Chemical Co., Ltd.]," Swaclean "(Maruzen Petrochemical Co., Ltd.)," Rikasolv 900 " New Nippon Rika Co., Ltd.], aliphatic hydrocarbon solvents such as n-hexane and n-heptane; “Marcazole R or E”, “Swazol 310” [above, manufactured by Maruzen Petroleum Co., Ltd.], “LAWS” “HAWS”, “Shellsol 70 or 71” (manufactured by Shell of the Netherlands), “Diana Solvent No. 0 or No. 1” (manufactured by Idemitsu Kosan Co., Ltd.), “Exon naphtha” o.3, No. 5 or No. 6 ”[Exxon Chemical Co., Ltd.],“ Shellsol D-40 ”[Netherlands Shell Co., Ltd.],“ Sorvesso 100 ”[Exxon Chemical Co., Ltd.] In particular, it is possible to obtain a coating composition which is a solvent that does not easily attack the old coating film while maintaining the stability of the resin, and that has good paint workability with a brush or a roller. "LAWS" (manufactured by Shell) or "Solvesso 100" (manufactured by Exxon Chemical) is preferable.

  In addition, as the aliphatic hydrocarbon solvent, if necessary, aromatic hydrocarbon solvents such as toluene, xylene, etc .; acetate solvents such as ethyl acetate, butyl acetate, etc .; methyl ethyl ketone , Ketone solvents such as methyl isobutyl ketone; propylene glycol ether solvents, propylene glycol ether ester solvents or ethoxyethyl propionate can be used together, but the content of aliphatic hydrocarbons in the combined use is It is preferably 50% by weight or more, and more preferably 60% by weight or more.

  The method for producing the epoxy group-containing vinyl resin (A) modified with the unsaturated fatty acid is not particularly limited. For example, the epoxy group-containing radical polymerizable monomer (a1) and other copolymerizable monomers can be used. It can be obtained by reacting an epoxy group-containing vinyl copolymer obtained using the monomer (a2) with an unsaturated fatty acid (a3).

  Hereinafter, a method for producing an epoxy group-containing vinyl resin (A) modified with an unsaturated fatty acid by the above method will be described.

  First, as the epoxy group-containing radical polymerizable monomer (a1), (methyl) glycidyl (meth) acrylate, β-methylglycidyl (meth) acrylate, (meth) allyl glycidyl ether or the like;

Like equimolar adducts of α, β-ethylenically unsaturated carboxylic acids or hydroxyl group-containing vinyl monomers such as mono-2- (meth) acryloyloxymonoethyl phthalate and various polycarboxylic anhydrides An epoxy group-containing polymerizable compound obtained by addition reaction of an unsaturated carboxylic acid with a polyepoxy compound having at least two epoxy groups in one molecule at an equimolar ratio or less; it can.

  As the other copolymerizable monomer (a2), various compounds from the following group (a) to group (l) can be used.

  (A) Styrene monomers such as styrene, vinyl toluene, p-methyl styrene, ethyl styrene, propyl styrene, isopropyl styrene or p-tert-butyl styrene;

  (B) Methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, i-propyl (meth) acrylate, n-butyl (meth) acrylate, i-butyl (meth) acrylate, tert-butyl (meta ) Acrylate, sec-butyl (meth) acrylate, octyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, lauryl (meth) acrylate, “acryl ester SL” [Mitsubishi Rayon Co., Ltd., 12-carbon 13-methacrylate mixture], alkyl (meth) acrylates such as stearyl (meth) acrylate; cyclohexyl (meth) acrylate, 4-tert-butylcyclohexyl (meth) acrylate, isobornyl (meth) acrylate, adamantyl (meth) (A) (meth) acrylates containing no functional group in the side chain such as acrylate and benzyl (meth) acrylate;

  (C) 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 3-hydroxybutyl (meth) acrylate, 4- Hydroxybutyl (meth) acrylate, 3-chloro-2-hydroxypropyl (meth) acrylate, di-2-hydroxyethyl fumarate, mono-2-hydroxyethyl-monobutyl fumarate, polyethylene glycol mono (meth) acrylate, polypropylene Α such as glycol mono (meth) acrylate, adducts of these glycol mono (meth) acrylate and ε-caprolactone, “Placcel FM or FA monomer” (caprolactone addition monomer manufactured by Daicel Chemical Industries, Ltd.) Hydroxyalkyl esters of β- ethylenically unsaturated carboxylic acid;

  (D) Unsaturated mono- or dicarboxylic acids such as (meth) acrylic acid, crotonic acid, maleic acid, fumaric acid, itaconic acid or citraconic acid, dicarboxylic acid monoesters such as monoethyl fumarate and monobutyl maleate, Hydroxyl group-containing (meth) acrylates and polycarboxylic acids such as succinic acid, maleic acid, phthalic acid, hexahydrophthalic acid, tetrahydrophthalic acid, benzenetricarboxylic acid, benzenetetracarboxylic acid, "Hymic acid", tetrachlorophthalic acid, etc. Adducts with anhydrides, etc .;

  (E) alkoxyalkyl (meth) acrylates such as methoxyethyl (meth) acrylate, ethoxyethyl (meth) acrylate, methoxybutyl (meth) acrylate;

  (F) Diesters of dicarboxylic acids and monohydric alcohols such as dimethyl maleate, diethyl maleate, diethyl fumarate, di (n-butyl) fumarate, di (i-butyl) fumarate, dibutyl itaconate;

  (G) Vinyl esters such as vinyl acetate, vinyl benzoate, “Beoba” (a vinyl ester of a branched (branched) aliphatic monocarboxylic acid manufactured by Shell of the Netherlands);

  (H) “Biscoat 3F, 3FM, 8F, 8FM or 17FM” (fluorine-containing acrylic monomers manufactured by Osaka Organic Chemical Co., Ltd.), perfluorocyclohexyl (meth) acrylate, di-perfluorocyclohexyl fumarate, N- (per) fluoroalkyl group-containing vinyl esters such as i-propylperfluorooctanesulfonamidoethyl (meth) acrylate, (per) fluoroalkyl group-containing vinyl ethers, (per) fluoroalkyl group-containing (meth) acrylates, ( Fluorinated polymerizable compounds such as per) fluoroalkyl group-containing unsaturated polycarboxylic acid esters;

  (Li) Vinylethoxysilane, γ- (meth) acryloxypropyltrimethoxysilane, γ- (meth) acryloxypropyltriethoxysilane, γ- (meth) acryloxypropyltripropoxysilane, γ- (meth) acryloxy Propylmethoxydimethoxysilane, γ- (meth) acryloxypropylmethoxydiethoxysilane, γ- (meth) acryloxypropylmethoxydipropoxysilane, γ- (meth) acryloxybutylphenyldimethoxysilane, γ- (meth) acryloxy Silane monomers such as butylphenyldiethoxysilane, γ- (meth) acryloxybutylphenyldipropoxysilane, γ- (meth) acryloxypropyldimethylmethoxysilane, γ- (meth) acryloxypropyldimethylethoxysilane ;

  (Nu) (meth) acrylamide, N-methylol (meth) acrylamide butyl ether, amide bond-containing vinyl monomers such as dimethylaminopropyl acrylamide; dialkyl [(meth) acryloyloxyalkyl] phosphates, (meth) acryloyloxy Phosphorus atom-containing vinyl monomers such as alkyl acid phosphates, dialkyl [(meth) acryloyloxyalkyl] phosphites, (meth) acryloyloxyalkyl acid phosphites;

  (L) An alkyd resin (polyester resin) containing an oil component having an unsaturated double bond, a so-called oil-free polyester resin having no unsaturated double bond, into which an unsaturated double bond is introduced can be used. .

  Using these epoxy group-containing radically polymerizable monomers (a1) and other copolymerizable monomers (a2) as shown in the above (a) to (l), various copolymers are made. An epoxy group-containing vinyl copolymer can be produced by a method such as a reaction method or a grafting reaction method (graft copolymerization reaction method), but a solution radical polymerization method is particularly preferred.

  In that case, azobisisobutyronitrile (AIBN), benzoyl peroxide (BPO), tert-butyl perbenzoate (TBPB), tert-butyl hydroperoxide (TBHPO), di-tert-butyl peroxide (DTBPO) ), Cumene hydroperoxide (CHP) or o, o-tert-o- (1,2,2,6,6-pentamethyl-4-piperidinyl) monoperoxycarbonate (radical generating polymerization catalyst) Or radical polymerization initiators) can be used alone or in combination of two or more.

  The epoxy group-containing vinyl copolymer solution obtained as described above is reacted with an unsaturated fatty acid (a3) such as a (semi) drying oil fatty acid to contain an epoxy group modified with an unsaturated fatty acid. A solution of the vinyl resin (A) is obtained. As a reaction method at that time, the epoxy group-containing vinyl copolymer solution and the unsaturated fatty acid (a3) are allowed to coexist and heated, whereby the epoxy group contained in the epoxy group-containing vinyl copolymer solution is heated. A carboxyl group contained in the saturated fatty acid (a3) is easily added to obtain an epoxy group-containing vinyl resin (A) modified with an unsaturated fatty acid.

  In this case, in order to leave the epoxy group after adding the unsaturated fatty acid (a3), the amount of the unsaturated fatty acid (a3) added is the amount of the unsaturated fatty acid (a3) relative to the epoxy group of the epoxy group-containing vinyl copolymer. ) Carboxyl group molar ratio is required to be less than equimolar, and the epoxy group / carboxyl molar ratio is preferably in the range of 1.0 / 0.9 to 1.0 / 0.3. Of these, the range of 1.0 / 0.7 to 1.0 / 0.5 is more preferable.

  In addition, a tertiary amine such as N, N-dimethylaminoethanol and 2-methylimidazole, and a quaternary ammonium salt such as tetrabutylammonium bromide, as necessary, during the addition reaction of the unsaturated fatty acid (a3) to the epoxy group It is effective to shorten the reaction time to use an appropriate amount of the reaction catalyst.

  Examples of the unsaturated fatty acid (a3) include unsaturated fatty acids such as oleic acid, linoleic acid, linolenic acid, eleostearic acid, ricinoleic acid; “Pamorin 200 or 300” (synthetic drying oil fatty acid manufactured by Hercules, USA) ), (Semi) drying oils (fatty acids) such as China tung oil fatty acid, flaxseed oil fatty acid, dehydrated castor oil fatty acid, tall oil fatty acid, cottonseed oil fatty acid, soybean oil fatty acid, olive oil fatty acid, safflower oil fatty acid, castor oil fatty acid, rice bran oil fatty acid Can be used.

  The iodine value of these unsaturated fatty acids (a3) is preferably 100 or more, more preferably 120 or more from the viewpoint of coating performance (film resistance), although there is no particular upper limit, most preferably 120-160.

  Here, the proportion of the unsaturated fatty acid in the epoxy group-containing vinyl resin (A) modified with the unsaturated fatty acid is preferably 5 to 50% by weight in terms of solid content. In addition, a coating composition having a good overall balance of drying performance and the like can be obtained. In this respect, the more preferable range of the ratio is 5 to 30% by weight, and even more preferably 8 to 20% by weight.

  The modified vinyl resin is obtained by reacting the epoxy group-containing vinyl resin (A) modified with the unsaturated fatty acid obtained as described above, the acidic phosphate ester (B), and the acetoacetoxyalkyl ester (C). Obtainable.

  The reaction conditions when the epoxy group-containing vinyl resin (A) modified with the unsaturated fatty acid (A), the acidic phosphate ester (B), and the acetoacetoxyalkyl ester (C) are not particularly limited, but the reaction temperature is usually It is in the range of 80 to 200 ° C., preferably 100 to 150 ° C., and the reaction time is in the range of 1 to 24 hours, preferably 3 to 12 hours. In this reaction, the method for adding the epoxy group-containing vinyl resin (A) modified with an unsaturated fatty acid, the acidic phosphate ester (B), and the acetoacetoxyalkyl ester (C) is not particularly limited. For example, acidic phosphoric acid ester (B) and acetoacetoxyalkyl ester (C) are separately added to epoxy resin containing vinyl resin (A) modified with unsaturated fatty acid, for example, by adding these three components at once. The method etc. are mentioned.

  As said acidic phosphate ester, the compound shown by following General formula (1) is mentioned, for example.

（式中、Ｒ_１は炭素数１〜１３のアルキル基を表す。）

(In the formula, R ₁ represents an alkyl group having 1 to 13 carbon atoms.)

  Examples of the compound represented by the general formula (1) include “DP-4” [dibutyl phosphate manufactured by Daihachi Chemical Industry Co., Ltd.], “DP-8” [manufactured by Daihachi Chemical Industry Co., Ltd. 2-ethylhexyl phosphate] and the like. The use ratio is 0.5 to 5.0 parts by weight with respect to 100 parts by weight of the epoxy resin-containing vinyl resin (A) modified with an unsaturated fatty acid because a modified vinyl resin having excellent stability and the like is obtained. The range is preferable, and the range of 0.5 to 2.0 parts by weight is more preferable.

  As said acetoacetoxyalkyl ester (C), the compound shown by following General formula (2) is mentioned, for example.

（式中、Ｒ_２は炭素数１〜１０のアルキル基を表す。）

(In the formula, R ₂ represents an alkyl group having 1 to 10 carbon atoms.)

  Examples of the compound represented by the general formula (2) include acetoacetoxyethyl ester (manufactured by Eastman Chemical Japan), acetoacetoxy tertiary butyl ester (manufactured by Eastman Chemical Japan), and the like. The use ratio is 1.0 to 20.0 parts by weight with respect to 100 parts by weight of the epoxy resin-containing vinyl resin (A) modified with an unsaturated fatty acid because a modified vinyl resin having excellent water resistance is obtained. Is preferable, and the range of 1.0 to 10.0% by weight is more preferable.

  The number average molecular weight of the modified vinyl resin is preferably in the range of 3,000 to 30,000, more preferably 4,000 to 20 because of excellent paint performance (film resistance) and good handling of the resin solution. , 000.

  A non-aqueous dispersion resin composition as disclosed in JP-A-9-316275, particularly a non-aqueous dispersion using a fatty acid-modified vinyl resin solution as a dispersion stabilizer for the modified vinyl resin thus obtained. There is nothing wrong with using a John resin composition together.

  In order to obtain a one-pack crosslinkable coating composition using the modified vinyl resin, the modified vinyl resin and a metal dryer may be mixed together with other components as necessary. Among them, a sand mill, a ball mill, a three roll, It is preferable to knead using a kneading apparatus such as a paint conditioner. As the metal dryer, any of various metal dryers such as cobalt-based, lead-based, zirconium-based, calcium-based, etc. can be used. These may be used alone or in combination of two or more. The preferred amount used is 0.01 to 10 parts by weight, more preferably 0.1 to 5 parts by weight, based on 100 parts by weight of the solid content of the modified vinyl resin. It is.

  If the amount of the metal dryer used is within the above range, the oxidative polymerization is difficult to proceed, so that the coatability does not become poor, the stability of the paint is good, and the paint or paint film is discolored. There is no harmful effect and the water resistance, chemical resistance, weather resistance and the like can be further improved.

  Further, in the method for producing a one-component crosslinking coating composition of the present invention, a modified vinyl resin and a metal dryer are mixed together with various pigments such as titanium oxide and kneaded, or dispersed pigments and processed pigments. It is possible to produce so-called enamel paints by mixing them, or to produce metallic paints by dispersing aluminum powder, or to use so-called clear paints without using such pigments. Can also be manufactured.

  In the case of coating, for example, pigment dispersing agents such as “Disperbyk-161, BYK-P104” (manufactured by Big Chemie, Germany); leveling agents such as “BYK-302” (manufactured by Big Chemie, Germany) Defoaming agents such as “BYK-065” (manufactured by Big Chemie, Germany), “Disparon OX-70” (manufactured by Enomoto Kasei Co., Ltd.); “Disparon 6820-20M” (manufactured by Enomoto Kasei Co., Ltd.) Anti-sagging agents such as “Tinuvin P, 328” (manufactured by Ciba-Geigy, Switzerland), etc .; Lights such as “Chinubin 770, 765” (manufactured, by Ciba-Geigy, Switzerland) Stabilizers; various paint additives such as antifungal agents can be used.

  In addition, as an auxiliary crosslinking agent, the above dryers, aluminum-based, zirconium-based, titanium-based metal alkoxides, metal acylates, metal chelates {for example, “acetope” (manufactured by Hope Pharmaceutical Co., Ltd.), “ Chita Coat ”(manufactured by Nippon Soda Co., Ltd.),“ Plenact ”(manufactured by Ajinomoto Co., Inc.),“ Orgachix TA Series, TC Series, ZA Series, ZB Series, ZC Series, AL Series ”[Matsumoto Pharmaceutical Co., Ltd. ], "AIPD, AMD, ASBD, ALCH series" (manufactured by Kawaken Fine Chemical Co., Ltd.), "Aluminum Chelate A, D, M" (manufactured by Kawaken Fine Chemical Co., Ltd.), "Tencalate TP Series" [Tenka Polymer ( Etc.] can be used as long as the effects of the present invention are not impaired.

  Furthermore, plasticizers may be used for the purpose of improving the performance so long as they are soluble in the organic solvents used by being compatible with the one-component crosslinking coating composition obtained by the production method of the present invention. First, other resins, for example, acrylic copolymers, fibrin compounds, acrylated alkyd resins, alkyd resins, silicon resins, fluororesins, epoxy resins, etc. should be used as appropriate. However, even in such a case, it is possible to use various kinds of those listed above within a range not departing from the object of the present invention or within a range not impairing the effect of the present invention. it can.

  Examples of pigments include, for example, inorganic pigments such as titanium oxide, carbon black, petal, yellow flower; organic pigments such as cyanine blue and cyanine green; so-called extender pigments such as calcium carbonate, precipitated barium sulfate, talc, and clay; dispersion Examples thereof include pigments and processed pigments. The pigment is mixed together when the modified vinyl resin and the metal dryer and / or other additives are mixed, for example, kneaded using a kneading apparatus such as a sand mill, a ball mill, a three-roll, a paint conditioner, and dispersed. Can be made.

  The one-component cross-linking type coating composition obtained by the production method of the present invention can be applied to any old coating film, and has an optimum performance especially for repairing for building interior and exterior, It can also be applied to the objects to be coated (base materials) as listed below.

  In other words, if only typical examples of the above-mentioned base materials are shown as examples, aluminum sashes made of various metal materials such as aluminum, stainless steel, chrome plating, tin plate, tin plate, metal such as gates, etc. Products; tiles; various building interior and exterior materials such as building exterior walls and inorganic building materials.

  In painting at that time, various means such as spray, brush or roller can be used.

  Next, the present invention will be described more specifically with reference examples, examples and comparative examples. In the following, all parts and% are based on weight unless otherwise specified, except for 60 degree gloss retention in the weather resistance test.

Example 1
A four-necked flask equipped with a stirrer, a thermometer, a reflux condenser and a nitrogen gas inlet tube is equipped with “LAWS” (a mixture of aromatic hydrocarbons and aliphatic hydrocarbons containing 70% aliphatic hydrocarbons as the main component). A mixed organic solvent, boiling point 155 to 196 ° C., aniline point 44.5 ° C. (manufactured by Shell), 500 parts was charged, and the temperature was raised to 120 ° C. At this temperature, 75 parts of glycidyl methacrylate (hereinafter abbreviated as “GMA”), 100 parts of styrene (hereinafter abbreviated as “St”), isobutyl methacrylate (hereinafter referred to as “i-BMA”). Abbreviated.) 600 parts, 2-ethylhexyl acrylate (hereinafter abbreviated as “2-EHA”) 85 parts, 2-hydroxyethyl methacrylate (hereinafter abbreviated as “β-HEMA”) 40 parts, perbutyl O A mixture of 10 parts, 4 parts of perbutyl Z, and 500 parts of “LAWS” was added dropwise over 4 hours, held at the same temperature for 4 hours, and then 50 parts of dehydrated castor oil fatty acid (hereinafter abbreviated as “DCOFA”). , 50 parts of soybean oil fatty acid (hereinafter abbreviated as “SoyFA”) and 1 part of 2-methylimidazole were added and kept at the same temperature for 8 hours. A solution of an epoxy group-containing vinyl resin (A1) modified with a saturated fatty acid was obtained. Furthermore, 5 parts of tertiary butyl acetocetoxylate (hereinafter abbreviated as “TBAA”; acetoacetoxyalkyl ester manufactured by Eastman Chemical Japan) and DP-8 [di-2-ethylhexyl phosphate; Daihachi Chemical Industry Co., Ltd. 1) Acidic phosphate ester] 1 part was added and kept at the same temperature for 8 hours to obtain a solution of the modified vinyl resin (X1).

  The resulting modified vinyl resin (X1) solution has a non-volatile content of 50.1%; a Gardner viscosity at 25 ° C. of Z; a solution acid value of 0.8 mg KOH / g; a Gardner color number of 1-2; The number average molecular weight was 9,000.

Example 2
A modified vinyl resin was obtained in the same manner as in Example 1 except that a solution of an epoxy group-containing vinyl resin (A1) modified with an unsaturated fatty acid was obtained in the same manner as in Example 1, and then the amount of TBAA was changed to 10 parts. A solution of (X2) was obtained.

  The solution of the obtained modified vinyl resin (X2) has a non-volatile content of 50.3%; a Gardner viscosity at 25 ° C. of Z1-Z2; a solution acid value of 0.7 mgKOH / g; a Gardner color number of 1-2; The number average molecular weight of the resin was 9,200.

Example 3
In a four-necked flask equipped with a stirrer, a thermometer, a reflux condenser and a nitrogen gas introduction tube, 500 parts of “LAWS” was charged and heated to 120 ° C. At this temperature, a mixture of 90 parts GMA, 150 parts St, 530 parts i-BMA, 90 parts 2-EHA, 40 parts β-HEMA, 10 parts perbutyl O, 4 parts perbutyl Z, and 500 parts "LAWS" for 4 hours. The mixture was added dropwise and kept at the same temperature for 4 hours, and then 100 parts of linseed oil fatty acid (hereinafter abbreviated as “linseed oil FA”) and 1 part of 2-methylimidazole were added and kept at the same temperature for 8 hours. Thus, a solution of an epoxy group-containing vinyl resin (A3) modified with an unsaturated fatty acid was obtained. Furthermore, 5 parts of TBAA and 1.5 parts of DP-8 were added and kept at the same temperature for 8 hours to obtain a modified vinyl resin (X3) solution.

  The resulting modified vinyl resin (X3) solution has a non-volatile content of 50.4%; a Gardner viscosity at 25 ° C. of Z3-Z4; a solution acid value of 1.2 mg KOH / g; a Gardner color number of 3; The number average molecular weight was 9,500.

Example 4
In a four-necked flask equipped with a stirrer, a thermometer, a reflux condenser and a nitrogen gas introduction tube, 500 parts of “LAWS” was charged and heated to 120 ° C. At this temperature, 112.5 parts of GMA, 150 parts of St, 457.5 parts of i-BMA, 90 parts of 2-EHA, 40 parts of β-HEMA, 10 parts of perbutyl O, 4 parts of perbutyl Z, and 500 parts of “LAWS” The mixture was added dropwise over 4 hours, kept at the same temperature for 4 hours, then added 50 parts of DCOFA, 100 parts of SoyFA, and 1 part of 2-methylimidazole, and kept at the same temperature for 8 hours and modified with an unsaturated fatty acid. A solution of the group-containing vinyl resin (A4) was obtained. Furthermore, 10 parts of TBAA and 1.5 parts of DP-8 were added and kept at the same temperature for 8 hours to obtain a modified vinyl resin (X4) solution.

  The solution of the modified vinyl resin (X4) obtained had a non-volatile content of 50.3%; a Gardner viscosity at 25 ° C. of Z4; a solution acid value of 1.4 mg KOH / g; a Gardner color number of 2-3; The number average molecular weight was 9,300.

  The epoxy group-containing vinyl resin (A4) modified with unsaturated fatty acid has a non-volatile content of 50.0%; a Gardner viscosity at 25 ° C. of Y; a solution acid value of 0.1 mgKOH / g; a Gardner color. Number was 1; number average molecular weight was 8,900.

Comparative Example 1
A solution of an epoxy group-containing vinyl resin (A1) modified with an unsaturated fatty acid was obtained in the same manner as in Example 1, then the amount of TBAA used was changed to 10 parts and the use of DP-8 was omitted. In the same manner as in Example 1, a solution of the modified vinyl resin (Y1) was obtained.

  The resulting modified vinyl resin (Y1) solution has a non-volatile content of 50.1%; a Gardner viscosity at 25 ° C. of Z1; a solution acid value of 0.2 mg KOH / g; a Gardner color number of 1-2; The number average molecular weight was 9,000.

Comparative Example 2
A solution of an epoxy group-containing vinyl resin (A1) modified with an unsaturated fatty acid was obtained in the same manner as in Example 1, then the amount of DP-8 used was changed to 1.5 parts, and the use of TBAA was omitted. Obtained a modified vinyl resin (Y2) solution in the same manner as in Example 1.

  The solution of the modified vinyl resin (Y2) obtained had a non-volatile content of 50.3%; a Gardner viscosity at 25 ° C. of Z3; a solution acid value of 1.2 mgKOH / g; a Gardner color number of 3; The molecular weight was 9,500.

Comparative Example 3
In the same manner as in Example 4, a solution of an epoxy group-containing vinyl resin (A4) modified with an unsaturated fatty acid was obtained.

  The contents of Examples 1 to 4 are summarized in Table 1 below, and the contents of Comparative Examples 1 to 3 are summarized in Table 2 below.

Examples 5-8 and Comparative Examples 4-8
120 parts of each of the modified vinyl resins (X1) to (X4) obtained in Examples 1 to 4 and the vinyl resins (Y1), (Y2) and (A4) obtained in Comparative Examples 1 to 3 (solid content 60) Part), 40 parts of Typek R-930 [Titanium oxide manufactured by Ishihara Sangyo Co., Ltd.] and 100 parts of glass beads are mixed in a sand mill for 30 minutes, cooled, and after cooling, as a metal dryer, 6% cobalt naphthenate After adding 1.8 parts of a mixed solution of / 12% zirconium naphthenate / anti-skinning agent (MEK oxime) = 1/1/1 (weight ratio), each paint obtained was treated with “ "LAWS" and adjusted so that the Stormer viscosity at 25 ° C was 70 KU. These white paints are referred to as (W-X1) to (W-X4), (W-Y1), (W-Y2), and (W-A4), respectively.

  The white paints (W-X1) to (W-X4) are Examples 5 to 8, respectively, and the white paints (W-Y1), (W-Y2), and (W-A4) are Comparative Examples 4 and 5, respectively. 6. Commercial one-part non-water-acid type one-part acrylic white paint and commercially available long-oil alkyd white paint as Comparative Examples 7 and 8, respectively, according to the test methods shown below, initial drying properties, coatability, base Material adhesion, alkali resistance, and weather resistance were evaluated. The evaluation results are shown in Tables 3-7.

Initial drying property: Polishing the above white paint and applying a brush to a mild steel sheet to a dry film thickness of 40-50 μm. After drying at 25 ° C. for 6 hours and after leaving at 5 ° C. for 6 hours, the drying properties are as follows: Evaluation was based on the evaluation criteria. The evaluation results are shown in Table 3.
〔Evaluation criteria〕
A: No fingerprint is attached.
○: A slight fingerprint is attached.
Δ: A fingerprint is attached.
X: A coating film adheres to a finger.

Overcoatability: The above white paint is applied to the tin plate so that the wet film thickness is 100 μm, 150 μm, 200 μm, and 250 μm, respectively, and then the drying time is 6 hours under two conditions of 25 ° C. and 5 ° C. After and 24 hours later, the same paint was applied again, and after drying, the dissolution of the coating surface and the state of squeeze were visually determined according to the following evaluation criteria. The evaluation results are shown in Table 4.
〔Evaluation criteria〕
A: No abnormal appearance is observed.
○: Slight dissolution or blurring is observed at a certain film thickness.
Δ: Mild to moderate dissolution or blurring is observed depending on the film thickness.
X: Severe dissolution or blurring is observed in all film thicknesses.

  Adhesion to the base material: Apply the above white paint on the tinplate or the epoxy coating of the undercoat paint with a brush so that the dry film thickness is 40-50 μm, and dry at 25 ° C. for 7 days. After cutting into 1 mm square grids (10 × 10), a cellophane adhesive tape peeling test was performed, and the number of remaining eyes (X / 100) was evaluated. The evaluation results are shown in Table 5.

Alkali resistance: Brush the white paint described above onto a slate plate with the back and side surfaces sealed with an acrylic urethane clear paint so that the dry film thickness is 40-50 μm. After drying at 25 ° C. for 7 days, It was immersed in a saturated calcium hydroxide aqueous solution at 25 ° C. for 7 days, and appearance abnormalities such as glossiness and blistering after pulling and drying were visually determined according to the following evaluation criteria. The evaluation results are shown in Table 6.
〔Evaluation criteria〕
A: No abnormal appearance.
(Triangle | delta): The level in which some visual abnormality is recognized.
X: A level at which a remarkable appearance abnormality is observed.

  Weather resistance ··································································································· And 18-minute rainfall), the 60-degree gloss after 500 hours and 1000 hours was measured (SWOM; sunshine weatherometer test). The results are shown in Table 7.

  Gloss retention ratio: (60 degree specular reflectance after outdoor exposure / 60 degree specular reflectance before exposure) × retention ratio (%) determined by 100

Claims (6)

An epoxy group-containing vinyl resin (A) modified with an unsaturated fatty acid, an acidic phosphate ester (B), and an acetoacetoxyalkyl ester (C) are reacted in an aliphatic hydrocarbon solvent. A method for producing a modified vinyl resin. The epoxy group-containing vinyl resin (A) modified with the unsaturated fatty acid is an epoxy group-containing vinyl resin (a1) and an unsaturated fatty acid (a2), and the epoxy group in the epoxy group-containing vinyl resin (a1) is unsaturated. The method for producing a modified vinyl resin according to claim 1, wherein the modified vinyl resin is obtained by reacting under conditions that are excessive with respect to the carboxyl group in the fatty acid (a2). The acidic phosphate ester (B) is represented by the following general formula (1)

(In the formula, R ₁ represents an alkyl group having 1 to 13 carbon atoms.)
And a compound represented by
The acetoacetoxyalkyl ester (C) is represented by the following general formula (2)

(In the formula, R ₂ represents an alkyl group having 1 to 10 carbon atoms.)
The method for producing a modified vinyl resin according to claim 1, wherein the compound is represented by the formula: The method for producing a modified vinyl resin according to claim 4, wherein R ₁ in the general formula (1) is a 2-ethylhexyl group and R ₂ in the general formula (2) is a tertiary butyl group. Ratio of use of acidic phosphate ester (B) with respect to a total of 100% by weight of epoxy resin containing vinyl resin (A) modified with unsaturated fatty acid (A), acidic phosphate ester (B) and acetoacetoxyalkyl ester (C) Is in the range of 0.5 to 2.0% by weight, and the use ratio of the acetoacetoxyalkyl ester (C) is in the range of 1.0 to 10.0% by weight. The manufacturing method of modified vinyl resin as described in claim | item. A modified vinyl resin obtained by the production method according to any one of claims 1 to 5 and a metal dryer are mixed together.