JP6775876B2 - Putty composition and repair painting method using it - Google Patents

Description

Unsaturated polyester resins are generally relatively inexpensive compared to other resins, have excellent workability because they cure in a short time even at room temperature, and have various excellent physical and chemical properties depending on the selection of the main raw material. It is used for various purposes such as putty, paint, FRP molded product, resin concrete, and cast product.

Conventionally, a styrene monomer has been used in a putty composition as a reactive diluent for an unsaturated polyester resin in terms of curability and physical properties.

However, in recent years, styrene monomers have been regulated by the Regulations for Prevention of Damage to Specified Chemical Substances, and there is an urgent need to develop putty compositions that do not contain styrene, so-called non-styrene putty compositions.

As a non-styrene putty composition, for example, Patent Document 1 describes an unsaturated polyester resin composition in which hydroxyalkyl methacrylate is used as a reactive diluent instead of the styrene monomer. According to this composition, although the odor is low, the curing stability is excellent, and the surface drying property is excellent, the adhesion to the base material may be insufficient.

Further, Patent Documents 2 to 3 disclose a putty composition containing a specific polymerizable unsaturated compound as a reactive diluent and a specific aromatic amine compound as a curing assisting accelerator. For example, it has good surface drying property, has a good appearance without yellowing on the finished surface after top coating, and also has excellent internal drying property when thickly coated, and has adhesion to the base material and top coating paint. Although it is possible to form an excellent putty layer, the surface of the composition may be skinned during storage.

Regarding these problems, Patent Documents 4 to 5 disclose unsaturated polyester resin compositions using a carboxylic acid compound having a conjugated double bond conjugated to a carbonyl moiety of a carboxyl group. According to such a composition, both storage stability and surface drying property are good, but there is a problem that the surface of the cured layer is difficult to polish when this composition is applied as a repair putty.

By the way, at the site of automobile repair painting, the damaged part of the vehicle is filled with putty, dried to the inside, polished with sandpaper so that the surface of the putty layer on which it is placed is flat, and then a primer surfacer or the like is applied to the polished surface. The undercoat paint is applied, and the repair colored topcoat base paint, which is toned to a color that does not give a sense of discomfort to the unrepaired part, is applied.

In the putty process, which is the initial process of repair painting, it is necessary to fill the damaged part with putty and then dry it in a short time so that the polishing work can be performed at an early stage without making the operator wait. However, if the putty layer dries too quickly, there is a problem that the putty filling work becomes difficult, and a putty composition that satisfies all the filling workability of the putty composition, the drying workability of the putty layer, and the polishing workability is designed. It was extremely difficult to do.

Japanese Unexamined Patent Publication No. 2005-162830 Japanese Unexamined Patent Publication No. 2005-206781 Japanese Unexamined Patent Publication No. 2006-206863 Japanese Unexamined Patent Publication No. 2008-63528 Japanese Unexamined Patent Publication No. 2008-115217

An object of the present invention is to provide a novel putty composition which is particularly useful for automobile repair coating applications.

As a result of diligent studies on the above-mentioned problems, the present inventors have found that the rate of nucleophilic addition reaction of carbanion by an active methylene group is extremely suitable for a putty composition, and that it is curable without using styrene. They have found that a putty composition having excellent physical properties can be obtained, and have reached the present invention.

That is, the present invention
A multi-component putty composition for preparing a putty composition by mixing two or more components before painting.
Compound (A) having two or more active methylene groups in the molecule,
Compound (B), which has two or more groups in the molecule to which a carbanion generated from an active methylene group is nucleophilically added.
Pigment component (C) containing extender pigment (c)
And the curing catalyst component (D) containing the organic acid salt of the amine catalyst.
It is a composition containing
The content of the extender pigment (c) is in the range of 80 to 300 parts by mass with reference to 100 parts by mass of the non-volatile content of the compound (A) and the compound (B).
A B-type viscometer after mixing the first component (I) and the second component (II) , a putty composition having a viscosity in the range of 50 to 2000 Pa · s under the condition of a rotation speed of 2 rpm, and a coated body. The present invention relates to a repair coating method in which the damaged portion of the above is filled with the putty composition, dried, the putty layer is polished, and the repair coating composition is applied thereto.

According to the putty composition of the present invention, a putty layer having good putty filling workability while having quick-drying property even under normal temperature drying or forced drying conditions, and excellent surface drying property and hardness can be obtained. The surface of this putty layer has a property of being easily polished and has excellent adhesion to a base material, and is extremely useful as a base treatment agent for automobile repair coating.

The putty composition of the present invention has a compound (A) having two or more active methylene groups in the molecule, and a compound (B) having two or more groups in the molecule to which a carbanion generated from the active methylene group is nucleophilically added. The composition is characterized by containing the pigment component (C) and the pigment component (C).

<Compound (A) having two or more active methylene groups in the molecule>
In the present invention, the active methylene group means a group in which an electron-withdrawing group is bonded to at least one side (preferably both sides) of the methylene group, and the electron-withdrawing group includes a carbonyl group, an ester group, and a cyano group. Examples thereof include a group, a nitro group, a sulfonyl group, a sulfinyl group, a phosphono group, and the like, and a group in which a carbonyl group is bonded to both sides of a methylene group, that is, a -CO-CH _2- CO- structure is particularly suitable.

In the present invention, the compound (A) having two or more such active methylene groups is not limited in terms of production method, structure, etc. as long as it has an active methylene group in the molecule, but for example, the concentration of active hydrogen. However, it is suitable that the compound is in the range of 0.5 to 60 mol / Kg, preferably 2 to 45 mol / Kg.

As used herein, the active hydrogen concentration is the number of moles of active hydrogen atom derived from an active methylene group contained in 1 kg of the compound.

In the present invention, the molecular weight of the compound (A) is in the range of 100 to 100,000, preferably 200 to 50,000, in terms of the abrasiveness and water adhesion resistance of the putty composition. Is suitable.

In the present specification, the weight average molecular weight is a value obtained by converting the weight average molecular weight measured by a gel permeation chromatograph (manufactured by Tosoh Corporation, “HLC8120GPC”) with reference to the weight average molecular weight of polystyrene. In this measurement, the columns are "TSKgel G-4000H x L", "TSKgel G-3000H x L", "TSKgel G-2500H x L", "TSKgel G-2000H x L" (all trade names, Tosoh Corporation). It is assumed that the measurement conditions of mobile phase tetrahydrofuran, measurement temperature 40 ° C., flow velocity 1 mL / min, and detector RI are used.

Further, the compound (A) preferably has no acid value or has an acid value in the range of 10 mgKOH / g or less from the viewpoint of surface dryness of the putty layer formed from the putty composition. ..

The acid value in the present specification means a value measured by the titration method defined in JIS K 5601 (1999).

In the present invention, as the compound (A), for example, pentane-2,4-dione, hexane-2,4-dione, heptane-2,4-dione, 1-methoxy-2,4-pentanedione, 1- Phenyl-1,3-butandione, 1,3-diphenyl-1,3-propanedione, 4,6-dioxoheptanoic acid methyl ester, 5,7-dioxooctanoic acid methyl ester, benzoylacetic acid methyl ester, benzoylacetic acid Ethyl ester, benzoyl acetate butyl ester, propionyl acetate ethyl ester, propionyl acetate butyl ester, butyryl acetate methyl ester, acetoacetic acid methyl ester, acetoacetic acid ethyl ester, acetoacetic acid isopropyl ester, acetoacetic acid butyl ester, acetoacetate tert-butyl ester, Acetacetic acid- (2-methoxyethyl) ester, acetoacetic acid- (2-ethylhexyl) ester, acetoacetic acid lauryl ester, 2-acetacetoxyethyl acrylate, 2-acetacetoxyethyl methacrylate, acetoacetic acid benzyl ester, 1,4-butane Didiol diacet acetate, 1,6-hexanediol diacet acetate, neopentyl glycol diacet acetate, 2-ethyl-2-butyl-1,3-propanediol diacet acetate, cyclohexanedimethanol diacet acetate, ethoxylated Bisphenol A diacetacetate, trimethylolpropane triacetate, glycerol triacetate, pentaerythritol triacetate, pentaerythritol tetraacetate, ditrimethylolpropanetetraacetate, dipentaerythritol hexaacetate, etc. A polymer containing an acetoacetate group obtained by an ester exchange reaction between a polyol and an acetoacetate ethyl ester, and a malonic acid dimethyl ester, malonic acid diethyl ester, malonic acid dipropyl ester, malonic acid diisopropyl ester, and malonic acid dibutyl ester. , Malonic acid compounds such as malonic acid di (2-ethylhexyl ester), malonic acid dilauryl ester; and polymers obtained by polyol and dialkyl malonate.

Examples of the polymer having two or more active methylene groups in the molecule include an acrylic resin compound, an active methylene group-containing polyester resin compound, an active methylene group-containing polyurethane resin compound, and an active methylene group-containing epoxy resin compound. In addition, a modified product obtained by combining these two or more types can be exemplified.

Examples of the active methylene group-containing compound which is a constituent component of the polymer having two or more active methylene groups include an active methylene group-containing carboxylic acid and an active methylene group-containing (meth) acrylic monomer.

Examples of the active methylene group-containing carboxylic acid include acetoacetic acid, malonic acid, cyanoacetic acid and derivatives thereof.

Specific examples of the esterified product among the above active methylene group-containing carboxylic acid derivatives include acetoacetate esters such as methyl acetoacetate, ethyl acetoacetate, isopropyl acetoacetate, n-propyl acetoacetate, benzyl acetoacetate, and phenyl acetoacetate. Malonic acid diesters such as diethyl malonate, diethyl malonate, diisopropyl malonate, di-n-propyl malonate, diethyl methyl malonate, benzylmethyl malonate, dibenzyl malonate, and diphenyl malonate can be mentioned. Can be used alone or in combination of two or more.

On the other hand, specific examples of the active methylene group-containing (meth) acrylic monomer include, for example, 2-ethoxymalonyloxyethyl (meth) acrylate, 2-acetoacetoxyethyl (meth) acrylate, and N- (2-acetoacetylaminoethyl). Acrylamide, 2- (N-acetoacetylaminoethyl) (meth) acrylate, 2-cyanoacetoxyethyl (meth) acrylate, N- (2-cyanoacetoxyethyl) acrylamide, N- (2-propionylacetoxybutyl) acrylamide, N Examples thereof include -4- (acetoacetoxymethyl) benzyl acrylamide, N- (2-acetoacetamide ethyl) acrylamide, N- (2-acetoacetamide ethyl) methacrylicamide, etc. It can also be combined.

The active methylene group-containing polyester resin-based compound as the active methylene group-containing compound (A) can be a reaction product of a component containing an active methylene group-containing carboxylic acid or a derivative thereof and a polyol.

The polyol for reacting with the active methylene group-containing carboxylic acid and its derivative may be a compound having at least two hydroxyl groups in the molecule, for example, ethylene glycol, diethylene glycol, propylene glycol, tetramethylene glycol, neo. Pentyl glycol, 1,6-hexanediol, 1,9-nonanediol, trimethylolpropane, glycerin, pentaerythritol, hydride bisphenol A, bisphenol A dihydroxypropyl ether, acrylic polyol, polyester polyol, polyether polyol, epoxy polyol, Examples thereof include polyols such as polyurethane polyols and silicone polyols.

As the polyester resin compound, a carboxylic acid other than the active methylene group-containing carboxylic acid can be used as a constituent component, if necessary.

Examples of such carboxylic acids include phthalic acid, phthalic acid anhydride, phthalic acid halide, isophthalic acid, terephthalic acid, hexahydrophthalic acid, hexahydrophthalic anhydride, hexahydroterephthalic acid, hexahydroisophthalic acid, and succinic acid. Maronic acid, glutaric acid, adipic acid, sebacic acid, 1,12-dodecanedioic acid, 2,6-naphthalenedicarboxylic acid, 2,7-naphthalenedicarboxylic acid, 2,3-naphthalenedicarboxylic acid, 2,3-naphthalenedicarboxylic acid Saturated polybasic acids such as acid anhydrides, 4,4'-biphenyldicarboxylic acids, and their dialkyl esters can be exemplified.

The active methylene group-containing acrylic resin-based compound can be, for example, a copolymer of an active methylene group-containing (meth) acrylic monomer and another polymerizable unsaturated monomer copolymerizable with the monomer.

The other polymerizable unsaturated monomer may be either a (meth) acrylic monomer or a non- (meth) acrylic monomer, and the (meth) acrylic monomer may be, for example, a methyl (meth) acrylate. , Ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, tert-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate , N-octyl (meth) acrylate, lauryl (meth) acrylate, stearyl (meth) acrylate, cyclohexyl (meth) acrylate, isobornyl (meth) acrylate, tridecyl (meth) acrylate and other linear, branched or cyclic alkyl groups. Containing (meth) acrylate; N-methoxymethyl (meth) acrylamide, N-butoxymethyl (meth) acrylamide, methoxyethyl (meth) acrylate, methoxypropyl (meth) acrylate, ethoxyethyl (meth) acrylate, ethoxypropyl (meth) Alkoxyalkyl (meth) acrylates such as acrylates; Polyalkylene glycols such as polyethylene glycol monomethoxy (meth) acrylates (meth) acrylates containing alkoxy groups such as monoalkoxy (meth) acrylates; glycidyl (meth) acrylates, 3,4-epoxy Epoxy group-containing (meth) acrylate such as cyclohexylmethyl (meth) acrylate; carboxyl group-containing (meth) acrylate such as half-esterified product of acrylic acid, methacrylic acid, hydroxyalkyl (meth) acrylate and acid anhydride; 2-acrylamide A sulfonic acid group-containing (meth) acrylate such as -2-methylpropanesulfonic acid; a phosphoric acid group such as an acid phosphooxyethyl (meth) acrylate and a phosphoric acid mono-[(2-hydroxyethyl) (meth) acrylic acid] ester. Containing (meth) acrylate; N, N-dimethylaminoethyl (meth) acrylate, N, N-diethylaminoethyl (meth) acrylate, N, N-dimethylaminopropyl (meth) acrylate, N-t-butylaminoethyl (meth) acrylate ) Acrylate, N, N-dimethylaminobutyl (meth) acrylate and other amino group-containing (meth) acrylate; (meth) acryloyloxyethyltrimethylammonium chloride, dimemethacrylate Tertiary ammonium base-containing (meth) acrylates such as tylaminoethylmethyl chloride; 2-hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, 2,3-dihydroxybutyl (meth) acrylate, 4-hydroxybutyl ( Hydroxyalkyl (meth) acrylate such as meta) acrylate, a compound obtained by ring-opening polymerization of lactone such as ε-caprolactone with the above hydroxyalkyl (meth) acrylate, and polyhydric alcohol such as polyethylene glycol mono (meth) acrylate and acrylic acid or Hydroxy group-containing (meth) acrylate such as monoesterified product with methacrylic acid; fluoroalkyl (meth) acrylate such as hexafluoroisopropyl (meth) acrylate, perfluorooctylmethyl (meth) acrylate, perfluorooctylethyl (meth) acrylate (Meta) acryloxyalkoxysilane, γ- (meth) acryloxypropyltrimethoxysilane, γ- (meth) acryloxypropyltriethoxysilane, β- (meth) acryloxyethyltrimethoxysilane, β- (meth) Acryloxyethyltriethoxysilane, γ- (meth) acryloxipropylmethyldimethoxysilane, γ- (meth) acryloxipropylmethyldiethoxysilane, γ- (meth) acryloxipropylmethyldipropoxysilane, γ- (meth) Hydrolytable silyl group-containing (meth) acrylates such as acryloxybutylphenyldimethoxysilane and γ- (meth) acryloxypropyldiethylmethoxysilane: and combinations thereof can be mentioned.

Examples of the non- (meth) acrylic monomer include aromatic vinyl compounds such as styrene and vinyl toluene; cyclohexyl vinyl ether, nonyl vinyl ether, 2-ethylhexyl vinyl ether, hexyl vinyl ether, ethyl vinyl ether, n-butyl vinyl ether, t-butyl vinyl ether and the like. Vinyl ethers; allyl ethers such as ethyl allyl ethers and hexyl allyl ethers; carboxylic acid vinyl esters such as "Beova-9" and "Beova-10" (both manufactured by Shell Chemical Co., Ltd., trade names); ethylene, propylene, isobutylene and the like. Olefin: Fluorovinyl ethers such as fluoroalkyl trifluorovinyl ethers and perfluoroalkyl trifluorovinyl ethers can be mentioned.

<Compound (B) having two or more groups in the molecule to which a carbanion generated from an active methylene group is nucleophilically added>
In the present invention, the compound (B) is a compound having two or more groups in the molecule that serve as nucleophilic additions of the carboxylic anion produced from the compound (A), and reacts with the active methylene group to form the carbon of the active methylene group. As a specific example of a group capable of forming a carbon-carbon bond with and a nucleophilic addition, for example, an α, β-unsaturated carbonyl group, preferably a (meth) acryloyl group can be mentioned. ..

The unsaturated group concentration of compound (B) is preferably in the range of 0.1 to 20 mol / kg, preferably 1 to 15 mol / kg, from the viewpoint of polishability of the putty layer.

In the present specification, the unsaturated group concentration is the number of moles of polymerizable unsaturated groups contained in 1 kg of the compound.

In the present invention, the molecular weight of compound (B) is preferably in the range of 50 to 20,000, preferably 100 to 5,000, from the viewpoint of surface drying property and water adhesion resistance of the putty layer.

In the present invention, as long as the compound (B) has two or more of the above groups in the molecule, the production method, structure and the like are not limited, and specific examples thereof include polyfunctional (meth) acrylate. it can.

The polyfunctional (meth) acrylate is a compound having at least two (meth) acryloyl groups in the molecule, and specifically, ethylene glycol diacrylate, diethylene glycol diacrylate, dipropylene glycol (meth) acrylate, and the like. Triethylene glycol di (meth) acrylate, tripropylene glycol di (meth) acrylate, butylene glycol (meth) acrylate, tetrabutylene glycol di (meth) acrylate, hexamethylene glycol di (meth) acrylate, 1,6-hexanediol di (Meta) acrylate, 1,9-nonanediol di (methacrylate), 1,10-decanediol di (meth) acrylate, neopentyl glycol di (meth) acrylate, 2,4-dimethyl-1,5-pentanediol di (Meta) acrylate, butyl ethylpropanediol (meth) acrylate, ethoxylated cyclohexane methanol di (meth) acrylate, polyethylene glycol di (meth) acrylate, oligoethylene glycol di (meth) acrylate, ethylene glycol di (meth) acrylate, 2-Ethyl-2-butyl-butanediol di (meth) acrylate, hydrovivalaldehyde-modified trimethylpropandi (meth) acrylate, hydroxypivalate neopentyl glycol di (meth) acrylate, caprolactone-modified hydroxyvivylate neopentyl Glycoldi (meth) acrylate, ethylene oxide modified bisphenol A di (meth) acrylate, bisphenol F polyethoxydi (meth) acrylate, polypropylene glycol di (meth) acrylate, oligopropylene glycol di (meth) acrylate, 1,4-cyclohexanedi (meth) acrylate ) Acrylate, 1,4-butanediol di (meth) acrylate, di (meth) acrylate of ethylene oxide adduct of bisphenol F, di (meth) acrylate of propylene oxide adduct of bisphenol F, dicyclopentanyldi (meth) ) Di (meth) acrylates such as acrylates, glycerol di (meth) acrylates, tricyclodecanedi (meth) acrylates, propoxylated ethoxylated bisphenol A di (meth) acrylates, tetrabromobisphenol A di (meth) acrylates; trimethylol. Propanetri (meth) acrylate, trimeticro Luetanetri (meth) acrylate, alkylene oxide-modified tri (meth) acrylate of trimethylolpropane, pentaerythritol tri (meth) acrylate, dipentaerythritoltri (meth) acrylate, trimethylpropanthry (meth) acryloyloxypropyl) ether, isocyanul Acid-alkylene oxide-modified tri (meth) acrylate, dipentaerythritol tri (meth) acrylate propionate, tri ((meth) acryloyloxyethyl) isocyanurate, hydroxypivalaldehyde-modified dimethylol propantri (meth) acrylate, sorbitol tri ( Tri (meth) acrylates such as meta) acrylates, propoxylated trimethylol propantri (meth) acrylates and ethoxylated glycerin triacrylates; pentaerythritol tetra (meth) acrylates, sorbitol tetra (meth) acrylates, ditrimethylol propantetra (meth). Tetra (meth) acrylate of ethylene oxide adduct of acrylate, ditrimethylol propane, tetra (meth) acrylate of propylene oxide adduct of ditrimethylol propane, tetra (meth) acrylate of dipentaerythritol propionate, pentaerythritol tetra (meth) ethoxylated. ) Acrylate, sorbitol penta (meth) acrylate, dipentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, sorbitol hexa (meth) acrylate, phosphazene alkylene oxide-modified hexa. Examples thereof include (meth) acrylate and caprolactone-modified dipentaerythritol hexa (meth) acrylate.

Further, the compound (B) includes a polyester resin compound or a polyamide resin compound containing α, β-unsaturated dicarboxylic acid such as fumaric acid and maleic acid as constituents; (meth) acryloyl group-containing acrylic resin compound and the like. Is also included.

The putty composition of the present invention is characterized in that the reaction of the compound (A) and the compound (B) is used for curing the putty layer, and the use of the compound (A) and the compound (B) is used. As a ratio, from the viewpoint of surface curability of the putty layer, the unsaturated group contained in the compound (B) is 0.1 to 2 to 1 equivalent of the active hydrogen derived from the active methylene group contained in the compound (A). It is suitable that the amount is adjusted to be in the range of 0 equivalents, preferably 0.3 to 1.5 equivalents.

<Pigment component (C)>
The putty composition of the present invention contains a pigment component (C) from the viewpoint of hiding the base of the putty layer and polishing property. As the pigment component (C), a conventionally known pigment used for paints can be used, but particularly preferably, a coloring pigment such as titanium white, red iron oxide, carbon black, iron black; talc, mica, barium sulfate, kaolin, etc. Examples thereof include extender pigments such as calcium carbonate, clay, silica, quartz, and glass. These can be used alone or in combination of two or more.

The blending amount of the pigment component (C) is 80 to 600 parts by mass, preferably 90 parts by mass with respect to 100 parts by mass of the total mass of the compound (A) and the compound (B) from the viewpoint of polishing workability and spatula attachment workability. It is suitable to be in the range of ~ 300 parts by mass.

In the present invention, the extender pigment (c) is contained as an essential component as the pigment component (C), and the content of the extender pigment (c) is based on 100 parts by mass of the non-volatile content of the compound (A) and the compound (B). It is characterized in that it is in the range of 80 to 300 parts by mass.

In the present specification, the non-volatile component means a residue excluding volatile components, and the residue may be solid or liquid at room temperature. The non-volatile fraction mass can be calculated, for example, by taking the ratio of the amount of residual substance after drying to the mass before drying as the non-volatile fraction and multiplying the non-volatile fraction by the mass of the sample before drying.

When the composition of the present invention contains the extender pigment (c), a putty composition having good sagging resistance and excellent workability for a painter can be obtained.

The extender pigment (c) is preferably contained in the range of 90 to 250 parts by mass, preferably 100 to 180 parts by mass.

If the content of the extender pigment (c) is less than 80 parts by mass, the putty filling workability becomes difficult and the polishability of the formed putty layer becomes insufficient, while if it exceeds 300 parts by mass, the putty filling workability becomes difficult. It is not preferable because the putty layer formed becomes difficult to adhere to the base material after being immersed in water.

<Curing catalyst component (D)>
In the present invention, it is preferable to include a curing catalyst component (D) that promotes the reaction between the compound (A) and the compound (B). As the curing catalyst component (D), a known component that promotes the reaction between the compound (A) and the compound (B) can be used without limitation.

Specific examples of such a curing catalyst component (D) include, for example, proline, triazabicyclodecene (TBD), 1,8-diazabicyclo [5.4.0] undecene-7 (DBU), hexahydromethylpyrimidpyridine ( MTBD), 1,5-diazabicyclo [4.3.0] nonen-5 (DBN), triethylamine (TEA), tributylamine (TBA), tetramethylguanidine (TMG), triethylenediamine (TEDA) and other amine catalysts;
The above amine-catalyzed organic acid salt;
Halogen catalysts such as tetraethylammonium bromide, tetrabutylammonium bromide, tetraethylammonium chloride, tetrabutylphosphonium bromide, triphenylbenzylphosphonium chloride;
Triphenylphosphine, tricyclopentylphosphine, tris (2,4,4-trimethylpentyl) phosphine, tricyclohexylphosphine, tri-n-hexylphosphine, tris (2-ethylhexyl) phosphine, tri-n-octylphosphine, tri-n Phosphine-based catalysts such as -decylphosphine, tri-n-dodecylphosphine, tristearylphosphine;
Alkali metal catalysts such as sodium methoxydo, sodium ethoxydo, potassium tertiary butoxide, potassium hydroxide, sodium hydroxide, sodium metal, lithium diisopropylamide (LDA), butyllithium, potassium carbonate, sodium carbonate;
Ruthenium cyclooctadiene Cyclooctadiene, ruthenium-based catalysts such as hydridoltenium;
Iron-based catalysts such as iron trichloride and iron acetylacetone;
Nickel catalysts such as nickel acetylacetonate, nickel acetate, nickel salicylaldehyde;
Copper-based catalysts; Palladium-based catalysts; Scandium-based catalysts; Lantern-based catalysts; Ytterbium-based catalysts; Tin-based catalysts;
Etc., and these can be used alone or in combination of two or more.

In the present invention, the curing catalyst component (D) is at least one selected from the group consisting of an amine catalyst, an amine catalyst organic acid salt, a halogen catalyst and a phosphine catalyst from the viewpoint of putty filling workability and dryness of the putty layer. It is preferable that the curing catalyst component (D) contains an amine-catalyzed organic acid salt as a part of the component (D).

Examples of the organic acid salt include phenol salt, octylate, oleate, p-toluenesulfonate, formate and the like, and among them, the organic acid amidine salt is preferable. Specific examples of the organic acid amidine salt include 1,8-diazabicyclo [5.4.0] undecene-7 (hereinafter sometimes referred to as DBU) and 1,5-diazabicyclo [4.3.0] nonen-5. Examples thereof include phenol salts (hereinafter sometimes referred to as DBN), octylate, oleate, p-toluenesulfonate, formate, etc. Among them, DBU-phenol salt, DBU-octylate, DBN -It is preferable to use octylate or the like.

Commercially available products of the above organic acid amidine salt include "U-CAT SA1", "U-CAT SA102", "U-CAT SA106", "U-CAT SA506", "U-CAT SA603", and "U-CAT". SA1102 ”(above, trade name, manufactured by Sun Appro) and the like can be mentioned.

The blending amount of the curing catalyst component (D) is 0.1 to 30 based on 100 parts by mass of the total mass of the compound (A) and the compound (B) from the viewpoint of putty filling workability and dryness of the putty layer. It can be in the range of parts by mass, preferably 0.5 to 20 parts by mass.

<Pate composition>
When the putty composition of the present invention is composed of a multi-component system from the viewpoint of storage stability, each component is mixed at the time of use. In the present invention, from the viewpoint of storage stability, the first component and the second component are mixed so that the compound (A), the compound (B) and the component (D) used as needed are mixed immediately before use. It is desirable to prepare the ingredients. Further, the pigment component (C) can be present in either the first component or the second component, or in both the first component and the second component.

That is, each component contained in the putty composition of the present invention is prepared as follows from the viewpoint of improving the storage stability of the putty composition and flexibly adapting to the use environment and use of the putty. Is preferable.
(1) The putty composition contains the first component (I) containing the compound (A) and
The second component (II) containing the compound (B) and
The first component (I) and / or the second component (II) contains the pigment component (C), and the curing catalyst component (D) is the first component (I) or the second component (I). Included in.
(2) The putty composition contains the compound (A) and the first component (I) containing the compound (B).
The second component (II) including the component (D) and
The first component (I) and / or the second component (II) contains a pigment component (C).

Further, if necessary, the putty composition of the present invention includes hollow particles such as a polymerization initiator, a solvent, a dehydrating agent, a rust preventive, a glass balloon, a plastic balloon, an ultraviolet stabilizer, an ultraviolet absorber, and low shrinkage. Agents, antioxidants, anti-skinning agents, polymerization inhibitors, plasticizers, aggregates, flame retardants, stabilizers, reinforcing materials, viscosity modifiers such as thickeners, pigment dispersants, modifying resins, silane cups A ring agent, an air blocking agent such as paraffin, etc. can be blended.

Of these, when the composition has a radically polymerizable group, the polymerization initiator is expected to act as a polymerization initiator for the radical polymerization reaction and contribute to the surface curability of the putty layer. Specific examples of such polymerization initiators include ketone peroxide compounds such as cyclohexanone peroxide, 3,3,5-trimethylcyclohexanone peroxide, and methylcyclohexanone peroxide; 1,1-bis (tert-butylperoxy)-. 3,3,5-trimethylcyclohexane, 1,1-bis (tert-butylperoxy) cyclohexane, n-butyl-4,4-bis (tert-butylperoxy) valerate, 2,2-bis (4,4) -Ditert-butylperoxycyclohexyl) propane, 2,2-bis (4,5-ditert-amylperoxycyclohexyl) propane, 2,2-bis (4,54-ditert-hexylperoxycyclohexyl) propane , 2,2-Bis (4,5-ditert-octylperoxycyclohexyl) propane, 2,2-bis (4,5-dicumylperoxycyclohexyl) propane and other peroxyketal compounds; cumenehydroperoxide, Hydroperoxide compounds such as 2,5-dimethylhexane-2,5-dihydroperoxide; 1,3-bis (tert-butylperoxy-m-isopropyl) benzene, 2,5-dimethyl-2,5- Dialkyl peroxide compounds such as di (tert-butylperoxy) hexane, diisopropylbenzene peroxide, tert-butylcumyl peroxide, ditert-butyl peroxide; decanoyl peroxide, lauroyl peroxide, benzoyl peroxide, 2, Diacyl peroxide compounds such as 4-dichlorobenzoyl peroxide; peroxycarbonate compounds such as bis (tert-butylcyclohexyl) peroxydicarbonate; tert-butylperoxy-2-ethylhexanoate, tert-butylperoxybenzoate , 2,5-Dimethyl-2,5-di (benzoylperoxy) A compound of a peroxyester compound such as hexane can be used, and one type or a combination of two or more types can be used.

The putty composition obtained as described above can obtain a putty layer having excellent surface drying property and internal curability even if it does not contain styrene, and can be provided as a non-styrene type, but it does not exclude the inclusion of styrene. Absent.

The putty composition of the present invention is characterized in that the viscosity is in the range of 50 to 2000 Pa · s, and is in the range of 80 to 1900 Pa · s, preferably 100 to 1800 Pa · s. Is suitable.

If the viscosity of the putty composition is less than 50 Pa · s, the putty composition may sag during the filling operation, which deteriorates workability, which is not preferable. On the other hand, if it exceeds 2000 Pa · s, the extensibility of the putty composition is insufficient during the filling operation, and the workability is deteriorated, which is not preferable.

In the present specification, the viscosity of the sample is adjusted to a temperature of 25 ° C., and the B-type viscometer "VISCOMETER TV-22" (trade name, manufactured by Toki Sangyo Co., Ltd.), No. 7. It is assumed that the measurement was performed using a rotor under the condition of a rotation speed of 2 rpm.

<Repair painting method using putty composition>
The base material surface to which the putty composition of the present invention is applied is not particularly limited, but is a metal surface such as iron, zinc, aluminum, a chemically treated surface thereof, plastic, wood, etc., and a coated body coated thereto. And so on.

When the putty composition of the present invention is a multi-component system, the putty can be obtained by mixing the first component (I), the second component (II) and other components that can be optionally contained. The obtained putty (mixed putty composition) is useful for repair painting of a painted body of a vehicle such as an automobile.

The method of mixing each component can be carried out according to a conventional method of mixing the components of a multi-component putty composition.

If necessary, sanding is performed around the damaged portion of the coated body, the putty composition mixed in the damaged portion is filled with a spatula or the like, and the inside of the coating film can be cured by normal temperature drying or forced drying.

Specifically, the drying conditions should be maintained at room temperature for 5 hours or more in the case of normal temperature drying, or set time of 3 to 30 minutes in the case of forced drying, and heated at a temperature of 40 to 120 ° C. for 5 to 60 minutes. Can be done.

The formed putty layer is polished with water resistant paper, sandpaper, or the like, and the repair coating composition can be applied to the polished surface.

The repair paint composition includes acrylic lacquer, acrylic melamine resin paint, two-component urethane curable paint containing hydroxyl group-containing resin and polyisocyanate compound, acid-epoxy curable paint, fluororesin paint, and alkyd resin paint. It can be used without particular limitation, such as paints, alkyd melamine resin paints, polyester melamine resin paints and other commonly used organic solvent paints, water paints, powder undercoat paints, coloring base paints, top clear paints and the like.

Hereinafter, the present invention will be described in more detail with reference to Examples, but the present invention is not limited to these Examples. In addition, "part" and "%" in the following example mean "part by mass" and "mass%" respectively.

<Manufacture of putty base and hardener base>
Example 1
In a container, 60 parts of malonic acid-modified polyester resin (A-1) (Note) as an active methylene component, 40 parts of talc, and 3 parts of "U-CAT SA1" (Note) are mixed and stirred, and kneaded at high speed. The mixture was mixed and dispersed in a machine for 20 minutes to obtain a base agent base for the putty composition (T-1).
Next, 38 parts of trimethylolpropane triacrylate and 40 parts of calcium carbonate were mixed and stirred in another container, and mixed and dispersed in a high-speed kneader for 20 minutes to obtain a curing agent base for the putty composition (T-1). ..

The main agent base and the curing agent base were mixed at the ratios shown in Table 1 to obtain a putty composition (T-1). At this time, the equivalent ratio of the acrylate group to the active hydrogen of the active methylene group was 1.0.

Examples 2-29 and Comparative Examples 1-4
In Example 1, each putty composition (T-2) to (T-33) was obtained in the same manner except that the compounding composition was as shown in Tables 1 to 9. In the table, the blending amount of the active methylene component is indicated by the non-volatile content.

(Note) Active methylene group-containing polyester resin (A) solution Neopentyl glycol / hexahydrophthalic anhydride / diethyl malonate = 17.31 mol / 8.03 mol / 10.44 mol condensate butyl acetate solution, 90% non-volatile content, weight average molecular weight 3400, active hydrogen content of active methylene group per non-volatile content 5.5 mol / kg
(Note) Active methylene group-containing polyester resin (B) solution 1,6-hexanediol / trimethylolpropane / oleic acid / diethyl malonate = 2.54 mol / 0.51 mol / 0.51 mol / 3.05 mol Butyl acetate solution of condensate, non-volatile content 90%, resin weight average molecular weight 3800, active hydrogen of active methylene group per non-volatile content 8.4 mol / kg
(Note) Active methylene group-containing acrylic resin solution Acetacetoxyethyl methacrylate / methyl methacrylate / n-butyl methacrylate = 70/20/10 copolymer butyl acetate solution, non-volatile content 60%, resin weight average molecular weight 5000, non-volatile content Amount of active hydrogen per active methylene group 6.0 mol / kg
(Note) Trimethylolpropane triacetoacetate: 15.5 mol / kg of active hydrogen of active methylene group
(Note) DBN: 1,5-diazabicyclo [4.3.0] Nonene-5
(Note) U-CAT SA1: Product name, manufactured by San-Apro, DBU-phenol salt (Note) U-CAT SA102: Product name, manufactured by San-Apro, DBU-octylate (Note) U-CAT SA1102: Product name, DBN-octylate (Note) TBAC: tetrabutylammonium bromide (Note) TMPTA: trimethylolpropane triacrylate, molecular weight 338, unsaturated group concentration 8.9 mol / kg
(Note) DiTMPTA: ditrimethylolpropane tetraacrylate, molecular weight 466.5, unsaturated group concentration 8.6 mol / kg
(Note) PETA: Pentaerythritol tetraacrylate, molecular weight 352.3, unsaturated group concentration 11.4 mol / kg
(Note) M-315: trade name, manufactured by Toagosei Co., Ltd., nurate skeleton acrylate, molecular weight 423, unsaturated group concentration 7.1 mol / kg.

<Evaluation method>
(*) Viscosity After adjusting the main agent base and the curing agent base to 25 ° C., B-type viscometer "VISCOMETER TV-22" (trade name, manufactured by Toki Sangyo Co., Ltd.), No. 7. Using a rotor, the measurement was performed within 10 seconds after mixing the main agent base and the curing agent base under the condition of a rotation speed of 2 rpm.
(*) Spatula attachment property Each base putty base and curing agent putty base are mixed, and a spatula is used to attach a spatula to the test piece.
I checked the nobi, the spatula, the spatula, and the sauce at that time.
◎: Nobi, cut spatula, spatula are all very good,
〇: Spatula cut, spatula is extremely good, nobi is slightly inferior, but practical level △: Nobi, spatula cut, spatula are all slightly defective,
×: Nobi, broken spatula, and spatula are all defective.
(*) The surface of the dryness "SPCC-SB" (iron plate manufactured by Nippon Test Panel Co., Ltd.) was lightly polished with water resistant paper # 240, and this was used as the base material surface. Each base agent base and curing agent base obtained above were mixed, and the homogenized putty composition was applied on each substrate surface with a spatula, and the one applied to a thickness of 2 mm was used as a test coating plate. After each test coating plate was left at room temperature (20 ° C.) for 40 minutes, the tack on the surface of each test coating plate and the degree of hardening inside were examined by touch.
◎: Very good,
〇: Good,
〇 △: There is some tack on the surface, but the inside is well cured.
Δ: There is some tack on the surface, and the inside is also slightly poorly cured.
×: There is a tack on the surface, and the inside is also poorly cured.
(*) Polishability The surface of each of the above test coated plates was polished with # 400 water resistant paper to evaluate the ease of polishing.
◎: Extremely easy to polish,
○: Easy to polish,
Δ: Slightly difficult to polish,
X: Difficult to polish.
(*) Water resistance Adhesion After leaving the above test coating plate at room temperature (20 ° C) for 6 hours to dry, the coated surface is lightly polished with # 400 water resistant paper, and "Retan PG80 White Base" (trade name, acrylic urethane) A resin-based topcoat paint (manufactured by Kansai Paint Co., Ltd.) was spray-coated so as to have a dry film thickness of 50 μm, and dried at 60 ° C. for 30 minutes to obtain each coated plate. After immersing each coated plate in water at 80 ° C. for 1 day, it was taken out from the water, bent from the central portion, and the coating film state of the bent portion was observed.
◯: No peeling,
Δ: The coating film is slightly peeled off from between the steel plate and the putty.
X: The coating film is completely peeled off from between the steel plate and the putty.

Claims (6)

A multi-component putty composition for preparing a putty composition by mixing two or more components before painting.
Compound (A) having two or more active methylene groups in the molecule,
Compound (B), which has two or more groups in the molecule to which a carbanion generated from an active methylene group is nucleophilically added.
Pigment component (C) containing extender pigment (c)
And the curing catalyst component (D) containing the organic acid salt of the amine catalyst.
It is a composition containing
The content of the extender pigment (c) is in the range of 80 to 300 parts by mass with reference to 100 parts by mass of the non-volatile content of the compound (A) and the compound (B).
A putty composition characterized in that the viscosity of the B-type viscometer after mixing the first component (I) and the second component (II) under the condition of a rotation speed of 2 rpm is in the range of 50 to 2000 Pa · s. A multi-component putty composition for preparing a putty composition by mixing two or more components before painting.
The first component (I) containing the compound (A) and
The second component (II) containing the compound (B) and
The first component (I) and / or the second component (II) contains the pigment component (C), and the curing catalyst component (D) is the first component (I) or the second component (I). The putty composition according to claim 1 , wherein the putty composition is contained in. A multi-component putty composition for preparing a putty composition by mixing two or more components before painting.
The first component (I) containing the compound (A) and the compound (B) and
The second component (II) containing the curing catalyst component (D) and
The putty composition according to claim 1, wherein the first component (I) and / or the second component (II) contains a pigment component (C). The putty composition according to any one of claims 1 to 3 , which is a non-styrene type. A putty composition obtained by mixing the first component (I) and the second component (II) according to any one of claims 1 to 4 . A repair coating method in which a damaged portion of a coated body is filled with the putty composition according to claims 1 to 5 , dried, and then the putty layer is polished, and the repair coating composition is applied thereto.