CN106536652A - Coating composition - Google Patents

Abstract

The present invention addresses the problem of providing a matting coating film having excellent luster stability, alkali resistance, storage stability, and impact resistance. The present invention provides a coating composition including a film-forming resin (A) and a matting agent (B), and further including a nonaqueous polymer dispersion (C) comprising a skin component and a core component, and/or a block polyisocyanate compound (D), the coating composition characterized in that: the nonaqueous polymer dispersion (C) is a nonaqueous polymer dispersion containing an acrylic polymer and/or a self-condensate of a fatty acid having a hydroxyalkyl group in which the alkyl chain thereof has a carbon number of 10-25, and containing, as at least a portion of the skin component, a macromonomer having an average of one or more polymerizable unsaturated groups per molecule thereof; and the block polyisocyanate compound (D) is an active methylene block polyisocyanate compound in which the compound detached in a crosslinking reaction detaches a C3-12 monofunctional alcohol.

Description

Coating composition

Technical field

[related application cross-referenced]

The application is based in Japan's patent application 2014-154437 description (these filed in 30 days July in 2014 A little disclosures are all by referring to quoting in this specification) carry out CLAIM OF PRIORITY.The present invention relates to coating composition.

Background technology

In the past, the outside plate film of the car body of automobile etc., usually had glossiness appearance design, in recent years as new outer See design, repressed so-called delustring (dumb light) appearance design of gloss to be paid close attention to by people.

Method as the film (hereinafter sometimes referred to " delustring film ") that delustring appearance design is presented is formed, for example, A kind of smearss with organic solvent as substrate have been recorded in patent documentation 1, and which includes the compound containing at least one hydroxyl, extremely The delustering agent of a kind of few cross-linking agent with hydroxyl reactive group and at least one silicic acid gel substrate, it is characterised in that Above-mentioned delustering agent carries out surface by more than one wax and is modified, and above-mentioned smearss are additionally containing at least one hydrophobicity The auxiliary rheological agents of silicic acid substrate.

In addition, having recorded a kind of thermosetting two-component-type coating composition in patent documentation 2, which contains specified quantitative respectively Hydroxy-containing resin, the barium sulfate of 1.0 μm to 15 μm of polyisocyanate compound and mean diameter, silicon dioxide microparticle and Rheology control agent.

In addition, having recorded a kind of non-aqueous dispersion type resin combination in patent documentation 3, which includes organic molten by dissolving in Dispersion stabilizer that the specific alkyd modified polyvinyls of agent is constituted, by the specific vinyl insoluble in organic solvent Discrete particles and organic solvent that polymer is constituted, wherein, the ratio of above-mentioned dispersion stabilizer and above-mentioned discrete particles is in spy In fixed scope.

Prior art literature

Patent documentation

Patent documentation 1:Japanese Unexamined Patent Application Publication 2013-544301 publication

Patent documentation 2:Japanese Unexamined Patent Publication 2013-53304 publications

Patent documentation 3:Japanese Unexamined Patent Publication 2003-335947 publications

The content of the invention

Problems to be solved by the invention

On the other hand, on the coated article of industrial product etc. application coating, it is desirable to excellent storage stability and then gloss The film performances such as stability, alkali resistance and resistance to impact are excellent.

Here, the gloss stability in the present invention is referred to meeting at least one in following three conditions：

I () gloss of the continuous film coated surface of application under the conditions of same application is uniform；

(ii) even if the thickness of the film for obtaining changes, the variation of gloss is also little；

(iii) even if application condition variation and coating solid composition variations, the variation of gloss is also little.

But, in the delustring film formed by the coating by described in patent documentation 1 to patent documentation 3, storage-stable Property, the various aspects (for example, stability of gloss etc.) in gloss stability, alkali resistance and resistance to impact are not enough.

Therefore, the problem to be solved in the present invention is to provide one kind to form storage-stable, gloss stability, alkaline-resisting The coating composition of the delustring film of property and excellent impact resistance.

The means of solve problem

In order to solve the above problems, the present inventor etc. is studied intensively.Its result finds, comprising envelope formative tree Fat (A) and delustering agent (B), and then include specific non-aqueous polymer dispersion liquid (C) and/or specific blocked polyisocyanates The coating composition of compound (D), can form disappearing for gloss stability, alkali resistance, storage-stable and excellent impact resistance Optical coating, so that complete the present invention.

I.e. the present invention provides the following technical scheme：

1st：A kind of coating composition, which includes envelope formative resin (A) and delustering agent (B), and then comprising by skin Non-aqueous polymer dispersion liquid (C), and/or blocked polyisocyanates compound (D) that composition and core component are constituted, its feature exist In,

Non-aqueous polymer dispersion liquid (C) divides containing at least one of acrylate copolymer as skin composition and/or greatly Sub- monomer, wherein, the self shrinking compound and each molecule that the macromonomer includes fatty acid averagely has more than one poly- Conjunction property unsaturated group, the fatty acid have the hydroxy alkyl that the carbon number of alkyl chain is 10 to 25,

Blocked polyisocyanates compound (D) is the simple function that the compound departed from cross-linking reaction is carbon number 3 to 12 The active methylene group class blocked polyisocyanates compound of alcohol.

2nd：Coating composition according to the 1st, wherein, delustering agent (B) is organic process silicon dioxide Granule.

3rd：Coating composition according to the 2nd, wherein, delustering agent (B) is that surface hydrophobicity processes dioxy Silicon carbide particle.

4th：Coating composition according to any one of the 1st to the 3rd, wherein, delustering agent (B's) is flat Particle diameter is 1 μm to 10 μm, and oil absorption is 100mL/100g to 400mL/100g.

5th：Coating composition according to any one of the 1st to the 4th, wherein, also containing cross-linking agent (E).

6th：Coating composition according to the 5th, wherein, cross-linking agent (E) contains polyisocyanates chemical combination Thing (E1).

7th：A kind of coating process, which is included on coated article application the 1st to the coating any one of the 6th The operation of compositionss.

8th：A kind of coated article, its be on coated article application the 1st to the coating group any one of the 6th Obtained from compound.

9th：A kind of coated article, which has is carried out the coating composition any one of the 1st to the 6th admittedly The film changed.

Invention effect

The present invention coating composition, can be formed on coated article storage-stable, gloss stability, alkali resistance and The delustring film of excellent impact resistance.

Specific embodiment

Below, for the coating composition of the present invention is described in detail.Coating composition (the letter sometimes below of the present invention Referred to as " this coating ") comprising envelope formative resin (A) and delustering agent (B), and then comprising specific non-aqueous polymer dispersion liquid And/or specific blocked polyisocyanates compound (D) (C).

Envelope formative resin (A)

As envelope formative resin (A), can be using resin known to itself used in coating all the time.Make For the species of resin, for example, acrylic resin, polyester resin, alkyd resin, polyurethane resin etc. can be enumerated.

Envelope formative resin (A), to carry out with blocked polyisocyanates compound (D) described later and/or cross-linking agent (E) For the purpose of reaction forms crosslinking film, preferably with cross-linking functional group.As the cross-linking functional group, hydroxyl, carboxylic can be enumerated Base, epoxy radicals, carbodiimide-based, carbonyl, hydrazide group, amino urea groups etc..Hydroxyl is preferably wherein.

As above-mentioned envelope formative resin (A), acrylic resin, the polyester of hydroxyl of hydroxyl for example, can be enumerated Resin, the polyurethane resin of hydroxyl, epoxy resin of hydroxyl etc..As preferred envelope formative resin (A), can enumerate Acrylic resin of hydroxyl etc..These envelopes formative resin (A) can be used alone or combine two or more using.

The excellent aspects such as gloss stability wherein, from the film for obtaining, alkali resistance and resistance to impact, it is above-mentioned Envelope formative resin (A) is more preferably the acrylic resin of hydroxyl.

The acrylic resin of hydroxyl, can be using known method by so that the polymerism unsaturated monomer of hydroxyl And other polymerism unsaturated monomer (a2) carries out copolymerization to manufacture (a1).

The polymerism unsaturated monomer (a1) of above-mentioned hydroxyl is that have more than one hydroxyl and poly- in a molecule respectively The compound of conjunction property unsaturated group.As the polymerism unsaturated monomer (a1) of the hydroxyl, specifically, acrylic acid or methyl Acrylic acid with the monoesters compound of the dihydroxylic alcohols of carbon number 2 to 10 be it is suitable, for example, can enumerate (methyl) acrylic acid -2- hydroxyl ethyl esters, (methyl) third of (methyl) 2-hydroxypropyl acrylate, (methyl) acrylic acid -3- hydroxypropyl acrylates, (methyl) acrylic acid -4- hydroxy butyl esters etc. Olefin(e) acid hydroxyalkyl acrylate.Further, as the polymerism unsaturated monomer (a1) of the hydroxyl, above-mentioned (methyl) acrylic acid can be enumerated Ring-opening polymerisation addition product of lactone compound such as hydroxyalkyl acrylate and 6-caprolactone etc..As ring-opening polymerisation addition product, it is concrete and Speech, for example, can enumerate " Placcel (プ ラ Network セ Le) FA-1 ", " Placcel FA-2 ", " Placcel FA-3 ", “Placcel FA-4”、“Placcel FA-5”、“Placcel FM-1”、“Placcel FM-2”、“Placcel FM-3”、 " Placcel FM-4 ", " Placcel FM-5 " (being the trade name of Daicel (Daicel) chemical company manufacture above) etc.. The polymerism unsaturated monomer (a1) of these hydroxyls can be used alone or combine two or more using.

In addition, in this manual, " (methyl) acrylate " expression " acrylate or methacrylate "." (first Base) acrylic acid " expression " acrylic or methacrylic acid ".In addition, " (methyl) acrylamide ", represents " acrylamide or methyl Acrylamide ".

As above-mentioned other polymerism unsaturated monomer (a2), the monomer of (a2-1) to (a2-8) can be enumerated.

(a2-1) the polymerism unsaturated monomer containing acidic group：

There is the compound of more than one acidic group (acid group) and a polymerism unsaturated group, for example, such as in one molecule The carboxylic polymerism unsaturated monomer of (methyl) acrylic acid .beta.-methylacrylic acid, itaconic acid, maleic acid and maleic anhydride etc.；Such as The polymerism unsaturated monomer containing sulfo group of vinyl sulfonic acid, (methyl) sulfoethyl acrylate etc.；2- (methyl) acryloxy Ethyl acid phosphate, 2- (methyl) acryloxypropyl phosphate ester acid, the acid of 2- (methyl) acryloxy -3- chloropropyls Phosphate ester acid Type of Collective unsaturated monomer of formula phosphate ester, 2- methaciylyloxyethylphenyl phosphoric acid etc. etc..

(a2-2) the monoesters compound of the monohydric alcohol of (methyl) acrylic acid and carbon number 1 to 20：

For example, (methyl) acrylic acid methyl ester., (methyl) ethyl acrylate, (methyl) propyl acrylate, (methyl) acrylic acid N-butyl, (methyl) Isobutyl 2-propenoate, (methyl) tert-butyl acrylate, (methyl) acrylic acid-2-ethyl caproite, (methyl) third The different monooctyl ester of olefin(e) acid, the different tetradecane base ester of (methyl) acrylic acid, acrylic acid isooctadecane base ester (trade name, Osaka organic chemistry work Industry society system), (methyl) dodecylacrylate, (methyl) tridecyl acrylate, (methyl) octadecyl acrylate Deng.

(a2-3) the polymerism unsaturated monomer with alicyclic type hydrocarbon：

(methyl) cyclohexyl acrylate, (methyl) isobornyl acrylate, (methyl) acrylic acid tricyclodecyl, (methyl) third Olefin(e) acid Buddha's warrior attendant alkyl ester, (methyl) acrylic acid -3,5- dimethyladamantane esters, methacrylic acid -3- tetracyclododecane base esters, (first Base) acrylic acid -4- methylcyclohexyl methyl ester, (methyl) acrylic acid -4- ethylcyclohexyl methyl ester, (methyl) acrylic acid -4- methoxies Butylcyclohexyl methyl ester, (methyl) t-butylcyclohexyl ester, (methyl) acrylic acid ring monooctyl ester, (methyl) acrylic acid cyclododecane Base ester, (methyl) acrylic acid tetrahydrofuran ester etc..Wherein, from from the viewpoint of acid resistance and stain resistance, preferably (methyl) Cyclohexyl acrylate, (methyl) isobornyl acrylate.

In addition, the polymerism unsaturated monomer with both alicyclic type hydrocarbon and hydroxyl, is considered as and is contained in hydroxyl Material in polymerism unsaturated monomer (a1).

(a2-4) aromatic series Type of Collective unsaturated monomer：

For example, styrene, α-methyl styrene, vinyltoluene etc..

(a2-5) the polymerism unsaturated monomer containing glycidyl：

There is in one molecule the compound of a glycidyl and polymerism unsaturated group respectively, specifically, have third Olefin(e) acid ester ethylene oxidic ester, glycidyl methacrylate etc..

(a2-6) nitrogenous polymerism unsaturated monomer：

For example, (methyl) acrylamide, DMAA, N, N- dimethyl propyl acrylamides, N- butoxy first Base acrylamide, N hydroxymethyl acrylamide, N- methylol methacrylamides, N-[2-(2-methyl-4-oxopentyl), (methyl) acrylic acid N, N- dimethylamino ethyl ester, vinylpyridine, vinyl imidazole etc..

(a2-7) other vinyl compounds：

For example, vinyl acetate, propionate, vinyl chloride, " VeoVa (ベ オ バ) 9 " as tertiary ethylene carbonate, " VeoVa 10 " (trade name, Japan Chemtech Ltd. (ジ ャ パ Application ケ ムテック societies) manufactures) etc..

(a2-8) nitrile compounds containing polymerism unsaturated group：

For example, acrylonitrile, methacrylonitrile etc..

The copolymerizable polymerism unsaturated monomer of above-mentioned others, can be used alone or combine two or more using.

The usage amount of the polymerism unsaturated monomer (a1) of above-mentioned hydroxyl, with the manufacture of the acrylic resin in hydroxyl Used in polymerism unsaturated monomer amount as 100 mass parts, be suitably for 15 mass parts to 50 mass parts, be preferably 20 mass Part is to 45 mass parts, more preferably 25 mass parts to 40 mass parts.

When the usage amount of polymerism unsaturated monomer (a1) of above-mentioned hydroxyl is set as more than 15 mass parts, by solid Change the crosslinking in film and be readily obtained alkali resistance, the resistance to impact of regulation, thus it is preferred that.On the other hand, when being set in 50 mass When part following, improve with the intermiscibility of other polymerism unsaturated monomer (a2) and/or copolyreaction, so with coating in Other compositions intermiscibility improve, thus improve film finished appearance, thus it is preferred that.

In addition, from the weatherability of film, alkali resistance, resistance to impact for being formed etc. it is excellent from the viewpoint of, as others At least one polymerism unsaturated monomer (a2-1) preferably used containing acidic group of polymerism unsaturated monomer (a2).

In this case, with the polymerism unsaturated monomer amount used in the manufacture of the acrylic resin of hydroxyl Used as 100 mass parts, the usage amount of the polymerism unsaturated monomer (a2-1) containing acidic group is suitably for 0.05 mass parts to 5 mass Part, preferably 0.1 mass parts to 3 mass parts, more preferably 0.5 mass parts are to 2 mass parts.

In addition, from from the viewpoint of alkali resistance of film, appearance of film for being formed etc., it is unsaturated as other polymerisms At least one of monomer (a2) is preferred, using the polymerism unsaturated monomer (a2-3) with alicyclic type hydrocarbon.

In this case, with the polymerism unsaturated monomer amount used in the manufacture of the acrylic resin of hydroxyl Used as 100 mass parts, the usage amount of the polymerism unsaturated monomer (a2-3) with alicyclic type hydrocarbon is suitably for 1 mass parts to 40 Mass parts, 5 mass parts to 30 mass parts, more preferably 10 mass parts are preferably gone up to 25 mass parts.

In addition, from viewpoints such as the alkali resistances of film, resistance to impact for being formed, it is unsaturated single as other polymerisms At least one of body (a2), preferably uses aromatic series Type of Collective unsaturated monomer (a2-4).

In this case, with the polymerism unsaturated monomer amount used in the manufacture of the acrylic resin of hydroxyl As 100 mass parts, the usage amount of aromatic series Type of Collective unsaturated monomer (a2-4) be suitably for 5 mass parts to 50 mass parts, Preferably 10 mass parts are to 40 mass parts, more preferably 15 mass parts to 35 mass parts.

For above-mentioned polymerism unsaturated monomer is carried out the copolymerization process that copolymerization obtains the acrylic resin of hydroxyl, do not have It is particularly limited to, copolymerization process known to itself can be used, can be wherein adapted for use with organic solvent, in polymerization initiator In the presence of the solution polymerization process that is polymerized.

As organic solvent used during above-mentioned solution polymerization process, for example, can enumerate：Toluene, dimethylbenzene, Swasolve (ス ワ ゾ Le) 1000 (trade name, high point petroleum class solvent, Cosmo Oil Co., Ltd.s (U ス モ oil society) system Make) etc. fragrant same clan's solvent；Ethyl acetate, 3- methoxybutyl acetates, ethylene glycol ether acetate, propylene glycol monomethyl ether vinegar The esters solvent of acid esters, propyl propionate, butyl propionate, ethoxyethyl propionate etc.；Methyl ethyl ketone, methyl iso-butyl ketone (MIBK), first Ketones solvent of base amyl ketone etc. etc..

These organic solvents, it is possible to use a kind of or combine two or more using.From the Coating material composition in the present invention The deliquescent aspect of the acrylic resin of the hydroxyl used in thing is set out, and preferably uses high boiling esters solvent, ketone Solvent.In addition, also high boiling fragrant same clan's solvent can be carried out appropriately combined using.

As the polymerization initiator that can be used during copolymerization in the acrylic resin of hydroxyl, for example, can enumerate：2,2’- Azodiisobutyronitrile, benzoyl peroxide, di-t-butyl peroxide, di t-amyl peroxide, the peroxidating isooctyl acid tert-butyl ester, 2, 2 '-azo double (2- methylbutyronitriles) etc. itself known to radical polymerization initiator.

The hydroxyl value of the acrylic resin of hydroxyl is adapted in the range of 80mgKOH/g to 200mgKOH/g, further excellent It is selected in the range of 100mgKOH/g to 170mgKOH/g.When hydroxyl value is in more than 80mgKOH/g, crosslink density is high, thus holds Be easy to get desired weatherability, alkali resistance, resistance to impact, appearance of film.In addition, when in below 200mgKOH/g, film Resistance to water is improved, thus it is preferred that.

The weight average molecular weight of the acrylic resin of hydroxyl is adapted in the range of 2500 to 40000, further preferably exists In the range of 4000 to 30000.When weight average molecular weight is more than 2500, desired weatherability, alkali resistance, resistance to punching is readily obtained The film performance of hitting property, appearance of film etc., thus it is preferred that.In addition, when weight average molecular weight is below 40000, film it is smooth Property improve, thus surface smooth finish (finishing property) is improved and preferably.

In addition, in this manual, weight average molecular weight is by by gel permeation chromatography (" HLC8120GPC ", eastern beautiful strain Formula commercial firm manufactures) weight average molecular weight that determines converts on the basis of the weight average molecular weight of polystyrene the value for obtaining.Following Under the conditions of carry out：Chromatographic column uses " TSKgel G-4000H × L ", " TSKgel G-3000H × L ", " TSKgel G-2500H × L ", " TSKgel G-2000H × L " (being the trade name of Dongli Ltd.'s manufacture) this four, mobile phase is tetrahydrochysene furan Mutter, temperature of the measurement is 40 DEG C, and flow velocity is 1cc/ minutes, and detector is RI.Number-average molecular weight is also in condition similar to the above Under be measured the value for obtaining.

The glass transition temperature of the acrylic resin of hydroxyl is usually -40 DEG C to 85 DEG C, and particularly preferably -30 DEG C extremely In the range of 80 DEG C.Desired hardness of film is obtained when glass transition temperature is more than -40 DEG C, and below 85 DEG C When film painting face flatness improve, thus it is preferred that.

The polyester resin of the hydroxyl that can be used as envelope formative resin (A), can adopt known method, for example, Manufactured by the esterification of polyprotic acid and polyhydric alcohol.

The polyprotic acid is the compound in a molecule with plural carboxyl, for example, can enumerate phthalic acid, Phthalic acid, p-phthalic acid, succinic acid, adipic acid, Azelaic Acid, decanedioic acid, tetrahydrophthalic acid, hexahydro O-phthalic Acid, maleic acid, fumaric acid, itaconic acid, trimellitic acid, Pyromellitic Acid and their acid anhydride etc..

In addition, the polyhydric alcohol is the compound with plural hydroxyl in a molecule, for example, can enumerate：Ethylene glycol, It is Propylene Glycol, 1,3- propane diols, 1,4- butanediols, 1,5- pentanediols, 1,6-HD, 2,2- diethyl -1,3- Propylene Glycol, new Pentanediol, 1,9- nonanediols, 1,4- cyclohexanediols, 3-hydroxypivalic acid DOPCP, 2-butyl-2-ethyl-1,3-propanediol, The diol compound of 3- methyl isophthalic acids, 5- pentanediols, 2,2,4- TMPDs, hydrogenated bisphenol A etc., trimethylolpropane, three The polyol component more than ternary of hydroxymethyl ethane, glycerol (glycerol), tetramethylolmethane etc., and 2,2- dihydroxymethyl third The hydroxyl of acid, 2,2- dimethylolpropionic acids, 2,2- dihydroxymethyl valeric acids, 2,2- dihydroxymethyl caproic acids, 2,2- dihydroxymethyl octanoic acids etc. Yl carboxylic acid etc..

In addition, can also make the alpha-olefin epoxide of expoxy propane and epoxy butane etc., Cardura (カ ジ ュ ラ) The monocyclic oxygen of (trade name synthesizes the ethylene oxidic ester of high chain is saturated fatty acid, Japanese epoxy resin Co., Ltd. manufacture) etc. Compound etc. is reacted with acid, and these compounds are imported in polyester resin.

To polyester resin import carboxyl in the case of, for example, can on the polyester of hydroxyl addition anhydride, by imposing It is half-esterification carrying out.

The hydroxyl value of the polyester resin of hydroxyl is adapted in the range of 80mgKOH/g to 200mgKOH/g, further preferably In the range of 100mgKOH/g to 170mgKOH/g.When value for more than 80mgKOH/g when, be readily obtained desired weatherability, Alkali resistance, resistance to impact, appearance of film etc., thus it is preferred that.In addition, when hydroxyl value be below 200mgKOH/g when, film it is water-fast Property improve, thus it is preferred that.

The weight average molecular weight of the polyester resin of hydroxyl is adapted in the range of 2500 to 40000, further preferably exists In the range of 5000 to 30000.When weight average molecular weight is more than 2500, desired weatherability, alkali resistance, resistance to punching is readily obtained The film performance of hitting property, appearance of film etc., thus it is preferred that.In addition, when weight average molecular weight is below 40000, the painting face of film Flatness is improved, thus it is preferred that.

The glass transition temperature of the polyester resin of hydroxyl is usually -40 DEG C to 85 DEG C, particularly preferably -30 DEG C to 80 In the range of DEG C.When glass transition temperature is more than -40 DEG C, desired hardness of film is readily obtained, thus it is preferred that.Separately Outward, when glass transition temperature is less than 85 DEG C, the painting face flatness of film is improved, thus it is preferred that.

In addition, in envelope formative resin (A), also comprising so-called polyurethane modified acrylic resin and polyurethane-modified Polyester resin.

The polyurethane resin of the hydroxyl that can be used as envelope formative resin (A), can enumerate by make polyhydric alcohol with Polyisocyanates carries out reacting the polyurethane resin of the hydroxyl for obtaining.

As polyhydric alcohol, for example, as the polyhydric alcohol of low-molecular-weight, can enumerate：Ethylene glycol, diethylene glycol, Propylene Glycol, fourth Trihydroxylic alcohols such as the dihydroxylic alcohols such as glycol, hexanediol, trimethylolpropane, glycerol, tetramethylolmethane etc..In addition, as high molecular Polyhydric alcohol, polyether polyol, PEPA, acryl polyol, epoxy polyol etc. can be enumerated.As polyether polyols Alcohol can enumerate Polyethylene Glycol, polypropylene glycol, polytetramethylene glycol etc..Above-mentioned dihydroxylic alcohols, dipropyl two can be enumerated as PEPA The polycondensation of the binary acid of the alcohol and adipic acid, Azelaic Acid, decanedioic acid of alcohol, 1,4- butanediols, 1,6-HD, neopentyl glycol etc. etc. The lactone ring-opening polymerization polymer polyhydric alcohol of thing, polycaprolactone etc., PCDL etc..In addition, for example, may also be and use 2,2- The carboxylic polyhydric alcohol of dihydromethyl propionic acid, 2,2- dimethylolpropionic acids etc..

As the polyisocyanates reacted with above-mentioned polyhydric alcohol, for example, can enumerate：Hexamethylene diisocyanate, The aliphatic polyisocyanic acid of trimethyl hexamethylene diisocyanate, dimer acid diisocyanate, lysinediisocyanate etc. Ester compounds, and biuret type addition product, the isocyanurate ring addition product of these polyisocyanates；Two isocyanide of isophorone Acid esters, 4,4 '-di-2-ethylhexylphosphine oxide (cyclohexyl isocyanate), hexahydrotoluene -2,4- (or -2,6-) diisocyanate, 1,3- (or 1,4-) two (isocyanatomethyl) hexamethylene, 1,4- cyclohexane diisocyanates, 1,3- Pentamethylene. diisocyanate, 1,2- hexamethylenes The alicyclic diisocyanate compound of alkane diisocyanate etc., and biuret addition product, the isocyanide of these polyisocyanates Urea acid esters cycloaddition thing；Xylylene diisocyanate, an xylylene diisocyanate, two Carbimide. of durol dimethyl Ester, toluene di-isocyanate(TDI), 4,4 '-methyl diphenylene diisocyanate, 1,5- naphthalene diisocyanates, two Carbimide. of 1,4- naphthalenes Ester, 4,4- toluidine diisocyanates, 4,4 '-diphenyl ether diisocyanate, (or to) phenylene vulcabond, 4, 4 '-diphenylene diisocyanate, 3,3 '-dimethyl -4,4 '-diphenylene diisocyanate, double (4- isocyanatophenyls) sulfones, The aromatic diisocyanate compounds of isopropylidene double (4- phenyl isocyanate) etc., and double contractings of these polyisocyanates Urea addition product, isocyanurate ring addition product；Triphenyl methane -4,4 ', 4 '-triisocyanate, tri- carbanils of 1,3,5-, Tri- TIs of 2,4,6-, 4,4 '-dimethyl diphenylmethane -2,2 ', 5,5 '-tetraisocyanate etc. has in a molecule There are the polyisocyanate compound of the NCO of more than 3, and biuret addition product, the isocyanide of these polyisocyanates Urea acid esters cycloaddition thing etc..

The hydroxyl value of the polyurethane resin of hydroxyl is adapted in the range of 80mgKOH/g to 200mgKOH/g, further excellent It is selected in the range of 100mgKOH/g to 170mgKOH/g.When hydroxyl value is more than 80mgKOH/g, it is obtained desired weather-proof Property, alkali resistance, resistance to impact, appearance of film etc., and in below 200mgKOH/g, the resistance to water of film is improved, thus excellent Choosing.

The weight average molecular weight of the polyurethane resin of hydroxyl is adapted in the range of 2500 to 40000, further preferably exists In the range of 4000 to 30000.When weight average molecular weight is more than 2500, desired weatherability, alkali resistance, resistance to punching is readily obtained The film performance of hitting property, appearance of film etc., thus it is preferred that.In addition, when weight average molecular weight is below 40000, the painting face of film Flatness is improved, thus it is preferred that.

The glass transition temperature of the polyurethane resin of hydroxyl is usually -40 DEG C to 85 DEG C, and particularly preferably -30 DEG C extremely In the range of 80 DEG C.Desired hardness of film is obtained when glass transition temperature is more than -40 DEG C, and below 85 DEG C When film painting face flatness improve, thus it is preferred that.

Delustering agent (B)

As delustering agent (B), can be using delustering agent known to itself used in coating all the time.As delustring The species of agent, for example, can enumerate inorganic particles, resin bead etc..

As inorganic particles, for example, can enumerate：Silica dioxide granule, alumina particle, titanium dioxide granule, zirconium oxide Granule, zircon particle, granules of stannic oxide, magnesium oxide particle, or their mixture.Wherein, particularly from extinction capability, storage From the viewpoint of hiding stable grade, inorganic particles are preferably silica dioxide granule.For the shape of above-mentioned silica dioxide granule does not have Be particularly limited to, can using spherical, hollow shape, Porous shape, bar-shaped, tabular, fibrous or indefinite shape granule.

As the commercially available product that above-mentioned silica dioxide granule can be used, for example, can enumerate：

Sylysia (the サ イ リ シ that chemistry of silicones Co., Ltd. of Fuji (Fuji Silysia Chemical Ltd.) manufactures ア) serial (Sylysia 350, Sylysia 430, Sylysia 435, Sylysia 436, Sylysia 450 etc.), Sylophobic (サ イ ロ ホ PVC ッ Network) series (Sylophobic 100, Sylophobic 200, Sylophobic 702, Sylophobic 100,4004 etc.), Sylosphere (サ イ ロ ス Off ェ ア) series (Sylosphere 1504, Sylosphere 1510 etc.)；

SYLOID series (the Syloid that Grace Japan K.K. (グ レ ス ジ ャ パ Application Co., Ltd.) are manufactured W300, Syloid W500 etc.)；

What Evonik Degussa Japan Co., Ltd. (エ ボ ニ ッ Network デ グ サ ジ ャ パ Application Co., Ltd.) were manufactured ACEMATT series (ACEMATT HK460, ACEMATT HK400, ACEMATT OK412, ACEMATT TS100, ACEMATT 3200th, ACEMATT 3300, ACEMATT 3600 etc.)；

NIPGEL series (the NIPGELAZ-200 that Japanese silication work Industrial Co., Ltd (Japanese シ リ カ works society) manufactures Deng), NIPSIL series (NIPSILE-200A, NIPSILSS-50b, NIPSILSS-178B etc.)；

Marshy land KCC manufacture Mizukasil (ミ ズ カ シ Le) series (Mizukasil P-73, Mizukasil P-526 etc.)；

The Carplex (カ プ レ ッ Network ス) series (Carplex CS-8 etc.) of Shionogi Seiyaku Kabushiki Kaisha's manufacture；

AEROSIL series (the AEROSIL that Nippon Aerosil Co., Ltd. (Japanese ア エ ロ ジ Le society) are manufactured 200th, AEROSIL R805 and AEROSIL R972 etc.)；

Showa chemical industry society manufacture Radiolite (ラ ヂ オ ラ イ ト) series (Radiolite 100, Radiolite 200, Radiolite 500, Radiolite 500R, Radiolite 500RS etc.)；Etc..

As above-mentioned inorganic particles, can be untreated inorganic particles and imposed with organic compound or inorganic compound Any one in the inorganic particles of surface treatment.Wherein, especially, from viewpoints such as storage-stables, preferred pair is inorganic micro- Grain carries out organic process.As the process of organic compound, there are polyethylene process, Tissuemat E process, surface hydrophobicity process etc., Wherein, from viewpoints such as storage-stable, alkali resistances, preferred surface hydrophobic treatment.As surface hydrophobicity process, can be adapted to make Known method is used, for example, can enumerate makes the organosilicon compounds such as the hydroxyl and polydimethylsiloxane of silica particles Thing carries out the process of chemical bonding.

Surface hydrophobicity process is carried out to inorganic particles in the present invention, is referred to and " is added the water of 5mL in developmental tube, by 0.3g Inorganic particles be slowly put into and wherein stood, after 12 hours, keep afloat in more than the 75% of inorganic particles State ".

As resin bead, for example, PMMA (polymethyl methacrylate) resin bead, MMA-EGDM (ethylene glycol bisthioglycolates can be enumerated Methacrylate) copolymer resinses pearl, nylon resin pearl, polyflon pearl etc..

As the commercially available product that above-mentioned resin bead can be used, for example, can enumerate：Sekisui Plastics Co., Ltd.'s manufacture " Dyneon (the ダ イ ニ that " Techpolymer series (trade name) ", Sumitomo 3M Co., Ltd. (Sumitomo ス リ エ system society) manufacture オ Application) serial (trade name) " etc..

For delustering agent (B), from viewpoints such as extinction capability, storage-stables, its mean diameter is suitably for 1 μm To 10 μm, preferably 2 μm to 8 μm, more preferably 3 μm to 7 μm.

Here, in this manual, the mean diameter of delustering agent refers to the particle size distribution using laser scattering method D50 values.So-called D50 values are the particle size distribution on the basis of volume, and the cumulative particle size distribution started from small particle side is 50% Particle diameter.In this manual, the particle size distribution with volume reference of delustering agent uses laser diffraction/scattering formula particle size distribution Device " Microtrac (マ イ Network ロ ト ラ ッ Network) NT3300 " (trade name, Nikkiso Company Limited's manufacture) is measured.This When, apply in the mixed solvent of acetone and isopropanol one minute ultrasound wave and be used as pre- place by silica dioxide granule is made an addition to Reason is disperseed, and delustring agent concentration is adjusted to the concentration for reaching the regulation transmitance scope set by device.

For delustering agent (B), from from the viewpoint of extinction capability, its oil absorption is suitably for 100mL/100g extremely 400mL/100g, preferably 100mL/100g to 380mL/100g, more preferably 100mL/100g to 360mL/100g.

Here, in this manual, the oil absorption of delustering agent is according to JIS K5101-13-2：2004 are measured Value.

Non-aqueous polymer dispersion liquid (C)

Non-aqueous polymer dispersion liquid (C) is made up of skin composition and core component.Typically in macromolecular dispersion stabilizer (C1) polymer particles for and being obtained by carrying out being polymerized at least one unsaturated monomer (C3) in the presence of organic solvent (C2) The dispersion liquid of grain.Resulting non-aqueous polymer dispersion liquid (C) has skin portion and core segment.Macromolecular dispersion stabilizer (C1) Skin composition is primarily formed, the polymer beads (C4) obtained from unsaturated monomer (C3) primarily form core component.

In the present invention, non-aqueous polymer dispersion liquid (C) is containing at least one of acroleic acid polymerization as skin composition Thing and/or macromonomer, the macromonomer comprising fatty acid self shrinking compound and each molecule averagely with one with On polymerism unsaturated group, the fatty acid has the hydroxy alkyl that the carbon number of alkyl chain is 10 to 25.

The non-aqueous polymer dispersion liquid (C) of the present invention, typically, must contain third as macromolecular dispersion stabilizer (C1) Olefin(e) acid polymer (C1-1) and/or macromonomer (C1-2), macromonomer (C1-2) self condensing containing fatty acid Thing, and average each molecule has more than one polymerism unsaturated group, and wherein, the fatty acid has the carbon of alkyl chain Number is 10 to 25 hydroxy alkyl.That is, non-aqueous polymer dispersion liquid (C) is containing at least one of acrylic acid as skin composition Polymer (C1-1) and/or macromonomer (C1-2), the self shrinking compound of macromonomer (C1-2) containing fatty acid and Average each molecule has more than one polymerism unsaturated group, and wherein, it is 10 that the fatty acid has the carbon number of alkyl chain To 25 hydroxy alkyl.Below, sometimes by comprising with alkyl chain carbon number be 10 to 25 hydroxy alkyl fatty acid from The macromonomer (C1-2) that condensation substance and average each molecule have more than one polymerism unsaturated group is referred to as " greatly Molecule monomer (C1-2) ".

Macromolecular dispersion stabilizer (C1)

Macromolecular dispersion stabilizer (C1), it is containing acrylate copolymer (C1-1) and/or macromonomer (C1-2), described Self shrinking compound of the macromonomer (C1-2) containing fatty acid and average each molecule has more than one polymerism insatiable hunger And base, the fatty acid has the hydroxy alkyl that the carbon number of alkyl chain is 10 to 25.

Acrylate copolymer (C1-1)

Acrylate copolymer (C1-1), optionally will be other unsaturated single usually in long-chain unsaturated monomer Body carries out the polymer of copolymerization.

Long-chain unsaturated monomer used in the polymer, the performance that can be required according to film are suitably selected.Make It is, from copolymerizable, the long-chain unsaturated monomer preferably used to viewpoints such as the dissolubilities of organic solvent, can to illustrate following Material.

For example, can enumerate：(methyl) n-butyl acrylate, (methyl) Isobutyl 2-propenoate, (methyl) tert-butyl acrylate, (methyl) acrylic acid-2-ethyl caproite, (methyl) cyclohexyl acrylate, (methyl) n-octyl, (methyl) acrylic acid ten (methyl) of dialkyl ester, (methyl) tridecyl acrylate, (methyl) octadecyl acrylate etc. acrylic acid carbon number 4 To 18 alkyl or cycloalkyl ester；(methyl) methoxyethyl butyl ester, (methyl) methoxyethyl acrylate, (methyl) propylene (methyl) acrylic acid alkoxy alkyl of sour Ethoxybutyl etc.；The aromatic alcohols of (methyl) benzyl acrylate etc. and (first Base) acrylic acid ester；(methyl) glycidyl acrylate or (methyl) acrylic acid hydroxyalkyl acrylate and capric acid, lauric acid, The addition product of the monocarboxylic acid compounds such as linoleic acid, Oleic acid；(methyl) acrylic acid and " Cardura (カ ジ ユ ラ) E10 " etc. The addition product of mono-epoxy compounds；Styrene, α-methyl styrene, vinyltoluene, to chlorostyrene, p-tert-butylstyrene Deng vinyl aromatic compounds；Itaconic acid, itaconic anhydride .beta.-methylacrylic acid, maleic acid, maleic anhydride, fumaric acid, citraconic acid etc. The alpha, beta-unsaturated carboxylic acid in addition to (methyl) acrylic acid and butanol, amylalcohol, enanthol, capryl alcohol, stearyl alcohol etc. carbon number 4 to The monoesters or diester compound of 18 single methanol；“Viscoat(ビスコート)8F”、“Viscoat 8FM”、“Viscoat 3F”、 " Viscoat 3FM ", (manufacture of Osaka organic chemistry Co., Ltd. is, trade name, side chain have (methyl) propylene of fluorine atom Ester compound), (methyl) perfluoroethyl cyclohexyl, the compound containing fluorine atom of perfluorohexyl ethylene etc. etc..

As the unsaturated monomer in addition to above-mentioned long-chain unsaturated monomer, as long as except the long-chain enumerated as described above Unsaturated monomer beyond unsaturated monomer is just not particularly limited, and for example, can enumerate：(methyl) acrylic acid methyl ester., (methyl) The Arrcostab of (methyl) of ethyl acrylate, (methyl) propyl acrylate etc. acrylic acid carbon number 1 to 3；(methyl) acrylic acid contracts The addition product of the monocarboxylic acid compound of carbon number 2 to 3 such as water glyceride and acetic acid, propanoic acid；Itaconic acid, itaconic anhydride .beta.-methylacrylic acid, horse Come sour, maleic anhydride, fumaric acid, citraconic acid etc. the alpha, beta-unsaturated carboxylic acid in addition to (methyl) acrylic acid and methanol, third The monoesters or diester compound of the single methanol of the carbon numbers 1 to 3 such as alcohol；The unsaturated compound of the cyano-containings such as (methyl) acrylonitrile；Such as second Vinyl ester compound as vinyl acetate；The vinyl ether compounds such as ethyl vinyl ether, methyl vinyl ether；Ethylene, Alpha-olefines compound such as propylene, vinyl chloride, vinylidene chloride etc..In the unsaturated monomer in addition to long-chain unsaturated monomer In, also so the above-mentioned unsaturated monomer enumerated is taken with hydroxyl etc. including (methyl) acrylic acid -2- hydroxyl ethyl esters etc. Compound obtained from generation.

The polymerization of long-chain unsaturated monomer and the polymerization of long-chain unsaturated monomer and the unsaturated monomer in addition to them Copolymerization, generally can be carried out using radical polymerization initiator.As radical polymerization initiator, for example, can enumerate：2,2 '-even The azo-initiator of nitrogen bis-isobutyronitrile, 2,2 '-azo double (2,4- methyl pentane nitriles) etc.；Benzoyl peroxide, lauryl mistake Peroxide type initiators of oxide, the peroxidating isooctyl acid tert-butyl ester, t-butylperoxy -2-ethylhexanoate etc. etc..Phase For every 100 mass parts of monomer for being generally used for being polymerized, these polymerization initiators can be in 0.2 mass parts to 10 mass parts or so In the range of, use preferably in the range of 0.5 mass parts to 5 mass parts.Reaction temperature during polymerization is usually 60 DEG C to 160 DEG C or so, response time during polymerization is usually 1 hour to 15 hours or so.

When (C) composition is manufactured, it is combined with polymer beads (C4) by making acrylate copolymer (C1-1), can Improve storage-stable and the mechanical property of non-aqueous polymer dispersion liquid (C).Even if in addition, acrylate copolymer (C1-1) with In the case that polymer beads (C4) are combined, apparent dispersity also has almost no change, polymer beads it is flat Particle diameter also has almost no change.

Method as making acrylate copolymer (C1-1) be combined with polymer beads (C4), for example, can adopt down State method to carry out：In the stage of previously fabricated acrylate copolymer (C1-1), will be with hydroxyl, acidic group, anhydride group, epoxy The monomer component of the functional group of base, methylol, NCO, amide groups, amino etc. carries out a part of copolymerization, used as further shape Into polymer beads monomer component using with the hydroxyl, acidic group, anhydride group, epoxy radicals reacted with above-mentioned functional group, The monomer of the functional group of methylol, NCO, amide groups, amino etc..As the combination of these compounds, for example, can enumerate NCO and hydroxyl, NCO and methylol, epoxy radicals and sour (acid anhydride) base, epoxy radicals and amino, NCO With the combination of amide groups, acid (acid anhydride) base and hydroxyl etc..

As the monomer with this functional group, for example, can enumerate：(methyl) acrylic acid .beta.-methylacrylic acid, maleic acid, Malaysia The α of anhydride, itaconic acid, itaconic anhydride, fumaric acid, citraconic acid etc., β-ethylene unsaturated carboxylic acid；(methyl) acrylic acid shrinks sweet The compound containing glycidyl of grease, vinyl glycidyl ether, allyl glycidyl ether etc.；(methyl) acryloyl Amine, N, N- dimethyl (methyl) acrylamide, N- alkoxy methyls (methyl) acrylamide, N-[2-(2-methyl-4-oxopentyl), N- hydroxyl first The carboxamide compounds of base (methyl) acrylamide etc.；To styrene sulfonamide, N- methyl-to styrene sulfonamide, N, N- bis- The compound containing sulfoamido of methyl-to styrene sulfonamide etc.；(methyl) tbutylaminoethylacrylate etc. containing ammonia The compound of base；(methyl) acrylic acid -2- hydroxyl ethyl esters and phosphoric acid or the condensation substance of phosphate compound, contract in (methyl) acrylic acid The chemical combination of addition phosphoric acid or phosphate compound on the glycidyl of the compound with glycidyl of water glyceride etc. The compound of the phosphorous acid group of thing etc.；The compound containing sulfo group of 2- acrylamide -2- methyl-propanesulfonic acids etc.；Between isopropenyl- Bis (alpha, alpha-dimethylbenzyl) based isocyanate, isophorone diisocyanate or toluene di-isocyanate(TDI) and hydroxyl (methyl) acrylate Equimolar addition product, the compound containing NCO of methylacryoyloxyethyl isocyanates etc. etc..

In addition, as the additive method for being combined acrylate copolymer (C1-1) and polymer beads (C4), can be Carried out by making polymerization of unsaturated monomers in the presence of macromolecular dispersion stabilizer with polymerism unsaturated group.

For polymerism unsaturated group is to the importing in acrylate copolymer (C1-1), for example, can be by using carboxylic acid, phosphorus Copolymer composition of the monomer containing acidic group of acid, sulfonic acid etc. as the resin, and make the acidic group and (methyl) glycidyl The unsaturated monomer containing glycidyl of ester, allyl glycidyl ether etc. reacts to carry out.In addition, can also pass through phase Instead make in acrylate copolymer (C1-1) containing glycidyl and make which react to come with the unsaturated monomer containing acidic group Carry out.These reactions can be carried out according to known reaction condition.

In addition, as the further others side for making acrylate copolymer (C1-1) be combined with polymer beads (C4) Method, can import mutual nonreactive functional group by manufacture in acrylate copolymer (C1-1) with polymer beads (C4) After non-aqueous polymer dispersion liquid (C), make the material with make both combine bonding agent react to carry out.

Specifically, can carry out in the following way：In the acrylate copolymer (C1-1) of such as hydroxyl and organic In the presence of solvent (C2), by the unsaturated monomer of hydroxyl individually or as entering with the mixture of other unsaturated monomers Row polymerization, manufactures non-aqueous polymer dispersion liquids (C) containing hydroxyl in both, then coordinates isocyanate compound etc., and React a few hours to a couple of days at normal temperatures, react 1 to 5 hour or so at 60 DEG C to 100 DEG C or so.

As polyisocyanate compound, as long as in molecule, the compound with plural NCO is Can, for example, can enumerate：Toluene di-isocyanate(TDI), xylylene diisocyanate, 4,4 '-methyl diphenylene diisocyanate etc. Aromatic diisocyanate or its hydride；Hexamethylene diisocyanate, lysinediisocyanate, dimeric dibasic acid (appropriate that The dimer of fatty acid oil) diisocyanate etc. aliphatic diisocyanate；The ester ring type of isophorone diisocyanate etc. Diisocyanate etc..

In addition, in addition to the foregoing, also can be by the acrylate copolymer containing acidic group (C1-1) and polymer beads (C4) with the combination of polyepoxide, the acrylate copolymer containing epoxy radicals (C1-1) and polymer beads (C4) and polycarboxylic acids Combination, the acrylate copolymer containing epoxy radicals or NCO (C1-1) and polymer beads (C4) and polysulfide Combination etc. carrying out.

As polyepoxide, for example, can enumerate bisphenol A type epoxy resin, bisphenol f type epoxy resin, phenolic varnish type ring Oxygen tree fat, the acrylic resin containing epoxy radicals etc..As polycarboxylic acids, can for example enumerate adipic acid, decanedioic acid, Azelaic Acid, Phthalic acid etc..Pentamethylene disulphide, hexa-methylene disulphide, poly- (ethylene curing can be enumerated as polysulfide Thing) etc..

By being operated as above, acrylate copolymer (C1-1) can be made to carry out chemical key with polymer beads (C4) Close, various functional groups and/or polymerism unsaturated group are imported into acrylate copolymer (C1-1) and/or polymer beads now (C4) amount in, as long as averagely reach in a molecule of the acrylate copolymer (C1-1) and/or polymer beads (C4) to Few 0.1 amount is i.e. abundant.

Non-aqueous polymer dispersion liquid (C) so obtained by operation, due to acrylate copolymer (C1-1) and polymer particles Grain (C4) carries out chemical bonding, thus excellent storage stability, and the film for being formed can show that chemical, mechanicalness are excellent Different property.

Macromonomer (C1-2)

The self shrinking compound of the fatty acid comprising the hydroxy alkyl that the carbon number with alkyl chain is 10 to 25 and average each point Son has the macromonomer (" macromonomer (C1-2) ") of more than one polymerism unsaturated group, can illustrate following chemical combination Thing：Polyester macromonomers (C1-2a), which is, in the fatty acid of the hydroxy alkyl that the carbon number with alkyl chain is 10 to 25 Self condense on the carboxyl in polyester resin, the acrylic acid ethylene oxidic ester of addition (methyl), so that each molecule imports about 1.0 Individual polymerism unsaturated group is formed；Comb-shaped polymer (C1-2b), which is, makes the polymerism in the macromonomer (C1-2a) Unsaturated group is polymerized with polymerism unsaturated monomer；Comb-shaped polymer (C1-2c), which is, makes macromonomer (C1-2a) it is polymerized with the polymerism unsaturated monomer containing (methyl) acrylic acid ethylene oxidic ester, and then in the polymerization Addition α on glycidyl in thing, β-ethylene unsaturated acids simultaneously import polymerism unsaturated group and form.

Also, 12- hydroxyls are preferably as the fatty acid of the hydroxy alkyl that the above-mentioned carbon number with alkyl chain is 10 to 25 Stearic acid.

From from the viewpoint of gloss stability, storage-stable etc., macromolecular dispersion stabilizer (C1) is preferred and uses propylene Acid polymer (C1-1) and macromonomer (C1-2).

The molecular weight of above-mentioned macromolecular dispersion stabilizer (C1), generally in terms of number-average molecular weight 2500 to 50000 or so, It is preferred that in the range of 2500 to 25000 or so.The copolymer of the molecular weight with above range is being used as into dispersion stabilizer In the case of, by the stabilisation of discrete particles, it is obtained in that coagulation and sedimentation are suppressed and viscosity is too high, easy behaviour The coating for dealing with, thus it is preferred that.

As macromolecular dispersion stabilizer (C1), can be further as desired and with others such as such as alkyd resin Dispersion stabilizer.

Organic solvent (C2)

As the organic solvent (C2) used in above-mentioned polymerization, although the dispersed polymeres particle generated by the polymerization Actually do not dissolve, but can to widely use for above-mentioned macromolecular dispersion stabilizer (C1) and unsaturated monomer (C3) be good solvent Known organic liquid.As the specific example of this organic liquid, can enumerate：The aliphatic hydrocarbons such as hexane, heptane, octane； The aromatic hydrocarbons such as benzene,toluene,xylene；The alcoholic compounds such as methanol, isopropanol, n-butyl alcohol, isobutanol, capryl alcohol；Cellosolve, butyl The ether compounds such as cellosolve, diethylene glycol monobutyl ether；Methyl iso-butyl ketone (MIBK), diisobutyl ketone, methyl ethyl ketone, methylhexyl The assimilation compound such as ketone, ethyl butyl ketone；The esterification such as ethyl acetate, isobutyl acetate, pentyl acetate, 2- ethylhexyl acetates is closed Thing etc..These organic liquids, individually can use, and can also mix two or more uses, be generally adapted using with aliphatic hydrocarbon For main body, wherein obtained from appropriately combined aromatic hydrocarbon, alcoholic compound, ether compound, assimilation compound or ester compounds etc. Organic liquid.

Unsaturated monomer (C3)

It is as the unsaturated monomer (C3) for forming polymer beads (C4), excellent using polymerism and carbon number is used for high score The few unsaturated monomer of carbon number that the monomer that the monomer component of sub- dispersion stabilizer (C1) is used has, this is from as dispersin polymerization Composition granule is suitable from the viewpoint of easily being formed.

As this unsaturated monomer, for example, can enumerate：(methyl) acrylic acid methyl ester., (methyl) ethyl acrylate, (first Base) propyl acrylate, (methyl) n-butyl acrylate, (methyl) Isobutyl 2-propenoate, (methyl) tert-butyl acrylate, (methyl) Acrylic acid-2-ethyl caproite, (methyl) cyclohexyl acrylate, (methyl) n-octyl, (methyl) lauryl base (methyl) of ester, (methyl) tridecyl acrylate, (methyl) octadecyl acrylate etc. acrylic acid carbon number 1 to 18 Arrcostab or cycloalkyl ester；(methyl) methoxyethyl butyl ester, (methyl) methoxyethyl acrylate, (methyl) acrylic acid second (methyl) acrylic acid alkoxy alkyl of epoxide butyl ester etc.；(methyl) third of the aromatic alcohols of (methyl) benzyl acrylate etc. The ester of olefin(e) acid；(methyl) glycidyl acrylate and the carbon number 2 to 18 of acetic acid, propanoic acid, Oleic acid, p-tert-butyl benzoic acid etc. The addition product of monocarboxylic acid compound；The addition product of the mono-epoxy compounds of (methyl) acrylic acid and " Cardura E10 " etc.；Benzene second Alkene, α-methyl styrene, vinyltoluene, the vinyl aromatic compounds to chlorostyrene, p-tert-butylstyrene etc.；Clothing Health acid, itaconic anhydride .beta.-methylacrylic acid, maleic acid, maleic anhydride, fumaric acid, citraconic acid etc. in addition to (methyl) acrylic acid The monoesters or diester compound of the single methanol of the carbon number 1 to 18 of alpha, beta-unsaturated carboxylic acid and methanol, butanol, hexanol, stearyl alcohol etc.； (trade name is Osaka organic chemistry for " Viscoat 8F ", " Viscoat 8FM ", " Viscoat 3F ", " Viscoat 3FM " Co., Ltd. manufactures, and side chain has (methyl) acrylate compounds of fluorine atom), it is perfluor (methyl) cyclohexyl acrylate, complete The fluorine-containing atomic compound of fluorine hexyl ethylene etc.；The unsaturated compound of the cyano-containing of (methyl) acrylonitrile etc.；Such as vinyl acetate The vinyl ester compound such as ester, vinyl benzoate, " VeoVa (VEOVA) " (Shell (シ ェ Le) Co. Ltd. system)；Positive fourth The vinyl ether compound of base vinyl ethers, ethyl vinyl ether, methyl vinyl ether etc.；(methyl) propylene of 1,6-HD The polyvinyl of acid diesters, three ester of (methyl) acrylic acid of trimethylolpropane, divinylbenzene etc.；Ethylene, propylene, chlorine Alpha-olefines compound of ethylene, vinylidene chloride etc. etc..

For the unsaturated monomer (C3) of polymer beads (C4) is formed, as described above, by using carbon number than high The few material of the carbon number of the monomer component of molecular dispersion stabilizer (C1), can be stably formed particulate component.Go out from the viewpoint Send out, can be adapted to using carbon number below 8, be preferably less than 4 (methyl) acrylate compounds, vinyl aromatic compounds, (methyl) acrylonitrile etc..These unsaturated monomers, can be used alone or combine two or more using.

The polymerization of above-mentioned unsaturated monomer (C3) is usually used radical polymerization initiator to carry out.As can use from By base polymerization initiator, for example, can enumerate：The idol of 2,2 '-azodiisobutyronitrile, 2,2 '-azo double (2,4- methyl pentane nitriles) etc. Nitrogen class initiator；Benzoyl peroxide, lauryl peroxide, the peroxidating isooctyl acid tert-butyl ester, t-butylperoxy -2- ethyls Peroxide type initiators of alkyl caproate etc. etc..Relative to every 100 mass parts of monomer for being generally used for being polymerized, these polymerizations are drawn Send out agent to use in the range of 0.2 mass parts to 10 mass parts or so, preferably in the range of 0.5 mass parts to 5 mass parts.

For the macromolecular dispersion stabilizer (C1) that exists during above-mentioned polymerization and unsaturated monomer (C3) use ratio and Speech, relative to 100 mass parts of macromolecular dispersion stabilizer (C1), usual unsaturated monomer (C3) is 3 mass parts to 240 mass parts Left and right, preferably 5 mass parts to 82 mass parts or so.Further, in organic solvent (C2) macromolecular dispersion stabilizer (C1) and Total concentration of unsaturated monomer (C3), usually 30 mass parts to 70 mass % or so, preferably 30 mass parts are to 60 matter Amount % or so.

Polymerization can be carried out by method known to itself, reaction temperature during polymerization be usually 60 DEG C to 160 DEG C it is left The right side, response time during polymerization are usually 1 hour to 15 hours or so.

Polyreaction is carried out as described above, stable non-aqueous polymer dispersion liquid (C) can be obtained, and wherein liquid phase is Macromolecular dispersion stabilizer (C1) is dissolved in the solution that organic solvent (C2) is obtained, and solid phase is polymerized for unsaturated monomer (C3) The polymer beads (C4) for obtaining.The mean diameter of polymer beads (C4), ordinarily be about 0.1 μm to 1.0 μm of scope.Pass through Make the mean diameter of polymer beads (C4) in above range, the viscosity of non-aqueous polymer dispersion liquid (C) does not become too high, and Can suppress the swelling or coagulation of polymer beads (C4) of the coating in storage, thus it is preferred that.

Blocked polyisocyanates compound (D)

Blocked polyisocyanates compound (D), is at least will have two in a molecule with active methylene group class end-capping reagent The NCO of the polyisocyanate compound of NCO carries out the compound for blocking, and is taken off in cross-linking reaction From compound be 3 to 12 for carbon number, be preferably active methylene group class blocked polyisocyanates as 6 to 8 monofunctional alcohol Compound.

In the present invention, as blocked polyisocyanates compound (D), preferred isocyanate base can be included by following (d1) carry out blocked polyisocyanates compound (D) for blocking etc..

In the case that the compound departed from cross-linking reaction is monofunctional alcohol of the carbon number below 2, the film for obtaining disappears Photosensitiveness is poor.On the other hand, in the case of monofunctional alcohol of the compound for departing from cross-linking reaction for carbon number more than 13, it is difficult to draw Play cross-linking reaction, therefore the alkali resistance of the film for obtaining, resistance to water and resistance to impact equal difference.

The compound departed from cross-linking reaction is that the active methylene group class end-blocking of the monofunctional alcohol for departing from carbon number 3 to 12 is more Isocyanate compound (D), for example, can be an off carbon number 3 to 12 by causing the compound departed from cross-linking reaction Monofunctional alcohol activity methene compound (d1) (being sometimes referred to simply as " activity methene compound (d1) " below) and polyisocyanate Cyanate esters (d2) react to obtain.

Activity methene compound (d1)

As above-mentioned activity methene compound (d1), for example, can enumerate diester malonate, the acetoacetic acid of following presentation Ester, isobutyl ethyl sodio acetoacetic ester etc..

As diester malonate, can enumerate：Malonic acid di-n-propyl ester, diethyl malonate, Diisopropyl malonate, the third two Sour di-n-butyl, malonic acid diisobutyl ester, malonic acid di-secondary butyl ester, malonic acid di tert butyl carbonate, two n-pentyl ester of malonic acid, malonic acid The double hendecane base esters of two just own esters, two -2- Octyl Nitrites of malonic acid, malonic acid dioctyl ester, malonic acid, malonic acid double hexadecyl Ester, two -9- stearyls of malonic acid, malonic acid two (methyl isopropyl ester), malonic acid two (ethylisopropyl ester), malonic acid two (methyl N-butyl), malonic acid two (ethyl N-butyl), malonic acid two (methyl tert-butyl ester), malonic acid two (ethyl isobutyl ester), Malonic acid two (the secondary butyl ester of methyl), malonic acid two (the secondary butyl ester of ethyl), diphenyl malonate, malonic acid dibenzyl ester, malonic acid two 2- methoxy acrylates, two 2- ethoxy ethyl esters of malonic acid, two 2- propoxy ethyls of malonic acid, two 2- isopropoxy second of malonic acid Ester, two 2- butoxyethyls of malonic acid, two 2- isobutoxy ethyl esters of malonic acid, two 2- amoxy ethyl esters of malonic acid, malonic acid two 2- hexyloxy ethyl esters, two 2- octyloxy ethyl esters of malonic acid, two 2- decyloxy ethyl esters of malonic acid, two 2- of malonic acid (2- methoxyl group second Epoxide) ethyl ester, two 2- of malonic acid (2- ethoxy ethoxies) ethyl ester, two 2- of malonic acid (2- propoxyl group ethyoxyls) ethyl ester, the third two Acid two 2- (2- Butoxyethoxies) ethyl ester, two 2- of malonic acid (2- Benzyloxyethoxies) ethyl ester, two 2- of malonic acid [2- (2- first Epoxide ethyoxyl) ethyoxyl] ethyl ester, two 2- of malonic acid [2- (2- ethoxy ethoxies) ethyoxyl] ethyl ester, two 2- [2- of malonic acid (2- Butoxyethoxies) ethyoxyl] ethyl ester, two 1- methoxyl group -2- propyl ester of malonic acid, two 1- ethyoxyl -2- propyl ester of malonic acid, Two 1- propoxyl group -2- propyl ester of malonic acid, two 1- butoxy -2- propyl ester of malonic acid, two 1- amoxy -2- propyl ester of malonic acid, the third two Sour two 1- hexyloxy -2- propyl ester, two 1- octyloxy -2- propyl ester of malonic acid, malonic acid two (2- methoxymethylethoxies) -1- third Ester, two 3- of malonic acid (3- ethoxy-c epoxides) -1- propyl ester, two 1- of malonic acid (1- methyl -2- propoxyl group ethyoxyls) -2- third Ester, malonic acid two (2- butoxymethyl ethyoxyls) -1- propyl ester, two 2- of malonic acid { 2- [2- methoxyl groups (methyl) ethyoxyl] (first Base) ethyoxyl (methyl) ethyl ester, two 1- of malonic acid [1- methyl -2- (1- methyl -2- propoxyl group ethyoxyls) ethyoxyl] -2- third The monofunctional alcohol of ester etc., preferably carbon number 3 to 12 and the diester of malonic acid etc..

As acetoacetic ester, can enumerate：Acetoacetic acid n-propyl, isopropyl acetoacetate, acetoacetic acid N-butyl, second The just own ester of the secondary butyl ester of ethyl acetoacetic acid isobutyl ester, acetoacetic acid, tert-butyl acetoacetate, acetoacetic acid n-pentyl ester, acetoacetic acid, acetyl 2-ethyl hexyl ethanoate, acetoacetic acid monooctyl ester, acetoacetic acid hendecane base ester, acetoacetic acid cetyl ester, acetoacetic acid- 9- stearyls, acetoacetic acid phenyl ester, benzyl acetoacetate, acetoacetic acid -2- methoxy acrylates, acetoacetic acid -2- ethoxies Base ethyl ester, acetoacetic acid -2- propoxy ethyls, acetoacetic acid -2- isopropoxyethyl cyanoacrylates, acetoacetic acid -2- butoxyethyls, second Ethyl acetoacetic acid -2- isobutoxy ethyl esters, acetoacetic acid -2- amoxy ethyl esters, acetoacetic acid -2- hexyloxy ethyl esters, acetoacetic acid -2- Octyloxy ethyl ester, acetoacetic acid -2- decyloxy ethyl esters, acetoacetic acid -2- (2- methoxy ethoxy) ethyl ester, acetoacetic acid -2- (2- ethoxy ethoxies) ethyl ester, acetoacetic acid -2- (2- propoxyl group ethyoxyls) ethyl ester, acetoacetic acid -2- (2- butoxy ethoxies Base) ethyl ester, acetoacetic acid -2- (2- Benzyloxyethoxies) ethyl ester, acetoacetic acid -2- [2- (2- methoxy ethoxy) ethyoxyl] Ethyl ester, acetoacetic acid -2- [2- (2- ethoxy ethoxies) ethyoxyl] ethyl ester, acetoacetic acid -2- [2- (2- Butoxyethoxies) Ethyoxyl] ethyl ester, acetoacetic acid -1- methoxyl group -2- propyl ester, acetoacetic acid -1- ethyoxyl -2- propyl ester, the third oxygen of acetoacetic acid -1- Base -2- propyl ester, acetoacetic acid -1- butoxy -2- propyl ester, acetoacetic acid -1- amoxy -2- propyl ester, the own oxygen of acetoacetic acid -1- Base -2- propyl ester, acetoacetic acid -1- octyloxy -2- propyl ester, acetoacetic acid (2- methoxymethylethoxies) -1- propyl ester, acetyl second Acid -3- (3- ethoxy-c epoxides) -1- propyl ester, acetoacetic acid -1- (1- methyl -2- propoxyl group ethyoxyls) -2- propyl ester, acetyl second Sour (2- butoxymethyl ethyoxyls) -1- propyl ester, acetoacetic acid -2- { 2- [2- methoxyl groups (methyl) ethyoxyl] (methyl) ethoxies Base } (methyl) ethyl ester, acetoacetic acid -1- [1- methyl -2- (1- methyl -2- propoxyl group ethyoxyls) ethyoxyl] -2- propyl ester etc., it is excellent Elect the monofunctional alcohol of carbon number 3 to 12 and the diester of acetoacetic acid etc. as.

As ethyl isobutyryl, can enumerate：Isobutyryl n-propyl acetate, isobutyryl isopropyl acetate, isobutyryl second Sour N-butyl, isobutyryl isobutyl acetate, isobutyryl sec-butyl acetate, isobutyryl tert-butyl acetate, isobutyryl n-amyl acetate, It is isobutyryl n-hexyl acetate, isobutyryl 2-ethyl hexyl ethanoate, isobutyryl Caprylyl acetate, isobutyl ethyl acetoacetic acid undecyl ester, different Butyryl acetic acid cetyl ester, isobutyl ethyl acetoacetic acid -9- octadecane esters, isobutyl ethyl acetoacetic acid phenyl and isobutyryl benzyl acetate, isobutyl Ethyl acetoacetic acid -2- methoxy acrylates, isobutyryl acetic acid -2-ethoxy-ethyl ester, isobutyl ethyl acetoacetic acid -2- propoxy ethyls, isobutyryl second Acid -2- isopropoxyethyl cyanoacrylates, isobutyl ethyl acetoacetic acid -2- butoxyethyls, isobutyl ethyl acetoacetic acid -2- isobutoxy ethyl esters, isobutyryl second Acid -2- amoxy ethyl esters, isobutyl ethyl acetoacetic acid -2- hexyloxy ethyl esters, isobutyl ethyl acetoacetic acid -2- octyloxy ethyl esters, isobutyl ethyl acetoacetic acid -2- Decyloxy ethyl ester, isobutyl ethyl acetoacetic acid -2- (2- methoxy ethoxy) ethyl ester, isobutyl ethyl acetoacetic acid -2- (2- ethoxy ethoxies) second Ester, isobutyl ethyl acetoacetic acid -2- (2- propoxyl group ethyoxyls) ethyl ester, isobutyl ethyl acetoacetic acid -2- (2- Butoxyethoxies) ethyl ester, isobutyryl Acetic acid -2- (2- Benzyloxyethoxies) ethyl ester, isobutyl ethyl acetoacetic acid -2- [2- (2- methoxy ethoxy) ethyoxyl] ethyl ester, isobutyl Ethyl acetoacetic acid -2- [2- (2- ethoxy ethoxies) ethyoxyl] ethyl ester, isobutyl ethyl acetoacetic acid -2- [2- (2- Butoxyethoxies) ethoxies Base] ethyl ester, isobutyl ethyl acetoacetic acid -1- methoxyl group -2- propyl ester, isobutyl ethyl acetoacetic acid -1- ethyoxyl -2- propyl ester, isobutyl ethyl acetoacetic acid -1- third Epoxide -2- propyl ester, isobutyl ethyl acetoacetic acid -1- butoxy -2- propyl ester, isobutyl ethyl acetoacetic acid -1- amoxy -2- propyl ester, isobutyl ethyl acetoacetic acid - 1- hexyloxy -2- propyl ester, isobutyl ethyl acetoacetic acid -1- octyloxy -2- propyl ester, isobutyl ethyl acetoacetic acid (2- methoxymethylethoxies) -1- Propyl ester, isobutyl ethyl acetoacetic acid -3- (3- ethoxy-c epoxides) -1- propyl ester, isobutyl ethyl acetoacetic acid -1- (1- methyl -2- propoxyl group ethoxies Base) -2- propyl ester, isobutyl ethyl acetoacetic acid (2- butoxymethyl ethyoxyls) -1- propyl ester, isobutyl ethyl acetoacetic acid -2- { 2- [2- methoxyl group (first Base) ethyoxyl] (methyl) ethyoxyl (methyl) ethyl ester, isobutyl ethyl acetoacetic acid -1- [1- methyl -2- (1- methyl -2- propoxyl group ethoxies Base) ethyoxyl] -2- propyl ester etc., diester of the excellent monofunctional alcohol for carbon number 3 to 12 and isobutyl ethyl acetoacetic acid etc..

Above-mentioned activity methene compound (d1) can be used alone or combine two or more using.

Wherein, from from the viewpoint of gloss stability of film for being formed etc., activity methene compound (d1) is suitably for Malonic acid -1- methoxyl group -2- propyl ester, malonic acid -1- ethyoxyl -2- propyl ester, malonic acid -1- propoxyl group -2- propyl ester.

Polyisocyanate compound (d2)

Polyisocyanate compound (d2) be in a molecule at least with two NCOs compound, example Such as, can enumerate：Aliphatic polyisocyante, alicyclic polyisocyanates, aromatic-aliphatic polyisocyanates, many isocyanides of aromatic series Acid esters, derivant of these polyisocyanates etc..

As above-mentioned aliphatic polyisocyante, for example, can enumerate：Trimethylene diisocyanate, tetramethylene two are different Cyanate, hexamethylene diisocyanate, pentamethylene diisocyanate, 1,2- trimethylene diisocyanates, 1,2- butylidenes Diisocyanate, 2,3- tetramethylene diisocyanates, 1,3- tetramethylene diisocyanates, 2,4,4- or 2,2,4- trimethyls six are sub- Methyl diisocyanate, dimer acid diisocyanate, bis- isocyanate group methyl caproate (common names of 2,6-：Two Carbimide. of lysine Ester) etc. aliphatic diisocyanate；Bis- isocyanate group caproic acid -2- isocyanatoethyl methacrylates of 2,6-, bis- isocyanate group -3- of 1,6- are different Cyanic acid ylmethyl hexane, tri- isocyanate group octanes of 1,4,8-, tri- isocyanate group hendecanes of 1,6,11-, bis- isocyanate group -4- of 1,8- Isocyanatometyl octane, tri- isocyanate group hexanes of 1,3,6-, two isocyanate group -5- isocyanate groups of 2,5,7- trimethyls -1,8- Aliphatic triisocyanate of methyloctane etc. etc..

As above-mentioned alicyclic polyisocyanates, for example, can enumerate：1,3- cyclopentene diisocyanates, 1,4- hexamethylene Diisocyanate, 1,3- cyclohexane diisocyanates, 3- isocyanatometyl -3,5,5- trimethylcyclohexylisocyanates are (logical With name：Isophorone diisocyanate), 4- methyl isophthalic acids, 3- cyclohexene diisocyanate (common names：Hydrogenation TDI), 2- methyl- Double (isocyanatometyl) hexamethylene (common names of 1,3- cyclohexene diisocyanate, 1,3- or 1,4-：Hydrogenated xylylene two is different Cyanate) or its mixture, di-2-ethylhexylphosphine oxide (4,1- cyclohexanediols) diisocyanate (common name：Hydrogenation MDI), norbornane two The alicyclic diisocyanate of isocyanates etc.；Tri- isocyanate group hexamethylene of 1,3,5-, 1,3,5- trimethyl isocyanate group hexamethylenes Alkane, 2- (3- isocyanate group propyl group) -2,5- two (isocyanatometyl)-bicyclic (2.2.1) heptane, 2- (3- isocyanate groups third Base) -2,6- two (isocyanatometyl)-bicyclic (2.2.1) heptane, 3- (3- isocyanate group propyl group) two (isocyanate group first of -2,5- Base)-bicyclic (2.2.1) heptane, 5- (2- isocyanatoethyls) -2- isocyanatometyl -3- (3- isocyanate group propyl group)-bicyclic (2.2.1) heptane, 6- (2- isocyanatoethyls) -2- isocyanatometyl -3- (3- isocyanate group propyl group)-bicyclic (2.2.1) Heptane, 5- (2- isocyanatoethyls) -2- isocyanatometyl -2- (3- isocyanate group propyl group)-bicyclic (2.2.1)-heptane, 6- (2- isocyanatoethyls) -2- isocyanatometyl -2- (3- isocyanate group propyl group)-bicyclic (2.2.1) heptane etc. it is alicyclic Triisocyanate etc..

As above-mentioned aromatic-aliphatic polyisocyanates, for example, can enumerate：Di-2-ethylhexylphosphine oxide (4,1- phenylenes) two Carbimide .s Ester (common name：MDI), 1,3- or 1,4- xylylene diisocyanates or its mixture, ω,-two Carbimide. -1,4- two of ω ' Double (1- Carbimide. -1- Methylethyls) phenyl ester (common names of ethyl phenyl ester, 1,3- or 1,4-：Two Carbimide. of durol dimethyl Ester) or its mixture etc. araliphatic diisocyanate；The aromatic-aliphatic three of tri- TIs of 1,3,5- etc. is different Cyanate etc..

As above-mentioned aromatic polyisocyanate, for example, can enumerate：M-benzene diisocyanate, PPDI, 4, 4'- diphenyl diisocyanates, 1,5- naphthalene diisocyanates, 2,4 toluene diisocyanate (common name：2,4-TDI) or 2,6- Toluene di-isocyanate(TDI) (common name：2,6-TDI) or its mixture, 4,4'- toluidine diisocyanates, 4,4'- diphenyl ethers The aromatic diisocyanate of diisocyanate etc.；Triphenyl methane -4,4', 4 "-triisocyanate, tri- Carbimide. benzene of 1,3,5- The aromatic tri-isocyanates of ester, tri- TIs of 2,4,6- etc.；Tetra- isocyanide of 4,4'- diphenyl methane -2,2', 5,5'- Aromatic series tetraisocyanate of acid esters etc. etc..

In addition, as the derivant of above-mentioned polyisocyanates, for example, can enumerate above-mentioned polyisocyanates dimer, Trimer, biuret, allophanate, urea diketone (uretdione), uretonimine (uretoneimine), isocyanuric acid ester, Diazine triketone, poly methylene poly phenyl poly isocyanate (thick MDI, polymeric MDI), thick TDI etc..

Above-mentioned polyisocyanates and its derivant, individually can use or and with two or more.In addition, in these polyisocyanates In cyanate, as above-mentioned polyisocyanate compound (d2), from the blocked polyisocyanates compound (D) for obtaining in heating The angle for being difficult to xanthochromia is set out, preferably aliphatic diisocyanate, alicyclic diisocyanate and its derivant.Its In, from the viewpoint of improving from the flexibility of the film for being formed, more preferably aliphatic diisocyanate and its derivant.

In addition, as above-mentioned polyisocyanate compound (d2), it is possible to use under conditions of NCO excess by It is pre- that above-mentioned polyisocyanates and its derivant and the compound that can be reacted with the polyisocyanates are reacted and formed Polymers.As the compound that can be reacted with the polyisocyanates, for example, the reactive hydrogen with hydroxyl, amino etc. can be enumerated The compound of base, specifically, for example, can be using polyhydric alcohol, low molecular weight polyester resin, amine, water etc..

In addition, as above-mentioned polyisocyanate compound (d2), can use：Polymerism containing NCO is unsaturated single The polymer of body, or this contain the polymerism unsaturated monomer of NCO with except the polymerism containing NCO not The copolymer of the polymerism unsaturated monomer beyond saturation monomer.

Above-mentioned polyisocyanate compound (d2), from the blocked polyisocyanates compound (D) for obtaining reactivity and From the viewpoint of the intermiscibility of the blocked polyisocyanates compound (D) and other paint ingredients, number-average molecular weight is preferably 300 To in the range of 20000, more preferably in the range of 400 to 8000, further preferably in the range of 500 to 2000.

In addition, above-mentioned polyisocyanate compound (d2), from the reactivity of the blocked polyisocyanates compound (D) for obtaining And from the viewpoint of the intermiscibility of the blocked polyisocyanates compound (D) and other paint ingredients, it is average in a molecule Isocyanate functional group's number is preferably in the range of 2 to 20.From the reaction for improving the blocked polyisocyanates compound (D) for obtaining From the viewpoint of property, 3 are more preferably as lower limit.Gelation is prevented when manufacture in blocked polyisocyanates compound (D) From the viewpoint of, 20 are more preferably as the upper limit.

Reacted by the end-blockingization of the NCO of activity methene compound (d1), can be urged using reaction as needed Agent.As the catalysts, for example, metal hydroxidess, metal alkoxide, metal carboxylate, metal acetyl can be enumerated Acetone salt, the hydroxide of salt, carboxylate (onium carboxylate), the slaine of activity methene compound, work The alkali compoundss of the salt of property methylene compound, amino silane compounds, amines, phosphine compound etc..These materials In, ammonium salt, salt, sulfonium salt etc. is suitably for as salt.The usage amount of the catalysts, generally with polyisocyanate compound (d2) and activity methene compound (d1) total solid constituent quality as benchmark, preferably 10ppm's to 10000ppm In the range of, further preferably in the range of 20ppm to 5000ppm.

In addition, the isocyanate-terminatedization reaction based on above-mentioned activity methene compound (d1) can be at 0 DEG C to 150 DEG C Under carry out.The end-blockingization is reacted, and can carry out or carry out in appropriate solvent in the absence of solvent.It is preferred as solvent Non-protonic solvent, particularly preferred ester, ether, N- alkylamides, ketone etc..If reaction is carried out by purpose requirement, acid can be added Composition and neutralize as catalyst alkali compoundss and stopped reaction.

In the end-blockingization reaction of the NCO based on activity methene compound (d1), to active methylene group chemical combination The usage amount of thing (d1), is not particularly limited；It is adapted to relative to 1 mole isocyanate base in polyisocyanate compound (d2) Using 0.1 mole to 3 moles, 0.2 mole is preferably used to 2 moles.In addition, with polyisocyanate compound (d2) in isocyanide The activity methene compound not reacted by perester radical, can remove after the completion of end-blockingization reaction.

In addition, the compound departed from cross-linking reaction is an off the active methylene group class of the monofunctional alcohol of carbon number 3 to 12 Blocked polyisocyanates compound (D), makes activity methene compound (d1) and aforementioned polyisocyanates compound except adopting (d2), beyond the method reacted, can also adopt with the following method to be manufactured：Make diethyl malonate and polyisocyanic acid Ester compounds (d2) are reacted, sequentially for the reaction product for obtaining, by the simple function of carbon number 3 to 12 (preferably 6 to 8) Alcohol (being only meant as sometimes long-chain alcohol) carries out ester exchange.

With regard to the reaction condition that diethyl malonate and polyisocyanate compound (d2) react, except using the third two Diethyl phthalate replaces beyond activity methene compound (d1), can be with aforementioned activity methene compound (d1) and polyisocyanates The reaction condition that compound (d2) reacts similarly is appropriately configured.

For the ester that the reaction product of diethyl malonate and polyisocyanate compound (d2) is carried out by long-chain alcohol Exchange, catalysts can be used as needed.As the catalysts, for example, can enumerate metal hydroxidess, metal Alkoxide, metal carboxylate, metal acetylacetonate salt, the hydroxide of salt, carboxylate, the metal of activity methene compound The alkali compoundss of salt, the salt of activity methene compound, amino silicone alkanes, amine, phosphine etc..The catalysts make Consumption, the generally total solid constituent quality with diethyl malonate with the reaction product of polyisocyanate compound (d2) are made On the basis of, preferably in the range of 10ppm to 10000ppm, further preferably in the range of 20ppm to 5000ppm.

In addition, above-mentioned ester exchange reaction can be carried out at 0 DEG C to 150 DEG C.The ester exchange reaction, can be in appropriate solvent Carry out or carry out in the absence of solvent.Non-protonic solvent, particularly preferably ester, ether, N- alkane are preferably as solvent Base amide, ketone etc..If reaction is carried out by purpose requirement, sour composition can be added and the alkali compoundss as catalyst are neutralized And stopped reaction.

In above-mentioned ester exchange reaction, for the usage amount of long-chain alcohol is not particularly limited, relative to diethyl malonate With 1 mole of the reaction product of polyisocyanate compound (d2), it is adapted to using 0.1 mole to 100 moles, preferably uses 0.2 Mole to 10 moles.In addition, there is no the long-chain alcohol of above-mentioned ester exchange reaction, can be removed after completion of the reaction.

In the present invention, as the carbon number departed from from blocked polyisocyanates compound (D) in cross-linking reaction be 3 to 12, Preferably 6 to 8 monofunctional alcohol, for example, can enumerate：Propanol, isopropanol, butanol, amylalcohol, hexanol, capryl alcohol, 2-Ethylhexyl Alcohol, Aliphatic alkyl alcohol and its isomers such as 4- methyl -2- amylalcohols, decanol, dodecanol；1- propoxyl group -2- propanol, 2- butoxy Alcohols containing ether such as ethanol, 1- butoxy -2- propanol, diethylene glycol monoethyl ether, dipropylene glycol monomethyl ether etc..

Cross-linking agent (E)

In the coating composition of the present invention, cross-linking agent (E) can be contained as needed.Cross-linking agent (E) is formed with envelope Property resin (A) in hydroxyl, carboxyl, the functional group such as epoxy radicals react so as to the coating composition that can make the present invention occur it is solid The compound of change.As cross-linking agent (E), for example, polyisocyanate compound (E1) can be enumerated, except above-mentioned end-blocking polyisocyanic acid Blocked polyisocyanates compound, amino resins, the compound containing epoxy radicals beyond ester compounds (D), containing carbodiimides Compound of base etc..Wherein, preferably polyisocyanate compound (E1) and amino resins, and then preferably polyisocyanic acid esterification Compound (E1).Cross-linking agent can be used alone or be used in combination of two or more.

Polyisocyanate compound (E1)

Polyisocyanate compound (E1) is the compound with least two NCOs in a molecule, for example, can Enumerate：Aliphatic polyisocyante, alicyclic polyisocyanates, aromatic-aliphatic polyisocyanates, aromatic polyisocyanate, Derivant of these polyisocyanates etc..

As above-mentioned aliphatic polyisocyante, for example, can enumerate：Trimethylene diisocyanate, tetramethylene two are different Cyanate, hexamethylene diisocyanate, pentamethylene diisocyanate, 1,2- trimethylene diisocyanates, 1,2- butylidenes Diisocyanate, 2,3- tetramethylene diisocyanates, 1,3- tetramethylene diisocyanates, 2,4,4- or 2,2,4- trimethyls six are sub- Methyl diisocyanate, dimer acid diisocyanate, bis- Carbimide. caproic acid methyl (common names of 2,6-：Lysinediisocyanate) Deng aliphatic diisocyanate；Bis- Carbimide. caproic acid -2- ethyl isocyanates of 2,6-, bis- Carbimide. -3- isocyanatomethyls of 1,6- Hexane, Isosorbide-5-Nitrae, tri- Carbimide. octanes of 8-, 1,6,11- tri- Carbimide. hendecanes, 1,8- bis- Carbimide. -4- isocyanatomethyl octanes, Three isocyanide of aliphatic of tri- Carbimide. hexanes of 1,3,6-, two Carbimide. -5- isocyanatomethyl octanes of 2,5,7- trimethyls -1,8- etc. Acid esters etc..

As above-mentioned alicyclic polyisocyanates, for example, 1,3- cyclopentene diisocyanates, Isosorbide-5-Nitrae-hexamethylene two can be enumerated Isocyanates, 1,3- cyclohexane diisocyanates, 3- isocyanatomethyl -3,5,5- trimethylcyclohexylisocyanate (common names： Isophorone diisocyanate), 4- methyl isophthalic acids, 3- cyclohexene diisocyanate (common names：Hydrogenation TDI), 2- methyl isophthalic acids, 3- rings Double (isocyanatomethyl) hexamethylene (common names of hexene diisocyanate, 1,3- or 1,4-：Hydrogenated xylylene diisocyanate) Or its mixture, di-2-ethylhexylphosphine oxide (4,1- cyclohexanediol) diisocyanate (common name：Hydrogenation MDI), two Carbimide. of norbornane The alicyclic diisocyanate of ester etc.；Tri- cyclic isocyanate hexanes of 1,3,5-, 1,3,5- trimethyl cyclic isocyanate hexanes, (3- is different for 2- Cyanic acid propyl group) -2,5- two (isocyanatomethyl)-bicyclic (2.2.1) heptane, two (Carbimide. first of 2- (3- isocyanatopropyls) -2,6- Base)-bicyclic (2.2.1) heptane, 3- (3- isocyanatopropyls) -2,5- two (isocyanatomethyl)-bicyclic (2.2.1) heptane, 5- (2- Carbimide. ethyl) -2- isocyanatomethyl -3- (3- isocyanatopropyls)-bicyclic (2.2.1) heptane, 6- (2- Carbimide. ethyls) -2- Isocyanatomethyl -3- (3- isocyanatopropyls)-bicyclic (2.2.1) heptane, 5- (2- Carbimide. ethyls) -2- isocyanatomethyl -2- (3- isocyanatopropyls)-bicyclic (2.2.1)-heptane, 6- (2- Carbimide. ethyls) -2- isocyanatomethyl -2- (3- Carbimide .s third Base)-bicyclic (2.2.1) heptane etc. alicyclic triisocyanate etc..

As above-mentioned aromatic-aliphatic polyisocyanates, for example, di-2-ethylhexylphosphine oxide (4,1- phenylene) two Carbimide .s can be enumerated Ester (common name：MDI), 1,3- or Isosorbide-5-Nitrae-xylylene diisocyanate its mixture ,-two Carbimide .s of ω, ω '-Isosorbide-5-Nitrae-diethyl Double (1- Carbimide. -1- Methylethyls) phenyl ester (common names of base phenyl ester, 1,3- or 1,4-：Tetramethyl xylylene diisocyanate) Or the araliphatic diisocyanate of its mixture etc.；Three Carbimide. of aromatic-aliphatic of tri- TIs of 1,3,5- etc. Ester etc..

As above-mentioned aromatic polyisocyanate, for example, can enumerate m-benzene diisocyanate, PPDI, 4, 4'- diphenyl diisocyanates, 1,5- naphthalene diisocyanates, 2,4 toluene diisocyanate (common name：2,4-TDI) or 2,6- Toluene di-isocyanate(TDI) (common name：2,6-TDI) or its mixture, 4,4'- toluidine diisocyanates, 4,4'- diphenyl ethers The aromatic diisocyanate of diisocyanate etc.；Triphenyl methane -4,4', 4 "-triisocyanate, tri- Carbimide. benzene of 1,3,5- The aromatic tri-isocyanates of ester, tri- TIs of 2,4,6- etc.；Tetra- isocyanide of 4,4'- diphenyl methane -2,2', 5,5'- Aromatic series tetraisocyanate of acid esters etc. etc..

In addition, as the derivant of above-mentioned polyisocyanates, for example, can enumerate above-mentioned polyisocyanates dimer, Trimer, biuret, allophanate, urea diketone, uretonimine, isocyanuric acid ester, diazine triketone, polymethylene polyphenyl Polyisocyanates (thick MDI, polymeric MDI), thick TDI etc..

Above-mentioned polyisocyanates and its derivant, individually can use or and with two or more.In addition, more than these In isocyanates, from viewpoints such as resistance to impact, weatherabilities, can be adapted to using aliphatic diisocyanate and its derivant.

In addition, as above-mentioned polyisocyanate compound (E1), it is possible to use：Under conditions of NCO surplus, By above-mentioned polyisocyanates and its derivant and the work for example with hydroxyl, amino etc. that can be reacted with the polyisocyanates The compound of property hydrogen-based, the prepolymer for being reacted and being formed.As the compound that can be reacted with the polyisocyanates, example Such as, polyhydric alcohol, low molecular weight polyester resin, amine, water etc. can be enumerated.

Above-mentioned polyisocyanate compound (E1), can individually using or combine two or more using.

Blocked polyisocyanates compound beyond above-mentioned blocked polyisocyanates compound (D)

As the blocked polyisocyanates compound in addition to above-mentioned blocked polyisocyanates compound (D), in conduct Above-mentioned polyisocyanates and its NCO in derivant are carried out the end-blocking of the compound of end-blockingization with end-capping reagent In polyisocyanate compound, the compound departed from being usable in cross-linking reaction is carbon number 1 to 2 or more than 13 alcohol compound The blocked polyisocyanates compound of thing or polyfunctional alcohol.

As above-mentioned end-capping reagent, for example, can enumerate：Phenol, cresol, xylenols, nitrophenol, ethyl -phenol, hydroxyl The phenolic compound of hexichol, butylphenol, isopropyl-phenol, nonyl phenol, octyl phenol, methyl hydroxybenzoate etc.；ε-oneself The lactam analog compound of lactams, δ-valerolactam, butyrolactam, azetidinone etc.；Methanol, ethanol, propanol, fourth The aliphatic alcohol compound of alcohol, amylalcohol, lauryl alcohol etc.；Glycol monoethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, The ether compound of diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, propylene glycol monomethyl ether, methoxyl group methanol etc.；Benzylalcohol, ethanol Acid, methyl glycollate, ethyl glycolate, butyl glycolate, lactic acid, methyl lactate, ethyl lactate, butyl lactate, methylolurea, The alcohol compound of melamine methylol, DAA, acrylic acid 2- hydroxy methacrylates, 2-hydroxyethyl methacrylate etc.； The oximes of formyl amidoxime, acetyl amidoxime, acetone oxime, methyl ethyl ketone oxime, diacetyl monoxime, diphenyl-ketoxime, hexamethylene oxime etc. Compound；The activity of dimethyl malenate, diethyl malonate, ethyl acetoacetate, methyl acetoacetate, acetylacetone,2,4-pentanedione etc. is sub- Methyl class compound；Butanethiol, tert-butyl mercaptan, hexyl mercaptans, tert-dodecylmercaotan, 2-mercaptobenzothiazole, benzene sulfur The sulfur alcohol compound of phenol, methylbenzene phenyl-sulfhydrate, ethyl thiophenol etc.；Acetanilide, acetyl-anisidine, acetyl toluidine, propylene The amides compound of amide, Methacrylamide, acetamide, stearmide, Benzoylamide etc.；Butanimide, adjacent benzene two The imide analog compounds of carboximide, maleimide etc.；Diphenylamines, nonox, xylidine, two methyl of N- phenyl The aminated compoundss of aniline, carbazole, aniline, naphthylamines, butylamine, dibutyl amine, butylaniline etc.；The miaow of imidazoles, 2- ethyl imidazol(e)s etc. Azole compounds；The carbamide compounds of urea, thiourea, ethylene urea, ethylene thiourea, diphenylcarbamide etc.；N- phenylcarbamic acid phenyl esters etc. Carbamate compound；The imines of aziridine (ethyleneimine), propyleneimine (propyleneimine) etc. Class compound；The sulfites compound of sodium sulfite, Potassium acid sulfite etc.；Azole compounds etc..As above-mentioned azole Compound, can enumerate：Pyrazoles, 3,5- dimethyl pyrazoles, 3- methylpyrazoles, 4- benzyl -3,5- dimethyl pyrazoles, 4- nitro -3, The pyrazoles or pyrazole derivatives of the bromo- 3,5- dimethyl pyrazoles of 5- dimethyl pyrazoles, 4-, 3- methyl -5- Phenylpyrazoles etc.；Imidazoles, The imidazoles or imdazole derivatives of benzimidazole, 2-methylimidazole, 2- ethyl imidazol(e)s, 2- phenylimidazoles etc.；2-methylimidazole quinoline, 2- Imidazolidine derivatives of benzylimidazoline etc. etc..

When carrying out end-blocking (being reacted end-capping reagent), solvent can be added as needed.As in end-blockingization reaction The solvent for using, can be the solvent for not having reactivity relative to NCO, for example, can enumerate：Such as acetone, methyl second Assimilation compound as base ketone, ester compounds as such as ethyl acetate, such as METHYLPYRROLIDONE (NMP) are so Solvent.

For the blocked polyisocyanates compound in addition to above-mentioned blocked polyisocyanates compound (D), can be respectively It is used alone or combines two or more using.

Amino resins

As amino resins, can be using part methylolation amino obtained from the reaction by amino component with aldehyde composition Resin or complete methylolation amino resins.As amino component, for example, tripolycyanamide, urea, benzoguanamine, acetyl can be enumerated Guanamines, steroid guanamines (ス テ ロ グ ア Na ミ Application：Steroguanamine), spiral shell guanamines (ス ピ ロ グ ア Na ミ Application： Spiroguanamine), dicyandiamide etc..As aldehyde composition, formaldehyde, paraformaldehyde, acetaldehyde, benzaldehyde etc. can be enumerated.

In addition, can use the methylol of methylolation amino resins by appropriate alcohol partially or even wholly to carry out Material obtained from etherificate.As for the alcohol in etherificate, for example, methanol, ethanol, normal propyl alcohol, isopropanol, positive fourth can be enumerated Alcohol, isobutanol, 2-ethyl butanol, 2-Ethylhexyl Alcohol etc..

As above-mentioned amino resins, preferably melmac.As the melmac, specifically, can arrange Lift：Dihydroxymethyl tripolycyanamide, trimethylol melamine, tetra methylol tripolycyanamide, pentamethylol melamine, six hydroxyl first The melamine methylol of base tripolycyanamide etc.；The alkyl ether compound of these melamine methylols or condensation polymer；Methylol three Condensation polymer of alkyl ether compound of poly cyanamid etc..Melamine methylol it is alkyl etherified, for example, can using methanol, ethanol, third The single methanol of alcohol, isopropanol, butanol, isobutanol, 2-Ethylhexyl Alcohol etc. and carried out by known method.

In addition, above-mentioned melmac preferable weight-average molecular weight is in the range of 600 to 6000, more preferably 800 to In the range of 5000, further preferably in the range of 1000 to 4000.

As above-mentioned melmac, commercially available product can be used.As commercially available trade name, for example, Japan can be enumerated Cymel (the サ イ メ Le) 303, Cymel 323 of CYTEC Co., Ltd. manufacture, Cymel 325, Cymel 327, Cymel 350、Cymel 370、Cymel 380、Cymel 385、Cymel 212、Cymel 251、Cymel 254、Mycoat(マイコ ート)776；Rejimin (the レ ジ ミ Application) 735, Rejimin 740 of Monsanto Company's manufacture, Rejimin 741, Rejimin 745、Rejimin 746、Rejimin 747；Sumimal (the ス ミ マ Le) M55 of Sumitomo Chemical Co's manufacture, Sumimal M30W、Sumimal M50W；U-VAN (ユ バ Application) 20SB, U-VAN of Mitsui Chemicals, Inc's manufacture 20SE-60, U-VAN 28-60 etc..

Above-mentioned melmac can individually using or combine two or more using.

Coating composition

The coating composition of the present invention, comprising above-mentioned envelope formative resin (A) and delustering agent (B), and then contains specific Non-aqueous polymer dispersion liquid (C) and/or specific blocked polyisocyanates compound (D).By the coating composition of the present invention Carry out the film that application obtains and there is extinction.

It is in this specification, so-called to refer to according to JIS K 5600-4-7 with extinction:The 1999 formation films for determining The value of 60 ° of mirror surface lusters is less than 60.

In addition, extinction, gloss stability, alkali resistance and resistance to impact from storage-stable and formed film etc. Viewpoint is set out, and in coating composition preferably of the invention, the mixing ratio (solid constituent quality) of each composition is in following ranges.

With envelope formative resin (A), non-aqueous polymer dispersion liquid (C), blocked polyisocyanates compound (D) and according to The total amount of the solid constituent of cross-linking agent (E) for needing and using as 100 mass parts,

Envelope formative resin (A) (in terms of solid component content)：50 mass parts to 80 mass parts, preferably 60 mass parts To 80 mass parts, more preferably 60 mass parts to 75 mass parts,

Delustering agent (B)：5 mass parts to 50 mass parts, preferably 5 mass parts to 45 mass parts, more preferably 5 mass Part to 40 mass parts,

Non-aqueous polymer dispersion liquid (C) (in terms of solid component content)：0 mass parts to 10 mass parts, preferably 0.1 mass Part to 8 mass parts, more preferably 0.1 mass parts to 6 mass parts,

Blocked polyisocyanates compound (D) (in terms of solid component content)：0 mass parts to 50 mass parts, preferably 0 matter Part is measured to 45 mass parts, more preferably 0 mass parts to 40 mass parts,

Cross-linking agent (E) (in terms of solid component content)：0 mass parts to 50 mass parts, preferably 0 mass parts are to 45 mass Part, more preferably 0 mass parts are to 40 mass parts.

Wherein, there is no both non-aqueous polymer dispersion liquid (C) and blocked polyisocyanates compound (D) while being all 0 The situation of mass parts.

In addition, the coating composition of the present invention, and then organic solvent, curing catalysts, pigment, face can be contained as needed The coating that material dispersant, levelling agent, UV absorbent, light stabilizer, plasticizer etc. are usually used in paint field is with adding Plus agent.

As above-mentioned curing catalysts, for example, can enumerate：Tin octoate, dibutyl tin two (2-ethylhexanoate), dioctyl Stannum two (2-ethylhexanoate), dioctyl tin diacetate, dibutyltin dilaurate, Dibutyltin oxide, dioctyl oxygen Change the organo-metallic catalysts such as stannum, 2 ethyl hexanoic acid lead；Tertiary amine, p-methyl benzenesulfonic acid, DBSA, dinonylnaphthalene sulfonic acid Deng sulfonic acid；Salt of these acid and amine etc..These materials can be used alone or combine two or more using.

The coating composition of the present invention, in the case of containing curing catalysts, with the solid constituent in the coating composition 100 mass parts as benchmark, the use level of preferred consolidation catalyst in the range of 0.05 mass parts to 10 mass parts, more preferably In the range of 0.1 mass parts to 5 mass parts, further preferably in the range of 0.2 mass parts to 3 mass parts.

As pigment, for example, can enumerate：Titanium oxide, zinc white, white carbon black, cadmium red, chrome vermillion, chrome yellow, chromium oxide, it is Prussian blue, The coloring pigment of cobalt blue, AZOpigments, phthalocyanine color, quinoline azone pigment, isoindoline pigment, reduction class pigment, pigment etc.； The extender pigment of Pulvis Talci, clay, Kaolin, Barium monoxide, barium sulfate, brium carbonate, Calcium Carbonate, alumina white etc.；Aluminium powder, Muscovitum Powder, metallic pigments to aoxidize titanium coated mica powder etc. etc..These materials can be used alone or combine two or more To use.

In the case where the coating composition of the present invention is used as clear dope, when containing pigment, the cooperation of preferred pigments The amount of the degree for the film transparency obtained by not hindering is measured, such as with 100 mass of solid constituent in the coating composition Part is used as benchmark, it is usually preferred in the range of 0.1 mass parts to 20 mass parts, more preferably in 0.3 mass parts to 10 mass parts In the range of, further preferably in the range of 0.5 mass parts to 5 mass parts.

In addition, in the case where the coating composition of the present invention is used as pigmented finiss, when containing pigment, with the coating group 100 mass parts of resin solid content in compound are used as benchmark, it is usually preferred to which the use level of pigment is in 1 mass parts to 200 mass In the range of part, more preferably in the range of 2 mass parts to 100 mass parts, further preferably in 5 mass parts to 50 mass parts In the range of.

As UV absorbent, for example, benzotriazole absorption can be enumerated using known material all the time The UV absorbent of agent, triazines absorbent, salicyclic acid derivatives class absorbent, benzophenone absorbent etc..These things Matter can be used alone or combine two or more using.

The coating composition of the present invention, containing in the case of UV absorbent, with the solid in the coating composition into Point 100 mass parts as benchmark, the preferably use level of UV absorbent in the range of 0.1 mass parts to 10 mass parts, more It is preferred that in the range of 0.2 mass parts to 5 mass parts, further preferably in the range of 0.3 mass parts to 2 mass parts.

As light stabilizer, for example, hindered amine light stabilizer can be enumerated using known material all the time.

The coating composition of the present invention, in the case of containing light stabilizer, with the solid constituent in the coating composition 100 mass parts more preferably exist in the range of 0.1 mass parts to 10 mass parts as benchmark, the preferably use level of light stabilizer In the range of 0.2 mass parts to 5 mass parts, further preferably in the range of 0.3 mass parts to 2 mass parts.

The coating composition of the present invention, can be the multicomponent of based one-pack-type coating, or two-component-type coating etc. Type coating.In the coating composition of the present invention, in the polyisocyanates for not carrying out end-blockingization as above-mentioned cross-linking agent (E) use In the case of compound (E1), from from the viewpoint of storage-stable, it is preferably set to two-component-type coating and will using Front to mix two components, the two-component-type coating includes：Containing above-mentioned envelope formative resin (A), delustering agent (B), The host of non-aqueous polymer dispersion liquid (C) and/or blocked polyisocyanates compound (D), and, containing not carrying out above-mentioned end-blocking The cross-linking agent of the polyisocyanate compound (E1) of change.

Coating process

As the coated article that the coating composition (below, sometimes referred to simply as " this coating ") of the present invention is used, without special Limit, for example, can enumerate：The steel plate of cold-rolled steel sheet, galvanized steel plain sheet, galvanized alloy steel plate, stainless-steel sheet, tin plate etc., The metal base of aluminium sheet, aluminium alloy plate etc.；The plastics base of polyolefin, Merlon, ABS resin, polyurethane resin, polyamide etc. Material etc..Alternatively, it is also possible to being automobile, cart, the car body of the various vehicles of container etc. or its part formed by these materials.

In addition, as coated article, phosphate treated, chromate can be carried out in the metal surface of above-mentioned metal base or car body The surface treatments such as process, composite oxides process.Further, as coated article, can on above-mentioned metal base or car body etc. shape Into the primary coat film of various electrocoating paints etc., it is also possible to form the primary coat film and middle painting film, primary coat painting can also be formed Film, middle painting film and substrate coating (base coat) film, it is also possible to form primary coat film, middle painting film, substrate coating film With transparent coating (clear coat) film.

In addition, in the case where coated article is plastic basis material, can come as needed suitably to be taken off on the plastic basis material Fat process and/or surface treatment.Further, after plastic basis material face forms primary coat film, can application coating composition of the invention.

As the coating process of this coating, it is not particularly limited, for example, aerial spraying, airless spraying, rotation can be enumerated The coating process such as atomization spraying, curtain coating application, can form wet coating by these methods.In these coating process, Electrostatic can be applied as needed.In these methods, particularly preferred aerial spraying or rotary-atomizing application.The coating weight of this coating, 10 μm to 50 μm or so of amount is reached with solidification film thickness gauge generally preferably.

In addition, in the case where aerial spraying, airless spraying and rotary-atomizing application is carried out, preferably by this coating Viscosity is suitably adjusted using the solvent of organic solvent etc., so that range of viscosities of the viscosity in the suitable application, The range of viscosities of 15 second to 60 second or so is issued to No. 4 (No.4) viscometers of Ford cup at 20 DEG C generally.

The solidification of the wet coating of this coating of application on coated article, is carried out by heating, and heating is available known Heating means carrying out, for example, can be with drying ovens such as air stove, electric furnace, infrared guidance heating furnaces.There is no spy to heating-up temperature Do not limit, for example, be adapted at 60 DEG C to 200 DEG C, preferably in the range of 90 DEG C to 150 DEG C.Heat time heating time is not especially limited System, for example, is adapted at 10 minutes to 60 minutes, preferably in the range of 15 minutes to 30 minutes.

This coating, from the delustring that excellent storage stability, gloss stability, alkali resistance and excellent impact resistance is obtained The angle of film is set out, and can be suitable as applying top transparent coating (topclear coat) coating use.This coating is especially excellent It is elected to be as vehicle with coating to use.

Method for formation of multi-layered coating

It is used as the forming method of the upper multilayer coating film for applying the application of top transparent coating coating institute as this coating, one can be enumerated Kind of method for formation of multi-layered coating, the method is by coated article, application at least one of which colours substrate and is coated with coating and at least successively Layer of transparent is coated with coating to form multilayer coating film, wherein, including application coating composition of the invention as the saturating of the superiors Bright coating coating.

Specifically, for example, the method for formation of multi-layered coating that mode is dried in two painting one can be enumerated, in the method, is being carried out On the coated article of electrodeposition coating and/or middle painting application, application substrate coating coating is solidified the film, according to Need, for example, the preheating of 3 minutes to 30 minutes or so is carried out at 40 DEG C to 90 DEG C to promote the solvent in substrate coating coating Volatilization, on uncured substrate coating film, this coating of application is, as after transparent coating coating, be coated with substrate Solidified together with transparent coating.

In addition, can be adapted to saturating as three tops for applying two baking modes or the three upper painting applications for applying a baking mode using this coating Bright coating coating.

As the above-mentioned substrate coating coating for using, can be using all the time known common thermohardening type substrate coating Coating, specifically, for example, can use following coating：The coating is, for acrylic resin, polyester resin, alkyd tree The matrix resins such as fat, polyurethane type resin, make amino resins, polyisocyanate compound, blocked polyisocyanates compound etc. Cross-linking agent carry out proper combination with the reactive functional groups that matrix resin contains and form.

In addition, coating is coated with as substrate, and for example, can be using water paint, organic solvent class coating, powder coating etc.. Wherein, from from the viewpoint of reducing carrying capacity of environment, preferred water paint.

In method for formation of multi-layered coating, in the case of transparent coating layer more than application two-layer, as except most going up Transparent coating coating beyond layer, can use the transparent coating coating of all the time known common thermohardening type.

Embodiment

Below, Production Example, embodiment and comparative example is enumerated, the present invention is further specifically described.But, the present invention is not It is confined to these examples.In each case, in the case where not particularly indicating that, " part " and " % " is on the basis of quality.In addition, The thickness of film is based on cured coating film.Further, the use level in table is solid constituent quality.

The manufacture of envelope formative resin (A)

Production Example 1

In the four-hole boiling flask for possessing agitating device, thermometer, condensing tube and nitrogen inlet, load 31 parts of propanoic acid second Epoxide ethyl ester, is warming up to 120 DEG C in the case where nitrogen is passed through.After reaching 120 DEG C, stopping is passed through nitrogen, by by following shown list The monomer mixture that the composition that body and polymerization initiator are constituted coordinates carried out Deca through 4 hours.

Then, after being passed through nitrogen ripening 1 hour at 120 DEG C, by 0.5 part of 2,2 '-azodiisobutyronitrile and The mixture that 5 parts of ethoxyethyl propionate carried out Deca through 1 hour, and then, the ripening 1 hour at about 120 DEG C, by with third 27.5 parts of sour ethoxy ethyl ester is diluted, and obtains acrylic resin, the i.e. envelope formative of the hydroxyl of solid constituent 60% The solution of resin (A-1).Based on the envelope formative resin for obtaining solid constituent hydroxyl value be 140mgKOH/g, Weight-average molecular Amount about 8000, glass transition temperature is 42 DEG C.

Production Example 2

In possessing and having the reaction vessel of thermometer, thermostat, agitating device, reflux condensation mode machine and water separator, load Trimethylolpropane (molecular weight 134) 20.1g, neopentyl glycol (molecular weight 104) 83.2g, 1,2- cyclohexane dicarboxylic acid acid anhydride (molecule 154) 69.3g and adipic acid (molecular weight 146) 65.7g is measured, is warming up to from 160 DEG C after 230 DEG C, is being carried out by water separator 230 DEG C are held in while removing condensation water, after reaction is until acid number becomes 1mgKOH/g, 120 DEG C is cooled to, by with propanoic acid Ethoxy ethyl ester is diluted polyester resin, the i.e. envelope formative resin (A-2) of the hydroxyl for obtaining solid constituent 60% Solution.Hydroxyl value based on the solid constituent of the envelope formative resin for obtaining is 90mgKOH/g, and weight average molecular weight is about 4400.

The manufacture of macromolecular dispersion stabilizer (C1)

Production Example 3

In reaction vessel by dimethylbenzene 100 parts be heated to 130 DEG C, by 50 parts of acrylic acid 2- ethylhexyls methyl ester, propylene 33 parts of sour normal-butyl methyl ester, 15 parts of 2-hydroxyethyl methacrylate, 2 parts of methacrylic acid and 2,2 '-azodiisobutyronitrile 2 Part mixture Deca was carried out with even speed through 3 hours, and then ripening 2 hours.The solid of resulting acrylic resin Composition is 50%, and number-average molecular weight is 7000.

Then, in 202 parts of the acrylic resin for obtaining in above-mentioned, 1 part of glycidyl methacrylate of addition, uncle 4- 0.02 part of butyl-catechol, 0.1 part of dimethylaminoethanol, and stir 5 hours at 130 DEG C, obtain solid constituent 50% Macromolecular dispersion stabilizer (C1-1) solution.The average each molecule of resulting macromolecular dispersion stabilizer (C1-1) has about The polymerism unsaturated group of 1.0.

Production Example 4

12- hydroxy stearic acids are carried out into dehydrating condensation using methanesulfonic acid as catalyst under refluxing toluene, is condensed to Resinous acid value 30mgKOH/g.On the terminal carboxyl group for self condensing polyester resin of resulting number-average molecular weight about 1800, two are used Methyl amino ethanol is as the catalyst to addition glycidyl methacrylate, so as to import polymerism unsaturated group, obtains Macromolecular dispersion stabilizer (C1-2) solution of solid constituent 70%.Resulting macromolecular dispersion stabilizer (C1-2) is average every One molecule has about 1.0 polymerism unsaturated groups.

Production Example 5

Load 174 parts of butyl acetate in flask to be heated to reflux, by 70% macromolecular dispersion stabilizer (C1-2) 297.0 parts of solution, 195.9 parts of methyl methacrylate, 18.5 parts of glycidyl methacrylate, 163.0 parts of dimethylbenzene with And 2, the mixture that 9.6 parts of 2 '-azodiisobutyronitrile carried out Deca with even speed through 3 hours, and then ripening 2 hours.

Then, by 0.5 part of 0.05 part of p-tert-Butylcatechol, 3.8 parts of methacrylic acid and dimethylaminoethanol Mixture load in flask, the sustained response about 5 hours at 140 DEG C obtains solid until resinous acid value is 0.5mgKOH/g Macromolecular dispersion stabilizer (C1-3) solution of composition 50%.Resulting macromolecular dispersion stabilizer (C1-3) is glycerol polymerization Thing, wherein, the graft polymers have the first segment for carrying out autohemagglutination (12- hydroxy stearic acids) and from methyl methacrylate with Second segment of the copolymer of glycidyl methacrylate, and averagely there are in a molecule about four polymerism unsaturations Base.

Production Example 6

In possessing the generally reactive tank of manufacture polyester resin such as blender, thermometer, rectifier, return channel, load Following reacted constituent mixture, carry out common dehydration condensation, are condensed to acid number 4mgKOH/g.

In the resin solution being so condensed to yield, add 1.2 parts of isocyanatomethyl ethyl acrylate, carry out addition anti- Should be less than 0.5 to isocyanate value, obtain macromolecular dispersion stabilizer (C1-4) solution.The number-average molecular weight of the material is 15000, hydroxyl value is 114, and oil content is 30%, and acid number is 4mgKOH/g, and solid component content is 60%.

The manufacture of non-aqueous polymer dispersion liquid (C)

Production Example 7

In the four-hole boiling flask for possessing agitating device, thermometer, condensing tube and nitrogen inlet, load normal heptane 150 150 parts of part and dimethylbenzene, are blown into nitrogen and are warming up to 100 DEG C.By the macromolecular dispersion stabilizer of solid constituent 50% (C1-1) 100 parts of solution and other 50 parts of dispersion stabilizer (C1-3) solution, 75 parts of methyl methacrylate, acrylonitrile 18 Part, 70 parts of acrylic acid 2- hydroxy methacrylates, 7 parts of glycidyl methacrylate, 5 parts of methacrylic acid, 2,2 '-azo, two isobutyl 5 parts of nitrile carried out Deca through 5 hours, and then ripening 2 hours, obtained nonaqueous dispersion resin (C-1) solution.Resulting is non-aqueous It is 146nm that the solid constituent of resin dispersion (C-1) is 40%, mean diameter.

Production Example 8

In the four-hole boiling flask for possessing agitating device, thermometer, condensing tube and nitrogen inlet, load normal heptane 162 163 parts of part and dimethylbenzene, are blown into nitrogen and are warming up to 100 DEG C.By the macromolecular dispersion stabilizer of solid constituent 50% (C1-3) 100 parts of solution, 86 parts of methyl methacrylate, 20 parts of acrylonitrile, 80 parts of acrylic acid 2- hydroxy methacrylates, methacrylic acid 8 parts of ethylene oxidic ester, 6 parts of methacrylic acid, 2,2 parts of 2 '-azodiisobutyronitrile carried out Deca through 5 hours, and then ripening 2 is little When, obtain nonaqueous dispersion resin (C-2) solution.The solid constituent of resulting nonaqueous dispersion resin (C-2) is 40%, puts down Particle diameter is 330nm.

Production Example 9

In the four-hole boiling flask for possessing agitating device, thermometer, condensing tube and nitrogen inlet, load normal heptane 150 150 parts of part and dimethylbenzene, are blown into nitrogen and are warming up to 100 DEG C.By the macromolecular dispersion stabilizer of solid constituent 50% (C1-1) 150 parts of solution, 75 parts of methyl methacrylate, 18 parts of acrylonitrile, 70 parts of acrylic acid 2- hydroxy methacrylates, methacrylic acid 7 parts of ethylene oxidic ester, 5 parts of methacrylic acid, 2,5 parts of 2 '-azodiisobutyronitrile carried out Deca through 5 hours, and then ripening 2 is little When, obtain nonaqueous dispersion resin (C-3) solution.The solid constituent of resulting nonaqueous dispersion resin (C-3) is 40%, puts down Particle diameter is 157nm.

Production Example 10

In the four-hole boiling flask for possessing agitating device, thermometer, condensing tube and nitrogen inlet, load normal heptane 162 Part and dimethylbenzene 163, are blown into nitrogen and are warming up to 100 DEG C.By the macromolecular dispersion stabilizer of solid constituent 60% (C1-4) 125 parts of solution, 75 parts of methyl methacrylate, 18 parts of acrylonitrile, 70 parts of acrylic acid 2- hydroxy methacrylates, methacrylic acid 7 parts of ethylene oxidic ester, 6 parts of methacrylic acid, 2,2 parts of 2 '-azodiisobutyronitrile carried out Deca through 5 hours, and then ripening 2 is little When, obtain nonaqueous dispersion resin (C-4) solution.The solid constituent of resulting nonaqueous dispersion resin (C-4) is 40%, puts down Particle diameter is 400nm.

The manufacture of blocked polyisocyanates compound (D)

Production Example 11

In the 2L flasks of thermometer, thermostat, blender, reflux condenser, Deca pump etc. are installed, coordinate " Sumidur (ス ミ ジ ュ Le) N-3300 " (Sumitomo Baeyer polyurethane Co., Ltd. (Sumitomo Bayer Urethane Co., Ltd.) manufacture, the polyisocyanates containing isocyanurate structure, number-average molecular weight are about 600, isocyanate content and are 21.6%) 605g, diethyl malonate 413g, ethyl acetate 181g, add 28% first of the Feldalat NM of 7.0g under nitrogen flowing Alcoholic solution, is incubated 12 hours at 60 DEG C.Then, nco value is determined, is as a result that isocyanate content is 0.2%.Add wherein Plus ethyl acetate 99g, obtain resin solution.The SP values of the resin solution are 10.8, and the number-average molecular weight of resin is about 3000.

Then, be provided with thermometer, thermostat, blender, reflux condenser, Deca pump, remove solvent simply collect In the 2L flasks of device etc., load above-mentioned resulting resin solution 505g and propylene glycol monopropyl ether 450g, be warming up to 90 DEG C.Will Which keeps system temperature in 80 DEG C to 90 DEG C at reduced pressure conditions while carrying out distillating removal solvent through 2 hours, Obtain that a part for NCO is more with the end-blocking that malonic acid two (1- methyl -2- propoxy ethyls) carries out blocking Isocyanate compound (D-1) solution 642g.

In the simple catcher of solvent is removed, containing 42g ethanol.The SP values of blocked polyisocyanates and compound (D-1) For 10.1, number-average molecular weight is about 3500.Blocked polyisocyanates compound (D-1), is caused containing the third two by cross-linking reaction The alcohol mixture of alcohol list propyl ether departs from.

Production Example 12

In the 2L flasks of thermometer, thermostat, blender, reflux condenser, Deca pump etc. are installed, coordinate " Sumidur N-3300 " (Sumitomo Baeyer polyurethane Co., Ltd. manufactures, and the polyisocyanates containing isocyanurate structure, number are equal Molecular weight about 600, isocyanate content 21.6%) 605g, diethyl malonate 413g, ethyl acetate 181g, under nitrogen flowing 28% methanol solution of the Feldalat NM of addition 7.0g, is incubated 12 hours at 60 DEG C.Then, nco value is determined, is as a result isocyanide Acid and esters content is 0.2%.Add ethyl acetate 99g wherein, obtain resin solution.The number-average molecular weight of resin is about 3000.

Then, be provided with thermometer, thermostat, blender, reflux condenser, Deca pump, remove solvent simply collect In the 2L flasks of device etc., load above-mentioned resulting resin solution 505g and 1- propanol 310g, be warming up to 90 DEG C.By which in decompression Under the conditions of keep system temperature in 80 DEG C to 90 DEG C while carrying out distillating removal to solvent through 2 hours, incited somebody to action A part for NCO Dipropyl malonate. carries out blocked polyisocyanates compound (D-2) solution for blocking 560g.In the simple catcher of solvent is removed, containing 43g ethanol.The number-average molecular weight of resin is about 3100.End-blocking polyisocyanic acid Ester compounds (D-2), cause the alcohol containing normal propyl alcohol to depart from by cross-linking reaction.

Production Example 13

In the 2L flasks of thermometer, thermostat, blender, reflux condenser, Deca pump etc. are installed, coordinate " Sumidur N-3300 " (Sumitomo Baeyer polyurethane Co., Ltd. manufactures, and the polyisocyanates containing isocyanurate structure, number are equal Molecular weight about 600, isocyanate content is 21.6%) 605g, diethyl malonate 413g, ethyl acetate 181g, in nitrogen 28% methanol solution of the Feldalat NM of addition 7.0g is flowed down, and 12 hours is incubated at 60 DEG C.Then, nco value is determined, is as a result Isocyanate content is 0.2%.Add ethyl acetate 99g wherein, obtain resin solution.The number-average molecular weight of resin is about 3000。

Then, be provided with thermometer, thermostat, blender, reflux condenser, Deca pump, remove solvent simply collect In the 2L flasks of device etc., load above-mentioned resulting resin solution 505g and isodecanol 395g, be warming up to 90 DEG C.By which in decompression Under the conditions of keep system temperature in 80 DEG C to 90 DEG C while carrying out distillating removal to solvent with 2 hours, having obtained will be different A part for cyanic acid ester group two isodecyl ester of malonic acid carries out blocked polyisocyanates compound (D-3) solution for blocking 690g.In the simple catcher of solvent is removed, containing 41g ethanol.The number-average molecular weight of resin is about 3800.End-blocking polyisocyanic acid Ester compounds (D-3), cause the alcohol containing isodecanol to depart from by cross-linking reaction.

Production Example 14

In the 2L flasks of thermometer, thermostat, blender, reflux condenser, Deca pump etc. are installed, coordinate " Sumidur N-3300 " (Sumitomo Baeyer polyurethane Co., Ltd. manufactures, and the polyisocyanates containing isocyanurate structure, number are equal Molecular weight about 600, isocyanate content 21.6%) 605g and dipropylene glycol 337g, is warming up to 100 DEG C.Then, at 90 DEG C extremely Stir at 100 DEG C while be slowly added 3，5-dimethylpyrazole 308g, and then 12 hours are incubated at 100 DEG C, obtain Blocked polyisocyanates compound (D-4) solution that a part for NCO is carried out blocking with dimethyl pyrazole. Nco value is determined, is as a result that isocyanate content is 0.1%.The number-average molecular weight of resin is about 1100.

Production Example 15

In the 2L flasks of thermometer, thermostat, blender, reflux condenser, Deca pump etc. are installed, coordinate " Sumidur N-3300 " (Sumitomo Baeyer polyurethane Co., Ltd. manufactures, and the polyisocyanates containing isocyanurate structure, number are equal Molecular weight about 600, isocyanate content 21.6%) 605g, diethyl malonate 413g and tetrahydrofuran 370g, under nitrogen flowing 28% methanol solution of the Feldalat NM of addition 7.0g, at 60 DEG C is incubated 12 hours, has obtained NCO malonic acid Diethylester carries out blocked polyisocyanates compound (D-5) solution for blocking.Nco value is determined, is as a result isocyanates Content is 0.2%.The number-average molecular weight of resin is about 3000.

Production Example 16

In the 2L flasks of thermometer, thermostat, blender, reflux condenser, Deca pump etc. are installed, coordinate " Sumidur N-3300 " (Sumitomo Baeyer polyurethane Co., Ltd. manufactures, and the polyisocyanates containing isocyanurate structure, number are equal Molecular weight about 600, isocyanate content 21.6%) 605g, diethyl malonate 413g and ethyl acetate 181g, under nitrogen flowing 28% methanol solution of the Feldalat NM of addition 7.0g, is incubated 12 hours at 60 DEG C.Then, nco value is determined, is as a result isocyanide Acid and esters content is 0.2%.Add ethyl acetate 99g wherein, obtain resin solution.The number-average molecular weight of resin is about 3000.

Then, be provided with thermometer, thermostat, blender, reflux condenser, Deca pump, remove solvent simply collect In the 2L flasks of device etc., load above-mentioned resulting resin solution 505g and different tridecanol 500g, be warming up to 90 DEG C.Which is being subtracted Under press strip part, solvent is carried out slipping out removal by one side maintainer system temperature in 80 DEG C to 90 DEG C one side；However, it is possible to due to different Tridecanol is high boiling reason, it is impossible to fully carries out slipping out removal by solvent, have ceased manufacture.Therefore, fail to complete Thereafter coating, various performance evaluations.

The character of delustering agent

Evaluation procedure

Mean diameter, oil absorption and the surface of commercially available delustering agent (B-1) to (B-6) is evaluated according to below step Result is summarized in table 1 by treatment characteristic.

Mean diameter：Using laser diffraction/scattering formula particle size distribution device " Microtrac NT3300 " (commodity Name, Nikkiso Company Limited's manufacture) determining D50 values.Now, now, by silica dioxide granule is made an addition to acetone and different Apply one minute ultrasound wave to be used as pretreatment and disperseed in the mixed solvent of propanol, delustring agent concentration is adjusted to and reaches dress Put the concentration of set regulation transmitance scope.

Oil absorption：According to JIS K5101-13-2:2004 are measured.

Surface treatment characteristics：The water of 5mL is added in developmental tube, is gently added the inorganic particles of 0.3g wherein and is carried out Stand, after 12 hours, have rated the ratio of the inorganic particles kept afloat.

Table 1

The manufacture of coating composition

Embodiment and comparative example

By become shown in table 2 with being combined in the way of equably mixing each composition.Then, in resulting mixing Add retarder thinner in thing, obtained the Ford cup 4 (No.4) using 20 DEG C obtained by viscosity be the coating composition of 25 seconds.

Also, shown in table 2 is solid constituent, and (B-1) in table 1 to (B-6), (E-1) are as described below.

(B-1)“Sylysia 436”：Trade name, chemistry of silicones Co., Ltd. of Fuji manufacture, has carried out table with organic compound The silica dioxide granule that face is processed

(B-2)“Sylophobic 200”：Trade name, chemistry of silicones Co., Ltd. of Fuji manufacture, is entered with organo-silicon compound The silica dioxide granule of surface hydrophobicity of having gone process

(B-3)“ACEMATT OK-412”：Trade name, Evonik Industries companies manufacture, is entered with organic compound Gone surface treatment silica dioxide granule

(B-4)“Sylophobic 702”：Trade name, chemistry of silicones Co., Ltd. of Fuji manufacture, is entered with organo-silicon compound The silica dioxide granule of surface hydrophobicity of having gone process

(B-5)“ACEMATT 3300”：Trade name, Evonik Industries companies manufacture, is entered with organo-silicon compound The silica dioxide granule of surface hydrophobicity of having gone process

(B-6)“Sylysia 430”：Trade name, the manufacture of chemistry of silicones Co., Ltd. of Fuji, undressed silicon dioxide

(E-1)Sumidur N3300：Trade name, the manufacture of Sumitomo Baeyer polyurethane Co., Ltd., two Carbimide. of hexa-methylene The isocyanurate structure body (ヌ レ ト bodies) of ester, solid constituent is 100%, and isocyanate group content is 21.8%

Table 2

Continued 2

The making of bread board

Embodiment 1 to 17, comparative example 1 to 4

10cm × 15cm size and be applied with zinc phosphate chemical conversion treatment thickness 0.8mm matt steel plate On, by " Erekuron (エ レ Network ロ Application) GT-10 ", (Kansai Paint Co., Ltd manufactures, trade name, thermosetting epoxy resin class Cation electrodeposition coating) electrodeposition coating is carried out so that solidifying thickness for 20 μm, the heating at 170 DEG C carries out solid for 30 minutes Change, by " TP-65-2 ", (Kansai Paint Co., Ltd manufactures, trade name, in polyester melamine resinae vehicle thereon Apply coating) carry out aerial spraying to cause solidification thickness to be 35 μm, heat at 140 DEG C and solidified for 30 minutes.On the film By " WBC-713T No.202 ", (Kansai Paint Co., Ltd manufactures, and applies in acrylic acid-melmac class vehicle aqueouss Substrate be coated with coating, it is black to tint) carry out application so that thickness be 15 μm, room temperature place 5 minutes, at 80 DEG C preheat 10 points The coating composition (1) to (17) of table 2 and (20) are carried out application to (23) so that solid on the uncured film by Zhong Hou It is 20 μm and 40 μm to change thickness, after room temperature is placed 10 minutes, by the heating 20 minutes at 140 DEG C and by two film together Solidified, thus obtained bread board.The performance test results of resulting film are shown in table 2 (continued 2) in the lump.

Embodiment 18

On the matt steel plate of thickness 0.8mm for being applied with zinc phosphate chemical conversion treatment, by " Erekuron GT- 10 " (Kansai Paint Co., Ltd manufactures, trade name, thermosetting epoxy resin cationoid electrocoating paint) carries out electro-deposition painting It is filled with so that solidify thickness for 20 μm, heats at 170 DEG C and solidified for 30 minutes, thereon by the coating composition of table 2 (18) application is carried out so that solidifying thickness for 20 μm and 40 μm, heated 20 minutes after room temperature is placed 10 minutes at 140 DEG C, Thus obtain bread board.The performance test results of resulting film are shown in table 2 (continued 2) in the lump.

Embodiment 19

On ABS plates (black has completed ungrease treatment), by primer (primer) " SOFLEX (ソ Off レ ッ Network ス) 1000 " (trade name, organic solvent type coatings containing polyolefin conductive, Kansai Paint Co., Ltd manufacture) carry out aerial spraying with So that dry film thickness is 15 μm, preheat 3 minutes at 80 DEG C.Further, " WBC-713T No.202 " is carried out painting thereon to be filled with So that thickness is 15 μm, after room temperature is placed 5 minutes, preheat 10 minutes at 80 DEG C.Thereon, coating composition (19) is entered Row aerial spraying is so that solidify thickness for 20 μm and 40 μm, the heating at 80 DEG C carries out solidification for 30 minutes to obtain test painting Plate.The performance test results of resulting film are shown in table 2 (continued 2) in the lump.

Method for testing performance

Gloss stability (is changed the low in glossiness for causing) by thickness：

Will be according to JIS K5600-4-7:Film of the value of 1999 60 ° of mirror surface lusters being measured less than 60 is defined as Delustring film, the value of 60 ° of mirror surface lusters during by carrying out application with 20 μm of thickness with when carrying out application with 40 μm of thickness The difference of the value of 60 ° of mirror surface lusters is being evaluated.Evaluated according to following benchmark.S and A is qualified.

S：Difference is less than 5；

A：Difference is for 5 less than 10；

B：Difference is more than 10.

Also, in the case where the same amount of silicon dioxide of addition is compared, preferably 60 ° gloss values itself are little.And And, comparative example 1,4 does not meet the film of " with extinction " defined above.

Gloss stability (gloss uneven in plate)：

60 ° of mirror surface lusters at any 7 points of above-mentioned resulting test plate surface are determined, by maximum and minimum The difference of value is evaluated.Evaluated according to following benchmark.S and A is qualified.

S：Difference is less than 5；

A：Difference is for 5 less than 10；

B：Difference is more than 10.

Alkali resistance：

In 1% sodium hydrate aqueous solution of film coated surface Deca 0.5mL of bread board, in 20 DEG C of temperature, relative humidity After placing 24 hours under 65% atmosphere, painting face is wiped with gauze, pass through visual assessment outward appearance according to following benchmark.S and A are It is qualified.

S：Film coated surface is completely without abnormal；

A：It can be seen that the discoloration (albefaction) of film coated surface；

B：The discoloration (albefaction) of film coated surface is significantly.

Storage-stable：

In the form of using " Swasolve#1000 " (note 4), viscosity to become #4/20 DEG C of 25 seconds/Ford cup, will remember in table 1 What is carried stands 72 hours with the coating composition that the mixture being combined into is diluted under 50 DEG C of atmosphere.Then, recover To 20 DEG C, in the state of visual observations coating, evaluated according to following benchmark.

S：Have no the generation of precipitum；

A：Precipitum is produced, but recovers the state to storage if stirring 10 minutes or so；

B：Precipitum is produced, and precipitum does not also disappear under case above in stirring for 10 minutes.

Resistance to impact：

After each cladding envelope is placed 24 hours in 20 DEG C ± 1 of temperature, the thermostatic constant wet chamber of humidity 75 ± 2%, in JIS On Du Pont's impact tester of K 5600-5-3 (1999) defined, the pedestal of installation provision size and center of impact, make test The painting of plate is faced upwards, and is clamped therebetween, then makes the weight of 500g weight fall on center of impact (1/2 inch), determine because Impact and cause film (surface) that rupture, the height of fall (cm) peeled off occur.

S：More than 50cm；

A：45cm is less than 50cm；

B：Less than 45cm.

The making (2) of bread board

Embodiment 20 to 21, comparative example 5 to 6

10cm × 15cm size and be applied with zinc phosphate chemical conversion treatment thickness 0.8mm matt steel plate On, by " Erekuron GT-10 ", (Kansai Paint Co., Ltd manufactures, trade name, and thermosetting epoxy resin cationoid electricity is heavy Product coating) carry out electrodeposition coating to cause solidification thickness to be 20 μm, heat at 170 DEG C and solidified for 30 minutes, thereon will " TP-65-2 " (Kansai Paint Co., Ltd manufactures, trade name, coating in polyester melamine resinae vehicle) is carried out It is 35 μm that aerial spraying causes to solidify thickness, heats and solidified for 30 minutes at 140 DEG C." the WBC-713T on the film No.202 " (Kansai Paint Co., Ltd manufactures, and applies substrate coating coating in acrylic acid-melmac class vehicle aqueouss, It is black to tint) application is carried out so that thickness is 15 μm, place 5 minutes in room temperature, after carrying out preheating in 10 minutes at 80 DEG C, solid Change the film on the coating composition (1) of table 3, (3), (21), (22) are attached to after coated article one minute after as apply Covering the form that solid constituent is 52%, 62%, 72% carries out application, after room temperature is placed 10 minutes, by heating at 140 DEG C Solidified 20 minutes two film, thus obtain bread board.The regulation of coating solid constituent, with solvent or diluent (butyl acetate, second Base -3- ethoxy-c acid esters) mixed proportion carry out.The performance test results of resulting film are shown in Table 3 in the lump.

Here, the coating composition of table 3 is attached to the coating solid constituent after coated article one minute after, by as described below It is measured.

By the coating composition of table 3, on the tinplate of long 45cm × horizontal 30cm × thickness 0.8mm, rotary-atomizing type is used Cup type (bell-type) coating machine " cup type (Cartridge Bell) coating machine of ABB magazines " (trade name, ABB AB's manufacture), In the form of dry film thickness is 40 μm, diameter 70mm, rotation number 25000rpm of cup in cup (bell), shaping air pressure are 2.0kg/cm², output be that 250cc/ minutes, voltage are for the distance of -75kV, coated article and metal cup (metal bell) An application is carried out under conditions of 30cm, by the film in the coating composition of table 3 in tinplate and after a point A part is collected with scraper etc., can determine the coating solid constituent after being dried 1 hour at 110 DEG C.More correctly, By determine 110 DEG C to 1 ± 0.1g of coating be dried 1 hour after heating residual and by the heating residual divided by original painting Expect weight (value of the scope of 1 ± 0.1g) to obtain.

Gloss stability (low in glossiness for being changed and being caused by coating solid constituent)：

Will be according to JIS K5600-4-7:Film of the value of 1999 60 ° of mirror surface lusters being measured less than 60 is defined as Delustring film, by with coat solid constituent become 60 ° of mirror surface lusters when carrying out application in the form of 52% value and with into The difference of the value of 60 ° of mirror surface lusters when carrying out application for 72% form is being evaluated.Evaluated according to following benchmark. S and A is qualified.

S：Difference is less than 5；

A：Difference is for 5 less than 10；

B：Difference is more than 10.

Table 3

Claims (8)

1. a kind of coating composition, which includes envelope formative resin (A) and delustering agent (B), and then comprising by skin composition and core Non-aqueous polymer dispersion liquid (C), and/or blocked polyisocyanates compound (D) that composition is constituted, it is characterised in that

Non-aqueous polymer dispersion liquid (C) divides containing at least one of acrylate copolymer as skin composition and/or greatly Sub- monomer, wherein, the macromonomer comprising fatty acid self shrinking compound and each molecule averagely with more than 1 gather Conjunction property unsaturated group, the fatty acid have the hydroxy alkyl that the carbon number of alkyl chain is 10 to 25,

Blocked polyisocyanates compound (D) is the simple function that the compound departed from cross-linking reaction is carbon number 3 to 12 The active methylene group class blocked polyisocyanates compound of alcohol.

2. coating composition according to claim 1, wherein, delustering agent (B) is organic process silica dioxide granule.

3. coating composition according to claim 2, wherein, delustering agent (B) is that surface hydrophobicity processes silicon dioxide Granule.

4. coating composition according to any one of claim 1 to 3, wherein, the mean diameter of delustering agent (B) is 1 μm to 10 μm, and oil absorption is 100mL/100g to 400mL/100g.

5. coating composition according to any one of claim 1 to 4, wherein, also containing cross-linking agent (E).

6. coating composition according to claim 5, wherein, cross-linking agent (E) contains polyisocyanate compound (E1)。

7. a kind of coating process, which is included in the coating composition on coated article any one of application claim 1 to 6 Operation.

8. a kind of coated article, which has carries out what is solidified by the coating composition any one of claim 1 to 6 Film.