CN100587015C - Water coating composition - Google Patents

Abstract

The invention provides a coating composition for pots capable of forming a coating with good bending machinability, water resistance prewhitening property and good smell. A water coating composition is characterized by containing 0.1-20 phr resol (B) and 0.1-20 phr acrylic resin (C) with acid number 100-500mgKOH/g relative to 100 phr acrylic resin modified epoxy resin (A). The resin (A) and the resin (C) are dispersed in the water medium. The acrylic resin (C) has the following necessary components: ethylene copolymer chain (1) taking acid radical polymerized monomer as monomer component and ethylene copolymer chain (2) taking carboxyl radical polymerized monomer as monomer component.

Description

Water-based paint compositions

Technical field

The present invention relates to a kind of jar coating composition, its component parts that is useful on the metal tins such as edible jar and lid of beverage, fruit etc. applies, and gained the filming of the balance excellence that can form bending process, resistance to water-whitening, acidproof adaptation, smell of filming.

Background technology

From in the past, for jar coating composition, the jar coating composition with jar surfaces externally and internally and cover etc. of film performances such as processibility, cementability and erosion resistance grows up gradually.

At present, known have a following invention, this invention relates to the aqueous resin dispersion that has added acrylic resin (D) in the acrylic acid or the like modified epoxy, wherein, to comprise monoprotic acid be acrylic monomer composition (patent documentation 1) below 0 ℃ as neccessary composition and the glass transition point that comprises 40% above homopolymer to described acrylic resin (D).

In addition, known have a kind of water-based paint compositions, it is characterized in that, this water-based paint compositions is dispersed in and forms in the aqueous medium containing carboxyl Resins, epoxy and emulsion resin, wherein, this emulsion resin be contain the resinoid aqueous dispersions of carboxy acrylic in the presence of, the ethylenically unsaturated monomer letex polymerization is formed, its acid number is that 150～450mgKOH/g, number-average molecular weight are 2000～50000 (patent documentations 2).

In addition, known have a kind of water-based paint compositions, it is characterized in that, this water-based paint compositions contain acrylic resin modified epoxy (A), resole (B) and be selected from vibrin and polyvinyl butyral resin at least a resin of tackification (C) (patent documentation 3).

In addition, known have a kind of water-based paint compositions, it is characterized in that, this water-based paint compositions contains the acrylic acid or the like modified epoxy that obtains by following reaction, basic cpd and aqueous medium, this acrylic acid or the like modified epoxy is 10～135mgKOH/g by making a part of epoxy group(ing) and acid number in the Resins, epoxy, second-order transition temperature (Tg) is-20～20 ℃, weight-average molecular weight is that 10000～200000 contain carboxy acrylic resinoid and acid number are that a part of carboxyl reaction that contains in the carboxy acrylic resinoid of 180～450mgKOH/g obtains (patent documentation 4).

In addition, following invention is arranged: a kind of tin paint, it makes adaptation, excellent in workability by disperse core-shell particulate in aqueous resin composition, wherein, this aqueous resin composition is dispersed in the aqueous medium microgranular self-emulsifying epoxy resin and forms, and consider in filming the core shell particulate (island) that exists and microgranular self-emulsifying epoxy resin polymerization part (sea) between mutual adaptation, improved the adaptation and the processibility (patent documentation 5) of filming.

In addition, known have a kind of water-based paint compositions, and it contains acrylic resin modified epoxy, resole and styrol copolymer rubber (patent documentation 6).Yet, the coating coating put down in writing of patent documentation 1～6 and the over-all propertiess such as can not satisfying bending process, resistance to water-whitening, acidproof adaptation, smell of filming that obtains.

Patent documentation 1: Japanese kokai publication hei 8-302275 communique

Patent documentation 2: Japanese kokai publication hei 9-227824 communique

Patent documentation 3: Japanese kokai publication hei 11-343456 communique

Patent documentation 4: TOHKEMY 2005-187679 communique

Patent documentation 5: Japanese kokai publication hei 9-67543 communique

Patent documentation 6: Japanese kokai publication hei 11-263938 communique

Summary of the invention

Invent problem to be solved

The objective of the invention is to find out a kind of jar coating composition, it can form filming of bending process, resistance to water-whitening, smell excellence.

The method that is used to deal with problems

The inventor furthers investigate for addressing the above problem, found that by in acrylic resin modified epoxy (A), cooperating resole (B) and specific acrylic resin (C), thereby can address the above problem, finish the present invention.That is, the present invention can provide following water-based paint compositions and jar coating composition.

[1] a kind of water-based paint compositions, it is characterized in that, this water-based paint compositions is to disperse 100 mass parts acrylic resin modified epoxies (A) in aqueous medium, 0.1～20 mass parts resoles (B), 0.1 it is that the acrylic resin (C) of 100～500mgKOH/g forms that～20 mass parts have the acid number of following characteristics, wherein, described acrylic resin (C) has: contain acrylic to be selected from, the methylene-succinic acid base, sulfonic group, or at least a free radical polymerization monomer in the free radical polymerization monomer of phosphate is as the ethylenic copolymer chain (1) of moiety, with with the monomer component that contains methacrylic acid ethylenic copolymer chain (2) as moiety.

[2] according to above-mentioned [1] described water-based paint compositions, wherein, aforementioned acrylic resin (C) is to make following composition react the polymkeric substance that forms, and described composition is:

Vinyl copolymer resin (c1), it is selected from least a free radical polymerization monomer in the free radical polymerization monomer that contains acrylic, methylene-succinic acid base, sulfonic group or phosphate and other free-radical polymerised unsaturated monomer (1) of 40～90 quality % as monomer component with 10～60 quality %;

Vinyl copolymer resin (c2), it contains 10～60 quality % methacrylic acids and other free-radical polymerised unsaturated monomer (2) of 40～90 quality % as monomer component;

Low-molecular weight compound (c3), it has in 1 molecule more than 2 and has reactive complementary interaction group with acidic group and carboxyl.

[3] according to above-mentioned [2] described water-based paint compositions, it is characterized in that, total based on the solids component of vinyl copolymer resin (c1) and vinyl copolymer resin (c2), with vinyl copolymer resin (c1)/vinyl copolymer resin (c2)=60/40～95/5 (quality %), and the ratio of [vinyl copolymer resin (c1)+vinyl copolymer resin (c2)]/low-molecular weight compound (c3)=100/0.1～100/20 (quality) makes the vinyl copolymer resin (c1) that constitutes acrylic resin (C), ethylenic copolymer (c2) and low-molecular weight compound (c3) reaction.

[4] according to above-mentioned [2] or [3] described water-based paint compositions, wherein, low-molecular weight compound (c3) is at least a in 180～5000 Resins, epoxy, resole and the polycarbodiimide compound for being selected from the epoxy equivalent (weight) that has 2 above epoxy group(ing) in 1 molecule.

[5] according to above-mentioned [4] described water-based paint compositions, wherein, low-molecular weight compound (c3) is that the epoxy equivalent (weight) that has 2 above epoxy group(ing) in 1 molecule is 200～1000 Resins, epoxy.

[6] according to each described water-based paint compositions of above-mentioned [1]～[5], wherein, acrylic resin modified epoxy (A) is following resin, that is, to make number-average molecular weight be 2000～35000 bisphenol-type epoxy resin (a1) with contain carboxy acrylic resinoid (a2) carries out the resin that esterification forms or makes this bisphenol-type epoxy resin (a1) and the polymerizability unsaturated monomer composition that contains carboxyl polymerizability unsaturated monomer (a3) carry out the resin that graft polymerization forms.

[7] according to each described water-based paint compositions of above-mentioned [1]～[6], it is characterized in that, with respect to 100 mass parts acrylic resin modified epoxies (A), further contain the anionic property crosslinked polymer particulate (D) that 1～50 mass parts has following characteristics, wherein, anionic property crosslinked polymer particulate (D) is that the polymkeric substance of 10～100mgKOH/g is formed by the acid number of following manufacturing, promptly, in the presence of water, make 2～30 quality % contain carboxyl free radical polymerizable monomer (d1), the free-radical polymerised unsaturated monomer composition that other free-radical polymerised unsaturated monomer (d3) of many vinyl compounds of 2～30 quality % (d2) and 40～96 quality % is formed carries out polyreaction and the polymkeric substance that makes.

[8] a kind of jar coating composition is characterized in that, each described water-based paint compositions of above-mentioned [1]～[7] is used to be coated with and installs to tank body.

The invention effect

According to the present invention, owing to improved bending process, resistance to water-whitening, acidproof adaptation, so the metal tin of filming that can obtain having anti-content corrodibility excellence and smell excellence.

Description of drawings

Fig. 1 cooperates crosslinked polymer particulate (D) in coating, form the cross section of filming of island structure.

Embodiment

Below, describe at jar coating composition of the present invention.

[jar coating composition]

Acrylic resin modified epoxy (A):

Acrylic resin modified epoxy (A) can be any of following resin (1), resin (2).

Resin (1): make bisphenol-type epoxy resin (a1) (below, abbreviate " Resins, epoxy (a1) " as) with containing that carboxy acrylic resinoid (a2) (below, abbreviate " acrylic resin (a2) " as) carries out the ester addition reaction resin that obtains.About resin (1), for example can in organic solvent, in the presence of esterifying catalyst, Resins, epoxy (a1) and acrylic resin (a2) be heated, thereby easily carry out the ester addition reaction.

Resin (2): make bisphenol-type epoxy resin (a1) and the polymerizability unsaturated monomer composition that contains carboxyl polymerizability unsaturated monomer (a3) carry out graft polymerization and the resin that obtains.About resin (2), for example can in organic solvent, in the presence of free-radical generating agent such as benzoyl peroxide, make Resins, epoxy (a1) and polymerizability unsaturated monomer composition carry out graft polymerization.

As the bisphenol-type epoxy resin (a1) that uses in above-mentioned resin (1), the resin (2), can be any in the following resin, that is, for example, make Epicholorohydrin and bis-phenol in the presence of catalyzer such as alkaline catalysts, be condensed into high molecular as required and the resin that obtains; Make Epicholorohydrin and bis-phenol in the presence of catalyzer such as alkaline catalysts, carry out condensation as required, obtain low-molecular-weight resin, this low-molecular-weight epoxy resin and bis-phenol are carried out polyaddition reaction and the resin that obtains; And the epoxy ester resin that resulting these resins or above-mentioned low-molecular-weight epoxy resin and diprotic acid reaction are obtained.

As above-mentioned bis-phenol, can list two (4-hydroxyphenyl) methane [Bisphenol F], 1, two (4-hydroxyphenyl) ethane, 2 of 1-, two (4-hydroxyphenyl) propane [dihydroxyphenyl propane], 2 of 2-, two (4-hydroxyphenyl) butane [bisphenol b] of 2-, two (4-hydroxyphenyl)-1,1-Trimethylmethane, two (4-hydroxyl tert-butyl-phenyl)-2,2-propane, to (4-hydroxyphenyl) phenol, oxygen two (4-hydroxyphenyl), sulphonyl two (4-hydroxyphenyl), 4,4 '-dihydroxy benaophenonel, two (2-hydroxyl naphthyl) methane etc., wherein, preferably use dihydroxyphenyl propane, Bisphenol F.Above-mentioned bisphenols can use a kind or use mixture more than 2 kinds.

The diprotic acid that uses in the manufacturing as above-mentioned epoxy ester resin can preferably use the compound shown in the following formula (1).Specifically, can succsinic acid, hexanodioic acid, pimelic acid, nonane diacid, sebacic acid, dodecanedioic acid, hexahydrophthalic acid etc. be shown example.

HOOC-(CH ₂) _n-COOH formula (1)

In the formula, n is 1～12 integer.

Commercially available product as Resins, epoxy (a1), can list for example Japan EpoxyResins Co., the Araldit AER6099 that the Epikote 1007 that Ltd. makes (epoxy equivalent (weight) about 1700, number-average molecular weight (annotating 1) about 2900), Epikote1009 (epoxy equivalent (weight) about 3500, number-average molecular weight about 3750), Epikote1010 (epoxy equivalent (weight) about 4500, number-average molecular weight about 5500), Asahi Ciba company make (epoxy equivalent (weight) about 3500, number-average molecular weight about 3800); And the EPOMIK_R-309 that makes of Mitsui Chemicals (strain) (epoxy equivalent (weight) about 3500, number-average molecular weight about 3800) etc.

(annotating 1) number-average molecular weight: carry out based on JIS K0124-83, separator column uses TSKGEL4000H _XL+ G3000H _XL+ G2500H _XL+ G2000H _XL(TOSOHCORPORATION manufacturing), with 40 ℃, flow velocity 1.0ml/ minute, eluant uses gel permeation chromatography (GPC) use tetrahydrofuran (THF), and by the typical curve of color atlas that utilizes the RI refractometer to obtain and polystyrene, number-average molecular weight is tried to achieve in calculating.

As Resins, epoxy (a1), from the erosion resistance that gained is filmed, preferred number average molecular weight is 2000～35000, be preferably 4000～30000, epoxy equivalent (weight) is 1000～12000, be preferably the bisphenol-type epoxy resin of 3000～10000 scope.

In aforementioned resin (1), when the ester addition reaction, carboxyl generation ester addition reaction in epoxy group(ing) in the Resins, epoxy (a1) and the acrylic resin (a2), thereby, epoxy group(ing) is necessary in the Resins, epoxy (a1), and the epoxy group(ing) of per 1 molecule Resins, epoxy is suitably average 0.5～2, be preferably in 0.5～1.6 the scope.On the other hand, in aforementioned (2), graft reaction is that the dehydrogenation by the Resins, epoxy main chain begins and graft polymerization reaction goes on, and therefore, in fact can not have epoxy group(ing) in the Resins, epoxy (a1).

The acrylic resin (a2) that uses in resin (1) is to contain carboxyl polymerizability unsaturated monomer (a3) and other polymerizability unsaturated monomer (a4) fluoropolymer resin as monomer component.

As the above-mentioned carboxyl polymerizability unsaturated monomer (a3) that contains, for example can list monomers such as (methyl) vinylformic acid, toxilic acid, Ba Dousuan, methylene-succinic acid, fumaric acid, these can use separately also can make up more than 2 kinds and use.

Other polymerizability unsaturated monomer (a4) is so long as can get final product with the above-mentioned monomer that contains carboxyl polymerizability unsaturated monomer (a3) copolymerization, can suitably select to use according to desired performance, can list the mixture more than a kind or 2 kinds of following monomer etc., for example, fragrant same clan vinyl monomers such as vinylbenzene, Vinyl toluene, 2-methyl styrene, t-butyl styrene, chloro-styrene; Methyl acrylate, ethyl propenoate, the vinylformic acid n-propyl, isopropyl acrylate, n-butyl acrylate, isobutyl acrylate or tert-butyl acrylate, Ethyl acrylate, 2-EHA, the vinylformic acid n-octyl, decyl acrylate, lauryl acrylate, cyclohexyl acrylate, methyl methacrylate, Jia Jibingxisuanyizhi, n propyl methacrylate, isopropyl methacrylate, n-BMA, Propenoic acid, 2-methyl, isobutyl ester or methacrylic tert-butyl acrylate, N-Hexyl methacrylate, methacrylic acid 2-ethylhexyl, Octyl methacrylate, decyl-octyl methacrylate, lauryl methacrylate(LMA), the carbon atom of acrylic or methacrylic acid such as cyclohexyl methacrylate is 1～18 alkyl ester or cycloalkyl ester; The C of acrylic or methacrylic acid such as 2-hydroxy ethyl methacrylate, 2-hydroxypropyl acrylate, 3-hydroxypropyl acrylate, hydroxyl butylacrylic acid ester, 2-hydroxyethyl meth acrylate, 2-hydroxypropylmethyl acrylate, 3-hydroxypropylmethyl acrylate, hydroxyl butyl methyl acrylate ₂～C ₈Hydroxy alkyl ester; N-substituted acrylamide classes such as N hydroxymethyl acrylamide, N-butoxymethyl acrylamide, N-methoxymethyl propenamide, N-methylol methacrylamide, N-fourth oxygen methyl acrylamide or N-substituent methyl acrylamide monomers etc.

The mixture of special optimization styrene of this other polymerizability unsaturated monomer (a4) and ethyl propenoate, the composition mass ratio of styrene/acrylic ethyl ester be suitably 99.9/0.1～40/60, more preferably in 99/1～50/50 the scope.

Contain carboxy acrylic resinoid (a2) and be not particularly limited monomeric proportion of composing, kind, be preferably 15～80 quality %, be preferably 20～60 quality % especially but contain carboxyl free radical polymerizability unsaturated monomer usually, other polymerizability unsaturated monomer (a4) is preferably 85～20 quality %, is preferably 80～40 quality % especially.

Contain the modulation of carboxy acrylic resinoid (a2), can be by for example in the presence of polymerization starter, making above-mentioned monomer composition in organic solvent, carry out solution polymerization and easily carrying out.Containing carboxy acrylic resinoid (a2), to be suitably resinous acid value be that 100～400mgKOH/g, number-average molecular weight (with reference to annotating 1) are in 5000～100000 the scope.

Above-mentioned reaction can be carried out according to known method in the past, for example, in the uniform organic solvent solution of Resins, epoxy (a1) and acrylic resin (a2), cooperate esterifying catalyst, generally with 60～130 ℃ temperature of reaction it is reacted reacted, and all was consumed basically until epoxy group(ing) in about 1～6 hour.As above-mentioned esterifying catalyst, can enumerate for example tertiary amines such as triethylamine, dimethyl methyl hydramine, quaternary salt compounds such as triphenylphosphine etc., wherein preferred tertiary amine.

Solid component concentration in the reaction system of Resins, epoxy (a1) and acrylic resin (a2) is so long as just be not particularly limited in the range of viscosities that reaction system does not counteract reaction.In addition, when using esterifying catalyst when in the ester addition reaction, its usage quantity is suitably with respect to 1 equivalent epoxy group(ing) in the Resins, epoxy (a1), generally uses with 0.1～1 normal scope.

Resins, epoxy (a1) and acrylic resin (a2) contain proportional being not particularly limited; but usually Resins, epoxy (a1) is preferably 60～90 quality %, is preferably 70～85 quality % especially, and acrylic resin (a2) is preferably 15～30 quality %, is preferably 20 quality % especially.

When acrylic resin modified epoxy (A) was the resin that is obtained by aforementioned resin (2), graft polymerization can list the monomer component that uses in the manufacturing that contains carboxy acrylic resinoid (a2) that contains in aforementioned resin (1), promptly contain the polymerizability unsaturated monomer composition of carboxyl polymerizability unsaturated monomer (a3) to the polymerizability unsaturated monomer composition on the Resins, epoxy (a1).In addition, this polymerizability unsaturated monomer composition can also contain other polymerizability unsaturated monomer (a4) that uses in resin (1).

Graft polymerization reaction in above-mentioned resin (2) can carry out according to known method in the past, for example, in being heated to 80～150 ℃ the organic solvent solution of Resins, epoxy (a1), slowly add the homogeneous mixture solotion of free-radical generating agent and polymerizability unsaturated monomer composition, under uniform temp, keep carrying out graft polymerization reaction thus about 1～10 hour.As above-mentioned free-radical generating agent, for example can list azobis isobutyronitrile, benzoyl peroxide, the sad tert-butyl ester of benzoyl peroxide, the peroxidation 2 ethyl hexanoic acid tert-butyl ester etc.

Organic solvent during as modulation above-mentioned resin (1) and resin (2), just can use known in the past organic solvent as long as satisfy following condition, promptly, dissolved epoxy (a1) and acrylic resin (a2) or contain the polymerizability unsaturated monomer composition of carboxyl polymerizability unsaturated monomer (a3), and the acrylic resin modified epoxy (A) of reaction product to these neutralizes, during Water-borne modification, the organic solvent that can counteract not to the formation of emulsion.

Object lesson as above-mentioned organic solvent, can list Virahol, butanols, 2-hydroxy-4-methyl pentane, 2-Ethylhexyl Alcohol, hexalin, ethylene glycol, Diethylene Glycol, 1,3 butylene glycol, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether etc.

Consider from viewpoints such as water dispersible, film performances, the acrylic resin modified epoxy (A) that is obtained by above-mentioned resin (1) or resin (2) preferably has carboxyl, and resinous acid value be 10～160mgKOH/g, more preferably in the scope of 20～100mgKOH/g.

By with in the basic cpd and resin at least a portion carboxyl, acrylic resin modified epoxy (A) can be dispersed in the aqueous medium.

The employed basic cpd of the neutralization of above-mentioned carboxyl preferably uses amine, ammonia.As the typical example of above-mentioned amine, can list alkyl amines such as Trimethylamine, triethylamine, tributylamine; Alkanol amines such as dimethylethanolamine, diethanolamine, aminomethyl propanol; Cyclic amines such as morpholine etc.The degree of neutralization of acrylic resin modified epoxy (A) is not particularly limited, but preferably with respect to the carboxyl in the resin (A), is generally 0.1～2.0 equivalent neutral scope.

Above-mentioned aqueous medium can be a water, also can be the mixture of water and organic solvent.As this organic solvent, can use known in the past arbitrary organic solvent, can preferably use as the cited organic solvent of organic solvent that can when the manufacturing of aforementioned acrylic resin modified epoxy (A), use.From the viewpoint of environment protection etc., the amount of the organic solvent in the jar coating composition of the present invention is preferably the following scope of 20 quality % with respect to the resin solid composition of jar coating composition.

For making acrylic resin modified epoxy (A) in aqueous medium, neutralize, disperse, the use ordinary method gets final product, for example can list following method, that is, stir and down acrylic resin modified epoxy (A) slowly to be added to the method that contains as in the aqueous medium of the basic cpd of neutralizing agent; Utilize in the basic cpd and acrylic resin modified epoxy (A) after, under agitation, aqueous medium added in this corrective or add this corrective to method in the aqueous medium etc.

＜resole (B) 〉

The resole that uses in the jar coating composition of the present invention (B), it plays the effect of the linking agent of acrylic resin modified epoxy (A) and acrylic resin (C), also comprise: make aldehydes such as phenols such as phenol, dihydroxyphenyl propane and formaldehyde in the presence of catalysts, carry out condensation reaction and import the resol that methylol obtains, and be that alcohol below 6 carries out the material that the alkyl etherificate gets with the part of the methylol that is imported into carbonatoms.

Resole (B), its number-average molecular weight (annotate 1) is 200～2000, be preferably in 300～1200 the scope, and the mean number of the methylol of per 1 nuclear benzene nucleus is 0.3～3.0, be preferably 0.5～3.0, more preferably in 0.7～3.0 the scope.By using above-mentioned resole, can form filming of film performance excellences such as cementability.

In jar coating composition of the present invention, resole (B) is suitably for 0.1～20 mass parts, is preferably in the scope of 0.1～10 mass parts with respect to solids component 100 mass parts of acrylic resin modified epoxy (A).In addition, can also suitably contain tensio-active agent, defoamer, pigment, wax, spices etc. as required.

＜acrylic resin (C) 〉

Jar coating composition of the present invention is by cooperating acrylic resin (C), and it is good especially that acidproof adaptation becomes, and helps gained to film to form filming of bending process, resistance to water-whitening, erosion resistance, smell excellence.

Acrylic resin (C) has to be selected from least a free radical polymerization monomer in the free radical polymerization monomer that contains acrylic, methylene-succinic acid base, sulfonic group or phosphate as the ethylenic copolymer chain (1) of moiety with to contain the ethylenic copolymer chain (2) of methacrylic acid monomer composition as moiety.

Ethylenic copolymer chain (1):

Ethylenic copolymer chain (1) is preferably the following vinyl copolymer resin that makes (c1): will be with 10～60 quality %, be preferably 20～55 quality %, more preferably being selected from of 30～50 quality % contains acrylic, the methylene-succinic acid base, sulfonic group, or at least a free radical polymerization monomer in the free radical polymerization monomer of phosphate and 40～90 quality %, be preferably 45～80 quality %, more preferably other free-radical polymerised unsaturated monomer (1) of 50～70 quality % is as the mixture (1) of monomer component, in the solvent that is suitable for, carry out Raolical polymerizable, the vinyl copolymer resin that obtains thus (c1).

When being selected from least a free radical polymerization monomer in the free radical polymerization monomer that contains acrylic, methylene-succinic acid base, sulfonic group or phosphate less than 10 quality %, adaptation can descend, and when surpassing 60 quality %, may damage water tolerance.

As containing the sulfonic group free radical polymerization monomer, can list 2-acrylamide-2-methyl propane sulfonic acid.As phosphorous acidic group free radical polymerization monomer, can list list (methacrylic acid 2-hydroxyl ethyl ester) phosphoric acid ester.

As containing the acrylic free radical polymerization monomer, can list vinylformic acid, as containing methylene-succinic acid base free radical polymerization monomer, can list methylene-succinic acid.

As other free-radical polymerised unsaturated monomer (1), can list: for example vinylbenzene, alpha-methyl styrene, Vinyl toluene, to vinyl aromatic compounds such as chloro-styrene, vinyl pyridines;

For example, the C of acrylic or methacrylic acid such as 2-hydroxyethyl (methyl) acrylate, 3-hydroxypropyl (methyl) acrylate, 4-hydroxyl butyl (methyl) acrylate ₂～C ₈Hydroxyalkyl (methyl) acrylate; The free-radical polymerised unsaturated monomers of hydroxyl such as (gathering) glycol monomethyl (methyl) acrylate, polypropylene glycol list (methyl) acrylate, polytetramethylene glycol list (methyl) acrylate; The reactant of lactone compounds such as free-radical polymerised unsaturated monomer of these hydroxyls and beta-propiolactone, dimethyl propylene lactone, butyrolactone, γ-Wu Neizhi, γ-Ji Neizhi, γ-decalactone, γ-dodecalactone, ε-valerolactone, δ-Wu Neizhi etc.;

For example, Placcel FM-1, Plac cel FM-2, Placcel FM-3, Placcel FA-1, Placcel FA-2, Placcel FA-3 (above is trade(brand)name, DAICEL CHEMICAL INDUSTRIES, LTD. manufacturing, caprolactone modification (methyl) crylic acid hydroxy ester class) etc.;

For example, (methyl) acrylic acid C such as (methyl) methyl acrylate, (methyl) ethyl propenoate, (methyl) propyl acrylate, (methyl) butyl acrylate, (methyl) Ethyl acrylate, (methyl) Octyl acrylate, (methyl) lauryl acrylate, (methyl) cyclohexyl acrylate ₁～C ₁₈Alkyl or cycloalkyl ester class etc.;

For example, N-(2-hydroxyethyl) (methyl) acrylamide, N-(2-hydroxypropyl) (methyl) acrylamide, N-(3-hydroxypropyl) (methyl) acrylamide, N-methyl-N-(2-hydroxyethyl) (methyl) acrylamide, N-ethyl-N-(2-hydroxyethyl) (methyl) acrylamide, N-methyl-N-(2-hydroxypropyl) (methyl) acrylamide, N-methyl-N-(3-hydroxypropyl) (methyl) acrylamide, N-ethyl-N-(2-hydroxypropyl) (methyl) acrylamide, N-ethyl-N-(3-hydroxypropyl) (methyl) acrylamide, N, N-two-(2-hydroxyethyl) (methyl) acrylamide, N, N-two-nitrogenous free-radical polymerised unsaturated monomers such as (2-hydroxypropyl) (methyl) acrylamide;

For example, vinyltrimethoxy silane, the vinyl methyl dimethoxysilane, the vinyl-dimethyl methoxylsilane, vinyltriethoxysilane, vinyl methyl ethoxy silane, vinyl-dimethyl base oxethyl silane, vinyl tripropoxy silane, vinyl methyl dipropoxy silane, vinyl-dimethyl base propoxy-silane, γ-(methyl) acryloyl-oxy propyl trimethoxy silicane, γ-(methyl) acryloyl-oxy propyl group methyl dimethoxysilane, γ-(methyl) acryloyl-oxy propyl-dimethyl methoxy silane etc. contains the free-radical polymerised unsaturated monomer of alkoxysilane group; Vinylstyrene, ethylene glycol bisthioglycolate (methyl) acrylate, Diethylene Glycol two (methyl) acrylate, triethylene glycol two (methyl) acrylate, TEG two (methyl) acrylate, 1,3-butyleneglycol two (methyl) acrylate, 1,4-butyleneglycol two (methyl) acrylate, two (methyl) vinylformic acid glyceryl ester, three (methyl) vinylformic acid glyceryl ester, TriMethylolPropane(TMP) two (methyl) acrylate, trimethylolpropane tris (methyl) acrylate, two (methyl) vinylformic acid pentaerythritol ester, three (methyl) vinylformic acid pentaerythritol ester, four (methyl) vinylformic acid pentaerythritol ester, five (methyl) vinylformic acid dipentaerythritol ester, diacrylic acid pentyl diol ester, 1, the 6-hexanediyl ester, glyceryl allyloxy two (methyl) acrylate, 1,1,1-three (methylol) ethane two (methyl) acrylate, 1,1, many vinyl compounds such as 1-three (methylol) ethane three (methyl) acrylate etc.

In the manufacturing of vinyl copolymer resin (c1), containing the Raolical polymerizable that the mixture (1) of at least a free radical polymerization monomer that is selected from the free radical polymerization monomer that contains acrylic, methylene-succinic acid base, sulfonic group or phosphate and other free-radical polymerised unsaturated monomer (1) carries out is to use appropriate solvent to carry out in the presence of polymerization starter.Temperature of reaction is generally about 60～200 ℃, is preferably about 70～160 ℃, and the reaction times be generally approximately below 10 hours, be preferably about 0.5～about 6 hours.

Above-mentioned polymerization starter can use azobis isobutyronitrile (AIBN), the peroxidation 2 ethyl hexanoic acid tert-butyl ester (Perbutyl O), and use level is with respect to 0.05～3 quality % that adds up to of mixture (1).

As above-mentioned solvent, can list for example hydro carbons such as toluene, dimethylbenzene, hexanaphthene, normal hexane; Ester classes such as ritalin, vinyl acetic monomer, N-BUTYL ACETATE; Ketones such as acetone, methylethylketone, methyl iso-butyl ketone (MIBK), Methyl amyl ketone; Amides such as dimethyl formamide, N,N-DIMETHYLACETAMIDE; Alcohols such as methyl alcohol, ethanol, n-propyl alcohol, Virahol; Or these mixture etc.

Ethylenic copolymer chain (2):

The preferably following vinyl copolymer resin that makes of ethylenic copolymer chain (2) (c2): with 10～60 quality %, be preferably 15～55 quality %, more preferably 20～50 quality % methacrylic acid and 40～90 quality %, be preferably 45～80 quality %, more preferably other free-radical polymerised unsaturated monomer (2) of 50～75 quality % carries out Raolical polymerizable as the mixture (2) of monomer component in appropriate solvent, obtains ethylene copolymer resin (c2) thus.When methacrylic acid was less than 10 quality %, adaptation may descend, and when surpassing 60 quality %, may damage water tolerance.As other free-radical polymerised unsaturated monomer (2), can select to use more than a kind with vinyl polymer chain (1) in other identical free-radical polymerised unsaturated monomer of material of using.

Ethylenic copolymer chain (2) is characterised in that, do not use at least a free radical polymerization monomer in the free radical polymerization monomer that contains acrylic, methylene-succinic acid base, sulfonic group or phosphate of being selected from that uses in ethylenic copolymer chain (1).

For the manufacturing of vinyl copolymer resin (c2), the Raolical polymerizable that contains the mixture (2) of methacrylic acid and other free-radical polymerised unsaturated monomer (2) is to use appropriate solvent to carry out in the presence of polymerization starter.Temperature of reaction is generally about 60～200 ℃, is preferably about 70～160 ℃ scope, and the reaction times be generally about below 10 hours, be preferably about 0.5～about 6 hours.As above-mentioned polymerization starter and solvent, can suitably select to use and the same solvent of solvent that in ethylenic copolymer chain (1), uses.

In the manufacturing of acrylic resin (C), can the method for vinyl copolymer resin (c2) reaction be made by behind synthesis of vinyl copolymer resin (c1).

More preferably vinyl copolymer resin (c2) is added in the vinyl copolymer resin (c1) to the back and stir, and add low-molecular weight compound described later (c3) and obtain acrylic resin (C).

Low-molecular weight compound (c3):

Acrylic resin (C) makes to have more than 2 the polymkeric substance that has low-molecular weight compound (c3) reaction of reactive complementary interaction group with acidic group and carboxyl and make in 1 molecule preferably in the presence of vinyl copolymer resin (c1) and vinyl copolymer resin (c2).

As low-molecular weight compound (c3), can to use and be selected from the epoxy equivalent (weight) that has 2 above epoxy group(ing) in 1 molecule be 180～5000, be preferably 200～1000 Resins, epoxy, at least a in the resole, polycarbodiimide compound.

Commercially available product as Resins, epoxy, for example can list, the Epikote828 that Japan EpoxyResins Co., Ltd. make (epoxy equivalent (weight) about 180, number-average molecular weight about 360), Epikote 834 (epoxy equivalent (weight) about 235, number-average molecular weight about 470), Epikote 1007 (epoxy equivalent (weight) about 1700, number-average molecular weight about 2900), Epikote 1009 (epoxy equivalent (weight) about 3500, number-average molecular weight about 3750), Epikote 1010 (epoxy equivalent (weight) about 4500, number-average molecular weight about 5500); The Araldit AER6099 that Asahi Ciba company makes (epoxy equivalent (weight) about 3500, number-average molecular weight about 3800); And the EPOMIK R-309 that makes of Mitsui Chemicals (strain) (epoxy equivalent (weight) about 3500, number-average molecular weight about 3800) etc.

In these, from the viewpoint of the reaction efficiency of vinyl copolymer resin (c1) and vinyl copolymer resin (c2), as the preferred Epikote 828 of Resins, epoxy, Epikote834.

As resole, can use and the same material of resole (B), for example as commercially available product, can list Shonol BKS377 (clear and polymer company makes).

As polycarbodiimide compound, polyisocyanate compound is reacted in the presence of the carbodiimide catalyzer and make.In addition, as polycarbodiimide compound, can also use two such carbodiimide compounds of dicyclohexyl carbodiimide.

As polyisocyanate compound, for example can list tolylene diisocyanate, xylylene diisocyanate, phenylene vulcabond, diphenylmethanediisocyanate, two (isocyanic ester methyl) hexanaphthene, tetramethylene diisocyanate, hexamethylene diisocyanate, methylene diisocyanate, aromatic series such as isophorone diisocyanate, alicyclic or aliphatic diisocyanate cpd and isocyanuric acid ester body thereof, and the excess quantity of these isocyanate compounds and ethylene glycol, propylene glycol, TriMethylolPropane(TMP), the reaction of low molecule active hydrogen-contg compound such as hexanetriol and the compound that contains terminal isocyanate that obtains.

As non-active solvent, for example can use aromatic hydrocarbon solvents such as toluene, dimethylbenzene; Ketones solvent such as acetone, methylethylketone; Ether solvents such as diox; And dimethyl formamide equal solvent.Catalyzer as the carbodiimideization that promotes polyisocyanate compound, various materials be can use, but corresponding isomer, 3-phospholene class of 1-phenyl-2-phospholene (phospholene)-1-oxide compound, 3-methyl isophthalic acid-phenyl-2-phospholene-1-oxide compound, 1-phenyl-2-phospholene-1-sulfide, 1-methyl-2-phospholene-1-oxide compound, 1-ethyl-3-methyl-2-phospholene-1-oxide compound, these compounds etc. are preferably.The amount of catalyzer can be used in the scope of 0.01～1 weight % with respect to the polyisocyanate compounds total amount.Can list CARBODILITE (registered trademark) series that the company of spinning clearly day makes, for example, CARBODILITE V-02, CARBODILITE V-04 etc. as commercially available product.

In the manufacturing of acrylic resin (C), use temperature of reaction in the Raolical polymerizable that above-mentioned vinyl copolymer resin (c1), vinyl copolymer resin (c2) and low-molecular weight compound (c3) carry out to be generally about 60～200 ℃, be preferably 70～160 ℃, 100～130 ℃ scope more preferably, and the reaction times is generally about below 10 hours, is preferably about 0.5～about 6 hours.Then, with organic solvent diluting postcooling such as propylene glycol positive propyl ethers, obtain acrylic resin (C).

Reaction ratio as vinyl copolymer resin (c1), vinyl copolymer resin (c2) and low-molecular weight compound (c3), it is characterized in that vinyl copolymer resin (c1), vinyl copolymer resin (c2) and low-molecular weight compound (c3) add up to based on the solids component of vinyl copolymer resin (c1) and vinyl copolymer resin (c2):

Make vinyl copolymer resin (c1)/vinyl copolymer resin (c2)=60/40～95/5 (quality %), be preferably 75/25～85/15 (quality %),

And [vinyl copolymer resin (c1)+vinyl copolymer resin (c2)]/low-molecular weight compound (c3)=100/0.1～100/20 (mass parts), be preferably 100/2～100/10 (mass parts).By making the cooperation ratio of this scope, can obtain the overlay film of adaptation, excellent corrosion resistance.

The acrylic resin that obtains thus (C) is preferred: its acid number is 100～500mgKOH/g, be preferably 200～480mgKOH/g, 300～450mgKOH/g more preferably.In addition, number-average molecular weight is 1000～25000, is preferably 2000～20000, more preferably 3000～10000.

Jar coating composition among the present invention is with respect to the above-mentioned acrylic resin modified epoxy (A) that obtains of 100 mass parts, can contain 0.1～20 mass parts, is preferably 1～10 mass parts, 2～5 mass parts acrylic resins (C) more preferably.

＜anionic property crosslinked polymer particulate (D) 〉

Jar coating composition of the present invention can also cooperate anionic property crosslinked polymer particulate (D).Anionic property crosslinked polymer particulate (D) is by containing the made polymer formation of free-radical polymerised unsaturated monomer that carboxyl free radical polymerizable monomer (d1), many vinyl compounds (d2) and other free-radical polymerised unsaturated monomer (d3) are formed.At this, the content of each free-radical polymerised unsaturated monomer adds up to respect to the solids component of the free radical polymerization monomer of forming: to contain carboxyl free radical polymerizable monomer (d1) be 2～30 quality %, be preferably 5～15 quality %, many vinyl compounds (d2) are 2～30 quality %, be preferably 5～15 quality %, and other free-radical polymerised unsaturated monomer (d3) is 40～96 quality %, be preferably 70～90 quality %.

When containing carboxyl free radical polymerizable monomer (d1) and being less than 2 quality %, water dispersible is insufficient, when surpassing 30 quality %, can damage erosion resistance.When many vinyl compounds (d2) were less than 2 quality %, resistance to water-whitening was insufficient, and when surpassing 30 quality %, it is big that particle diameter becomes, so not preferred.In addition, as the object lesson of anionic property crosslinked polymer particulate (D), can list following anionic property crosslinked polymer particulate (D1) or anionic property crosslinked polymer particulate (D2).

Anionic property crosslinked polymer particulate (D1):

Contain 5 quality % following, be preferably containing carboxyl free radical polymerizable monomer (d1), 4～35 quality %, the many vinyl compounds (d2) that are preferably 10～25 quality % and 60～96 quality %, being preferably the mixture (3) of free radical polymerization monomer of other free-radical polymerised unsaturated monomer (d31) of 75～90 quality % in the presence of water of 3 quality %, carry out the letex polymerization of fs, obtain water dispersion (I).

Then, contain 10～35 quality %, be preferably containing carboxyl free radical polymerizable monomer (d1) and 65～90 quality %, being preferably the mixture (4) of free radical polymerization monomer of other free-radical polymerised unsaturated monomer (d32) of 75～85 quality % in the presence of above-mentioned dispersion (I) and water of 15～25 quality %, carry out the letex polymerization of subordinate phase, obtain anionic property crosslinked polymer particulate (D1).

Contain carboxyl free radical polymerizable monomer (d1) as what in mixture (3), use, for example can list, monomers such as (methyl) vinylformic acid, toxilic acid, Ba Dousuan, methylene-succinic acid, fumaric acid, these can be used alone or in combination of two or more kinds.

As above-mentioned many vinyl compounds (d2), can list Vinylstyrene, ethylene glycol bisthioglycolate (methyl) acrylate, Diethylene Glycol two (methyl) acrylate, triethylene glycol two (methyl) acrylate, TEG two (methyl) acrylate, 1,3-butyleneglycol two (methyl) acrylate, 1, the 4-butylene glycol diacrylate, two (methyl) vinylformic acid glyceryl ester, three (methyl) vinylformic acid glyceryl ester, TriMethylolPropane(TMP) two (methyl) acrylate, trimethylolpropane tris (methyl) acrylate, two (methyl) vinylformic acid pentaerythritol ester, three (methyl) vinylformic acid pentaerythritol ester, four (methyl) vinylformic acid pentaerythritol ester, five (methyl) vinylformic acid dipentaerythritol ester, diacrylic acid pentyl diol ester, 1, the 6-hexanediyl ester, glycerine allyloxy two (methyl) acrylate, 1,1,1-three (methylol) ethane two (methyl) acrylate, 1,1,1-three (methylol) ethane three (methyl) acrylate etc. can suitably be selected to use from these.

As many vinyl compounds (d2), can also use the epoxy equivalent (weight) that has 2 above epoxy group(ing) in the molecule is the affixture that 180～1000 Resins, epoxy and methacrylic acid and/or vinylformic acid reaction obtain.Specifically, it is the following affixture that makes, promptly, with respect to 1 mole of functional group in the Resins, epoxy, make 0.5～0.98 mole, be preferably 0.65～0.95 mole, more preferably 0.75～0.9 mole methacrylic acid and/or vinylformic acid, under 60～150 ℃ of temperature of reaction, carry out 10 minutes～180 minutes addition reaction and the affixture that makes.

As other free-radical polymerised unsaturated monomer (d31), for example can list vinylbenzene, alpha-methyl styrene, Vinyl toluene, to vinyl aromatic compounds such as chloro-styrene, vinyl pyridines; For example, the C of acrylic or methacrylic acid such as 2-hydroxyethyl (methyl) acrylate, 3-hydroxypropyl (methyl) acrylate, 4-hydroxyl butyl (methyl) acrylate ₂～C ₈The free-radical polymerised unsaturated monomers of hydroxyl such as hydroxyalkyl (methyl) acrylate, (gathering) glycol monomethyl (methyl) acrylate, polypropylene glycol list (methyl) acrylate, polytetramethylene glycol list (methyl) acrylate; The reactant of lactone compounds such as free-radical polymerised unsaturated monomer of these hydroxyls and beta-propiolactone, dimethyl propylene lactone, butyrolactone, γ-Wu Neizhi, γ-Ji Neizhi, γ-Xin Neizhi, γ-dodecalactone, 6-caprolactone, δ-caprolactone etc.; For example, Placcel FM-1, Placcel FM-2, Placcel FM-3, Placcel FA-1, Placcel FA-2, Placcel FA-3 (above is trade(brand)name, DAICEL CHEMICALINDUSTRIES, LTD. manufacturing, caprolactone modification (methyl) crylic acid hydroxy ester class) etc.; For example, (methyl) acrylic acid C such as (methyl) methyl acrylate, (methyl) ethyl propenoate, (methyl) propyl acrylate, (methyl) butyl acrylate, (methyl) Ethyl acrylate, (methyl) Octyl acrylate, (methyl) lauryl acrylate, (methyl) cyclohexyl acrylate ₁～C ₁₈Alkyl or cycloalkyl ester class etc.; For example, N-(2-hydroxyethyl) (methyl) acrylamide, N-(2-hydroxypropyl) (methyl) acrylamide, N-(3-hydroxypropyl) (methyl) acrylamide, N-methyl-N-(2-hydroxyethyl) (methyl) acrylamide, N-ethyl-N-(2-hydroxyethyl) (methyl) acrylamide, N-methyl-N-(2-hydroxypropyl) (methyl) acrylamide, N-methyl-N-(3-hydroxypropyl) (methyl) acrylamide, N-ethyl-N-(2-hydroxypropyl) (methyl) acrylamide, N-ethyl-N-(3-hydroxypropyl) (methyl) acrylamide, N, N-two (2-hydroxyethyl) (methyl) acrylamide, N, nitrogenous free-radical polymerised unsaturated monomers such as N-two (2-hydroxypropyl) (methyl) acrylamide; For example, vinyltrimethoxy silane, the vinyl methyl dimethoxysilane, the vinyl-dimethyl methoxylsilane, vinyltriethoxysilane, the vinyl methyldiethoxysilane, vinyl-dimethyl base oxethyl silane, vinyl tripropoxy silane, vinyl methyl dipropoxy silane, vinyl-dimethyl base propoxy-silane, γ-(methyl) acryloyl-oxy propyl trimethoxy silicane, γ-(methyl) acryloyl-oxy propyl group methyl dimethoxysilane, γ-(methyl) acryloyl-oxy propyl-dimethyl methoxy silane etc. contains the free-radical polymerised unsaturated monomer of alkoxysilane group.

Use emulsifying agent, make the mixture (3) of the free radical polymerization monomer that contains carboxyl free radical polymerizable monomer (d1), many vinyl compounds (d2) and other free-radical polymerised unsaturated monomer (d31) carry out letex polymerization, can make water dispersion (I) thus.The temperature of reaction of this moment is generally 60～90 ℃, is preferably about 75～85 ℃ scope, and the reaction times be generally about below 10 hours, be preferably about 0.5～about 6 hours.

Then, in the presence of water dispersion (I), mixture (4) and water, use emulsifying agent and polymerization starter to carry out subordinate phase and later letex polymerization thereof.Use in the mixture (4) contain carboxyl free radical polymerizable monomer (d1) can select to use more than at least a kind with mixture (3) in the identical monomer of monomer that uses.

As other the free-radical polymerised unsaturated monomer (d32) that uses in the mixture (4), select in many vinyl compounds (d2) that can from the polyreaction of fs, use and other the free-radical polymerised unsaturated monomer (d31) to use more than at least a kind.

In addition, the water dispersion (I) when being used for the manufacturing of anionic property crosslinked polymer particulate (D1) and the mass ratio of mixture (4), based on the total amount of each mixture, can be at water dispersion (I)/mixture (4)=50/50～90/10 (mass ratio), be preferably in the scope of 70/30 (mass ratio)～85/15 (mass ratio) and adjust.

As polymerization starter, can use ammonium persulphate, Potassium Persulphate, Sodium Persulfate, use level is suitably 0.05～3 quality %, is preferably 0.1～1.0 quality %.

In addition, the emulsifying agent as using in the emulsion polymerization of fs, subordinate phase and the later emulsion polymerization thereof for example can list sodium salt, the ammonium salt of alkylsulphonic acid, alkyl benzene sulphonate (ABS), alkylphosphonic acid carboxylic acid etc.In addition, has the reactive anionic emulsifier that has these anionic property bases and polymerizability unsaturated group in the nonionic anionic emulsifier, 1 molecule of these anionic property bases and nonionic bases such as polyoxyethylene or polyoxytrimethylene chain in 1 molecule.

Specifically, can list non-ionic emulsifiers such as polyoxyethylene oleyl ether, polyoxyethylene stearyl ether, polyoxyethylene laurel ether, polyoxyethylene tridecyl ether, polyoxyethylene phenyl ether, polyoxyethylene nonylplenyl ether, polyoxyethylene octyl phenyl ether, Vinlub 73, polyoxyl 40 stearate, Aceonon 300 MO, Span-20, sorbitan monostearate, sorbitan trioleate, Tween-20; Zwitter-ion emulsifying agents such as dimethyl alkyl betaine class, dimethyl alkyl lauryl betaine class, alkyl glycine class.

The concentration of mentioned emulsifier with respect to the monomeric total amount that constitutes mixture (3) or mixture (4) be 0.1～20 quality %, to be preferably about 0.5～10 quality % for the performance of filming be preferred.Fs and subordinate phase and later polyreaction thereof generally can be in water with about 60～95 ℃, be preferably 75～85 ℃ temperature carry out about 1～5 hour, preferred about 2～4 hours.

Resulting anionic property crosslinked polymer particulate (D1), its acid number be 1～100mgKOH/g, be preferably 20～80mgKOH/g, more preferably 40～75mgKOH/g, median size (annotating 2) are 0.01～0.5 μ m, are preferably 0.1～0.35 μ m, 0.10～0.25 μ m more preferably.This scope is preferred for formation ironing shaping processability, filming of resistance to water-whitening excellence.

(annotating 2) median size: use subparticle analyser N4 (SubmicronParticle Size Analyzer, trade(brand)name, Beckman Coulter Inc. manufacturing, particle size distribution device), with deionized water sample is diluted to the concentration that is suitable for measuring, measures at normal temperature (about 20 ℃).

Anionic property crosslinked polymer particulate (D2):

At first, make and contain 20～60 quality %, be preferably that 35～55 quality % contain carboxyl free radical polymerizable monomer (d1) and 40～80 quality %, the mixture (5) that is preferably the free radical polymerization monomer of other free-radical polymerised unsaturated monomer (d33) of 45～65 quality % carries out Raolical polymerizable, obtain polymkeric substance (I).Then, in the presence of above-mentioned polymkeric substance (I) and water, make the mixture (6) that contains 4～33 quality %, is preferably many vinyl compounds of 10～25 quality % (d2) and 67～96 quality %, is preferably the free radical polymerization monomer of other free-radical polymerised unsaturated monomer (d34) of 75～90 quality % carry out letex polymerization, obtain anionic property crosslinked polymer particulate (D2).

When making polymkeric substance (I), contain carboxyl free radical polymerizable monomer (d1) as what use in the mixture (5), can use the monomer that uses in the manufacturing with anionic property crosslinked polymer particulate (D1) identical contain carboxyl free radical polymerizable monomer (d1), for example can list, monomers such as (methyl) vinylformic acid, toxilic acid, Ba Dousuan, methylene-succinic acid, fumaric acid, these can be used alone or in combination of two or more kinds.

As other free-radical polymerised unsaturated monomer (d33), can suitably select in many vinyl compounds (d2) of using in the manufacturing of anionic property crosslinked polymer particulate (D1) and other the free-radical polymerised unsaturated monomer (d31) at least a kind with on use.

Use the Raolical polymerizable of mixture (5), can use polymerization starter, in appropriate solvent, with about 90～about 170 ℃, preferred about 100～about 150 ℃ temperature carry out about 1～5 hour, preferred about 2～4 hours, thereby obtain polymkeric substance (I).

As the solvent that uses in the above-mentioned reaction, for example can list hydro carbons such as toluene, dimethylbenzene, hexanaphthene, normal hexane; Ester classes such as ritalin, vinyl acetic monomer, N-BUTYL ACETATE; Ketones such as acetone, methylethylketone, methyl iso-butyl ketone (MIBK), Methyl amyl ketone; Amides such as dimethyl formamide, N,N-DIMETHYLACETAMIDE; Alcohols such as methyl alcohol, ethanol, n-propyl alcohol, Virahol; Or these mixture etc.

As above-mentioned polymerization starter, can use azobis isobutyronitrile (AIBN), the peroxidation 2 ethyl hexanoic acid tert-butyl ester (Perbutyl O) etc.

Then, in the presence of above-mentioned polymkeric substance (I) and water, use the mixture (6) contain 4～33 quality %, be preferably many vinyl compounds of 5～25 quality % (d2) and 67～96 quality %, be preferably other free-radical polymerised unsaturated monomer (d34) of 60～90 quality % to carry out emulsion polymerization.

As above-mentioned many vinyl compounds (d2), the identical monomer of monomer that can select more than at least a kind to use in the manufacturing with anionic property crosslinked polymer particulate (D1) uses.As other free-radical polymerised unsaturated monomer (d34), can and contain from other free-radical polymerised unsaturated monomer (d31) and suitably select at least a kind the carboxyl free radical polymerizable monomer (d1) to use.

During reaction, can also use ammonium persulphate, Potassium Persulphate, Sodium Persulfate and azobis isobutyronitrile (AIBN), peroxidation 2 ethyl hexanoic acid tertiary butyl ester polymerization starter, redox class initiators such as (Perbutyl O).

In addition, the polymkeric substance (I) when in the manufacturing of the crosslinked particulate of anionic property (D2), using and the mass ratio of mixture (6), based on the total amount of each mixture, can be at polymkeric substance (I)/mixture (6)=25/75～85/15 (mass ratio), be preferably in the scope of 60/40 (mass ratio)～80/20 (mass ratio) and adjust.

The concentration of above-mentioned polymerization starter is 0.05～3 quality %, is preferably 0.1～10 quality % with respect to the monomeric total amount that constitutes mixture (6) or polymkeric substance (I).

The concentration of mentioned emulsifier is 0.3～3 quality %, is preferably about 0.5～2 quality % that with respect to the monomeric total amount that constitutes mixture (6) or polymkeric substance (I) this is preferred for film performance.In addition, if selection condition then also can not use emulsifying agent ground to carry out granulating.

In addition, in the presence of polymkeric substance (I) and water, use that temperature of reaction is generally about 60～95 ℃, preferred about 75～85 ℃ scope in the emulsion polymerization that mixture (6) carries out, and the reaction times be generally about below 10 hours, preferred about 0.5～about 6 hours.

Resulting anionic property crosslinked polymer particulate (D2), its acid number be 10～120mgKOH/g, be preferably 30～100mgKOH/g, 50～90mgKOH/g more preferably.Median size (annotate 2) is 0.05～1.0 μ m, be preferably 0.10～0.50 μ m, 0.10～0.30 μ m more preferably.This scope is preferred for formation ironing shaping processability, filming of resistance to water-whitening excellence.

In the jar coating composition of the present invention, by in coating, cooperating above-mentioned anionic property crosslinked polymer particulate (D1) or anionic property crosslinked polymer particulate (D2), can also obtain the filming of balance excellence of bending process, resistance to water-whitening, smell.

The use level that is coupled to anionic property crosslinked polymer particulate (D1) in this jar coating composition or anionic property crosslinked polymer particulate (D2) is suitably 1～50 mass parts, is preferably in the scope of 5～30 mass parts with respect to the acrylic acid or the like modified epoxy (A) of per 100 mass parts.When being less than 1 mass parts, the raising of film performances such as bending process, resistance to water-whitening, smell there is not effect, when surpassing 50 mass parts, not only damage paint stability in addition, also effectively little to the raising of film performance.

Jar coating composition of the present invention goes for various base materials, for example can list, aluminium sheet, steel plate, tin plate etc. are untreated or surface treated metal sheet and be coated with jar that metal sheet etc., these metal sheets of priming paint such as epoxies, vinyl are housed process etc. on these metal sheets.

As jar coating composition of the present invention is coated with the method that installs on the base material, can be suitable for various known methods, for example, roller coat application, spray-coating, dipping coating, electrodeposition coating etc.Wherein, preferred roller coat application or spray-coating.Coating thickness can suitably be selected according to purposes, but generally is preferably about 3～20 μ m.As the drying conditions of filming after the application, generally be suitably the raw-material Da Wendu of being up to and be and carry out 10 second～30 minute under 120～300 ℃ the condition, be preferably 200～280 ℃ down in the scope of 15 second～10 minute.

In addition, application jar coating composition of the present invention and the cross section of filming that obtains are characterised in that, it is 0.01～0.5 μ m that formation has diameter, be preferably 0.05～0.35 μ m, the island structure of the island portion of 0.08～0.15 μ m (with reference to figure 1) more preferably, by forming such island structure, can help the raising of bending process.

Embodiment

Further specifically describe the present invention by embodiment.Below, " part " and " % " represents " mass parts " and " quality % " respectively.

[manufacturing of acrylic resin modified epoxy (A) (Production Example 1～3)]

Production Example 1: the manufacturing of epoxy resin solution (a1)

In the four-hole boiling flask that return line, thermometer, stirrer are installed, add 558 parts of Epikote 828EL (annotating 3), 329 parts of dihydroxyphenyl propanes, 0.6 part of Tetrabutyl amonium bromide, and under stream of nitrogen gas, react in 160 ℃.Reaction is by following the tracks of with epoxy equivalent (weight), and carries out about 5 hours reaction, obtains that number-average molecular weight is about 11000, the bisphenol A type epoxy resin of epoxy equivalent (weight) about 8000.

(annotate 3) Epikote 828EL:Japan Epoxy Resins Co., about 190, the molecular weight about 350 of Ltd. manufacturing, bisphenol A type epoxy resin, epoxy equivalent (weight)

Production Example 2: contain the manufacturing (a2) of carboxy acrylic resinoid solution

In the four-hole boiling flask that return line, thermometer, dropping funnel, stirrer are installed, add 882 parts of propyl carbinols, the mixture of 180 parts of methacrylic acids, 240 parts of vinylbenzene, 180 parts of ethyl propenoates, 18 parts of peroxidation 2 ethyl hexanoic acid tert-butyl esters is heated to 100 ℃ and drip with about 3 hours from dropping funnel under stream of nitrogen gas, under same temperature, continue again after the dropping to stir 2 hours, then cooling obtains solids component and is 40% acrylic resin solution.The resinous acid value of resulting resin (solids component) is 196mgKOH/g, number-average molecular weight about 19000.

Production Example 3: the manufacturing (A) of acrylic acid or the like modified epoxy dispersion

In the four-hole boiling flask that return line, thermometer, stirrer are installed, add 40% acrylic resin solution (20 parts of solids components), 33 parts of Diethylene Glycol single-butyl ethers of obtaining in the bisphenol A type epoxy resin (solids component) that obtains in 80 parts of Production Examples 1, the 50 parts of Production Examples 2, be heated to 100 ℃ make its dissolving after, add 2 parts of N, the N-dimethylaminoethanol, reacted about 2 hours, add 3 parts of N then, the N-dimethylaminoethanol continues reaction 20 minutes.Then, with 165 parts of deionized waters of dropping in 1 hour, carry out water-dispersion, obtaining acid number is that 34mgKOH/g, solids component are 30% acrylic acid or the like modified epoxy dispersion.

[manufacturing of resole (B)]

Production Example 4: the manufacturing of resole solutions

In the four-hole boiling flask that return line, thermometer, stirrer are installed, in flask, add 188 parts of phenol, 324 part of 37% formalin, be heated to 50 ℃, and content is dissolved equably.Then, add zinc acetate and mixing, the pH in the system is adjusted to after 5.0, be heated to 90 ℃, carry out 5 hours reaction.Then, be cooled to 50 ℃, slowly add 32% calcium hydroxide aqueous dispersions, pH is adjusted to 8.5 after, 50 ℃ of down reactions 4 hours.

After reaction finishes, after with 20% hydrochloric acid pH being adjusted to 4.5, mixed solvent with toluene/propyl carbinol/hexanaphthene=1/2/1 (mass ratio) carries out the extraction of resinous principle, remove catalyzer, neutralized salt, then under reduced pressure carry out azeotropic dehydration, obtain solids component and be 60% faint yellow and transparent resole solutions.

[manufacturing of resole (C) (Production Example 5～10)]

Production Example 5

In reaction vessel, add 70 parts of propylene glycol positive propyl ethers, and in stream of nitrogen gas, mix, be warming up to 100 ℃ with thermometer, thermostatted, agitator, reflux exchanger and dropper.

Then, use pump of constant delivery type in reactor, to drip monomer mixture (20 parts of methyl methacrylates, 30 parts of 2-EHAs, 50 parts in vinylformic acid) and polymerization starter solution (mixed solutions of 8 parts of peroxidation 2 ethyl hexanoic acid tert-butyl esters, 50 parts of propylene glycol positive propyl ethers), carry out after dropping finishes wearing out in 0.5 hour with 4 hours.Then, drip 0.5 hour polymerization starter solution (mixed solutions of 0.5 part of peroxidation 2 ethyl hexanoic acid tert-butyl ester, 30 parts of propylene glycol positive propyl ethers), carry out wearing out in 2 hours.Then, be cooled to 60 ℃, filter, discharge, obtain the acrylic resin (c1) of solids component 40%, acid number 390mgKOH/g, number-average molecular weight 4000 with 100 purpose nylon cloths.Under 100 ℃, in this acrylic resin (c1), add resin (c2) (annotating 4).

(annotating 4) resin (c2):

In reaction vessel, add 70 parts of propylene glycol positive propyl ethers, and under stream of nitrogen gas, mix, be warming up to 100 ℃ with thermometer, thermostatted, agitator, reflux exchanger and dropper.Then, use pump of constant delivery type in reactor, to drip monomer mixture (50 parts of methacrylic acids, 30 parts of ethyl propenoates, 20 parts of vinylbenzene) and polymerization starter solution (mixed solutions of 8 parts of peroxidation 2 ethyl hexanoic acid tert-butyl esters, 50 parts of propylene glycol positive propyl ethers), carry out after dropping finishes wearing out in 0.5 hour with 4 hours.Then, drip 0.5 hour polymerization starter solution (mixed solutions of 0.5 part of peroxidation 2 ethyl hexanoic acid tert-butyl ester, 30 parts of propylene glycol positive propyl ethers), carry out wearing out in 2 hours.Then, be cooled to 60 ℃, filter, discharge, obtain the resin (c2) of solids component 40%, acid number 326mgKOH/g, number-average molecular weight 4000 with 100 purpose nylon cloths.

Then, add 5 parts of Epikote834 (Japan Epoxy Resins Co., Ltd. manufacturing, Resins, epoxy, be equivalent to low-molecular weight compound (c3)), be warming up to 130 ℃, carry out 3 hours aging.Then, dilute, be cooled to 60 ℃, filter, discharge, obtain the acrylic resin No.1 of solids component 40%, acid number 347mgKOH/g with 100 purpose nylon cloths with the propylene glycol positive propyl ether.

Production Example 6～10

Except employed monomer adopts the cooperation content of table 1, obtain acrylic resin No.2～No.6 in the same manner with Production Example 5.

Table 1

Numeric representation mass parts in the cooperation

(annotate 5) Shonol BKS-377F: clear and polymer company manufacturing, trade(brand)name, resole, solids component 50%

Compare Production Example 1 (according to Japanese kokai publication hei 8-302275 communique)

In reaction vessel, add 70 parts of propylene glycol positive propyl ethers, and under stream of nitrogen gas, mix, be warming up to 100 ℃ with thermometer, thermostatted, agitator, reflux exchanger and dropper.

Then, use pump of constant delivery type in reactor, to drip monomer mixture (10 parts of vinylformic acid, 40 parts of methyl methacrylates, 50 parts of ethyl propenoates) and polymerization starter solution (mixed solutions of 8 parts of peroxidation 2 ethyl hexanoic acid tert-butyl esters, 50 parts of propylene glycol positive propyl ethers), carry out after dropping finishes wearing out in 0.5 hour with 4 hours.Then, drip 0.5 hour polymerization starter solution (mixed solutions of 0.5 part of peroxidation 2 ethyl hexanoic acid tert-butyl ester, 30 parts of propylene glycol positive propyl ethers), carry out wearing out in 2 hours.Then, be cooled to 60 ℃, filter, discharge, obtain the acrylic resin No.7 of solids component 40%, acid number 78mgKOH/g, number-average molecular weight 3500 with 100 purpose nylon cloths.

Compare Production Example 2

In reaction vessel, add 70 parts of propylene glycol positive propyl ethers, and under stream of nitrogen gas, mix, be warming up to 100 ℃ with thermometer, thermostatted, agitator, reflux exchanger and dropper.

Then, use pump of constant delivery type in reactor, to drip monomer mixture (50 parts of vinylformic acid, 20 parts of methyl methacrylates, 30 parts of ethyl propenoates) and polymerization starter solution (mixed solutions of 8 parts of peroxidation 2 ethyl hexanoic acid tert-butyl esters, 50 parts of propylene glycol positive propyl ethers), carry out after dropping finishes wearing out in 0.5 hour with 4 hours.Then, drip 0.5 hour polymerization starter solution (mixed solutions of 0.5 part of peroxidation 2 ethyl hexanoic acid tert-butyl ester, 30 parts of propylene glycol positive propyl ethers), carry out wearing out in 2 hours.Then, be cooled to 60 ℃, filter, discharge, obtain the acrylic resin (being equivalent to resin (c1)) of solids component 40%, acid number 390mgK OH/g, number-average molecular weight 4000 with 100 purpose nylon cloths.Then, under 100 ℃, in above-mentioned reaction vessel, add the resin (c2) (annotating 4) that similarly makes with Production Example 5.

Then, add 5 parts of Epikote834 (Japan Epoxy Resins Co., Ltd. manufacturing, Resins, epoxy, be equivalent to low-molecular weight compound (c3)), be warming up to 130 ℃, carry out 3 hours aging.Then, dilute, be cooled to 60 ℃, filter, discharge, obtain the acrylic resin No.8 of solids component 40%, acid number 330mgKOH/g, number-average molecular weight 4500 with 100 purpose nylon cloths with the propylene glycol positive propyl ether.

Compare Production Example 3～6

Except employed monomer adopts the cooperation content of table 2, obtain acrylic resin No.9～No.12 in the same manner with comparison Production Example 2.

Table 2

Numeric representation mass parts in the cooperation

(annotate 5) Shonol BKS-377F: clear and polymer company manufacturing, trade(brand)name, resole

[manufacturing of the crosslinked particulate of anionic polymer (D)]

Production Example 11: the manufacturing of the crosslinked particulate of anionic polymer (D1)

In reaction vessel, add 150 parts of deionized waters, 0.5 part " Newcol 562SF " (annotating 6) (solids component), in stream of nitrogen gas, mix, be warming up to 85 ℃ with thermometer, thermostatted, agitator, reflux exchanger and dropper.

Then, 1% and 5.2 part " 2% ammonium persulfate aqueous solution " in following " monomer mixture 1 " imported in the reaction vessel, kept 20 minutes down at 85 ℃.Then, use pump of constant delivery type residual monomers emulsification and ammonium persulfate aqueous solution to be added drop-wise in the reactor, carry out after dropping finishes wearing out in 2 hours with 3 hours.Be cooled to 30 ℃, filter, discharge, obtain the anionic property crosslinked polymer particle (D1) of median size (annotating 2) 0.1 μ m, solids component 25%, acid number 65mgKOH/g with 100 purpose nylon cloths.

[monomer mixture 1]

135 parts of deionized waters

30 parts of vinylbenzene

50 parts of ethyl propenoates

10 parts of methacrylic acids

10 parts of ethylene glycol dimethacrylates

" Newcol 562SF " (annotating 6) 1 part (solids component)

" 2% ammonium persulfate aqueous solution "

0.2 part of ammonium persulphate

10 parts of deionized waters

(annotate 6) Newcol 562SF: the manufacturing of Japanese emulsifying agent Co., Ltd., trade(brand)name, polyxyethylated ammonium benzene sulfonate, effective constituent 60%

Production Example 12: the manufacturing of anionic property crosslinked polymer particulate (D2)

In reaction vessel, add 95 parts of ethylene glycol mono hexyl ether, 32 parts of propyl carbinols, in stream of nitrogen gas, mix, be warming up to 100 ℃ with thermometer, thermostatted, agitator, reflux exchanger and dropper.

Then, simultaneously monomer mixture (50 parts of methacrylic acids, 45 parts of vinylbenzene, 5 parts of ethyl propenoates) and polymerization starter (2 parts of Perbutyl O, 10 parts of propyl carbinols) solution were dripped 3 hours, dropping is carried out clock aging in 30 fens after finishing.Then, drip polymerization in 30 minutes and cause solution (0.4 part of Perbutyl O, 10 parts of propyl carbinols), after carrying out wearing out in 2 hours,, obtain the polymkeric substance No.1 of solids component 32%, acid number 326mgKOH/g, weight-average molecular weight 37000 with 63 parts of propyl carbinols dilutions.

Then, in reaction vessel,, stirred 15 minutes, add 250 parts of deionized waters then with in 3.88 parts of dimethylethanolamines and behind 25 parts (solids component) above-mentioned polymkeric substance No.1 with thermometer, thermostatted, agitator, reflux exchanger.

Then,, in deionized water, add following " monomer mixture ", make emulsification, be added drop-wise in the reaction vessel with about 1 hour below 30 ℃.Then, be warmed up to 85 ℃, under stream of nitrogen gas, dripped the polymerization starter aqueous solution (0.2 part of ammonium persulphate, 22 parts of deionized waters) with 1 hour after, carry out 2 hours aging.Then, be cooled to 30 ℃, filter, discharge, and to obtain solids component with the deionized water adjustment be 20% anionic property crosslinked polymer particulate (D2) with 100 purpose nylon cloths.The acid number of anionic property crosslinked polymer particulate (D2) is that 82mgKOH/g, median size are 0.18 μ m.

[monomer mixture]

75 parts of deionized waters

7.5 parts of ethylene glycol dimethacrylates

37.5 parts of ethyl propenoates

30 parts of vinylbenzene

0.75 part of (annotating 6) Newcol 562SF

Embodiment 1: the manufacturing of jar coating composition

The solids component that obtains in 100 parts of (solids component) Production Examples 3 is in 30% the acrylic acid or the like modified epoxy dispersion, add 1.7 parts of (solids component) resole solutions, 5 parts (solids component) in advance with in the dimethylethanolamine and the acrylic resin No.1 that makes in the Production Example 5 of equimolar amount acid, behind the stir about 30 minutes, slowly add deionized water and modulate, obtain solids component and be 25% tin paint No.1.

Embodiment 2～9

Except the cooperation content that adopts table 3, obtain solids component similarly to Example 1 and be tin paint No.2～No.10 of 25%.

Table 3

Numeric representation mass parts (solids component) in the cooperation

Comparative example 1

The solids component that obtains in 100 parts of (solids component) Production Examples 3 is in 30% the acrylic acid or the like modified epoxy dispersion, add 1.7 parts of (solids component) resole solutions, 5 parts in advance with in the dimethylethanolamine and the acrylic resin No.7 that makes in the comparison Production Example 1 of equimolar amount acid, behind the stir about 30 minutes, slowly add deionized water and modulate, obtain solids component and be 25% tin paint No.11.

Comparative example 2～10

Except the cooperation content that adopts table 4, similarly obtaining solids component with comparative example 1 is tin paint No.12～No.20 of 25%.

Table 4

Numeric representation mass parts (solids component) in the cooperation

The making of test board

Each tin paint spray-coating of obtaining in the foregoing description and the comparative example on the #5182 of the thick 0.26mm behind phosphoric acid chromate treating aluminium sheet, so that dry coating thickness is 10 μ m, with 200 ℃ of sintering 3 minutes, is made its curing and obtains coated plate.Performance test is undertaken by following method.

(annotating 7) observes the cross section (μ m) of filming: with the cross section of filming behind scanning electron microscope (5000 times of multiplying powers) the observation cut-out test board, in the time that island structure can be confirmed, try to achieve mean value (μ m) at the length direction width (major diameter) of identifiable 30 circles of the areal extent of 10 μ m * 10 μ m or oval-shaped island portion.

(annotating 8) winding folding processibility of T:

After will testing coated plate and cutting into rolling direction 5cm, vertical direction 4cm, indoor at 20 ℃, use special wiring dit Du Pont shock-testing machine, between the kink of the test coated plate that the bottom is converted into two foldings, sandwich the aluminium sheet of two thick 0.26mm, put into trier, the weight of the iron of the smooth and heavy 1kg of contact surface is fallen and after kink applied impact from high 50cm, the bending leading section was switched on for 6 seconds to apply voltage 6.5V, measure the wide current value (mA) of bending leading section 20mm, estimate with following standard.

◎ is less than 20mA

The 0th, more than the 20mA and less than 40mA

△ is more than the 40mA and less than 80mA

* be more than the 80mA.

(annotating 9) winding folding of T adds Ministry of worker's rice steamer adaptation

After will testing coated plate and cutting into rolling direction 5cm, vertical direction 4cm, indoor at 20 ℃, use special wiring dit Du Pont shock-testing machine, between the kink of the test coated plate that the bottom is converted into two foldings, sandwich the aluminium sheet of two thick 0.26mm, put into trier, the weight of the iron of the smooth and heavy 1kg of contact surface is fallen and after kink applied impact from high 50cm, in autoclave, this test film is immersed in 125 ℃ of water 30 minutes.Then, wipe moisture away, carry out stripping test to adding the Ministry of worker, the wide current value (mA) of bending leading section 20mm to apply voltage 6.5V energising, is measured in this position, estimate with following standard with scotch tape.

◎ is less than 20mA

The 0th, more than the 20mA and less than 40mA

△ is more than the 40mA and less than 80mA

* be more than the 80mA.

(annotating 10) anti-rice steamer albefaction

To test coated plate and be immersed in the water, in autoclave, handle 30 minutes, the albefaction state of filming after handling be estimated according to following standard with 125 ℃.

◎ does not find albefaction fully

The 0th, find few albefaction

△ is the albefaction of finding a little

* be to find significant albefaction.

(annotating 11) acid resistance

The test coated plate be impregnated in each aqueous solution of 0.5% of citric acid and oxysuccinic acid, in autoclave, handle 30 minutes with 125 ℃ after, its state of visual observation is also estimated according to following benchmark.

◎ does not find deterioration fully

The 0th, find a bit to peel off or expand

△ is the whole expansion of discovery or peels off

* be to find that the embrittlement of expanding comprehensively, peeling off comprehensively or filming is remarkable.

Erosion resistance after (annotating 12) processing

Similarly prepare test film with the curved processing experiment of above-mentioned T, to carry out the sample after the same bending process, be impregnated in the mixed aqueous solution that respectively is dissolved with 1% citric acid, oxysuccinic acid, sodium-chlor, at 40 ℃ down after 2 weeks of storage, the state of its bending process portion of visual observation is also estimated according to following standard.

◎ does not find corrosion

The 0th, find slight corrosion

△ finds quite to have corrosion

* be that corrosion is remarkable.

(annotating 13) smell

Each test board is impregnated in deionized water d-limonene (spices) back that adds 30ml, disperses in the solution that S-1170 (Mitsubishi Chemical Ind's system, sucrose fatty ester) forms with 1g/l, at 35 ℃ of dipping 1 month and storages down.For being adsorbed in the d-limonene (spices) on filming behind the mensuration storage, in diethyl ether, after 1 week of dipping, extracting under 20 ℃, the d-limonene (spices) that utilizes gas Chromatographic Determination to extract is estimated according to following standard.

The 0th, every 120mg weight of filming, the d-limonene (spices) that extracts is less than 0.6mg

△ is every 120mg weight of filming, and the d-limonene (spices) that extracts is above and be less than 1.6mg for 0.6mg

* be every 120mg weight of filming, the d-limonene (spices) that extracts is for more than the 1.6mg.

Practicality on the industry

Owing to improved bending process, resistance to water-whitening, therefore can have been had The metal can of filming of anti-content corrosivity excellence and smell excellence.

Claims (7)

1. water-based paint compositions, it is characterized in that, this water-based paint compositions is to disperse 100 mass parts acrylic resin modified epoxies (A) in aqueous medium, 0.1～20 mass parts resoles (B), 0.1 it is that the acrylic resin (C) of 100～500mgKOH/g forms that～20 mass parts have the acid number of following characteristics, wherein, described acrylic resin (C) has: to be selected from 2-acrylamide-2-methyl propane sulfonic acid, single (methacrylic acid 2-hydroxyl ethyl ester) phosphoric acid ester, at least a free radical polymerization monomer in vinylformic acid and the methylene-succinic acid is as the ethylenic copolymer chain (1) of moiety, with the monomer component that contains methacrylic acid ethylenic copolymer chain (2) as moiety.

2. water-based paint compositions according to claim 1, described acrylic resin (C) are to make following composition react the polymkeric substance that forms, and described composition is:

Vinyl copolymer resin (c1), it is selected from least a free radical polymerization monomer in 2-acrylamide-2-methyl propane sulfonic acid, list (methacrylic acid 2-hydroxyl ethyl ester) phosphoric acid ester, vinylformic acid and the methylene-succinic acid and other free-radical polymerised unsaturated monomer (1) of 40～90 quality % as monomer component with 10～60 quality %;

Vinyl copolymer resin (c2), its with 10～60 quality % methacrylic acids and other free-radical polymerised unsaturated monomer (2) of 40～90 quality % as monomer component;

Low-molecular weight compound (c3), it is that to be selected from the epoxy equivalent (weight) that has 2 above epoxy group(ing) in 1 molecule be at least a in 180～5000 Resins, epoxy, resole and the polycarbodiimide compound.

3. water-based paint compositions according to claim 2, wherein, low-molecular weight compound (c3) is that the epoxy equivalent (weight) that has 2 above epoxy group(ing) in 1 molecule is 200～1000 Resins, epoxy.

4. water-based paint compositions according to claim 2, it is characterized in that, total based on the solids component of vinyl copolymer resin (c1) and vinyl copolymer resin (c2), in vinyl copolymer resin (c1)/vinyl copolymer resin (c2)=60/40～95/5 by quality %, and, the vinyl copolymer resin (c1) that constitutes acrylic resin (C) and ethylenic copolymer (c2) and low-molecular weight compound (c3) are reacted by the ratio of [vinyl copolymer resin (c1)+vinyl copolymer resin (c2)]/low-molecular weight compound (c3)=100/0.1～100/20 of mass parts.

5. according to each described water-based paint compositions of claim 1～4, wherein, acrylic resin modified epoxy (A) is following resin, that is, to make number-average molecular weight be 2000～35000 bisphenol-type epoxy resin (a1) with contain carboxy acrylic resinoid (a2) carries out the resin that esterification forms or makes this bisphenol-type epoxy resin (a1) and the polymerizability unsaturated monomer composition that contains carboxyl polymerizability unsaturated monomer (a3) carry out the resin that graft polymerization forms.

6. according to each described water-based paint compositions of claim 1～4, it is characterized in that, with respect to 100 mass parts acrylic resin modified epoxies (A), further contain the anionic property crosslinked polymer particulate (D) that 1～50 mass parts has following characteristics, wherein, anionic property crosslinked polymer particulate (D) is that the polymkeric substance of 10～100mgKOH/g is formed by the acid number of following manufacturing, promptly, in the presence of water, make 2～30 quality % contain carboxyl free radical polymerizable monomer (d1), the free-radical polymerised unsaturated monomer composition that other free-radical polymerised unsaturated monomer (d3) of many vinyl compounds of 2～30 quality % (d2) and 40～96 quality % is formed carries out polyreaction and the polymkeric substance that makes.

7. a jar coating composition is characterized in that, each described water-based paint compositions of claim 1～4 is used to be coated with and installs to tank body.

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