CN101089104A - Two surface coating steel plate for tank - Google Patents

Abstract

The surface of the tank used two sides coating steel plate which becomes outside surface when the tank manufacturing is over, is formed with a coating film containing a vestopal (A) which includes hydroxyl, at least one kind of cross linkers (B) chosen from amine resin and soluble phenolic resin consisting group, and a tank used coating color (I) which includes aluminum paint (C1) or white paint (C2) with a special ratio, and the surface which becomes the inside surface when the tank manufacturing is over, is formed with a coating film containing crystalline vestopal particulates (D) which includes the terephthalic acid glycol ester monomer as main body, a crystalline vestopal particulate (E) which includes the terephthalic acid butanediol ester as main body, and a tank used coating color (II) whose dissolvability to the particulate (D) and the particulate (E) is less than 5 mass percentage below 40 centigrade and is more than 99 mass percentage above 170 mass percentage.

Description

Two surface coating steel plate for tank

Technical field

The present invention relates to two surface coating steel plate for tank.

Background technology

Beverage/food with jar etc. jar inner face and outside form usually and film.In the past, as on jar, forming the mode film, carrying out under the use of pressure oil forming sheet metals such as steel plate are processed as lacquered can surfaces externally and internally behind jar shape after be coated with mode.

In recent years, follow from elimination shorten operation, reduce manufacturing cost and the processing that is shaped after the viewpoint of the environmental problem handled of pressure oil, be coated with mode after above-mentioned and replace with and will be processed as the precoating mode of jar shape in advance at the forming sheet metal of two surface coating.When the precoating mode,, require the deep drawn processibility (hereinafter referred to as D﹠amp jar, particularly jar inboard filming of forming; The I processibility), the film performance excellence of boiling resistance, fragrance retentivity, wholesomeness etc., be very difficult but all satisfy these.In addition, when the precoating mode,, require printing trader's name of an article, the isochronous printing color developing of commodity pattern, D﹠amp filming that the jar outside forms; The I excellent in workability.

As the two surface coating metal sheet that in the precoating mode, uses, disclosing becomes jar inboard filming, coating with the vibrin that contains hydroxyl and resol resin forms, become jar filming of the outside, the two surface coating metal sheet (with reference to TOHKEMY 2003-34322 communique) that forms with the coating of the vibrin that contains hydroxyl and aminoresin and/or resol resin.But, on this two surface coating metal sheet, jar inboard D﹠amp that films; The printing color developing of filming in I processibility, boiling resistance, fragrance retentivity, wholesomeness etc. and the jar outside may not be abundant.Therefore, require to improve these characteristics.

As the inboard coating of using of the jar that can satisfy above-mentioned requirements, the jar coating composition that use polyethylene terephthalate (PET) arranged, still, because the crystallinity height of PET, so in the general organic solvent that uses, be difficult to dissolving, be not easy to give full play to the characteristic of precoating with coating.

For example, as the jar coating composition that can in the precoating mode, use, known (with reference to TOHKEMY 2001-234115 communique) be in solvent, slowly cool off after dissolving non-crystalline polyester resin and the crystalline polyester resin and obtain contain the jar application resin combination of crystalline polyester resin with dispersion state.But, this jar of application application resin-coated metal sheet of resin combination on metal sheet, D﹠amp; The I processibility is insufficient.

In addition, be well known that make crystalline polyester resin and non-crystalline polyester resin in organic solvent, heat, dissolve after, this resin solution is cooled to the temperature below the glass tansition temperature of crystalline polyester resin rapidly from the temperature more than the intensification crystallization start temperature of crystalline polyester resin and obtain polyester resin solution is used (with reference to TOHKEMY 2004-2671 communique) as jar coating composition.But, when using such jar coating composition, D﹠amp is arranged in the precoating mode; Any one inadequate situation of the I processibility and the smoothness of filming.

Summary of the invention

The object of the present invention is to provide two surface coating steel plate for tank, what become jar inboard films D﹠amp; The film performance excellence of I processibility, boiling resistance, fragrance retentivity, wholesomeness, tack, preservative property, the smoothness of filming etc., and, filming of jar outside become, printing color developing, D﹠amp; The film performance excellence of I processibility etc.

The inventor is in order to finish above-mentioned problem, to have carried out deep investigation.Its result, discovery is by after jar processing, form the vibrin (A) that contains hydroxyl respectively with specified proportion on the face outside becoming, be selected from the filming of tin paint (I) of at least a kind of linking agent (B) of aminoresin and resol resin and aluminium pigment (C1) or white pigment (C2), and after jar processing, become to form on the inboard face respectively and contain crystalline polyester resin particulate (D) based on the ethylene glycol terephthalate monomer with specified proportion, based on the two surface coating steel plate of filming of the tin paint (II) of the crystalline polyester resin particulate (E) of mutual-phenenyl two acid bromide two alcohol ester's monomer and specific organic solvent (F), can finish above-mentioned problem.The present invention is based on such opinion and the invention finished.

The present invention provides the invention of following two surface coating steel plate for tank.

1. two surface coating steel plate for tank, after jar processing, become the face in the outside, formation contains the vibrin (A) of hydroxyl, be selected from solids component 100 mass parts by at least a kind of linking agent (B) of aminoresin and resol resin and relative this vibrin (A) and be the filming of tin paint (I) of the white pigment (C2) of the aluminium pigment (C1) of 5～60 mass parts or 60～140 mass parts, and after jar processing, become inboard face, formation contains the crystalline polyester resin particulate (D) based on the ethylene glycol terephthalate monomer, based on the crystalline polyester resin particulate (E) of mutual-phenenyl two acid bromide two alcohol ester's monomer and contain the solubleness of this particulate (D) and be less than 5 quality % below 40 ℃ to the solubleness of this particulate (E), more than 170 ℃ be organic solvent (F) more than the 99 quality %, the ratio of this particulate (D) and this particulate (E), based on their total amount, the former is 95～30 quality %, the latter is 5～70 quality %, and total 100 mass parts of the content relatively small particle (D) of organic solvent (F) and particulate (E) are the filming of tin paint (II) of 40～800 mass parts.

2. as above-mentioned 1 described two surface coating steel plate for tank, the dry film thickness that tin paint (I) is filmed is that the dry film thickness that 1～20 μ m and tin paint (II) are filmed is 1～30 μ m.

3. as above-mentioned 1 described two surface coating steel plate for tank, the aluminium pigment (C1) of tin paint (I) is non-floating type aluminium pigment.

4. as above-mentioned 1 described two surface coating steel plate for tank, the crystalline polyester resin particulate (D) of tin paint (II) is that the resin intrinsic viscosity is that 0.4～1.4dl/g, glass tansition temperature (Tg) are that 55～130 ℃, fusing point (Tm) are 160～260 ℃ resin particle.

5. as above-mentioned 1 described two surface coating steel plate for tank, the particulate that the crystalline polyester resin particulate (D) of tin paint (II) is made up of 80 moles of vibrin more than the % of ethylene glycol terephthalate monomer containing ratio.

6. as above-mentioned 1 described two surface coating steel plate for tank, the crystalline polyester resin particulate (E) of tin paint (II) is that the resin intrinsic viscosity is that 0.4～1.4dl/g, glass tansition temperature (Tg) are that 0～40 ℃, fusing point (Tm) are 130～250 ℃ resin particle.

7. as above-mentioned 1 described two surface coating steel plate for tank, the particulate that the crystalline polyester resin particulate (E) of tin paint (II) is made up of 90 moles of vibrin more than the % of mutual-phenenyl two acid bromide two alcohol ester's monomer containing ratio.

8. as above-mentioned 1 described two surface coating steel plate for tank, total 100 mass parts of tin paint (II) relative crystallinity vibrin particulate (D) and crystalline polyester resin particulate (E) also contain the vibrin (A) of the hydroxyl of 0.1～100 mass parts.

9. as above-mentioned 8 described two surface coating steel plate for tank, the vibrin (A) of the hydroxyl of tin paint (II), glass tansition temperature (Tg) is 55～150 ℃.

10. as above-mentioned 1 described two surface coating steel plate for tank, tin paint (II) also contains dispersion agent (G).

11. as above-mentioned 10 described two surface coating steel plate for tank, dispersion agent (G) is the phosphate compound with general formula (1) expression.

(in the formula, R ¹, R ²And R ³Respectively identical or different, the aliphatic hydrocarbon of expression carbonatoms 6～18 or aromatic hydrocarbons or-C _mH _2mOC _nH _2n+1Here, m and n are that integer more than 1 and m+n are the integers more than 6.)

12. as above-mentioned 1 described two surface coating steel plate for tank, total 100 mass parts of tin paint (II) relative crystallinity vibrin particulate (D) and crystalline polyester resin particulate (E) also contain the resol resin of 0.1～10 mass parts.

13. as above-mentioned 1 described two surface coating steel plate for tank, total 100 mass parts of tin paint (II) relative crystallinity vibrin particulate (D) and crystalline polyester resin particulate (E) also contain the Resins, epoxy of 0.5～20 mass parts.

14. a cylinder of steel body is obtained as above-mentioned 1 described two surface coating steel plate for tank by deep-draw processing or deep drawn processing.

Two surface coating steel plate for tank

Using the inside coated steel plate for of the present invention jar, is to become a side of outside surface to form filming of tin paint (I) after the jar processing of steel plate, and becomes the coated steel plate of filming of the side formation tin paint (II) of internal surface after the jar processing of steel plate.

Steel plate

As the steel plate of respectively filming that forms tin paint (I) and tin paint (II), if can beverage/food with jar etc. various jars use in the steel plates of use just have no particular limits.For example, can enumerate cold-rolled steel sheet, tin plate, steel plate galvanized, chromium plating steel plate, exempt from tin steel plate (tin free steel sheet) etc.These steel plates both can not done the surface and handle the ground use, also can use after the surface treatment of carrying out phosphatizing, zirconates processing, chromate treating etc.

In addition, the shape of steel plate both can be tabular, also can be that volume is for spiral helicine metal strip.The thickness of steel plate, 0.15～0.4mm normally, the length of vertical and horizontal is any.In addition, when being metal strip, be suitable about common, wide 1m.

Tin paint (I)

Tin paint (I) contains the vibrin (A) of hydroxyl, at least a kind of linking agent (B) that is selected from aminoresin and resol resin, relative solids component 100 mass parts that contain the vibrin (A) of hydroxyl are the aluminium pigment (C1) of 5～60 mass parts or the white pigment (C2) of 60～140 mass parts.

Tin paint (I), by becoming the face application in the outside after sheet pot processing, the color of bottom steel plate blackout behind the hidden system jar can obtain the printing color developing in the excellent jar outside, in addition, D﹠amp; The film performance of I processibility etc. is also excellent.

The vibrin (A) that contains hydroxyl

Containing the vibrin (A) of hydroxyl, in the mensuration of being undertaken by differential scanning calorimeter, is the resin that does not show sharp melting point, be with normal temperature easy dissolved resin in organic solvent, and linking agent (B) carries out cross-linking and curing reaction, forms and film.

Vibrin (A) preferred number average molecular weight that contains hydroxyl is 8000～100000, is more preferably 10000～80000.In addition, hydroxyl value preferably about 1～20mgKOH/g, be more preferably 1～15mgKOH/g.

The vibrin (A) that contains hydroxyl can and obtain by the reaction of polyprotonic acid composition and polyhydroxy reactant.

The polyprotonic acid composition, for example, can use and be selected from phthalate anhydride, m-phthalic acid, terephthalic acid, tetrahydrobenzene dicarboxylic acid anhydride, hexahydrobenzene dicarboxylic acid anhydride, succsinic acid, fumaric acid, hexanodioic acid, sebacic acid, maleic anhydride, 2,6-naphthalene diacid, 1, diprotic acid and these the sour low alkyl group esterification things more than a kind such as 6-suberic acid, cyclohexane diacid; The polyprotonic acid that 3 valencys such as trihemellitic acid acid anhydride, methylcyclohexyl tricarboxylic acid, PMA are above, the also monoprotic acid of usefulness phenylformic acid, p-tert-butyl benzoic acid etc.

Polyhydroxy reactant for example, can make spent glycol, glycol ether, propylene glycol, 1,4-butyleneglycol, season pentanediol, 3-methyl pentanediol, 1,4-hexylene glycol, 1, the dibasic alcohol of 6-hexylene glycol, butyl ethyl propylene glycol, cyclohexanediol etc.; The polyvalent alcohol that 3 valencys of glycerine, trimethylolethane, TriMethylolPropane(TMP), tetramethylolmethane etc. are above etc.

Contain the vibrin (A) of hydroxyl, can use commercially available product.As commercially available product, for example, can enumerate " UE-3201 ", " UE-3203 ", " XA-0653 " (trade(brand)name, above), " GK-640 ", " GK-880 " (trade(brand)name, above) etc. by Japan's weaving (strain) production by ユ ニ チ カ (strain) production.

Linking agent (B)

Linking agent (B) uses at least a kind that is selected from aminoresin and resol resin.

Above-mentioned aminoresin can be enumerated the methylolation aminoresin that is obtained by the reaction of amino component and aldehyde composition; By alcohol with product of the methylol etherization of this methylolation aminoresin etc.

Amino component for example, can be enumerated trimeric cyanamide, urea, benzoguanamine, methyl guanamines, steroid guanamines, volution guanamines, Dyhard RU 100 etc.The aldehyde composition for example, can be enumerated formaldehyde, Paraformaldehyde 96, acetaldehyde, benzo aldehyde etc.In addition, operable alcohol in etherificate for example, can be enumerated methyl alcohol, ethanol, n-propyl alcohol, Virahol, propyl carbinol, isopropylcarbinol, 2-ethyl butanol, 2-Ethylhexyl Alcohol etc.

Aminoresin preferably uses the methylol of methylolation aminoresin by the complex etherified alkoxyl group melamine resin of methyl etherified or methyl etherified and butyl etherificate.The molecular weight of this methyl etherified alkoxyl group melamine resin or methyl etherified butyl etherificate alkoxyl group melamine resin preferably 300～2000.

Above-mentioned resol resin, preferably in the phenol composition, in the presence of catalysts, make formaldehydes heat condensation reaction, import methylol, obtain methylolation resol, the then product that a part of hydroxymethyl alkyl etherificate is obtained with alcohol.

Operable phenolic compound in the manufacturing of resol resin, for example, can enumerate phenol, ortho-cresol, p-cresol, p-tert-butylphenol, p-ethyl phenol, 2,3-xylenol, 2,5-xylenol, meta-cresol, m-ethylphenol, 3,5-xylenol, meta-methoxy phenol, dihydroxyphenyl propane, Bisphenol F etc.These phenolic compound can be independent a kind or mix more than 2 kinds and use.

Operable formaldehydes in the manufacturing of resol resin for example, can be enumerated formaldehyde, Paraformaldehyde 96, trioxane etc.These aldehyde can be independent a kind or mix more than 2 kinds and use.

Operable alcohol in a part of hydroxymethyl alkyl etherificate of methylolation resol, 1 yuan of alcohol that preferred carbonatoms is 1～8, more preferably 1 yuan of alcohol of 1～4 of carbonatoms.Particularly, especially preferably use 1 yuan of alcohol of methyl alcohol, ethanol, n-propyl alcohol, propyl carbinol, isopropylcarbinol etc.

Be selected from the use level of at least a kind of linking agent (B) of aminoresin and resol resin, contain the solids component of the vibrin (A) of hydroxyl based on 100 mass parts, preferably 0.1～20 mass parts, be more preferably 0.5～5 mass parts.

Aluminium pigment (C1) and white pigment (C2)

The tin paint of Shi Yonging (I) in the present invention, when the metalluster sense must be arranged, for hidden on cylinder of steel distinctive blackout color, obtain the printing color developing of excellent jar Outboard Sections, cooperate aluminium pigment (C1).In addition, because aluminium pigment (C1) is the metal of processing ductility excellence,, also has the effect of avoiding the smooth stress by the outside to cause to the privileged site stress concentration so extend in the smooth man-hour easy deformation of adding.

The median size of aluminium pigment (C1) is the median size (D that measures with laser light scattering formula particle size distribution device ₅₀) 5～50 μ m, reflecting feel and designability after jar processing are wished.Laser light scattering formula particle size distribution device, can use commercially available product.As commercially available product, for example, can enumerate " SALD-1100 type " (trade(brand)name, Shimadzu Seisakusho Ltd. produce).

Aluminium pigment (C1) can be to apply surface-treated pigment such as evaporation, coating, surface grinding.As such aluminium pigment (C1), can enumerate floating type aluminium pigment, non-floating type aluminium pigment etc., but obtain in the tank body by deep drawn processing, preferably use non-floating type aluminium pigment.Non-floating type aluminium pigment is by the surface-treated pigment of lipid acid such as oleic acid, because surface tension is little and the affinity of solvent, coating is strong, so disperse equally, shows excellent glossiness thus in filming.

In addition, the purity of aluminium pigment (C1) is removed surface treatment, is the aluminium pigment more than 99.5%, wishes from the viewpoint that produces external coating by ductility and the smooth aluminium that adds man-hour.

Aluminium pigment (C1) can use commercially available product.As commercially available product, for example, can enumerate " ア Le ミ ニ ウ system ペ one ス ト MC-666 ", " ア Le ミ ニ ウ system ペ one ス ト MH-8801 ", " ア Le ミ ニ ウ system ペ one ス ト MH-8805 " (trade(brand)name, above), " ア Le ミ ペ one ス ト 564NS ", " ア Le ミ ペ one ス ト 1950M ", " ア Le ミ ペ one ス ト 1700NAL ", " ア Le ミ ペ one ス ト 7160N ", " ア Le ミ ペ one ス ト 7680NS ", (trade(brand)name, above) etc. by the production of Japan ア Le ミ ニ ウ system society by the production of the メ of Asahi Chemical Industry Le ズ society.

The use level of aluminium pigment (C1), relative 100 mass parts contain the vibrin (A) of hydroxyl solids component, must be 5～60 mass parts.The content of aluminium pigment (C1) is if more than 5 mass parts, though the filming of filming of system jar back, jar Outboard Sections, also can hidden bottom steel plate blackout color, can obtain the printing color developing of excellent jar outer side part.In addition, if below 60 mass parts, can prevent the decline of the deep drawn processibility that causes to the outstanding of the top layer of filming by aluminium and the decline of coating sedimentation stability.

The use level of aluminium pigment (C1), contain relatively hydroxyl vibrin (A) solids component 100 mass parts, preferably 10～50 mass parts, be more preferably 15～40 mass parts.

In addition, jar with pigment (I), when not requiring the metalluster sense, for the distinctive blackout color of hidden cylinder of steel, obtain the printing color developing of excellent jar outer side part and cooperate white pigment (C2).

White pigment (C2) can be enumerated titanium oxide, zinc oxide, zinc sulphide, lithopone etc., but in order to obtain excellent printing color developing, preferred titanium oxide.Titanium oxide is preferred use usually as coating with and printing ink titanium oxide that use, the about 0.05～about 2 μ m of median size, the titanium oxide of 0.1～about 1 μ m more preferably from about.

Titanium oxide can use commercially available product.As commercially available product, can enumerate " JR-301 ", " JR-600 ", " JR-701 ", " JR-901 " (trade(brand)name, above produce), " CR-50 " (trade(brand)name, produce) etc. by the former industry of stone society by テ イ カ society.

The use level of white pigment (C2), relative 100 mass parts contain the vibrin (A) of hydroxyl solids component, must be 60～140 mass parts.The content of white pigment (C2) is if more than 60 mass parts, though in system jar back, jar outer side part film become film, also can hidden bottom steel plate the blackout color, can obtain an excellent jar outer side and partly print color developing.In addition, if below 140 mass parts, can prevent to uprise the deep drawn processibility decline that causes and process the generation of cutting problems such as abrasion by hardness of film.

The use level of white pigment (C2), relative 100 mass parts contain the solids component of the vibrin (A) of hydroxyl, preferably 60～120 mass parts, be more preferably 80～100 mass parts.

Use in the pigment (I) at jar, also can and use aluminium pigment (C1) and white pigment (C2).

Other composition

Jar with pigment (I) in, containing the vibrin of hydroxyl (A), linking agent (B) and aluminium pigment (C1) or white pigment (C2) in addition, as required, in order to promote curing reaction, can to add acid catalyst.

Acid catalyst as object lesson, for example can be enumerated the acid of the sulfoacid compound, phosphoric acid etc. of tosic acid, Witco 1298 Soft Acid, dinonylnaphthalene sulfonic acid, dinonylnaphthalene disulfonic acid etc.; The amine corrective that these are sour etc.Wherein, the amine corrective of above-mentioned sulfoacid compound, sulfoacid compound is fit to.

From the rerum natura of filming that obtains etc., contain the solids component amount of the vibrin (A) of hydroxyl based on 100 mass parts, the use level of acid catalyst, as acid amount, preferred 0.1～5 mass parts, more preferably 0.5～2 mass parts.The acid amount, for example when the amine corrective of sulfoacid compound, refer to from this corrective remove amine and residual sulfoacid compound amount tin paint (I), as required, can also add organic resin, wax, defoamer, flow agent, anti-settling agent, tinting pigment, pigment extender, organic solvent etc.

Above-mentioned organic resin is particularly by adding Resins, epoxy, improve hardness, sticking power, boiling resistance etc., wherein preferred phenolic resin varnish type epoxy resin.

Phenolic resin varnish type epoxy resin can be enumerated phenol novolak type epoxy resin, cresols phenolic resin varnish type epoxy resin, be had the various phenolic resin varnish type epoxy resins of the phenol oxalic dialdehyde type Resins, epoxy etc. of a plurality of epoxy group(ing) at intramolecularly.Wherein, obtain film performance equilibrated phenol novolak type epoxy resin easily, the cresols phenolic resin varnish type epoxy resin is fit to.

Above-mentioned wax adds when being used to adjust the kinetic friction coefficient that tin paint (I) films, in application the steel plate carrying and being shaped of this coating useful when adding the generation that is used to man-hour suppress to abrade etc.As wax, the wax of preferred softening temperature more than 30 ℃, the more preferably wax of 33～150 ℃ of softening temperatures, for example, can enumerate the fatty acid ester wax, silicon class wax, fluorine class wax, polyolefin-wax, animal class wax, plant class wax etc. of the carboxylate that is polyol blends and lipid acid.

Become the polyol compound of above-mentioned fatty acid ester wax stock, can enumerate ethylene glycol, glycol ether, tri-ethylene glycol, tetrem allyl diglycol, 1,3-butyleneglycol, 1,4-butyleneglycol, season pentanediol, 1,6-hexylene glycol, glycerine, two or its above Polyglycerine, TriMethylolPropane(TMP), tetramethylolmethane, Dipentaerythritol etc.Wherein, preferably have the polyol compound of 3 above hydroxyls in 1 molecule, wherein, Polyglycerine, TriMethylolPropane(TMP), tetramethylolmethane are fit to.

Become the lipid acid of above-mentioned another raw material of fatty acid ester wax, can enumerate saturated or unsaturated fatty acids, preferably the lipid acid of carbonatoms 6～32.As the object lesson of the lipid acid that is fit to, can enumerate the saturated fatty acid of n-caprylic acid, n-nonanoic acid, n-capric acid, lauric acid, tetradecanoic acid, palmitinic acid, stearic acid, arachic acid, behenic acid, hexacosanoic acid, octocosoic acid, triacontanoic acid etc.; The unsaturated fatty acids of decylenic acid, undecylenic acid, brown tung oil acid, oleic acid, linolic acid, linolenic acid, eleostearic acid, Decosahedaenoic acid, sinapinic acid, brazilnut oleic acid, ricinoleate acid, eicosatetraenoic acid etc.

The preferred above-mentioned polyol compound hydroxyl value of fatty acid ester at least 1/3 with fatty acid-esterified wax.

Silicon class wax can use commercially available product.As commercially available product, for example, can enumerate " BYK-300 ", [BYK-320 "; " BYK-330 " [trade(brand)name; above]; " シ Le ウ エ Star ト L-77 "; " シ Le ウ エ Star ト L-720 "; " シ Le ウ エ Star ト L-7602 " [trade(brand)name by the production of BYK Chemie (PVC Star Network ケ ミ one) society, more than produce by Japanese コ ニ カ one (strain)], " ペ イ Application Star De 29 ", " ペ イ Application Star De 32 ", " ペ イ Application Star De M " [trade(brand)name, more than produce by ダ ウ コ one ニ Application グ society], " the シ リ コ one Application KF-96 of SHIN-ETSU HANTOTAI " [trade(brand)name, produce by SHIN-ETSU HANTOTAI's chemistry (strain)] etc., in addition, fluorine class wax, for example, can enumerate " シ ヤ system ロ Star Network ワ Star Network ス SST-1MG ", " シ ヤ system ロ Star Network ワ Star Network ス SST-3 ", " シ ヤ system ロ Star Network ワ Star Network ス Off Le オ ロ ス リ Star プ 231 " [trade(brand)name, more than produce by シ ヤ system ロ Star Network ケ ミ カ Le ズ society], " POLYFLUO150 ", " POLYFLUO400 " [trade(brand)name, more than produce by マ イ Network ロ パ ウ ダ one society] etc.

Polyolefin-wax can use commercially available product.As commercially available product, for example, can enumerate " シ ヤ system ロ Star Network ワ Star Network ス S-394 ", " シ ヤ system ロ Star Network ワ Star Network ス S-395 " [trade(brand)name, above] by the production of シ ヤ system ロ Star Network ケ ミ カ Le ズ society, " ヘ キ ス ト ワ Star Network ス PE-520 ", " ヘ キ ス ト ワ Star Network ス PE-521 " [trade(brand)name, above] by the production of ヘ キ ス ト society, " Mitsui Ha イ ワ Star Network ス " " trade(brand)name, Mitsui Chemicals (strain) are produced " etc.

Animal class wax for example, can be enumerated lanolin wax, beeswax etc., and plant class wax for example, can be enumerated carnauba wax, water wax etc.

Above-mentioned wax can be independent a kind or make up more than 2 kinds and use.

The addition of these waxes, from the paint stability excellence and can access the processibility of anti-deep drawn processing of filming, relative 100 mass parts contain the solids component of the vibrin (A) of hydroxyl, preferably 20 mass parts following, be more preferably 0.01～10 mass parts.

Above-mentioned tinting pigment can use the tinting pigment of in the past using always in coating.As tinting pigment, for example, can use organic class pigment of solubility azo class pigment, phthalein mountain valley with clumps of trees and bamboo class pigment, indigo class pigment, perylene kinds pigment, perillene class pigment, Kui phthalein ketone pigment, dioxazines pigment, quinacridine ketone pigment, isoindoline ketone pigment, metal complex pigment etc., the mineral-type pigment of lead and yellow-collation, iron oxide yellow, red iron oxide etc.

The addition of tinting pigment can at random be set according to the form and aspect of institute's application color.

Above-mentioned pigment extender can use the pigment extender of in the past using always in coating.As object lesson, can enumerate barium sulfate, lime carbonate, silicon-dioxide, carclazyte, barium oxide etc., these can separately or mix use more than 2 kinds.

Above-mentioned organic solvent can use and can be dissolved to the organic solvent that disperses each composition, and is concrete, for example, can enumerate the varsol of toluene, dimethylbenzene, high point petroleum class hydrocarbon etc.; The ketones solvent of methylethylketone, mibk, pimelinketone, isophorone etc.; The esters solvent of vinyl acetic monomer, N-BUTYL ACETATE, ethylene glycol monoethyl ether acetate, glycol ether monoethyl ether acetate etc.; The alcoholic solvent of methyl alcohol, ethanol, butanols etc.; The ether solvents of ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, diethylene glycol monobutyl ether etc. etc., these can separately or mix use more than 2 kinds.

The preparation of coating (I)

The tin paint of Shi Yonging (I) in the present invention can be according to known method, contain vibrin (A), linking agent (B) and the aluminium pigment (C1) of hydroxyl or the necessary composition of white pigment (C2) by mixing, and other composition as required and preparing.

The coating that obtains (I), organic solvent type coating composition normally, the solid component content of coating composition are usually to become 5～50 quality % for well.

Tin paint (II)

The tin paint of Shi Yonging (II) in the present invention, be contain crystalline polyester resin particulate (D) based on the ethylene glycol terephthalate monomer, based on the crystalline polyester resin particulate (E) of mutual-phenenyl two acid bromide two alcohol ester's monomer and to the solubleness of this particulate (D) and to the solubleness of this particulate (E) all be below 40 ℃ less than 5 quality %, be the coating of the organic solvent (F) more than the 99 quality % more than 170 ℃.In addition, in tin paint (II), the ratio of this particulate (D) and this particulate (E), based on these total amount, the former is that 95～30 quality %, the latter are 5～70 quality %, and the content of organic solvent (F), is 40～800 mass parts at relative this particulate (D) and total 100 mass parts of this particulate (E).

Tin paint (II) is to become inboard face application after sheet pot processing, can form D﹠amp; The coating of filming of I processibility, boiling resistance, fragrance retentivity, wholesomeness, sticking power, preservative property, the film performance excellences such as smoothness of filming.

In tin paint (II), be resin intrinsic viscosity, glass tansition temperature, fusing point and the median size of vibrin characteristic, measure as operate followingly.

(1) resin intrinsic viscosity: according to the method for in JIS Z8803, stipulating, use the mixing solutions of phenol/tetrachloroethane=1/1 (mass ratio), obtain 25 ℃ of mensuration.

(2) glass tansition temperature: be the value of obtaining by the method for regulation among the JIS K71219.3 (1987).

(3) fusing point: the value that is to use differential scanning type calorimeter measurement.As the calorimetric commercially available product of differential scanning type, for example, can use " DSC-60A " (trade(brand)name, society of Shimadzu Seisakusho Ltd. (strain) produce).

(4) volume average particle size: the value that is to use laser scattering type particle size distribution device to measure.As the commercially available product of such particle size distribution device, for example, can use " MICROTRACHRA model 9320-X100 " (trade(brand)name, a day machine dress (strain) are produced).

Crystalline polyester resin particulate (D)

Crystalline polyester resin particulate (D) in tin paint (II) is the particulate based on the vibrin of ethylene glycol terephthalate monomer.So-called crystallinity refers to the clear and definite fusing point of demonstration in the mensuration of being undertaken by differential scanning type calorimeter.Vibrin based on the ethylene glycol terephthalate monomer, obtain by the polycondensation of terephthalic acid or its lower alkyl esters and ethylene glycol, but also can with m-phthalic acid, hexanodioic acid etc. other polyprotonic acid or its lower alkyl esters replaces a part of terephthalic acid or its lower alkyl esters or with propylene glycol, 1, other polyvalent alcohol such as 4-cyclohexyl dimethanol replaces a part of ethylene glycol.

Based on the vibrin of ethylene glycol terephthalate monomer, be 80 moles of vibrin, preferred more than the % from the viewpoint of fragrance retentivity excellence based on the monomeric containing ratio of ethylene glycol terephthalate of terephthalic acid or its lower alkyl esters and ethylene glycol.At the monomeric containing ratio of ethylene glycol terephthalate is in 80 moles of limits more than the %, for example, both can be that ethylene glycol terephthalate monomer containing ratio is the polyethylene terephthalate (PET) of 100 moles of %, also can is other monomeric multipolymers such as ethylene glycol terephthalate monomer and ethylene isophthalate monomer.In addition, also comprise have the rubber-like polyester construction resin of (for example chain section of forming by the low polyethers of glass tansition temperature).

Micronisation process as the crystalline polyester resin that is used to obtain this particulate (D); for example; can enumerate comminuting method, dissolving method of cooling, spray-drying process etc., but from the appearance of film aspect, preferably use the crystalline polyester resin particulate that obtains in the dissolving method of cooling that makes it by the organic solvent heating for dissolving.

The characteristic of operable in the present invention crystalline polyester resin particulate (D), resin intrinsic viscosity preferably 0.4～1.4dl/g, be more preferably 0.7～1.2dl/g.In addition, preferably 55～130 ℃ of glass tansition temperatures, preferably 160～260 ℃ of fusing points.In addition, the volume average particle size of crystalline polyester resin particulate (D) is normally in the scope of 0.1～25 μ m, particularly 0.1～10 μ m.

Crystalline polyester resin particulate (D) also can use commercially available product.As commercially available product, for example, can enumerate " PA-200 " (trade(brand)name, Mitsubishi's レ イ ヨ Application (strain) are produced), " J125 " (trade(brand)name, Mitsui Chemicals (strain) are produced), " J135 " (trade(brand)name, Mitsui Chemicals (strain) are produced), " TN8756 " (trade(brand)name, Supreme Being people change into (strain) and produce) etc.

Crystalline polyester resin particulate (E)

Crystalline polyester resin particulate (E) in coating (II) is the vibrin particulate based on mutual-phenenyl two acid bromide two alcohol ester's monomer.So-called crystallinity refers to the clear and definite fusing point of demonstration in the mensuration of being undertaken by differential scanning type calorimeter.Vibrin based on mutual-phenenyl two acid bromide two alcohol ester's monomer, by terephthalic acid or its lower alkyl esters and 1, the polycondensation of 4-butyleneglycol and obtaining, but also can with m-phthalic acid, hexanodioic acid, sebacic acid etc. other polyprotonic acid or its lower alkyl esters replaces a part of terephthalic acid or its lower alkyl esters or with 1,6-hexylene glycol, 1, other polyvalent alcohol such as 4-cyclohexyl dimethanol replaces a part 1,4-butyleneglycol.

Based on the vibrin of mutual-phenenyl two acid bromide two alcohol ester's monomer, preferably based on terephthalic acid or its lower alkyl esters and 1, the monomeric containing ratio of the mutual-phenenyl two acid bromide two alcohol ester of 4-butyleneglycol is the above vibrin of 90 moles of %.At the monomeric containing ratio of mutual-phenenyl two acid bromide two alcohol ester is in 90 moles of limits more than the %, for example, both can be that mutual-phenenyl two acid bromide two alcohol ester's monomer containing ratio is the polybutylene terephthalate (PBT) of 100 moles of %, also can is other monomeric multipolymers such as mutual-phenenyl two acid bromide two alcohol ester's monomer and m-phthalic acid butanediol ester monomer.In addition, also comprise have the rubber-like polyester construction resin of (for example chain section of forming by the low polyethers of glass tansition temperature).

Micronisation process as the crystalline polyester resin that is used to obtain this particulate (E); for example; can enumerate comminuting method, dissolving method of cooling, spray-drying process etc., but from formation property aspect of filming, preferably use the crystalline polyester resin particulate that makes it refrigerative dissolving method of cooling after by the organic solvent heating for dissolving and obtain.

The characteristic of operable in the present invention crystalline polyester resin particulate (E), resin intrinsic viscosity preferably 0.4～1.4d1/g, be more preferably 0.7～1.2d1/g.In addition, preferably 0～40 ℃ of glass tansition temperature, preferably 130～250 ℃ of fusing points.In addition, the volume average particle size of crystalline polyester resin particulate (E) is normally in the scope of 0.1～25 μ m, particularly 0.1～7 μ m.

Crystalline polyester resin particulate (E) also can use commercially available product.As commercially available product, for example, can enumerate " N-1000 " (trade(brand)name, Mitsubishi's レ イ イ ヨ Application (strain) are produced) etc.

The ratio of crystalline polyester resin particulate (D) and crystalline polyester resin particulate (E)

The crystalline polyester resin particulate (D) in coating (II) and the usage ratio of crystalline polyester resin particulate (E), based on the aggregate value of neutral corpuscle, the former is that 95～30 quality %, the latter are 5～70 quality %.When these particulates are dispersion state in organic solvent, in the solids component mated condition of particulate (D) and particulate (E), mix use to become this ratio ground.

The ratio one of crystalline polyester resin particulate (D) is greater than 95 quality %, the deep drawn processibility (D﹠amp that films; The I processibility) just descends.In addition, the ratio one of crystalline polyester resin particulate (D) is less than 5 quality %, and is undesirable because the fragrance retentivity of filming is descended.

The usage ratio of crystalline polyester resin particulate (D) and crystalline polyester resin particulate (E), aggregate value based on these particulates, preferably the former is that 90～40 quality %, the latter are 10～60 quality %, and more preferably the former is that 80～50 quality %, the latter are 20～50 quality %

Organic solvent (F)

Organic solvent (F), the solubleness of the solubleness of relative crystallinity vibrin particulate (D) and relative crystallinity vibrin particulate (E), all be below 40 ℃ for less than 5 quality %, be the organic solvent more than the 99 quality % more than 170 ℃.Organic solvent (F) is by being such solubleness, and coating composition of the present invention is mobile excellent dispersion state at normal temperature, and when being used to form the heating of filming, the common fusion of particulate (D) and particulate (E), formation are filmed uniformly.

Organic solvent (F), concrete, for example, can enumerate mixed solvent (170～205 ℃ of boiling spreads), N-N-methyl-2-2-pyrrolidone N-, isophorone of dimethyl adipate and Methyl glutarate and Succinic acid dimethylester etc.The mixed solvent of this dimethyl adipate and Methyl glutarate and Succinic acid dimethylester can use commercially available product.As commercially available product, for example, can enumerate " DBE " (trade(brand)name, デ ユ Port Application society produce) etc.

Total 100 mass parts of relative crystallinity vibrin particulate (D) and crystalline polyester resin particulate (E), the content of organic solvent (F) is 40～80 mass parts, from the dispersiveness of these particulates and painting operation for good.The content of organic solvent (F), total 100 mass parts of this particulate (D) and this particulate (E), preferably 50～500 mass parts relatively.

The vibrin (A) that contains hydroxyl

In tin paint (II), as required, can be engaged in the vibrin that contains hydroxyl (A) that uses in the above-mentioned tin paint (I).The vibrin (A) that contains hydroxyl, the resin that in the mensuration of being undertaken, does not show sharp melting point by differential scanning type calorimeter, it is dissolved resin in organic solvent easily under the normal temperature, when filming formation, can enumerate the crystalline polyester resin particulate (D) of molten state and the affinity and the high resin of intermiscibility of crystalline polyester resin particulate (E), or and the resin of the crystalline polyester resin particulate (D) of molten state and crystalline polyester resin particulate (E) reaction, formation successive layers.By such character, this vibrin (A) helps to improve the appearance of film of smoothness of filming of coating (II) etc.

The vibrin that contains hydroxyl (A) that cooperates in coating (II), is more preferably 65～110 ℃ at preferred 55～150 ℃, more preferably 60～120 ℃ of glass tansition temperatures (Tg).

Contain the raw material, manufacture method, commercially available product of the vibrin (A) of hydroxyl etc., as explanation in above-mentioned coating (I).

In tin paint (II), contain the vibrin (A) of hydroxyl, total solids component 100 mass parts of relative crystallinity vibrin particulate (D) and crystalline polyester resin particulate (E), cooperation 0.1～100 mass parts can make appearance of film improve.The use level of this resin (A), total 100 mass parts of this particulate (D) and this particulate (E), 5～100 mass parts preferably relatively.

Dispersion agent (G)

Dispersion agent (G) can be in order to improve crystalline polyester resin particulate (D) and crystalline polyester resin particulate (E) dispersiveness in organic solvent (F) and to use.

Dispersion agent (G) for example, can use the straight catenate high score subclass dispersion agent that has the affinity base at the monolateral end of main chain or two ends and particulate (D) and particulate (E).This affinity base can be enumerated uncle's amino, quaternary ammonium group, be had the heterocyclic radical of nitrogen-atoms etc., as straight catenate polymer, for example, can enumerate polyacrylic ester, urethane, polyester etc.In addition, such heterocyclic radical for example, can be enumerated pyrryl, imidazolyl, pyridyl, pyrimidyl etc.

The dispersion agent of such high score subclass can use commercially available product.As commercially available product, for example, can use " BYK-160 ", " BYK-161 ", " BYK-162 ", " BYK-180 ", " BYK-181 ", " BYK-182 " [trade(brand)name, above], " ソ Le ス パ one ス 20000 " (trade(brand)name, ゼ ネ カ society produce) etc. by the production of BYK Chemie (PVC Star Network ケ ミ one) society.

In addition, the also preferred phosphate compound that uses with following general formula (1) expression of dispersion agent (G).

(in the formula, R ¹, R ²And R ³, respectively identical or different, the aliphatic hydrocarbon of expression carbonatoms 6～18 or aromatic hydrocarbons or-C _mH _2mOC _nH _2n+1Here, m and n are the integers more than 1, and m+n is the integer more than 6.)

The phosphate compound of general formula (1), concrete, can enumerate 2-ethylhexyl diphenyl phosphate, three (2-ethylhexyl) phosphoric acid ester, three (butoxyethyl group) phosphoric acid ester, triphenyl, phosphoric acid trimethylbenzene phenolic ester etc.

These dispersion agents (G) can be independent a kind or make up more than 2 kinds and use.

The use level of dispersion agent (G), the viewpoint that improves from the dispersiveness that makes crystalline polyester resin particulate (D) and crystalline polyester resin particulate (E), relative total 100 mass parts of this resin particle (D) and resin particle (E), preferably 0.1～10 mass parts, be more preferably 0.5～5 mass parts.

Other composition

In tin paint (II), as required, can cooperate the vibrin resin in addition of resol resin, Resins, epoxy, aminoresin etc.Wherein, resol resin and Resins, epoxy are from making with the film adhesive raising of steel plate and preferred.

Resol resin, especially preferably with alcohol will be under catalysts, heating phenol composition and formaldehydes, make it to carry out condensation reaction importing methylol and a part of methylolation resol alkyl etherificate of obtaining and the resin that forms.

Operable phenolic compound in the manufacturing of resol resin, for example, can enumerate phenol, ortho-cresol, p-cresol, p-tert-butylphenol, to ethyl phenol, 2,3-xylenol, 2,5-xylenol, meta-cresol, an ethyl phenol, 3,5-xylenol, meta-methoxy phenol, dihydroxyphenyl propane, Bisphenol F etc.These phenolic compound can be independent a kind or mix more than 2 kinds and use.

Operable formaldehydes in the manufacturing of resol resin can be enumerated formaldehyde, Paraformaldehyde 96, trioxane etc.These can be independent a kind or mix more than 2 kinds and use.

Carry out operable alcohol in the alkyl etherificate at a part of methylol, can use 1～8 of carbonatoms, the preferred 1 valency alcohol that compatibly uses 1～4 of carbonatoms methylolation resol.As the 1 valency alcohol that is fit to, can enumerate methyl alcohol, ethanol, n-propyl alcohol, propyl carbinol, isopropylcarbinol etc.

The use level of soluble phenolic resin resol is from appearance of film and D﹠amp; I processibility equilibrated viewpoint is set out, total 100 mass parts of relative crystallinity vibrin particulate (D) and crystalline polyester resin particulate (E), preferred 0.1～10 mass parts, more preferably 0.5～5 mass parts.

Above-mentioned Resins, epoxy, when the vibrin that is crystalline polyester resin particulate (D) and/or crystalline polyester resin particulate (E) has carboxyl, play a role effectively as its linking agent, even when this Resins, epoxy does not have carboxyl, also by as the strongthener of vibrin or and the film forming component of the crosslinked generation of above-mentioned resol resin play a role effectively.

Add Resins, epoxy, as phenolic resin varnish type epoxy resin, can enumerate phenol novolak type epoxy resin, soluble phenolic resin type phenolic resin varnish type epoxy resin, have the various phenolic resin varnish type epoxy resins of the phenol oxalic dialdehyde type Resins, epoxy etc. of a plurality of epoxy group(ing) at intramolecularly.Wherein, obtain film performance equilibrated phenol novolak type epoxy resin easily, soluble phenolic resin type phenolic resin varnish type epoxy resin is fit to.

The use level of Resins, epoxy is from appearance of film and D﹠amp; I processibility equilibrated viewpoint is set out, total 100 mass parts of relative crystallinity vibrin particulate (D) and crystalline polyester resin particulate (E), preferred 0.5～20 mass parts, more preferably 2～10 mass parts.

In tin paint (II), as required, can also add and use other organic resin, wax, defoamer, flow agent, anti-agglutinant, tinting pigment, bright pigment, pigment extender, rust-stabilising pigment, organic solvent (F) organic solvent in addition etc.

Above-mentioned wax is used to adjust the kinetic friction coefficient of filming of tin paint (II) and adds, in application the carrying and the shaping of steel plate of said composition add man-hour, useful during the generation that is used to suppress to abrade etc.As wax, the wax of preferred softening temperature more than 30 ℃, more preferably 33～150 ℃ wax for example, can be enumerated the fatty acid ester wax, silicon class wax, fluorine class wax, polyolefin-wax, animal class wax, plant class wax of the carboxylate that is polyol compound and lipid acid etc.

The object lesson of above-mentioned wax is identical with the wax that uses in above-mentioned coating (I), and its raw material, method for making, commercially available product etc. are as what illustrate in above-mentioned coating (I).

In tin paint (II), the addition of wax, from the paint stability excellence and film and to tolerate the processibility aspect of deep drawn processing, total 100 mass parts of relative crystallinity vibrin particulate (D) and crystalline polyester resin particulate (E), preferably 5 mass parts following, be more preferably 0.5～2.5 mass parts.

Above-mentioned organic solvent (F) organic solvent in addition for example, can be enumerated the ketone of acetone, methylethylketone, mibk, pimelinketone, methylpentanone etc.; The alcohols of methyl alcohol, ethanol, 2-propyl alcohol, n-propyl alcohol, Virahol, 2-methyl isophthalic acid-propyl alcohol, 1-butanols, 2-methyl cellosolve etc.; Tetrahydrofuran (THF), 1,4-diox, 1, the ethers of 2-glycol dimethyl ether etc.; The ester class of ritalin, vinyl acetic monomer, N-BUTYL ACETATE etc.; The amides of dimethyl formamide, N,N-DIMETHYLACETAMIDE etc.; The hydro carbons of toluene, dimethylbenzene, hexanaphthene, normal hexane etc.; Methyl Benzene-o-dicarboxylate, diethyl phthalate, dibutyl phthalate, ethylene glycol monobutyl ether, diethylene glycol monobutyl ether etc.Can use these more than a kind or 2 kinds.

Above-mentioned curing catalysts, for example, as object lesson, can enumerate acid catalyst or these sour amine correctives of tosic acid, Witco 1298 Soft Acid, dinonylnaphthalene sulfonic acid, dinonylnaphthalene disulfonic acid, phosphoric acid etc.

The preparation of coating (II)

Tin paint (II), can be according to known method, by hybrid junctions crystallinity vibrin particulate (D), crystalline polyester resin particulate (E) and organic solvent (F) each must composition, as required, mix each any composition of the vibrin (A) that contains hydroxyl and dispersion agent (G) and above-mentioned other composition and prepare.

The coating that obtains (II), organic solvent type coating composition normally, becomes 5～50 quality % usually at the solid component content of coating composition.

In tin paint (II), from giving full play to the D﹠amp that films; The I processibility is set out, and preferred its solids component aggregate value relatively, the solids component aggregate value of crystalline polyester resin particulate (D) and crystalline polyester resin particulate (E) is adjusted into more than the 50 quality %.

The preparation of two surface coating steel plate for tank

Two surface coating steel plate for tank of the present invention form it by the face application tin paint (I) that becomes the outside after sheet pot processing and film, and the face application tin paint (II) that becomes the inboard after sheet pot processing forms it and films, and can easily prepare.

The application of tin paint (I) and tin paint (II) is not particularly limited in proper order, can be coated with earlier.In addition, two sintering of filming preferably carry out simultaneously.Concrete, for example by following coating process, the coated steel plate of the steel plate preparation two surface coating that can use etc. in beverage, food cans.

As preferred coating process, can be set forth in the operation of the face application tin paint (I) that becomes the sheet pot outside, in the operation of the face application tin paint (II) that becomes the sheet pot inboard, then, two coating that are coated by heating are filmed, the agglomerating operation, are obtained the method for two surface coating steel plate.

To the tin paint (I) of steel plate and the coating process of tin paint (II), there is no particular limitation.Two kinds of coating can be undertaken by for example atomized spray painting, roller coating machine application, episodic curtain coater application, the application of bar varnishing machine etc., but as to the effective coating process of steel plate, the roller coating machine application is fit to.

The glue spread of each coating is as follows.Tin paint (I), the dry coating amount before processing, 10～200mg/100cm preferably ², be more preferably 10～80mg/100cm ²In addition, tin paint (II), the dry coating amount before processing, 10～300mg/100cm preferably ², be more preferably 50～200mg/100cm ²

Two sintering temperatures of filming of application, preferably in coating (II) contained crystalline polyester resin particulate (D) and the temperature more than the fusing point (E), be more preferably the temperature higher 30～100 ℃ than this fusing point.Concrete sintering temperature, usually, preferably 180～300 ℃, be more preferably 200～280 ℃.In addition, sintering time, normally 1～180 second, the steel billet temperature of preferred especially coated article are held 5～60 seconds.Thus, two dried coating films of tin paint (I) and tin paint (II) or curing.

Then, filming behind the sintering, wish be blown into cold wind and a large amount of water coolants or in chilled water the method for impregnating cool off rapidly.By the rapid cooling behind this sintering, contained vibrin amorphization in will filming tin paint (I) and tin paint (II) two is from improving D﹠amp; The viewpoint of I processibility is set out to preferably.Speed of cooling, to become below 40 ℃, at 5 seconds with internal cooling, from obtaining D﹠amp; The viewpoint of filming of I excellent in workability is set out to preferably.

Operation like this, jar at steel plate is processed the back, is become on the face in the outside, with the filming of tin paint (I), become 1～20 μ m, especially preferably become 1～10 μ m with dry film thickness, and, jar at steel plate is processed the back, is become on the inboard face, with the filming of tin paint (II), become 1～30 μ m, especially preferably become 5～20 μ m with dry film thickness

If according to two surface coating steel plate for tank of the present invention, can obtain following unusual effect.

(1) becomes jar the filming of medial surface that forms by tin paint (II), normally film D﹠amp clearly; The film performance excellence of I processibility, boiling resistance, fragrance retentivity, wholesomeness, sticking power, preservative property, the smoothness of filming etc.In addition, becoming jar the filming of outer side that is formed by tin paint (I), is metal deposit or water white filming, printing color developing, D﹠amp; The film performance excellence of I processibility etc.

(2) two surface coating steel plate for tank of the present invention by implementing the processing of deep-draw processing or deep drawn, does not damage the printing color developing in the jar outside, at the jar inner face, can obtain excellent cylinder of steel body such as boiling resistance, fragrance retentivity, wholesomeness.Therefore, use two surface coating steel plate of the present invention and the tank body that obtains, can compatibly be used as beverages can and food cans.

Embodiment

Below, enumerate Production Example, embodiment and comparative example, illustrate in greater detail the present invention.But the present invention is not limited to these.In each example, " part " and " % " all is benchmark with the quality.

The manufacturing of tin paint (I)

Production Example 1

In the container of stirrer is housed, use mixed solvent (pimelinketone/dimethylbenzene=50 part/50 parts), 100 parts of (solids component) resins (A) " バ イ ロ Application 200 " (annotate 1), 6.3 parts of linking agents " サ イ メ Le 303 " (annotating 2), 43.8 parts of (solids component) pigment (C1) " ア Le ペ one ス ト 5640NS " (annotating 3), 6.3 parts of (solids component) waxes " S-394N1 " (annotating 4) are adjusted into viscosity 50 seconds (Ford cup #4,25 ℃), obtain a jar outside coating I-1.(annotating 1)～(annotating 4) represented following material.

(annotate 1) " バ イ ロ Application 200 ": trade(brand)name, Japan weaving society produce, contain 67 ℃ of vibrin, number-average molecular weight 17,000, hydroxyl value 6mgKOH/g, the glass tansition temperatures of hydroxyl.

(annotating 2) " サ イ メ Le 303 ": trade(brand)name, Japanese サ イ テ Star Network イ Application ダ ス ト リ-ズ (strain) production, methyl etherified melamine resin, molecular weight 600.

(annotating 3) " ア Le ペ one ス ト 5640NS ": trade(brand)name, the production of Japan ア Le ミ ニ ウ system society, non-floating type aluminium pigment paste, aluminum particulate median size 14 μ m, aluminium purity 99.8%.

(annotating 4) " S-394N1 ": シ ヤ system ロ Star Network society produces, polyethylene wax.

Production Example 2～3

Become beyond the content of table 1 and jar outer side is operated, obtained to Production Example 1 equally with a coating I-2～I-3.

Production Example 4

In the container of stirrer is housed, use mixed solvent (pimelinketone/dimethylbenzene=50 part/50 parts), after " バ イ ロ Application 200 " (the annotating 1) of 100 parts (solids components), 5.7 parts " サ イ メ Le 303 " (annotating 2), 64.9 parts of (solids component) pigment (C2) " JR-301 " (annotating 5), the even stirring of 5.4 parts of (solids component) " S-394N1 " (annotating 4), in sand mill, use 1mm Φ granulated glass sphere to disperse, obtain that colo(u)rant dispersion particle diameter 5 μ m are following, the jar outside coating I-4 of viscosity 50 seconds (Ford cup #4,25 ℃).The following material of (annotating 5) expression.

(annotating 5) " JR-301 ": the production of テ イ カ society, anatase type titanium oxide, median size 0.3 μ m

Production Example 5

Become beyond the cooperation content of table 1 and jar outer side coating I-5 is operated, obtained to Production Example 4 equally.

Contrast Production Example 1～4

Become beyond the content of table 2 and jar outer side is operated, obtained to Production Example 1 equally with a coating I-6～I-9.

Contrast Production Example 5

Become beyond the cooperation content of table 2 and jar outer side coating I-10 is operated, obtained to Production Example 4 equally.

The expression jar outer side cooperation content of coating I-1～I-10 in table 1 and table 2.Use level is all represented solids component (part).

[table 1]

Production Example		1	2	3	4	5
							Use coating No. outside jar		I-1	I-2	I-3	I-4	I-5
Resin (A)	" バ イ ロ Application 200 " (annotating 1)	100	100	100	100
							" エ リ one テ Le UE3600 " (annotating 6)					100
	Linking agent (B)	" サ イ メ Le 303 " (annotating 2)	6.3	5.6	6.1	5.7							4.6
Pigment (C1)							" ア Le ペ one ス ト 5640NS " (annotating 3)	43.8	27.8	9.8
	Pigment (C2)	" JR-301 " (annotating 5)				64.9							99.6
Wax							" S-394N1 " (annotating 4)	6.3	5.6	6.1	5.4	6.8

[table 2]

The contrast Production Example		1	2	3	4	5
							Use coating No. outside jar		I-6	I-7	I-8	I-9	I-10
Resin (A)	" バ イ ロ Application 200 " (annotating 1)	100	100	100	100	100
							" エ リ one テ Le UE3600 " (annotating 6)
	Linking agent (B)	" サ イ メ Le 303 " (annotating 2)	6.3	6.3	6.3	6.3							6.3
Pigment (C1)							" ア Le ペ one ス ト 5640NS " (annotating 3)	1.0	3.0	80	100
	Pigment (C2)	" JR-301 " (annotating 5)											160
Wax							" S-394N1 " (annotating 4)	6.3	6.3	6.3	6.3	6.3

In table 1 and table 2, " エ リ one テ Le UE3600 " (annotating 6) represented following content.

(annotating 6) " エ リ one テ Le UE3600 ": trade(brand)name, ユ ニ チ カ society produce, contain vibrin, number-average molecular weight 20,000, the hydroxyl value 4mgKOH/g of hydroxyl.

The manufacturing of tin paint (II)

The manufacturing of Production Example 6 crystallinity pet resin particulates

Polyprotonic acid composition, the raw material that becomes terephthalic acid/isophthalic acid=85 mole %/15 moles of % are formed, in addition, the raw material that polyhydroxy reactant, ethylene glycol are become 100 moles of % is formed and the pet resin (PET) that obtains, pulverize with micronizer mill cooling by usual method, classification repeatedly, obtain crystallinity pet resin particulate (being called PET-No.1).

The manufacturing of Production Example 7 crystallinity pet resin particulates

The pet resin that use is formed at raw material shown in the table 3, with this resin and 400 parts " DBE " (trade(brand)name, production of デ ユ Port Application society, the mixed solvent of dimethyl adipate, Methyl glutarate, Succinic acid dimethylester, 205 ℃ of boiling points) heating for dissolving while stirring together, then, after dropping into 500 parts of pimelinketone (155 ℃ of boiling points) while cooling off, crystal fine grain being separated out, filtration and drying under reduced pressure, obtain crystallinity pet resin particulate (being called PET-No.2).

The manufacturing of Production Example 8 crystallinity pet resin particulates

The pet resin that use is formed at raw material shown in the table 3, dissolution solvent is changed to N-N-methyl-2-2-pyrrolidone N-(202 ℃ of boiling points) in addition, operate equally with Production Example 2, obtain crystallinity pet resin particulate (being called PET-No.3).

The manufacturing of Production Example 9 crystallinity pet resin particulates

The polybutylene terephthalate resin that use is formed at raw material shown in the table 2, with this resin and 400 parts " DBE " (trade(brand)name, production of デ ユ Port Application society, the mixed solvent of dimethyl adipate, Methyl glutarate, Succinic acid dimethylester, 205 ℃ of boiling points) heating for dissolving while stirring together, then, after dropping into 500 parts of pimelinketone (155 ℃ of boiling points) while cooling off, crystal fine grain being separated out, filtration and drying under reduced pressure, obtain crystallinity polybutylene terephthalate resin particle (being called PBT-No.1).

The manufacturing of Production Example 10 crystallinity polybutylene terephthalate resin particles

Use beyond the polybutylene terephthalate resin that raw material shown in the table 3 is formed and Production Example 4 operate equally, obtain crystallinity polybutylene terephthalate resin particle (being called PBT-No.2).

Being illustrated in the crystallinity pet resin particulate that Production Example 6～10 obtains and the raw material of crystallinity polybutylene terephthalate resin particle in table 3 forms and resin intrinsic viscosity, glass tansition temperature, fusing point and volume average particle size.

[table 3]

Production Example		6	7	8	9	10
							The resin particle title		PET-No.1	PET-No.2	PET-No.3	PBT-No.1	PBT-No.2
Raw material is formed (mole %)	Ethylene glycol	100	100	100
							1, the 4-butyleneglycol				100	100
	Terephthalic acid	85	85	100	100	95
							M-phthalic acid	15	10
	Hexanodioic acid		5
							Sebacic acid					5
	Resin properties	Resin intrinsic viscosity (IV)	0.7	0.8	0.9	0.9							1.1
The glass tansition temperature (℃)							71	60	74	35	25
		Fusing point (℃)	223	209	255	223						217
Volume average particle size (μ m)							8.6	3.4	5.6	6.6	5.5

The manufacturing of Production Example 11 jar coating composition II-1

Will be with the paint vibrator 50 parts of PET-No.1 shown in the table 3,50 parts of PBT-No.1,500 parts " DBE " (annotating 7), 5 parts " BYK-161 " (annotating 8) and 2 parts (solids component) " シ ヨ one ノ one Le CKS394 " (notes 9) blending dispersion 60 minutes, in pimelinketone/dimethylbenzene (50/50 mass ratio), adjust solids component, obtain the inboard coating II-1 that uses of jar of solids component 12%.(annotating 7)～(annotating 9) represented following content.

(annotating 7) " DBE ": the mixed solvent of trade(brand)name, the production of デ ユ Port Application society, dimethyl adipate, Methyl glutarate, Succinic acid dimethylester.

(annotating 8) " BYK-161 ": trade(brand)name BYK Chemie (PVC Star Network ケ ミ-) society produces, is the dispersion agent of the urethane resin of hydroxyl value 11mgKOH/g.

(annotate 9) " シ ヨ one ノ one Le CKS394 ": trade(brand)name, clear and polymer (strain) is produced, resol resin.

The manufacturing of coating II-2～II-8 of 12～18 jars of medial surfaces of Production Example

Become beyond the cooperation content of table 4 and jar medial surface that solids component 12% was operated, obtained to Production Example 11 equally with coating II-2～II-8.

The expression jar medial surface cooperation content of coating II-1～II-8 in table 4.Use level is all represented solids component.

[table 4]

Production Example		11	12	13	14	15	16	17	18
										The inboard coating No. that uses of jar		II-1	II-2	II-3	II-4	II-5	II-6	II-7	II-8
Resin particle (D)	PET-No.1	50			30			10	95
										PET-No.2		80		30	30	50
	PET-No.3			40			10	20
										Resin particle (E)	PBT-No.1	50		60	30	70	40	50
PBT-No.2		20		10			20	5
									Organic solvent (F)		The N-N-methyl-2-2-pyrrolidone N-			200	100	100	50	100	40
" DBE " (annotating 7)	500	300	200	100	200	100	300	10
										Resin (A)	" GK-640 " (annotating 10)						60	10	100
Dispersion agent (G)	" BYK-16 " (annotating 8)	5			5		3	5	2
										2-ethylhexyl diphenyl phosphate		3			3
	" シ ヨ one ノ one Le CKS394 " (annotating 9)		2		5		3		5
Diluting solvent										Pimelinketone/methylethylketone	In right amount

In table 4, the cooperation ratio of resin (D) and dispersion agent (G) is represented solids component.In addition, " GK-640 " (annotating 10) represented following content.

(annotate 10) " GK-640 ": trade(brand)name, Japan weaving society produce, contain 79 ℃ of vibrin, number-average molecular weight 18000, hydroxyl value 5mgKOH/g, the glass tansition temperatures of hydroxyl.

The manufacturing of coating II-9～II-10 of 5～6 jars of medial surfaces of contrast Production Example

Become beyond the cooperation content of table 5 and jar medial surface that solids component 12% was operated, obtained to Production Example 11 equally with coating II-9～II-10.

The expression jar medial surface cooperation content of coating II-9～II-10 in table 5.Use level is all represented solids component.

[table 5]

The contrast Production Example		5	6
				Jar medial surface coating No.		II-9	II-10
Resin particle (D)	PET-No.1
				PET-No.2	100
	PET-No.3		20
				Resin particle (E)	PBT-No.1
PBT-No.2		80
			Organic solvent (F)		The N-N-methyl-2-2-pyrrolidone N-	200	50
" DBE " (annotating 7)		200
				Resin (A)	" GK-640 " (annotating 10)
Dispersion agent (G)	" BYK-16 " (annotating 8)	5
				2-ethylhexyl diphenyl phosphate		5
	" シ ヨ one ノ one Le CKS394 " (annotating 9)						2
Diluting solvent				Pimelinketone/methylethylketone	In right amount

The preparation of two surface coating steel plate

Embodiment 1

Coated article uses sheet iron of wuxi (thickness 0.22mm, total chromium adhesion amount 120mg/m ²), according to following operation 1～operation 3, make two surface coating steel plate No.1.

Operation 1: the coated article surface that obtains in Production Example 19 becomes dry film thickness 5 μ m ground with bar varnishing machine lacquered can outer side coating I-1, with 80 ℃ of 60 seconds of drying, make solvent evaporates.

Operation 2:, become dry film thickness 10 μ m ground with bar varnishing machine lacquered can medial surface coating II-1 in this coated article the inside.

Operation 3: then, become 20 seconds of condition sintering that are up to 270 ℃ of Da Wendu, after this promptly drop in 20 ℃ the water coolant with coated article.

Embodiment 2～8

Become beyond the coating of table 6 and the operation content and embodiment 1 operates, makes two surface coating steel plate No.2～No.8 equally.

In table 6, to coated steel plate No.1～No.8, expression operation 1～3.

[table 6]

Embodiment		1	2	3	4	5	6	7	8
										Two surface coating steel plate No.		1	2	3	4	5	6	7	8
Operation 1	Use coating outside jar	I-1	I-2	I-3	I-4	I-5	I-1	I-1	I-1
										Thickness (μ m)	5	5	5	5	5	5	5	5
	Operation 2	Jar inboard coating	II-1	II-2	II-3	II-4	II-5	II-6	II-7										II-8
Thickness (μ m)										10	10	10	10	10	10	10	10
		Operation 3	Sintering temperature (℃)	270	270	270	270	280	280									280	280
Sintering time (second)	20									20	20	20	20	20	20	20

Comparative example 1

Coated article uses sheet iron of wuxi (thickness 0.22mm, total chromium adhesion amount 120mg/m ²), according to following operation 1～operation 3, make two surface coating steel plate No.9.

Operation 1: the coated article surface that obtains in Production Example 19 becomes dry film thickness 5 μ m ground with bar varnishing machine lacquered can outer side coating I-1.

Operation 2:, become dry film thickness 10 μ m ground with bar varnishing machine lacquered can medial surface coating II-9 in this coated article the inside.

Operation 3: then, become 20 seconds of condition sintering that are up to 270 ℃ of Da Wendu, after this promptly drop in 20 ℃ the water coolant with raw material.

Comparative example 2～9

Become beyond the coating of table 7 and the operation content and two surface coating steel plate No.10～No.17 is operated, made to comparative example 1 equally.

In table 7, to coated steel plate No.9～No.17, expression operation 1～3.

[table 7]

Comparative example		1	2	3	4	5	6	7	8	9
											Two surface coating steel plate No.		9	10	11	12	13	14	15	16	17
Operation 1	Use coating outside jar	I-1	I-2	I-3	I-4	I-6	I-7	I-8	I-9	I-10
											Thickness (μ m)	5	5	5	5	5	5	5	5	5
	Operation 2	Jar inboard coating	II-9	II-9	II-10	II-10	II-1	II-1	II-1	II-1											II-1
Thickness (μ m)											10	10	10	10	10	10	10	10	10
		Operation 3	Sintering temperature (℃)	270	270	270	270	270	270	270										270	270
Sintering time (second)	20										20	20	20	20	20	20	20	20

To the two surface coating steel plate No.10～No.17 of embodiment 1～8 and comparative example 1～9, with following test method investigation outer side with 50 ℃ of pencil hardnesss of filming, 60 ℃ of kinetic friction coefficient, D﹠amp; I processibility and printing color developing, in addition, the investigation medial surface D﹠amp that films; I processibility, boiling resistance, fragrance retentivity and wholesomeness.

50 ℃ of pencil hardnesss: place each coated steel plate on 50 ℃ the hot-plate being set at, confirm that with land surface pyrometer specimen surface becomes 50 ℃ after, according to JIS K-5400 8.4.2 (1990), carry out pencil and scratch test.Evaluation is carried out with the method for breaking.

60 ℃ of kinetic friction coefficient: the hot-plate of " FRICTION TESTER TR-2 " (trade(brand)name, the production of Japan smart machine society, kinetic friction determinator) is set at 60 ℃, place each coated steel plate thereon, after confirming that with land surface pyrometer specimen surface becomes 60 ℃, measure kinetic friction coefficient with loading 2kg, draw speed 1000mm/ minute condition.

D﹠amp; The I processibility: according to following formula, with each coated steel plate carry out deep drawn be processed as tank body the thick rate that subtracts of thin part become N=60%.

Subtract thick rate N=1-(n ₁/ n ₀)

(in the formula, n ₁Be thickness, the n of the coated steel plate after the processing ₀Be the thickness of the coated steel plate before the processing.)。

Then, cut extend smooth jar that obtains, with the state of following benchmark evaluation " medial surface is with filming " and " outer side is with filming ".

◎: the albefaction that on filming, does not have crackle and cause, and smoothness excellence by processing.

Zero: on filming, do not have crackle, can confirm that albefaction is arranged slightly.

△: on filming, can confirm crackle, but peeling off of can not confirming to film.

*: that can confirm to film peels off and comes off.

Printing color developing: cut at above-mentioned " D﹠amp; The I processibility " test in the smooth jar tank body of extending that obtains, being coated with loading amount after its outer side is with drying on filming becomes 3.6g/m ²Ground is with bar varnishing machine application vibrin/melamine resin curing pigmented coating (trade(brand)name " KP-1593 is white ", Northwest ペ イ Application ト (strain) production, coating white), material becomes and is up to 60 seconds of 220 ℃ of Da Wendu ground sintering, forms the white printing and films.

Use " カ ラ one コ Application ピ ユ one SM-4 " (trade(brand)name, ス ガ trier (strain) are produced, colour meter), measure that this white printing films based on the L that in JIS Z8729, stipulates ^*a ^*b ^*Brightness (the L of coloring system ^*Value), by following benchmark evaluation printing color developing.

Zero: L ^*Value is more than 70, and the printing color developing is good.

*: L ^*Value is less than 70, and the printing color developing is bad.

Boiling resistance: each coated steel plate is immersed in the water, with following benchmark evaluation in autoclave, 125 ℃ of medial surfaces when handling 30 minutes are with the albefaction state of filming.

Zero: can not confirm albefaction fully.

△: can confirm albefaction slightly.

*: can confirm significant albefaction.

Fragrance retentivity: in deionized water, add the concentration that d-limonene (spices) becomes 30mg/l, add again " S-1170 " (trade(brand)name, Mitsubishi Chemical society produce, sucrose fatty ester) become 1g/l concentration and in the dispersive liquid, with 35 ℃ of dippings, store each coated steel plate 1 month that the sealing outer side is used the side of filming.After the storage, in order to be determined at the d-limonene (spices) of adhering in filming, after the erasing medial surface film coated surface, in 20 ℃ of 1 weeks of dipping in ether, the d-limonene of extracting with gas Chromatographic Determination (spices) is with following benchmark evaluation.

Zero: the d-limonene (spices) that is extracted is less than 0.6mg at the medial surface every 120mg of weight that films, fragrance retentivity excellence.

△: the d-limonene (spices) that is extracted is more than the 0.6mg, less than 1.6mg at the medial surface every 120mg of weight that films, and the fragrance retentivity is bad.

*: the d-limonene (spices) that is extracted is more than the 1.6mg at the medial surface every 120mg of weight that films, and the fragrance retentivity is poor.

Wholesomeness: relative coating area 1cm ², the tap water crossed of activated carbon treatment the amount ratio ground that becomes 1ml will seal film each coated steel plate of a side of outer side usefulness, dipping in the bottle that the thermal glass that is full of the tap water that activated carbon treatment crosses is made carries out handling in 30 minutes with 125 ℃ in the autoclave of adding a cover.To the content liquid after handling, according to the test method of food hygiene law record, based on consumption (ppm), the evaluation wholesomeness of potassium permanganate.

◎: consumption is less than 2ppm, wholesomeness excellence.

Zero: consumption is that 2ppm is above, good less than 5ppm, wholesomeness.

△: consumption is that 5ppm is above, bad less than 10ppm, wholesomeness.

*: consumption is that 10ppm is above, wholesomeness is poor.

Result in table 8 and the test of table 9 expression film performance.

[table 8]

Embodiment		1	2	3	4	5	6	7	8
										Two surface coating steel plate No.		1	2	3	4	5	6	7	8
The jar outside is with filming	50 ℃ of pencil hardnesss	2H	2H	2H	2H	3H	3H	3H	3H
										60 ℃ of kinetic friction coefficient	0.20	0.14	0.12	0.11	0.11	0.18	0.18	0.18
	The D﹠I processibility	○	◎	◎	◎	○	○	○	○
										The printing color developing	○	○	○	○	○	○	○	○
	Jar is inboard with filming	The D﹠I processibility	◎	◎	○	◎	○	◎	○										○
Boiling resistance										○	○	○	○	○	○	○	○
		The fragrance retentivity	○	○	○	○	○	○	○									○
Wholesomeness										◎	◎	◎	◎	◎	○	◎	○

[table 9]

Comparative example		1	2	3	4	5	6	7	8	9
											Two surface coating steel plate No.		9	10	11	12	13	14	15	16	17
The jar outside is with filming	50 ℃ of pencil hardnesss	2H	2H	2H	2H	2H	2H	2H	2H	2H
											60 ℃ of kinetic friction coefficient	0.20	0.14	0.12	0.11	0.16	0.14	0.11	0.12	0.12
	The D﹠I processibility	○	◎	◎	◎	◎	◎	×	×	×
											The printing color developing	○	○	○	○	×	×	-	-	-
	Jar is inboard with filming	The D﹠I processibility	△	△	○	○	◎	◎	◎	◎											◎
Boiling resistance											×	×	△	△	○	○	○	○	○
		The fragrance retentivity	○	○	×	×	○	○	○	○										○
Wholesomeness											○	○	△	△	◎	◎	◎	◎	◎

In table 9, "-" on printing color developing hurdle, expression is because peeling off of filming and come off and can not estimate.

Claims (14)

1. two surface coating steel plate for tank, after jar processing, become the face in the outside, formation contains the vibrin (A) of hydroxyl, be selected from by at least a kind of linking agent (B) of aminoresin and resol resin and relative this vibrin (A) 100 mass parts solids components is the filming of tin paint (I) of the white pigment (C2) of the aluminium pigment (C1) of 5～60 mass parts or 60～140 mass parts, and after jar processing, become inboard face, formation contains the crystalline polyester resin particulate (D) based on the ethylene glycol terephthalate monomer, based on the crystalline polyester resin particulate (E) of mutual-phenenyl two acid bromide two alcohol ester's monomer and contain the solubleness of this particulate (D) and all be less than 5 quality % below 40 ℃ to the solubleness of this particulate (E), more than 170 ℃ all be organic solvent (F) more than the 99 quality %, the ratio of this particulate (D) and this particulate (E), based on their total amount, the former is 95～30 quality %, the latter is 5～70 quality %, and total 100 mass parts of the content relatively small particle (D) of organic solvent (F) and particulate (E) are the filming of tin paint (II) of 40～800 mass parts.

2. two surface coating steel plate for tank as claimed in claim 1, the dry film thickness that tin paint (I) is filmed are that the dry film thickness that 1～20 μ m and tin paint (II) are filmed is 1～30 μ m.

3. two surface coating steel plate for tank as claimed in claim 1, the aluminium pigment (C1) of tin paint (I) are non-floating type aluminium pigment.

4. two surface coating steel plate for tank as claimed in claim 1, the crystalline polyester resin particulate (D) of tin paint (II) are that the resin intrinsic viscosity is that 0.4～1.4dl/g, glass tansition temperature (Tg) are that 55～130 ℃, fusing point (Tm) are 160～260 ℃ resin particle.

5. two surface coating steel plate for tank as claimed in claim 1, the particulate that the crystalline polyester resin particulate (D) of tin paint (II) is made up of 80 moles of vibrin more than the % of ethylene glycol terephthalate monomer containing ratio.

6. two surface coating steel plate for tank as claimed in claim 1, the crystalline polyester resin particulate (E) of tin paint (II) are that the resin intrinsic viscosity is that 0.4～1.4dl/g, glass tansition temperature (Tg) are that 0～40 ℃, fusing point (Tm) are 130～250 ℃ resin particle.

7. two surface coating steel plate for tank as claimed in claim 1, the particulate that the crystalline polyester resin particulate (E) of tin paint (II) is made up of 90 moles of vibrin more than the % of mutual-phenenyl two acid bromide two alcohol ester's monomer containing ratio.

8. two surface coating steel plate for tank as claimed in claim 1, total 100 mass parts of tin paint (II) relative crystallinity vibrin particulate (D) and crystalline polyester resin particulate (E) also contain the vibrin (A) of the hydroxyl of 0.1～100 mass parts.

9. two surface coating steel plate for tank as claimed in claim 8, the vibrin that contains hydroxyl (A) of tin paint (II), glass tansition temperature (Tg) is 55～150 ℃.

10. two surface coating steel plate for tank as claimed in claim 1, tin paint (II) also contains dispersion agent (G).

11. two surface coating steel plate for tank as claimed in claim 10, dispersion agent (G) are the phosphate compounds with general formula (1) expression,

In the formula, R ¹, R ²And R ³Respectively identical or different, the aliphatic hydrocarbon of expression carbonatoms 6～18 or aromatic hydrocarbons or-C _mH _2mOC _nH _2n+1, here, m and n are that integer more than 1 and m+n are the integers more than 6.

12. two surface coating steel plate for tank as claimed in claim 1, total 100 mass parts of tin paint (II) relative crystallinity vibrin particulate (D) and crystalline polyester resin particulate (E) also contain the resol resin of 0.1～10 mass parts.

13. two surface coating steel plate for tank as claimed in claim 1, total 100 mass parts of tin paint (II) relative crystallinity vibrin particulate (D) and crystalline polyester resin particulate (E) also contain the Resins, epoxy of 0.5～20 mass parts.

14. a cylinder of steel body is processed two surface coating steel plate for tank as claimed in claim 1 and is obtained by deep-draw processing or deep drawn.