Title of Invention

"SURFACE TREATED STEEL SHEET"

Abstract

A surface treated steel sheet has a surface treatment film including a metallic compound containing titanium, a metallic compound containing magnesium, a cationic urethane resin having at least one cationic functional group selected from primary to tertiary amino groups and quaternary ammonium bases, and a cationic phenol polycondensate which is a polycondensate of a phenol compound with an aldehyde and has a cationic functional group, wherein the titanium content in the surface treatment film is in the range of 1 mass% to 4 mass% based on a total solid content; the magnesium content in the surface treatment film is in the range of 0.2 mass% to 2 mass% based on a total solid content; the cationic urethane resin content in the surface treatment film is in the range of 20 mass% to 35 mass% based on a total solid content; the cationic phenol polycondensate content in the surface treatment film is in the range of 25 mass% to 40 mass% based on a total solid content; and the mass ratio of the cationic urethane resin to the cationic phenol polycondensate is in the range of 33.3:66.7 to 49:51.

Full Text

[Document Type] SPECIFICATION [Title of the Invention] SURFACE TREATED STEEL SHEET [Technical Field] [0001] The present invention relates to a surface treated steel sheet suitable for use in household appliances, building materials, or the like, particularly to an environment-friendly, surface treated steel sheet for which chromium is not used upon production and chromium is not contained at all in the product The application claims priority from Japanese Patent Application No 2006-343531, and the content of which is incorporated herein by reference [Background Art] [0002] On a surface of a zinc-plated steel sheet for use in household appliances and building materials, white rust may be formed under a salt component-, such as sea water, containing atmosphere or a high temperature and high humid atmosphere In this case, the appearance may be significantly deteriorated or ability for protecting a surface of iron base may be lowered In the past, a chromate-based surface treatment agent containing chromium has been used to prevent white rust However, regulations on chrome has been significantly intensified in view of problems of effects on environment and the human body, and in response to this, development of a chromium-free surface treatment agent has been proceeded [0003] As a method for treating the surface of a metallic material with a chromium-free surface treatment agent, in Patent Document 1, there disclosed a method for treating a surface with the use of a metal surface treatment agent containing a specific silane coupling agent and a phenolic resin-based polymer with a specific structure In Patent Document 2, there disclosed a method for treating a surface with the use of a metal surface treatment agent containing a silane coupling agent, silica, and a specific metallic compound as the essential components, and further optionally comprising a thiocarbonyl group-containing compound and/or a water-soluble acrylic resin Further, m Patent Document 3, there disclosed a method for treating a surface with the use of a metal surface treatment agent containing a specific water-soluble resin or water-based emulsion resin, a phenolic resin-based polymer with a specific structure, and a specific metallic compound [0004] However, the above-mentioned methods are not for forming a film imparting high corrosion resistance in place of the chromate-based surface treatment agent In particular, corrosion resistance of scratched parts and formed parts, or corrosion resistance after degreasmg with alkali, is deteriorated as compared to the chromate film Consequently, development of a method for treating a surface having a corrosion resistance equal to or better than that of a chromate film and not containing chromium has been demanded [0005] Furthermore, as a method for treating the metallic material surface containing no chromium, in Patent Document 4, there disclosed a surface treatment agent for metal prepared by blending a catiomc urethane resin, a catiomc polycondensate of a phenolic compound, a zirconium compound, and/or a titanium compound, in an aqueous medium, a surface treatment method, and a surface treated metallic material In Patent Document 5, there disclosed a metal surface treatment agent prepared by blending a catiomc urethane resm, a catiomc polycondensate of a phenolic compound, a zirconium compound, and a compound containing at least one metal selected from Li, Mg, Al, Ca, Mn, Co, Ni, Zn, Sr, W, Ce, and Mo, in an aqueous medium, a surface treatment method, and a surface treated metallic material In addition, in Patent Document 6, there disclosed a metal surface treatment agent prepared by blendmg a catiomc urethane resin, a catiomc polycondensate of a phenolic compound, a titanium compound, and a compound containing at least one metal selected from Li, Mg, Al, Ca, Mn, Co, Ni, Zn, Sr, W, Ce, and Mo, in an aqueous medium, a surface treatment method, and a surface treated metallic material, etc [0006] [Patent Document 1] Japanese Unexamined Patent Application, First Publication No H09-241576 [Patent Document 2] Japanese Unexamined Patent Application, First Publication No 2001-31684 [Patent Document 3] Japanese Unexamined Patent Application, First Publication No 2003-13252 [Patent Document 4] Japanese Unexamined Patent Application, First Publication No 2006-118012 [Patent Document 5] Japanese Unexamined Patent Application, First Publication No 2006-152435 [Patent Document 6] Japanese Unexamined Patent Application, First Publication No 2006-152436 [Disclosure of the Invention] [Problems to be Solved by the Invention] [0007] However, the above-mentioned three methods are not satisfactory m providmg corrosion resistance on a planar surface (white rust resistance) and ethanol resistance, particularly corrosion resistance after forming such as cup molding which is close to an actual use than the simple bulge molding Consequently, development of a method for treating the surface having corrosion resistance after forming which is required, for example, in motor cases or cartridge tanks for kerosene stoves and containing no chromium has been demanded [0008] The present invention is to solve the problems of related art mentioned above, and an object of which is to provide a chromium-free, steel sheet subjected to a metal surface treatment, for which a film excellent in corrosion resistance after forming can be formed on the surface of a zmc-plated steel sheet [Means for Solving the Problems] [0009] The present mventors have earned out an investigation on constitutions of a film for a surface treated steel sheet to solve the above-mentioned problems As a result, they have found that a surface treated steel sheet excellent in corrosion resistance after forming can be obtained by forming on the surface of a zmc-plated steel sheet, a surface treatment film which includes a metallic compound containing titanium, a metallic compound containing magnesium, an urethane resin containing a specific cationic functional group, and a catiomc phenol polycondensate with a specific chemical structure, and thus they have completed the present invention [0010] That is, the present invention provides a surface treated sheet including a surface treatment film which mcludes (A) a metallic compound containing titanium (hereinafter, referred to as 'titanium compound (A)'), (B) a metallic compound containing magnesium (hereinafter, referred to as 'magnesium compound (B)'), (C) a catiomc urethane resin having at least one catiomc functional group selected from primary to tertiary ammo groups and quaternary ammonium bases, and (D) a catiomc phenol polycondensate which is a polycondensate of a phenol compound with an aldehyde and has a catiomc functional group, wherein the titanium content m the surface treatment film is m the range of 1 mass% to 4 mass% based on a total solid content, the magnesium content in the surface treatment film is m the range of 0 2 mass% to 2 mass% based on a total solid content, a content of the catiomc urethane resin (C) in the surface treatment film is m the range of 20 mass% to 35 mass% based on a total solid content, a content of the catiomc phenol polycondensate (D) in the surface treatment film is in the range of 25 mass% to 40 mass% based on a total solid content, and the mass ratio of the catiomc urethane resin (C) to the catiomc phenol polycondensate (D) is in the range of 33 3 66 7 to 49 51 [0011] The coating weight of the surface treatment film may be in the range of from 0 1 g/m2 to 3 g/m2 In addition, an organic-inorganic composite film may be further formed on an upper layer of the surface treatment film in a coating weight of 0 2 g/m to 5 g/m [Effects of the Invention] [0012] The chromium-free surface treated steel sheet related to the present mvention provides corrosion resistance after forming equal to or better than that provided with a chromate-based surface treatment agent The production method thereof is also simple and the steel sheet can be produced at low cost [Best Mode for Carrying Out the Invention] [0013] Hereinbelow, preferred embodiments of the present invention will be described in detail [0014] For the titanium compound (A) in a composition for surface treatment in the invention, there are no particular limitation for counter anions, but examples may include oxides, hydroxides, complex compounds and salts with organic or inorganic acids of titanium, and the like, and those having a good compatibility with the catiomc urethane resin (C) and the catiomc phenol polycondensate (D) are preferable Specific examples of the titanium compound (A) include titanyl sulfate T1OSO4, diisopropoxytitamum bisacetylacetone (C5H702)2Ti[OCH(CH3)2]2, a reaction product of lactic acid and titanium alkoxide, titanium laurate, titanium acetylacetonate Ti(OC(=€H2)CH2COCH3))3, titanium acetate, titanium nitrate, titanium sulfate, titanium phosphate, titanium carbonate, titanium hydrofluorate, ammonium fluorotitanate, and the like [0015] The titanium compound (A) contains 1 mass% to 4 mass% of titanium based on a total solid content At a content less than 1 mass%, corrosion resistance on a planar surface (white rust resistance) is insufficient, and at a content greater than 4 mass%, the resin readily forms into a gel in a coating liquid state, thereby causing a deteriorated corrosion resistance after cylindrical forming due to an insufficient film formabihty [0016] For the magnesium compound (B) in a composition for surface treatment in the invention, there are no particular limitation for counter anions, but examples may include oxides, hydroxides, complex compounds and salts with organic or inorganic acids of magnesium, and the like, and those havmg a good compatibility with the catiomc urethane resm (C) and the catiomc phenol polycondensate (D) are preferable Specific examples include magnesium nitrate, magnesium sulfate, magnesium biphosphate, magnesium carbonate, magnesium acetate, magnesium fluoride, magnesium oxide, magnesium hydroxide, and the like [0017] The magnesium compound (B) contains 0 2 mass% to 2 mass% of magnesium based on a total solid content At a content less than 0 2 mass%, corrosion resistance on a planar surface (white rust resistance) is insufficient, and at a content greater than 2 mass%, the resin readily forms into a gel in a coating liquid state, thereby causing a deteriorated corrosion resistance after cylindrical forming due to an insufficient film formabihty In addition, coatability of top coating tends to deteriorate [0018] The contents of titanium and magnesium in the above-described composition for surface treatment can be, for example, determined with the use of ICP (Inductively Coupled Plasma) emission spectrometry or the like [0019] The term 'cationic' for the catiomc urethane resin (C) which to be blended m the metal surface treatment agent of the present invention means that the resin has a catiomc functional group in the molecular structure The catiomc functional group may be exemplified by groups represented by the following general formulas (I) to (IV), or the like The catiomc functional group may be included in any amount as long as the resin stably exists in a dissolution or dispersion state in the metal surface treatment agent of the invention [0020] (Formula Removed) [0021] Herein, R1, R2, R3, R6, and R7 rn general formulas are each independently a hydrogen atom, a linear or branched alkyl group having 1 to 10, preferably 1 to 6 carbon atom(s), or a linear or branched hydroxyalkyl group having 1 to 10, preferably 1 to 6 carbon atom(s) R4 and R5 are each mdependently a linear or branched alkylene group having 2 to 10, preferably 2 to 6 carbon atoms Each of A" and B" represents a hydroxyl ion or an acid ion [0022] Examples of the alkyl group having 1 to 10 carbon atom(s) represented for R , R2 , R3 , R6 and R7 in the above general formulas (I), (II), (III), and (IV) include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a nonyl group, a decyl group, and the like In addition, examples of the hydroxyalkyl group having 1 to 10 carbon atom(s) include a hydroxymethyl group, a 2-hydroxyethyl group, a 1-hydroxyethyl group, a 3-hydroxypropyl group, a 4-hydroxybutyl group, a 5-hydroxypentyl group, a 6-hydroxyhexyl group, a 7-hydroxyheptyl group, an 8-hydroxyoctyl group, a 9-hydroxynonyl group, a 10-hydroxydecyl group, and the like Examples of the alkylene group having 2 to 10 carbon atoms represented for R4 and R5 m the general formulas (III) and (IV) mclude an ethylene group, a propylene group, a tnmethylene group, a tetramethylene group, a pentamethylene group, a hexamethylene group, an octamethylene group, a 2-ethyl-hexylene group, a decamethylene group, and the like Examples of the acid ion represented for A and B in the general formulas (II) and (IV) include inorganic acid ions such as halogen ion (chlorine ion, bromine ion, fluorine ion, etc ), sulfate ion, nitrate ion, and phosphate ion, and organic acid ions such as acetate ion and formate ion [0023] The cationic urethane resin (C) useful in the invention, for example, may either be a water-soluble or aqueous emulsion type [0024] The cationic urethane resin (C) for use in the invention needs to have the cationic functional group as described above, and the catiomc functional group contributes to compatibility with the cationic phenol polycondensate (D) (that is, a catiomc polycondensate of a phenol-based compound with an aldehyde (D)), the titanium compound (A), or the magnesium compound (B) Solubility or dispersibihty of the cationic urethane resin (C) in water may either be achieved by solubility or dispersibihty possessed by the resin itself or by bemg assisted with a catiomc surfactant (e g, alkyl quaternary ammonium salt, etc ) and/or a nomomc surfactant (e g, alkyl phenyl ether, etc) [0025] Examples of the catiomc urethane resin (C) include a urethane resm which is a polycondensate of polyol such as polyol, polyether polyol, or polyester polyol with an aliphatic, alicychc, or aromatic polyisocyanate wherem polyol having a (substituted) ammo group or polyol having a nitrogen atom on its main cham is used as a part of the polyol to be used, a urethane resm wherein a nitrogen atom of the urethane resm is quaternized with a quaternizing agent, and the like [0026] The polyol mentioned above may be exemplified by aliphatic diol compounds such as ethylene glycol, diethylene glycol, tnethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, neopentyl glycol, 1,2-butylene glycol, 1,3-butylene glycol, 1,4-butylene glycol, hexamethylene glycol, bisphenol A, hydrogenated bisphenol A, tnmethylolpropane, 1,2-propanediol, 1,3-propanediol, 2-methyl-1,3-propanediol, 2-butyl-2-ethyl-1,3-propanediol, 1,4-butanediol, neopentyl glycol, 3-methyl-2,4-pentanediol, 2,4-pentanediol, 1,5-pentanediol, 3-methyl-1,5-pentanediol, 2-methyl-2,4-pentanediol, 2,4-diethyl-l,5-pentanediol, 1,6-hexanediol, 1,7-heptanediol, 3,5-heptanediol, 1,8-octanediol, 2-methyl-l,8-octanediol, 1,9-nonanediol, and 1,10-decanediol, tn- or higher valent aliphatic or alicyclic alcohol compounds such as trimethylolethane, tnmethylolpropane, hexitols, pentitols, glycerine, diglycenne, polyglycenne, pentaerythritol, dipentaerythntol, and tetramethylolpropane, or the like [0027] The polyether polyol mentioned above may be exemplified by ethyleneoxide adducts such as ethylene glycol, diethylene glycol, and tnethylene glycol, propyleneoxide adducts such as propylene glycol, dipropylene glycol, and tnpropylene glycol, ethyleneoxide and/or propylene oxide adducts of above-mentioned polyols, polytetramethylene glycol, or the like [0028] The polyester polyol mentioned above may be exemplified by compounds which can be obtained by direct estenfication reaction and/or transestenfication of the above-mentioned polyol with an ester-forming derivative having a smaller stoichiometric amount such as polyvalent carboxyhc acid or anhydnde thereof, hahde, and esters, compounds which can be obtained by rmg-openmg reaction of lactones with the above-mentioned polyol, polycarbonate polyol, or the like Examples of the polyvalent carboxyhc acid include aliphatic dicarboxylic acids such as oxalic acid, malomc acid, succinic acid, glutanc acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, dodecanedioic acid, 2-methylsuccmic acid, 2-methyladipic acid, 3-methyladipic acid, 3-methylpentanedioic acid, 2-methyloctanedioic acid, 3,8-dimethyldecanedioic acid, 3,7-dimethyldecanedioic acid, dimer acid, and hydrogenated dimer acid, alicyclic dicarboxylic acids such as cyclohexane dicarboxylic acids, aromatic dicarboxylic acids such as phthalic acid, isophthalic acid, terephthalic acid, and naphthalene dicarboxylic acid, tricarboxylic acids such as rnmelhtic acid, trimesic acid, and castor oil fatty acid tnmer, tetracarboxyhc acid such as pyromellitic acid, and the like Examples of the ester-forming derivative thereof include acid anhydrides of polyvalent carboxyhc acid thereof, halides such as chloride or bromide of the polyvalent carboxyhc acid, lower aliphatic esters, such as methyl ester, ethyl ester, propyl ester, isopropyl ester, butyl ester, isobutyl ester, or amyl ester, of the polyvalent carboxyhc acid, and the like Examples of the lactones include y-caprolactone, 5-caprolactone, s-caprolactone, dimethyl-e-caprolactone, 8-valerolactone, y-valerolactone, y-butyrolactone, and the like [0029] The above mentioned polyol having a (substituted) amino group or polyol havmg a nitrogen atom on its mam cham may be exemplified by polyol represented by the following general formula (V) or (VI), or the like Specific examples of such polyol mclude N,N-dimethylammo dimethylolpropane, N-methyl-N,N-diethanolamine, and the like The quaternizmg agent may be exemplified by R3C1, R3Br, R7C1, R7Br, (wherein R and R have the same meanings as defined m the general formulas (II) and (IV)), or the like [0030] (Formula Removed) [0031] Herein, R1, R2, R4, R5, and R6 in the above general formulas have the same Q meanings as defined in the above-mentioned general formulas (I) and (III) R represents a linear or branched alkylene group having 2 to 10, preferably 2 to 6 carbon atoms, wherein a -NR!R2 group is substituted on any of the carbon atoms [0032] For the cationic urethane resm (C), examples of the aliphatic, alicyclic, or aromatic polyisocyanate mclude tetramethylene dnsocyanate, hexamethylene dusocyanate, lysine dnsocyanate ester, hydrogenated xylylene dnsocyanate, 1,4-cyclohexylene dnsocyanate, 4,4'-dicyclohexylmethane dnsocyanate, 2,4'-dicyclohexylmethane dnsocyanate, isophorone dnsocyanate, 3,3'-dimethoxy-4,4'-biphenylene dnsocyanate, 1,5-naphthalene dnsocyanate, 1,5-tetrahydronaphthalene dnsocyanate, 2,4-tolylene dnsocyanate, 2,6-tolylene dnsocyanate, 4,4'-diphenyl methane dnsocyanate, 2,4'-diphenyl methane dnsocyanate, phenylene dnsocyanate, xylylene dnsocyanate, tetramethyl xylylene dnsocyanate, and the like Among these, when the aliphatic or alicyclic polyisocyanate compound such as tetramethylene dnsocyanate, hexamethylene dnsocyanate, lysme dnsocyanate ester, hydrogenated xylylene dnsocyanate, 1,4-cyclohexylene dnsocyanate, 4,4'-dicyclohexylmethane dnsocyanate, 2,4'-dicyclohexylmethane dnsocyanate, or isophorone dnsocyanate, is used, a film having excellent weather resistance can be obtamed, thus is preferably used [0033] The cationic urethane resin (C) of the invention, for example, may be a silyl modified, cationic, water-soluble or aqueous emulsion urethane resin When such silyl-modified urethane resm is used, corrosion resistance and alkali resistance of a film to be formed are further improved This silyl modification is carried out by using a silane coupling agent at a step of synthesizing a water-soluble or aqueous emulsion urethane resm, and although a more specific modification method is not particularly limited, for example, the medication may be earned out by reactmg polyol (polyol having a (substituted) ammo group or polyol having a nitrogen atom on a mam chain is partly used) with a silane coupling agent, and then polycondensatmg an aliphatic, alicyclic, or aromatic polyisocyanate, or alternatively by subjecting a polycondensate of polyol (polyol having a (substituted) ammo group or polyol having a mtrogen atom on a mam cham is partly used) with an aliphatic, alicyclic, or aromatic polyisocyanate to a reaction with a silane couplmg agent [0034] A type of silane coupling agent for use m the silyl modification is not particularly limited A preferred example of the silane couplmg agent for use in the silyl modification include a silane coupling agent having an ammo group (primary or secondary ammo group) or epoxy group [0035] An amount of silane coupling agent to be used in the silyl modification is not particularly limited, but the amount, for example, is m the range of preferably 0 05 mass% to 10 mass%, more preferably 0 5 mass% to 5 mass%, based on a sum of mass amounts of the polyol (polyol havmg a (substituted) ammo group or polyol having a nitrogen atom on a mam chain is partly used), the aliphatic, alicyclic, or aromatic polyisocyanate, and the silane coupling agent, in the view of exhibiting the above-mentioned effects The reaction temperature when reacting the silane coupling agent is not particularly limited, and for example, the reaction may be carried out at a temperature between 0°C and 50°C [0036] The reason for improved corrosion resistance by silyl modification is not clear, but it is assumed to be because, by silyl modification, adhesiveness of the catiomc urethane resin (C) with a metal substrate is increased and further a barrier property is improved by preventing penetration of corrosion factors such as oxygen and chlorine [0037] Among the above-mentioned catiomc urethane resm (C), more preferred are soap-free compounds in which a surfactant as an emulsifier or solubilizer that may cause an adverse effect on adhesiveness of the film to a metallic material or water resistance of the film is not used, and compounds in which the used amount is controlled [0038] The catiomc urethane resm (C) is contained in an amount of 20 mass% to 35 mass% with respect to the total solid content Accordmg to the catiomc urethane resm (C) contained in a specific ratio, the corrosion resistance after cylindrical forming can be improved At a content less than 20 mass%, corrosion resistance after cylindrical forming is deteriorated, and at a content greater than 35 mass%, ethanol resistance is significantly deteriorated, thereby causing problems such as that the resin readily forms into a gel in a coating liquid state, thus is not preferable [0039] The term 'catiomc' for the catiomc phenol polycondensate (D) (that is, a catiomc phenol polycondensate of a phenol compound with an aldehyde) which to be contained m the metal surface treatment agent of the invention means that the polycondensate has a cationic functional group The cationic functional group may be exemplified by groups represented by the following general formula (I) or (II) The cationic phenol polycondensate (D) should have at least one of such cationic functional groups These functional groups, for example, can be introduced by allowing ammonia or amine corresponding to the (substituted) amino group represented in the general formula (I) to be co-existed when carrying out a polycondensation of phenol compound with aldehyde The cationic phenol polycondensate (D) for use in the invention is preferably, for example, a novolak phenol polycondensate obtained by carrying out the polycondensation reaction in the presence of an acid catalyst The catiomc phenol polycondensate (D) for use in the invention may also be those obtained by modifying the above-mentioned novolak phenol polycondensate m accordance with a generally known technique such as a boron modification, a silicon modification, a phosphorus modification, a heavy metal modification, a nitrogen modification, a sulfur modification, an oil modification, or a rosm modification [0040] The phenol compound which to be used for obtaining the catiomc phenol polycondensate (D) for use m the invention is not particularly limited as long as the catiomc phenol polycondensate (D) can be formed by a polycondensation with aldehyde in the presence of an acid catalyst and ammonia or amine corresponding to the (substituted) ammo group represented in the above general formula (I) Examples of such phenol compound include phenol, m-cresol, m-ethylphenol, m-propylphenol, m-butylphenol, p-butylphenol, o-butylphenol, resorcinol, hydroquinone, catechol, 3-methoxyphenol, 4-methoxyphenol, 3-methylcatechol, 4-methylcatechol, methylhydroqumone, 2-methylresorcmol, 2,3-dimethylhydroquinone, 2,5- dimethylresorcinol, 2-ethoxyphenol, 4-ethoxyphenol, 4-ethylresorcinol, 3-ethoxy-4-methoxyphenol, 2-propenylphenol, 2-isopropylphenol, 3-isopropylphenol, 4-lsopropylphenol, 3,4,5-tnmethylphenol, 2-isopropoxyphenol, 4-propoxyphenol, 2-allylphenol, 3,4,5-tnmethoxyphenol, 4-isopropyl-3-methylphenol, pyrogallol, phloroglycmol, 1,2,4-benzenetnol, 5-isopropyl-3-methylphenol, 4-butoxyphenol, 4-t-butylcatechol, t-butylhydroquinone, 4-t-pentylphenol, 2-t-butyl-5-methylphenol, 2-phenylphenol, 3-phenylphenol, 4-phenylphenol, 3-phenoxyphenol, 4-phenoxyphenol, 4-hexyloxyphenol, 4-hexanoylresorcmol, 3,5-dnsopropylcatechol, 4-hexylresorcmol, 4-heptyloxyphenol, 3,5-di-t-butylphenol, 3,5-di-t-butylcatechol, 2,5-di-t-butylhydroqumone, di-sec-butylphenol, 4-cumylphenol, nonylphenol, 2-cyclopentylphenol, 4-cyclopentylphenol, bisphenol A, bisphenol F, and the like These may be used alone or in combination of two or more kinds Among these, preferred are phenol, o-cresol, m-cresol, p-cresol, bisphenol A, 2,3-xylenol, 3,5-xylenol, m-butylphenol, p-butylphenol, o-butylphenol, 4-phenylphenol, and resorcmol, and most preferred examples are phenol and bisphenol A [0041] The aldehyde which to be used for obtaining the catiomc phenol polycondensate (B) for use in the invention is not particularly limited as long as the catiomc phenol polycondensate (B) can be formed by a polycondensation with the phenol compound in the presence of an acid catalyst and ammonia or amine corresponding to the (substituted) amino group represented m the above general formula (I) Examples of such aldehyde include formaldehyde, tnoxane, furfural, paraformaldehyde, benzaldehyde, methylhemiformal, ethylhemiformal, propylhemiformal, butylhemiformal, phenylhemiformal, acetoaldehyde, propylaldehyde, phenylacetaldehyde, a-phenylpropylaldehyde, P-phenylpropylaldehyde, o-hydroxybenzaldehyde, m- hydroxybenzaldehyde, p-hydroxybenzaldehyde, o-chlorobenzaldehyde, o-nitrobenzaldehyde, m-nitrobenzaldehyde, p-mtrobenzaldehyde, o-methylbenzaldehyde, m-methylbenzaldehyde, p-methylbenzaldehyde, p-ethylbenzaldehyde, p-n-butylbenzaldehyde, and the like These compounds may be used alone or in combination of two or more kinds Among these compounds, for example, preferred are formaldehyde, paraformaldehyde, furfural, benzaldehyde, and salicylaldehyde, and most preferred are formaldehyde and paraformaldehyde [0042] Examples of the amine which to be used for obtaining the catiomc phenol polycondensate (D) for use in the invention include monomethylamme, dimethylamine, trimethylamme, monoethylamine, diethylamine, tnethylamine, isopropylamine, dnsopropylamme, n-butylamine, di-n-butylamme, tri-n-butylamine, lsobutylamme, dnsobutylamme, sec-butylamine, n-amylamine, di-n-amylamine, tri-n-amylamme, sec-amylamme, sec-hexylamrne, 2-ethylhexylamme, dioctylamme, ethanolamme, diethanolamme, triethanolamine, N-methylethanolamme, N-ethylethanolamme, N-butylethanolamine, N,N-dimethylethanolamine, N,N-diethylethanolamme, N-ethyldiethanolamine, N-n-butyldiethanolamme, N,N-di-n-butylethanolamme, N-methylpropanolamine, tnisopropanolamine, and the like As the quatermzing agent, agents described for the production of the catiomc urethane resin (C) can be used [0043] The acid catalyst which to be used for obtaining the catiomc phenol polycondensate (D) for use in the invention is not particularly limited to the following examples including hydrochloric acid, sulfuric acid, phosphoric acid, formic acid, acetic acid, oxalic acid, butyric acid, lactic acid, benzenesulfonic acid, p-toluenesulfonate, tartaric acid, bone acid, and metal salts such as zmc chloride and zinc acetate These catalysts may be used alone or in combination of two or more kinds [0044] The cationic phenol polycondensate (D) for use in the invention is contained in an amount of 25 mass% to 40 mass% with respect to the total solid content At a cationic phenol polycondensate (D) content less than 25 mass%, ethanol resistance is deteriorated thereby causing problems such as that the resin readily forms into a gel in a coating liquid state, and at a catiomc phenol polycondensate (D) content greater than 40 mass%, corrosion resistance after cylindrical forming is deteriorated [0045] The mass ratio (mass%) of the catiomc urethane resm (C) to the cationic phenol polycondensate (D), which are contained in the metal surface treatment agent of the invention is preferably in the range of 40 60 to 49 51, more preferably in the range of 42 58 to 48 52, and most preferably 45 55 At a mass ratio of the cationic urethane resin (C) greater than 49 mass%, ethanol resistance is deteriorated [0046] The above-mentioned composition for surface treatment may also include other components as necessary, such as phosphoric acid or phosphate such as ammonium phosphate for the purpose of reducmg coating appearance to take on a yellow tinge, or an organic solvent, a surfactant, or the like considering the coatability For the surface treatment film, a catiomc component excluding titanium and magnesium of metallic compounds is mcluded, and additive components may also selectively be contained [0047] The zinc-plated steel sheet to which a surface treatment shall be subjected using the composition for surface treatment of the invention is not particularly limited, and examples thereof mclude zinc or zmc alloy-plated steel sheets such as a zinc-plated steel sheet, a zinc-mckel-plated steel sheet, a zinc-cobalt-plated steel sheet, a zmc-alummum-plated steel sheet, a zinc-magnesium-plated steel sheet, a zinc-aluminum-magnesium-plated steel sheet, a zinc-iron-plated steel sheet, a zinc-chrome-plated steel sheet, and a zinc-manganese-plated steel sheet, which are applied by electroplating, hot dipping, or vapor-phase plating [0048] Next, a method of producing the surface treated steel sheet of the invention will be described In order to form the surface treatment film on the surface of a zinc-plated steel sheet, a surface treatment agent which forms a film of the composition described above is applied until giving a predetermined value of dry film weight, and the resultant is heat dried without being washed with water As the coating method, generally well-known method such as roll coater coating, dipping coating, or spray coating can be employed As the means for heat drying after the coating, for example, a dryer, a hot-air oven, a high-frequency induction furnace, an infrared furnace, or the like can be used The drying treatment is conducted preferably at a peak sheet temperature of about 50°C to 250°C When a drying temperature is below 50°C, a large amount of water content in the film remams and thus the corrosion resistance on a planar surface becomes insufficient When a drying temperature is above 250°C, it is uneconomical and also there is a possibility that defects may be occurred to a film due to a partial heat decomposition of the resin component in the film The surface treatment film described above may either be formed on one side or both sides of the steel sheet [0049] The dry weight of the film formed from the surface treatment agent of the invention is, for example, in the range of 0 1 g/m2 to 3 g/m2 At a film weight less than 0 1 g/m2, corrosion resistance after cylindrical forming is insufficient, while at a film weight greater than 3 g/m , appearance after cylindrical forming is deteriorated [0050] In addition, for use in household appliances, a surface treated steel sheet having excellent lubrication property for the purpose of acting against the film receiving damages due to a squeeze molding, for example, in a cartridge tank for kerosene stoves, as well as having excellent corrosion resistance after forming, is demanded Accordingly, the present inventors have found that to attain the corrosion resistance after the squeeze forming, it is effective if a well-known organic-inorganic composite film is provided on an upper layer of the surface treatment film for the above-mentioned surface treated steel sheet [0051] Hereinafter, a film agent for forming an organic-inorganic composite film will be described [0052] Examples of a resin to be used for the organic-morgamc composite film include an acrylic resm, an ethylene-acrylic acid copolymer resin, an epoxy resin, a polyol-based urethane resin, a polycarbonate-based urethane resin, an acryl-modified silicone resm, a sihcone-modified urethane resm, a melamme-alkyd resm, fluorine-based resins, mixed products or addition polymers of two or more resins thereof, and the like As the inorganic component, silica or the like is used for the purpose of improving the corrosion resistance In addition, for a press molding, polyolefin wax, tetrafluoroethylene wax, or the like, may also be used as the solid lubricant to impart sliding or abrasion resistance to a steel sheet and to prevent surface galling or mold damage In addition, for example, coloring agents such as inorganic/organic pigment and dyes, water-soluble epoxy, a curing agent such as a silane couplmg agent, a solvent, a surfactant, or the like, may also be included [0053] The drying treatment after applying the organic-inorganic composite film agent is conducted at a peak sheet temperature of about 100°C to 250°C When a heating temperature is below 100°C, curing is insufficient and corrosion resistance on a planar surface deteriorates, and when a heating temperature is above 250°C, it is uneconomical and also the corrosion resistance on a planar surface deteriorates due to film defects caused by resin decomposition As the surface treatment sheet, the resm film described above may also either be formed on one side or both sides of the steel sheet ' [0054] The film weight of the organic-inorganic composite film is, for example, m the range of 0 2 g/m2 to 5 g/m2 At a film weight less than 0 2 g/m2, corrosion resistance after squeeze forming is insufficient, while at a film weight greater than 5 g/m , scum readily generates upon the squeeze forming thereby causing problems such as poor molding upon continuous press molding [0055] By providing an organic-inorganic composite film and/or a surface treatment (post-treatment) film including a titanium compound, a magnesium compound, a catiomc urethane resm (hereinafter, referred to as urethane resin) which has at least one catiomc functional group selected from primary to tertiary amino groups and quaternary ammonium bases, and a phenol polycondensate (hereinafter, referred to as phenol resm) which is a polycondensate of bisphenol A, amine, and formaldehyde, on the surface of the chromate-free surface treated steel sheet of the invention, remarkable white rust resistance, corrosion resistance after the forming, and ethanol resistance can be obtained Mechanisms of exhibiting such properties are not clear, but possible exhibition mechanisms will be described below However, the invention is not restricted to these [0056] It can be assumed that the following film-forming reaction and property exhibition are occurred when a post-treating agent of the invention is applied on a surface of the surface treated steel sheet and baking is performed [0057] An OH group on a benzene ring of the above-mentioned phenol resm in the surface treating (post-treating) agent of the invention, is polarized due to differences in electronegativities in water giving H (hydrogen) 8+ and O (oxygen) 8-, as well as titanium and magnesium m the metallic compounds contaimng titanium and magnesium give 8+ whereas the remamder gives 8- Since change in both sides is occurred upon the film-forming reaction, positively charged titanium or magnesium forms a bond with O on a benzene ring due to an electrical interaction Further, the above-mentioned positively charged titanium or magnesium combines with the surface of the surface treated steel sheet through negatively charged oxygen, thereby forming a strong crosshnked structure for the entire film In particular, titanium provides strong covalent and thus contributes to enhance the crosshnked structure [0058] It is assumed that a strong adhesiveness is generated on the surface treated steel sheet/post-treated film interface due to the formation of crosslmked structure An excellent interface adhesion property indicates that the corrosion factors such as water and salts hardly invade the interface A barrier effect on corrosion factors of post-treated film itself, which is formed by a strong crosslmked structure as described above, is a fundamental factor for exhibiting corrosion resistance on a planar surface (corrosion resistance which is the base for a post-treated plated steel sheet) of unformed plate [0059] In addition, a surface potential uniformizmg effect described below is also assumed to be the factor for exhibiting corrosion resistance on a planar surface [0060] The phenol resin is a compound having a resonance stabilization structure, and a titanium compound is a transition metal compound The electron configuration of titanium is 3d24s2, and electron acceptance takes place in the 3d orbital of inner shell whereas the electronic state in the 4s orbital of outermost shell does not change Thus, titanium has an electronic buffer effect of 3d orbital, and the electrochemical property hardly changes even when electrons are accepted A film formed by containing the phenol resin and the titanium compound reacts with a metallic surface and firmly bonds thereto, and thus an action of delocahzmg electrons generated due to the corrosion of surface treated steel sheet, m 3d orbital of titanium and/or in a benzene ring of the phenol resm, is provided Accordmgly, the surface potential is uniformly kept This is thought to be the cause of corrosion resistance provided on a planar surface [0061] However, the corrosion resistance on a planar surface of the surface treated steel sheet, and particularly the white rust resistance on a planar surface of the zmc-plated steel sheet, are insufficiently obtained only by the factor mentioned above These properties are further unproved by addmg magnesium in a post-treated film A mechanism for this exhibition is as follows [0062] Since magnesium m the crosshnked structure as described above exists near a surface of the surface treated steel sheet, thereby achieving stabilization of a dense initial corrosion product a representative example of which is basic zinc chloride produced on the surface treated steel sheet, particularly on an outermost layer of zinc plate, where the dense corrosion product serves as a barrier film, it can be assumed that the effect of preventing a white rust generation is thus exhibited Therefore, it is essential for the invention that the phenol resin, the titanium compound, and the magnesium compound are coexisted, and remarkable effect of improving the corrosion resistance on a planar surface is found for the first tune by allowing them to coexist [0063] Further to the above description, although titanium and magnesium provided from the metallic compounds containing titanium and magnesium which are blended in a post-treating agent are incorporated in a crosslmked structure in excess or deficiency, the excess distributes in the post-treated film or over the surface of a plating steel sheet as a metal salt, and migrates over the course of time in a corrosive environment over the surface of a plating steel sheet in a form of salt or cation Accordingly, it can be assumed that the synergistic effect of passivation function of titanium and stabilization effect of magnesium on the dense initial corrosion product a representative example of which is basic zinc chloride contribute to prevention of rust generation on a plated steel sheet, particularly white rust generation on a zinc plate [0064] In addition, the corrosion resistance exhibiting effect of titanium and magnesium described above is also effective in parts of the plate where the plated steel sheet substrate is exposed which is caused by cracks or exfoliation of the post-treated film due to forming Especially, m the case of zinc plate, smce magnesium existing in the post-treated film migrates m a form of salt or cation over an exposed part of the plate and acts thereon, a dense initial corrosion product a representative example of which is basic zinc chloride is stabilized, and thus the corrosion resistance after forming is improved by preventing the white rust generation [0065] Meanwhile, corrosion resistance after forming such as cylindrical molding which accompanies cracks or surface rubbing of the post-treated film cannot be defined to be sufficient Therefore, the present inventors have tried to introduce the above-mentioned urethane resin which provides flexibility for cracks and extension so as to improve the corrosion resistance after forming When a suitable amount of urethane resin is added to a post-treating agent, and the post-treating agent is applied and then baking is subjected, a crosslmked structure is formed through a hydrogen bond, a van der Waals' force, or a strong mteraction between a functional group on a side chain of the urethane resin and a polar group such as an OH group of the phenol resin In addition, since the urethane resm and the phenol resin are distributed m a randomly entangled state over the entire film, the entire film is provided with flexibility and bears film cracking and exfoliation even upon a cylindrical molding Thus, the post-treated film maintains the effect of preventing penetration of corrosion factors such as water and salts possessed by the film, and it is assumed to exhibit an excellent corrosion resistance after forming Evaluation on the appearance of cylindrical molded article is preferably conducted in accordance with the following appearance evaluation (AL values before and after the test) of cylindrical molding forming The AL value said herein indicates a difference of L values before and after the test which are measured by colonmetry in accordance with Hunter technique The evaluation can be made in accordance with the following standards VG = white rust generated area is less than 5% G = white rust generated area is 5% or more to less than 15% NG = white rust generated area is 15% or more to less than 30% B = white rust generated area is 30% or more to less than 50% VB = white rust generated area is 50% or more [0066] The urethane resm is generally fully compatible with alcohol such as ethanol, and thus the resm has a property of swelling when brought into contact with alcohol, which thereby causes decrease in film properties such as that softening of post-treated film and film strength are deteriorated and penetration of corrosion factors into the film are promoted According to the invention, the present inventors have found that decrease m ethanol resistance is prevented by controlling the mass ratio of the urethane resin to be not greater than that of the phenol resin in the film In the case of a film wherein the urethane resm and the phenol resm are in a randomly entangled state and the phenol resm is mainly comprised, effect of controlling slack of the film caused by swelling of the urethane resm is exhibited, and thus exfoliation and damage of the film are hardly occurred even in a condition of contact with ethanol which accompanies rubbing, thereby it is assumed to exhibit significantly excellent ethanol resistance For the sliding test, a commercially available gauze is attached on a flat slide having a sliding side of 20 mm in diameter, ethanol is thoroughly impregnated, and then reciprocal sliding is repeated for 10 times under test conditions of pressure of 100 g/cm2, amplification of 100 mm, and speed of 20 mm/sec, with the use of a commercially available Bowden tester Thereafter, change in appearance of the sliding part of the treated sheet is evaluated m accordance with the following standards VG = no change in appearance G = slight change in appearance NG = obvious change in appearance B = partial exposure of substrate VB = complete exposure of substrate [0067] As above, the present inventors have conducted extensive studies, and as a result, they have found that excellent ethanol resistance, corrosion resistance on a planar surface (white rust resistance), and corrosion resistance after forming can be obtained with balance by providing a post-treated film on a plating steel sheet by applymg a post treatment agent containing a titanium compound, a magnesium compound, a urethane resin, and a phenol resin From the viewpoint of improving the corrosion resistance after forming, there are no known methods as revealed in this invention that the above-mentioned 4 components are essentially blended for a post treatment m a suitable proportion and suitable amount, and the present mvention is the first one showing such technique [0068] Also, it is hard to ensure that sufficient corrosion resistance can be obtained only by the above described way after carrying out a harsh molding, which may cause change in steel sheet thickness of the plating steel sheet, such as squeezmg accompanying damages on a surface film According to the invention, remarkable improvement on corrosion resistance even after a harsh forming such as squeezmg can be obtained by providing an organic-inorganic composite film on the post-treated film An assumed mechanism of exhibiting this property will be described [0069] When the organic-inorganic composite treating agent is applied and then baking > is subjected, a crosslmked structure is formed through a hydrogen bond, a van der Waals' force, or a strong interaction between a side chain functional group having polarity of the urethane resin and an OH group or a polar group of a side chain functional group of the phenol resin, on an under layer of the post-treated film, and a side chain functional group having polarity on an upper layer of the orgamc-inorgamc composite film As a result, a double layer of organic-inorganic composite film and post-treated film providing interface adhesiveness is formed Since the orgamc-inorgamc composite film, in addition to many other properties of the post-treated film, has a function of preventing cracks or peeling off of the post-treated film due to a harsh forming such as squeezing, and also a barrier effect on corrosion factors of the film itself, it is assumed to exhibit excellent corrosion resistance after forming [Examples] [0070] Hereinafter, the present invention will be described in more detail with reference to Examples and Comparative Examples, but the invention is not limited to these Examples [0071] The metallic materials to be treated, and the component (A), the component (B), the component (C), and the component (D), of the surface treatment composition, which were used for Examples and Comparative Examples are shown in Table 1, Table 2, Table 3, and descriptions below, respectively The orgamc-inorgamc composite film composition is shown m Table 4 Also, treatment methods of applying a treatment liquid and evaluation methods are described below, and the evaluation results are shown in Tables 5 to 14 [0072] [Table 1] TABLE 1 Zinc-plated Steel Sheet (Table Removed) [0073] [Table 2] TABLE 2 Titanium Compound (A) (Table Removed) Note) each component is mixed in equal amount and mass ratio O represents constituent [0074] [Table 3] TABLE 3 Magnesium (Table Removed) Note) each component is mixed in equal amount and mass ratio O represents constituent [0075] (Components of Surface Treatment Composition) (1) Catiomc Urethane Resins (C) (1-1) catiomc urethane resin (C-l) 150 parts by mass of polyether polyol (synthesis components tetramethylene glycol and ethylene glycol, molecular weight of 1,500), 6 parts by mass of tnmethylolpropane, 24 parts by mass of N-methyl-N,N-diethanolamine, 94 parts by mass of isophorone dnsocyanate, and 135 parts by mass of methyl ethyl ketone were charged into a reaction vessel, and the mixture was reacted for 1 hour while maintaining the temperature at 70°C to 75 °C, to produce a urethane prepolymer Into the reaction vessel, 15 parts by mass of dimethyl sulfate was charged, and the mixture was reacted for 30 to 60 minutes at a temperature between 50 and 60°C to produce a catiomc urethane prepolymer Further into the reaction vessel, 576 parts by mass of water was charged, the mixture was homogeneously emulsified, and then the methyl ethyl ketone was recovered, to obtain a water-soluble catiomc urethane resin (C-l) [0076] (1-2) catiomc urethane resin (C-2) 135 parts by mass of polyester polyol (synthesis components isophthalic acid, adipic acid, and 1,6-hexanediol, and ethylene glycol, molecular weight of 1,700), 5 parts by mass of tnmethylolpropane, 22 parts by mass of N-methyl-N,N-diethanolamme, 86 parts by mass of isophorone dnsocyanate, and 120 parts by mass of methyl ethyl ketone were charged into a reaction vessel, and the mixture was reacted for 1 hour while mamtaimng the temperature at 70°C to 75°C, to produce a urethane prepolymer Into the reaction vessel, 17 parts by mass of dimethyl sulfate was charged, and the mixture was reacted for 30 minutes to 60 minutes at a temperature between 50°C and 60°C to produce a catiomc urethane prepolymer Further mto the reaction vessel, 615 parts by mass of water was charged, the mixture was homogeneously emulsified, and then the methyl ethyl ketone was recovered, to obtain a water-soluble catiomc urethane resm (C-2) [0077] (1-3) catiomc polyurethane resm (C-3) 130 parts by mass of polycarbonate polyol (synthesis components 1,6-hexanecarbonatediol, and ethylene glycol, molecular weight of 2,000), 4 parts by mass of tnmethylolpropane, 21 parts by mass of N-methyl-N,N-diethanolamine, 75 parts by mass of isophorone dnsocyanate, and 115 parts by mass of methyl ethyl ketone were charged into a reaction vessel, and the mixture was reacted for 1 hour while maintaining the temperature at 70°C to 75 °C, to produce a urethane prepolymer Into the reaction vessel, 22 parts by mass of dimethyl sulfate was charged, and the mixture was reacted for 30 minutes to 60 minutes at a temperature between 50°C and 60°C to produce a catiomc urethane prepolymer Further into the reaction vessel, 633 parts by mass of water was charged, the mixture was homogeneously emulsified, and then the methyl ethyl ketone was recovered, to obtain a water-soluble catiomc polyurethane resin (C-3) [0078] (1-4) catiomc polyurethane resm (C-4) 135 parts by mass of polyester polyol (synthesis components isophthalic acid, adipic acid, 1,6-hexanediol, and ethylene glycol, molecular weight of 2,000), 5 parts by mass of trimethylolpropane, 22 parts by mass of N-methyl-N,N-diethanolamme, 86 parts by mass of isophorone dnsocyanate, 1 part by mass of y-aminopropyltriethoxysilane, and 120 parts by mass of methyl ethyl ketone were charged into a reaction vessel, and the mixture was reacted for 1 hour while maintaining the temperature at 70°C to 75°C, to produce a urethane prepolymer Into the reaction vessel, 17 parts by mass of dimethyl sulfate was charged, and the mixture was reacted for 30 to 60 mmutes at a temperature between 50°C and 60°C to produce a catiomc urethane prepolymer Further into the reaction vessel, 615 parts by mass of water was charged, the mixture was homogeneously emulsified, and then the methyl ethyl ketone was recovered, to obtain a silyl-modified, water-soluble catiomc polyurethane resin (C-4) [0079] (1-5) catiomc polyurethane resin (C-5) 150 parts by mass of polycarbonate polyol (synthesis components 1,3-dioxolan-2-one and 1,6-hexanediol, molecular weight of 1,700), 6 parts by mass of tnmethylolpropane, 24 parts by mass of N-methyl-N,N-diethanolamine, 94 parts by mass of isophorone dnsocyanate, 2 part by mass of N-(P-ammoethyl)y-aminopropyltnmethoxysilane, and 135 parts by mass of methyl ethyl ketone were charged mto a reaction vessel, and the mixture was reacted for 1 hour while maintaining the temperature at 70°C to 75°C, to produce a urethane prepolymer Into the reaction vessel, 15 parts by mass of dimethyl sulfate was charged, and the mixture was reacted for 30 minutes to 60 minutes at a temperature between 50°C and 60°C to produce a catiomc urethane prepolymer Further into the reaction vessel, 576 parts by mass of water was charged, the mixture was homogeneously emulsified, and then the methyl ethyl ketone was recovered, to obtain a silyl-modified, water-soluble catiomc polyurethane resm (C-5) [0080] (2) Catiomc Phenol Polycondensates (D) (2-1) catiomc phenol polycondensate (D-l) Into a 1000 mL flask equipped with a reflux condenser, 1 mole of bisphenol A (228 g), and 0 3 g of p-toluenesulfonate as a catalyst, were charged, and the temperature inside was raised to 100°C Thereto, 0 85 mol (69 g) of an aqueous solution of formaldehyde was added over 1 hour, and the mixture was reacted for 2 hours under reflux at 100°C Thereafter, the reaction vessel was cooled with water and allowed to stand still Once the cloudiness of an aqueous layer separated as an upper layer had disappeared, decantation was subjected to remove the aqueous layer, and the resultant was heated under stirring until it reaches the temperature between 170°C and 175°C, to remove unreacted compounds and water content [0081] Next, the temperature was lowered down to 100°C, 234 g of butyl cellosolve was added to completely dissolve the polycondensate, and then 234 g of pure water was added At a point where the temperature inside the system is 50°C, 1 mole of diethanolamme (75 g) was added Thereto, 1 mole of an aqueous solution of formaldehyde (81 1 g) was added dropwise over about 1 hour at 50°C Then, the temperature was raised to 80°C, and the reaction was allowed to take place under stirring for about 3 hours, to obtain a catiomc phenol polycondensate (D-l) [0082] (2-2) catiomc phenol polycondensate (D-2) Into a 1000 mL flask equipped with a reflux condenser, 1 mole of phenol (96 g), and 0 3 g of p-toluenesulfonate as a catalyst, were charged, and the temperature inside was raised to 100° C Thereto, 0 7 mol (56 8 g) of an aqueous solution of formaldehyde was added over 1 hour, and the mixture was reacted for 2 hours under reflux at 100°C Thereafter, the reaction vessel was cooled with water and allowed to stand still Once the cloudiness of an aqueous layer separated as an upper layer had disappeared, decantation was subjected to remove the aqueous layer, and the resultant was heated under stirring until it reaches the temperature between 170°C and 175°C, to remove unreacted compounds and water content [0083] Next, the temperature was lowered down to 100°C, 234 g of butyl cellosolve was added to completely dissolve the polycondensate, and then 234 g of pure water was added At a point where the temperature mside the system is 50°C, 1 mole of N-methylpropanolamine (89 g) was added Thereto, 0 7 mole of an aqueous solution of formaldehyde (56 8 g) was added dropwise over about 1 hour at 50°C Then, the temperature was raised to 80°C, and the reaction was allowed to take place under stirring for about 3 hours, to obtain a catiomc phenol polycondensate (D-2) [0084] (2-3) catiomc phenol polycondensate (D-3) Into a 1000 mL flask equipped with a reflux condenser, 1 mole of o-cresol (108 g), and 0 3 g of p-toluenesulfonate as a catalyst, were charged, and the temperature inside was raised to 100°C Thereto, 0 85 mol (69 g) of an aqueous solution of formaldehyde was added over 1 hour, and the mixture was reacted for 2 hours under reflux at 100°C Thereafter, the reaction vessel was cooled with water and allowed to stand still Once the cloudmess of an aqueous layer separated as an upper layer had disappeared, decantation was subjected to remove the aqueous layer, and the resultant was heated under stirring until it reaches the temperature between 170°C and 175°C, to remove unreacted compounds and water content [0085] Next, the temperature was lowered down to 100°C, 234 g of butyl cellosolve was added to completely dissolve the polycondensate, and then 234 g of pure water was added At a point where the temperature mside the system is 50°C, 1 mole of N,N-diethylethanolamme (117 g) was added Thereto, 1 mole of an aqueous solution of formaldehyde (81 1 g) was added dropwise over about 1 hour at 50°C Then, the temperature was raised to 80°C, and the reaction was allowed to take place under stirring for about 3 hours, to obtain a cationic phenol poly condensate (D-3) [0086] [Table 4] TABLE 4 Organic-inorganic Composite Film (Table Removed) Note) lubricant component is mixed in equal amount and mass ratio 0 represents constituent [0087] (Treatment Method) (1) Degreasmg A metallic material to be treated was degreased using PALKLIN N364S, an alkaline degreaser from Nihon Parkenzing Co , Ltd (spraying the 20 g/L bath at 60°C for 10 seconds with a spray pressure of 0 5 kg/cm2), followed by rinsing with a 10-second spray of water (2) Application and Drying The compositions for surface treatment and the treatment liquids for organic-morgamc composite film described in Tables 5 to 10 and Tables 11 to 14, were applied together on zinc-plated steel sheets with a roller coater, and the sheets were dried with heatmg at peak sheet temperatures of each condition The film weight was adjusted by a solid content concentration of the treatment liquid or coating conditions (such as pressure of roller or rotation speed) [0088] (Method of measuring the film amount adhered) The weight difference before and after the application of the composition for surface treatment and the treatment liquid for organic-inorganic composite film to the steel sheet followed by dry is determined by a weight method, and divided by a coated area to give a film adhered amount [0089] (Method of measuring Titanium content and Magnesium content) The titanium content and the magnesium content in the composition for surface treatment were measured using an ICP emission spectrometry [0090] (Evaluation Methods) (1) Ethanol Resistance The treated sheet samples prepared in Examples 1 to 90 and Comparative Examples 1 to 31 were directly subjected to ethanol resistance test without being subjected to forming (planar surface) The evaluation method is as follows [0091] As mentioned above, for the sliding test, a commercially available gauze is attached on a flat slide having a sliding side of 20 mm in diameter, ethanol is thoroughly impregnated, and then reciprocal sliding is repeated for 10 times under test conditions of pressure of 100 g/cm2, amplification of 100 mm, and speed of 20 mm/sec, with the use of a commercially available Bowden tester Thereafter, change in appearance of the sliding part of the treated sheet is evaluated in accordance with the following standards [0092] VG = no change in appearance G = slight change in appearance NG = obvious change in appearance B = partial exposure of substrate VB = complete exposure of substrate [0093] (2) Corrosion Resistance on Planar Surface (White rust Resistance) The treated sheet samples prepared in Examples 1 to 90 and Comparative Examples 1 to 31 were directly subjected to corrosion resistance test without being subjected to forming (planar surface) The evaluation method is as follows [0094] The white rust generated area was determined after 120 hours of salt spray in accordance with JIS-Z-2371, 'Salt-spray Testing Method' [0095] VG - white rust generated area is less than 5% G = white rust generated area is 5% or more to less than 15% NG = white rust generated area is 15% or more to less than 30% B = white rust generated area is 30% or more to less than 50% VB = white rust generated area is 50% or more [0096] (3) Evaluation on Appearance after cylindrical forming and Corrosion Resistance The treated sheet samples prepared in Examples 1 to 90 and Comparative Examples 1 to 31 were subjected to cylindrical forming, and the appearance evaluation and the corrosion resistance test were conducted The evaluation method is as follows [0097] For the cylindrical molding forming, the treated sheet samples prepared in Examples 1 to 90 and Comparative Examples 1 to 31 were punched mto a circular form to give a blank diameter of 60 mm, a Press oil (PG 3080, produced by Nihon Kohsakuyu Co , Ltd) was applied, and the resulting sheets were formed using a die for cylindrical molding forming having a dice diameter of 32 mm and a dice R of 2 mm, with a crank presser under the condition of 30 spm [0098] The evaluation on appearance of the cylindrical molded articles was evaluated using AL values before and after the test As mentioned before, the AL value indicates a difference of L values before and after the test, provided that the degree of brightness classified from black (0) to white (100) is given as an L value In specific, the measurement can be carried out with the use of a color-difference meter CR-300 (manufactured by MINOLTA) [0099] VG = AL is less than 2 G = AL is 2 or more to less than 5 NG = AL is 5 or more to less than 10 B = ALis 10 or more [0100] The corrosion resistance of cylindrical molded articles was evaluated by determining the white rust generated area after 24 hours of salt spray in accordance with JIS-Z-2371, 'Salt-spray Testing Method' [0101] VG = white rust generated area is less than 10% G = white rust generated area is 10% or more to less than 20% NG = white rust generated area is 20% or more to less than 40% B = white rust generated area is 40% or more to less than 80% VB = white rust generated area is 80% or more [0102] (4) Evaluation on Appearance after squeeze forming and Corrosion Resistance The treated sheet samples prepared m Examples and Comparative Examples were subjected to squeeze molding forming, and the appearance (generation of scum) evaluation and the corrosion resistance test were conducted The evaluation method is as follows [0103] For the squeeze molding forming, the treated sheet samples prepared in Examples 91 to 135 and Comparative Examples 34 to 78 were punched into a circular form to give a blank diameter of 60 mm, a Press oil (PG 3080, produced by Nihon Kohsakuyu Co , Ltd ) was applied, and the resulting sheets were formed usmg a die for cylindrical molding forming having a dice diameter of 30 mm and a dice R of 2 mm, with a crank presser under the condition of 30 spm Thereafter, a second forming was conducted under conditions of a dice diameter of 25 mm and a dice R of 1 mm, with a combination of punch and dice that the clearance is 15% mmus side to the thickness of the original sheet [0104] Scum developed upon the squeeze molding forming was removed by degreasmg with a hydrocarbon solvent The amount of scum developed was evaluated on the basis of weight variation between before and after the test, and also further evaluation was conducted on the basis of AL value variation between before and after the test [0105] VG = weight decrease is less than 0 05 g/m2, or AL is less than 2 G = weight decrease is 0 05 to less than 0 1 g/m2, or AL is 2 to less than 5 NG = weight decrease is 0 1 to less than 0 5 g/m2, or AL is 5 to less than 10 B = weight decrease is 0 5 g/m2 or more, or AL is 10 or more [0106] The corrosion resistance of squeeze molded articles was evaluated by determining the white rust generated area after 16 hours of salt spray in accordance with JIS-Z-2371, 'Salt-spray Testing Method' [0107] VG = white rust generated area is less than 10% G = white rust generated area is 10% or more to less than 20% NG = white rust generated area is 20% or more to less than 40% B = white rust generated area is 40% or more to less than 80% VB = white rust generated area is 80% or more [0108] The evaluation results are shown below [0109] [Table 5] (Table Removed) [0110] [Table 6] (Table Removed) [0111] [Table 7] (Table Removed) [0112] [Table 8] (Table Removed) [0113] [Table 9] (Table Removed) temp* temperature, adhere amt* adhered amount [0114] [Table 10] (Table Removed) temp* temperature, adhere amt* adhered amount [0115] [Table 11] (Table Removed) Comp Examples Comparative Examples [0116] [Table 12] (Table Removed) Comp Examples Comparative Examples [0117] [Table 13] (Table Removed) Comp Examples Comparative Examples temp* temperature, adhere amt* adhered amount [0118] [Table 14] (Table Removed) Comp Examples Comparative Examples temp* temperature, adhere amt* adhered amount [0119] As shown from evaluation results of Tables 5 and 6, the steel sheets of the present invention (Examples 1 to 90) which were prepared by employing the method of producing a surface treatment film according to the invention were excellent in all of ethanol resistance, corrosion resistance on a planar surface, corrosion resistance after cylindrical forming, and appearance after cylindrical forming In comparison, as shown from evaluation results of Tables 11 and 12, when conditions were outside the range of the invention (Comparative Examples 1 to 31), at least one of the above evaluations was poor [0120] In addition, as shown from evaluation results of Tables 9 and 10, the steel sheets of the invention (Examples 91 to 135) in which an organic-inorganic composite film was applied on the surface treatment film, respectively, were excellent in corrosion resistance after squeeze forming and appearance after squeeze forming In comparison, as shown from evaluation results of Table 6-2, when conditions were outside the range of the invention (Comparative Examples 34 to 78), at least one of the above evaluations was poor [0121] Accordingly, it is realized that the present invention exhibits all of excellent ethanol resistance, corrosion resistance on a planar surface, corrosion resistance after cylindrical forming, appearance after cylindrical forming, corrosion resistance after squeeze forming, and appearance after squeeze forming, by providing a predetermined weight of the film comprising each constitution mentioned above on the surface of a zmc-plated steel sheet [0122] As described above, the surface treated steel sheet according to the invention is a chromium-free surface treated composition and exhibits corrosion resistance after forming equal to or better than that provided with a chromate-based surface treatment agent In addition, the invention is suitable for various uses such as household appliances and building matenals, as the production method thereof is simple and it can be produced at low cost [0123] Up to now, preferred embodiments of the invention are described, but there is no doubt that the invention is not limited to those Examples It is obvious that various changed examples or modified examples can be suggested by those skilled in the art within the category mentioned in claims, and those examples certainly are thought to be in the technical scope of the invention [Industnal Applicability] [0124] The chromium-free zinc-plated steel sheet subjected to a metal surface treatment of the present mvention is provided with all of excellent ethanol resistance, corrosion resistance on a planar surface, corrosion resistance after cylindrical forming, appearance after cylindrical forming, corrosion resistance after squeeze forming, and appearance after squeeze forming, and thus is effective as one of proposed measures for social problems such as environmental conservation The present invention is particularly expected to be used in the fields of household appliances provided by accompanying forming such as motor cases or cartridge for kerosene stoves and building materials provided by accompanying forming such as guardrails. We Claim : 1. A method of manufacturing an electrode system, the method comprising : providing a layer of material having an aperture through it and having an electrode located adjacent to the aperture on one side of the material; locating the material between two reservoirs, such that one of the reservoirs is on said side of the material and the other of the reservoirs is on the other side of the material; providing a reactant, and depositing conductive material, at least a component of which comprises the reactant, onto the electrode; wherein the reactant is provided in a higher concentration in said one of the reservoirs than in the other, such that the electrode grows within the aperture. 2. A method according to claim 1 wherein the aperture has a length in one direction and a width in a perpendicular direction, and is longer than it is wide. 3. A method according to claim 2, wherein the electrode is located at an end of the aperture. 4. A method according to claim 3, wherein a further electrode is provided at the other end of the aperture. 5. A method according to claim 3 or 4, wherein the electrode or electrodes are wider than the aperture prior to the depositing of conductive material. 6. A method according to any of claims 1 to 5 wherein the electrode is arranged to grow further in the direction down into the aperture than in the opposite direction. 7. A method according to any of claims 1 to 6 wherein the conductive material is a SERS active material. 8. An electrode system comprising a layer of material having an aperture through it and an electrode formed on the material, wherein the electrode is formed on a surface of the material adjacent to the aperture, and extends into the aperture. 9. An electrode system according to claim 8 wherein the surface is substantially planar, and the aperture has a side surface and a rim between the planar surface and the side surface, and the electrode extends over the rim and onto the side surface of the aperture. 10. An electrode according to claim 8 or claim 9 wherein the aperture is longer than it is wide and has two ends, the electrode being provided at one end of the aperture and a further electrode being provided at the opposite end. 11. An electrode system according to claim 8 or claim 9 wherein the aperture comprises a plurality of connected slots each having an open end and a closed end, a respective electrode being provided at the closed end of each slot. 12. A method of characterizing a molecule comprising : providing two electrodes which define a tunneling gap between them; applying a potential difference between the electrodes; passing the molecule through the tunneling gap; and measuring the tunnelling current between the electrodes over a measuring period, wherein at least a part of the molecule is within the gap for at least a part of the measuring period. 13. A method according to claim 12 wherein the molecule is a polymer. 14. A method according to claim 13 further comprising guiding the poymer so that parts of the polymer pass through the gap sequentially in the order in which they are located along the molecule. 15. A method according to any of claim 12 to 14 further comprising recording the tunnelling current as a function of time. 16. A method of characterizing a polymer molecule comprising : providing two electrodes which define a gap between them; applying a potential difference between the electrodes; passing the polymer molecule through the gap so that parts of the molecule pass between the electrodes in the order in which they are located along the molecule; and measuring the current between the electrodes as the molecule passes between them. 17. A method according to claim 16 comprising providing a plurality of guide means each having a respective pair of electrodes associated with it, wherein molecules are passed through the guide means and the currents between the respective pairs of electrodes measured simultaneously. 18. A method according to claim 17 further comprising applying a driving potential to the solution to drive the molecule through the gap, wherein the driving potential is varied so as to vary the speed at which the molecule moves. 19. A method according to any of claims 12 to 18 further comprising measuring the time for which a part of the molecule is located between the electrodes as the molecule passes between the electrodes, thereby to measure the length of the molecule. 20. Apparatus for characterizing molecules comprising a pair of electrodes defining a tunnelling gap between them across which a tunnelling current can flow, and guide means arranged to guide the molecules between the electrodes.

Documents:

3822-delnp-2009-Abstract-(14-03-2014).pdf

3822-delnp-2009-abstract.pdf

3822-DELNP-2009-Claims-(02-09-2009).pdf

3822-delnp-2009-Claims-(14-03-2014).pdf

3822-delnp-2009-claims.pdf

3822-delnp-2009-Correspondence Others-(11-07-2013).pdf

3822-delnp-2009-Correspondence Others-(14-03-2014).pdf

3822-DELNP-2009-Correspondence-Others (25-09-2009).pdf

3822-DELNP-2009-Correspondence-Others-(02-09-2009).pdf

3822-DELNP-2009-Correspondence-Others-(10-12-2009).pdf

3822-delnp-2009-correspondence-others.pdf

3822-delnp-2009-description (complete).pdf

3822-delnp-2009-Form-1-(11-07-2013).pdf

3822-delnp-2009-form-1.pdf

3822-delnp-2009-form-13-(02-09-2009).pdf

3822-delnp-2009-form-18.pdf

3822-delnp-2009-Form-2-(11-07-2013).pdf

3822-delnp-2009-form-2.pdf

3822-DELNP-2009-Form-3-(10-12-2009).pdf

3822-delnp-2009-Form-3-(14-03-2014).pdf

3822-delnp-2009-form-3.pdf

3822-delnp-2009-form-5.pdf

3822-DELNP-2009-GPA (25-09-2009).pdf

3822-delnp-2009-GPA-(11-07-2013).pdf

3822-delnp-2009-GPA-(14-03-2014).pdf

3822-delnp-2009-pct-210.pdf

3822-delnp-2009-pct-304.pdf

3822-delnp-2009-Petition-137-(14-03-2014).pdf