CN103121316B

CN103121316B - The surface-treated metal plate of corrosion resistance and excellent electric conductivity

Info

Publication number: CN103121316B
Application number: CN201210452794.6A
Authority: CN
Inventors: 梶田富男; 小西友英; 川上彬
Original assignee: Kobe Steel Ltd
Current assignee: Kobe Steel Ltd
Priority date: 2011-11-18
Filing date: 2012-11-13
Publication date: 2015-09-16
Anticipated expiration: 2032-11-13
Also published as: JP5478588B2; TWI473906B; JP2013108126A; KR101452051B1; KR20130055532A; CN103121316A; TW201335428A

Abstract

Surface-treated metal plate of the present invention has metallic plate and is formed at the resin involucra obtained by resin aqueous solution of at least one side of this metallic plate, aforementioned resin aqueous solution contains fixedness resinous principle and silicon dioxide granule, as aforementioned fixedness resinous principle, by quality ratio, with EC: PU=90: 10 ~ 40: 60 containing the fixedness resinous principle (EC) of ethene-copolymers of unsaturated carboxylic acids aqueous liquid dispersion and the fixedness resinous principle (PU) of carboxylic polyurethane resin water-based liquid, and then, relative to total 100 mass parts of aforementioned fixedness resinous principle and silicon dioxide granule, also containing the silane coupler of 5 ~ 20 mass parts and the alkoxy silane of 1 ~ 14 mass parts.With regard to surface-treated metal plate of the present invention, its corrosion resistance, resistance to alkali degreasing, electric conductivity, coating, mar proof and resistance to tape stripping improve further.

Description

The surface-treated metal plate of corrosion resistance and excellent electric conductivity

Technical field

The present invention relates to surface-treated metal plate, in more detail, the surface-treated metal plate of the corrosion resistance that automobile, household appliances, building materials etc. use, resistance to alkali degreasing, electric conductivity, coating (film adaptation), mar proof, resistance to tape stripping excellence is related to.

Background technology

As the material that automobile, household appliances, building materials etc. use, except the steel plate of the zinc-plated systems such as the steel plate of electrogalvanizing, the steel plate of molten zinc plating, rise to object further with the further raising of corrosion resistance and anti-finger printing, the steel plate that zinc-based metal plated steel sheet is implemented perchromate process and trbasic zinc phosphate process is also widely used.In addition, with the further raising of corrosion resistance and coating, processability rise to object further, propose the resin-coated steel plate being formed with organic resin epithelium on the surface treated steel plate implementing perchromate process.

In recent years, from the view point of environment of preserving our planet, the demand not implementing the steel plate of chromate process increases, and proposes the various steel plate not being formed with organic resin epithelium containing 6 valency chromium.But be just difficult to guarantee corrosion resistance owing to not carrying out chromate process, so utilize film to guarantee, sufficient corrosion resistance is in very difficult situation.

On the other hand, for the steel plate used for the high performance with electrical equipment, in order to tackle antistatic and electromagnetic wave shielding, to the increase in demand of the material of excellent electric conductivity.About electric conductivity, when zinc-plated steel plate applies epithelium, need the adhesion amount reducing epithelium to guarantee electric conductivity.But for be provided with the product of organic resin epithelium on zinc-plated steel plate for, if the adhesion amount of organic resin epithelium is low, then corrosion resistance and processability deterioration, the characteristic therefore beyond electric conductivity becomes insufficient, is unsuitable for practicality.

In order to solve the problems referred to above that so resin-coated steel plate has, propose the epithelium that is formed with and there is inorganic macromolecule compound and kollag as the lubricated steel sheet of resin involucra, further provide the epithelium that is formed with and there is water-base resin as the lubricated steel sheet of resin involucra.But; from the view point of environment of preserving our planet; the cleaning replacing the organic solvent system degreasing agents such as in the past used trichloro-ethylene and carrene by alkali degreasing is added in washing procedure after extrusion process; but for these products; because resistance to alkali degreasing is insufficient, is therefore in and is unsuitable for practical situation.In addition, such as, in No. 2006-43913, Japanese Unexamined Patent Publication, also proposed the resin involucra containing silica and silane coupler in resin aqueous solution.

But in the surface-treated metal plate described in above-mentioned patent gazette, the polyurethane resin containing ratio in the fixedness resinous principle of formation resin involucra is up to 67 ~ 90 quality %.Therefore, not talkative under the using state of alkali degreasing more severe have sufficient resistance to alkali degreasing, but the surface-treated metal plate needing resistance to alkali degreasing more excellent.

Summary of the invention

The present invention completes in view of the foregoing, its object is to, and provides a kind of corrosion resistance, resistance to alkali degreasing, electric conductivity, coating, mar proof and resistance to tape stripping to obtain the surface-treated metal plate improved further.

The surface-treated metal plate of the present invention that can solve above-mentioned problem has metallic plate and is formed at the resin involucra obtained by resin aqueous solution of at least one side of this metallic plate, wherein,

Aforementioned resin aqueous solution is the silicon dioxide granule of 4 ~ 20nm with the average grain diameter of fixedness resinous principle and 55 ~ 80 mass parts that the mode amounting to 100 mass parts contains 20 ~ 45 mass parts,

As aforementioned fixedness resinous principle, containing the fixedness resinous principle (PU) of the fixedness resinous principle (EC) and carboxylic polyurethane resin water-based liquid that have plenty of ethene-copolymers of unsaturated carboxylic acids aqueous liquid dispersion, their compounding ratio is EC: PU=90: 10 ~ 40: 60 by quality ratio

Relative to total 100 mass parts of aforementioned fixedness resinous principle and silicon dioxide granule, also containing the silane coupler represented by formula (a) of 5 ~ 20 mass parts and the alkoxy silane represented by formula (b) of 1 ~ 14 mass parts,

The adhesion amount of aforementioned resin epithelium is 0.05 ~ 1g/m ².

[in formula (a), R ¹, R ²represent alkoxyl, R ³represent the alkyl of alkoxyl or carbon number 1 ~ 4, X represents the alkylidene of carbon number 1 ~ 5.]

[in formula (b), R ⁴, R ⁵, R ⁶represent alkoxyl, R ⁷represent the alkyl of carbon number 5 ~ 7.]

With regard to surface-treated metal plate of the present invention, resin involucra is formed by resin aqueous solution, aforementioned resin aqueous solution contains as the ethene-copolymers of unsaturated carboxylic acids of resinous principle and carboxylic polyurethane resin and silicon dioxide granule using ormal weight, and containing specific silane coupler and specific alkoxy silane.Ethene particularly in resinous principle-copolymers of unsaturated carboxylic acids containing ratio has uprised.Therefore, the corrosion resistance of surface-treated metal plate of the present invention, electric conductivity, coating, mar proof and resistance to tape stripping are excellent, and resistance to alkali degreasing is also excellent.

Detailed description of the invention

Surface-treated metal plate of the present invention has metallic plate and is formed at the resin involucra obtained by resin aqueous solution of at least one side of this metallic plate.

The average grain diameter of fixedness resinous principle and 55 ~ 80 mass parts that the resin aqueous solution that the present invention uses contains 20 ~ 45 mass parts in the mode amounting to 100 mass parts is the silicon dioxide granule of 4 ~ 20nm.At this, as aforementioned fixedness resinous principle, containing the fixedness resinous principle (PU) of the fixedness resinous principle (EC) and carboxylic polyurethane resin water-based liquid that have plenty of ethene-copolymers of unsaturated carboxylic acids aqueous liquid dispersion, their compounding ratio is adjusted to EC: PU=90: 10 ~ 40: 60 by quality ratio.And then, relative to total 100 mass parts of fixedness resinous principle and silicon dioxide granule, aforementioned resin aqueous solution contains the silane coupler (hereinafter referred to as " silane coupler (a) ") represented by formula (a) of 5 ~ 20 mass parts and the alkoxy silane (hereinafter referred to as " alkoxy silane (b) ") represented by formula (b) of 1 ~ 14 mass parts.

As mentioned above, use to fixedness resin and the content of silicon dioxide granule, the kind of fixedness resin and for the specific silane coupler (a) of the compatibility that improves above-mentioned fixedness resin and silicon dioxide granule and alkoxy silane (b) content all in addition Altitude control and the resin aqueous solution that obtains to form resin involucra, corrosion resistance, electric conductivity, coating, mar proof and resistance to tape stripping can be obtained thus excellent, further, the surface-treated metal plate that resistance to alkali degreasing is also excellent.

Below, the present invention is described in detail.

1. fixedness resinous principle

Aforementioned resin aqueous solution contains ethene-copolymers of unsaturated carboxylic acids and carboxylic polyurethane resin is used as fixedness resinous principle.

In the present invention, by also using ethene-copolymers of unsaturated carboxylic acids and carboxylic polyurethane resin, thus the surface-treated metal plate of coating, corrosion resistance, mar proof and resistance to alkali degreasing excellence can be obtained.Aforementioned ethene-copolymers of unsaturated carboxylic acids and carboxylic polyurethane resin are made respectively ethene-copolymers of unsaturated carboxylic acids aqueous liquid dispersion, carboxylic polyurethane resin water-based liquid, thus fit in resin aqueous solution.

1-1. ethene-copolymers of unsaturated carboxylic acids aqueous liquid dispersion

The ethene used in the present invention-copolymers of unsaturated carboxylic acids aqueous liquid dispersion is described.

The ethene used in the present invention-copolymers of unsaturated carboxylic acids aqueous liquid dispersion is if by ethene-copolymers of unsaturated carboxylic acids dispersion liquid in an aqueous medium, be not particularly limited.In aforementioned aqueous medium, in addition to water, also can contain the hydrophilic solvents such as alcohol, 1-METHYLPYRROLIDONE, acetone micro-ly.

Aforementioned ethene-copolymers of unsaturated carboxylic acids is the copolymer of ethene and alkene unsaturated carboxylic acid.As unsaturated carboxylic acid, methacrylic acid, crotonic acid, iso-crotonic acid, maleic acid, fumaric acid, itaconic acid etc. can be listed, by making more than one and the Ethylene polymerizes in them with known high temperature high-pressure polymerization process etc., thus can copolymer be obtained.As copolymer, most preferably be random copolymer, but also can be block copolymer, unsaturated carboxylic acid part carried out the copolymer of grafting.It should be noted that, as unsaturated carboxylic acid, be preferably (methyl) acrylic acid.In addition, also can change a part for ethene and use the olefinic monomers such as propylene, 1-butylene.In this case, the content of the olefinic monomers except ethene is preferably below 10 quality %.And if then in the scope not hindering object of the present invention, then other known ethene base system monomers of a part can be made to carry out copolymerization (about 10 quality % are following).

Preferably when monomer total amount is set to 100 quality %, aforementioned ethene-copolymers of unsaturated carboxylic acids copolymerization has the unsaturated carboxylic acid composition of 10 ~ 40 quality %.If unsaturated carboxylic acid is at more than 10 quality %, then becomes the basic point of the Interpolymer Association produced by ion cluster or become and become many with the carboxyl of the crosslinking points of crosslinking agent.Therefore, epithelium intensity effect improves, and the corrosion resistance after degreasing process is more good, and the emulsion stability of aqueous liquid dispersion also improves.More preferably the lower limit of unsaturated carboxylic acid is 15 quality %.On the other hand, if unsaturated carboxylic acid is below 40 quality %, then the corrosion resistance of resin involucra, resistance to water improve further, and the corrosion resistance after alkali degreasing operation is more good.More preferably the upper limit is 25 quality %.

Ethene-the copolymers of unsaturated carboxylic acids used in the present invention has carboxyl, by utilizing organic base and metal ion to neutralize aforesaid carboxyl, thus can form aqueous liquid dispersion.

As aforementioned organic base, preferably use the amine of boiling point less than 100 DEG C.The amine of boiling point more than 100 DEG C easily remains in the resin involucra on metallic plate when making resin aqueous solution dry, the water imbibition of resin involucra increases, and therefore causes the reduction of corrosion resistance.Therefore, in ethene used in the present invention-copolymers of unsaturated carboxylic acids aqueous liquid dispersion, preferably not containing the amine of boiling point more than 100 DEG C.In addition, because also do not confirm the additive effect of ammonia, therefore preferably also not containing ammonia.Above-mentioned boiling point adopts the boiling point under atmospheric pressure.

As the concrete example of the amine of aforementioned boiling point less than 100 DEG C, triethylamine, N can be listed, N-dimethyl butylamine, N, the tertiary amines such as N-DMAA, N-crassitude, tetramethyl diaminomethane, trimethylamine, the secondary amine such as N-methyl ethyl-amine, diisopropylamine, diethylamine, the primary amine etc. such as propylamine, tert-butylamine, sec-butylamine, isobutyl amine, 1,2-dibutyl propylamine, 3-amylamine, can mix one or more to use.Wherein be preferably tertiary amine, most preferably be triethylamine.

Relative to the carboxyl in ethene-copolymers of unsaturated carboxylic acids 1 mole, the amount of the amine of aforementioned boiling point less than 100 DEG C is preferably the scope of 0.2 ~ 0.8 mole (20 ~ 80 % by mole).If in this scope, then corrosion resistance is good.If the amine that boiling point is less than 100 DEG C is more than 0.2 mole, then the particle diameter of the resin particle of aqueous liquid dispersion diminishes, and can think that above-mentioned effect improves.In addition, if below 0.8 mole, then can suppress aqueous liquid dispersion thickening and gelation.More preferably the upper limit of the amount of above-mentioned amine is 0.6 mole, more preferably 0.5 mole, and more preferably the lower limit of above-mentioned amine amount is 0.3 mole.

In the present invention, except the amine of aforementioned boiling point below 100 DEG C, monovalent metallic ion is also preferably used to be used for neutralization.This is effective to the raising of solvent resistance and epithelium hardness.As the compound of monovalent metal, preferably containing one or more the metal be selected from sodium, potassium, lithium, be preferably the hydroxide of these metals, carbonated or oxide.Wherein, be preferably NaOH, KOH, LiOH etc., NaOH performance is best and preferably.

For the amount of the compound of this monovalent metal, relative to the carboxyl in ethene-copolymers of unsaturated carboxylic acids 1 mole, preferably contained monovalent metal amount is set to the scope of 0.02 ~ 0.4 mole (2 ~ 40 % by mole).If above-mentioned amount of metal is more than 0.02 mole, then emulsion stability is more good, if be less than 0.4 mole, then the hygroscopicity (particularly for alkaline solution) of obtained resin involucra reduces, and the corrosion resistance after degreasing process improves further.The lower limit of preferred amount of metal is 0.03 mole, and preferred lower limit is 0.1 mole further, and the upper limit of preferred amount of metal is 0.3 mole, and the preferred upper limit is 0.2 mole further.

The preferable range of the amine of above-mentioned boiling point less than 100 DEG C and the metallic compound use amount separately of above-mentioned monovalence is as above-mentioned, and they all carry out Water-borne modification for the carboxyl in neutralization of ethylene-copolymers of unsaturated carboxylic acids.Thus, if their total amount (dosis neutralisata) is too much, then the viscosity of aqueous liquid dispersion sharply rises and solidifies sometimes, and the alkali of surplus becomes to be divided into the reason of corrosion resistance deterioration, or needs a lot of energy to make it volatilize, therefore not preferred.But it is not if dosis neutralisata is very few, then emulsibility is poor, therefore preferred yet.Thus, relative to the carboxyl in ethene-copolymers of unsaturated carboxylic acids 1 mole, preferably the amine of boiling point less than 100 DEG C and the total use amount of above-mentioned monovalent metal are set to the scope of 0.3 ~ 1.0 mole.

The ethene used in the present invention-copolymers of unsaturated carboxylic acids aqueous liquid dispersion is by amine and the monovalent metallic ion also with boiling point less than 100 DEG C, carry out emulsification, thus be the dispersion liquid that particulate (oil droplet) state that 5 ~ 50nm is minimum like this disperses to obtain in an aqueous medium with average grain diameter.Therefore, presumption can realize obtained resin involucra make film, to the adaptation of metallic plate, the densified of epithelium, improve corrosion resistance.In above-mentioned aqueous medium, in addition to water, the hydrophilic solvent such as alcohol, ether can also be contained.It should be noted that, the particle diameter of the resin particle of above-mentioned aqueous liquid dispersion, such as, can be measured by the laser diffractometry employing light scattering photometer (great Zhuo electronics corporation etc.).

In ethene-copolymers of unsaturated carboxylic acids that the amine and monovalent metallic ion that utilize boiling point less than 100 DEG C carry out and in operation (Water-borne modification operation), preferably the amine of boiling point less than 100 DEG C and the compound of monovalent metal are added in copolymer simultaneously, or first add the amine of boiling point less than 100 DEG C.This is because: although reason is still uncertain, if the rear amine adding boiling point less than 100 DEG C, then the raising effect of corrosion resistance is insufficient.

As the preparation method of ethene used in the present invention-copolymers of unsaturated carboxylic acids aqueous liquid dispersion, ethene-copolymers of unsaturated carboxylic acids is put into together with aqueous medium in such as homogenizer apparatus etc., reaching under the heating of 70 ~ 250 DEG C as required, the compound of the amine and monovalent metal that suitably add boiling point less than 100 DEG C with forms such as the aqueous solution (first adds the amine of boiling point less than 100 DEG C, or add the amine of boiling point less than 100 DEG C and the compound of monovalent metal roughly simultaneously), stir with high shear force.

1-2. carboxylic polyurethane resin water-based liquid

As the carboxylic polyurethane resin water-based liquid used in the present invention, carboxylic polyurethane resin can be used to disperse to form any one in aqueous liquid dispersion or the aforementioned carboxylic polyurethane resin dissolving aqueous solution in an aqueous medium in an aqueous medium.In aforementioned aqueous medium, in addition to water, the hydrophilic solvents such as alcohol, 1-METHYLPYRROLIDONE, acetone can also be contained by trace.

Aforementioned carboxylic polyurethane resin preferably makes polyurethane prepolymer carry out chain reaction with cahin extension agent and obtains.

For aforementioned polyurethane prepolymer, such as, polisocyanate component described later and polyol component can be made to carry out reacting and obtaining.As the polisocyanate component forming aforementioned polyurethane prepolymer, preferably use at least one PIC be selected from toluene di-isocyanate(TDI) (TDI), methyl diphenylene diisocyanate (MDI) and dicyclohexyl methyl hydride diisocyanate resin (hydrogenation MDI).By using such PIC, and the resin involucra of excellent in stability of corrosion resistance, reaction controlling can be obtained.

Except foregoing polyisocyanates, in the scope not making the stability of corrosion resistance, reaction controlling reduce, also can use other PIC.As the PIC beyond above-mentioned polisocyanate component, such as can enumerate tetramethylene diisocyanate, hexamethylene diisocyanate, dodecane methylene diisocyanate (dodecanemethylene diisocyanate), IPDI, XDI, phenylene diisocyanate fat etc.Above-mentioned PIC can mix two or more use separately or at least.When using other PIC, preferably the containing ratio of above-mentioned polisocyanate component (TDI, MDI, hydrogenation MDI) is set to more than the 70 quality % of whole polisocyanate component.If the containing ratio of these polisocyanate component is more than 70 quality %, then the stability of corrosion resistance, reaction controlling improves further.

As forming the polyol component of aforementioned polyurethane prepolymer, preferably using 1,4-CHDM, PPG and there are these whole three kinds of polyalcohols of polyalcohol of carboxyl, more preferably making whole three kinds to be glycol.By using such polyol component, and the resin involucra of corrosion resistance, excellent in sliding property can be obtained.In addition, as polyol component, by using 1,4-CHDM, and the rust-proof effect of obtained polyurethane resin can be improved.

With regard to foregoing polyethers polyalcohol, as long as at least there is the hydroxyl of more than 2 on strand and the PPG that is made up of epoxy alkane unit of main framing, just be not particularly limited, such as can enumerate polyethylene glycol (polyoxyethylene glycol) (being sometimes called simply " polyethyleneglycol "), polypropylene glycol (polyoxypropylene glycol) (being sometimes called simply " polypropylene glycol "), polytetramethylene glycol (polyoxytetramethylene glycol) (being sometimes called simply " polytetramethylene glycol " or " polytetramethylene etherglycol ") etc., the PPG of market sale can be used.Among above-mentioned PPG, preferably use polypropylene glycol or polytetramethylene glycol.As long as the functional group number of foregoing polyethers polyalcohol is at least more than 2, being just not particularly limited, such as, also can be the multifunctional of more than trifunctional, four senses.

Foregoing polyethers polyalcohol, such as, to have the compound of reactive hydrogen for initator, can obtain by making the alkylene oxide such as oxirane, expoxy propane carry out addition.As the aforementioned compound with reactive hydrogen, such as, can enumerate the glycol such as propane diols, ethylene glycol; The triols such as glycerine, trimethylolpropane, hexanetriol, triethanolamine; The tetrol such as diglycerol, pentaerythrite; Also can enumerate sorbierite, sucrose, phosphoric acid etc. in addition.Now, as used initator, if use glycol, then the PPG of two senses can be obtained, if use triol, then the PPG of trifunctional can be obtained.In addition, with regard to polytetramethylene glycol, such as, ring-opening polymerisation by oxolane obtains.

Foregoing polyethers polyhydric alcohols is as preferably used the commercially available product of number-average molecular weight about about 400 ~ 4000.If number-average molecular weight is about more than 400, then the flexibility of resin involucra improves, if be less than 4000, then can suppress soft.It should be noted that, number-average molecular weight is tried to achieve by measuring OH value (hydroxyl value).

In the present invention, the mass ratio of aforementioned 1,4-CHDM and PPG is set to 1,4-CHDM: PPG=1: be also preferred mode at 1 ~ 1: 19.Use the 1,4-CHDM with rust-proof effect by certain ratio, and the rust-proof effect of obtained polyurethane resin epithelium can be improved further.

With regard to the aforementioned polyalcohol with carboxyl, as long as have the carboxyl of more than at least 1 and the hydroxyl of more than at least 2, be just not particularly limited, such as, can enumerate dihydromethyl propionic acid, dimethylolpropionic acid, dihydroxypropionic acid, dihydroxysuccinic acid etc.The use amount with the polyalcohol of carboxyl is adjusted according to required hydroxyl value.

Except aforementioned three kinds of polyol components, in the scope that corrosion resistance can not be made to reduce, also can use other polyalcohol.In this case, the containing ratio of above-mentioned three kinds of polyol components is preferably more than the 70 quality % of whole polyol component.If the containing ratio of above-mentioned three polyol components is more than 70 quality %, then corrosion resistance improves further.As the polyalcohol beyond above-mentioned three kinds of polyol components, as long as have multiple hydroxyl, be just not particularly limited, such as, can enumerate the polyalcohol etc. of low-molecular-weight polyalcohol, HMW.

The low-molecular-weight polyalcohol polyalcohol that to be mean molecule quantity be below about 500, the glycol such as such as ethylene glycol, diethylene glycol, triethylene glycol, 1,3-BDO, BDO, neopentyl glycol, 1,6-hexylene glycol; The triols such as glycerine, trimethylolpropane, hexanetriol.

The polyalcohol of HMW is the polyalcohol of mean molecule quantity more than about 500, such as, can enumerate the condensation system PEPAs such as polyethylene glycol adipate (PEA), poly adipate succinic acid ester (PBA), poly-adipic acid hexylene glycol ester (PHMA); The lactone system PEPA that poly-6-caprolactone (PCL) is such; The polycarbonate polyols such as poly-carbonic acid hexylene glycol ester; And acryl polyol etc.

In addition, as the cahin extension agent making above-mentioned polyurethane prepolymer carry out chain reaction, be not particularly limited, such as, can use polyamine, low-molecular-weight polyalcohol, alkanolamine etc.As aforementioned low-molecular-weight polyalcohol, polyalcohol same as described above can be used.As aforementioned polyamine, the aliphatic polyamines such as ethylenediamine, propane diamine, hexamethylene diamine can be enumerated; The aromatic polyamine such as toluenediamine, xylylene diamine, diaminodiphenyl-methane; The ester ring type polyamine such as diaminourea cyclohexyl-methane (diaminocyclohexylmethane), piperazine, IPD; The hydrazine classes etc. such as hydrazine, amber acid dihydrazide, adipic dihydrazide, O-phthalic acid dihydrazide.Wherein, preferably ethylenediamine and/or hydrazine are become to assign to use as cahin extension agent.In addition, as aforementioned alkanolamine, such as, diethanol amine, MEA etc. can be enumerated.

The making of the aqueous solution of the carboxylic polyurethane resin used in the present invention can adopt known method.Such as just like inferior method: use in alkali and the carboxyl of carboxylic polyurethane prepolymer, carry out emulsion dispersion in an aqueous medium, make it the method for carrying out chain reaction; Under the existence of emulsifying agent, utilize high shear force to carry out emulsion dispersion to carboxylic polyurethane resin, make it the method for carrying out chain reaction.Below, based on in alkali and the carboxyl of carboxylic polyurethane prepolymer, make it the method for emulsion dispersion in water, the preparation method of the aqueous solution of polyurethane resin is described, but the present invention is not limited to this method.

First, use above-mentioned PIC and above-mentioned polyalcohol, in NCO/OH ratio, according to making the mode of NCO surplus to make lower molecular weight, carboxylic NCO end polyurethane prepolymer.The temperature of synthesis of polyurethane prepolymer is not particularly limited, and can synthesize with the temperature of 50 ~ 200 DEG C.In addition, known catalyst can be used in the synthesis of polyurethane prepolymer.As Above-mentioned catalytic agent, such as, can enumerate the monoamine such as triethylamine, N, N-dimethyl cyclohexyl amine; N, N, N ', N '-tetramethylethylenediamine, N, N, N ', N ", N " the polyamine class such as-five methyl diethylentriamine; 1,8-diazabicylo [5.4.0] 11 carbon-7-alkene (DBU), the cyclic diamine classes such as triethylenediamine; The tin such as dibutyl tin dilaurate, dibutyltin diacetate series catalysts etc.

In addition, when the synthesis of polyurethane prepolymer, can one-step method be adopted, also can adopt prepolymer method in addition.So-called one-step method is the method for instigating PIC and polyalcohol one to react, so-called prepolymer method refers to the method utilizing the multistage to make PIC and polyol reaction, such as, after temporarily synthesis is low to moderate the polyurethane prepolymer of middle-molecular-weihydroxyethyl, then carry out the method for macromolecule quantification.

In the present invention, such as, suitably select to carry out synthesis of polyurethane prepolymer as inferior mode, that is, make PIC and whole modes of reacting of above-mentioned three kinds of polyalcohols one; Among above-mentioned three kinds of polyol components, first PIC is reacted with PPG, then then again with 1,4-CHDM and the mode of polyol reaction with carboxyl; Among polyol component, first make PPG and 1,4-CHDM reaction, then then make the mode of the polyol reaction with carboxyl.

When making carboxylic NCO end polyurethane prepolymer, from the view point of the adjustment of viscosity and make the emulsifying dispersivity of this prepolymer improve, solvent is used also to be preferred mode.As aforementioned solvents, preferred use for NCO for the solvent of inertia and the higher solvent of hydrophily, such as can use 1-METHYLPYRROLIDONE, acetone, ethyl acetate, methyl ethyl ketone, DMF etc., preferably use 1-METHYLPYRROLIDONE.This is because 1-METHYLPYRROLIDONE is high for the dissolubility of the polyalcohol with carboxyl, and the reaction preparing NCO end polyurethane prepolymer can be made even.It should be noted that, for the reaction of polyurethane prepolymer, such as, n-dibutylamine titration method can be utilized to obtain isocyanate group concentration, thus obtain reactivity.

After polyurethane prepolymer reaction terminates, utilize alkali to neutralize obtained carboxylic NCO end polyurethane prepolymer, thus emulsion dispersion can be carried out in water.As previous neutralizers, be not particularly limited, can ammonia be used; The tertiary amine such as triethylamine, triethanolamine; The alkali-metal hydroxide such as NaOH, potassium hydroxide, preferably uses triethylamine.

After making carboxylic NCO end polyurethane prepolymer emulsion dispersion, the cahin extension agents such as polyamine can be used in water to carry out chain reaction.It should be noted that, chain reaction can according to the reactivity of used cahin extension agent, and before emulsion dispersion, emulsion dispersion carries out simultaneously or after emulsion dispersion aptly.

The acid number of the carboxylic polyurethane resin used in the present invention is preferably more than 10mgKOH/g, below 60mgKOH/g.This be due to: if acid number is lower than 10mgKOH/g, then polyurethane resin water-based dispersion liquid stability reduce.In addition, if acid number is more than 60mgKOH/g, then the corrosion resistance of obtained resin involucra has the tendency of reduction.The beasurement base JIS-K0070 of aforementioned acid number carries out.

The use level of 1-3. resinous principle

For the resin aqueous solution used in the present invention, when above-mentioned ethene-copolymers of unsaturated carboxylic acids aqueous liquid dispersion and the carboxylic fixedness resinous principle of polyurethane resin water-based liquid and the total amount of silicon dioxide granule described later are set to 100 mass parts, the content of aforementioned fixedness resinous principle is more than 20 mass parts, be more preferably more than 25 mass parts, and containing below 45 mass parts, more preferably containing below 35 mass parts.If above-mentioned fixedness resinous principle amount is very few, then corrosion resistance, resistance to alkali degreasing and coating have the tendency of deterioration.On the other hand, if the amount of above-mentioned fixedness resinous principle is too much, then mar proof, resistance to tape stripping, electric conductivity have the tendency of reduction.

At this, the fixedness resinous principle of aforementioned ethene-copolymers of unsaturated carboxylic acids aqueous liquid dispersion is above-mentioned ethene-copolymers of unsaturated carboxylic acids, and the fixedness resinous principle of aforementioned polyurethane aqueous liquid is above-mentioned carboxylic polyurethane resin.Above-mentioned fixedness resinous principle can utilize known method in the technical field of aqueous solution or aqueous liquid dispersion to measure, such as, be by aqueous solution or the little evaporated residue constantly of aqueous liquid dispersion heat drying 1 ~ 3 at 100 DEG C ~ 130 DEG C.

In addition, aforementioned ethene-copolymers of unsaturated carboxylic acids (EC) is EC: PU=90: 10 ~ 40: 60 with the compounding ratio of carboxylic polyurethane resin (PU) by quality ratio, is preferably 80: 20 ~ 50: 50.As the compounding ratio of the fixedness composition (EC) of ethene-copolymers of unsaturated carboxylic acids aqueous liquid dispersion with the fixedness composition (PU) of polyurethane resin water-based liquid, if the ratio of EC 90: 10 is large, then resistance to tape stripping deterioration.On the other hand, if the ratio of EC 40: 60 is little, then resistance to alkali degreasing reduces.

2. silicon dioxide granule

In resin aqueous solution used in the present invention, except the fixedness resinous principle of above-mentioned ethene-copolymers of unsaturated carboxylic acids aqueous liquid dispersion and carboxylic polyurethane aqueous liquid, also containing silicon dioxide granule.

For aforementioned silicas particle, while giving electric conductivity, corrosion resistance, coating to the resin involucra of gained, the hardness of epithelium can be improved, improve mar proof.

In addition, in order to play the effect of aforementioned silicas particle to greatest extent, the average grain diameter of preferred silicon dioxide granule is in the scope of 4 ~ 20nm.This be due to: the average particle diameter became of silicon dioxide granule is less, then the corrosion resistance of resin involucra improves more, but if average grain diameter is less than about 4nm, then the raising effect of corrosion resistance is in saturated tendency, in addition, the stability of resin aqueous solution reduces and easily gelation occurs.On the other hand, if the average grain diameter of silicon dioxide granule is more than 20nm, then the film of making of resin involucra reduces, and corrosion resistance, coating, resistance to alkali degreasing likely reduce.

As the measuring method of the average grain diameter of aforementioned silicas particle, preferably adopt SEARS method (4 ~ 6nm) or BET method (4 ~ 20nm).In addition, when chain silica, preferably dynamic light scattering method is adopted.Such silicon dioxide granule is known as colloidal silica usually, about colloidal silica of the present invention, can adopt commercially available colloidal silica.

As an example of commercially available colloidal silica, " Snowtex (registration mark) " of Nissan Chemical Industries Inc., " アデライト (registration mark) " of ADEKA Inc., " シリカ De one Le (registration mark) " of Japan Chemical Industry Inc. etc. can be enumerated.Be the colloidal silica of 4 ~ 6nm as average grain diameter, such as can use " Snowtex (registration mark) XS " of Nissan Chemical Industries Inc., be the colloidal silica of 10 ~ 20nm as average grain diameter, " Snowtex (registration mark) 40 ", " Snowtex (registration mark) N ", " Snowtex (registration mark) C " etc. of Nissan Chemical Inc. can be used, " アデライト (registration mark) AT-30 " of ADEKA Inc. etc.

In resin aqueous solution used in the present invention, when above-mentioned ethene-copolymers of unsaturated carboxylic acids aqueous liquid dispersion and the fixedness resinous principle of carboxylic polyurethane aqueous liquid and the total amount of silicon dioxide granule are set to 100 mass parts, the content of aforementioned silicas particle is more than 55 mass parts, be preferably more than 65 mass parts, and be below 80 mass parts, be preferably below 75 mass parts.If the content of silicon dioxide granule is fewer than 55 mass parts, then electric conductivity, mar proof and resistance to tape stripping have the tendency of reduction.In addition, if the content of silica is more than 80 mass parts, then the film of making of resin involucra reduces, and corrosion resistance, resistance to alkali degreasing have the tendency of reduction.

3. silane coupler

The resin aqueous solution used in the present invention is also containing silane coupler.Silane coupler for improving mar proof, coating, corrosion resistance etc., and uses in order to the adaptation improving metallic plate and formation resin involucra on a metal plate.

As aforementioned silane coupling agent, use the silane coupler of following formula (a).By the silane coupler containing formula (a), the coating of formed resin involucra, corrosion resistance can be improved.

As R ¹, R ², R ³represented alkoxyl, can enumerate methoxyl group, ethyoxyl, positive propoxy, isopropoxy, n-butoxy, isobutoxy, tert-butoxy, n-pentyloxy, just own oxygen base etc.Wherein, be preferably the alkoxyl of carbon number 1 ~ 4, be more preferably methoxyl group, ethyoxyl.In addition, if the alcohol produced because of the hydrolysis of alkoxyl remains in epithelium, then likely cause deterioration in characteristics, therefore, compared to the ethyoxyl that can generate ethanol, and preferably can generate the methoxyl group of low-boiling methyl alcohol.

As R ³the alkyl of represented carbon number 1 ~ 4, can enumerate the straight-chain alkyl such as methyl, ethyl, n-pro-pyl, normal-butyl; The branched-chain alkyls such as isopropyl, isobutyl group, the tert-butyl group; The cyclic alkyl such as cyclopropyl, cyclobutyl.Wherein, preferred straight-chain alkyl, more preferably methyl, ethyl.

It should be noted that, from the hydrolysis based on alkoxyl, deliquescent viewpoint in water, as silane coupler, be " dialkoxy silicane " of 2 compared to alkoxyl, and preferably alkoxyl is " trialkoxy silane " of 3.Therefore, preferred R ³for alkoxyl.

As the alkylidene represented by X, methylene, dimethylene can be enumerated, trimethylene, tetramethylene, pentamethylene etc.Wherein, carbon number 2 ~ 4 is preferably.

As the silane coupler with glycidoxy represented by above-mentioned chemical formula (a), 3-glycidoxypropyl dimethoxysilane, 3-glycidoxypropyltrime,hoxysilane, 3-glycidoxypropyl diethoxy silane, 3-glycidoxypropyl group triethoxysilane etc. can be enumerated, in the present invention, can be used one or more in them.

Silane coupler represented by above-mentioned chemical formula (a) is commercially available, such as can enumerate " KBE-403 ", " KBM-403 ", " KBE-402 " of chemical industrial company of SHIN-ETSU HANTOTAI, " KBM-402 ", Dong Li Dow Corning Corporation system " Z-6040 ", " Z-6044 ", " Z-6041 ", " Z-6042 ", " Z-6043 " etc.

Relative to total 100 mass parts of above-mentioned fixedness resinous principle and silicon dioxide granule, the content of the silane coupler in resin aqueous solution is more than 5 mass parts, is preferably more than 10 mass parts, and is below 20 mass parts, is preferably below 15 mass parts.

If the content of silane coupler is very few, then the reactivity of silicon dioxide granule and above-mentioned ethene-copolymers of unsaturated carboxylic acids, carboxylic polyurethane resin etc. reduces, wear-resistant, the reduction such as coating, corrosion resistance.On the other hand, if the content of silane coupler is too much, then the stability of resin aqueous solution reduces, and likely gelation occurs, and do not have the quantitative change of helpful silane coupler many to reaction, there is the situation that metallic plate reduces with the adaptation being formed at the resin involucra on metallic plate.

4. alkoxy silane

The resin aqueous solution used in the present invention is also containing alkoxy silane.Use alkoxy silane to be to make the compatibility of silica and resin improve, forming finer and close epithelium, improve corrosion resistance, resistance to alkali degreasing etc.

As aforementioned alkoxy silane, use the alkoxy silane of following formula (b).

As R ⁴, R ⁵, R ⁶represented alkoxyl, can enumerate aforementioned R ¹, R ², R ³in illustrated alkoxyl.Wherein, the alkoxyl of preferred carbon number 1 ~ 4, is more preferably methoxyl group, ethyoxyl.In addition, if the alcohol produced due to the hydrolysis of alkoxyl remains in epithelium, then likely cause deterioration in characteristics, therefore, compared to the ethyoxyl that can generate ethanol, preferably can generate the methoxyl group of low-boiling methyl alcohol.

As R ⁷the alkyl of represented carbon number 5 ~ 7, can enumerate the straight-chain alkyl such as n-pentyl, n-hexyl, n-heptyl; The branched-chain alkyl such as isopentyl, sec-amyl, tertiary pentyl, neopentyl, isohesyl, Sec-Hexyl, tertiary hexyl, different heptyl, Zhong Gengji, tertiary heptyl; The cyclic alkyls etc. such as cyclopenta, cyclohexyl, suberyl.It should be noted that, if the molecular weight of alkyl is little, then the stability degradation in treatment fluid.On the other hand, if the molecular weight of alkyl is large, then dissolves in treatment fluid and become difficulty.Therefore, be wherein preferably straight-chain alkyl, be more preferably n-hexyl.

As mentioned above, as alkoxy silane (b) of the present invention, without functional group, the alkoxy silane with a specific alkyl, amyltrimethoxysilane, amyl triethoxysilane, hexyl trimethoxy silane, hexyl triethoxysilane, heptyl trimethoxy silane, heptyl triethoxysilane etc. can be enumerated, in the present invention, can be used in them one or more.Wherein, hexyl trimethoxy silane is particularly preferably.

Aforementioned alkoxy silane (b) is commercially available, include, for example " KBM3033 ", " KBM3063 ", " KBE3063 " of chemical industrial company of SHIN-ETSU HANTOTAI, " Z-6582 ", " Z-6583 ", " Z-6586 " etc. of Dong Li Dow Corning Corporation.

When the total mass parts of above-mentioned fixedness resinous principle and silicon dioxide granule is set to 100 mass parts, the content of the alkoxy silane (b) in resin aqueous solution is more than 1 mass parts, be preferably more than 3 mass parts, and be below 14 mass parts, be preferably below 12 mass parts.

If the content of alkoxy silane (b) is very few, then the compatibility of silicon dioxide granule and above-mentioned ethene-copolymers of unsaturated carboxylic acids, carboxylic polyurethane resin etc. reduces, the reduction such as corrosion resistance, resistance to alkali degreasing.On the other hand, if the content of alkoxy silane is too much, then the stability of resin aqueous solution reduces and gelation likely occurs, and the adaptation such as coating, resistance to tape stripping reduces.

5. other additive

For by the amine of above-mentioned boiling point less than 100 DEG C and monovalent metallic ion neutralization, for the ethene-copolymers of unsaturated carboxylic acids with carboxyl, form the Interpolymer Association (ionomer) based on ion cluster, form the resin involucra of excellent corrosion resistance.But, in order to form more tough epithelium, and be cross-linked to each other to make polymer chain preferably by make use of the chemical bond reacted between functional group.Therefore, the ethene used in the present invention-copolymers of unsaturated carboxylic acids aqueous liquid dispersion preferably containing have more than 2 can with the crosslinking agent of the functional group of carboxyl reaction.

When fixedness resinous principle (EC) in ethene-copolymers of unsaturated carboxylic acids aqueous liquid dispersion is set to 100 mass parts, the ratio that contains of aforementioned crosslinking agent is preferably more than 1 mass parts, is more preferably more than 5 mass parts, and preferably to contain with the ratio below 10 mass parts below 20 mass parts, more preferably.

If be more than 1 mass parts, then crosslinked respond well based on chemical bond, the raising effect of corrosion resistance is played further.On the other hand, if be below 20 mass parts, then the crosslink density of resin involucra can be suppressed to become too high and cause hardness to rise, distortion during extrusion process can also be followed.Therefore, being inhibited of crackle during extrusion process, consequently corrosion resistance and coating improve further.

As have in 1 molecule more than 2 can with the crosslinking agent of the functional group of carboxyl reaction, be not particularly limited, as preferred example, can enumerate the polyglycidyl ethers such as sorbitol polyglycidylether, (gathering) glycerol polyglycidylether, pentaerythrite polyglycidyl ether, trimethylolpropane polyglycidylether, neopentylglycol diglycidyl ether, (gathering) ethylene glycol diglycidylether, many glycidyl amines (Japanese: Port リグリシジ Le アミ Application) class etc. are containing the crosslinking agent of glycidyl; 4,4 '-bis-(ethylidene iminocarbonyl is amino) diphenyl methane, N, N '-hexa-methylene-1, two (the 1-aziridine Carboxylamide) N of 6-, N '-diphenyl methane-4,4 '-bis-(1-aziridine Carboxylamide) [N, N '-hexamethylene-1,6-bis (1-aziridinecarboxamide), N, N '-diphenylmethane-4,4 '-bis (1-aziridinecarboxamide)], the two sense aziridine cpds such as two aziridine Carboxylamides of toluene; Three-1-aziridinyl phosphine oxides, three [1-(2-methyl) aziridinyl] phosphine oxide, trimethylolpropane-three (β-aziridinyl propionic ester), three-2,4,6-(1-aziridinyl)-1,3,5-triazine, more than the trifunctional such as tetramethyl propane four aziridinyl propionic ester aziridine cpd or derivatives thereof etc. is containing the crosslinking agent of aziridinyl; Can use in them one or more.Wherein, preferably containing the crosslinking agent of aziridinyl.It should be noted that, can be used together polyfunctional aziridines and a sense aziridine (ethylene imine etc.).

Surface treating composition of the present invention can also contain spherical polyolefin-wax particle (being preferably spherical polyethylene wax particle).By making it containing spherical polyolefin-wax particle, thus the lubricity of resin coating metal plate can be improved, adding man-hour at extrusion molding etc., the contact impedance of metallic plate and metal die can be reduced.

Average grain diameter for the spherical polyolefin-wax particle playing lubricity is expeditiously preferably more than 0.6 μm, is more preferably more than 1 μm.If but its average grain diameter is excessive, then film adaptation is likely deteriorated, therefore the average grain diameter of spherical polyolefin-wax particle is preferably less than 4 μm, is more preferably less than 3 μm.The average grain diameter of spherical polyolefin-wax particle measures by coulter counter method.

As spherical polyolefin-wax particle, such as can enumerate " ケミパ mono-Le (registration mark) " series (polyolefin water-borne dispersions) that Mitsui Chemicals (strain) is made, in more detail, ケミパ mono-Le W-100, W-300, W-400, W-500, W-700 and W-900 etc. can be enumerated.

From the view point of lubricity and film adaptation, relative to total mass parts 100 mass parts of above-mentioned fixedness resinous principle and silicon dioxide granule, the amount of spherical polyolefin-wax particle is preferably more than 0.5 mass parts, be more preferably more than 1.0 mass parts, and be preferably below 5 mass parts, be more preferably below 4 mass parts.

And then in the scope not hindering effect of the present invention, surface treating composition also can contain diluent, anti skinning agent, surfactant, emulsifying agent, dispersant, levelling agent, defoamer, bleeding agent, membrane producing promoter, dyestuff, pigment, tackifier and antirust agent etc.

6. the preparation method of resin aqueous solution

The preparation method of aforementioned resin aqueous solution is not particularly limited, by aforementioned ethene-copolymers of unsaturated carboxylic acids aqueous liquid dispersion, carboxylic polyurethane aqueous liquid, silicon dioxide granule, silane coupler (a), alkoxy silane (b) and the wax added as required, crosslinking agent etc. are carried out coordinating with ormal weight and obtained.Silicon dioxide granule, silane coupler (a), alkoxy silane (b), wax and crosslinking agent etc. add all passable in any one stage, but after crosslinking agent and silane coupler (a) add, there is not gelation to make cross-linking reaction carry out, preferably not heating.And then, based on above-mentioned situation, preferably also do not heat when the keeping of aforementioned aqueous solution, be preferably less than 30 DEG C, more preferably below 20 DEG C, carry out keeping.

In addition, when preparing treatment fluid, in order to make surface tension reduce, improving the wetability to metallic plate, a small amount of organic solvent can be coordinated.As for this organic solvent, such as, can enumerate methyl alcohol, ethanol, isopropyl alcohol, butanols, hexanol, 2-Ethylhexyl Alcohol, glycol ethyl ether, ethylene glycol butyl ether, diethylene glycol, propane diols etc.

7. metallic plate

The metallic plate used in the present invention is steel plate, aluminium sheet, and Ti plate etc., are not particularly limited, but the steel plate of preferred zinc-plated system.Such as preferably can use the steel plate of melting pure zinc plating, hot dip alloyed zinc-plated steel plate, the steel plate of melting plating Zn-5%Al, steel plate, the steel plate of electric pure zinc plating, the steel plate etc. of electroplating Zn-Ni of melting plating Zn-55%Al.In addition, before formation resin involucra, the substrate processing of the process such as Co or Ni, inhibitor process or various non-chromate can be carried out to metal sheet surface.

8. the formation method of resin involucra

In order to form resin involucra on a metal plate, use known coating process, that is, rolling method, spray-on process, curtain flow rubbing method etc., be coated on the single or double of metal sheet surface, then carry out heat drying by above-mentioned resin aqueous solution.For heat drying temperature, carry out at the temperature that the moisture preferably in aqueous solution fully evaporates.In addition, as lubricant, when using spherical Tissuemat E, be maintained and spherically make the processability in manufacturing procedure below become good, therefore the preferred scope at 70 ~ 130 DEG C carries out drying.

For the adhesion amount (thickness) of resin involucra for metallic plate, be preferably 0.05g/m after the drying ²above, 0.2g/m is more preferably ²above, and be preferably 1g/m ²below, 0.5g/m is more preferably ²below.If adhesion amount is very few, then wear-resistant, corrosion resistance and resistance to alkali degreasing reduce.On the other hand, if adhesion amount is too much, then electric conductivity, coating have the tendency of reduction.This surface-treated metal plate directly can use according to purposes after manufacturing procedure, or re-uses after can implementing electrodeposition coating under existence conditions, powder body coating, serigraphy (130 ~ 160 DEG C, about 20 ~ 30 minutes).

[embodiment]

Below enumerate embodiment and further illustrate the present invention, but the present invention does not limit by following embodiment, front/rearly state in the scope of aim can meet, also suitably can change and implement, these are all included in technical scope of the present invention.

[evaluation method]

1. corrosion resistance

For obtained surface-treated metal plate (resin-coated steel plate), implement the salt spraytest through the flat-sheet material of edge seal according to JIS Z2371, with until the time that white rust produces 5% evaluate.

Evaluation criterion

◎: white rust produced more than 240 hours

Zero: white rust produce more than 120 hours ~ lower than 240 hours

△: white rust produce more than 72 hours ~ lower than 120 hours

×: white rust produced lower than 72 hours

2. resistance to alkali degreasing

Alkali cleaner (the Nihon Parkerizing Co.Ltd. system of 60 DEG C is adjusted in liquid temperature, " L-4460 ") in 20g/l, dipping is for trying material 2 minutes, pull out, after washing, drying, according to JIS Z2371, to this for examination material implement salt spraytest, with until white rust produce 1% time evaluate.

Evaluation criterion

More than ◎: 168 hours

More than zero: 96 hour lower than 168 hours

More than △: 48 hours lower than 96 hours

×: lower than 48 hours

3. electric conductivity

Utilize surface resistivity meter (Dia Instruments Co.Ltd. system, " Loresta (registration mark)-EP ", four terminal four probe methods), 10 places are measured to the sheet resistance of obtained surface-treated metal plate (resin-coated steel plate).

Evaluation criterion

Below ◎: 1m Ω and overload 0 time/10 places

Below zero: 1m Ω and overload 1 time/10 places

Below △: 1m Ω and overload more than 2 times less than 4 times/10 places

×: more than 1m Ω and overload more than 5 times/10 places

4. coating

The mode of about 20 μm is reached according to dried coating thickness, atomized spray painting is implemented to obtained surface-treated metal plate (resin-coated steel plate) and comes coating (Kansai Paint Inc. of application melamine alkyd resins system, " アミラ Star Network (registration mark) #1000 "), and at 130 DEG C baking within 20 minutes, carry out again after application.Then, this confession examination material is immersed in boiling water and takes out after 1 hour, place after 1 hour, carve the square gridiron pattern of 1mm 100 pieces with cutter, in fact executing belt stripping test, according to the number of the remaining grid of film, point 4 grade evaluation film adaptations.

Evaluation criterion

◎: survival rate: 100%

Zero: survival rate: more than 90% ~ lower than 100%

△: survival rate: more than 80% ~ lower than 90%

×: survival rate: more than 70% ~ lower than 80%

5. mar proof

For obtained surface-treated metal plate (resin-coated steel plate), according to Bale Cargo-vibration test (JIS Z0232), implement vibration test, based on the outward appearance for examination material after the following standard evaluation stipulated time.It should be noted that, vibration testing device uses the trade name " BF-500UC " of IDEC Inc..

Evaluation criterion

◎: to epithelium not damaged

Zero: damage is caused to epithelium, but zinc-plated surface nondestructive is hindered

△: exist with the damage of the visual degree that can confirm zinc-plated surface

×: remarkable to the damage on zinc-plated surface

6. resistance to tape stripping

Reinforcing fiber adhesive tape (Japanese is Off イラメ Application トテ mono-プ) (Maxell Sliontec Ltd. system is attached on the surface for examination material, " reinforcing fiber adhesive tape #9510 "), under the atmosphere of 40 DEG C × RH98%, keeping is after 120 hours, peel off reinforcing fiber adhesive tape, measure the remaining ratio (survival rate) having the area of epithelium.

Evaluation criterion

◎: survival rate 100%

Zero: survival rate more than 90% is lower than 100%

△: survival rate more than 80% is lower than 90%

×: survival rate is lower than 80%

the preparation of ethene-copolymers of unsaturated carboxylic acids aqueous liquid dispersion

Have mixer, thermometer, temperature controller inner capacities 0.8L emulsifying device autoclave in, add water 626 mass parts, ethylene-acrylic acid copolymer (acrylic acid 20 quality %, melt index (MI) 300g/10min (190 DEG C, 2.16kg)) 160 mass parts, relative to the carboxyl 1 mole of ethylene-acrylic acid copolymer, add triethylamine 0.4 mole (40 % by mole), 0.15 mole, NaOH (15 % by mole).150 DEG C, carry out high-speed stirred under the atmosphere of 5Pa, be cooled to 40 DEG C, obtain the aqueous liquid dispersion of ethylene-acrylic acid copolymer.Then, in aforementioned aqueous liquid dispersion, according to the mode reaching the ratio of 5 mass parts for fixedness resinous principle 100 mass parts of ethylene-acrylic acid copolymer, add 4,4 '-bis-(ethylidene iminocarbonyl is amino) diphenyl methane (Japanese catalyst Co. system, " ケミタイト (registration mark) DZ-22E ") is used as crosslinking agent.

the preparation of carboxylic polyurethane resin water-based liquid

Have mixer, thermometer, temperature controller inner capacities 0.8L synthesizer in, polytetramethylene glycol (hodogaya chemical industrial group system is dropped into as polyol component, number-average molecular weight 1000) 60g, 1,4-cyclohexanedimethanol 14g, dihydromethyl propionic acid 20g, add 1-METHYLPYRROLIDONE 30.0g again as reaction dissolvent.As isocyanate prepolymer composition, drop into toluene di-isocyanate(TDI) 104g, be warming up to 85 DEG C from 80 DEG C and make it to carry out reaction in 5 hours.The NCO content of the prepolymer obtained is 8.9 quality %.Add triethylamine 16g again to neutralize, add the mixed aqueous solution of ethylenediamine 16g and water 480g, carry out emulsification in 4 hours with 50 DEG C, make it to carry out chain reaction, obtain polyurethane resin water-based dispersion liquid (fixedness resinous principle 29.1%, acid number 41.4mgKOH/g).

the preparation of resin aqueous solution and the making of surface-treated metal plate

Experimental example 1

According to the mode reaching the match ratio shown in table 1, convert with fixedness composition, coordinate carboxylic polyurethane resin water-based liquid obtained above, ethylene-acrylic acid copolymer aqueous liquid dispersion, silicon dioxide granule (Nissan Chemical Inc., " Snowtex (registration mark) XS ", average grain diameter (BET method) 4 ~ 6nm) add up to 100 mass parts, relative to this total 100 mass parts, further interpolation γ-glycidoxypropyltrime,hoxysilane (γ-glycidoxy propyltrimethoxysilane) (chemical industrial company of SHIN-ETSU HANTOTAI system, " KBM-403 ") 12 mass parts are as silane coupler, add hexyl trimethoxy silane (chemical industrial company of SHIN-ETSU HANTOTAI system, " KBM-3063 ") 6 mass parts are as alkoxy silane, thus prepare resin aqueous solution.

This resin aqueous solution compression roller is coated on the surface of the steel plate of electric pure zinc plating, with plate temperature 90 DEG C of heat dryings, obtains being formed with adhesion amount 0.5g/m ²the surface-treated metal plate (resin-coated steel plate) of resin involucra.For obtained resin-coated steel plate, evaluate with regard to corrosion resistance, electric conductivity, mar proof, resistance to alkali degreasing, coating etc., its result shows in Table 1 in the lump.

It should be noted that, as the steel plate of above-mentioned electric pure zinc plating, use steel plate (the Zn adhesion amount 20g/m of the electrogalvanizing not implementing chromate process ², thickness of slab 0.8mm).

[table 1]

For steel plate No.4 ~ 9,14 ~ 18, resin aqueous solution contains fixedness resinous principle 20 ~ 45 mass parts and silicon dioxide granule 55 ~ 80 mass parts in the mode amounting to 100 mass parts, contain the fixedness resinous principle (EC) of ethene-copolymers of unsaturated carboxylic acids aqueous liquid dispersion and the fixedness resinous principle (PU) of carboxylic polyurethane resin water-based liquid as aforementioned fixedness resinous principle, their compounding ratio is EC: PU=90: 10 ~ 40: 60 by quality ratio.It can thus be appreciated that: the corrosion resistance of any steel plate, resistance to alkali degreasing, electric conductivity, coating, mar proof, resistance to tape stripping are all excellent.

Steel plate No.1 ~ 3 are ratio situations lower than 20 mass parts of fixedness resinous principle, and corrosion resistance, resistance to alkali degreasing reduce.

Steel plate No.10,11 is ratio situations more than 45 mass parts of fixedness resinous principle, and electric conductivity, mar proof, resistance to tape stripping reduce.

Steel plate No.12,13 is the too high situations of the ratio of EC in fixedness resinous principle, and resistance to tape stripping reduces.

Steel plate No.19,20 is the too high situations of the ratio of PU in fixedness resinous principle, and resistance to alkali degreasing reduces.

Experimental example 2

Be 30 mass parts according to reaching fixedness resinous principle, silicon dioxide granule is that the mode of total 100 mass parts of 70 mass parts is to coordinate carboxylic polyurethane resin water-based liquid obtained above, above-mentioned ethylene-acrylic acid copolymer aqueous liquid dispersion and silicon dioxide granule, relative to this total 100 mass parts, further interpolation γ-glycidoxypropyltrime,hoxysilane (chemical industrial company of SHIN-ETSU HANTOTAI system, " KBM-403 ") 0 ~ 30 mass parts is as silane coupler, add hexyl trimethoxy silane (chemical industrial company of SHIN-ETSU HANTOTAI system, " KBM-3063 ") 6 mass parts are as alkoxy silane, thus prepare resin aqueous solution.It should be noted that, as silicon dioxide granule, use Nissan Chemical Inc. " Snowtex XS (average grain diameter (BET method) 4 ~ 6nm) ", the ethene-copolymers of unsaturated carboxylic acids (EC) in fixedness resinous principle is EC: PU=70: 30 with the compounding ratio of carboxylic polyurethane resin (PU) by quality ratio.

With compression roller, this resin aqueous solution is coated on the surface of the steel plate of electric pure zinc plating, carries out heat drying with plate temperature 90 DEG C, obtain being formed with adhesion amount 0.5g/m ²the surface-treated metal plate (resin-coated steel plate) of resin involucra.For obtained resin-coated steel plate, composition, corrosion resistance, electric conductivity, mar proof, resistance to alkali degreasing, coating etc. with regard to resin involucra are evaluated, and the display of its result in table 2.

[table 2]

For steel plate No.6,22 ~ 25, relative to total 100 mass parts of fixedness resinous principle and silicon dioxide granule, resin aqueous solution contains silane coupler (a) with the ratio of 5 ~ 20 mass parts, contain alkoxy silane (b) with the ratio of 6 mass parts, the corrosion resistance of known any steel plate, resistance to alkali degreasing, electric conductivity, coating, mar proof, resistance to tape stripping are all excellent.

On the other hand, for not containing the steel plate No.21 of silane coupler (a), corrosion resistance, resistance to alkali degreasing, coating, mar proof, resistance to tape stripping reduce.

In addition, the steel plate No.26 that the addition for silane coupler (a) is too much, 27, coating, mar proof, resistance to tape stripping reduce.

Experimental example 3

Be 30 mass parts according to reaching fixedness resinous principle, silicon dioxide granule is that the mode of total 100 mass parts of 70 mass parts is to coordinate carboxylic polyurethane resin water-based liquid obtained above and above-mentioned ethylene-acrylic acid copolymer aqueous liquid dispersion and silicon dioxide granule, relative to this total 100 mass parts, further interpolation γ-glycidoxypropyltrime,hoxysilane (chemical industrial company of SHIN-ETSU HANTOTAI system, " KBM-403 ") 12 mass parts are as silane coupler, add hexyl trimethoxy silane (chemical industrial company of SHIN-ETSU HANTOTAI system, " KBM-3063 ") 0 ~ 20 mass parts is as alkoxy silane, thus prepare resin aqueous solution.It should be noted that, as silicon dioxide granule, use " Snowtex XS (average grain diameter (BET method) 4 ~ 6nm) " of Nissan Chemical Industries Inc., the ethene-copolymers of unsaturated carboxylic acids (EC) in fixedness resinous principle is EC: PU=70: 30 with the compounding ratio of carboxylic polyurethane resin (PU) by quality ratio.

With compression roller, this resin aqueous solution is coated on the surface of the steel plate of electric pure zinc plating, with plate temperature 90 DEG C of heat dryings, obtains being formed with adhesion amount 0.5g/m ²the surface-treated metal plate (resin-coated steel plate) of resin involucra.For obtained resin-coated steel plate, composition, corrosion resistance, electric conductivity, mar proof, resistance to alkali degreasing, coating etc. with regard to resin involucra are evaluated, and the display of its result in table 3.

It should be noted that, as above-mentioned electric pure zinc plating steel plate, use steel plate (the Zn adhesion amount 20g/m of the electrogalvanizing not implementing chromate process ², thickness of slab 0.8mm).

[table 3]

With regard to steel plate No.6,29 ~ 33, relative to total 100 mass parts of fixedness resinous principle and silicon dioxide granule, resin aqueous solution contains silane coupler (a) with the ratio of 12 mass parts, contain alkoxy silane (b) with the ratio of 1 ~ 14 mass parts, the corrosion resistance of known any steel plate, resistance to alkali degreasing, electric conductivity, coating, mar proof, resistance to tape stripping are all excellent.

On the other hand, do not containing in the steel plate No.28 of alkoxy silane (b), corrosion resistance, resistance to alkali degreasing reduce.

In addition, the steel plate No.34 that the addition with regard to alkoxy silane (b) is too much, 35, corrosion resistance, resistance to alkali degreasing, coating, mar proof, resistance to tape stripping reduce.

Experimental example 4

Be 30 mass parts according to reaching fixedness resinous principle, silicon dioxide granule is that the mode of total 100 mass parts of 70 mass parts is to coordinate polyurethane resin water-based liquid obtained above, above-mentioned ethylene-acrylic acid copolymer aqueous liquid dispersion and average grain diameter are silicon dioxide granule (the Nissan Chemical Inc. of 4 ~ 100nm, " Snowtex " series), relative to this total 100 mass parts, further interpolation γ-glycidoxypropyltrime,hoxysilane (chemical industrial company of SHIN-ETSU HANTOTAI system, " KBM-403 ") 12 mass parts are as silane coupler, add hexyl trimethoxy silane (chemical industrial company of SHIN-ETSU HANTOTAI system, " KBM-3063 ") 6 mass parts are as alkoxy silane, thus prepare resin aqueous solution.It should be noted that, the ethene-copolymers of unsaturated carboxylic acids (EC) in fixedness resinous principle is EC: PU=70: 30 with the compounding ratio of carboxylic polyurethane resin (PU) by quality ratio.

With compression roller, this resin aqueous solution is coated on the surface of electric pure zinc plating steel plate, with plate temperature 90 DEG C of heat dryings, obtains being formed with adhesion amount 0.5g/m ²the surface-treated metal plate (resin-coated steel plate) of resin involucra.For obtained resin-coated steel plate, composition, corrosion resistance, electric conductivity, mar proof, resistance to alkali degreasing, coating etc. with regard to resin involucra are evaluated, and the display of its result in table 4.

[table 4]

With regard to steel plate No.36,37, the situation of to be the average grain diameter of silicon dioxide granule be 4 ~ 6nm or 10 ~ 20nm, the corrosion resistance of known any steel plate, resistance to alkali degreasing, electric conductivity, coating, mar proof, resistance to tape stripping are all excellent.

On the other hand, be in the steel plate No.38,39 of 40 ~ 60nm or 70 ~ 100nm in the average grain diameter of silicon dioxide granule, resistance to alkali degreasing, electric conductivity, coating, mar proof, resistance to tape stripping reduce.

Experimental example 5

Be 30 mass parts according to reaching fixedness resinous principle, silicon dioxide granule is that the mode of total 100 mass parts of 70 mass parts is to coordinate polyurethane resin water-based liquid obtained above, above-mentioned ethylene-acrylic acid copolymer aqueous liquid dispersion and silicon dioxide granule (Nissan Chemical Inc., " Snowtex XS ", average grain diameter (BET method) 4 ~ 6nm), relative to this total 100 mass parts, add silane coupler 12 mass parts shown in table 5 again, add hexyl trimethoxy silane (chemical industrial company of SHIN-ETSU HANTOTAI system, " KBM-3063 ") 6 mass parts are as alkoxy silane, thus prepare resin aqueous solution.It should be noted that, the ethene-copolymers of unsaturated carboxylic acids (EC) in fixedness resinous principle is EC: PU=70: 30 with the compounding ratio of carboxylic polyurethane resin (PU) by quality ratio.

With compression roller, this resin aqueous solution is coated on the surface of the steel plate of electric pure zinc plating, with plate temperature 90 DEG C of heat dryings, obtains being formed with adhesion amount 0.5g/m ²the surface-treated metal plate (resin-coated steel plate) of resin involucra.For obtained resin-coated steel plate, composition, corrosion resistance, electric conductivity, mar proof, resistance to alkali degreasing, coating etc. with regard to resin involucra are evaluated, and the display of its result in table 5.

[table 5]

As shown in table 5, with regard to employing steel plate No.42 ~ 44 of the compound except the silane coupler that formula (a) represents, the poor stability of resin aqueous solution, can not form resin involucra.

Experimental example 6

Be 30 mass parts according to reaching fixedness resinous principle, silicon dioxide granule is that the mode of total 100 mass parts of 70 mass parts is to coordinate polyurethane resin water-based liquid obtained above, above-mentioned ethylene-acrylic acid copolymer aqueous liquid dispersion and silicon dioxide granule (Nissan Chemical Inc., " Snowtex XS ", average grain diameter (BET method) 4 ~ 6nm), relative to this total 100 mass parts, further interpolation γ-glycidoxypropyltrime,hoxysilane (chemical industrial company of SHIN-ETSU HANTOTAI system, " KBM-403 ") 12 mass parts are as silane coupler, add alkoxy silane 6 mass parts shown in table 6, thus prepare resin aqueous solution.It should be noted that, the ethene-copolymers of unsaturated carboxylic acids (EC) in fixedness resinous principle is EC: PU=70: 30 with the compounding ratio of carboxylic polyurethane resin (PU) by quality ratio.

With compression roller, this resin aqueous solution is coated on the surface of the steel plate of electric pure zinc plating, with plate temperature 90 DEG C of heat dryings, obtains being formed with adhesion amount 0.5g/m ²the surface-treated metal plate (resin-coated steel plate) of resin involucra.For obtained resin-coated steel plate, composition, corrosion resistance, electric conductivity, mar proof, resistance to alkali degreasing, coating etc. with regard to resin involucra are evaluated, and its result is presented in table 6.

[table 6]

As shown in table 6, be that in the steel plate No.45,46 of the alkoxy silane of 1,2, the poor stability of resin aqueous solution, can not form resin involucra at the carbon number employing alkyl.In addition, be the steel plate No.47 of the alkoxy silane of 3,4 at the carbon number employing alkyl, in 48, resistance to tape stripping is poor.On the other hand, be that in the steel plate No.50,51 of the alkoxy silane of 8,10, alkoxy silane is poorly soluble to resin aqueous solution, can not prepare resin aqueous solution at the carbon number employing alkyl.

Experimental example 7

Be 30 mass parts according to reaching fixedness resinous principle, silicon dioxide granule is that the mode of total 100 mass parts of 70 mass parts is to coordinate polyurethane resin water-based liquid obtained above, above-mentioned ethylene-acrylic acid copolymer aqueous liquid dispersion and silicon dioxide granule (Nissan Chemical Inc., " Snowtex XS ", average grain diameter (BET method) 4 ~ 6nm), relative to this total 100 mass parts, further interpolation γ-glycidoxypropyltrime,hoxysilane (chemical industrial company of SHIN-ETSU HANTOTAI system, " KBM-403 ") 12 mass parts are as silane coupler, add hexyl trimethoxy silane (chemical industrial company of SHIN-ETSU HANTOTAI system, " KBM-3063 ") 6 mass parts are as alkoxy silane, thus prepare resin aqueous solution.It should be noted that, the match ratio of the ethene-copolymers of unsaturated carboxylic acids (EC) in fixedness resinous principle and carboxylic polyurethane resin (PU) by quality ratio, is EC: PU=70: 30.

With compression roller, this resin aqueous solution being coated on the surface of electric pure zinc plating steel plate, with plate temperature 90 DEG C of heat dryings, by changing the squeeze pressure of roller, obtaining being formed with adhesion amount 0.05 ~ 2.0g/m ²the surface-treated metal plate (resin-coated steel plate) of resin involucra.For obtained resin-coated steel plate, composition, corrosion resistance, electric conductivity, mar proof, resistance to alkali degreasing, coating etc. with regard to resin involucra are evaluated, and the display of its result in table 7.

[table 7]

As shown in table 7, if the adhesion amount of the resin involucra on metallic plate is at 0.05 ~ 1g/m ²scope, then can obtain the surface-treated metal plate of corrosion resistance, resistance to alkali degreasing, electric conductivity, coating, mar proof, resistance to tape stripping excellence.

Utilizability in industry

Surface-treated metal plate of the present invention, because corrosion resistance, resistance to alkali degreasing, electric conductivity, coating (film adaptation), mar proof, resistance to tape stripping are excellent, so be applicable in automobile, household appliances, building materials etc.

Claims

1. a surface-treated metal plate, its resin involucra obtained by resin aqueous solution of at least one side that there is metallic plate and be formed at this metallic plate, wherein,

Described resin aqueous solution is the silicon dioxide granule of 4 ~ 20nm with the average grain diameter of fixedness resinous principle and 55 ~ 80 mass parts that the mode amounting to 100 mass parts contains 20 ~ 45 mass parts,

As described fixedness resinous principle, containing the fixedness resinous principle PU of the fixedness resinous principle EC and carboxylic polyurethane resin water-based liquid that have plenty of ethene-copolymers of unsaturated carboxylic acids aqueous liquid dispersion, their compounding ratio is EC:PU=90:10 ~ 40:60 by quality ratio

And then, relative to total 100 mass parts of described fixedness resinous principle and silicon dioxide granule, the silane coupler represented by formula (a) containing 5 ~ 20 mass parts and the hexyl trimethoxy silane of 1 ~ 14 mass parts,

The adhesion amount of described resin involucra is 0.05 ~ 1g/m ²,

In formula (a), R ¹, R ²represent alkoxyl, R ³represent the alkyl of alkoxyl or carbon number 1 ~ 4, X represents the alkylidene of carbon number 1 ~ 5.

2. surface-treated metal plate according to claim 1, wherein, when monomer total amount is set to 100 quality %, described ethene-copolymers of unsaturated carboxylic acids copolymerization has the unsaturated carboxylic acid composition of 10 ~ 40 quality %.

3. surface-treated metal plate according to claim 1, wherein, described ethene-copolymers of unsaturated carboxylic acids aqueous liquid dispersion contain have more than 2 can with the crosslinking agent of the functional group of carboxyl reaction, when fixedness resinous principle EC in described ethene-copolymers of unsaturated carboxylic acids aqueous liquid dispersion is set to 100 mass parts, described crosslinking agent be more than 1 mass parts and below 20 mass parts containing ratio.

4. surface-treated metal plate according to claim 1, wherein, add up to 100 mass parts relative to fixedness resinous principle and silicon dioxide granule, described resin aqueous solution contain more than 0.5 mass parts and below 5 mass parts, average grain diameter is more than 0.6 μm and the spherical polyolefin-wax particle of less than 4 μm.

5. the surface-treated metal plate according to any one of Claims 1 to 4, wherein, described metallic plate is the steel plate of zinc-plated system.

6. surface-treated metal plate according to claim 5, wherein, has carried out the substrate processing of non-chromate to described metallic plate.