CN100333896C - Resin coating metal plate and its mfg method - Google Patents

Resin coating metal plate and its mfg method Download PDF

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Publication number
CN100333896C
CN100333896C CNB2005100078721A CN200510007872A CN100333896C CN 100333896 C CN100333896 C CN 100333896C CN B2005100078721 A CNB2005100078721 A CN B2005100078721A CN 200510007872 A CN200510007872 A CN 200510007872A CN 100333896 C CN100333896 C CN 100333896C
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unsaturated carboxylic
emulsion compositions
quality
amount
metal plate
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CN1651239A (en
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中元忠繁
梶田富男
贵答丰
今堀雅司
奥村和生
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Kobe Steel Ltd
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Kobe Steel Ltd
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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D123/00—Coating compositions based on homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Coating compositions based on derivatives of such polymers
    • C09D123/02—Coating compositions based on homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Coating compositions based on derivatives of such polymers not modified by chemical after-treatment
    • C09D123/04—Homopolymers or copolymers of ethene
    • C09D123/08—Copolymers of ethene
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D7/00—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials
    • B05D7/14—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials to metal, e.g. car bodies
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/02—Emulsion paints including aerosols
    • C09D5/022—Emulsions, e.g. oil in water
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/08—Anti-corrosive paints
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40—Additives
    • C09D7/66—Additives characterised by particle size
    • C09D7/67—Particle size smaller than 100 nm
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40—Additives
    • C09D7/66—Additives characterised by particle size
    • C09D7/68—Particle size between 100-1000 nm

Abstract

Disclosed is a resin-coated metal sheet which includes a resin film resulting from an emulsion composition containing an ethylene/unsaturated carboxylic acid copolymer as a main component. The emulsion composition contains, other than the ethylene/unsaturated carboxylic acid copolymer, an amine having a boiling point of 100 DEG C or less in an amount equal to 0.2 to 0.8 mol per mole of the carboxyl groups contained in the ethylene/unsaturated carboxylic acid copolymer, and a monovalent metal compound in an amount equal to 0.02 to 0.4 mol per mole of the carboxyl groups contained in the ethylene/unsaturated carboxylic acid copolymer, and in addition, a crosslinking agent having two or more functional groups capable of reacting with the carboxylic groups in an amount of 1 to 20 mass% per 100 mass% of the solid content of the emulsion composition, and does not substantially contain an amine having a boiling point of more than 100 DEG C, and ammonia. The resin-coated metal sheet is not only excellent in various characteristics such as coatability, lubricity, formability, grounding property, but also excellent in corrosion resistance after an alkali degreasing step, and also excellent in tape peeling resistance.

Description

Resin coating metal plate and manufacture method thereof
Technical field
The present invention relates to the resin coating metal plate of excellent anti-corrosion performance, it can be preferred for household electrical appliance, construction material etc., and relates to its manufacture method.
Background technology
Conventionally, except that aluminium sheet and corrosion resistant plate, surface treated steel plate such as plated steel sheet and hot-dip galvanized steel sheet have extensive use as the sheet metal that can be used for household electrical appliance and building materials.Wherein, zinc-plated type surface treated steel plate is handled through chromaking or the phosphatization processing, and be widely used in various structure members, machine element and the bottom plate of microwave oven of acoustic instrument, comprise most home electronics.Yet in recent years, the user is more and more higher to the requirement of these surface treated steel plates, causes the demand to various film performances.
For example, when surface treated steel plate uses with naked form, need them to have decay resistance, ground connection performance, anti-finger printing energy, even like this under situation about being in contact with it, fingerprint is so unobvious yet, and chemical resistance, stain resistance etc. are to the tolerance of alkali, solvent etc.Yet, when steel plate is compression moulding or stamping-out, need them to have lubricity, cracking resistance line performance, drawability, resistant to mold wear energy, stampability, anti-moulding sliding surface melanism performance and to oil resistance of punching oil/quick-drying oil etc.
In order to satisfy these requirements to performance, for example Japanese publication communique No.6-246229 discloses a kind of steel plate of organic composite material coating, it is included in the resin molding on the chromizing layer, wherein neutralizes with the carboxyl of sodium ion with 60-80% in the olefinic ionomer.Yet, Japan Patent No.2759620 discloses a kind of resin-coated metallic plate, comprise the film that forms at metal sheet surface from a kind of composition, said composition contains intermolecular via ion cluster polyolefin copolymer resin emulsion that associates and the organic compound that has aziridinyl.Japan Patent No.2759620 to the effect that, the preferred chromaking of metallic plate.
Yet, in recent years since in order to preserve our planet environment to the reasons such as development that do not contain chromium (non-chromaking) product, need resin molding than had higher decay resistance in the past.
As mentioned above, each will be stacked on the decay resistance that the resin molding that does not contain on the chromium metallic plate also begins need have and be coated on each the resin molding par on the chromaking metallic plate.Under these circumstances, even behind applying date this patent No.2759620, the inventor has still carried out the research that continues.The resin molding of describing among the Japan Patent No.2759620 also demonstrates certain excellent decay resistance to not containing the chromium plate material.Yet, for example in defatting step, remove after the lubricating oil of using in the compression moulding process, owing to resin molding is degraded unfriendly, caused the decline of decay resistance with alkali treatment.Yet, do not containing coating resin film on the chromium metallic plate, then, on surface resin film, stick adhesive tape and make it to keep long-time.Then, peel off adhesive tape, this in addition make resin molding also be stripped from.Thereby, there is the problem of such shortcoming fissility of anti-adhesive tape the (adhesion between metallic plate and the resin molding).
Summary of the invention
Therefore, under these circumstances, target of the present invention provides a kind of resin coating metal plate, it has the resin molding of various aspects of performance excellence, but as coating (the adhesion ability of film on resin coating metal plate), lubricity, formability and ground connection property as the regulation performance, and behind defatting step excellent decay resistance and the fissility of anti-the adhesive tape.
One aspect of the present invention is a kind of resin coating metal plate, and it comprises: metallic plate; With the resin molding that is coated on the metal sheet surface, this resin molding is obtained by emulsion compositions, and wherein this emulsion compositions comprises: as the ethene/copolymers of unsaturated carboxylic acids of key component; Measure the amine that is included in the carboxyl in ethene/copolymers of unsaturated carboxylic acids for the 0.2-0.8 moles/mole, the boiling point of this amine is 100 ℃ or lower; Amount is a divalent metal compound of carboxyl contained in 0.02-0.4 moles/mole ethene/copolymers of unsaturated carboxylic acids; Be the crosslinking agent of 1-20 quality %/100 quality % emulsion compositions solid contents with amount, this crosslinking agent have 2 or a plurality of can with the functional group of contained carboxyl reaction in ethene/copolymers of unsaturated carboxylic acids, and wherein emulsion compositions does not contain the amine that boiling point is higher than 100 ℃ substantially, and does not contain ammonia substantially.
According to this aspect, in ethene/copolymers of unsaturated carboxylic acids, the unsaturated carboxylic acid of preferred 10-40 quality % is by copolymerization, and most preferably the unsaturated carboxylic acid of 15-25 quality % is by copolymerization.Amine with 100 ℃ or lower boiling point is triethylamine, and this also is the preferred embodiments of the invention.
According to this aspect, in the emulsion compositions solid content of per 100 quality %, the average grain diameter that preferred amount is 5-40 quality % is the silica dioxide granule of 1-200nm.The spherical polyethylene wax that also preferably contains 0.5-20 quality %.This has formed the resin molding with various performances, but as coating, lubricity, formability and ground connection performance, and this resin molding also has excellent decay resistance and the fissility of anti-the adhesive tape behind defatting step.By the way, even under the situation that does not form the chromaking film, resin coating metal plate of the present invention has also demonstrated excellent decay resistance.
According to this aspect of the invention, in resin coating metal plate, be 100 ℃ or lower amine and metallic compound by the boiling point that is used in combination specified quantitative, with ethene/copolymers of unsaturated carboxylic acids neutralization, formed a kind of emulsion.Therefore, can obtain to have the emulsion compositions of minimum particle diameter.Therefore, can obtain to be coated with the resin coating metal plate of film with various excellent properties, but as coating, lubricity, formability and ground connection performance, and behind defatting step excellent decay resistance and the fissility of anti-the adhesive tape.
Another aspect of the present invention is a kind of method of making resin coating metal plate, and it may further comprise the steps: the preparation emulsion compositions; This emulsion compositions of coating on metallic plate; Heating and the drying coated metallic plate of emulsion compositions.
The specific embodiment
Resin coating metal plate of the present invention comprises the resin molding that forms in the supreme side of metallic plate from specific emulsion compositions.Metallic plate is not particularly limited.For example, can should be mentioned that steel plate, aluminium sheet, aluminum series alloy plate or titanium plate zinc-plated or zinc system.And, metallic plate is handled or other surface treatment through known antirust surface treatment such as phosphatization, and to form resin molding thereon also be acceptable.From the viewpoint of environmental problem, preferably this sheet material is handled without chromaking.
The emulsion compositions that is used for forming in the present invention resin molding contains the ethene/copolymers of unsaturated carboxylic acids (comprising neutral condition) as key component, boiling point is 100 ℃ or lower amine, its amount is contained carboxyl in 0.2-0.8 mole (20-80 mole %)/molar ethylene/copolymers of unsaturated carboxylic acids, one divalent metal compound, its amount is contained carboxyl in 0.02-0.4 mole (2-40 mole %)/molar ethylene/copolymers of unsaturated carboxylic acids, also has crosslinking agent, its amount is 0.5-20 quality %/100 quality % emulsion compositions solid contents, this crosslinking agent have 2 or a plurality of can with the functional group of carboxyl reaction, and said composition does not contain amine and ammonia that boiling point is higher than 100 ℃ substantially.
Described ethene/copolymers of unsaturated carboxylic acids is the copolymer of ethene and ethylenic unsaturated carboxylic acid.As unsaturated carboxylic acid, can should be mentioned that (methyl) acrylic acid, crotonic acid, iso-crotonic acid, maleic acid, fumaric acid, itaconic acid etc.By known method polymerizations such as high temperature high-pressure polymerization process one or more and ethene wherein, can obtain described copolymer.This copolymer most preferably is a random copolymer.Yet it also can be block copolymer or the copolymer of partly locating grafting at unsaturated carboxylic acid.By the way, unsaturated carboxylic acid (methyl) acrylic acid preferably.And, also can adopt olefinic type monomers such as propylene or 1-butylene to replace a part of ethene.And then, the also monomer of other known vinyl type of copolymerization (amount for about 10 quality % or lower) partly, only otherwise damaging purpose of the present invention gets final product.
For the copolymerization ratio of unsaturated carboxylic acid and ethene, when the monomer total amount was considered as 100 quality %, the amount of unsaturated carboxylic acid was preferably 10-40 quality %.When the amount of unsaturated carboxylic acid is lower than 10 quality %, too little as the amount of the carboxyl of the crosslinking points of the basic point of intermolecular association or crosslinking agent via ion cluster.Therefore, disadvantageously, do not bring into play the film-strength effect, like this, the decay resistance behind fissility of anti-adhesive tape the and the defatting step can be insufficient.In addition, the emulsion stability of emulsion compositions is poor.The more preferably lower limit of unsaturated carboxylic acid amount is 15 quality %.On the other hand, when the amount of unsaturated carboxylic acid surpassed 40 quality %, the decay resistance and the water resistance of resin molding were poor.Therefore, disadvantageously, the decay resistance behind the defatting step can reduce equally.The preferred upper limit is 25 quality %.
Described ethene/copolymers of unsaturated carboxylic acids has carboxyl.Therefore, can it be neutralized, make emulsion (making aqueous dispersion) thus with organic base or metal ion.In the present invention, be that 100 ℃ or lower amine are as organic base with boiling point.Boiling point is higher than 100 ℃ amine and is retained in easily on the steel plate when resin-coated film is dry, causes resin-coated film water absorbing properties to improve.This causes the decline of decay resistance.For this reason, boiling point not being higher than 100 ℃ amine is included in the emulsion compositions that is used to form film of the present invention.And, do not comprise ammonia, because do not observe the additive effect of ammonia as yet yet.As boiling point, employing be boiling point under the atmospheric pressure.
Boiling point is that the instantiation of 100 ℃ or lower amine comprises: tertiary amine such as triethylamine, N, N-dimethyl butylamine, N, N-DMAA, N-methyl pyrrolidone, tetramethyl diaminourea methane and trimethylamine; Secondary amine such as N-Methylethyl amine, diisopropylamine and diethylamine; With primary amine such as propylamine, tert-butylamine, sec-butylamine, isobutyl amine, 1,2-dibutyl propyl group amine and 3-amylamine.These can use separately or with two or the form of more kinds of mixture use.Wherein, preferred tertiary amine, most preferably triethylamine.
With boiling point is that the amount of 100 ℃ or lower amine is set at the carboxyl in 0.2-0.8 mole (20-80 mole %)/molar ethylene/copolymers of unsaturated carboxylic acids.This is because the amount in this scope can cause excellent corrosion resisting performance and the fissility of anti-the adhesive tape.When boiling point is the amount of 100 ℃ or lower amine during less than 0.2mol, the particle diameter of resin particle is bigger in the emulsion., can contemplate for this reason, can not bring into play aforesaid effect.Yet when boiling point is the consumption of 100 ℃ or lower amine during greater than 0.8mol, viscosity can take place and raise and gel in emulsion compositions unfriendly.The amount of amine more preferably on be limited to 0.6mol, 0.5mol more preferably.The amount of amine more preferably be limited to 0.3mol down.
In the present invention, also monovalent metallic ion is used for neutralization.This is effective for improving solvent resistance and film hardness.Therefore, in emulsion compositions, add a divalent metal compound.A described divalent metal compound preferably contains one or two or more kinds of metal that is selected from sodium, potassium and lithium.Hydroxide, oxycarbide or the oxide of more preferred metals.Wherein, preferred NaOH, KOH, LiOH etc., NaOH most preferably is because it has optimum performance.And, for two or more the high price metallic compound, do not observe the effect that interpolation produces.Therefore, the emulsion compositions that is used for film forming does not in the present invention contain two or high-valency metal compound more as the reactive component of ethene/copolymers of unsaturated carboxylic acids.
The amount of one divalent metal compound is set in carboxyl in 0.02-0.4 mole (2-40 mole %)/molar ethylene/copolymers of unsaturated carboxylic acids.When the amount of described metallic compound was lower than 0.02mol, it is insufficient that emulsion stability becomes.Yet when this amount surpassed 0.4mol, the moisture pick-up properties of the resin molding that obtains (particularly to alkaline solution) improved, and caused the decay resistance variation behind the defatting step unfriendly.The more preferably lower limit of described metallic compound amount is 0.03mol.Further preferred lower limit is 0.1mol.The more preferably upper limit of metallic compound amount is 0.5mol, and further preferred upper limit is 0.2mol.
Using boiling point with preferred amount in above-mentioned scope separately is 100 ℃ or a lower amine and a divalent metal compound.The two all is used for the carboxyl and the emulsified copolymer of neutralization of ethylene/copolymers of unsaturated carboxylic acids.Therefore, when its total amount (dosis neutralisata) was too big, disadvantageously, the viscosity of emulsion compositions improved rapidly and solidifies, and in addition, excessive alkaline constituents causes the corrosion resistance variation.And, need lot of energy to make excessive alkaline constituents volatilization.Yet, when dosis neutralisata too hour, disadvantageously, but also variation unfriendly of emulsibility.Therefore, boiling point is that the total amount of 100 ℃ or a lower amine and a divalent metal compound preferably sets the carboxyl in 0.3-1.0 moles/mole ethene/copolymers of unsaturated carboxylic acids.
Being used in combination boiling point and being 100 ℃ or lower amine and a divalent metal compound carries out emulsification and has formed and be used for emulsion compositions of the present invention.As a result, the resin particle in the composition stably is present in the water-bearing media with superfine little particle (oil droplet) form that is of a size of 5～50nm.Infer this filming performance that can realize the resin molding that obtains, densified to the adhesion of metallic plate and film, obtained improvement decay resistance and the fissility of anti-the adhesive tape.Described water-bearing media can contain hydrophilic solvent such as alcohol or ether beyond water.By the way, the resin particle particle diameter in the emulsion can be measured by the laser diffractometry that for example adopts light scattering photometer (OTSUKA ELECTRONICSCo., Ltd. makes).
Be in the single neutralization procedure (emulsifying step) that belongs to ethene/copolymers of unsaturated carboxylic acids that compound carries out of 100 ℃ or lower amine and monovalence with boiling point, wish that almost side by side adding boiling point in copolymer is 100 ℃ or a lower amine and a divalent metal compound, perhaps adding boiling point earlier is 100 ℃ or lower amine.This is because it is that 100 ℃ or lower amine can cause the insufficient of the decay resistance/fissility of anti-adhesive tape improvement effect that the back adds boiling point, although its reason and not clear.
Carboxyl is that the ethene/copolymers of unsaturated carboxylic acids of 100 ℃ or lower amine and divalent metal compound neutralization forms intermolecular association (being converted into ionomer) via ion cluster by boiling point, to form the resin molding of the decay resistance/fissility of anti-adhesive tape excellence.Yet,, wish that polymer chain utilizes the reaction between functional group to be cross-linked to each other via chemical bond for forming more strong film.Under these circumstances, emulsion compositions of the present invention contains crosslinking agent as solvent, and it has two or the functional group of the enough and carboxyl reaction of multipotency more.Its amount is set in the emulsion compositions solid content of 1-20 quality %/100 quality %.When this amount is lower than 1 quality %, become insufficient by the crosslinked effect of chemical bond.Therefore, so easy performance is to the improvement effect of decay resistance/fissility of anti-the adhesive tape.On the other hand, when when sneaking into crosslinking agent greater than the amount of 20 quality %, the crosslink density of resin molding excessively increases, and causes the raising of hardness.Therefore, resin molding become can not be along the time with compression moulding distortion, this causes the formation of crackle.As a result, but decay resistance and coating have been reduced unfriendly.Preferred dosage of crosslinking agent is the solids content of 5-10 quality %/100 quality % emulsion compositions.By the way, for the ratio of the amount of the amount of crosslinking agent and ethene/copolymers of unsaturated carboxylic acids, the amount of wishing crosslinking agent suitably changes according to the amount of carboxyl in the copolymer.Usually, the amount of crosslinking agent is preferably 0.5-50 mass parts (more preferably 5-20 mass parts)/100 mass parts copolymers.
Each molecule have 2 or more the crosslinking agent of the functional group of the enough and carboxyl reaction of multipotency be not particularly limited.Yet, its preferred embodiment can comprise: the crosslinking agent that contains glycidyl, comprise the many glycidyl ethers of many glycidyl ethers such as D-sorbite, the many glycidyl ethers of (gathering) glycerine, the many glycidyl ethers of pentaerythrite, the many glycidyl ethers of trimethylolpropane, neopentyl glycol diglycidyl ether and (gathering) ethylene glycol bisthioglycolate glycidyl ether and many glycidyl group amines; Two sense aziridine cpds are as 4,4 '-two (aziridine carbonylamino) diphenyl methane, N, N '-hexa-methylene-1,6-two (1-aziridine Carboxylamide), N, N '-diphenyl methane-4,4 '-two (1-aziridine Carboxylamides) and the two aziridine Carboxylamides of toluene; With the crosslinking agent that contains '-aziridino, comprise three or more polyfunctional aziridine cpd, as three-1-'-aziridino phosphine oxide, three [1-(2-methyl) '-aziridino] phosphine oxide, trimethylolpropane tris (β-'-aziridino propionic ester), three-2,4,6-(1-'-aziridino)-1,3,5-triazine and tetramethyl propane four '-aziridino propionic esters, or derivatives thereof.They can use separately, or make up two or more uses.Wherein, the crosslinking agent that preferably contains '-aziridino.By the way, can be used in combination polyfunctional aziridines class and simple function aziridines (as aziridine).
The emulsion compositions that is used for the present invention can contain silica dioxide granule with the amount of 5-40 quality %, based on solid content meter.But this is for improving decay resistance coating, anti-crack performance etc. effectively, and is also effective to decay resistance and the fissility of anti-adhesive tape the after the improvement degreasing.When this amount is lower than 5 quality %, be not easy to generate these effects so.Yet when this amount surpassed 40 quality %, the ratio of silica dioxide granule excessively increased, and causes the reduction to filming performance.Therefore, in the resin molding crackle can take place, cause the reduction of decay resistance unfriendly in drying steps.And silica dioxide granule is as buffing compound, and the lubricity that this has improved film causes the decline of coefficient of friction.This causes in the forming process the wearing and tearing of mould, has shortened the life-span of mould.The silica dioxide granule amount more preferably be limited to 20 quality % down, be limited to 30 quality % on it.
In order to make the above-mentioned maximum effect of silica dioxide granule, the average grain diameter of silica dioxide granule is preferably 1-200nm.Along with the decline of silica dioxide granule particle diameter, the decay resistance of film is improved.Can infer and be due to the fact that.Resin molding is by densified, and adhesion improves, and this has further improved decay resistance.Based on this viewpoint, wish that silica dioxide granule has littler particle diameter.Yet, when they are superfine little particle, the aforementioned effect state that reaches capacity.For this reason, the lower limit of particle diameter is preferably 1nm.On the other hand, when the silica dioxide granule particle diameter surpassed 200nm, surface resin film was roughened.Therefore, can not form fine and close resin molding.And also as buffing compound, this has caused the deterioration of formability to silica dioxide granule unfriendly.Especially, when the decay resistance after the attention degreasing, the particle mean size of silica dioxide granule is preferably set to 4-20nm.
The so-called cataloid of silica dioxide granule like this.In the present invention, can for example preferably adopt (Nissan Chemical Industries, the cataloids that Ltd. produces) such as " XS ", " SS ", " 40 ", " N ", " UP " of " Snow Tex series ".
In emulsion compositions of the present invention, can contain the wax of 0.5-20 quality %, based on solid content meter.Described wax has the lubricity of the resin molding that obtains and the improvement effect of anti-crack performance.And, it is preferred for improving in the required drawability of compression moulding and stamping-out and stampability, resistant to mold wear energy and the moulding anti-sliding surface melanism performance and excellent formability is provided.
When the amount based on solid content meter wax was lower than 0.5 quality %, the lubricity of the resin molding of formation became insufficient.Therefore, can not improve anti-crackle and the gratifying formability of acquisition.On the other hand, when this amount surpassed 20 quality %, the resin molding of formation had sufficient lubricity, and still, when making it through the back coating of electro-deposition, powder coated or serigraphy, the adhesiveness of its film (but coating) is relatively poor.And decay resistance after the degreasing and the stripping performance of anti-the adhesive tape be variation also.May be due to the fact that.Wax can perhaps change in time by heating to come softening/liquefaction or frosting in the application step of back, and concentrate between resin molding and back coated film at the interface or metallic plate and resin molding at the interface.Therefore, with the adhesion of back coated film or with the adhesion variation of metallic plate.Preferred higher limit is 10 quality %, even preferred higher limit is 5.0 quality %.
Described wax is not particularly limited, and available wax is native paraffin and synthetic wax and composition thereof etc.The example of available native paraffin comprises Brazil wax, rice wax, candelila wax and brown coal type wax, and derivative, mineral oil origin wax, microwax, paraffin etc., and by adding the derivative that carboxyl obtains.
As synthetic wax, can should be mentioned that the oxidized petroleum waves of the copolymer waxes of polyethylene, PEO, polypropylene, ethylene/propene copolymer type wax and ethene and other monomer.As this individual system,, can adopt the polytype that also comprises the terpolymer type according to the variation of copolyreaction component.And, can mention maleic acid adduct wax, fatty acid ester type etc.And fluorine resin type wax also is available as polytetrafluoroethylene (PTFE), polyvinyl fluoride, polyvinylidene fluoride and tetrafluoroethene.
As wax, preferably from above example, select softening point and be those of 80-140 ℃.When softening point was lower than 80 ℃, when compression moulding or stamping-out, Wax particles softened along with the rising of mold temperature/liquefaction.Therefore, the sliding surface place between resin-coated steel plate and mould, the liquid that liquefied wax can take place exhausts phenomenon, causes the decline of plastic performance.This causes scratch unfriendly and stings mould.And, can adhesion melanism material on slipper, badly damaged product appearance.And still decay resistance and the stripping performance of anti-adhesive tape viewpoint behind the defatting step shows that low excessively softening point is not preferred.On the other hand, when softening point surpassed 140 ℃, the lubricity that wax produces became insufficient.Therefore, stampability, anti-mould friction property, drawability etc. can not be improved.Decay resistance after the degreasing also shows slight downward trend.
Described wax most preferably is spherical Tissuemat E.In this case, in order to make the maximum effect of spherical polyethylene wax, the particle diameter of Wax particles is preferably 0.1-3 μ m.When the particle diameter of Wax particles during, be difficult to significantly improve lubricity, stampability, anti-mould friction property and drawability energy less than 0.1 μ m.On the other hand, when the particle diameter of Wax particles surpasses 3 μ m, be difficult to Wax particles is distributed in the emulsion compositions equably with the form of fine particle.This may reduce the adhesion of resin molding to metallic plate.The particle diameter of preferred spherical polyethylene wax is 0.3-1.0 μ m.
As aforesaid spherical polyethylene wax, can adopt and for example be purchased product as " DAIJETE-17 " (GOO Chemical Co., Ltd. production), " KUE-1 ", " KUE-5 " and " KUE-8 " (Sanyo Chemical Industries, Ltd. produce), (Mitsui Chemicals production) and " Elepon E-20 " (NICCA Chemical Co., Ltd. produces) such as " W-100 ", " W-200 " of " Chemipearl " series, " W-300 ", " W-400 ", " W-500 ", " W-640 ", " W-700 ".
Emulsion compositions of the present invention preferably contains ethene/copolymers of unsaturated carboxylic acids as key component, and boiling point is 100 ℃ or lower amine, a divalent metal compound, crosslinking agent such as aziridine cpd, and the silica dioxide granule that uses as required, wax etc.Described ethene/copolymers of unsaturated carboxylic acids wishes to comprise with such amount, so that regulate the amount of aziridine cpd, silica dioxide granule, wax etc., the content that makes these resin Compositions is 50 quality % or more of emulsion compositions solids content.
Prepare emulsion compositions in the following manner.At first, with ethene/copolymers of unsaturated carboxylic acids as key component in the middle of water-bearing media for example is fed to homogenizer device etc., as required, under 70-250 ℃ heating.Under high shear force stirs, suitably adding boiling point with forms such as the aqueous solution is 100 ℃ or lower amine and a divalent metal compound (at first adding boiling point is 100 ℃ or lower amine, or almost side by side add boiling point be 100 ℃ or a lower amine and a divalent metal compound).Can add silica dioxide granule, wax, crosslinking agent etc. in any stage.Yet, after adding crosslinking agent, wish not heating, to prevent the carrying out of cross-linking reaction and gelation.
Can suitably in emulsion compositions, add retarder thinner, anti-skinning agent, levelling agent, defoamer, bleeding agent, emulsifying agent, coalescents, coloring pigment, thickener, silane coupler and other resin etc., as long as purpose of the present invention is without prejudice.
Can on metallic plate, form resin molding in the following manner.On side surface of metallic plate or opposite flank, be coated with emulsion compositions by known coating process, for example, roll coater method, spraying process, curtain formula flow coater method etc., and heating and dry.Preferably under the temperature that the cross-linking reaction between used crosslinking agent and the carboxyl is carried out, heat and drying.And, when spherical polyethylene wax is used as lubricant, keep spherical form obtaining more excellent formability in the forming step subsequently.Therefore, wish under 70-130 ℃ temperature, to carry out drying.
The amount (thickness) of the resin molding of coating is preferably dry back 0.2-2.5g/m 2When resin molding is too thin, be difficult to evenly coating on metallic plate, and be difficult to obtain balanced target film characteristic, but as formability, corrosion resistance and coating.Yet, when coating weight surpasses 2.5g/m 2The time, when resin coating metal plate is used for computer case etc., the ground connection performance, promptly electric conductivity has been reduced unfriendly.And the amount with the resin molding of being stripped from the compression moulding process increases, and the deposition of stripping film on mould can take place like this.This has hindered compression moulding, says it is useless from manufacturing cost.The following 0.5g/m that is limited to of the deposition of preferred resin molding 2, on be limited to 2.0g/m 2
By forming resin molding, can obtain resin coating metal plate of the present invention.Can make resin coating metal plate carry out forming step, and be used for the purpose of its plan.Perhaps, also can make its under normal condition (at 130-160 ℃ of about 20-30 minute) to carry out electro-deposition/powder coated/silk-screen and use.
Embodiment
Below, will the present invention be described in more detail in the mode of embodiment.Yet following embodiment should not be construed as limitation of the scope of the invention, should be appreciated that to implement the present invention through suitable change within the scope of the present invention, and it all is included in the present invention.
[method of testing]
The method of testing that is used for following examples is as follows.
(1) decay resistance behind the defatting step
In the alkaline defatting agent that is adjusted to 60 ℃ 20g/l (Nihon ParkerizingCo., " CL-N364S " that Ltd. produces), soaked resin coating metal plate 2 minutes, mention then, then washing and dry.Implement neutral salt spray test according to JISZ2371 then, the white rust of measuring until 1% amount forms required time span.Evaluation criterion is as follows: two circles: 240 hours or longer, and circle: be lower than 120 to 240 hours, triangle: be lower than 72-120 hour, cross: be lower than 72 hours.
(2) fissility of anti-the adhesive tape
Paste adhesive tape (the thread adhesive tape of No.9510 that Sliontec Corp. produces to resin coating metal plate; Rubber adhesive).In thermostatic constant wet equipment, in 40 ℃, 98%RH atmosphere, stored metallic plate 24 hours.Then, peel off adhesive tape to determine the revolution mark ratio of film according to JIS K 5400 from it.Evaluation criterion is as follows: two circles: film keeps than 100%, and circle: film keeps than 90-99%, triangle: film keeps than 89-70%, cross: film keeps than 70% or lower.
(3) coefficient of kinetic friction
In order to assess the lubricity of resin coating metal plate, be determined at the load that the pull speed lower slider of 5.4MPa plus-pressure and 300mm/ minute produces by the slip experimental provision, calculate the coefficient of kinetic friction thus.
EXPERIMENTAL EXAMPLE 1 (kind of organic base and slaine and the effect of amount)
As metallic sheet material, (the Zn coating weight is 20g/m to have used plated steel sheet 2, thickness of slab 0.8mm).
In order to prepare emulsion compositions, in autoclave, add 626 mass parts (being designated hereinafter simply as " part ") water, 160 parts of ethylene/acrylic acid copolymer (acrylic acid 20 quality %, melt index (MI) (MI) is 300).And, at 150 ℃, under the 5Pa atmosphere, under high-speed stirred, add organic base and metallic compound with the amount shown in separately in the table 1, form the ethylene/acrylic acid copolymer emulsion.Subsequently, in the emulsion that obtains, add 4,4 '-two ('-aziridino carbonylamino) diphenyl methane (" CHEMITITE DZ-22E " with the amount of counting 5 quality % based on solids content (value when the solids content of emulsion compositions being got work 100 quality % :) to following same being suitable for; " CHEMITITE " is trade name; By NIPPON SHOKUBAI Co., Ltd produces) as crosslinking agent.
In the mixture that obtains, under agitation add another kind of crosslinking agent (outside cross-linking agent) with the amount of counting 5 quality % based on solids content, it is that (" EPICLON CR5L " is following to be called CR5L with it: " EPICLON " is trade name to a kind of compound that contains glycidyl; Produce by DAINIPPON INK AND CHEMICALS Inc.), adding particle diameter with the amount of counting 30 quality % based on solids content is the silica dioxide granule (" SNOWTECHS 40 " of 10-20nm; NISSAN CHEMICAL INDUSTRIES Ltd. produces), and to add softening point with the amount of counting 5 quality % based on solids content be that 120 ℃ and average grain diameter are the spherical Tissuemat E of 1 μ m, to prepare various emulsion compositions.
Each composition is applied on the side of galvanized steel plain sheet by the excellent coating machine that winds the line, heating and drying are 1 minute under 90 ℃ plate temperature.This has formed resin-coated steel plate, wherein with 1.0g/mm 2Coating weight formed resin molding.Assessment result separately is shown in Table 1.
Table 1
Sequence number The kind of amine and consumption thereof 1)(mole %) The kind of slaine and consumption thereof 1)(mole %) Corrosion resistance after the degreasing The fissility of anti-the adhesive tape
1 Triethylamine 20 NaOH 15 ◎ ◎
2 Triethylamine 40 NaOH 15 ◎ ◎
3 Triethylamine 60 NaOH 15 ◎ ◎
4 Triethylamine 70 NaOH 15 ◎ ◎
5 Triethylamine 80 NaOH 15 ○ ◎
6 Triethylamine 40 NaOH 2 ○ ○
7 Triethylamine 40 NaOH 5 ◎ ○
8 Triethylamine 40 NaOH 10 ◎ ◎
9 Triethylamine 40 NaOH 20 ◎ ◎
10 Triethylamine 40 NaOH 30 ◎ ◎
11 Triethylamine 40 NaOH 40 ○ ◎
12 Triethylamine 20 NaOH 2 ○ ○
13 Triethylamine 80 NaOH 40 ○ ◎
14 Triethylamine 20 NaOH 40 ○ ◎
15 Triethylamine 80 NaOH 2 ○ ○
16 Triethylamine 40 KOH 15 ○ ○
17 Triethylamine 40 LiOH 15 ○ ○
18 Triethylamine 40 NaOH 1 △ ×
19 Triethylamine 40 NaOH 45 △ ○
20 Triethylamine 18 NaOH 15 △ △
21 Triethylamine 85 NaOH 15 △ △
22 Tetramethyl diaminourea methane 20 NaOH 15 ◎ ○
23 Tetramethyl diaminourea methane 40 NaOH 15 ◎ ◎
24 Tetramethyl diaminourea methane 60 NaOH 15 ◎ ◎
25 Tetramethyl diaminourea methane 80 NaOH 15 ◎ ○
26 Ammonia 40 NaOH 15 △ ×
27 Ethylenediamine 40 NaOH 15 △ ×
28 MEA 40 NaOH 15 × ×
29 Diethanol amine 40 NaOH 15 × ×
30 Ammonia 60 NaOH 15 × ×
1), 2): the carboxyl in mole %/molar ethylene-acrylic copolymer
EXPERIMENTAL EXAMPLE 2 (effect of cross-linked dosage)
Having obtained every kind of resin-coated steel plate with the mode identical with EXPERIMENTAL EXAMPLE 1, is 40% except the consumption that makes triethylamine is constant, and the consumption of NaOH is constant to be 15%, and with the amount of " CHEMITITEDZ-22E " by changing shown in the table 2.Then, the characteristic of every kind of resin-coated steel plate of assessment.The results are shown in the table 2.
Table 2
Sequence number The DZ-22E melting concn 1)(quality %) Corrosion resistance after the degreasing The fissility of anti-the adhesive tape
31 1 ○ ○
32 3 ◎ ○
33 5 ◎ ◎
34 10 ◎ ◎
35 15 ○ ○
36 20 ○ ○
37 0.3 × △
38 25 × ×
1): the concentration in the emulsion compositions solids content
EXPERIMENTAL EXAMPLE 3 (effect of silica dioxide granule)
Obtained every kind of resin-coated steel plate with the mode identical with EXPERIMENTAL EXAMPLE 2, except the amount of crosslinking agent is identical with EXPERIMENTAL EXAMPLE 1, the particle diameter of silica dioxide granule and melting concn are by changing shown in the table 3.Then, the characteristic of every kind of resin-coated steel plate of assessment.The results are shown in the table 3.
Table 3
Sequence number Silica dioxide granule Corrosion resistance after the degreasing The fissility of anti-the adhesive tape
Particle diameter (nm) Melting concn 1)(quality %)
39 4 to 6 30 ◎ ◎
40 10 to 20 30 ◎ ◎
41 30 to 50 30 ○ ◎
42 40 to 200 30 ○ ◎
43 10 to 20 5 ○ ○
44 10 to 20 10 ○ ○
45 10 to 20 15 ○ ○
46 10 to 20 20 ◎ ◎
47 10 to 20 26 ◎ ◎
48 10 to 20 30 ◎ ◎
49 10 to 20 35 ◎ ◎
50 10 to 20 40 ○ ○
51 10 to 20 3 △ △
52 10 to 20 45 △ △
53 1 or littler 30 ○ ○
54 200 or bigger 30 △ △
1): the concentration in the emulsion compositions solids content
EXPERIMENTAL EXAMPLE 4 (effect of wax)
Obtained every kind of resin-coated steel plate with the mode identical with EXPERIMENTAL EXAMPLE 2, except the particle diameter of silica dioxide granule identical with melting concn with EXPERIMENTAL EXAMPLE 1, and with particle diameter, melting concn and the softening temperature of spherical polyethylene wax by changing shown in the table 4.Then, the characteristic of every kind of resin-coated steel plate of assessment.The results are shown in the table 4.
Table 4
Sequence number Spherical polyethylene wax The coefficient of kinetic friction Corrosion resistance after the degreasing The fissility of anti-the adhesive tape
Particle diameter (μ m) Melting concn 1)(quality %) Softening temperature (℃)
55 1.0 0.5 120 0.085 ◎ ◎
56 1.0 1 120 0.070 ◎ ◎
57 1.0 5 120 0.065 ◎ ◎
58 1.0 10 120 0.065 ◎ ◎
59 1.0 15 120 0.065 ◎ ◎
60 1 0 20 120 0.065 ○ ○
61 1.0 0.3 120 0.125 ◎ ◎
62 1.0 25 120 0.065 △ △
63 0.1 5 120 0.085 ◎ ◎
64 0.3 5 120 0.065 ◎ ◎
65 0.5 5 120 0.065 ◎ ◎
66 1.0 5 120 0.065 ◎ ◎
67 1.5 5 120 0.077 ◎ ◎
68 3.0 5 120 0.085 ○ ○
69 ＜0.1 5 120 0.248 ◎ ◎
70 3.5 5 120 0.125 △ △
71 1.0 5 80 0.068 ○ ◎
72 1.0 5 100 0.064 ◎ ◎
73 1.0 5 120 0.065 ◎ ◎
74 1.0 5 140 0.072 ◎ ◎
75 1.0 5 70 0.070 △ △
76 1.0 5 150 0.262 △ ◎
1): the concentration in the emulsion compositions solids content
More than with the formal description of preferred embodiment the present invention.Yet, those skilled in the art will recognize that the mode of texturing that has many these embodiments.Expect that these distortion will drop in the scope of the present invention and claims.

Claims (9)

1. resin coating metal plate comprises:
Metallic plate; With
Be coated on the resin molding on the metal sheet surface, this resin molding is obtained by emulsion compositions, and wherein this emulsion compositions comprises:
Ethene/copolymers of unsaturated carboxylic acids is as key component;
Amine, its amount is included in carboxyl in ethene/copolymers of unsaturated carboxylic acids for the 0.2-0.8 moles/mole, and the boiling point of this amine is 100 ℃ or lower;
One divalent metal compound, its amount is included in carboxyl in ethene/copolymers of unsaturated carboxylic acids for the 0.02-0.4 moles/mole; With
Crosslinking agent, its amount be for 1-20 quality %/100 quality % emulsion compositions solid contents, this crosslinking agent have 2 or a plurality of can with the functional group of contained carboxyl reaction in ethene/copolymers of unsaturated carboxylic acids, and
Wherein this emulsion compositions does not contain the amine that boiling point is higher than 100 ℃, and does not conform to ammonia.
2. the resin coating metal plate of claim 1, wherein in ethene/copolymers of unsaturated carboxylic acids, the unsaturated carboxylic acid of copolymer-1 0-40 quality %.
3. the resin coating metal plate of claim 1, the amine that wherein has 100 ℃ or lower boiling point is triethylamine.
4. the resin coating metal plate of claim 1, wherein in the emulsion compositions solid content of per 100 quality %, containing its amount is the silica dioxide granule of 1-200nm for average grain diameter of 5-40 quality %.
5. the resin coating metal plate of claim 1 wherein in the emulsion compositions solid content of per 100 quality %, contains its amount and is the spherical polyethylene wax of 0.5-20 quality %.
6. the resin coating metal plate of claim 1 does not wherein form the chromaking film on metallic plate.
7. prepare the method for the resin coating metal plate of claim 1, comprise following steps:
Prepare this emulsion compositions;
This emulsion compositions of coating on metallic plate; With
Heating and the dry metallic plate that has been coated with emulsion compositions.
8. claim 7 prepares the method for resin coating metal plate, wherein in heating and drying steps, heats under the temperature that the reaction in can making crosslinking agent and ethene/copolymers of unsaturated carboxylic acids between the contained carboxyl is carried out and drying.
9. claim 7 prepares the method for resin coating metal plate, and wherein in application step, during the coating emulsion compositions, the resin molding quantitative change that is coated with behind feasible process heating and the drying steps is 0.2-2.5g/m 2
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