CN102049377A - Method for coating ferrous substrate with powder coating film - Google Patents
Method for coating ferrous substrate with powder coating film Download PDFInfo
- Publication number
- CN102049377A CN102049377A CN2010105222768A CN201010522276A CN102049377A CN 102049377 A CN102049377 A CN 102049377A CN 2010105222768 A CN2010105222768 A CN 2010105222768A CN 201010522276 A CN201010522276 A CN 201010522276A CN 102049377 A CN102049377 A CN 102049377A
- Authority
- CN
- China
- Prior art keywords
- chemical conversion
- acid
- base material
- amino
- coating
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Landscapes
- Application Of Or Painting With Fluid Materials (AREA)
- Paints Or Removers (AREA)
- Chemical Treatment Of Metals (AREA)
- Laminated Bodies (AREA)
Abstract
The invention provides a method for coating ferrous substrates with powder coating films, wherein a method for obtaining the coating film is provided.The powder coating film sintered at a low temperature has excellent secondary physical properties, such as water resistance, light resistance and heat resistance.The method for coating ferrous substrates is characterized by comprising the following steps:Step A: the surface of a ferrous substrate is treated with a chemical conversion treatment agent to form a chemical conversion treatment layer. The chemical conversion treatment agent contains at least one component (a) selected from zirconium, titanium and hafnium, fluorine (b) and an amino functional compound (c).Step B: chemical conversion treatment layer is coated with polyester resin with an acid value of 30 to 70 mg KOH/g and a powder coating composition containing beta-hydroxyalkyl amide curing agent represented as the general formula I.Step C: the powder coating composition is sintered and solidified. In the formula, R1 represents a hydrogen atom, methyl or ethyl group; R2 represents a hydrogen atom, an alkyl group with the carbon atom number thereof 1 to 5, or HO-CH(R1)-Ch 2-; A represents a divalent hydrocarbon group.
Description
Technical field
The present invention relates to the film method of coating iron class base material of powder.
Background technology
As powdery paints, be well known that, be main binder with epoxy resin, acrylic resin and mylar etc., allocate the coating of curing agent such as polybasic carboxylic acid, melmac and blocked isocyanate as required into.These coating are used for various fields such as household electrical appliances, automobile, building materials.Wherein, based on the powder paint compositions of compositions of thermosetting resin need more than the uniform temperature, be generally the sintering condition of the high temperature more than 180 ℃.
Such high temperature sintering is owing to needing lot of energy, and is therefore unfavorable to environment.
In order to address this problem, the spy opens and has proposed a kind of powder paint compositions in the 2001-294805 communique, it contains with represented beta-hydroxy alkylamide curing agent of following formula and resin solid composition acid number is that 10-100, softening point are that 80-150 ℃ mylar is the particle of main component, the volume average particle size of this particle is 5-30 μ m, and the hydroxyl equivalent number of described curing agent is 0.4-1.3 with the ratio of the carboxyl equivalent number of described mylar:
[changing 1]
(in the formula, R
1Expression hydrogen atom, methyl or ethyl, R
2Expression hydrogen atom, carbon number are alkyl or the HOCH (R of 1-5
1)-CH
2-, A represents the divalent alkyl).
By using this powder paint compositions, can form curability at low temperatures excellence, good the filming of outward appearance, but in order to be coated with iron class base material, the powder that need obtain secondary physical properties excellent such as resistance to water, light resistance and hear resistance is filmed, from this viewpoint, this powder paint compositions also has the leeway of improvement.
The iron class base material that applies by powdery paints, usually, for improve corrosion resistance, performance such as the adaptation of filming, can before apply, carry out chemical conversion and handle with powdery paints.Handle the chemical conversion processing method that has the trbasic zinc phosphate class inorganic agent of economy, operational problem as can further improving the adaptation or the corrosion resistance of filming, do not use poisonous metal chromium and not relying on draining, be known that the method for the metal conditioner that use is formed by zirconium compounds.(for example, patent documentation 2).
The prior art document
Patent documentation 1: the spy opens the 2001-294805 communique
Patent documentation 2: the spy opens the 2004-218070 communique
Summary of the invention
The problem that invention will solve
The present invention is in view of described background, the present invention films with powder to be coated with the method for iron class substrate base material, its purpose is to provide a kind of can obtain the method that following powder is filmed, this powder sintering at low temperatures of filming, and comprising secondary physical properties excellent such as resistance to water, light resistance and hear resistance.
The means of dealing with problems
One embodiment of the invention are methods of coating iron class base material, it is characterized in that having following steps:
Steps A by the surface of handling this iron class base material with the chemical conversion treating agent that contains following composition, forms the chemical conversion processing layer:
That (a) selects from zirconium, titanium and hafnium is at least a,
(b) fluorine, and
(c) amino-functional compounds;
Step B, coating contains mylar that acid number is 30-70mgKOH/g and the powder paint compositions of the beta-hydroxy alkylamide curing agent represented with following general formula I on described chemical conversion processing layer:
[changing 2]
(in the formula, R
1Expression hydrogen atom, methyl or ethyl, R
2Expression hydrogen atom, carbon number are alkyl or the HO-CH (R of 1-5
1)-CH
2-, A represents the divalent alkyl); And
Step C is with this powder paint compositions sintering, curing.
In described step C, preferably, make described powder paint compositions 130 ℃-160 ℃ sintering temperature, curing.
Preferably, described amino-functional compounds is from amino-functional silane coupler, its hydrolysate and condensation product thereof,
PAH,
Amine-modified epoxy resin, and
That selects in the amine modified phenolic resin is at least a.
Preferably, the content of amino-functional compounds described in the described chemical conversion treating agent based on the gross mass meter of described chemical conversion treating agent in the 5-5000ppm scope.
Preferably, the pH value of described chemical conversion treating agent is 2.5-5.0.
Preferably, the weight average molecular weight of described mylar is 1,000-150,000.
Preferably, described iron class base material is from cold and hot rolled plate, plated steel sheet, and that selects in hot-dip galvanized steel sheet, tin plate, the stainless steel is at least a.
In described powder composition, preferably, the mass ratio of described beta-hydroxy alkylamide curing agent and described mylar is 3/97-10/90.
Preferably, the volume average particle size of described powder paint compositions is 20-40 μ m.
Another embodiment of the invention is the iron class base material with described method coating.
Another embodiment of the invention is the article that contain the iron class base material of useful described method coating.
In this manual, if no special instructions, ppm means mg/kg.
The invention effect
According to the coating process of iron class base material of the present invention, obtained at low temperatures the powder of secondary physical properties excellent such as sintering and resistance to water, light resistance and hear resistance and filmed.
In addition, with the iron class base material of " coating process of iron class base material " of the present invention coating and contain the article of this iron class base material, its excellence aspect secondary rerum naturas such as resistance to water, light resistance and hear resistance of filming.
The specific embodiment
Below, the present invention is described in detail.
Below, the coating process of metal of the present invention (being specially iron class base material) is elaborated.
＜steps A 〉
The coating process of iron class base material of the present invention has steps A:
By the surface of handling this iron class base material, form the chemical conversion processing layer with the chemical conversion treating agent that contains following composition:
That (a) selects from zirconium, titanium and hafnium is at least a,
(b) fluorine, and
(c) amino-functional compounds.
Be used for described chemical conversion treating agent " from zirconium, titanium and hafnium select at least a " be that chemical conversion tunicle (oxide coating film) forms composition, contain at least a chemical conversion tunicle of from zirconium, titanium and hafnium, selecting by on base material, forming, the corrosion resistance and the mar proof of base material be can improve, and itself and the adaptation of filming improved.
For example, under the situation of the chemical conversion treating agent that contains zirconium, zirconium in the chemical conversion treating agent and fluorine form complex compound.Can think, carry out the surface treatment of iron class base material with this chemical conversion treating agent, then the solubilizing reaction metal ion that elution goes out in chemical conversion treating agent by metal is with ZrF
6 2-In fluorine extract, or the rising by interface pH value, the hydroxide or the oxide of generation zirconium, the hydroxide or the oxide of this zirconium are separated out at substrate surface.But, the invention is not restricted to have this mechanism.Carry out surface treatment with described chemical conversion treating agent, can obtain by chemical reaction securely attached to the chemical conversion tunicle on the object being treated, therefore, the washing after also handling.
Supply source as described zirconium is not particularly limited, and for example, can enumerate K
2ZrF
6, (NH
4)
2ZrF
6, H
2ZrF
6Deng soluble fluoride zirconates such as fluorine zirconic acid and salt thereof etc., zirconium fluoride, zirconia etc.
Supply source as described titanium is not particularly limited, and for example, can enumerate alkali metal fluosilicate titanate, (NH
4)
2TiF
6Deng fluotitanate; H
2TiF
6Deng soluble fluoride titanate of fluotitanic acid etc. etc.; Titanium fluoride; Titanium oxide etc.
Supply source as described hafnium is not particularly limited, and for example, can enumerate H
2HfF
6Deng the acid of fluorine hafnium; Hafnium fluoride etc.
As at least a supply source of from described zirconium, titanium and hafnium, selecting, form the high aspect of ability from tunicle, be preferably from ZrF
6 2-, TiF
6 2-, HfF
6 2-Middle select at least a.
Preferably, the content of " that selects from zirconium, titanium and hafnium is at least a " that described chemical conversion treating agent contained based on the gross mass meter of described chemical conversion treating agent, converts with metal, within the range having a lower limit of 20ppm, on be limited in the scope of 10000ppm.Under the situation of described content less than described lower limit, the inadequate phenomenon of performance of chemical conversion tunicle might appear.On the other hand, described content surpasses under the situation of the described upper limit, can not occur than its better effect, and may be unfavorable economically.Described lower limit is 50ppm more preferably, and the described upper limit is 2000ppm more preferably.Described lower limit is 150ppm more preferably, and the described upper limit is 500ppm more preferably.
The fluorine performance that described chemical conversion treating agent contained is as the function of base material etchant.Supply source as described fluorine is not particularly limited, and for example, fluorine can be from the fluorochemical as described zirconium source, titanium source and hafnium source.In addition, supply source as fluorine, also can further enumerate, fluorides such as hydrofluoric acid, ammonium fluoride, fluoboric acid, ammonium acid fluoride, sodium fluoride, sodium bifluoride, and hexafluorosilicate complex fluorides such as (for example fluosilicic acid, zinc fluosilicate, manganese fluosilicate, magnesium fluosilicate, nickelous fluosilicate, fluosilicic acid iron, calcium fluosilicates) etc.
The content of the fluorine ion that described chemical conversion treating agent contained (free fluorine) is different because of pH value of chemical conversion treating agent etc., and based on the gross mass meter of described chemical conversion treating agent, preferably it is in lower limit 20ppm, the upper limit 10, in the scope of 000ppm.Described lower limit is 50ppm more preferably, the described upper limit more preferably 2,000ppm.Described lower limit is 150ppm more preferably, and the described upper limit is 700ppm more preferably.In addition, the content of this fluorine ion can be measured by the fluorine ionometer measuring device.
The amino-functional compounds that described chemical conversion treating agent contained is the compound that contains the amido functional group of (preferred more than two) in the molecule at least.Can infer, act on the both sides that film of described chemical conversion tunicle and the formation of described powder paint compositions, can improve both adaptations by making this amino-functional compounds.But, the invention is not restricted to have this mechanism.
As described amino-functional compounds, be not particularly limited, but preferably, can enumerate
Amino-functional silane coupler, its hydrolysate and condensation product thereof,
PAH,
Amine-modified epoxy resin, and
The amine modified phenolic resin.
As the described amino silicane coupling agent that contains, be not particularly limited, for example, can enumerate N-2 (amino-ethyl) 3-aminopropyl methyl dimethoxysilane, N-2 (amino-ethyl) 3-TSL 8330, N-2 (amino-ethyl) 3-aminopropyltriethoxywerene werene, the 3-TSL 8330, the 3-aminopropyltriethoxywerene werene, 3-triethoxysilyl-N-(1,3-dimethyl-butylidene) propylamine, N-phenyl-3-TSL 8330, N, known silane couplers such as N-two [3-(trimethoxysilyl) propyl group] ethylenediamine etc.Also can use commercially available amino silicane coupling agent KBM-602, KBM-603, KBE-603, KBM-903, KBE-9103, KBM-573 (above is that Shin-Etsu Chemial Co., Ltd makes), the XS1003 (manufacturing of チ Star ソ Co., Ltd.) etc. of containing.
The described hydrolysate that contains amino silicane coupling agent can be made with existing known method, for example, the described amino silicane coupling agent that contains is dissolved in ion exchange water, with sour arbitrarily it is adjusted into acid method etc.
As the described condensation product that contains amino silicane coupling agent, be not particularly limited, for example, can be with サ イ ラ エ one ス S-330 (γ-An Jibingjisanyiyangjiguiwan; The manufacturing of チ Star ソ Co., Ltd.), サ イ ラ エ one ス S-320 (N-(2-amino-ethyl)-3-TSL 8330; チ Star ソ Co., Ltd. makes) etc. the commercially available prod make its hydrolysis, condensation with known method and use.Active ingredient 32%) as condensation product, (Shin-Etsu Chemial Co., Ltd makes: commercially available prod such as can to use KBP-90.
As described PAH, be water-soluble resin with the represented formation unit of following formula (1).Preferably, described PAH is the water-soluble resin that only is made of the represented formation unit of following formula (1).
[changing 3]
As described PAH, can use for example PAA series (Co., Ltd. is spun in day east).
Wherein, preferably use PAA10C (PAH resin, molecular weight are 15,000, and Co., Ltd. is spun in day east).
As described amine-modified epoxy resin, be not particularly limited, so long as it is just passable to have a resin of amino epoxy skeleton.As above-mentioned epoxy resin, be not particularly limited, for example can enumerate bisphenol A type epoxy resin, bisphenol f type epoxy resin, bisphenol-A epoxy resin, A Hydrogenated Bisphenol A F type epoxy resin, bisphenol-A epoxy propane add-on type epoxy resin, Bisphenol F expoxy propane add-on type epoxy resin, phenolic resin varnish type epoxy resin etc.Wherein, preferred bisphenol f type epoxy resin, more preferably Bisphenol F chloropropylene oxide type epoxy resin.As described amino, be not particularly limited, for example can enumerate-NH
2Base, alkyl monosubstituted amino, dialkyl amido, monohydroxy amino, dihydroxy amino, other have primary amine to compound of tertiary amine etc.As in forming the epoxy resin of described skeleton, importing amino reaction, be not particularly limited, can be set forth in the solvent methods commonly used such as method that epoxy resin and amines are mixed.
Be not particularly limited as described amine modified phenolic resin, so long as it is just passable to have a resin of amino phenol skeleton.For example, can use NPK series (Sumitomo ベ one Network ラ イ ト), suitably use ス ミ ラ イ ト レ ジ Application-NPK-261 (amine modified phenolic resin, Sumitomo ベ one Network ラ イ ト) etc.
Described amino-functional compounds can be used separately, also can be used in combination.
For the content of amino-functional compounds described in the described chemical conversion treating agent, based on the gross mass meter of chemical conversion treating agent, preferably in lower limit 5ppm, upper limit 5000ppm scope.If less than 5ppm, might can not get having the tunicle of enough adaptations of filming.If surpass 5000ppm, can not occur than its better effect, also might be unfavorable economically.Described lower limit is 10ppm more preferably, more preferably 50ppm.The described upper limit is 1000ppm more preferably, more preferably 500ppm.
Described chemical conversion treating agent is preferably the material that does not contain phosphate ion in fact.So-called " not containing phosphate ion in fact " meaning is that the phosphate ion that contains is not enough to play a role as the composition in the chemical conversion treating agent.Because the chemical conversion treating agent that uses among the present invention does not contain phosphate ion in fact, therefore, there is not to use the phosphorus become carrying capacity of environment in fact, the generation of the sludge that the ferric phosphate that just can suppress to be occurred under the situation of use trbasic zinc phosphate class inorganic agent, trbasic zinc phosphate etc. are such.
The pH of described chemical conversion treating agent is preferably in the scope of lower limit 2.5, the upper limit 5.0.If pH less than this lower limit, might etching excessively can not fully form tunicle.On the other hand, if pH surpasses this upper limit, might etching insufficient and can not get good tunicle.Described lower limit more preferably 3.0, the described upper limit more preferably 4.5.The pH of described chemical conversion treating agent can adjust with alkali compounds such as acid compounds such as nitric acid, sulfuric acid and NaOH, calcium hydroxide, ammonia.
Described chemical conversion treating agent also preferably contain as give adaptation and corrosion resistance reagent from magnesium ion, zinc ion, calcium ion, aluminium ion, gallium ion, indium ion, tin ion and copper ion, select at least a.By making it contain the described reagent of giving adaptation and corrosion resistance, can obtain having the chemical conversion tunicle of better adaptation and corrosion resistance.
At least a content of from described magnesium ion, zinc ion, calcium ion, aluminium ion, gallium ion, indium ion, tin ion and copper ion, selecting in the described chemical conversion treating agent, based on the gross mass meter of chemical conversion treating agent, preferably in the scope of lower limit 1ppm, upper limit 5000ppm.If described content is less than described lower limit, possible effect is insufficient.If described content surpasses the described upper limit, may there be the further raising of effect, and unfavorable economically, the phenomenon that the back adaptation descends also might appear applying.Described lower limit is 25ppm more preferably, and the described upper limit is 3000ppm more preferably.
Described chemical conversion treating agent also can use any composition as required simultaneously except mentioned component.As operable composition, can enumerate silica etc.By adding such composition, can improve the corrosion resistance after the coating.
Chemical conversion in the steps A of the present invention is handled and is not particularly limited, and can be undertaken by make chemical conversion treating agent contacting metal surface under the treatment conditions of routine.The treatment temperature that described chemical conversion is handled is preferably in the scope of 20 ℃ of lower limits, 70 ℃ of the upper limits.More preferably 30 ℃ of described lower limits, more preferably 50 ℃ of the described upper limits.The processing time that described chemical conversion is handled is preferably in lower limit 5 seconds, 20 minutes scope of the upper limit.Described lower limit more preferably 30 seconds, the described upper limit more preferably 2 minutes.Be not particularly limited as chemical conversion processing method, for example can enumerate infusion process, spray-on process, rolling method etc.
In the chemical conversion of steps A of the present invention is handled, carrying out before described chemical conversion handles, also can handle the washing that carry out after ungrease treatment and the degreasing on the surface of iron class base material.After described chemical conversion was handled, the washing that can carry out after the chemical conversion was handled, and also can not carry out.
Described ungrease treatment is the processing of carrying out for oil content and the dirt of removing attached to substrate surface, also can use degreasing agents such as without phosphorus no nitrogen degreasing cleaning fluid as required, usually the 30-55 ℃ of impregnation process of making an appointment with a few minutes.As requested, also can before ungrease treatment, carry out pre-ungrease treatment.
It is in order to wash the degreasing agent after the ungrease treatment that washing after the described degreasing is handled, can be by using a large amount of washing water to carry out once or once above spraying is handled and carried out.
Washing processing intent after the described chemical conversion is not bring harmful effect to the adaptation after the various coatings thereafter, corrosion resistance etc., preferably, carries out once or once above washing processing.In this case, final washing is fit to carry out with pure water.During washing after this chemical conversion is handled, spraying washing or dipping washing which kind of can, also can be used in combination these methods and wash.
Washing after the described chemical conversion according to known method, is carried out drying after handling as required.Carry out the coating of the powder paint compositions of hereinafter illustrated step B thereafter.
As the iron class base material that the method according to this invention was coated with, can enumerate material of from SPCC steel plate (cold and hot rolled plate), SECC Bond (ボ Application デ) steel plate (plated steel sheet), SGCC (hot-dip galvanized steel sheet), SPTE (latten), stainless steel, selecting etc.As described stainless steel, also can use SUS304, SUS304L, SUS303, SUS316, SUS316L etc.
The pre-treatment of described iron class base material does not have special restriction, promptly, as described iron class base material, also can enumerate the galvanized steel plain sheet such as plating, hot-dip, evaporation steel plate of zinc classes such as galvanized steel plain sheet, zinc-plated-the nickel steel plate, zinc-plated-the iron steel plate, zinc-plated-the chromium steel plate, zinc-plated-the aluminum steel plate, zinc-plated-titanium steel plate, zinc-plated-the magnesium steel plate, zinc-plated-manganese steel plate or zinc-plated class alloy-steel plate etc.
By the tunicle amount of the resulting chemical conversion tunicle of coating pre-treating method of the present invention, calculate with metal (zirconium, titanium, hafnium) the total amount that is contained in the chemical conversion treating agent, preferably at lower limit 0.1mg/m
2, upper limit 500mg/m
2Scope in.If should the total amount less than described lower limit, might can not get the chemical conversion tunicle of homogeneous.On the other hand, if should the total amount surpass the described upper limit, may can not get better effect and unfavorable economically.Described lower limit is 5mg/m more preferably
2, the described upper limit is 200mg/m more preferably
2
＜step B 〉
The coating process of iron class base material of the present invention also has step B: on the chemical conversion processing layer that forms in described steps A, coating contains the powder paint compositions of the represented beta-hydroxy alkylamide curing agent of mylar that acid number is 30-70mgKOH/g and general formula I:
[changing 4]
(in the formula, R
1Expression hydrogen atom, methyl or ethyl, R
2Expression hydrogen atom, carbon number are alkyl or the HO-CH (R of 1-5
1)-CH
2-, A represents the divalent alkyl).
The acid number of described mylar is 30-70mgKOH/g.
In this specification, the acid number of mylar mean in and the mg number (mgKOH/g) of the needed potassium hydroxide of nonvolatile component of this mylar of 1g.
In this specification, the acid number of mylar can determine with the method for foundation JIS K 0070.
Acid number is under the situation outside the described scope, and curing of filming and corrosion resistance might reduce.
In addition, the softening point of described mylar is preferably 80-150 ℃, more preferably 90-130 ℃.When described softening point was lower than 80 ℃, resistance to blocking may reduce, and when being higher than 150 ℃, the flatness of filming that obtains may reduce.
On the other hand, the weight average molecular weight of described mylar is preferably 1,000-150,000, more preferably 3,000-70,000, more preferably 4,000-50,000.If described weight average molecular weight is too small, the performance transitivity of filming that obtains may reduce.On the other hand, if described weight average molecular weight is excessive, flatness of filming that obtains and outward appearance possible deviation.
In this specification, the softening point of mylar can be determined according to the method for JIS K 2207.In addition, in this specification, this weight average molecular weight and number-average molecular weight can be that standard substance is determined with the polystyrene according to gel permeation chromatography (GPC).
Described mylar also can be the compound of two or more mylar.In this case, described physics value and special numerical value (special numerical value) mean the value of compound integral body.
Sour composition that such mylar can be by will mainly containing polybasic carboxylic acid and the pure composition that mainly contains polyalcohol be as raw material, uses conventional method to carry out polycondensation and obtain.By select separately composition and the condition of polycondensation, can obtain having the mylar of described physics value and special numerical value.At this, " mainly " is meant and accounts for whole 70 moles more than the %.
As described sour composition, be not particularly limited, for example can enumerate terephthalic acid (TPA), M-phthalic acid, phthalic acid, trimellitic acid and acid anhydrides thereof, 2,6-naphthalenedicarboxylic acid, 2, aromatic dicarboxylic acid class and acid anhydrides thereof such as 7-naphthalenedicarboxylic acid, succinic acid, adipic acid, azelaic acid, decanedioic acid, dodecanedicarboxylic acid, 1, saturated aliphatic dicarboxylic acids class such as 4-cyclohexane dicarboxylic acid and acid anhydrides thereof etc.In addition, can enumerate lactone such as gamma-butyrolacton, 6-caprolactone and corresponding hydroxy acid class, to aromatic series oxygen base monocarboxylic acid classes such as oxygen base oxethyl benzoic acid or the like.Described sour composition also can be two or more.Wherein, from durability, rerum natura and cost aspect, preferred M-phthalic acid and terephthalic acid (TPA).In all acid composition, the ratio of terephthalic acid (TPA) and isophthalic acid comprises is 70 moles more than the %, preferred 75 moles more than the %, and preferred especially 80 moles more than the %.At this, " is 70 moles more than the % as the total ratio of the terephthalic acid (TPA) of sour composition and M-phthalic acid " is meant and uses these materials as primary raw material.About the upper content limit of terephthalic acid (TPA) and M-phthalic acid, whole amounts of the sour composition that modulation can be used during mylar are terephthalic acid (TPA) and/or M-phthalic acid.In addition,, then make isophthalic acid comprises all acid components in proportions at 70 moles more than the % if want to improve weatherability especially, preferred 80 moles more than the %, preferred especially 90 moles more than the %.At this, " isophthalic acid comprises all acid components in proportions at 70 moles more than the % " is meant and uses M-phthalic acid to be primary raw material.
As described pure composition, be not particularly limited, for example can enumerate ethylene glycol, 1, ammediol, 1, the 4-butanediol, 1, the 5-pentanediol, 1, the 5-hexylene glycol, diethylene glycol (DEG), triethylene glycol, 1, the 4-cyclohexanediol, 1, the 4-cyclohexanedimethanol, bisphenol-A epoxy alkane addition product, bisphenol S alkylene oxide addition product, 1, the 2-propane diols, neopentyl glycol, 1, the 2-butanediol, 1, the 3-butanediol, 1, the 2-pentanediol, 2, the 3-pentanediol, 1, the 4-pentanediol, 1, the 4-hexylene glycol, 2, the 5-hexylene glycol, the 3-methyl isophthalic acid, the 5-pentanediol, 1, the 2-dodecanediol, 1, glycol such as 2-octacosanol, trimethylolpropane, glycerine, polyalcohols more than 3 yuan such as pentaerythrite etc.Described pure composition also can be for two or more.
Described beta-hydroxy alkylamide curing agent is represented with general formula I:
[changing 5]
(in the formula, R
1Expression hydrogen atom, methyl or ethyl, R
2Expression hydrogen atom, carbon number are alkyl or the HO-CH (R of 1-5
1)-CH
2-, A represents the divalent alkyl).
R in the formula
1Be hydrogen atom or methyl, R
2Be HOCH (R
1) CH
2-, A is that carbon number is that the alkylidene of 2-10 (more preferably 4-8) is suitable.
Described curing agent obtains with known synthetic method, particularly, for example, in the presence of the alkoxide catalysis of sodium or potassium etc., carboxylic acid and/or carboxylate and β-hydroxyalkyl amine is reacted etc.
As carboxylic acid used herein and carboxylate, for example can enumerate succinic acid, adipic acid, glutaric acid, dimethyl succinate, diethyl succinate, dimethyl adipate etc.
As β-hydroxyalkyl amine, for example can enumerate N-methylethanolamine, diethanol amine, N-methyl-prop hydramine etc.
In addition, the represented beta-hydroxy alkylamide curing agent of general formula I also can be used as the commercial goods and obtains.Such beta-hydroxy alkylamide curing agent, can enumerate the プ リ ミ De XL552 (EMS-PRIMD society) that the chemistry that for example has following formula constitutes:
[changing 6]
The employed powder paint compositions of method of the present invention contains described beta-hydroxy alkylamide curing agent and the described carboxylic acid polyester resin that contains as main component.At this, " as main component " is meant, for example, the content of described beta-hydroxy alkylamide curing agent and the described summation that contains the content of carboxylic acid polyester resin account for more than the 80 quality % of powder paint compositions integral body.
In the described powder composition, the content of described curing agent is preferably 3/97-10/90 with respect to the mass ratio of the content of described mylar.If outside this scope, the curing of filming may be insufficient.
The ratio of the equivalents of the equivalents of the hydroxyl of described curing agent and described mylar carboxyl is preferably 0.4-1.3.If outside this scope, the curing of filming may be insufficient.
The volume average particle size of the particle of described powder composition is preferably 20-40 μ m.If volume average particle size less than 20 μ m, owing to the conveyance reduction of powdery paints, the problem of operability aspect may occur applying, cause coating efficiency to reduce.On the contrary, if average volume particle diameter surpasses 40 μ m, the flatness that may occur filming reduces, the problem that outward appearance worsens.Volume average particle size is 20-30 μ m more preferably.In addition, described volume average particle size can be measured by grain size analysis meter (for example, day system マ イ of machine dress society Network ロ ト ラ Star Network HRA X-100).
And then particularly for the coated thing of the complicated shape with non-flat face, in order to form filming of homogeneous, the preferred particle diameter that contains is that the ratio of the particle below 1/5 of volume average particle size is below the 5 quality %.
The lowest melt viscosity of the employed powder paint compositions of method of the present invention is preferably 60-2,000 pool.If lowest melt viscosity is low excessively, may can not get having filming of good appearance, if lowest melt viscosity is too high, the effect of described particle diameter may weaken, and the flow of filming of fusion (sagging property) may worsen.
At this, lowest melt viscosity is according to the resulting viscosity of following mensuration:
With coated article with the heating of one minute speed of 10 ℃ up to reaching target temperature, thereafter, measure the melt viscosity of filming under the condition of target temperature in time remaining on, obtain the MV minium viscosity of this moment, with it as lowest melt viscosity.
The mensuration of lowest melt viscosity is preferably used the complex viscosity according to Measurement of Dynamic Viscoelasticity.
The employed powder paint compositions of method of the present invention also can contain surface conditioner as required.As such surface conditioner, be fit to use one or more acrylic resins that obtain as raw material with (methyl) acrylic acid alkyl group ester classes such as (methyl) methyl acrylate, (methyl) ethyl acrylate, (methyl) butyl acrylate, (methyl) 2-EHA, (methyl) lauryl acrylates, the SP value of this acrylic resin is below 9.0, number-average molecular weight is 300-50,000, preferred 1,000-30,000, glass transition temperature is preferably below 0 ℃ less than 20 ℃.
Under the too high situation of SP value, if surpass 9.0, because it is approximate with the SP value of described mylar, form in the process of filming in the powdery paints fusion that applies, the intermiscibility of itself and this mylar is higher, therefore, be difficult for moving on film coated surface energetically, this result is considered to owing to can not give due to the flowability of film coated surface.
At this, the SP value is meant solubility parameter, is documented in the document (SUH, CLARKE, J.P.S.A-1,5,1671-1681 (1967)), and this assay method is those skilled in the art's known method such as nephelometry.
In addition, if glass transition temperature (Tg) surpasses 20 ℃, may can not get good appearance of film.In addition, if its number-average molecular weight less than 300, even can move on film coated surface, weakens but give mobile effect, if surpass 50,000, moving on film coated surface may become difficult.
In the employed powder paint compositions of method of the present invention, amount as the acrylic resin of described surface conditioner is the 0.01-5 mass parts with respect to described curing agent and described mylar total amount 100 mass parts, preferred 0.05-3 mass parts, more preferably 0.1-2 mass parts.If the amount of acrylic resin is very few, then can not carry out surface adjustment fully, the probability of bad order uprises, and on the other hand, if the amount of acrylic resin is too much, the adhesive of coating may worsen.
Powder paint compositions used in the present invention can also contain inorganic particles or organic fine particles as mobility donor.This is because by containing such particulate, can further improve conveyance and adhesive.
As described inorganic particles, can enumerate hydrophobic silica, hydrophily silica or aluminium oxide, titanium oxide etc.Commercial goods as this inorganic particles, for example can enumerate AEROSIL 130, AEROSIL 200, AEROSIL 300, AEROSIL R-972, AEROSIL R-812, AEROSIL R-812S, titanium dioxide T-805, titanium dioxide P-25, Alminium Oxide C (Japanese ア エ ロ ジ Le society make), カ one プ レ Star Network ス FPS-1 (manufacturing of Shionogi society) etc.From give effect, the viewpoint of the flatness of filming and coating efficiency, preferably, the addition of described inorganic particles is the 0.05-2 mass parts with respect to the powder paint compositions integral body of 100 mass parts, more preferably the 0.1-1 mass parts.If addition is very few, then effect weakens, if addition is too much, the flatness that then may occur filming reduces, produces problems such as gloss.
On the other hand, preferably, organic fine particles is that particle diameter is that non-crosslinked organic resin granulation of 0.001-0.5 μ m, preferred 0.01-0.5 μ m or the crosslinked organic resin of particle diameter 0.01-2 μ m, preferred 0.01-1 μ m are granulated sub.In addition,, can enumerate vinyl, acrylic resin, epoxy resin, mylar etc. as this organic resin, but since the easy suitability for industrialized production of acrylic resin, preferred acrylic resins.
Described non-crosslinked organic resin of granulating for example is directly to make the particle that obtains by emulsion polymerisation or suspension polymerisation, or makes resin by polymerisation in solution or polymerisation in bulk etc., and with its pulverizing also classification and the particle that obtains.In addition, the glass transition temperature (Tg) of described non-crosslinked organic resin particle is 50-150 ℃, and preferred 70-120 ℃ scope is fit to.Use under the situation of non-crosslinked organic resin particle, to the powdery paints heating, then this organic resin particle self also flows, and just can obtain good the filming of outward appearance.If Tg less than 50 ℃, is difficult to fully guarantee the resistance to blocking of the powdery paints in storage, conveying etc.; On the other hand, Tg surpasses 150 ℃, does not then have practicality.Preferably, the average grain diameter of described non-crosslinked organic resin particulate is at 0.001-0.5 μ m, in the scope of preferred 0.01-0.5 μ m.In addition, its addition is about the 0.05-35 mass parts with respect to the described powdery paints integral body of 100 mass parts, about preferred 0.1-10 mass parts.This is based on following understanding and sets, that is: there is proportionate relationship between the average grain diameter of non-crosslinked organic resin particulate and its addition, from the easy aspect of the suitability for industrialized production that makes the organic resin particulate, the lower limit of particle diameter is about about 0.001 μ m, in this case, make the effect of adding particle manifest the just addition about needs 0.05 quality %; Along with particle diameter becomes big, the addition of giving the required resin particle of resistance to blocking also increases; Particle diameter surpasses 0.5 μ m, the mobile variation of powdery paints, during with coating rifle coating powders coating, the powdery paints particle apply adhering on the rifle tip portion, aggegation becomes easy, because the effusion of agglutination particle can cause filming and depression etc. occur, just be difficult to reach the goal of the invention that the acquisition high-quality apperance is filmed, therefore limiting particle diameter is 0.5 μ m to the maximum, and addition in this case must be to be about 35 quality % with respect to the powdery paints maximum.
Make the used monomer of noncrosslinking acrylic resin if exemplify, can enumerate acrylic acid, butenoic acid, itaconic acid, maleic acid, fumaric acid, (methyl) acrylic acid 2-hydroxyl ethyl ester, (methyl) hydroxypropyl acrylate, (methyl) acrylic acid hydroxy butyl ester, (methyl) acrylic acid dimethylamino ethyl ester, acrylamide, Methacrylamide, acrylonitrile, methacrylonitrile, (methyl) methyl acrylate, (methyl) ethyl acrylate, (methyl) n-butyl acrylate, (methyl) 2-EHA, styrene etc.
Described crosslinked organic resin particle is the organic resin particulate with three-dimensional structure, is to be insoluble to solvent in fact, or the particle that down heating can fusion about sintering temperature.
This crosslinked organic resin particle is to make resin by polymerisation in solution or polymerisation in bulk etc., and with its pulverizing, classification and the particle that obtains, but also can be the particle that directly makes by emulsion polymerisation or suspension polymerisation or after non-crosslinked organic resin particle forms, carry out the particle that cross-linking reaction obtains.
The average grain diameter of preferred described crosslinked organic resin particulate is 0.01-2 μ m.If this average grain diameter surpasses 2 μ m, these particles form particle (Block Star) easily when filming; On the other hand, if less than 0.01 μ m then do not have effect.Its amount is whole with respect to the described powdery paints of 100 mass parts to be that 0.05-10 mass parts (more preferably 0.1-5 mass parts) is suitable.If the amount of being somebody's turn to do is very few, may can not get the resistance to blocking improved effect, on the contrary, if should measure too much, presentation quality may descend.
Described crosslinked organic resin particulate and non-crosslinked organic resin particle are same, be preferably the particulate that is obtained by vinyl, acrylic resin, epoxy resin, mylar etc., but wherein the acrylic resin suitability for industrialized production are easier to, so preferred acrylic resins.
Crosslinked organic resin particle by this acrylic resin obtains for example can be obtained by crosslinkable acrylic monomer more than the 1 quality % and other monomer mixture.The crosslinkable acrylic monomer is meant to have two monomers that can carry out the unsaturated group of radical polymerization in the molecule at least, or at least two kinds of monomers that have the functional group that can react mutually separately and can carry out the unsaturated group of radical polymerization.If the amount of described crosslinkable acrylic monomer may can not get enough cross-linked structures less than 1 quality %, in powdery paints, be partly dissolved during sintering, expand, may make the flatness of filming descend.
As having two monomers that can carry out the unsaturated group of radical polymerization in the described molecule at least, can enumerate the unsaturated alcohol ester of polymerizable of polymerizable unsaturated monocarboxylic acid ester, polyacid of polyalcohol and the aromatic compound that is replaced by plural vinyl etc.The example of these monomers has two (methyl) acrylic acid glycol ester, two (methyl) acrylic acid triglycol ester, two (methyl) acrylic acid TEG ester, two (methyl) acrylic acid 1, the 3-butanediol ester, trimethylolpropane tris (methyl) acrylate, (methyl) acrylic acid 1, the 4-butanediol ester, two (methyl) acrylic acid DOPCP, two (methyl) acrylic acid 1,6-hexylene glycol ester, two (methyl) acrylic acid pentaerythritol ester, four (methyl) acrylic acid pentaerythritol ester, two (methyl) acrylic acid glyceride, 1,1,1-trihydroxy methyl ethane two (methyl) acrylate, triallyl cyanurate, triallyl isocyanurate, the trimellitic acid triallyl, diallyl p phthalate, diallyl phthalate, (methyl) allyl acrylate and divinylbenzene etc.
Having the example of combination of monomers that two kinds of having the functional group that can react to each other respectively can carry out the unsaturated group of radical polymerization has, and glycidyl acrylate, GMA etc. contain carboxylic ethylenically unsaturated monomers such as the ethylenically unsaturated monomers of epoxy radicals and acrylic acid, methacrylic acid, butenoic acid.As the combination of the functional group that can react to each other, in addition also have amino and carboxylic acid group, epoxy radicals and carboxylic acid or its acid anhydrides etc., the described functional group that can react to each other is meant the functional group that extensively comprises these combinations.
As described other monomer, can enumerate the monomer that is used to make described non-crosslinked acrylic resin.
Powder paint compositions used in the present invention also can contain pigment and additive as required.
There is no particular restriction for the kind of described pigment, particularly, can enumerate painted pigment such as titanium dioxide, di-iron trioxide, yellow iron oxide, carbon black, phthalocyanine blue, phthalocyanine green, quinacridine ketone pigment, AZOpigments, metallic pigments of all kinds, pearlescent pigment of all kinds, metal dust and it is carried out filler pigments such as surface-treated material, talcum, silica, calcium carbonate, precipitability barium sulfate etc.In addition, in order to reduce gloss, preferably it contains organic class delustering agent that mineral-type delustering agent such as talcum, silica, calcium carbonate, barium sulfate, feldspar, wollastonite or organic fine particles constitute.The preferred 3-30 μ of the volume average particle size of described delustering agent m.
As described additive, can enumerate for example charge control agent, plasticizer, ultra-violet absorber, antioxidant, defoamer etc.Can use the additive that is generally used for powdery paints for these additives.
Then, the manufacture method to powder paint compositions used in the present invention describes.That is,, just can obtain powder paint compositions used in the present invention by with described beta-hydroxy alkylamide curing agent with have the acid number of particular range and the described polyester and resin composition of softening point is the particle that specified particle diameter is arranged that main component obtains.In addition, also can add the little particulate of the particle diameter of this particle of size ratio as mobility donor.
At first, pack into the described beta-hydroxy alkylamide curing agent of main composition composition of the described particle of conduct of scheduled volume and described polyester and resin composition, and the described surface conditioner of the scheduled volume of packing into as required, pigment, other additive etc., with mixer equably with its mixing.As this mixer, can use mixer commonly used such as Henschel mixer, ball mill, banbury mixers.
Then, the resulting mixture of fusion kneading.At this, by masticators such as extruder or hot-rolling machine heat, fusion.Then, use pulverizers such as atomizer or jet mill to pulverize the granula that in this fusion kneading step, obtains.In addition, after described composition carried out the fusion kneading and mixing, also can handle the mixture that obtains by spray drying process (spray-dry method) directly is pulverous particle.The volume average particle size of the powder paint compositions used in the present invention that obtains like this is preferably 20-40 μ m, preferably, uses the particle carried out in order to after removing huge particle and fine particle and adjusting the classification of size distribution.
The particle that obtains like this can directly use as powdery paints, but also can use the powdery paints that contains described particulate.
Described particulate can add before granula is pulverized, and also can add to and pulverize afterwards or in the particle after the classification, also can mix with super mixer mixers such as (ス one パ one ミ キ サ one).Can think that by such adding method, common described particulate is with the state attached to the surface of described particle, and imbed the state on the surface of this particle a little, be present in the described powdery paints.
Powder paint compositions used in the present invention can be filmed by heating after coated thing is applied.As described coated thing, be not particularly limited, can enumerate iron plate, steel plate, aluminium sheet etc. particularly and it has been carried out surface-treated material etc.
As described painting method, be not particularly limited, can use methods well known to those skilled in the art such as spraying process, electrostatic powder cladding process, slipper dip method, but, be fit to use the electrostatic powder cladding process from coating efficiency.
Coating thickness when applying powder paint compositions used in the present invention is not particularly limited, and can be set at 20-100 μ m.
＜step C 〉
The coating process of iron class base material of the present invention also has this powder paint compositions that will apply and carries out sintering, step of curing C in described step B.
Normally used condition and device when the sintering of this powder paint compositions can use the powder paint compositions sintering.In addition, in the coating process of iron class base material of the present invention,, also can carry out the sintering of powder paint compositions aptly even under than the lower temperature of the sintering temperature of common powder paint compositions.From reducing the viewpoint of sintering energy needed, the lower sintering temperature of preferred use.
But, if sintering temperature is low excessively, just may can not get 2 rerum naturas such as excellent water tolerance, light resistance and hear resistance, moreover different with liquid coating, under low sintering situation, have to be difficult to obtain the level and smooth tendency of filming.This is because before attached to uncured the filming on the coated thing curing reaction taking place, the resinous principle fusion, therefore, though can expect to keep the flatness of filming that finally obtains, but, just be difficult to give the meltbility that it is produced by solvent if from not uncured the filming of solvent-laden powdery paints.In order to address this problem, can consider to reduce the method for the molecular weight and the glass transition temperature of the resinous principle that is used for powdery paints, if but these values reduce too much, and the storage-stable that contains the powdery paints of this resin descends.Therefore, in most cases, guarantee curability at low temperatures and guarantee that the storage-stable of powdery paints is conflicting that only reducing sintering temperature has been technical big problem.
In the present invention,, be conceived to chemical conversion and handle in order to solve described problem, the result successfully up to now the sintering temperature lower limit of known powdery paints further reduce.Particularly, this sintering temperature is preferably 130 ℃-160 ℃, more preferably 130 ℃-145 ℃.Especially, if 130 ℃-145 ℃ sintering temperature just can use conventional solvent based coating to come described powder paint compositions is carried out sintering with baking oven.
By the coating process of iron class base material of the present invention, even, also can obtain having filming of 2 rerum naturas such as excellent water tolerance, light resistance and hear resistance in the common lower sintering temperature of sintering temperature of described ratio.Like this, in this application,, also can guarantee representative film performances such as excellent water tolerance, weatherability, hear resistance, appearance of film even under the temperature more much lower, carry out sintering than the sintering temperature of known up to now powdery paints.Its reason is not clear, but can think it might is that arbitrary composition of (a)-(c) that contained in the chemical conversion treating agent of metallic substrate surface has produced some catalytic action etc. to the curing reaction of the employed powdery paints of step B.In addition, can think, handle by described chemical conversion the tunicle surface that forms and by described powdery paints form film below interlayer, obtained the effect of certain promotion driving fit.
Sintering time can suitably be adjusted according to sintering temperature, is generally 10-120 minute, preferred 15-60 minute.
Preferably, preferred item and other the preferred items that above describes in detail is used in combination.
The iron class base material that is coated with " coating process of iron class base material " of the present invention also is one embodiment of the invention, and the article that contain this iron class base material also are one embodiment of the invention.
Embodiment
Below, enumerate embodiment, the present invention will be described in more detail, but the present invention is not only limited to these embodiment.
＜embodiment 1-21, comparative example 1-9 〉
The manufacturing of powdery paints
(powdery paints 1)
With the following substances is raw material, carries out about three minutes mixing with mixer super mixer (Japanese ス ピ Application De Le society system), and then mediates extruder (コ ニ one ダ one, Off ス society system) with the fusion masticator and carry out the fusion kneading under about 110 ℃:
The CRYLCOAT2617-3 of 100 mass parts (mylar of ダ イ セ Le サ イ テ Star Network society system, acid number is 33, glass transition temperature is 62 ℃),
The Off ア イ Application デ イ Star Network A241 of 5 mass parts (big Japanese イ Application キ chemical industry society system contains the vinyl class in polymer of epoxy radicals, and epoxide equivalent is 600, and softening point is 109 ℃),
The エ Port ト one ト YD-014 of 5 mass parts (Dongdu changes into society's system, and epoxy resin, epoxide equivalent are 950),
The プ リ ミ De XL552 (the beta-hydroxy alkylamide curing agent of EMS-PRIMD society system, hydroxyl equivalent are 84) of 5 mass parts,
0.5 the ア Network ロ Na one Le 4F of mass parts (BASF society system, acrylate copolymer, Tg are-55 ℃, solubility parameter SP is 9.3, number-average molecular weight is 16,500 surface conditioner),
The benzoin of 1 mass parts and
The タ イ ペ one Network CR-90 of 65 mass parts (the former industry of stone society system, rutile titanium dioxide pigment).
Thereafter, after the fusion kneading thing that obtains is cooled to room temperature, pulverize with pulverizer atomizer (only パ ウ ダ Le society system), with gas flow sizing machine DS-2 type (the industrial society of Japanese ニ ユ one マ チ Star Network system) powder that obtains is carried out classification, by removing fine particle and oversize grain, the content that obtains volume average particle size and be 25 μ m and particle diameter and be the powder below 1/5 of volume average particle size is the powdery paints of 2 quality %.
(powdery paints 2)
Use CRYLCOAT4420-0 (ダ イ セ Le サ イ テ Star Network society system mylar, acid number is 50, glass transition temperature is 64 ℃) to substitute CRYLCOAT2617-3, in addition, use the method for making identical to make powdery paints 2 with powdery paints 1.
(powdery paints 3)
Use CRYLCOAT2621-2 (ダ イ セ Le サ イ テ Star Network society system mylar, acid number is 70, glass transition temperature is 62 ℃) to substitute CRYLCOAT2617-3, in addition, use the method for making identical to make powdery paints 3 with powdery paints 1.
(powdery paints 4)
With the following substances is raw material, carries out about three minutes mixing with mixer super mixer (Japanese ス ピ Application De Le society system), and then mediates extruder (Block ス society system) with the fusion masticator and carry out the fusion kneading under about 110 ℃:
The Off ア イ Application デ イ Star Network M8020 of 85 mass parts (hydroxyl value is 30 for big Japanese イ Application キ chemical industry society system, hydroxy polyester resin, and weight average molecular weight is 18,000),
The ベ ス タ go Application B-1530 of 15 mass parts (デ グ サ ヒ ユ Le ス society system, blocked isocyanate curing agent),
0.5 the ア Network ロ Na one Le 4F of mass parts,
The benzoin of 1 mass parts,
The タ イ ペ one Network CR-90 of 50 mass parts and
The precipitability barium sulfate 100 of 35 mass parts.
Thereafter, after the fusion kneading thing that obtains is cooled to room temperature, pulverize with pulverizer atomizer (only パ ウ ダ Le society system), with gas flow sizing machine DS-2 type (the industrial society of Japanese ニ ユ one マ チ Star Network system) powder that obtains is carried out classification, by removing fine particle and oversize grain, the content that obtains volume average particle size and be 25 μ m and particle diameter and be the powder below 1/5 of volume average particle size is the powdery paints of 2 quality %.
The manufacturing of amine-modified epoxy resin (amino-functional compounds)
(AME-I)
AME-I is by following method manufacturing.
Possessing mixer, cooler, temperature control equipment, nitrogen ingress pipe, in the reaction vessel of dropping funel, the liquid epoxy resin DER-331 of 386 mass parts of packing into (ダ ウ ケ ミ カ Le society system bisphenol A type epoxy resin), the bisphenol-A of 114 mass parts, the propylene glycol monomethyl ether of 56 mass parts, 0.06 the 2-ethyl-4-methylimidazole of mass parts, as solid component concentration is the composition of 90 quality %, purging this reaction vessel with nitrogen and be warming up to after 145 ℃, be incubated 3 hours, having synthesized epoxide equivalent is 500, number-average molecular weight is 1,000 bisphenol A type epoxy resin composition.By in the bisphenol A type epoxy resin composition that obtains, adding the propylene glycol monomethyl ether of 69 mass parts, be the bisphenol A type epoxy resin composition of 80 quality % as solid component concentration, it is cooled to 90 ℃.
Then, in the bisphenol A type epoxy resin composition that is cooled to 90 ℃ 625 mass parts (is 500 mass parts as solid constituent), add the aminoethyl ethanolamine MIBK end-blocking body (aminoethyl ethanolamine blockade body) of 236 mass parts, with the epoxy with respect to 1 equivalent, amine (except that the amine that is blocked by methyl iso-butyl ketone (MIBK)) is that the mode of 1 equivalent is allocated.And then, it is 70 quality % that the propylene glycol monomethyl ether that adds 119 mass parts is solid component concentration, thereafter, the temperature of composition is adjusted into 115 ℃ and be incubated one hour, make its reaction, make it be cooled to 100 ℃ by shelving subsequently, thus synthetic addition the epoxy resin of single ketones imines (aminoethyl ethanolamine MIBK end-blocking body).
Then, stir the container of the pure water of the acetate of the 90 quality % put into 66 mass parts and 322 mass parts with KEM agitator (ケ ミ ス タ one ラ one), the addition that obtains of 970 mass parts of dripping simultaneously the epoxy resin of single ketones imines (aminoethyl ethanolamine MIBK end-blocking body), the synthesis of solid constituent concentration is that 50 quality %, neutralization ratio are 50% resin combination, by the pure water that drips in turn again, modulating solid component concentration is the solubility epoxy resin solution AME-I (NH of 10 quality %
2And/or-NH
3 +About 0.2 mole/resin 100g).
(AME-II)
Make AME-II according to following method.
In being 190 Bisphenol F chloropropylene oxide type epoxide, the epoxide equivalent of 190 mass parts adds 30 parts of diethanol amine, 110 parts of cellosolve acetates, make it 100 ℃ of down reactions two hours, obtain nonvolatile component and be 70% contain amino water-soluble epoxide AME-II.
[chemical conversion processing]
With commercially available cold rolling steel plate (SPCC-SD, Japanese テ ス ト パ ネ Le society system, 70mm * 150mm *, under the condition of addressing table 1 record down, carry out chemical conversion respectively and handle 0.8mm) as base material.
In the table 1, APS represents KBM-603 (N-2 (amino-ethyl) 3-TSL 8330, valid density is 100%, Shin-Etsu Chemial Co., Ltd's system),
PAA10C represents PAA10C (PAH resin, molecular weight are 15,000, and Co., Ltd. is spun in day east),
AME-I represents the AME-I (amine-modified epoxy resin) that above-mentioned manufacture method is put down in writing,
AME-II represents the AME-II (amine-modified epoxy resin) that above-mentioned manufacture method is put down in writing, and
NPK-261 represents ス ミ ラ イ ト レ ジ Application-NPK-261 (amine modified phenolic resin, Sumitomo ベ one Network ラ イ ト).
In addition, FF represents fluorinion concentration in the table 1.
(a) (zirconium processing) handled in chemical conversion: embodiment 1-21, comparative example 2-3
Ungrease treatment: the spraying of carrying out under 40 ℃ in the aqueous solution of the サ of 2 quality %, one Off Network リ, one Na 1 (Japanese ペ イ Application ト society system degreasing agent) two minutes is handled.
Washing after the degreasing is handled: handle with the spraying that running water carried out 30 seconds.
Chemical conversion is handled: use each chemical conversion treatment solution of the condition that is adjusted into table 1, the spraying that base material carried out 60 seconds is handled.
Chemical conversion treatment solution: the driving fit reinforcing agent (amino-functional compounds) in fluorine zirconic acid and the table 1 is dissolved in running water, is modulated into each chemical conversion treatment solution.Use under the situation of chemical conversion treatment solution of KBM-603, making KBM-603 is that the mode of 5 quality % is dissolved in after the running water with concentration, at room temperature stirs 3 hours, obtains hydrolysate and condensation product is used.The pH of chemical conversion treatment solution adjusts with NaOH.The fluorine total amount of chemical conversion treatment solution sodium bifluoride (acid Off Star
ソ one ダ) adjusts.
Washing after the chemical conversion is handled: the impregnation process of carrying out 30 seconds in running water.And then handle with the spraying that ion exchange water carried out 10 seconds.Carry out powder coated after at room temperature air-dry thereafter.
In addition, the tunicle amount is that cold rolling steel plate after washing is handled is carrying out under 80 ℃ on 5 minutes dry bases in the electric drying stove, with " XRF1700 " (fluorescent x-ray analyzer that Shimadzu Seisakusho Ltd. makes), analyze as the total metal content that comprises in the chemical conversion treating agent.
(b) (trbasic zinc phosphate processing) handled in chemical conversion: comparative example 1,4-9
With commercially available cold rolling steel plate (SPCC-SD, Japanese テ ス ト パ ネ Le society system, 70mm * 150mm * 0.8mm) as base material, after the degreasing after washing is handled, at room temperature carry out 30 seconds surface adjustment with サ one Off Off ア イ Application 5N-8M (Japanese ペ イ Application ト society system), handle by the spraying of under 35 ℃, carrying out 2 minutes with サ one Off ダ イ Application SD-5350 (the trbasic zinc phosphate class chemical conversion treating agent of Japanese ペ イ Application ト society system) and to implement chemical conversion and handle, in addition identical with embodiment 1, obtained breadboard.
[coating of powdery paints and sintering]
To having carried out the base material that chemical conversion is handled,, carry out the coating and the sintering of powdery paints according to the condition of table 1 record.
Powdery paints is with corona discharge type electrostatic powder coating machine (trade name " MXR-100VT-mini " rising sun サ Na Star Network Co., Ltd. system), apply voltage 80kV, it is coated on has finished surface-treated (on the base material of 30cm * 40cm), then sintering under the condition of table 1 record is made coated plate thus.
In the table 1, AV represents acid number, and OHV represents hydroxyl value.In addition, in this specification, hydroxyl value is meant the hydroxyl value of trying to achieve with the method for JIS K0070 record.
Test
The coated plate (test film) that obtains is tested and estimated according to the evaluation method of appointment hereinafter.The results are shown in table 1.
(1) impact test
Under Du Pont's formula of foundation JIS K54008.3.2 is impacted, check to film under the condition hereinafter to have or not spalling.Spalling is arranged on filming is qualified not observe.
Weight: 500g
The size of hitting core and being hit platform: 1/2 inch
Fall distance: 30cm
(2) salt spraytest
On the breadboard that obtains, traverse (cross-cut) that draw to go up dark and base material in remaining on 35 ℃ salt spraytest machine, carries out 500 hours continuous spraying afterwards with the aqueous solution of 5%NaCl.Thereafter, mensuration is from the expansion width (side rust is wide) of notch.
(3) water resistant test
Each test film flooded 500 hours in 40 ℃ warm water after, placing 24 hours, then, is 10 cracks of each stroke in length and breadth at interval with 1mm with scraper on the filming of each test film, and is stained with adhesive tape thereon and throws off, and calculates the grid that is left in 100 grids.
(4) moisture-proof experiment
Breadboard was placed 240 hours in constant temperature and moisture test machine (50 ℃ of humidity 95%, temperature).Then, breadboard placed 1 hour in atmosphere after, on the filming of each test film, be 10 cracks of each stroke in length and breadth at interval with 1mm with scraper, be stained with adhesive tape thereon and throw off, calculate the grid that is left in 100 grids.
[table 1]
Claims (11)
1. method that is coated with iron class base material is characterized in that having following steps:
Steps A by the surface of handling this iron class base material with the chemical conversion treating agent that contains following composition, forms the chemical conversion processing layer:
That (a) selects from zirconium, titanium and hafnium is at least a,
(b) fluorine, and
(c) amino-functional compounds;
Step B, coating contains mylar that acid number is 30-70mgKOH/g and the powder paint compositions of the beta-hydroxy alkylamide curing agent represented with following general formula I on described chemical conversion processing layer:
[changing 1]
(in the formula, R
1Expression hydrogen atom, methyl or ethyl, R
2Alkyl or the HO-CH (R of expression hydrogen atom, carbon number 1-5
1)-CH
2-, A represents the divalent alkyl); And
Step C is with this powder paint compositions sintering, curing.
2. the described method of claim 1 is characterized in that, in described step C, makes described powder paint compositions 130 ℃-160 ℃ sintering temperature, curing.
3. claim 1 or 2 described methods is characterized in that, described amino-functional compounds is from amino-functional silane coupler, its hydrolysate and condensation product thereof,
PAH,
Amine-modified epoxy resin, and
That selects in the amine modified phenolic resin is at least a.
4. each described method of claim 1-3 is characterized in that, the content of amino-functional compounds described in the described chemical conversion treating agent based on the gross mass meter of described chemical conversion treating agent in the 5-5000ppm scope.
5. each described method of claim 1-4 is characterized in that, the pH value of described chemical conversion treating agent is 2.5-5.0.
6. each described method of claim 1-5 is characterized in that, the weight average molecular weight of described mylar is 1,000-150,000.
7. each described method of claim 1-6 is characterized in that, described iron class base material is from cold and hot rolled plate, plated steel sheet, and that selects in hot-dip galvanized steel sheet, tin plate, the stainless steel is at least a.
8. each described method of claim 1-7 is characterized in that, in described powder composition, the mass ratio of described beta-hydroxy alkylamide curing agent and described mylar is 3/97-10/90.
9. each described method of claim 1-8 is characterized in that, the volume average particle size of described powder paint compositions is 20-40 μ m.
10. the iron class base material of using each described method of claim 1-9 to apply.
11. contain the article of the iron class base material of each described method coating of useful claim 1-9.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2009244141A JP5231377B2 (en) | 2009-10-23 | 2009-10-23 | Method of coating iron-based substrate with powder coating |
| JP2009-244141 | 2009-10-23 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN102049377A true CN102049377A (en) | 2011-05-11 |
Family
ID=43954368
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2010105222768A Pending CN102049377A (en) | 2009-10-23 | 2010-10-25 | Method for coating ferrous substrate with powder coating film |
Country Status (2)
| Country | Link |
|---|---|
| JP (1) | JP5231377B2 (en) |
| CN (1) | CN102049377A (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105938754A (en) * | 2015-03-04 | 2016-09-14 | 株式会社村田制作所 | Electronic component and method for manufacturing electronic component |
| CN108025329A (en) * | 2015-09-07 | 2018-05-11 | 旭硝子株式会社 | The manufacture method of coated article |
| CN113286706A (en) * | 2018-11-13 | 2021-08-20 | 东洋制罐集团控股株式会社 | Coating composition and coated metal substrate having coating film formed from the coating composition |
Families Citing this family (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP5732671B2 (en) * | 2011-09-01 | 2015-06-10 | 日本ペイント株式会社 | Metal surface treatment composition |
| JP2013087312A (en) * | 2011-10-14 | 2013-05-13 | Nippon Paint Co Ltd | Paint pretreatment agent for coating-type paint, and coating-type painting method |
| JP6063701B2 (en) * | 2011-10-14 | 2017-01-18 | 日本ペイント・サーフケミカルズ株式会社 | Chemical conversion agent |
| JP6055263B2 (en) * | 2011-10-14 | 2016-12-27 | 日本ペイント・サーフケミカルズ株式会社 | Manufacturing method of automobile parts |
| KR101601514B1 (en) | 2014-10-27 | 2016-03-21 | 현대자동차주식회사 | Coating Composition for Insulation Film of Fe-Zr based Amorphous Magnetic Alloy |
| JP6418086B2 (en) * | 2015-07-06 | 2018-11-07 | 信越化学工業株式会社 | Powder coating composition and coated product thereof |
| JP6375043B1 (en) | 2017-10-31 | 2018-08-15 | 日本パーカライジング株式会社 | Pretreatment agent, pretreatment method, metal material having chemical conversion film and method for producing the same, and painted metal material and method for producing the same |
| JP6334048B1 (en) * | 2017-10-31 | 2018-05-30 | 日本パーカライジング株式会社 | Method for producing multilayer coating |
| JP6690771B1 (en) * | 2018-11-13 | 2020-04-28 | 東洋製罐グループホールディングス株式会社 | Painted metal plate and squeezed ironing can |
| WO2020100774A1 (en) * | 2018-11-13 | 2020-05-22 | 東洋製罐グループホールディングス株式会社 | Coated metal plate and drawn-and-ironed can |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1081699A (en) * | 1992-07-27 | 1994-02-09 | 罗姆和哈斯公司 | But the lipid acid hydroxyalkyl amide is as the stablizer of the coreaction of powder coating |
| JP2001294805A (en) * | 2000-04-17 | 2001-10-23 | Nippon Paint Co Ltd | Powder coating composition |
| CN1510165A (en) * | 2002-12-24 | 2004-07-07 | �ձ�������ʽ���� | Coating pretreatment method |
| JP2006241579A (en) * | 2005-03-07 | 2006-09-14 | Nippon Paint Co Ltd | Chemical conversion treatment agent and surface-treated metal |
| US20080085965A1 (en) * | 2004-10-06 | 2008-04-10 | Kansai Paint Co., Ltd | Thermosetting Powder Coating Composition |
| CN101208460A (en) * | 2005-07-01 | 2008-06-25 | 本田技研工业株式会社 | Method and agent for chemical conversion treatment and chemically conversion-treated members |
Family Cites Families (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2001106774A (en) * | 1999-10-04 | 2001-04-17 | Nippon Ester Co Ltd | Polyester resin and composition for powder coating material and powder coating material produced by using the resin |
| JP4598230B2 (en) * | 2000-04-17 | 2010-12-15 | 日本ペイント株式会社 | Powder coating composition |
| JP2003155578A (en) * | 2001-11-20 | 2003-05-30 | Toyota Motor Corp | Chemical conversion treatment agent for iron and/or zinc |
| TW200424273A (en) * | 2002-11-14 | 2004-11-16 | Kansai Paint Co Ltd | Powder coating, method for production thereof, method for using the powder coating and coated article |
| JP2006161110A (en) * | 2004-12-08 | 2006-06-22 | Nippon Paint Co Ltd | Coating pretreatment method for metallic surface for chassis of vehicle and coating method for powder coating |
| JP2006255540A (en) * | 2005-03-15 | 2006-09-28 | Nippon Parkerizing Co Ltd | Coating method of metal material |
| CA2644789C (en) * | 2006-03-01 | 2015-04-28 | Nippon Paint Co., Ltd. | Composition for metal surface treatment, metal surface treatment method, and metal material |
-
2009
- 2009-10-23 JP JP2009244141A patent/JP5231377B2/en active Active
-
2010
- 2010-10-25 CN CN2010105222768A patent/CN102049377A/en active Pending
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1081699A (en) * | 1992-07-27 | 1994-02-09 | 罗姆和哈斯公司 | But the lipid acid hydroxyalkyl amide is as the stablizer of the coreaction of powder coating |
| JP2001294805A (en) * | 2000-04-17 | 2001-10-23 | Nippon Paint Co Ltd | Powder coating composition |
| CN1510165A (en) * | 2002-12-24 | 2004-07-07 | �ձ�������ʽ���� | Coating pretreatment method |
| US20080085965A1 (en) * | 2004-10-06 | 2008-04-10 | Kansai Paint Co., Ltd | Thermosetting Powder Coating Composition |
| JP2006241579A (en) * | 2005-03-07 | 2006-09-14 | Nippon Paint Co Ltd | Chemical conversion treatment agent and surface-treated metal |
| CN101208460A (en) * | 2005-07-01 | 2008-06-25 | 本田技研工业株式会社 | Method and agent for chemical conversion treatment and chemically conversion-treated members |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105938754A (en) * | 2015-03-04 | 2016-09-14 | 株式会社村田制作所 | Electronic component and method for manufacturing electronic component |
| CN105938754B (en) * | 2015-03-04 | 2018-06-26 | 株式会社村田制作所 | The manufacturing method of electronic unit and electronic unit |
| CN108025329A (en) * | 2015-09-07 | 2018-05-11 | 旭硝子株式会社 | The manufacture method of coated article |
| CN113286706A (en) * | 2018-11-13 | 2021-08-20 | 东洋制罐集团控股株式会社 | Coating composition and coated metal substrate having coating film formed from the coating composition |
Also Published As
| Publication number | Publication date |
|---|---|
| JP5231377B2 (en) | 2013-07-10 |
| JP2011088083A (en) | 2011-05-06 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN102049377A (en) | Method for coating ferrous substrate with powder coating film | |
| JP5010806B2 (en) | Powder coating composition and method for coating aluminum wheel | |
| US20080085965A1 (en) | Thermosetting Powder Coating Composition | |
| TWI414633B (en) | Galvanized steel plate | |
| MX2007012675A (en) | Process for the coating of metallic components with an aqueous organic composition. | |
| JP2009256634A (en) | Anticorrosive paint composition | |
| CN101293238A (en) | Multilayer coating film- forming method | |
| JP6957466B2 (en) | Water-based anticorrosion paint composition and anticorrosion coating method | |
| JP4970773B2 (en) | Metal surface treatment agent, metal material surface treatment method and surface treatment metal material | |
| CA1111596A (en) | Thermosetting acrylic resine powder coating compositions | |
| JP2016176053A (en) | Powder coating composition and method for forming coated film | |
| JP4846118B2 (en) | Pigment for corrosion prevention coating composition and corrosion prevention coating composition using the same | |
| JPH0459878A (en) | Powder coating composition | |
| KR0180612B1 (en) | Thermosetting powder paint coating method using said paint and article coated with said paint | |
| CN102344708A (en) | Cured electrodeposition coating film and process for forming multi layered coating film | |
| JP5677337B2 (en) | Pre-treatment metal plate surface treatment agent, coated ground metal plate coated with the same, and pre-coat metal plate using the same | |
| JP2006022127A (en) | Composition for water dispersion type rust-preventing coating | |
| JP4027403B1 (en) | Method of painting aluminum alloy wheel and aluminum alloy wheel | |
| JP2007126565A (en) | Coating composition for galvanized steel sheet or zinc alloy-plated steel sheet and steel sheet coated therewith | |
| JP6080162B2 (en) | Paint composition | |
| JPH09324148A (en) | Composition for aqueous coating material and corrosion resistant metal board using the same | |
| JP4608233B2 (en) | Undercoating composition for production of non-chromate pre-coated metal sheet for forming uneven pattern, and non-chromate pre-coated metal sheet | |
| JP4998376B2 (en) | Polyester resin composition for outdoor paint and water dispersion thereof | |
| JP5927857B2 (en) | Chromate-free colored painted metal plate | |
| JP2008081670A (en) | Powder coating composition |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C02 | Deemed withdrawal of patent application after publication (patent law 2001) | ||
| WD01 | Invention patent application deemed withdrawn after publication |
Application publication date: 20110511 |