CN101379152A - Thermosetting coating composition for precoating and metal sheet precoated therewith - Google Patents
Thermosetting coating composition for precoating and metal sheet precoated therewith Download PDFInfo
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- CN101379152A CN101379152A CNA2007800040948A CN200780004094A CN101379152A CN 101379152 A CN101379152 A CN 101379152A CN A2007800040948 A CNA2007800040948 A CN A2007800040948A CN 200780004094 A CN200780004094 A CN 200780004094A CN 101379152 A CN101379152 A CN 101379152A
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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
- C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
- C09D175/04—Polyurethanes
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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
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/60—Additives non-macromolecular
- C09D7/61—Additives non-macromolecular inorganic
- C09D7/62—Additives non-macromolecular inorganic modified by treatment with other compounds
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K9/00—Use of pretreated ingredients
- C08K9/04—Ingredients treated with organic substances
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- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Wood Science & Technology (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Paints Or Removers (AREA)
- Application Of Or Painting With Fluid Materials (AREA)
Abstract
A thermosetting coating composition for precoating that without vaporization of formaldehyde being a substance causing sick house syndrome, adsorbs and decomposes toxic substances vaporized indoors, providing a precoated metal sheet excelling in coating properties; and a metal sheet precoated therewith. There is provided a thermosetting coating composition for precoating characterized by containing (A) coat forming resin composition containing a hydroxylated resin and a blocked isocyanate curing agent, (B) inorganic compound with its surface treated with a nitrogenous compound capable of adsorbing aldehyde compounds and (C) titanium phosphate compound in such a proportion that 0.1 to 10 parts by mass of component (B) and 0.1 to 10 parts by mass of component (C) are used per 100 parts by mass of component (A). Further, there is provided a metal sheet precoated with the composition.
Description
Technical field
The present invention relates to novel precoating with thermosetting coating composition and used its precoating metal sheet with deodorization.More particularly, relate to can obtain following precoating metal sheet precoating with thermosetting coating composition and used its prefinished metal plate, described pre-coated steel plate promptly can not give out the formaldehyde as the inducement material of indoor disease syndrome (sick-house syndrome), also can adsorb in addition, decompose to the objectionable impurities of distributing within doors.
Background technology
In recent years, in buildingss such as ordinary residence, office building, arenas or kino, shop or vehicles such as automobile, electric car etc., be full of cooling/heating equipment, in these living space, in order to improve its cooling/heating effect, resistance to air loss compared with the past is enhanced.From inner decoration materials for building such as wall material, top ceiling material, partition material, wallpaper materials; Used vehicle interior exterior material in the vehicle chamber of the vehicles such as automobile or electric car; Be disposed within doors or vehicle chamber in etc. in furniture or the indoor disease syndrome that objectionable impuritiess such as formaldehyde caused that in people's living space, gives out in used various inner decoration materials or the articles for daily use etc. (inner decoration material) with material etc. of articles for daily use such as daily necessities etc. become social concern.
Particularly, in the construction and decoration at home, in indoor floor wall, top ceiling, be main flow as the dry process finishing that inner decoration material uses with plasterboard, glued board, shaving board, ethene wallpaper, vinylchlorid flooring material etc.Therefore this method has the high advantage of economical efficiency because production cost is low, construction is easy.But, in their finishings as inner decoration material, as a rule, in the caking agent of the glued board part in contained formaldehyde (formalin) or organic solvent and the vinyl material objectionable impuritiess such as contained softening agent, fire retardant can distribute to indoor.Thus, the concentration of these objectionable impuritiess in the living space raises, thereby produce human body is had dysgenic problem.For example, it is said relevantly, thereby strengthened restriction by building standard law with atopy, supersensitivity or carinogenicity.
On the other hand, in electrical equipment, shaving board, indoor implements, vehicle interior trim etc., used pre-coated steel plate, particularly,, must consider the emission limit set of PARA FORMALDEHYDE PRILLS(91,95) etc. according to aforesaid situation for carrying out shaving board used in the interior space of daily life etc. the people.Now, in such field the main flow of used coated steel plates be by primary coat film and on the bilayer that constitutes of filming film, and the main flow of used coating is to have made up the coating of Synolac with hydroxyl, acrylic resin, Resins, epoxy etc. and aminoresin (melamine derivative, urea derivative etc.) in the coating.Under this situation, consider that aminoresin is the relation by formaldehyde generation hydroxymethylation is made, even behind formaldehyde reaction, also contains free formaldehyde, also can be remaining after sintering is filmed, thus the problem that comes out existence meeting the filming on being coated on shaving board.
At this kind problem, proposed to carry out crosslinked sintered type coating with hydroxy-containing resin and blocked isocyanate (blockisocyanate) solidifying agent.If this method, then in coating, can not contain formaldehyde, do not have the situation that contains formaldehyde in the filming behind sintering, even yet objectionable constituent such as contained solvent or lower-molecular substance also can remain in behind sintering and film in the coating micro-ly, can not fully remove, in addition, if consider the volatilization of formaldehyde, film then and primary coat is filmed and all needed to use cured with isocyanates type coating system, as pre-coated steel plate, with regard to have aspect the film performance, economic aspect all is subjected to the problem of suitable restriction.
As the method for dealing with problems, disclose and contained water-soluble or water-dispersed resin (A) and be selected from the water-borne coatings (for example with reference to patent documentation 1) that more than one the reply indoor pollution of pigment (B) in activated alumina, atlapulgite, zeolite, the diatomite is used.But this coating composition is that (coating of slow-drying) is unsuitable for sintering between high temperature, short time, and is in addition, abundant inadequately with the processibility of filming as pre-coated steel plate for the slow curing type of water system.
As the material of having improved this processibility, following thermohardening type precoating coating composition was disclosed, be to carry out crosslinked sintered type coating with hydroxy-containing resin and blocked isocyanate solidifying agent, in addition, also contain the nitrogen compound that PARA FORMALDEHYDE PRILLS(91,95) has absorption property, as required, contain more than one pigment (for example with reference to patent documentation 2) that are selected from activated alumina, atlapulgite, zeolite, the diatomite.But, though this coating composition can absorb a certain amount of formaldehyde, there is receptivity to reach capacity, absorbing certain can't resorbent shortcoming after a certain amount of.
In addition, disclose and comprised ceramic (A) with ion generating capability and the synthetic resin coated feed composition of the glass micro mist (B) that contains heavy metal ion (for example with reference to patent documentation 3).But the absorption property that utilizes the PARA FORMALDEHYDE PRILLS(91,95) of filming that this coating composition forms is problem fully inadequately.
In addition, also disclose with titanium phosphate based compound or its condenses antibiotic, reodorant (for example with reference to patent documentation 4) as effective constituent.But that this is not antibiotic, reodorant adds the record in filming to, even add, formed filming also has the sufficient inadequately problem of the absorption property of PARA FORMALDEHYDE PRILLS(91,95).
Though known supporting by the surface at silicon oxide contained the material (for example with reference to patent documentation 5) that amino silicoorganic compound embody the deodoriging properties of formaldehyde, but, also have to reach capacity in absorption that effect can significantly reduced problem in the state for this material.
The photocatalysis that just can utilize titanium oxide realizes the coating (for example with reference to patent documentation 6) of self-regeneration if known deodorizing capability reaches capacity, if yet do not have the irradiation of light (ultraviolet ray), then can't bring into play activation effect, so in the darkroom, can not bring into play effect.As the approach that solves it, even have in titanium oxide and with silver or golden method that also can display effect in the darkroom, yet worrying be environmental problem or to the influence of human body.
Patent documentation 1: 2000-No. 095979 communique of TOHKEMY
Patent documentation 2: 2005-No. 255698 communiques of TOHKEMY
Patent documentation 3: 2002-No. 038099 communique of TOHKEMY
Patent documentation 4: 2002-No. 308712 communiques of TOHKEMY
Patent documentation 5: 9-No. 173830 communiques of Japanese kokai publication hei
Patent documentation 6: 11-No. 130985 communiques of Japanese kokai publication hei
Summary of the invention
The objective of the invention is to, provide the precoating that can obtain following prefinished metal plate with thermosetting coating composition and used its prefinished metal plate, it does not have situation about giving out as the formaldehyde of the inducement material of indoor disease syndrome, can adsorb, decompose to the objectionable impurities of distributing within doors, also very good aspect the rerum natura of filming in addition.
The inventor furthers investigate in order to address the above problem, found that, utilize following coating composition to form the situation that the prefinished metal plate of filming does not have formaldehyde emissions, and can adsorb or decomposing formaldehyde etc., in addition, also find to obtain in processibility, shock resistance, pencil hardness, good the filming in rerum natura aspect of filming such as anti-boiling water, thereby finished the present invention, described coating composition is to form resin combination with containing the resin of hydroxyl and the overlay film of blocked isocyanate solidifying agent, the nitrogenous compound that has an aldehydes adsorptive power with utilization has carried out surface-treated mineral compound and specific titanium phosphate based compound and has cooperated and form.
Promptly, the invention provides a kind of precoating thermosetting coating composition, it is characterized in that, contain the overlay film formation resin combination that (A) contains hydroxy-containing resin and blocked isocyanate solidifying agent in following ratio, (B) utilize nitrogenous compound to carry out the surface-treated mineral compound with aldehyde cpd adsorptive power, (C) titanium phosphate based compound, described ratio promptly, with respect to (A) composition 100 mass parts (B) composition be 0.1～10 mass parts and (C) composition be 0.1～10 mass parts.
In addition, the present invention also provides the above-mentioned precoating thermosetting coating composition with following feature, promptly, (B) nitrogenous compound with aldehyde cpd adsorptive power of composition is at least a material that is selected from primary amine, secondary amine, hydrazine, hydrazine derivative, aminotriazole and the ethylidene-urea, and mineral compound is at least a material that is selected from porous silica, activated carbon, porous metal oxide, potassium titanate and the zirconium phosphate.
In addition, the present invention also provides the above-mentioned precoating thermosetting coating composition with following feature, that is, (A) in the composition contained hydroxy-containing resin be that to be selected from hydroxyl value be that 5～200mgKOH/g, number-average molecular weight are at least a resin in 1000～20000 hydroxyl group containing polyester resin, hydroxyl Synolac and the hydroxy acryl acid resin.
In addition, the present invention also provides a kind of prefinished metal plate that applies aforementioned coating composition and get.
According to the present invention, form and film by in indoor wall etc., using thermosetting coating composition of the present invention, just can block the objectionable impuritiess such as formaldehyde that from these inner decoration materials, come out, or with its absorption or decomposition, thereby can prevent indoor pollution effectively, formed film also very good aspect the rerum naturas of filming such as processibility, shock resistance, pencil hardness, anti-boiling water.
Embodiment
As contained hydroxy-containing resin in (A) composition used in the invention, can enumerate vibrin, Synolac, acrylic resin etc., as hydroxyl value, be preferably the scope of 5～200mgKOH/g, more preferably the scope of 10～150mgKOH/g.Under the situation of hydroxyl value less than 5mgKOH/g, the solidified nature deficiency of filming, resistance to chemical reagents, solvent resistance reduce.In addition, owing to surpass under the situation of 200mgKOH/g in hydroxyl value, processibility reduces, and is therefore not ideal enough.In addition, number-average molecular weight is preferably 1000～20000 scope, more preferably 1000～15000 scope, more preferably 1200～13000 scope.
Number-average molecular weight less than 1000 situation under because processibility reduces, therefore not ideal enough.In addition, under 15000 the situation of surpassing, resistance to chemical reagents, solvent resistance reduce.As described vibrin with hydroxyl, for example can enumerate macromolecule polyester resin, oily modified polyester resin, oil-free polyester resin, organosilicon modified polyester resin etc., as the material of market sale, for example can enumerate Beckolite M-6003-60, Beckolite M-6601-60-S (big Japanese ink chemical industry (strain) system), Vylon GK-13CS (Japan's weaving (strain) system), Aroplat 1711, Aroset 5534-SB60 (Japanese catalyzer (strain) system), Arakyd 7052L (waste river chemical industry (strain) system) etc.These resins both can use a kind of, also can be used in combination two or more.
Example as blocked isocyanate curative compound contained in (A) composition used among the present invention, for example can enumerate hexamethylene diisocyanate, isophorone diisocyanate, tolylene diisocyanate, diphenylmethanediisocyanate, xylylene diisocyanate, dicyclohexyl methyl hydride-4, the compound that is known as diisocyanate monomer of 4 '-vulcabond and so on; Part or all material made from the end-capping reagent end-blockingization with the isocyanate group of the polyisocyanate compounds such as polyisocyanate derivatives of their biuret derivatives, isocyanuric acid ester (isocyanurate) derivative, affixture of TriMethylolPropane(TMP) and so on.Example as the agent of this kind end-blocking, for example can enumerate ketoximes such as ε-hexanolactam, methyl ethyl ketoxime, methyl isoamyl ketoxine, hexone oxime is the end-blocking agent, phenol such as phenol, cresols, catechol, nitrophenols are the end-blocking agent, alcohol such as Virahol, TriMethylolPropane(TMP) is the end-blocking agent, malonic ester, the agent of acetylacetic ester isoreactivity methylene base system end-blocking etc.These poly-blocked isocyanate compounds both can have been used a kind of, also can be used in combination two or more.
, contain the nitrogenous compound that (B) usefulness has the aldehyde cpd adsorptive power as essential composition and carried out the surface-treated mineral compound with in the thermosetting coating composition at precoating of the present invention; Reach (C) titanium phosphate based compound.
Among the present invention used (B) composition to have carried out the surface-treated mineral compound with nitrogen compound be not the mineral compound of representing to have mixed simply, supported nitrogen compound, but by the nitrogen compound that contains the functional group utilize chemical reaction with the mineral compound surface modification mineral compound.
The nitrogenous compound that has the aldehyde cpd adsorptive power in the usefulness of (B) composition has carried out in the surface-treated mineral compound, as nitrogenous compound with aldehyde cpd adsorptive power, be can utilize chemical bond catch in molecule, the containing of aldehydes such as formaldehyde-NH base ,-NH
2The compound of base for example can be enumerated primary amine, secondary amine, hydrazine, hydrazine derivative, amino-triazole compound thing, ethylidene-urea.As primary amine and secondary amine, for example can enumerate lauryl amine, tridecyl amine, tetradecylamine, imidazolone etc. or as amino acid whose Methionin, arginine, Histidine and derivative thereof etc.
In addition, hydrazine derivative is the material that has plural at least hydrazide group or Semicarbazido in a molecule, as this hydrazine derivative, for example can enumerate representative examples of saturated aliphatic carboxylic two hydrazides that oxalic acid two hydrazides, propanedioic acid two hydrazides, pentanedioic acid two hydrazides, succinic acid hydrazide ii, adipic dihydrazide, sebacic dihydrazide etc. have 2～18 carbon atoms; Monoene unsaturated dicarboxylic acid two hydrazides such as Malaysia acid dihydrazide, fumaric acid two hydrazides, methylene-succinic acid two hydrazides; Two hydrazides of phthalic acid, terephthalic acid or isophthalic dihydrazide and pyromellitic acid, three hydrazides or four hydrazides; Nitrotrimethylolmethane acetate three hydrazides, citric acid three hydrazides, 1,2,4-benzene, three hydrazides, ethylenediamine tetraacetic acid (EDTA) four hydrazides, 1,4,5,8-naphthoic acid, four hydrazides etc.
In addition, as aminotriazole, for example can enumerate 3-amino-1,2,4-triazole, 4-amino-1,2,4-triazole, 3,5-diamino-1,2,4-triazole, 5-amino-3-sulfydryl-1,2,4-triazole, 3-amino-5-phenyl-1,2,4-triazole.In addition, also preferred ethylidene-urea.
In addition, as by the surface-treated mineral compound, it is at least a material that is selected from porous silica, activated carbon, porous metal oxide, potassium titanate and the zirconium phosphate, as the porous metal oxide shown in here, for example can enumerate porous alumina, titanium oxide, zirconium white etc., also can be their composite oxides that comprise porous silica.Specifically, being activated alumina, atlapulgite, zeolite, diatomite, all is the compound that has vesicular structure with very big adsorptive power.
Activated alumina be with hydrated aluminas such as gibbsite, boehmite, bayerite, amorphous hydrated gels under suitable temperature, be generally burn till under 200～1000 ℃ and the intermediate alumina with pore structure.Atlapulgite is with a kind of acidic white earth acid treatment as clay as principal constituent of the clay mineral of montmorillonite family and mensuration dissolubility silicic, with the material of a part of stripping of alkaline components.In zeolite, have with hydrous alumino silicates as the natural zeolite of principal constituent, with Na
2OAl
2O
3XSiO
2YH
2O is as the synthetic zeolite of principal constituent.Synthetic zeolite is also referred to as permutite (permutite), can be by the drying process that yellow soda ash, silicon oxide, aluminum oxide or kaolin are melted altogether; Perhaps water glass and sodium aluminate are merged and the damp process of gel precipitation is made.
Natural zeolite, synthetic zeolite all have ion-exchange capacity, even the dehydration crystalline structure can not change yet, can obtain the pore of molecular dimension after the dehydration, have very big adsorptive power.In addition, also can use at the molecular sieve that utilizes the synthetic pore that can obtain certain size after with sodium aluminium silicate gel crystalsization and dehydration of hydro-thermal etc.Diatomite is Silicon dioxide, hydrate, owing to have vesicular structure, therefore the character that absorbs liquid is well arranged.
Nitrogenous compound with aldehyde cpd adsorptive power uses 0.1～10 mass parts in general with respect to by surface-treated mineral compound 100 mass parts.
As commercially available product, for example can enumerate with nitrogenous compound metal oxide has been carried out surface-treated Saubersuper#100, Formclean H-300 (big and chemical industry (strain) system), with amine silicon oxide carried out surface-treated Kesmon NS-103, NS-13T, TNS-110, TNS-120 (East Asia synthetic (strain) system) etc.
(B) nitrogenous compound of the usefulness of composition with the aldehyde cpd adsorptive power median size of having carried out the surface-treated mineral compound is preferably 0.1～20 μ m, more preferably 0.5～10 μ m.Under the situation of its median size less than 0.1 μ m, film to the adsorptive power reduction of objectionable impuritiess such as formalin or ammonia, surpassing under the situation of 20 μ m, the tendency of appearance of film variation is then arranged.
(B) nitrogenous compound of the usefulness of composition with aldehyde cpd adsorptive power carried out the surface-treated mineral compound with respect to above-mentioned resin solid composition 100 weight parts, preferably is made as 0.1～10 mass parts, more preferably is made as 0.2～8 mass parts.Because under the situation of this usage ratio less than 0.1 mass parts, it is poor to the adsorptive power of objectionable impuritiess such as formalin or ammonia to film, surpassing under the situation of 10 mass parts, the processibility of filming reduces, and is therefore not ideal enough.
As the titanium phosphate based compound of (C) composition used among the present invention, can enumerate titanium phosphate based compound or its condenses with general formula (1) expression.
Ti(OH)x(PO
4)y(HPO
4)z(H
2PO
4)m(OR)n (1)
(in the formula, R is that carbon number is 1～4 alkyl, and x, y, z, m and n are respectively the numbers more than 0, are the numbers that satisfies x+y+z+m+n=3 or 4.)
If the carbon number of R is few, then have the tendency that the de-odorised effect reduces.If opposite carbon number is too much, then has and be difficult to the dispersive tendency.R is preferably ethyl or sec.-propyl.
As this titanium phosphate based compound, for example be preferably Ti (OH) (H
2PO
4)
2(OR), Ti (OH) (PO
4), Ti (OH)
2(H
2PO
4) (OR), Ti (OH) (HPO
4) (OR), Ti (OH) (HPO
4) (H
2PO
4), Ti (OH)
2(H
2PO
4)
2, Ti (OH)
3(H
2PO
4), Ti (OH)
3(OR) etc.
As commercially available product, for example can enumerate Ecokimera SE-50E, Ecokimera SW-50 ((having) (YOO corporate system), Nanofine-2 (JSEP (strain) system) etc.
The titanium phosphate based compound of used (C) composition preferably is made as with respect to above-mentioned resin solid composition 100 mass parts and reaches 0.1～10 mass parts among the present invention.0.2～8 mass parts more preferably.Under the situation of this usage ratio less than 0.1 mass parts, the capacity of decomposition of objectionable impuritiess such as formalin that absorbs filming or ammonia is poor, is surpassing under the situation of 10 mass parts, because the water tolerance of filming reduction is therefore not ideal enough.
In addition, precoating of the present invention also can suitably select to cooperate for example painted pigment such as titanium dioxide, carbon black, red iron oxide, phthalocyanine blue with in the thermosetting coating composition as required as pigment, lime carbonate, talcum, mica, clay, silica sand, filler pigment such as perlite or aggregate etc.As above-mentioned pigment integral body, consider that from the aspect of the compactness of filming, barrier fits best is to make that the volume ratio of shared whole pigment (comprise with the nitrogenous compound with formolation compound adsorptive power and carried out the surface-treated mineral compound) reaches 2～70 quality % in the total solids composition in coating.
In addition, precoating of the present invention can be gone back coating additives such as matching surface promoting agent, dispersion agent, defoamer, thickening material as required with thermosetting coating composition.In addition, the method for manufacturing does not have special method, can utilize himself known method to carry out.For example, can be by the coating additive that in matrix resin, adds solidifying agent, pigment composition, uses as required, utilize known mechanism such as stirrer equably its dispersion to be carried out.In addition, as required, can cooperate antibiotic, mould inhibitor or anion-generating materials such as antistatic agent and tourmalinite.
As using the starting material of precoating of the present invention with thermosetting coating composition, various metal sheets be can use, cold-rolled steel sheet, electrogalvanizing steel plate, plating alloy zinc steel plate, plating fused zinc steel plate (non-alloying) zinc-iron plate, plating fused zinc steel plate (alloying), plating fused zinc-steel plate galvanizeds such as aluminium alloy steel plate, stainless steel plate, aluminium sheet, aluminium alloy plate etc. for example can be enumerated.In addition, on metal sheet, be coated with in the bottom-coating, preferably the coating pre-treatment is implemented on the surface of metal sheet, as this coating pre-treatment, so long as of the change into processing of precoating metal with the pre-treatment use, then any one all can use, and for example can enumerate that chromic salt changes into processing, phosphoric acid salt changes into processing, the processing of combined oxidation overlay film etc.
The precoating metal sheet that uses precoating of the present invention to obtain with thermosetting coating composition can utilize coating processing as follows to obtain.Promptly, can enumerate after being coated with bottom-coating on the metal sheet as required and it is solidified, be coated with precoating thermosetting coating composition of the present invention as coating, be heated the coating working method of solidified metal sheet with aldehyde cpd adsorptive power.
The coating method of bottom-coating and coating of the present invention can utilize various coating methods to carry out, yet preferably utilizes the coating method of roller coating machine, flow coating machine or spraying machine etc.Under the situation of utilizing roller coating machine coating coating, can consider nature (nature) mode or reverse (reverse) mode, yet consider preferred reverse mode from the aspect of the surface smoothing that is coated with face.
Solidified successively in each coating back with filming of being coated with of bottom-coating and coating of the present invention, this curing is usually under 100～300 ℃, get final product under 5 seconds～5 minutes the condition of cure, for example in the coating field of the precoating metal sheet that utilizes coiled material coating etc. to apply, preferably to be up to Da Wendu at starting material usually be 120～260 ℃, carry out solidified method under 15～120 seconds the condition of cure.
The thickness of filming that has been coated with bottom-coating is preferably 1～10 μ m, more preferably 3～8 μ m.In addition, the thickness of filming that has been coated with coating of the present invention is preferably 10～40 μ m, more preferably 15～30 μ m.
Embodiment
Below, will enumerate embodiment and comparative example is described in more detail the present invention, yet the present invention is not subjected to any qualification of these embodiment.And the evaluation of physical property of filming in embodiment, the comparative example is to utilize following method to carry out.
(1) processibility-1
Under 20 ℃ room temperature, under the situation of 4T,, 4 coated plates identical with test film are clipped in the inboard to being cut into the test film of wide 5cm, will film is made as the outside, has carried out 180 degree driving fit bendings (tight bending).Evaluation is with the cellulose film jointing tape it to be peeled off thereafter, estimates according to following benchmark.
◎: do not peel off (no problem).
Zero: peel off at (no problem in practicality) below 10%.
*: peeling off (is having problem) more than 50%.
(2) processibility-2
Under 20 ℃ room temperature, under the situation of 8T,, 8 coated plates identical with test film are clipped in the inboard for the test film that is cut into wide 5cm, will film is made as the outside, has carried out 180 degree driving fit bendings.Evaluation is with 10 times of magnifying glass viewing head ends, estimates according to following benchmark.
◎: do not have crackle (no problem).
Zero: crackle is at (no problem in practicality) below 10%.
*: crackle (is having problem) more than 50%.
(3) shock resistance
Use JIS K-5400 (1990) 8.3.2 Du Pont types,, utilize the visual weight that the makes 500g damage of filming when the height of 40cm falls of having judged with the Impact mould clamping test film of radius 6.35mm.
(4) pencil hardness
Utilize the pencil test machine to obtain the pencil hardness that does not produce damage according to JIS K-5400 (1990) 8.4.1 (a).
(5) anti-boiling water
After according to JIS K-5400 (1990) 8.20 test film having been flooded 2 hours in boiling water, observe film unusual, judge according to following benchmark.
Zero: not unusual fully in filming.
△: can see the expansion of filming slightly.
*: can see the expansion of filming significantly.
(6) formaldehyde adsorptivity (revision test)
The test film that is cut into the size of vertical 10cm, horizontal 10cm is put into 1L volumetrical Tedlar bag, after sealing, the degassing, inject the formaldehyde gas of the 10ppm of 1L.After at room temperature placing 2 hours, use detector tube to measure formaldehyde gas concentration in the Tedlar bag, according to following benchmark evaluation formaldehyde adsorption property.
◎: be in 0.1～3ppm (very good scope).
Zero: surpass 3ppm to 5ppm (in practicality, can think good scope).
*: surpass 5ppm (the good scope of can not saying so).
After above-mentioned test, in new Tedlar bag, put into test film, inject the 1L air.50 ℃ down keep 3 hours after, use detector tube to measure concentration of formaldehyde in the Tedlar bag, according to following benchmark evaluation release performance again.
◎: be in 0.1～0.3ppm (very good scope).
Zero: surpass 0.3ppm to 0.5ppm (in practicality, can think good scope).
*: surpass 0.5ppm (the good scope of can not saying so).
Outgas after the evaluation, enclose the 1L air, placed 19 hours.
Repeat above-mentioned absorption property and tested, emitted again test.
The evaluation utilization of repeating performance will adsorb, emit again test carried out 3 circulations, 5 round-robin results estimate.
The manufacturing of (embodiment 1) " thermohardening type precoating coating 1 "
Vylon GK13CS (Japan's weaving (strain) system with (A) composition, vibrin, hydroxyl value 20mgKOH/g, number-average molecular weight 7,000, nonvolatile component 50 quality %) 93 mass parts, (C) the Ecokimera SE-50E of composition ((having) (YOO corporate system, titanium phosphate) 2 mass parts, JR-602 (Tayca (strain) system as pigment, carbonic acid gas) 36 mass parts, Solvesso 100 (Esso (strain) system as solvent, the aromatic base crude oil petroleum naphtha) 23.1 mass parts, pimelinketone 23.2 mass parts are disperseed with sand mill, make granularity reach below the 10 μ m, obtained the abrasive (mill base) of pigment.
In this pigment grind material, add DesmodurBL3175 (Bayer corporate system, blocked isocyanate compounds, effectively NCO11.1 quality %, nonvolatile component 75 quality %) 7 mass parts of (A) composition, the Saubersuper #100 of (B) composition (big and chemical industry (strain) system, reodorant) 2 mass parts, surface conditioner BYK-325 (Byk-Chemie (strain) system) 0.2 mass parts, as the dibutyltin dilaurate 0.5 mass parts mixing of isocyanic ester dissociation catalyst, made solvent based coating.Utilize Solvesso #100 (Esso (strain) system, aromatic base crude oil petroleum naphtha)/pimelinketone (50 mass parts/50 mass parts) to carry out the viscosity adjustment coating of gained, make that utilizing Ford cup No.4 to measure reaches 120 ± 10 seconds, obtained " thermohardening type precoating coating 1 ".The cooperation of coating composition is shown in the table 1.
Then, the carrying out of plating fusion 55% aluminium-Zn based alloy steel plate (Galvalume steel plate), thickness of slab 0.35mm on the steel plate starting material of application type chromate treating, as bottom-coating coating precolor priming paint HP-32 (trade(brand)name, BASF Coatings Japan (strain) system, epoxy resin coating), so that steel plate be up to the mode sintering that Da Wendu reaches 210 ℃ after, use roller coating machine coated heat curing precoating steel plate coating 1, make thickness reach the thickness of 20 μ m, so that the mode that Da Wendu reaches 240 ℃ that is up to of steel plate applies.The test board of gained is used to the physical property test of filming.Its evaluation result is shown in the table 1.
(embodiment 2～7, comparative example 2～4)
Except the vibrin with (A) composition of embodiment 1 replaces with Arakyd 7052L (waste river chemical industry (strain) system, vibrin, hydroxyl value 60mgKOH/g, number-average molecular weight 4000, nonvolatile component 60 quality %), (C) composition is replaced with beyond the kind and amount of the pigment shown in table 1 and the table 2, made the abrasive of pigment in the same manner with embodiment 1.In addition, identical with embodiment 1, remaining raw material shown in table 1 and the table 2 added in the pigment grind material mix, utilize Solvesso #100 (Esso (strain) system, aromatic base crude oil petroleum naphtha)/pimelinketone (50 mass parts/50 mass parts) to carry out the viscosity adjustment, make that utilizing Ford cup No.4 to measure reaches 120 ± 10 seconds, obtained " thermohardening type precoating coating 2～7,9～11 ".Then, identical with embodiment 1, at sintering primary coat film on, use roller coating machine coated heat curing precoating steel plate with coating 2～7,9～11 respectively, make thickness reach the thickness of 20 μ m, so that the mode that Da Wendu reaches 240 ℃ that is up to of steel plate applies successively.The test board of gained is used to the physical property test of filming.Its evaluation result is shown in table 1, the table 2.
(comparative example 1,5)
With vibrin Arakyd 7052L 80 mass parts of (A) composition and titanium dioxide JR-60240 mass parts, utilize sand mill to disperse as Solvesso 100 (Esso (strain) system aromatic base crude oil petroleum naphtha) 19.6 mass parts, pimelinketone 19.6 mass parts of solvent, make granularity reach below the 10 μ m, obtained the abrasive of pigment.Then, in this pigment grind material, add Desmodur BL3175 20 mass parts, surface conditioner BYK-325 0.2 mass parts of (A) composition respectively and mix.In this coating, remaining raw material shown in the interpolation table 2 and mixing, utilize Solvesso #100 (Esso (strain) system, aromatic base crude oil petroleum naphtha)/pimelinketone (50 mass parts/50 mass parts) to carry out the viscosity adjustment, make that utilizing Ford cup No.4 to measure reaches 120 ± 10 seconds, has obtained thermohardening type precoating coating 8,12.
Then, identical with embodiment 1, at sintering primary coat film on, use roller coating machine coated heat curing precoating steel plate with coating 8,12 respectively, make thickness reach the thickness of 20 μ m, so that the mode that Da Wendu reaches 240 ℃ that is up to of steel plate applies successively.The test board of gained is used to the physical property test of filming.Its evaluation result is shown in table 1, the table 2.
[table 1]
[table 2]
In table 1, the table 2, the material of footnote is a material shown below.
1) Vylon GK13CS: trade(brand)name, Japan's weaving (strain) system, vibrin hydroxyl value 20mgKOH/g, number-average molecular weight 7000, nonvolatile component 50 quality %
2) Arakyd 7052L: trade(brand)name, waste river chemical industry (strain) system, vibrin, hydroxyl value 60mgKOH/g, number-average molecular weight 4000, nonvolatile component 60 quality %
3) DesmodurBL3175: trade(brand)name, Bayer corporate system, blocked isocyanate compounds, effective NCO11.1 quality %, nonvolatile component 75 quality %
4) Saubersuper #100: trade(brand)name, the mineral compound that on metal oxide, has adsorbed nitrogenous compound, median size 1 μ m
5) Kesmon NS-103: trade(brand)name, the mineral compound that on silicon oxide, has adsorbed amine, median size 4 μ m
6) Ecokimera SE-50E: trade(brand)name, (having) YOO company, titanium phosphate solution
7) JR-602: trade(brand)name, Tayca (strain) system, titanium dioxide
8) Solvesso 100:Esso (strain) system, aromatic base crude oil petroleum naphtha
9) BYK-325:Byk-Chemie (strain) system, surface conditioner
Embodiment 1～7 is no problem aspect the rerum natura of filming of processibility, shock resistance, pencil hardness, anti-boiling water, and is in addition, good aspect formaldehyde adsorptivity, anti-release performance again, repetition deodorization.For comparative example 1 is the example that does not contain (C) composition, though have the formaldehyde adsorptive power, repeats poor performance.Comparative example 2 is examples that the content of (B) composition surpasses the upper limit, though at formaldehyde adsorptivity, anti-release performance again, repeat aspect the deodorization goodly, processibility, shock resistance are poor.Comparative example 3 is examples that the content of (C) composition surpasses the upper limit, though good aspect formaldehyde adsorptivity, anti-release performance again, repetition deodorization, anti-boiling water is poor.Comparative example 4 is the examples that do not contain (B) composition, and the formaldehyde adsorptive power is poor.Comparative example 5 is not contain (B), both examples of (C) composition, in the formaldehyde adsorptive power, to repeat aspect of performance all very poor.
Claims (4)
1. precoating thermosetting coating composition, it is characterized in that, contain the overlay film formation resin combination that (A) contains hydroxy-containing resin and blocked isocyanate solidifying agent in following ratio, (B) utilize nitrogenous compound to carry out the surface-treated mineral compound with aldehyde cpd adsorptive power, (C) titanium phosphate based compound, described ratio is, with respect to (A) composition 100 mass parts, (B) composition be 0.1～10 mass parts and (C) composition be 0.1～10 mass parts.
2. precoating thermosetting coating composition according to claim 1, it is characterized in that, (B) nitrogenous compound that has the aldehyde cpd adsorptive power in the composition is at least a material that is selected from primary amine, secondary amine, hydrazine, hydrazine derivative, aminotriazole and the ethylidene-urea, and mineral compound is at least a material that is selected from porous silica, activated carbon, porous metal oxide, potassium titanate and the zirconium phosphate.
3. precoating thermosetting coating composition according to claim 1 and 2, it is characterized in that, (A) contained hydroxy-containing resin is at least a resin that is selected from hydroxyl group containing polyester resin, hydroxyl Synolac and the hydroxy acryl acid resin in the composition, and wherein said hydroxyl group containing polyester resin is that hydroxyl value is that 5～200mgKOH/g, number-average molecular weight are 1000～20000 resin.
One kind on metal sheet coating in the claim 1～3 any described precoating with thermosetting coating composition and prefinished metal plate.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP024245/2006 | 2006-02-01 | ||
| JP2006024245A JP2007204579A (en) | 2006-02-01 | 2006-02-01 | Thermosetting coating composition for precoat and precoated metal plate using it |
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| CN101379152A true CN101379152A (en) | 2009-03-04 |
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| CNA2007800040948A Pending CN101379152A (en) | 2006-02-01 | 2007-01-30 | Thermosetting coating composition for precoating and metal sheet precoated therewith |
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| Country | Link |
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| JP (1) | JP2007204579A (en) |
| KR (1) | KR20080083694A (en) |
| CN (1) | CN101379152A (en) |
| TW (1) | TW200734421A (en) |
| WO (1) | WO2007088834A1 (en) |
Cited By (3)
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| CN103282453A (en) * | 2011-02-18 | 2013-09-04 | 浦项工科大学校产学协力团 | Paint composition for pre-oated steel plate and a curing method for pre-coated steel plate using same |
| CN104017479A (en) * | 2014-06-24 | 2014-09-03 | 博罗县石湾美源涂料有限公司 | Bicomponent silicofluoride acrylic polyurethane coating as well as preparation and application methods thereof |
| CN104302718A (en) * | 2010-12-10 | 2015-01-21 | 威士伯采购公司 | Coating composition for aldehyde abatement |
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| JP5924072B2 (en) * | 2012-03-30 | 2016-05-25 | 大日本印刷株式会社 | Decorative sheet and decorative board |
| JP6184266B2 (en) | 2013-09-11 | 2017-08-23 | 株式会社Uacj | Aluminum paint for capacitor case |
| CN103709921B (en) * | 2013-12-20 | 2017-01-25 | 中远关西涂料化工（天津）有限公司 | Low-temperature shock-resistant fluorocarbon finishing paint for bridges and preparation method thereof |
| KR102640735B1 (en) * | 2021-10-07 | 2024-02-27 | 주식회사 케이씨씨 | Coating Composition |
| NL2030722B1 (en) * | 2022-01-26 | 2023-08-07 | Hunan Guocai New Mat Co Ltd | Multi-functional interior wall art paint with formaldehyde removal, mosquito repellence, and negative ion release |
Family Cites Families (10)
| Publication number | Priority date | Publication date | Assignee | Title |
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| JP3455000B2 (en) * | 1995-12-28 | 2003-10-06 | 株式会社日本自動車部品総合研究所 | Method for producing adsorbent for deodorization |
| JP2000095980A (en) * | 1998-09-21 | 2000-04-04 | Kansai Paint Co Ltd | Room pollution remedy water paint |
| JP3506670B2 (en) * | 2000-12-04 | 2004-03-15 | ロックペイント株式会社 | Aqueous resin composition |
| JP2002200148A (en) * | 2000-12-28 | 2002-07-16 | Toagosei Co Ltd | Deodorant for unsaturated hydrocarbon-based aldehyde gas |
| JP3829640B2 (en) * | 2001-04-10 | 2006-10-04 | 大阪市 | Antibacterial and antifungal agents and antibacterial or antifungal methods |
| JP2004314031A (en) * | 2003-04-14 | 2004-11-11 | Enclar Business:Kk | Composition for environmental improvement |
| JP2005054316A (en) * | 2003-08-05 | 2005-03-03 | Teijin Techno Products Ltd | Stainproof sheet |
| JP2005255698A (en) * | 2004-03-09 | 2005-09-22 | Basf Coatings Japan Ltd | Thermosetting coating composition for precoating |
| JP2005298694A (en) * | 2004-04-13 | 2005-10-27 | Kansai Paint Co Ltd | Coating composition for pre-coated steel plate and pre-coated steel plate using the same |
| JP2006021167A (en) * | 2004-07-09 | 2006-01-26 | Sogo Giken:Kk | Negative ion generation oxygen catalyst composition, coating method therefor and fitting article |
-
2006
- 2006-02-01 JP JP2006024245A patent/JP2007204579A/en active Pending
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2007
- 2007-01-30 KR KR1020087018961A patent/KR20080083694A/en not_active Application Discontinuation
- 2007-01-30 WO PCT/JP2007/051449 patent/WO2007088834A1/en active Application Filing
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104302718A (en) * | 2010-12-10 | 2015-01-21 | 威士伯采购公司 | Coating composition for aldehyde abatement |
| CN103282453A (en) * | 2011-02-18 | 2013-09-04 | 浦项工科大学校产学协力团 | Paint composition for pre-oated steel plate and a curing method for pre-coated steel plate using same |
| CN103282453B (en) * | 2011-02-18 | 2016-07-13 | 浦项工科大学校产学协力团 | Pre-coated metal coating composition and the use said composition method to pre-coated metal cured |
| US9505947B2 (en) | 2011-02-18 | 2016-11-29 | Postech Academy-Industry Foundation | Paint composition for pre-coated metal and method of curing treatment of pre-coated metal by using the composition |
| CN104017479A (en) * | 2014-06-24 | 2014-09-03 | 博罗县石湾美源涂料有限公司 | Bicomponent silicofluoride acrylic polyurethane coating as well as preparation and application methods thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| TW200734421A (en) | 2007-09-16 |
| KR20080083694A (en) | 2008-09-18 |
| JP2007204579A (en) | 2007-08-16 |
| WO2007088834A1 (en) | 2007-08-09 |
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