CN100451081C - Electrodeposition paint - Google Patents
Electrodeposition paint Download PDFInfo
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- CN100451081C CN100451081C CNB2005100713476A CN200510071347A CN100451081C CN 100451081 C CN100451081 C CN 100451081C CN B2005100713476 A CNB2005100713476 A CN B2005100713476A CN 200510071347 A CN200510071347 A CN 200510071347A CN 100451081 C CN100451081 C CN 100451081C
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Abstract
The invention provides electrodeposition paint of reduced volatile organic compound content, in which specific polyether compound(s) having a molecular weight not more than 1,000 is (are) incorporated and which excel in corrosion resistance, electrocoating ability of rustproof steel sheet, film-forming ability, pin holing resistance and stability.
Description
Technical field
Excellent electrodeposition paints such as the content that the present invention relates to volatile organic compounds is few, solidity to corrosion, electrolytic deposition coating, film-forming properties, anti-pin hole, paint stability to Rustproof Steel Plate.
Background technology
Electrodeposition paint is used in the extensive use that with car body, automobile component is representative, all the time, people have developed the electrodeposition paint of tool various characteristics, have for example developed excellent electrodeposition paint such as solidity to corrosion, the electrolytic deposition coating to Rustproof Steel Plate, film-forming properties, paint stability.
In order to keep the film-forming properties of electrodeposition paint in long-term, usually being mixed with boiling point in the electrodeposition paint, to be about 120 ℃ or following organic solvent (for example methyl iso-butyl ketone (MIBK) (116 ℃), methyl ethyl ketone (80 ℃) etc.), organic solvent (for example ethylene glycol monobutyl ether (171 ℃), Glycol Monomethyl ether (121 ℃) etc.), molecular weight that boiling point is 120-200 ℃ be 4,000 or following lower molecular weight soft resin (for example xylene resin, polypropylene glycol etc.) etc.Consider from influence that in recent years because low VOC (volatile organic compounds) regulation, HAPs (hazardous property atmospheric polluting material) regulation, their application is restricted to environment etc.
On the other hand, if the content of volatile organic compounds in the limit electrolysis deposition coating, then along with the prolongation of time, film-forming properties (thickness retention) slowly reduces, be difficult to electrolytic deposition coating cloth and become the regulation thickness, processibility reduces, in addition, produce pin hole (so-called pore) in the alloyed hot-dip galvanized steel plate of in automobile exterior panel part (for example door, splash pan), using always (Rustproof Steel Plate that is covered by the alloy layer of zinc and iron), problems such as paint film defect take place.
In order to reduce volatile organic compounds, also can remove by underpressure distillation etc., the containing ratio that makes volatile components such as organic solvent contained in the electrodeposition paint is 1 weight % or following, but what obtain like this is cured coating film, be difficult to be coated with 20 μ m or above thickness, the fusion faculty of filming reduces, the problem of the easy generation of appearance pin hole etc.
A kind of cationic electrolytic deposition coating is disclosed in the special fair 6-45772 communique of Japan, this coating contains the alkylation polyethers, each molecule of described alkylation polyethers has at least 3 ether oxygenses and 1-4 saturated hydrocarbyl between this ether oxygen, but does not have hydroxyl.The low VOC of this cationic electrolytic deposition coating and processibility of filming and corrosion resistance excellent are difficult to solve part but have at solidity to corrosion, aspects such as electrolytic deposition coating, film-forming properties, paint stability to Rustproof Steel Plate, can not fully meet the demands.
In addition, a kind of cationic electrolytic deposition coating is disclosed in the TOHKEMY 2001-3005 communique, this coating contains polyether glycols such as aromatic ring polyether glycol, and it is used separately or with diol combination by alkylene base system polyether glycol such as polymethylene glycol, polyoxyethylene glycol, polypropylene glycol, polytetramethylene glycol or bis-phenol and obtains.Low VOC of this cationic electrolytic deposition coating and film-forming properties excellence, formation is filmed to the electrolytic deposition coating (the anti-pin hole of alloyed hot-dip galvanized steel plate) of Rustproof Steel Plate, corrosion resistance excellent, but with this polyether glycol heavy addition in coating, then there are solidity to corrosion (under harsh corrosive environment significantly reduce), paint stability to reduce, or the problems such as sealing lacquer tack reduction of electrolytic deposition on filming.
Summary of the invention
The electrodeposition paint of the object of the present invention is to provide the content of volatile organic compounds few, solidity to corrosion, the electrolytic deposition coating to Rustproof Steel Plate, film-forming properties, anti-pin hole, paint stability etc. are excellent.
The inventor finds through further investigation: in electrodeposition paint combined molecular weight be 1,000 or following special polyether compound as additive, then can realize above-mentioned purpose, thereby finish the present invention.
That is to say, the invention provides electrodeposition paint, this electrodeposition paint contains at least a polyether compound that is selected from following formula (1)-(4):
In the formula,
R
1And R
3The alkyl or phenyl of independent respectively expression carbonatoms 1-10;
R
2Expression hydrogen atom or methyl are when p and q are respectively 2 or when above, a plurality of R in formula (1) or (2)
2Respectively can identical or mutual difference;
R
4R valency aliphatic series or the ester ring type alkyl of expression carbonatoms 2-10;
R
5A straight chain shape or the chain alkylidene group of expression carbonatoms 4-24;
R
6And R
7Respectively independent expression hydrogen atom, methyl or ethyl are when m and n are respectively 2 or when above, a plurality of R in the formula (4)
6With a plurality of R
7Respectively can identical or mutual difference;
P is the integer of 0-4;
Q is the integer of 1-4;
R is the integer of 2-4;
M and n are independent respectively to be the integer of 1-10.
The content of volatile organic compounds is few in the electrodeposition paint of the present invention, the solidity to corrosion of not only filming, excellent in workability, film-forming properties is also excellent, has in addition not see the excellent specific property that pin hole generation etc. is arranged when alloyed hot-dip galvanized steel plate implemented the electrolytic deposition coating.Electrodeposition paint stability of the present invention is also excellent, in paint line, use behind the electrodeposition paint long-time in above-mentioned characteristic do not change yet.
Electrodeposition paint of the present invention shows excellent aspect above-mentioned characteristic, its reason is not correctly known as yet, but about solidity to corrosion, may be because hydroxyl and the matrix resin in formula (1)-(4) compound, solidifying agent react, crosslinked in filming, form the cubic network structure, therefore improve for patience from the causticize material of outside.In addition, about processibility, may be that the molecular weight ratio of formula (1)-(4) compound is lower, therefore when sintering, demonstrate the effect of flow characteristics.
And the compound of formula (1)-(4) plays the effect of softening agent, makes separating out own the softening of filming the influence of the Jiao Erre that produces during by electrolytic deposition, the pin hole that produces during the coating of landfill electrolytic deposition.
Below electrodeposition paint of the present invention is further described.
Electrodeposition paint of the present invention has novel characteristics on as this aspect of additive containing at least a polyether compound that is selected from following formula (1), (2), (3) and (4).Therefore, at first these polyether compounds are described.
Polyether compound used in the present invention is solubility or easily disperse in electrolytic deposition is bathed preferably, has 100-1 usually, the molecular weight of 000 scope, preferred especially 250-800, further preferred 250-600.
Among the present invention, for example can obtain by making the alkylol cpd reaction shown in glycidyl ether compound shown in the following formula (5) and the following formula (6) as the polyether compound shown in the following formula (1) of additive use:
Formula (1)
In the formula,
R
1And R
3The alkyl or phenyl of independent respectively expression carbonatoms 1-10, preferred 2-9, further preferred 3-8,
R
2Expression hydrogen atom or methyl, when p is 2 or when above, a plurality of R in the formula
2Can distinguish identical or mutual difference,
P is the integer of 0-4;
Formula (5)
In the formula, R
1Identical with above-mentioned implication;
Formula (6)
In the formula, R
2, R
3Identical with p with above-mentioned implication.
The example of the glycidyl ether compound of following formula (5) has: butylglycidyl ether, 2-ethylhexyl ether, phenyl glycidyl ether etc.
The example of the alkylol cpd of formula (6) has: ethylene glycol monobutyl ether, ethylene glycol one 2-ethylhexyl ether, glycol ether one 2-ethylhexyl ether, ethylene glycol one hexyl ether, Glycol Monomethyl ether, propylene glycol monobutyl ether, butanols etc.
The alkylol cpd of formula (6) does not limit with respect to the usage ratio of the glycidyl ether compound of formula (5) is strict, usually with respect to the glycidyl ether compound of per 1 mole of formula (5), the preferred alkylol cpd of use formula (6) in the scope of 0.5-2 mole, preferred especially 0.5-1.5 mole, further preferred 1-1.2 mole.
Above-mentioned reaction usually can be by in solvent-free or suitable inert solvent, with about 150 ℃ of about 50-, the preferred temperature in the about 140 ℃ of scopes of about 130-, with about 30 minutes-6 hours, preferred about 1-3 hour, carry out in the glycidyl ether compound with the alkylol cpd drawing-in system (5) of formula (6).Reaction product can directly be used, and also can reduce pressure to use after heating up in a steamer unreacted reactant.
Operable solvent for example has hydrocarbon system solvents such as toluene, dimethylbenzene, hexanaphthene, normal hexane in the above-mentioned reaction; Ester series solvents such as methyl acetate, ethyl acetate, butylacetate; Ketone series solvents such as acetone, methylethylketone, methyl iso-butyl ketone (MIBK), Methyl amyl ketone; Perhaps their mixture etc.
Among the present invention, for example can obtain by making the alkylol cpd reaction shown in multi-shrinking glyceryl compound shown in the following formula (7) and the following formula (8) as the polyol compound shown in the following formula (2) of additive use:
Formula (2)
In the formula,
R
2Expression hydrogen atom or methyl, when q is 2 or when above, a plurality of R in the formula
2Can identical or mutual difference,
R
3The alkyl or phenyl of expression carbonatoms 1-10, preferred 2-9, further preferred 3-8,
R
4R valency aliphatic series or the ester ring type alkyl of expression carbonatoms 2-10, preferred 3-9, further preferred 4-8,
Q is the integer of 1-4,
R is the integer of 2-4;
Formula (7)
In the formula, R
4Identical with r with above-mentioned implication;
Formula (8)
In the formula, R
2, R
3Identical with q with above-mentioned implication.
The example of the multi-shrinking glyceryl compound of following formula (7) has: trishydroxymethyl triglycidyl ether, T 55 etc.
The alkylol cpd of formula (8) can exemplify the alkylol cpd of the following formula (6) except that butanols.
The alkylol cpd of formula (8) does not limit with respect to the usage ratio of the multi-shrinking glyceryl compound of formula (7) is strict, usually with respect to the glycidyl of the multi-shrinking glyceryl compound of per 1 equivalent formula (7), the preferred alkylol cpd of use formula (8) in the scope of 0.5-2 mole, preferred especially 0.5-1.5 mole, further preferred 1-1.2 mole.
Above-mentioned reaction usually can be by in solvent-free or suitable inert solvent, with about 150 ℃ of about 50-, the preferred temperature in the about 140 ℃ of scopes of about 130-, with about 30 minutes-6 hours, preferred about 1-3 hour, carry out in the multi-shrinking glyceryl compound with the alkylol cpd drawing-in system (7) of formula (8).Reaction product can directly be used, and also can reduce pressure to use after heating up in a steamer unreacted reactant.
Operable solvent for example has hydrocarbon system solvents such as toluene, dimethylbenzene, hexanaphthene, normal hexane in the above-mentioned reaction; Ester series solvents such as methyl acetate, ethyl acetate, butylacetate; Ketone series solvents such as acetone, methylethylketone, methyl iso-butyl ketone (MIBK), Methyl amyl ketone; Perhaps their mixture etc.
Among the present invention, for example can obtain by making the polyol reaction shown in glycidyl ether compound shown in the following formula (5) and the following formula (9) as the polyether compound shown in the following formula (3) of additive use:
Formula (3)
In the formula,
R
1The alkyl or phenyl of expression carbonatoms 1-10, preferred 2-9, further preferred 3-8,
R
4R valency aliphatic series or the ester ring type alkyl of expression carbonatoms 2-10, preferred 3-9, further preferred 4-8,
R is the integer of 2-4;
Formula (9)
R
4(OH)
r (9)
In the formula, R
4Identical with r with above-mentioned implication.
The polyvalent alcohol of following formula (9) for example has ethylene glycol, propylene glycol, glycol ether, trimethylene, tetramethylene glycol, triglycol, dipropylene glycol, 1, the 4-butyleneglycol, 1, the 3-butyleneglycol, 2, the 3-butyleneglycol, 1, the 2-butyleneglycol, the 3-methyl isophthalic acid, the 2-butyleneglycol, 1, the 2-pentanediol, 1, the 5-pentanediol, 1, the 4-pentanediol, 2, the 4-pentanediol, 2,3-dimethyl trimethylene, tetramethylene glycol, 3-methyl-4, the 3-pentanediol, 3-methyl-4, the 5-pentanediol, 2,2,4-trimethylammonium-1, the 3-pentanediol, 1, the 6-hexylene glycol, 1, the 5-hexylene glycol, 1,4 cyclohexane dimethanol, neopentyl glycol; Glycerine, TriMethylolPropane(TMP), trimethylolethane, Glycerol dimer, triglycerin, 1,2,6-hexanetriol, tetramethylolmethane, Dipentaerythritol, sorbyl alcohol etc.Wherein, preferred especially ethylene glycol, 1,4-butyleneglycol.
The polyvalent alcohol of formula (9) does not limit with respect to the usage ratio of the glycidyl ether compound of formula (5) is strict, usually with respect to the glycidyl of the glycidyl ether compound of per 1 equivalent formula (5), the hydroxyl of preferred polyol uses in 0.5-2 equivalent, the preferred especially normal scope of 0.5-1.5.
Above-mentioned reaction usually can be by in solvent-free or suitable inert solvent, with about 150 ℃ of about 50-, the preferred temperature in the about 140 ℃ of scopes of about 130-, with about 30 minutes-6 hours, preferred about 1-3 hour, carry out in the glycidyl ether compound with the polyol compound drawing-in system (5) of formula (9).Reaction product can directly be used, and also can reduce pressure to use after heating up in a steamer unreacted reactant.
Operable solvent for example has hydrocarbon system solvents such as toluene, dimethylbenzene, hexanaphthene, normal hexane in the above-mentioned reaction; Ester series solvents such as methyl acetate, ethyl acetate, butylacetate; Ketone series solvents such as acetone, methylethylketone, methyl iso-butyl ketone (MIBK), Methyl amyl ketone; Perhaps their mixture etc.
Among the present invention, for example can obtain by making the alkylene oxide reaction (addition) shown in the glycol shown in the following formula (10) and following formula (11) and (12) as the polyether compound shown in the following formula (4) of additive use:
Formula (4)
In the formula,
R
5The straight chain shape of 4-24 of expression carbonatoms, preferred 5-18, further preferred 6-15 or a chain alkylidene group,
R
6And R
7Respectively independent expression hydrogen atom, methyl or ethyl are when m and n are respectively 2 or when above, a plurality of R in the formula
1With a plurality of R
2Can distinguish identical or mutual difference,
The integer of the independent respectively expression 1-10 of m and n, preferred 1-7, further preferred 1-5,
Polyoxyalkylene part (CH (R in the formula
6) CH
2O) m and (CH (R
7) CH
2O) n can be the R of the m in each repeating unit separately
6With n R
7Identical homopolymer type also can be the R of the m in each repeating unit
6With n R
7Mutual different random or segmented copolymer type;
Formula (10)
HO-R
5-OH (10)
In the formula, R
5Identical with above-mentioned implication;
Formula (11) and (12)
In the formula, R
6And R
7Identical with above-mentioned implication.
Glycol shown in the following formula (10) for example has 1, the 4-butyleneglycol, 1,3 butylene glycol, 2, the 3-butyleneglycol, 1, the 2-butyleneglycol, the 3-methyl isophthalic acid, the 2-butyleneglycol, 1, the 2-pentanediol, 1, the 5-pentanediol, 1, the 4-pentanediol, 2, the 4-pentanediol, 2,3-dimethyl trimethylene, tetramethylene glycol, the 2-methyl isophthalic acid, ammediol, 2-butyl-2-ethyl-1, ammediol, 3-methyl-4, the 3-pentanediol, 3-methyl-4, the 5-pentanediol, 2,2,4-trimethylammonium-1, the 3-pentanediol, 1, the 6-hexylene glycol, 1, the 5-hexylene glycol, 2, the 5-hexylene glycol, neopentyl glycol etc., wherein preferred especially 2-methyl isophthalic acid, ammediol and 2-butyl-2-ethyl-1, ammediol.
Alkylene oxide shown in following formula (11) or (12) comprises oxyethane, propylene oxide and butylene oxide ring.
The alkylene oxide of formula (11) and (12) does not limit with respect to the usage ratio of the glycol of formula (10) is strict, usually with respect to the hydroxyl of the glycol of per 1 equivalent formula (2), the preferred alkylene oxide of use formula (11) and (12) in the scope that adds up to 1-10 mole, preferred especially 1-7 mole, further preferred 1-5 mole.
Above-mentioned reaction usually can be by in solvent-free or suitable inert solvent, with about 150 ℃ of about 50-, the preferred temperature in the about 140 ℃ of scopes of about 130-, with about 30 minutes-6 hours, preferred about 1-3 hour, carry out in the glycol with the alkylene oxide drawing-in system (10) of formula (11) and (12).Reaction product can directly be used, and also can reduce pressure to use after heating up in a steamer unreacted reactant.
When using 2 kinds or above alkylene oxide as the alkylene oxide of formula (11) and (12), they can add simultaneously, also can be according to order interpolation respectively arbitrarily.When for example using oxyethane and propylene oxide simultaneously, can at first add a spot of propylene oxide and make its reaction, then add oxyethane and make its reaction.
Operable solvent for example has hydrocarbon system solvents such as toluene, dimethylbenzene, hexanaphthene, normal hexane in the above-mentioned reaction; Ester series solvents such as methyl acetate, ethyl acetate, butylacetate; Ketone series solvents such as acetone, methylethylketone, methyl iso-butyl ketone (MIBK), Methyl amyl ketone; Perhaps their mixture etc.
The polyether compound that is selected from as above the formula that is selected from (1), (2), (3) and (4) of preparation is blended in the electrodeposition paint that contains matrix resin and solidifying agent, the preferred cationic electrodeposition paint.This polyether compound can distinguish separately or with 2 kinds or above combined hybrid in electrodeposition paint.
Below, as cationic electrolytic deposition coating, describe for common containing, but the present invention is not limited by it as the cation type resin of matrix resin with as the cationic electrolytic deposition coating of the blocked polyisocyanates compound of solidifying agent.
The cation type resin that uses as matrix resin is the resin that has cationizable groups such as amino, ammonium salt base, sulfonium salt Ji, phosphonium salt base in the molecule, the kind of resin can be the common resin that uses as the matrix resin of electrodeposition paint, and for example Resins, epoxy, acrylic resin, polybutadiene, Synolac, vibrin etc. are any.Special preferred epoxy with contain the amine addition Resins, epoxy that amino compound addition reaction obtains.
Above-mentioned amine addition Resins, epoxy for example has: (1) Resins, epoxy and uncle monobasic and polyamines, Zhong Yiyuan and polyamines or primary, the secondary adduct (for example with reference to United States Patent (USP) the 3rd, 984, No. 299 specification sheetss) that mixes polyamines; (2) Resins, epoxy with have the Zhong Yiyuan of ketoimine primary amino and an adduct of polyamines (for example with reference to United States Patent (USP) the 4th, 017, No. 438 specification sheetss); (3) reaction product (for example with reference to Japanese kokai publication sho 59-43013 communique) that obtains by etherificate of Resins, epoxy and the oxy-compound with ketoimine primary amino etc.
Employed Resins, epoxy is to have 1 epoxy group(ing) in 1 molecule at least, preferably have a compound of 2 or above epoxy group(ing) in the preparation of above-mentioned amine addition Resins, epoxy, usually preferably have at least 200, preferred 400-4,000, further preferred 800-2, number-average molecular weight in 500 scopes (annotating 1) and at least 160, preferred 180-2,500, further preferred 400-1, the interior epoxy equivalent (weight) of 500 scopes, especially preferably obtain by polyphenolic substance and epihalohydrin reaction.
(annotating 1) number-average molecular weight:, use TSKGEL40000H according to the method for JIS K 0124-83 record
XL+ G3000H
XL+ G2500H
XL+ G2000H
XL(eastern ソ-Co., Ltd.) as separator column, use tGPC with tetrahydrofuran (THF) as elutriant, under 40 ℃ and 1.0ml/ minute flow velocity, calculate the value of obtaining by color atlas and the polystyrene working curve that obtains by the RI refractometer.
The example that can be used for forming the polyphenolic substance of this Resins, epoxy has: two (4-hydroxy phenyls)-2,2-propane, 4,4 '-dihydroxy benzophenone, two (4-hydroxy phenyl)-1,1-ethane, two (4-hydroxy phenyl)-1,1-Trimethylmethane, two (4-hydroxyl-2 or the 3-tertiary butyl-phenyl)-2,2-propane, two (2 hydroxy naphthalene base) methane, four (4-hydroxy phenyl)-1,1,2,2-ethane, 4,4 '-dihydroxy diphenylsulphone, phenol lacquer resins, cresols lacquer resins etc.
This Resins, epoxy can with partial reactions such as polyvalent alcohol, polyether glycol, polyester polyol, polyamide-based amine, poly carboxylic acid, polyisocyanate compound, can also the graft polymerization 6-caprolactone etc. caprolactone, Acrylic Acid Monomers etc.
Employed uncle's monobasic and polyamines, Zhong Yiyuan and polyamines or primary, the secondary example that mixes polyamines have in the preparation of the amine addition Resins, epoxy of above-mentioned (1): Monomethylamine, dimethylamine, monoethylamine, diethylamine, monoisopropylamine, Diisopropylamine, monobutylamine (MBA), dibutylamine etc. one or dialkylamine; Monoethanolamine, diethanolamine, list (2-hydroxypropyl) amine, monomethyl monoethanolamine etc. alkanolamine; Alkylene polyamines such as quadrol, propylene diamine, butanediamine, hexanediamine, diethylenetriamine, Triethylenetetramine (TETA) etc.
Employed in the amine addition Resins, epoxy of above-mentioned (2) preparation have the Zhong Yiyuan of ketoimine primary amino and the example of polyamines has: make that employed uncle's monobasic and polyamines, Zhong Yiyuan and polyamines or primary, the secondary compound (for example Monomethylamine, monoethanolamine, quadrol, diethylenetriamine etc.) that has primary amino in the polyamines that mixes react the ketoimine thing that obtains in the amine addition Resins, epoxy preparation of ketone compound and above-mentioned (1).
In the amine addition Resins, epoxy of above-mentioned (3) preparation there being employed oxy-compound example with ketoimine primary amino: makes that employed uncle's monobasic and polyamines, Zhong Yiyuan and polyamines or primary, the secondary compound (for example monoethanolamine, list (2-hydroxypropyl) amine etc.) that has primary amino and hydroxyl in the polyamines that mixes react the hydroxyl ketoimine thing that obtains in the amine addition Resins, epoxy preparation of ketone compound and above-mentioned (1).
Above-mentioned amine addition Resins, epoxy also comprise and preferably use polyalcohol modified amine addition Resins, epoxy, this polyalcohol modified amine addition Resins, epoxy be make have in above-mentioned Resins, epoxy, caprolactone and 1 molecule 2 or more than contain the polyol compound that the compound addition of the group of active hydrogen obtains and contain the aminocompound reaction and form.
Have in above-mentioned 1 molecule 2 or more than contain the group of active hydrogen compound preferably have 62-5 usually, 000,70-3 particularly, molecular weight in 000 scope, contain 2-30, particularly 3-25 group that contains active hydrogen in each molecule, this example that contains the group of active hydrogen has hydroxyl, primary amino, secondary amino group etc.
Have in above-mentioned 1 molecule 2 or more than contain the group of active hydrogen the object lesson of compound have: ethylene glycol, propylene glycol, 1,3-butyleneglycol, 1,4-butyleneglycol, 1, low molecular weight polyols such as 6-hexylene glycol, glycol ether, dipropylene glycol, neopentyl glycol, glycerine, TriMethylolPropane(TMP), tetramethylolmethane; A chain or a chain polyether glycol such as polyoxyethylene glycol, polypropylene glycol, polytetramethylene glycol, polymer with bis phenol A glycol ether; Organic dicarboxylic acids such as succsinic acid, hexanodioic acid, nonane diacid, sebacic acid, toxilic acid, cyclohexane cyclohexanedimethanodibasic, phthalic acid, m-phthalic acid, terephthalic acid or organic diols such as its acid anhydrides and above-mentioned low molecular weight polyols carry out the polyester polyol that polycondensation obtains under the excessive condition of organic diol; Butanediamine, hexanediamine, tetren, penten, monoethanolamine, diethanolamine, trolamine, list (2-hydroxypropyl) amine, two (2-hydroxypropyl) amine, 1, amine compound such as 3-diamino methylcyclohexanone, isophorone diamine, dimethylphenylene diamine, m-xylene diamine, diaminodiphenyl-methane, phenylenediamine, quadrol, propylene diamine, diethylenetriamine, Triethylenetetramine (TETA); With piperazine or by the amine adduct of above-mentioned amine compound deutero-polymeric amide, polyamide-based amine, epoxy compounds, ketoimine, aldimine etc.
And have in above-mentioned 1 molecule 2 or more than contain the group of active hydrogen the example of caprolactone of compound addition reaction have: γ-Ji Neizhi, 6-caprolactone, δ-caprolactone etc., preferred especially 6-caprolactone.
Have in above-mentioned 1 molecule 2 or more than contain the compound of group of active hydrogen and the addition reaction of caprolactone can be carried out according to itself known method, by this addition reaction, can obtain polyol compound.
The employed aminocompound that contains gives composition for import cationic amino, that make this resin have cationic in resin in the above-mentioned polyalcohol modified amine addition Resins, epoxy preparation, can use to have at least 1 with the active hydrogen of epoxy reaction.
Its object lesson has: can be used as employed uncle's monobasic and polyamines, Zhong Yiyuan and polyamines or primary in the amine addition Resins, epoxy preparation of above-mentioned (1), the secondary polyamines that mixes, employed Zhong Yiyuan and polyamines in the amine addition Resins, epoxy preparation of above-mentioned (2) with ketoimine primary amino, the compound that employed oxy-compound with ketoimine primary amino uses in the amine addition Resins, epoxy preparation of above-mentioned (3).
Usually the number-average molecular weight of cationic resin is 700-6,000, particularly 1, and 000-4 in 000 scope, has the cationic group with 0.5-3 equivalent, preferred especially 0.7-2 when the measurer in the weight range in preferred every 1kg resin.
When the cationic resin has amino group as cationicallyization, can pass through organic carboxyl acids such as formic acid, acetate, propionic acid, lactic acid; Acid such as mineral acid such as hydrochloric acid, sulfuric acid neutralize, and carry out water dissolution or water-dispersion thus, on the other hand, when having alkali such as ammonium salt base, sulfonium salt Ji Huo phosphonium salt base as the group of cationicallyization, need not neutralization, can directly carry out water dissolution or water-dispersion.
Matrix resin also comprises and contains aminoepoxy resin, and this contains aminoepoxy resin is xylene formaldehyde resin and contains aminocompound and epoxy equivalent (weight) is 180-3, and 000, preferred 250-2,000 Resins, epoxy reacts and obtains.
Prepare the above-mentioned employed Resins, epoxy of starting raw material that contains aminoepoxy resin preferably with the same Resins, epoxy of compound described in the above-mentioned cationic resin.
Xylene formaldehyde resin has inside plasticising (modification) effect of Resins, epoxy, for example, can carry out condensation reaction by the phenols that makes dimethylbenzene and formaldehyde and according to circumstances use and prepare in the presence of an acidic catalyst.
The example of above-mentioned formaldehyde has: the formalin of industrial easy acquisition, paraformaldehyde, trioxane etc. produce the compound of formaldehyde etc.
Above-mentioned phenols comprises 1 or 2 yuan of phenoloid with 2 or 3 reaction site, concrete example has: phenol, cresols, paraoctyl phenol, nonylphenol, bisphenol A, bis-phenol methane, Resorcinol, pyrocatechol, quinhydrones, p-tert-butylphenol, bisphenol sulphone, bis-phenol ether, p-phenyl phenol etc., they can independent respectively or 2 kinds or above being used in combination.Wherein preferred especially phenol, cresols.
Employed an acidic catalyst for example has sulfuric acid, hydrochloric acid, tosic acid, oxalic acid etc., usually special preferably sulfuric acid in the condensation reaction of above-described dimethylbenzene and formaldehyde and the phenols that adopts as required.
Condensation reaction for example can be by being heated to backflows such as the dimethylbenzene that is present in the reaction system, phenols, water, formalin temperature, be generally the about 100 ℃ temperature of about 80-and carry out, can stop in about 2-6 hour back of reaction usually.
Under the above-mentioned condition, in the presence of an acidic catalyst, carry out reacting by heating, can obtain xylene formaldehyde resin by phenols with dimethylbenzene and formaldehyde and employing as required.
The above-mentioned xylene formaldehyde resin that obtains can have 20-50 usually, 000 centipoise (25 ℃), preferred 25-30,000 centipoise (25 ℃), further preferred 30-15, viscosity in 000 centipoise (25 ℃) scope, preferably has 100-50 usually, 000, preferred especially 150-30,000, further preferred 200-10, the hydroxyl equivalent in 000 scope.
It is amino for introducing to Resins, epoxy to contain aminocompound, makes the cationic of this cationic epoxy resinization give composition, can use the employed identical aminocompound that contains when preparing above-mentioned cationic resin.
Above-mentioned xylene formaldehyde resin and the reaction that contains aminocompound and above-mentioned Resins, epoxy can be carried out according to random order, usually preferred xylene formaldehyde resin and contain the aminocompound while and react with Resins, epoxy.
Above-mentioned addition reaction usually can be in appropriate solvent, carries out under about 170 ℃ of about 80-, temperature that preferably about 90-is about 150 ℃ about 1-6 hour, preferred about 1-5 hour.The example of above-mentioned solvent has: hydrocarbon system solvents such as toluene, dimethylbenzene, hexanaphthene, normal hexane; Ester series solvents such as methyl acetate, ethyl acetate, butylacetate; Ketone series solvents such as acetone, methylethylketone, methyl iso-butyl ketone (MIBK), Methyl amyl ketone; Acid amides such as dimethyl formamide, N,N-DIMETHYLACETAMIDE series solvent; Pure series solvents such as methyl alcohol, ethanol, n-propyl alcohol, Virahol; Perhaps their mixture etc.
The usage ratio of each reacted constituent is not strict in the above-mentioned addition reaction limits, can appropriate change, and be benchmark with Resins, epoxy, xylene formaldehyde resin and the solid shape branch gross weight that contains three kinds of compositions of aminocompound, preferred respectively in following scope.That is, Resins, epoxy is generally 50-90 weight %, preferred 50-85 weight %; Xylene formaldehyde resin is generally 5-45 weight %, preferred 6-43 weight %; Contain aminocompound and be generally 5-25 weight %, preferred 6-20 weight %.
Consider from aspects such as solidified nature and solidity to corrosions, with the preferred blocked polyisocyanates compound of solidifying agent that aforesaid matrix resin uses, this blocked polyisocyanates compound is polyisocyanate compound and end-capping reagent by the addition reaction product of chemical theory amount roughly.
Here employed polyisocyanate compound can use compound known in the past, for example tolylene diisocyanate, Xylene Diisocyanate, phenylene diisocyanate, ditan-2,4 '-vulcabond, ditan-4, aromatics, aliphatic series or alicyclic polyisocyanates compounds such as 4 '-vulcabond (being commonly referred to " MDI "), thick MD I, two (isocyanato-methyl) hexanaphthene, tetramethylene diisocyanate, hexamethylene diisocyanate, methylene diisocyanate, isophorone diisocyanate; The cyclized polymer of these polyisocyanate compounds, isocyanic ester biuret body; The low molecule active hydrogen-contg compound of ethylene glycol, propylene glycol, TriMethylolPropane(TMP), hexanetriol, castor-oil plant wet goods and above-mentioned excessive polyisocyanate compound react the compound etc. that the end that obtains contains isocyanic ester.They can independent respectively or 2 kinds or above being used in combination.
On the other hand, end-capping reagent is that the isocyanate group of polyisocyanate compound is carried out addition and end capped reagent, preferably the blocked polyisocyanates compound that generates by addition is stablized at normal temperatures, but when being heated to the sintering temperature of filming (about 200 ℃ of about usually 100-), end-capping reagent dissociates, and can produce the free isocyanate group again.
The example that satisfies the end-capping reagent of above-mentioned important document has: lactam analog compounds such as ε-Ji Neixianan, butyrolactam; Oxime compounds such as methyl ethyl ketoxime, cyclohexanone-oxime; Phenol system compounds such as phenol, p-tert-butylphenol, cresols; Aliphatic alcohol class such as propyl carbinol, 2-Ethylhexyl Alcohol; Aromatics such as phenylcarbinol, methylbenzyl alcohol alkanols; Ether alcohol such as ethylene glycol monobutyl ether, ethyl carbitol compounds etc.
Can also use this blocked polyisocyanates as solidifying agent, wherein said blocked polyisocyanates uses the glycol of molecular weight 76-150 or the carboxylic diol that contains of molecular weight 106-500 as end-capping reagent.
Above-mentioned glycol can be for having 2 reactive different hydroxyls, for example have primary hydroxyl and secondary hydroxyl, primary hydroxyl and tert-hydroxyl, 2 hydroxyls of the combination of secondary hydroxyl and tert-hydroxyl, and glycol with 76-150 molecular weight, propylene glycol is for example arranged, dipropylene glycol, 1, the 3-butyleneglycol, 1, the 2-butyleneglycol, the 3-methyl isophthalic acid, the 2-butyleneglycol, 1, the 2-pentanediol, 1, the 4-pentanediol, 3-methyl-4, the 3-pentanediol, 3-methyl-4, the 5-pentanediol, 2,2,4-trimethylammonium-1, the 3-pentanediol, 1, the 5-hexylene glycol, 1,4-hexylene glycol etc. has the glycols of 2 reactive different hydroxyls.
Wherein, consider preferred propylene glycol from reactivity, the reduction of weight loss on heating, the coating package stability equal angles of blocked polyisocyanates.These glycol are begun and the isocyanic ester radical reaction by the high hydroxyl of reactivity usually, the blocked isocyanate base.
Above-mentionedly contain the carboxylic diol that contains that carboxylic diol comprises molecular weight 106-500, because have carboxyl in the molecule, then dissociating property of low temperature raising can improve the solidified nature under the low temperature, when particularly using organo-tin compound, can significantly improve the solidified nature under the low temperature as curing catalysts.
The example that contains carboxylic diol has 2,2-dimethylol propionic acid, 2,2-dimethylolpropionic acid, dihydroxymethyl valeric acid, R-Glyceric acid etc.
Above-described matrix resin and solidifying agent are divided into benchmark with both total shapes admittedly usually, and matrix resin can be in 50-95 weight %, particularly 65-85 weight % scope, and solidifying agent is at 5-50 weight %, particularly use in the 15-35 weight % scope.In addition, the matrix resin that cationic electrolytic deposition coating contains and the concentration of solidifying agent are divided in total shape admittedly, can be 10-40 weight %, particularly 15-25 weight % scope.
In the cationic electrolytic deposition coating of the present invention except that at least a polyether compound, matrix resin and the solidifying agent that is selected from formula (1), (2), (3) and (4), also can contain other paint additive with normally used amount as required, for example tinting pigment, pigment extender, rust-stabilising pigment, organic solvent, pigment dispersing agent, surface conditioner, tensio-active agent, acid, catalyzer etc.
Aforesaid polyether compound, can carry out water-dispersion with other suitable paint additive, make the cationic electrolytic deposition coating emulsion as the amine addition Resins, epoxy of matrix resin and as the blocked polyisocyanates compound of solidifying agent.
This emulsion can be prepared as follows: for example with at least a other paint additive that is selected from polyether compound, matrix resin, the solidifying agent of formula (1), (2), (3) and (4) and according to circumstances adopts thorough mixing together, make the dissolving lacquer, then in aqueous medium to wherein adding the neutralizing agent be selected from formic acid, acetate, lactic acid, propionic acid, citric acid, oxysuccinic acid, thionamic acid, its a kind or multiple mixture etc., carry out water-dispersion.
The polyether compound that is selected from formula (1), (2), (3) and (4) can be according to the changes such as kind of desiring the blended electrodeposition paint with respect to the combined amount of electrodeposition paint, consider from the stable equal angles of coating, divide in solid shape, usually the total shape branch admittedly of per 100 weight part matrix resins and solidifying agent, preferred 0.1-20 weight part, preferred especially 1-10 weight part, more preferably in the 2-8 weight part scope.
Then, add pigment dispersed slurry in emulsion, use medium as required, preparation cationic electrolytic deposition coating to above-mentioned cationic electrolytic deposition coating.As mentioned above, prepared electrodeposition paint can be applied to desired substrate surface by electrolytic deposition.
Dilutions such as common available deionized water, make the concentration that solid shape is divided in the bath be the about 40 weight % of about 5-, and use pH regulator to the cationic electrolytic deposition coating in the 5.5-9.0 scope to bathe, under the condition of warm 15-35 ℃ of bath and impressed voltage 100-400V, carry out the electrolytic deposition coating usually.
Being not particularly limited for the coating thickness that uses cationic electrolytic deposition coating to form, is in the scope of preferred 10-40 μ m based on cured coating film usually.
The preferred coated article of the sintering temperature of filming surface is generally about 200 ℃ of about 120-, the temperature in the about 180 ℃ of scopes of especially preferably about 140-, and sintering time is generally 5-60 minute, preferred about 10-30 minute.
Contain that the content that at least a electrodeposition paint of the present invention that is selected from the polyether compound of formula (1), (2), (3) and (4) has volatile organic compounds is few, solidity to corrosion, to excellent characteristics such as the electrolytic deposition coating of Rustproof Steel Plate, film-forming propertiess, and excellent in stability, even long-time open stirring the in paint line is bathed, above-mentioned characteristic is also without any variation.
Embodiment
Below exemplify embodiment and further specify the present invention, but the present invention is not limited to these embodiment." part " and " % " is " weight part " and " weight % ".
Preparation example 1 additive No.1
In reaction vessel, add 264 parts of butylglycidyl ethers (molecular weight about 130), 261 parts of glycol monomethyl 2-ethylhexyl ethers (molecular weight about 174), be warming up to 100 ℃.Keep this temperature to stir 3 hours, obtain molecular-weight average and be 304 additive No.1 (the solid shape of resin is divided into 100%).
Preparation example 2 additive No.2
In reaction vessel, add 288 parts of デ Na コ-Le EX-216L (Na ガ セ ケ system テ Star Network ス, trade(brand)name, hexanaphthene diglycidylether, molecular weight about 288) and 212.4 parts of ethylene glycol monobutyl ethers (molecular weight about 118), be warming up to 100 ℃.Keep this temperature to stir 3 hours, obtain molecular-weight average and be 406 additive No.2 (the solid shape of resin is divided into 100%).
Preparation example 3 additive No.3
Add 264 parts of butylglycidyl ethers (molecular weight about 130), 90.1 part 1 in reaction vessel, 4-butyleneglycol (polyvalent alcohol, molecular weight about 90.1) is warming up to 100 ℃.Keep this temperature to stir 3 hours, obtain molecular-weight average and be 354 additive No.3 (the solid shape of resin is divided into 100%).
Preparation example 4 matrix resin No.1
Pack in the detachable flask of 2 liters of tool thermometer, reflux exchanger and stirrer, internal volumes 240 part of 50% formalin, 55 parts of phenol, 101 part of 98% industrial sulphuric acid and 212 parts of m-xylenes were 84-88 ℃ of reaction 4 hours.Reaction is left standstill after finishing, and separation resin phase and aqueous sulfuric acid phase are washed resin 3 times mutually, under 20-30mmHg/120-130 ℃ condition unreacted m-xylene are desolvated 20 minutes, and obtaining viscosity is the xylene formaldehyde resin (1) of 1050 centipoises (25 ℃).
In the another one flask, add 1000 parts of エ ピ コ-ト 828EL (ジ ヤ パ Application エ Port キ シ レ ジ Application (strain), trade(brand)name, Resins, epoxy, epoxy equivalent (weight) 190, molecular weight 350), 400 parts of dihydroxyphenyl propanes and 0.2 part of dimethyl benzylamine, 130 ℃ react to epoxy equivalent (weight) be 750.
The ketoimine thing that then adds 300 parts of above-mentioned xylene formaldehyde resins (1), 140 parts of diethanolamine and 65 parts of diethylenetriamine, 120 ℃ of reactions 4 hours, add 420 parts of ethylene glycol butyl ethers then, what obtain that the solid shape of amine value 52mgKOH/g, resin is divided into 80% xylene formaldehyde resin modification contains aminoepoxy resin (matrix resin No.1).
Preparation example 5 matrix resin No.2
In 400 parts of PP-400 (Sanyo changes into society, trade(brand)name, polypropylene glycol, molecular weight 400), add 300 parts of 6-caprolactones, be warming up to 130 ℃.Add 0.01 part of four titanium butoxide then, be warming up to 170 ℃.Keeping this temperature to take a sample at any time, follow the trail of unreacted 6-caprolactone amount by infrared absorption spectrometry, is 98% or above time cooling in reactivity, obtains properties-correcting agent 1.
In 1000 parts of エ ピ コ-ト 828EL (ジ ヤ パ Application エ Port キ シ レ ジ Application (strain), trade(brand)name, Resins, epoxy, epoxy equivalent (weight) 190, molecular weight 350), add 400 parts of dihydroxyphenyl propanes and 0.2 part of dimethyl benzylamine in addition, 130 ℃ react to epoxy equivalent (weight) be 750.
To wherein adding 120 parts of nonylphenols, 130 ℃ react to epoxy equivalent (weight) be 1000.Then, the ketoimine thing that adds 1,95 parts of diethanolamine of 200 parts of properties-correcting agent and 65 parts of diethylenetriamine, 120 ℃ of reactions 4 hours, add 414 parts of ethylene glycol monobutyl ethers then, obtain amine value and be 40mg KOH/g, the solid shape of resin and be divided into the polyalcohol modified aminoepoxy resin (matrix resin No.2) that contains that 80% addition has nonylphenol.
Preparation example 6 solidifying agent
In 270 parts of コ ス モ ネ-ト M-2000 (Mitsui Chemicals, Inc, trade(brand)name, rough MD I), add 46 parts of methyl iso-butyl ketone (MIBK), be warming up to 70 ℃.Slowly add 281 parts of ethyl carbitols again, be warming up to 90 ℃.
Keep this temperature to take a sample at any time, confirm not have the absorption of unreacted isocyanic ester by infrared absorption spectrometry, termination reaction is regulated quantity of solvent, obtains solid shape and is divided into 90% blocked polyisocyanates type solidifying agent.
Preparation example 7 emulsion No.1
The additive No.1 that obtains in 6.25 parts of (Gu shape is divided into 5 parts) preparation examples 1,50 parts of (Gu shape is divided into 40 parts) matrix resin No.1,37.5 parts of (Gu shape is divided into 30 parts) matrix resin No.2,33.3 parts of (Gu shape is divided into 30 parts) solidifying agent and 8.2 part of 10% formic acid are mixed, evenly stir, vigorous stirring dripped 173.8 parts of deionized waters with about 15 minutes on one side on one side then, obtained solid shape and was divided into 34% emulsion No.1.
Preparation example 8-12 emulsion No.2-No.6
According to the blending ratio shown in the table 1, similarly obtain solid shape with preparation example 7 and be divided into 34% emulsion No.2-No.6.
Table 1
The solid shape branch of expression in ()
(annotating 2) polyether glycol (a): HO-(C
2H
4O)
3-Be-C (CH
3)
2-Be-(OC
2H
4)
3-OH (here, Be represents benzene).
(annotating 3) サ Application ニ Star Network ス PP-1000: Sanyo changes into society, trade(brand)name, polypropylene glycol.
Preparation example 13 pigment dispersed slurry
5.83 parts of (Gu shape is divided 3.5 parts) 60% quaternary Resins, epoxy, 14.5 parts of titanium whites, 0.3 part of carbon black, 7.0 parts of pigment extenders, 1.0 parts of bismuth hydroxides, 1 part of di-n-octyltin oxide and 20 parts of deionized waters are mixed, obtain the pigment dispersed slurry that solid shape is divided into 55.0 weight %.
Embodiment 1
In 309 parts of (Gu shape is divided into 105 parts) emulsion No.1, add 49.6 parts of pigment dispersed slurry and 302.9 parts of deionized waters that (Gu shape is divided into 27.3 parts), preparation example 13 obtained, obtain solid shape and be divided into 20% cationic electrolytic deposition coating No.1.
Embodiment 2-3, comparative example 1-3
According to the blending ratio shown in the table 2, obtain cationic electrolytic deposition coating No.2-No.6 similarly to Example 1.
Table 2
The solid shape branch of expression in ()
The making of test board
Use each cationic electrolytic deposition coating of the foregoing description and comparative example gained, carrying out implementing the electrolytic deposition coating on chemically treated cold-rolled steel sheet and the alloyed hot-dip galvanized steel plate with パ Le ボ Application De #3020 (Japanese パ-カ ラ イ ジ Application グ company, trade(brand)name, zinc phosphate treatment agent) respectively.
The gained test board is tested according to following test conditions.The result is as shown in table 3.
Table 3
| Embodiment 1 | Embodiment 2 | Embodiment 3 | Comparative example 1 | Comparative example 2 | Comparative example 3 | |
| Cationic electrolytic deposition coating | No.1 | No.2 | No.3 | No.4 | No.5 | No.6 |
| (annotating 4) thickness retention Δ μ m | 0 | 0 | 0 | 3 | 4 | 8 |
| The suitable property of electrolytic deposition coating of (annotating 5) Rustproof Steel Plate | ○ | ○ | ○ | △ | △ | × |
| (annotating 6) solidity to corrosion | ○ | ○ | ○ | △ | × | ○ |
| (annotating 7) sealing lacquer tack | ○ | ○ | ○ | △ | × | ○ |
| (annotating 8) paint stability | ○ | ○ | ○ | △ | △ | ○ |
(annotating 4) thickness retention:
Cold-rolled steel sheet as negative electrode, is dipped in during each cationic electrolytic deposition coating bathes, and making and bathing temperature is 30 ℃, with 250V voltage electrolytic deposition coating 3 minutes, 170 ℃ of sintering 20 minutes, measures thickness then.Initial film thickness (1)
Afterwards, with opening above each cationic electrolytic deposition coating bath is under 30 ℃, with container for paint, stirred for 4 weeks.Use this bath, with similarly above-mentioned, 30 ℃ down with 250V voltage electrolytic depositions coating 3 minutes, 170 ℃ of sintering 20 minutes, measure thickness then.Thickness behind the certain hour (2)
Obtain the film thickness difference (μ m) of the thickness (2) behind initial film thickness (1) and the certain hour, with this index as thickness retention.
(annotating 5) is to the suitable property of electrolytic deposition coating of Rustproof Steel Plate
Use employed each cationic electrolytic deposition bath in thickness retention (the annotating 4) test, behind certain hour (4 weeks, 30 ℃, the open stirring), alloyed hot-dip galvanized steel plate is dipped in wherein as negative electrode, switched on 3 minutes down for 30 ℃ in the bath temperature, apply the voltage that can obtain 20 μ m coating thicknesses and be coated with, carry out the sintering drying.Count the test board (pinhole number in 10 * 10cm) afterwards.
Zero expression does not produce pin hole
△ represents to produce 1-5 pin hole
* expression produces 6 or above pin hole.
(annotating 6) solidity to corrosion
On cold-rolled steel sheet, carry out the electrolytic deposition coating, go up with cutter the electrolytic deposition mark signature cut of filming at each electrolytic deposition coated panel of gained (being coated with thickness 20 μ m), make cut arrive base material,, it is carried out salt water resistance spray testing in 840 hours according to the method for JIS Z-2371.By rusty stain, the foaming width at tool marks place, estimate according to following benchmark.
◎ represents that rusty stain, blistered maximum width are extended less than 2mm (one-sided) by tool marks
Zero expression rusty stain, blistered maximum width extends 2mm or above but less than 3mm (one-sided) by tool marks
△ represents that rusty stain, blistered maximum width extend 3mm or above but less than 4mm (one-sided) by tool marks
* expression rusty stain, blistered maximum width extend 4mm or above (one-sided) by tool marks.
(annotating 7) sealing lacquer tack
On cold-rolled steel sheet, be coated with electrodeposition paint No.1-No.6, making thickness is 20 μ m, obtain each test board thus, thereon with 10mm * 6mm * 6mm (vertical * horizontal * thick) coating サ Application ス -1065T (サ Application ス -company, sealing lacquer, trade(brand)name), coated panel is vertically hung up, measured the displacement of sealing lacquer after 12 hours.
Zero not displacement of sealing lacquer, no problem
The displacement of △ sealing lacquer is at 5mm or following
The landing from the coated plate of * sealing lacquer.
(annotating 8) paint stability
Will be under 30 ℃ with container for paint above open each cationic electrolytic deposition coating that stirred for 4 weeks bathe with 400 order filtering nets and filter the mensuration filtration residue.
Zero less than 10mg/L
△ 10mg/L or above and less than 15mg/L
* above 15mg/L.
Preparation example 14 additive No.4
In the stainless steel autoclave of tool stirrer and thermometer, pack into 160.3 parts of butyl ethyl propylene glycol (consonance fermentation chemistry (strain), trade(brand)name, 2-butyl-2-ethyl-1, ammediol, molecular weight 160.3) and 1.0 parts of potassium hydroxide as catalyzer, with the nitrogen displacement, dewater then in the container.Then at 130 ℃ with introducing 88 parts of oxyethane (molecular weight: about 44) in 1.5 hours.Afterwards the alkaline catalysts in the reaction solution is neutralized with 1.0 parts of acetate, obtain molecular-weight average and be 248 additive No.4 (Gu shape is divided into 100%).
Preparation example 15 additive No.5
In the stainless steel autoclave of tool stirrer and thermometer, pack into 160.3 parts of butyl ethyl propylene glycol (consonance fermentation chemistry (strain), trade(brand)name, 2-butyl-2-ethyl-1, ammediol, molecular weight 160.3) and 1.0 parts of potassium hydroxide as catalyzer, with the nitrogen displacement, dewater then in the container.Then at 130 ℃ with introducing 116 parts of propylene oxide (molecular weight: about 58) in 1.5 hours.Afterwards the alkaline catalysts in the reaction solution is neutralized with 1.0 parts of acetate, obtain molecular-weight average and be 276 additive No.5 (Gu shape is divided into 100%).
Preparation example 16 additive No.6
In the stainless steel autoclave of tool stirrer and thermometer, pack into 160.3 parts of butyl ethyl propylene glycol (consonance fermentation chemistry (strain), trade(brand)name, 2-butyl-2-ethyl-1, ammediol, molecular weight 160.3) and 1.0 parts of potassium hydroxide as catalyzer, with the nitrogen displacement, dewater then in the container.Then at 130 ℃ about 44) and 116 parts of propylene oxide (molecular weight: about 58) with introducing 88 parts of oxyethane (molecular weight: in 1.5 hours.Afterwards the alkaline catalysts in the reaction solution is neutralized with 1.0 parts of acetate, obtain molecular-weight average and be 364 additive No.6 (Gu shape is divided into 100%).
Preparation example 17 additive No.7 (putting down in writing in the special fair 6-45772 communique example I of Japan)
Add 324 parts of butylcarbitol, 31.6 part of 95% paraformaldehyde and 0.3 part of methylsulfonic acid in reaction vessel, with the nitrogen displacement, in the about 120 ℃ of reflux of about 100-, reflux state kept 2 hours at least then in the reaction vessel.Then add toluene, on reaction vessel, install back flow condenser and デ イ-Application ス -Network water trap, reflux once more, azeotropic removes fully and anhydrates.Afterwards, the methylsulfonic acid in the reaction solution is neutralized with aqueous sodium carbonate, obtain additive No.7 (Gu shape is divided into 100%).
The preparation of preparation example 18 emulsion No.7
Additive No.4,87.5 parts of (Gu shape is divided into 70 parts) matrix resin No.1,33.3 parts of (Gu shape is divided into 30 parts) solidifying agent and 8.2 part of 10% formic acid that 5 parts (Gu shape is divided into 5 parts) are obtained by preparation example 13 mix, evenly stir, vigorous stirring dripped 175 parts of deionized waters with about 15 minutes on one side on one side then, obtained solid shape and was divided into 34% emulsion No.7.
The preparation of preparation example 19-21 emulsion No.8-No.10
According to the blending ratio shown in the table 4, similarly obtain solid shape with preparation example 18 and be divided into 34% emulsion No.8-No.10.
Table 4
The solid shape branch of expression in ()
The preparation of preparation example 22-29 emulsion No.11-No.18
According to the blending ratio shown in the table 5, similarly obtain solid shape with preparation example 18 and be divided into 34% emulsion No.11-No.18.
Table 5
The solid shape branch of expression in ()
The preparation of preparation example 30 pigment dispersed slurry
The quaternary Resins, epoxy of 5.83 parts of (Gu shape are divided 3.5 parts) 60%, 14.5 parts of titanium whites, 0.3 part of carbon black, 7.0 parts of pigment extenders, 1.0 parts of bismuth hydroxides, 1 part of di-n-octyltin oxide and 20 parts of deionized waters are mixed, obtain the pigment dispersed slurry that solid shape is divided into 55.0 weight %.
Embodiment 4
In 309 parts of (Gu shape is divided 105 parts) emulsion No.7, add pigment dispersed slurry and the 302.9 parts of deionized waters that obtain in 49.6 parts of (Gu shape is divided into 27.3 parts) preparation examples 29, obtain solid shape and be divided into 20% cationic electrolytic deposition coating No.7.
Embodiment 5-7
According to the blending ratio shown in the table 6, obtain cationic electrolytic deposition coating No.8-No.10 similarly to Example 4.
Table 6
The solid shape branch of expression in ()
Comparative example 4-11
According to the blending ratio shown in the table 7, obtain cationic electrolytic deposition coating No.11-No.18 similarly to Example 4.
Table 7
The solid shape branch of expression in ()
The making of test board
Use each cationic electrolytic deposition coating of the foregoing description and comparative example gained, carrying out implementing the electrolytic deposition coating on chemically treated cold-rolled steel sheet and the alloyed hot-dip galvanized steel plate with パ Le ボ Application De #3020 (Japanese パ-カ ラ イ ジ Application グ company, zinc phosphate treatment agent, trade(brand)name) respectively.
The gained test board is tested according to test conditions same as described above.The result of embodiment 4-7 is illustrated in table 8, and the result of comparative example 4-11 is illustrated in table 9.
Table 8
| Embodiment 4 | Embodiment 5 | Embodiment 6 | Embodiment 7 | |
| Cationic electrolytic deposition coating | No.7 | No.8 | No.9 | No.10 |
| (annotating 4) thickness retention Δ μ m | 0 | 0 | 0 | 0 |
| The suitable property of electrolytic deposition coating of (annotating 5) Rustproof Steel Plate | ○ | ○ | ○ | ○ |
| (annotating 6) solidity to corrosion | ◎ | ◎ | ◎ | ○ |
| (annotating 7) sealing lacquer tack | ○ | ○ | ○ | ○ |
| (annotating 8) paint stability | ○ | ○ | ○ | ○ |
Table 9
| Comparative example 4 | Comparative example 5 | Comparative example 6 | Comparative example 7 | Comparative example 8 | Comparative example 9 | Comparative example 10 | Comparative example 11 | |
| Cationic electrolytic deposition coating | No.11 | No.12 | No.13 | No.14 | No.15 | No.16 | No.17 | No.18 |
| (annotating 4) thickness retention Δ μ m | 4 | 3 | 3 | 2 | 2 | 2 | 6 | 7 |
| The suitable property of electrolytic deposition coating of (annotating 5) Rustproof Steel Plate | △ | △ | × | ○ | ○ | ○ | △ | × |
| (annotating 6) solidity to corrosion | ○ | ○ | △ | △ | △ | × | ○ | ○ |
| (annotating 7) sealing lacquer tack | ○ | ○ | △ | △ | × | × | × | ○ |
| (annotating 8) paint stability | ○ | ○ | ○ | △ | △ | △ | ○ | ○ |
Claims (7)
1. it is the polyether compound that is selected from following formula (1)-(4) below 1,000 that electrodeposition paint, this electrodeposition paint contain at least a molecular weight:
In the formula,
R
1And R
3The alkyl or phenyl of independent respectively expression carbonatoms 1-10;
R
2Expression hydrogen atom or methyl are when p and q are respectively 2 when above, a plurality of R in formula (1) or (2)
2Can distinguish identical or mutual difference;
R
4R valency aliphatic series or the ester ring type alkyl of expression carbonatoms 2-10;
R
5A straight chain shape or the chain alkylidene group of expression carbonatoms 4-24;
R
6And R
7Respectively independent expression hydrogen atom, methyl or ethyl are when m and n are respectively 2 when above, a plurality of R in the formula (4)
6With a plurality of R
7Can distinguish identical or mutual difference;
P is the integer of 0-4;
Q is the integer of 1-4;
R is the integer of 2-4;
M and n are independent respectively to be the integer of 1-10.
2. the electrodeposition paint of claim 1, wherein the molecular weight of polyether compound is in the 250-800 scope.
3. the electrodeposition paint of claim 1, the polyether compound of its Chinese style (1) obtains by making the reaction of alkylol cpd shown in glycidyl ether compound shown in the formula (5) and the formula (6):
In the formula, R
1Identical with the implication of claim 1;
In the formula, R
2, R
3Identical with p with claim 1 implication.
4. the electrodeposition paint of claim 1, the polyether compound of its Chinese style (2) obtains by making the reaction of alkylol cpd shown in multi-shrinking glyceryl compound shown in the formula (7) and the formula (8):
In the formula, R
4Identical with r with the implication of claim 1;
In the formula, R
2, R
3Identical with q with claim 1 implication.
5. the electrodeposition paint of claim 1, polyol reaction obtains the polyether compound of its Chinese style (3) shown in glycidyl ether compound shown in the formula (5) and the formula (9) by making:
In the formula, R
1Identical with the implication of claim 1;
R
4(OH)
r(9)
In the formula, R
4Identical with r with claim 1 implication.
6. the electrodeposition paint of claim 1, alkylene oxide reaction obtains the polyether compound of its Chinese style (4) shown in glycol shown in the formula (10) and formula (11) and the formula (12) by making:
HO-R
5-OH(10)
In the formula, R
5Identical with claim 1 implication;
In the formula, R
6And R
7Identical with the implication of claim 1.
7. coated article, it has been coated with the electrodeposition paint of claim 1.
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| JP5110962B2 (en) * | 2006-10-31 | 2012-12-26 | 関西ペイント株式会社 | Cationic electrodeposition coating composition and articles coated with the electrodeposition coating |
| JP7355032B2 (en) * | 2018-11-29 | 2023-10-03 | 三菱瓦斯化学株式会社 | Urethane (meth)acrylate resin, curable resin composition, and cured product |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4468307A (en) * | 1981-09-14 | 1984-08-28 | Ppg Industries, Inc. | Method of cationic electrodeposition |
| EP0339795A2 (en) * | 1988-04-25 | 1989-11-02 | Ppg Industries, Inc. | Cationic electrocoating compositions |
| US6342546B1 (en) * | 1999-04-21 | 2002-01-29 | Kansai Paint Co., Ltd. | Cationic electrodeposition coating composition |
| US6423425B1 (en) * | 1998-05-26 | 2002-07-23 | Ppg Industries Ohio, Inc. | Article having a chip-resistant electrodeposited coating and a process for forming an electrodeposited coating |
| CN1422918A (en) * | 2001-11-22 | 2003-06-11 | 关西油漆株式会社 | Cationic coating composition |
-
2005
- 2005-05-17 CN CNB2005100713476A patent/CN100451081C/en not_active Expired - Fee Related
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4468307A (en) * | 1981-09-14 | 1984-08-28 | Ppg Industries, Inc. | Method of cationic electrodeposition |
| EP0339795A2 (en) * | 1988-04-25 | 1989-11-02 | Ppg Industries, Inc. | Cationic electrocoating compositions |
| US6423425B1 (en) * | 1998-05-26 | 2002-07-23 | Ppg Industries Ohio, Inc. | Article having a chip-resistant electrodeposited coating and a process for forming an electrodeposited coating |
| US6342546B1 (en) * | 1999-04-21 | 2002-01-29 | Kansai Paint Co., Ltd. | Cationic electrodeposition coating composition |
| CN1422918A (en) * | 2001-11-22 | 2003-06-11 | 关西油漆株式会社 | Cationic coating composition |
Also Published As
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|---|---|
| CN1699484A (en) | 2005-11-23 |
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