CN103304773A - Ionic curing agent and preparation method thereof - Google Patents
Ionic curing agent and preparation method thereof Download PDFInfo
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- CN103304773A CN103304773A CN2013102534066A CN201310253406A CN103304773A CN 103304773 A CN103304773 A CN 103304773A CN 2013102534066 A CN2013102534066 A CN 2013102534066A CN 201310253406 A CN201310253406 A CN 201310253406A CN 103304773 A CN103304773 A CN 103304773A
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Abstract
The invention relates to an ionic curing agent and a preparation method thereof. The general formula (I) of the ionic curing agent is as shown in the specification; the ionic curing agent obtains an ionic structure through polyhydroxy sulfide and avoids the application of traditional compounds containing tertiary nitrogen atoms; the ionic curing agent is free of the tertiary nitrogen atoms in the molecules, thereby reducing the unfavorable factors of violent heat release and increased side reactions in the preparation process of the ionic curing agent, ensuring easier process control and facilitating industrial production; and the curing agent is cationic, thereby capable of being compatible to a traditional cationic electrophoretic coating; the curing agent carries charges per se, thereby capable of being dispersed into water without assistance of cation exchange resin and greatly improving the stability of liquid in an electrophoresis bath; and furthermore, the curing agent is unlikely to precipitate or stratify.
Description
[technical field]
The present invention relates to a kind of ionic solidifying agent and preparation method thereof, specifically a kind of positively charged, preparation method that can carry out ionic solidifying agent electrophoresis, that do not contain tertiary N atom.
[background technology]
Cation electrophoretic coating is a kind of coating of developing for electrophoresis coating technique, and it is equipped with components such as an amount of solubility promoter, solidifying agent and pigment based on resin cation (R.C.), obtains by self-emulsifying as solvent with water.At present, the most frequently used solidifying agent great majority of electrophoretic paint are non-water-soluble blocked isocyanate, technology in its introducing electrophoretic paint adopts the method for mechanical blending usually, being about to solidifying agent and ionic resin mixes both by the physics mode that stirs or disperse, mixed product water-dispersion the time, by the ionic water soluble resin thereby non-water-soluble solidifying agent is wrapped in interior formation emulsion, the similar non-water soluble substance of its emulsification principle makes it to be dispersed in the water by the tensio-active agent parcel.Under the extra electric field effect, ionic resin drives and is moved to electrode by the solidifying agent of its parcel, and galvanic deposit is to being coated with on the workpiece then.Because solidifying agent self is water-insoluble, therefore after being configured to electrophoresis groove liquid, the stability of tank liquor is not good, and the easy precipitated and separated of solidifying agent causes tank liquor composition and proportioning instability, influences the quality stability of paint film.
In order to address the above problem the singularity of considering cation electrophoretic coating simultaneously, design and the dispersed blocked isocyanate curing agent of exploitation cationic water are very meaningful for electrophoretic paint.At present, the main method of preparation positively charged ion isocyanate curing agent is that the compound that will contain tertiary N atom is incorporated into isocyanate molecule by reaction and gets on.For example: dimethylaminomethylphenol, pyridol and the alcohol that contains tertiary N atom can obtain blocked isocyanate with isocyanate reaction.After adding the acid neutralization, isocyanate molecule can be transformed into ammonium salt, thereby obtains the cation water-soluble blocked isocyanate, and this type of solidifying agent can significantly improve the stability of electrophoresis groove liquid.Though the introducing of tertiary N atom can obtain cationic solidifying agent, as everyone knows, the material that contains tertiary N atom himself is exactly good catalyzer, in the process of blocked isocyanate, can accelerate the reaction between isocyanic ester and the encapsulant, therefore can cause the generation of some uncontrollable factors, for example: side reaction increase and heat release are violent.In case be amplified to industrial production, these side reactions will bring many negative issues to the production technique of solidifying agent and the performance of the finished product, also can influence the final performance of electrophoretic paint.
[summary of the invention]
In order to improve the water-soluble of isocyanate curing agent, avoid introducing the shortcoming that produces behind the tertiary N atom simultaneously, the invention provides a kind of preparation method of ionic solidifying agent, specifically a kind of positively charged, preparation method that can carry out ionic solidifying agent electrophoresis, that do not contain tertiary N atom.
In order to address the above problem the ionic solidifying agent that the invention provides a kind of following general formula (I):
R wherein
1And R
2Represent C respectively
1～C
4Alkyl; R
3Expression C
mH
2m+1O
pOr phenyl ring, m=1～5, p=0～2; R
4Expression C
1～C
9Alkyl, phenyl ring or both repeated combinations; B represents C
1～C
9Alkyl, phenyl ring, alicyclic ring or three's repeated combination; N 〉=2.
The present invention also comprises the preparation method of above-mentioned ion solidifying agent, it is characterized in that this method is made up of following steps:
The poly-hydroxy thioether of the polyepoxy compound of step 1, general formula (II), general formula (III) and general formula (IV) monobasic organic acid are according to adding among mol ratio 1:1:1～1:1.5:1 in the reaction vessel, be warming up to 50～80 ℃ of afterreactions 1～5 hour, reaction is carried out according to following formula:
Behind ratio＜0.05 of actual measurement acid number and initial acid number, stopped reaction, the component one that obtains containing formula V is stand-by;
Step 2, the mol ratio that contains compound bearing active hydrogen by isocyanate group and general formula (VII) in general formula (VI) polyisocyanates are that 1:0.5～1:0.65 adds and adds compound and polyisocyanates in the reaction vessel, be warming up to 50～80 ℃ of afterreactions 1～5 hour, reaction is carried out according to following formula:
After residual isocyanate content reached calculated value, wherein, residual isocyanate content calculated value was 5%～30%, stopped reaction, and the component two that obtains containing general formula (VIII) is stand-by;
Step 3, in reaction vessel, add component one and component two, in the component one in hydroxyl and the component two mol ratio of isocyanate group be 1:1～1:0.5, be warming up to 50～80 ℃ after, reaction is carried out according to following formula:
Reacted 1～5 hour, stopped reaction obtains the compound of general formula (I).
Above-mentioned preparation method also has following optimization technology
Described polyepoxy compound is the aliphatics that contains two or more epoxide groups, alicyclic, aromatic series or heterogeneous ring compound, and the epoxy equivalent (weight) of polyepoxy compound is between 50-2000.
Polyepoxy compound is preferred but be not limited to ethylene glycol diglycidylether, propylene glycol diglycidylether, butanediol diglycidyl ether, hexanediol diglycidyl ether, the propanedioic acid 2-glycidyl ester, the hexanodioic acid 2-glycidyl ester, the glycol ether diglycidylether, the dipropylene glycol 2-glycidyl, the tripropylene glycol 2-glycidyl, neopentylglycol diglycidyl ether, glycerin diglycidyl ether, the tetramethylolmethane diglycidylether, trihydroxymethylpropanyltri diglycidyl ether, the tetramethylolmethane triglycidyl ether, T 55, two T 55s, two glycerine, four glycidyl ethers, tetramethylolmethane four glycidyl ethers, in Dipentaerythritol four glycidyl ethers or the cylohexanediol diglycidyl ether one or more.
The poly-hydroxy sulfide compound is preferred but be not limited to two (2-hydroxyethyl) thioether, two (3-hydroxypropyl) thioether, two (2-hydroxypropyl) thioether, two (4-hydroxyl butyl) thioether, two (3-hydroxyl butyl) thioether, 1-(2-hydroxyethyl sulfenyl)-2-propyl alcohol, 3-(2-hydroxyethyl sulfenyl)-1-propyl alcohol, 1-(3-hydroxypropyl sulfenyl)-2-propyl alcohol, 1-(2-hydroxyethyl sulfenyl)-3-butanols, 4-(2-hydroxyethyl sulfenyl)-1-butanols, 1-(3-hydroxypropyl sulfenyl)-3-butanols, 1-(2-hydroxypropyl sulfenyl)-3-butanols, 4-(3-hydroxypropyl sulfenyl)-1-butanols, in 4-(2-hydroxypropyl sulfenyl)-1-butanols or 4-(3-hydroxyl butyl sulfenyl)-1-butanols one or more.
Described monobasic organic acid is preferred but be not limited to formic acid, acetic acid, propionic acid, butyric acid, lactic acid, 2,2-dimethylol propionic acid, 2, in 2-dimethylolpropionic acid, the phenylformic acid one or more.
Polyisocyanates is preferred but be not limited in tolylene diisocyanate, '-diphenylmethane diisocyanate, polymethylene polyphenyl vulcabond, hexamethylene diisocyanate, xylylene diisocyanate, isophorone diisocyanate, dicyclohexyl methyl hydride isocyanic ester, trimethyl hexamethylene diisocyanate and the hydrogenated tolylene diisocyanate one or more.
It is preferred but be not limited in methyl alcohol, ethanol, propyl alcohol, butanols, hexanol, octanol, phenylcarbinol, phenylethyl alcohol, ethylene glycol monomethyl ether, ethylene glycol monobutyl ether, ethylene glycol ether, propylene glycol monomethyl ether, propylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monobutyl ether, Diethylene Glycol monohexyl ether, methyl ethyl ketoxime, acetoxime, cyclohexanone-oxime, diisopropylamine, 3, N-tert-butyl benzyl amine or the hexanolactam one or more to contain compound bearing active hydrogen.
Beneficial effect of the present invention is:
1, adopts the poly-hydroxy thioether to obtain the ionization structure, avoided using traditional compound that contains tertiary N atom;
2, because the existence of no tertiary N atom in the molecule, thus reduced heat release in the ionic solidifying agent preparation process acutely, the unfavorable factor that increases of side reaction, be easier to technology controlling and process, be conducive to suitability for industrialized production;
3, solidifying agent is from as cationic, can with traditional cation electrophoretic coating compatibility because himself is electrically charged, need just can not be distributed in the water by resin cation (R.C.), improved electrophoresis groove liquid stability widely, and solidifying agent is difficult for precipitated and separated.
[embodiment]
In order to be easy to further understand the present invention, the following example has been set forth more specific details.
Embodiment 1
Epoxy group(ing), poly-hydroxy thioether and monobasic organic acid mol ratio are in the component A(polyepoxy compound: 1:1:1)
101), 122g two (2-hydroxyethyl) thioether and 60g acetic acid in the 500mL there-necked flask of agitator and thermometer was housed, (epoxy equivalent (weight) was: to add the 101g butanediol diglycidyl ether successively.Start stirring after adding finishes, after reaction system stirs, reaction system is warming up to 80 ℃, be accompanied by tangible exothermic phenomenon in the temperature-rise period.Reaction system is maintained 80 ℃ of insulation 1h, and sampling detection reaction system residue acid number (the initial theoretical acid number of reaction system is: 198mgKOH/g), after acid number is less than 10, stopped reaction.
(isocyanate group with the mol ratio that contains compound bearing active hydrogen is B component in the polyisocyanates: 1:0.5)
In the 1L there-necked flask of agitator and thermometer is housed, add the 522g tolylene diisocyanate, reaction system is warming up to 70 ℃ after, slowly drip the 261g methyl ethyl ketoxime.After dropwising, under this temperature, continue to use residue isocyanato content in the standard Di-n-Butyl Amine back titration method analytical reaction system behind the reaction 2h, and when residue isocyanato content reaches theoretical value (observed value: 15.7%, theoretical value 16.1%), termination reaction.
The ionic solidifying agent (among the component A in hydroxyl and the B component mol ratio of isocyanate group be: 1:0.5)
The amount of substance that adds hydroxyl among the 141.5g component A(component A in the 500mL there-necked flask of agitator and thermometer is housed is 1.5mol), after reaction system is warming up to 70 ℃, slowly drip 195.75g B component (amount of substance of isocyanate group is 0.75mol in the B component).After dropwising, under this temperature, continue reaction 1h, after the absorption peak completely dissolve of isocyanate groups in the infrared spectra detection reaction system, termination reaction.
The ionic solidifying agent of above-mentioned preparation is applied in the cation electrophoretic coating, every performance index of coating are tested, and compare with traditional solidifying agent, correlation parameter sees the following form.
The cationic solidifying agent of table 1 the present invention and traditional curing agents are relatively
Embodiment 2
Epoxy group(ing), poly-hydroxy thioether and monobasic organic acid mol ratio are in the component A(polyepoxy compound: 1:1.5:1)
101), 183g two (2-hydroxyethyl) thioether and 60g acetic acid in the 500mL there-necked flask of agitator and thermometer was housed, (epoxy equivalent (weight) was: to add the 101g butanediol diglycidyl ether successively.Start stirring after adding finishes, after reaction system stirs, reaction system is warming up to 80 ℃, be accompanied by tangible exothermic phenomenon in the temperature-rise period.Reaction system is maintained 80 ℃ of insulation 1h, and sampling detection reaction system residue acid number (the initial theoretical acid number of reaction system is: 163mgKOH/g), after acid number is less than 8, stopped reaction.
(isocyanate group with the mol ratio that contains compound bearing active hydrogen is B component in the polyisocyanates: 1:0.65)
In the 1L there-necked flask of agitator and thermometer is housed, add the 522g tolylene diisocyanate, reaction system is warming up to 70 ℃ after, slowly drip the 339.3g methyl ethyl ketoxime.After dropwising, under this temperature, continue to use residue isocyanato content in the standard Di-n-Butyl Amine back titration method analytical reaction system behind the reaction 2h, and when residue isocyanato content reaches theoretical value (observed value: 9.8%, theoretical value 10.2%), termination reaction.
The ionic solidifying agent (among the component A in hydroxyl and the B component mol ratio of isocyanate group be: 1:1)
The amount of substance that adds hydroxyl among the 86g component A(component A in the 1L there-necked flask of agitator and thermometer is housed is 1mol), reaction system is warming up to 70 ℃ after, slowly drip the 410g B component.After dropwising, under this temperature, continue reaction 1h, after the absorption peak completely dissolve of isocyanate groups in the infrared spectra detection reaction system, termination reaction.
Embodiment 3
Polyepoxy compound among the embodiment 1 component A is become trihydroxymethylpropanyltri diglycidyl ether, and the poly-hydroxy thioether becomes 4-(3-hydroxypropyl sulfenyl)-1-butanols, and the monobasic organic acid becomes butyric acid, and temperature of reaction becomes 60 ℃, and the reaction times becomes 3h; Polyisocyanates in embodiment 1 B component is become isophorone diisocyanate, contain compound bearing active hydrogen and become ethylene glycol monobutyl ether, temperature of reaction becomes 50 ℃, and the reaction times becomes 5h; The mol ratio of isocyanate group in hydroxyl and the B component among the component A among the embodiment 1 is become 1:0.7, and temperature of reaction becomes 50 ℃, and the reaction times becomes 2h, and other reaction conditionss finally obtain being different from the ionic solidifying agent of embodiment 1 as described in example 1 above.
Embodiment 4
Polyepoxy compound among the embodiment 1 component A is become the mixture of ethylene glycol diglycidylether and T 55, the poly-hydroxy thioether becomes the mixture of two (3-hydroxypropyl) thioethers and 1-(3-hydroxypropyl sulfenyl)-3-butanols, the monobasic organic acid becomes lactic acid and 2, the mixture of 2-dimethylol propionic acid, other reaction conditionss finally obtain being different from the ionic solidifying agent of embodiment 1 as described in example 1 above.
Embodiment 5
Polyisocyanates in embodiment 1 B component is become the mixture of tolylene diisocyanate and '-diphenylmethane diisocyanate, contain compound bearing active hydrogen and become 3, the mixture of 5-dimethyl pyrazole and ethylene glycol monobutyl ether, other reaction conditionss finally obtain being different from the ionic solidifying agent of embodiment 1 as described in example 1 above.
Embodiment 6
Polyepoxy compound among the embodiment 1 component A is become the mixture of hexanediol diglycidyl ether, propanedioic acid 2-glycidyl ester and tetramethylolmethane triglycidyl ether, the poly-hydroxy thioether becomes the mixture of two (3-hydroxypropyl) thioether two (2-hydroxypropyl) thioether and 1-(3-hydroxypropyl sulfenyl)-3-butanols, the monobasic organic acid becomes lactic acid, boric acid and benzoic mixture, and epoxy group(ing), poly-hydroxy thioether and monobasic organic acid mol ratio become 1:1.2:1 in the polyepoxy compound; Polyisocyanates in embodiment 1 B component is become the mixture of xylylene diisocyanate, isophorone diisocyanate and dicyclohexyl methyl hydride isocyanic ester, contain compound bearing active hydrogen and become methyl ethyl ketoxime, N-tert-butyl benzyl amine and hexanolactam, isocyanate group becomes 1:0.55 with the mol ratio that contains compound bearing active hydrogen in the polyisocyanates, temperature of reaction becomes 60 ℃, other reaction conditionss finally obtain being different from the ionic solidifying agent of embodiment 1 as described in example 1 above.
Claims (8)
1. the ionic solidifying agent of following general formula (I):
R wherein
1And R
2Represent C respectively
1～C
4Alkyl; R
3Expression C
mH
2m+1O
pOr phenyl ring, m=1～5, p=0～2; R
4Expression C
1～C
9Alkyl, phenyl ring or both repeated combinations; B represents C
1～C
9Alkyl, phenyl ring, alicyclic ring or three's repeated combination; N 〉=2.
2. the preparation method of claim 1 ion solidifying agent is characterized in that this method is made up of following steps:
The poly-hydroxy thioether of the polyepoxy compound of step 1, general formula (II), general formula (III) and general formula (IV) monobasic organic acid are according to adding among mol ratio 1:1:1～1:1.5:1 in the reaction vessel, be warming up to 50～80 ℃ of afterreactions 1～5 hour, reaction is carried out according to following formula:
Behind ratio＜0.05 of actual measurement acid number and initial acid number, stopped reaction, the component one that obtains containing formula V is stand-by;
Step 2, the mol ratio that contains compound bearing active hydrogen by isocyanate group and general formula (VII) in general formula (VI) polyisocyanates are that 1:0.5～1:0.65 adds and adds compound and polyisocyanates in the reaction vessel, be warming up to 50～80 ℃ of afterreactions 1～5 hour, reaction is carried out according to following formula:
When residual isocyanate content reaches 5%～30%, stopped reaction, the component two that obtains containing general formula (VIII) is stand-by;
Step 3, in reaction vessel, add component one and component two, in the component one in hydroxyl and the component two mol ratio of isocyanate group be 1:1～1:0.5, be warming up to 50～80 ℃ after, reaction is carried out according to following formula:
Reacted 1～5 hour, stopped reaction obtains the compound of general formula (I).
3. the preparation method of ionic solidifying agent as claimed in claim 2, it is characterized in that described polyepoxy compound is the aliphatics that contains two or more epoxide groups, alicyclic, aromatic series or heterogeneous ring compound, the epoxy equivalent (weight) of polyepoxy compound is between 50-2000.
4. the preparation method of ionic solidifying agent as claimed in claim 3 is characterized in that polyepoxy compound is selected from ethylene glycol diglycidylether, propylene glycol diglycidylether, butanediol diglycidyl ether, hexanediol diglycidyl ether, the propanedioic acid 2-glycidyl ester, the hexanodioic acid 2-glycidyl ester, the glycol ether diglycidylether, the dipropylene glycol 2-glycidyl, the tripropylene glycol 2-glycidyl, neopentylglycol diglycidyl ether, glycerin diglycidyl ether, the tetramethylolmethane diglycidylether, trihydroxymethylpropanyltri diglycidyl ether, the tetramethylolmethane triglycidyl ether, T 55, two T 55s, two glycerine, four glycidyl ethers, tetramethylolmethane four glycidyl ethers, in Dipentaerythritol four glycidyl ethers or the cylohexanediol diglycidyl ether one or more.
5. the preparation method of ionic solidifying agent as claimed in claim 2 is characterized in that the poly-hydroxy sulfide compound is selected from two (2-hydroxyethyl) thioether, two (3-hydroxypropyl) thioether, two (2-hydroxypropyl) thioether, two (4-hydroxyl butyl) thioether, two (3-hydroxyl butyl) thioether, 1-(2-hydroxyethyl sulfenyl)-2-propyl alcohol, 3-(2-hydroxyethyl sulfenyl)-1-propyl alcohol, 1-(3-hydroxypropyl sulfenyl)-2-propyl alcohol, 1-(2-hydroxyethyl sulfenyl)-3-butanols, 4-(2-hydroxyethyl sulfenyl)-1-butanols, 1-(3-hydroxypropyl sulfenyl)-3-butanols, 1-(2-hydroxypropyl sulfenyl)-3-butanols, 4-(3-hydroxypropyl sulfenyl)-1-butanols, in 4-(2-hydroxypropyl sulfenyl)-1-butanols or 4-(3-hydroxyl butyl sulfenyl)-1-butanols one or more.
6. the preparation method of ionic solidifying agent as claimed in claim 2 is characterized in that described monobasic organic acid is selected from formic acid, acetic acid, propionic acid, butyric acid, lactic acid, 2,2-dimethylol propionic acid, 2, in 2-dimethylolpropionic acid, the phenylformic acid one or more.
7. the preparation method of ionic solidifying agent as claimed in claim 2 is characterized in that described polyisocyanates is selected from one or more in tolylene diisocyanate, '-diphenylmethane diisocyanate, polymethylene polyphenyl vulcabond, hexamethylene diisocyanate, xylylene diisocyanate, isophorone diisocyanate, dicyclohexyl methyl hydride isocyanic ester, trimethyl hexamethylene diisocyanate and the hydrogenated tolylene diisocyanate.
8. the preparation method of ionic solidifying agent as claimed in claim 2, it is characterized in that the described compound bearing active hydrogen that contains is selected from methyl alcohol, ethanol, propyl alcohol, butanols, hexanol, octanol, phenylcarbinol, phenylethyl alcohol, ethylene glycol monomethyl ether, ethylene glycol monobutyl ether, ethylene glycol ether, propylene glycol monomethyl ether, propylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monobutyl ether, Diethylene Glycol monohexyl ether, methyl ethyl ketoxime, acetoxime, cyclohexanone-oxime, diisopropylamine, 3, N-tert-butyl benzyl amine or the hexanolactam one or more.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107936225A (en) * | 2017-11-01 | 2018-04-20 | 盐城安诺电泳涂料科技有限公司 | A kind of thio salt modified epoxy and preparation method and application |
| CN108102504A (en) * | 2017-11-20 | 2018-06-01 | 盐城安诺电泳涂料科技有限公司 | A kind of cathode electrophoresis dope for improving automobile sealant xanthochromia and preparation method and application |
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| US5074979A (en) * | 1990-06-20 | 1991-12-24 | Ppg Industries, Inc. | Cationic resin containing blocked isocyanate groups suitable for use in electrodeposition |
| CN101362919A (en) * | 2008-09-25 | 2009-02-11 | 江泽平 | Single-component cationoid water-soluble epoxy-polyurethane anticorrosion primer system drying at 150 DEG C |
| US20120100394A1 (en) * | 2009-02-05 | 2012-04-26 | Basf Coatings Gmbh | Coating agent for corrosion-stable paints |
| CN102533044A (en) * | 2010-12-10 | 2012-07-04 | 比亚迪股份有限公司 | Cathode electrophoretic coating and preparation method thereof and cathode electrophoretic coating method |
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| CN1036048A (en) * | 1988-01-22 | 1989-10-04 | 巴斯福拉克和法本股份公司 | To conductive substrate painted method and adopt the substrate and the water-based electrophoretic coating liquid of the coating of this method |
| US5074979A (en) * | 1990-06-20 | 1991-12-24 | Ppg Industries, Inc. | Cationic resin containing blocked isocyanate groups suitable for use in electrodeposition |
| US5074979B1 (en) * | 1990-06-20 | 1995-02-28 | Ppg Industries Inc | Cationic resin containing blocked isocyanate groups suitable for use in electrodeposition |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN107936225A (en) * | 2017-11-01 | 2018-04-20 | 盐城安诺电泳涂料科技有限公司 | A kind of thio salt modified epoxy and preparation method and application |
| CN108102504A (en) * | 2017-11-20 | 2018-06-01 | 盐城安诺电泳涂料科技有限公司 | A kind of cathode electrophoresis dope for improving automobile sealant xanthochromia and preparation method and application |
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Address after: No.158, Huiping Road, Nanxiang Town, Jiading District, Shanghai, 201802 Patentee after: HLS COATING (SHANGHAI) Co.,Ltd. Patentee after: HAOLISEN CHEMICAL TECHNOLOGY (JIANGSU) Co.,Ltd. Address before: No.158, Huiping Road, Nanxiang Town, Jiading District, Shanghai, 201802 Patentee before: HLS COATING (SHANGHAI) Co.,Ltd. Patentee before: HAOLISEN CHEMICAL TECHNOLOGY JIANGSU CO.,LTD. |