CN1493627A - Pigment dispersion resin for cathode electrophoresis paint and its pigment paste - Google Patents
Pigment dispersion resin for cathode electrophoresis paint and its pigment paste Download PDFInfo
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- CN1493627A CN1493627A CNA03158229XA CN03158229A CN1493627A CN 1493627 A CN1493627 A CN 1493627A CN A03158229X A CNA03158229X A CN A03158229XA CN 03158229 A CN03158229 A CN 03158229A CN 1493627 A CN1493627 A CN 1493627A
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Abstract
A pigment dispersed resin for cathode electrophoretic paint is a cationic resin containing urea group and quaternary ammonium salt group and prepared by reaction between quaternary aminating agent and epoxy resin. Saaid quaternary aminating agent is prepared from aromatic polyisocyanate, alcohol and/or ether, and primary amine through addition and neutralizing by organic acid. Said epoxy resin is the biphenol A or F and glycide ether type one. A pigment slurry is prepared from said pigment dispersed resin, conventional pigment, catalyst and deionized water.
Description
Technical field
The present invention relates to a kind of cathode electrophoresis dope starches with pigment dispersing resin and pigment thereof.
Background technology
Cathode electrophoresis dope be 20th century the mid-1970s grow up and obtain rapidly a kind of Novel anticorrosion coating variety of industrial applications. Along with the continuous expansion of technology development and application, cathode electrophoresis dope no longer is confined to simple corrosion-resisting function, also takes into account the decoration effect of material. Possess cathode electrophoresis dope such as each color celluloid paint and the look lacquer of decoration effect, must include pigment (comprising coloring pigment and physique pigment). Therefore, the dispersiveness of pigment in cathode electrophoresis dope and tank liquor thereof is outstanding aobvious important. Normally pigment is disperseed or grinding distribution in pigment dispersing resin, make the pigment slurry and store for subsequent use. Therefore, the pigment dispersing resin of dispersive property excellence is one of key factor that improves cathode electrophoresis dope and coating performance thereof. The pigment dispersing resin that adopts in cathode electrophoresis dope at present is a kind of cation resin with quaternary ammonium salt base, normally take aromatic diisocyanate and epoxy resin as raw material, make semi-enclosed aromatic diisocyanate with sealer first, again it is added to and contains-react in the tertiary amine aminating agent of OH, then make season ammonium agent with organic acid neutralization, form with season ammonium agent open loop epoxy resin at last. Although this kind pigment dispersing resin makes moderate progress to the dispersive property of pigment, but, semi-enclosed aromatic diisocyanate with contain-during the reaction of the tertiary amine aminating agent of OH, at lower temperature, be difficult to abundant reaction, and at the higher temperatures degree, contain-uncle in the tertiary amine aminating agent of OH is amino, there is again the catalysis self-polymeric reaction in isocyanates, so quality and performance are difficult to stable and consistent. Therefore, with the pigment slurry that this kind pigment dispersing resin is made, its storage phase is still shorter, after the resin emulsion of this kind pigment slurry and cathode electrophoresis dope is made into electrophoresis groove liquid, form easily precipitation, the storage less stable of tank liquor, and then increased the load of coating equipment.
Summary of the invention
The object of the invention is to, a kind of cathode electrophoresis dope pigment dispersing resin is provided, this kind pigment dispersing resin quality is stable, and the dispersibility of pigment is further improved.
Another object of the present invention is, provide a kind of cathode electrophoresis dope that contains pigment dispersing resin of the present invention to starch with pigment, the storage phase of this kind pigment slurry prolongs, and the electrophoresis groove liquid storage and the construction stability that contain it are better, and can improve the saturating power of swimming of electrophoretic coating.
Realize the technical scheme of the present invention's the first purpose: a kind of cathode electrophoresis dope pigment dispersing resin, it is the cation resin that contains urea groups and quaternary ammonium salt base, after 3 times of dilutions of deionized water, 25 ℃ are surveyed its pH value is 7.0 ± 0.8, and electrical conductivity is 2500 ± 500 μ s/cm; Described cation resin is to be reacted in solvent by season ammonium agent and epoxy resin to form, and in the two when reaction, the mole of the active hydrogen of season ammonium agent and the epoxy radicals of epoxy resin is than being 1～1.1: 1; Described season ammonium agent is by a kind of aromatic polyisocyanate that contains at least 2-NCO isocyanates base, contain-one or more alcohols, alcohol ether class or its mixture of OH hydroxyl and have a kind of addition thing of primary amine of the ≡ of containing uncle N amino at least, form with organic acid neutralization again, during reaction-NCO :-OH :-NH2Mole than being 1: 0.7～0.5: 0.3～0.5, in and the time, organic acid-mole of COOH carboxyl and all ≡ uncle N amino is than being 1～1.1: 1, in the season ammonium agent in ≡ N and the raw material aromatic polyisocyanate-NCO mole than being 0.3～0.5: 1; Described epoxy resin is one or more bis-phenol A shrink ethoxylated glycerol type epoxy resin, Bisphenol F shrink ethoxylated glycerol type epoxy resin or the two mixture, and ring oxygen equivalent is 180～2000.
Above-mentioned pigment dispersing resin, described season ammonium agent are that the primary amine that will have at least a kind of ≡ of containing uncle N amino is added in the partially enclosed aromatic polyisocyanate in the preparation. Like this, overcome prior art will glue thick partially enclosed polyisocyanates be added to contain-tertiary amine of OH in, restive its dropwise operation and equipment is not the drawback of easy cleaning.
Above-mentioned pigment dispersing resin, described season ammonium agent in the preparation, the used aromatic polyisocyanate that contains at least 2-NCO base is 2,4-toluene di-isocyanate(TDI), triphenylmenthane-4,4 ', 4 " triisocyanate, benzene-1; 3,5-triisocyanate, toluene-2,4; 6-triisocyanate, 2; the 4-toluene di-isocyanate(TDI) with as the prepolymer, 4,4 of the glycerine of polyol, own triol, trihydroxy methyl propane or Ji Wusi alcohol etc. '-diphenyl-dimethylmethane-2,2 '; 5,5 '-four isocyanates etc.
Above-mentioned pigment dispersing resin, described season ammonium agent in the preparation, used alcohols is isopropyl alcohol, butanols, isobutanol, octanol, isooctanol, DMAE, diethylaminoethanol or dimethylamino isobutanol etc.; Used alcohol ether class is glycol monomethyl ether, ethylene glycol monobutyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, dihydroxypropane single-ether, propylene glycol monobutyl ether, DPE, Dipropylene glycol mono-n-butyl Ether or propane diols list phenyl ether etc.
Above-mentioned pigment dispersing resin, described season ammonium agent in the preparation, used primary amine is ethamine, propylamine, butylamine, dimethylaminopropylamine, diethylaminopropylamine or lignocaine amylamine etc.
Above-mentioned pigment dispersing resin, described season ammonium agent in the preparation, used organic acid is formic acid, acetic acid, propionic acid, butyric acid, lactic acid, adipic acid, alkyl sulfonic acid or alkylbenzene sulfonic acid etc.
Above-mentioned pigment dispersing resin, when generating the cation resin, used solvent is ketone class, alcohols, alcohol ether class or its mixture, and more suitable is glycol monomethyl ether, ethylene glycol monobutyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether or its mixture.
Realize the technical scheme of another purpose of the present invention: a kind of right that contains requires the cathode electrophoresis dope of 1 pigment dispersing resin to starch with pigment, it is that above-mentioned pigment dispersing resin, at least a pigment, organic tin catalyst and deionized water form, its pigment dispersing resin is 1: 1～10 with the solid weight ratio of pigment, pigment slurry solid weight is 40～60%, and the organic tin catalyst accounts for 0.5～2% of pigment slurry total weight of solids; After described pigment slurry was used 1 times of dilution of deionized water, 25 ℃ are surveyed its pH values was 7.0 ± 0.6, and electrical conductivity is 1200 ± 500 μ s/cm.
Above-mentioned pigment dispersing resin, the pigment of starching for the preparation of pigment is any coloring pigment commonly used, physique pigment or rust resisting pigment. Described coloring pigment is that titanium white, carbon black, iron oxide yellow, barba hispanica, middle chrome yellow, phthalocyanine are blue, phthalocyanine is green, red etc.; Described physique pigment is kaolin, talcum powder, calcium carbonate, mica, tripoli, alumina silicate etc.; Described rust resisting pigment is trbasic zinc phosphate, phosphoric acid iron, phosphoric acid aluminium, calcium phosphate, zinc oxide, molybdic acid calcium, mica iron oxide etc.
Above-mentioned pigment slurry cooperates with the resin emulsion with cathode electrophoresis dope and makes electrophoresis groove liquid, and this tank liquor contains 8～22% nonvolatile matter, and its face base ratio is 0.05～0.5. These resin emulsions are ring oxygen class or acrylic compounds, the preferably emulsion of epoxy-amine-polyurethane system.
Technique effect of the present invention: the pigment dispersing resin of technical solution of the present invention, appropriately selected season ammonium agent, particularly employed primary amine when preparation season ammonium agent wherein has a kind of primary amine with uncle's amino at least. Like this, made the stable season ammonium agent of quality with method simple to operation, the more important thing is, the pigment dispersing resin that makes with it not only has quaternary ammonium salt base to also have urea groups, particularly the existence of urea groups makes pigment dispersing resin to the dispersibility of pigment, is better than the existing quaternary ammonium salt pigment dispersing resin that does not contain urea groups. Because pigment dispersing resin of the present invention has a plurality of hydrophilic bases and oleophylic base and hydrophilic base to be positioned at the centre of whole molecule, and by controlling the proportioning that forms each component of pigment dispersing resin, makes its HLB value between 10～15. Therefore, pigment dispersing resin of the present invention has good wetability and permeability, when pigment disperses, it adsorbs at the pigment particles surface orientation, changed the surface nature of pigment particles, form electric double layer and spatial masking effect on the granules of pigments surface, prevent that the pigment particles gathering from making pigment particles keep the suspension state in water. So that contain pigment dispersing resin of the present invention and adopt the pigment slurry of technical solution of the present invention, its stability of storing stability and electrophoresis groove liquid all is better than starching (seeing Table 1 and 2) with the pigment of existing quaternary ammonium salt pigment dispersing resin preparation like this. In addition, because the primary amine of tertiary-amino-containing is arranged in the aminating agent, make the pigment dispersing resin that makes have higher electrical conductivity, the urea groups of being introduced by it simultaneously, wet film resistance when having increased the electrophoresis film forming, thereby pigment dispersing resin of the present invention can improve again swimming saturating power (seeing Table 3) when cooperating with the cathode electrophoresis dope emulsion.
Concrete enforcement mode
Below in conjunction with embodiment, the present invention is further described in detail, but is not limited to this.
Raw materials used among the following embodiment, be unless stated otherwise industrial goods, consumption is weight part.
Embodiment 1
(1) preparation season ammonium agent A
| Component | Material name | Consumption |
| Polyisocyanates | 2,4-toluene di-isocyanate(TDI) | 174 |
| Alcohols | Isooctanol | 130 |
| DMAE (tertiary-amino-containing) | 17.8 | |
| Primary amine | Diethylaminopropylamine (tertiary-amino-containing) | 104 |
| Organic acid | Acetic acid solution (50%) | 126 |
| Solvent | Butanone | 201.6 |
| Ethylene glycol monobutyl ether | 61.3 | |
| Wherein :-NCO :-OH :-NH2Mole than being 1: 0.6: 0.4;-COOH: the mole of ≡ N is than being 1.05: 1; The mole of ≡ N :-NCO is than being 0.5: 1. | ||
In the dried and clean reactor that thermometer, agitator, returned cold condenser and high-order groove etc. are housed, add 2,4-toluene di-isocyanate(TDI) and butanone, drip respectively isooctanol, DMAE, temperature is controlled at 35～50 ℃, after dropwising, about 50 ℃ of insulations 2 hours drip diethylaminopropylamine after insulation finishes, temperature is controlled at 35～50 ℃, after dropwising, be warming up to 80～90 ℃ of insulations 2.5 hours, add ethylene glycol monobutyl ether and be cooled to 75 ℃ after insulation finishes, add acetic acid solution, cooling discharge after stirring evenly is season ammonium agent A, and is for subsequent use.
(2) preparation pigment dispersing resin A
| Component | Material name | Consumption |
| Epoxy resin | Bisphenol A epoxide resin Epikote1001 (ring oxygen equivalent 480) | 120 |
| Bisphenol A epoxide resin Epikote3004 (ring oxygen equivalent 909) | 227.25 | |
| Season ammonium agent | A (active hydrogen equivalent 814.7) | 407.4 |
| Solvent | Ethylene glycol monobutyl ether | 231.5 |
| Wherein: the mole of the epoxy radicals of the active hydrogen of season ammonium agent and epoxy resin is than being 1: 1. | ||
In the dried and clean reactor that thermometer, agitator, returned cold condenser and high-order groove etc. are housed, add ethylene glycol monobutyl ether, be warming up to 80 ℃, add epoxy resin Epikote1001 and 3004, add season ammonium agent A after the dissolving, at 80～90 ℃ of insulations cooling discharge after 2.5 hours, make solid content and be 60.0% pigment dispersing resin A.
Embodiment 2
(1) preparation season ammonium agent B
| Component | Material name | Consumption |
| Polyisocyanates | Triphenylmenthane-4,4 ', 4 " triisocyanates | 244.7 |
| Alcohols | Isooctanol | 156 |
| Primary amine | Diethylaminopropylamine (tertiary-amino-containing) | 104 |
| Organic acid | Acetic acid solution (50%) | 96 |
| Solvent | Butanone | 320.5 |
| Wherein :-NCO :-OH :-NH2Mole than being 1: 0.6: 0.4;-COOH: the mole of ≡ N is than being 1: 1; The mole of ≡ N :-NCO is than being 0.4: 1. | ||
Except using above-mentioned raw materials and consumption instead, all the other are all by the condition of embodiment 1, and it is for subsequent use to make season ammonium agent B.
(2) preparation pigment dispersing resin B
| Component | Material name | Consumption |
| Epoxy resin | Bisphenol A epoxide resin Epikote1001 (ring oxygen equivalent 480) | 240 |
| Season ammonium agent | B (active hydrogen equivalent 1151.5) | 575.8 |
| Solvent | Ethylene glycol monobutyl ether | 160 |
| Wherein: the mole of the epoxy radicals of the active hydrogen of season ammonium agent and epoxy resin is than being 1: 1. | ||
Except using above-mentioned raw materials and consumption instead, all the other are all by the condition of embodiment 1, make solids content and be 60.0% pigment dispersing resin B.
Embodiment 3
(1) preparation season ammonium agent C
| Component | Material name | Consumption |
| Polyisocyanates | The TDI-TMP prepolymer | 547.2 |
| Alcohols | Isooctanol | 117 |
| DMAE (tertiary-amino-containing) | 13.4 | |
| Primary amine | Diethylaminopropylamine (tertiary-amino-containing) | 58.5 |
| Organic acid | Acetic acid solution (50%) | 72 |
| Solvent | Butanone | 113.9 |
| Wherein: TDI-TMP prepolymer of 2,4 - toluene diisocyanate and trimethylol propane prepolymer with Conventional method, the-NCO equivalent weight of 364.8 and a solids content of 60%; -NCO:-OH:-NH2The molar ratio of 1:0.7:0.3; -COOH: ≡ N molar ratio of 1:1; ≡ N:-NCO molar ratio of 0.4:1. | ||
In addition to the raw material and the amount of use, the remaining conditions of Example 1 according to prepare a quaternizing agent C
Spare.
(2) Preparation of pigment dispersion resin of C
| Constituent | Material name | Dosage |
| Epoxy | Bisphenol A epoxy resin Epikote1001 (epoxy equivalent 480) | 240 |
| Quaternization agent | C (AHEW 1536.7) | 768.4 |
| Solvent | Butoxyethanol | 160 |
| Wherein: the quaternizing agent and the epoxy reactive hydrogen groups molar ratio of 1:1. | ||
In addition to the raw material and the amount of use, the remaining conditions of Example 1 according to obtain a solids content of
60.0% of the pigment dispersion resin C.
Example 4
(1) Preparation of quaternizing agent D
| Constituent | Material name | Dosage |
| Polyisocyanate | TDI-TMP prepolymer (same as in Example 3) | 547.2 |
| Alcohols, ethers | Isooctanol | 68.3 |
| Butoxyethanol | 53.1 | |
| Dimethylaminoethanol (containing a tertiary amino group) | 13.4 | |
| Primary amine | Diethylamino propylamine (containing a tertiary amino group) | 48.8 |
| Organic acids | Acetic acid solution (50%) | 63 |
| Solvent | Butanone | 111.9 |
| Where:-NCO:-OH:-NH2The molar ratio of 1:0.75:0.25; -COOH: ≡ N molar ratio of 1:1; ≡ N:-NCO molar ratio of 0.35:1. | ||
In addition to the raw material and the amount of use, the remaining conditions of Example 1 according to prepare a quaternizing agent D
Spare.
(2) Preparation of Pigment Dispersion Resin D
| Constituent | Material name | Dosage |
| Epoxy | Bisphenol A epoxy resin Epikote1001 (epoxy equivalent 480) | 240 |
| Quaternization agent | D (AHEW 1725.1) | 862.6 |
| Solvent | Butoxyethanol | 160 |
| Wherein: the quaternizing agent and the epoxy reactive hydrogen groups molar ratio of 1:1. | ||
In addition to the raw material and the amount of use, the remaining conditions of Example 1 according to obtain a solids content of
60.0% of the pigment dispersion resin D.
Example 5
(1) Preparation of quaternizing agent E
| Constituent | Material name | Dosage |
| Polyisocyanate | TDI-TMP prepolymer (same as in Example 3) | 547.2 |
| Alcohols | Isooctanol | 107.3 |
| Dimethylaminoethanol (containing a tertiary amino group) | 13.4 | |
| Primary amine | Diethylamino propylamine (containing a tertiary amino group) | 68.4 |
| Organic acids | Acetic acid solution (50%) | 81 |
| Solvent | Butanone | 112.5 |
| Where:-NCO:-OH:-NH2The molar ratio of 1:0.65:0.35; -COOH: ≡ N molar ratio of 1:1; ≡ N:-NCO molar ratio of 0.45:1. | ||
In addition to the raw material and the amount of use, the remaining conditions of Example 1 according to prepare a quaternizing agent E
Spare.
(2) Preparation of pigment dispersion resin E
| Constituent | Material name | Dosage |
| Epoxy | Bisphenol A / F epoxy resin DER642 (epoxy equivalent 530) | 265 |
| Quaternization agent | E (AHEW 1377.3) | 688.7 |
| Solvent | Butoxyethanol | 175 |
| Wherein: the quaternizing agent and the epoxy reactive hydrogen groups molar ratio of 1:1. | ||
In addition to the raw material and the amount of use, the remaining conditions of Example 1 according to obtain a solids content of
60.0% pigment dispersion resin of E.
The pigment dispersion resin of A, B, C, D and E, respectively, was diluted with deionized water three times, the 25
℃ pH values were measured in the range of 7.0 ± 0.8, conductivity were 2500 ± 500μs/cm ranges.
Comparative Example 1 Preparation of which does not contain a pigment dispersion resin ureido F
(1) Preparation of quaternizing agent F
| Constituent | Material name | Dosage |
| Polyisocyanate | Isooctanol semi-enclosed TDI butanone solution (solid Content of 65%) | 468.2 |
| Tertiary amines | Dimethylaminoethanol (containing tertiary amino alcohols) | 89 |
| Organic acids | Acetic acid solution (50%) | 120 |
| Solvent | Butanone | 20.2 |
| Butoxyethanol | 58.2 | |
| Wherein the semi-closed TDI ethylhexanol butanone solution was prepared as follows: Equipped with a thermometer, a stirrer, a reflux condenser and a dry cleaner and other elevated tank reactor, plus Into 348 parts of TDI, 327.7 parts of methyl ethyl ketone and 0.6 parts of dibutyl tin dilaurate was heated to 35 ℃, was added dropwise 260 isooctanol, temperature controlled at 35 ~ 50 ℃, after dropping about 50 ℃ and then incubated for 5 hours to the next, A solids content of 65%. | ||
Equipped with a thermometer, a stirrer, a reflux condenser and a dry cleaner and other elevated tank reactor,
In the above formulation were added and butanone dimethylaminoethanol, heating to 35 ℃, added ethylhexanol half closed
TDI butanone solution, the temperature controlled at 35 ~ 50 ℃, plus finished heating to 80 ~ 90 ℃ and incubated for 2.5 hours
After heat ethylene glycol monobutyl ether, and cooled to 75 ℃, adding acetic acid solution, stirring
After cooling the material is free of quaternary ammonium ureido agent F.
(2) Preparation of pigment dispersion resin F
| Constituent | Material name | Dosage |
| Epoxy | Bisphenol A epoxy resin Epikote1001 (epoxy equivalent 480) | 240 |
| Quaternization agent | F (AHEW 1725.1) | 377.8 |
| Solvent | Butoxyethanol | 160 |
In addition to the raw material and the amount of use, the remaining conditions of Example 1 according to obtain a solids content of
The pigment dispersion resin of 60.0% F, the resin does not contain urea groups.
Example 6 Preparation of cathodic electrophoretic coating pigment paste
(1) black pigment paste
| Constituent | Name and specifications of raw materials | Dosage |
| The pigment dispersion resin | A (Example 1 was made, solid content 60%) | 300 |
| Pigment | Kaolin | 406.5 |
| Carbon black | 35 | |
| Catalyst | Dibutyl tin oxide | 8.5 |
| Deionized water | Industrial, Ks ≤ 15μs/cm (25 ℃) | 650 |
After mixing the above ingredients, a sand mill to a fineness of dispersion ≤ 15μm, prepared pigments
Slurry solids content of 45%, the pigment to resin solids weight ratio of 2.5:1, dibutyl tin oxide pigment account
The slurry 1.3% of the total weight of solids.
(2) gray pigment paste
| Constituent | Name and specifications of raw materials | Dosage |
| The pigment dispersion resin | A (Example 1 was made, solid content 60%) | 220 |
| Pigment | Kaolin | 132 |
| Titanium | 380 | |
| Carbon black | 10 | |
| Catalyst | Dibutyl tin oxide | 6 |
| Deionized water | Industrial, Ks ≤ 15μs/cm (25 ℃) | 452 |
After mixing the above ingredients, a sand mill to a fineness of dispersion ≤ 15μm, prepared pigments
Slurry solids content of 55%, the pigment to resin solids weight ratio of 4:1, representing color dibutyl tin oxide
The slurry 0.9% of the total weight of solids.
Examples 7 to 10
In addition to the formulation of Example 6 A pigment dispersing resin, a pigment dispersion resin, respectively, B, C, D
Substituted and E, the other raw materials, usage and operation were the same as in Example 6 and the preparation of the corresponding black and gray, respectively,
Color pigment paste.
Comparative Example 2
Comparative Example 2...
Comparative Example 2...
In Examples 6 to 10 and Comparative Example 2 Preparation of a black pigment, the pigment slurry storage stability study
Sex. The pigment paste is placed above room temperature storage, monthly visual pigment dispersed state with Fineness gauge
Fineness study, a total of 4 months of storage, the results shown in Table 1.
Table 1 black pigment slurry storage stability test table
Note: ○ ◎ as good condition as a small amount of liquid precipitation △ is a small amount of soft sediment
hard to have a small amount of precipitation ◇ no significant return for the fineness fineness obvious coarse ◆ To return coarse
Being translated ...
Being translated ...
The Examples 6 to 10 and Comparative Example 2 Preparation of a pigment paste of the black pigment paste, used in accordance with the
Patent 98,111,237.4 resin emulsion prepared by emulsion: deionized water: Black pigment paste = 4:5:1,
Dubbed two liters cathodic electrodeposition coating bath, and stirred at 40 ℃ storage two weeks later, with a 380 mesh filter,
In electrophoretic coating residue on the filter was evaluated by weight, more weight showed poorer storage stability. Investigation Results
Results are shown in Table 2.
Table 2 cathodic electrodeposition coating bath storage stability test table
| Examples pigment paste | 6 | 7 | 8 | 9 | 10 | Comparative Example 2 |
| Storage stability evaluation (mg) | 15 | 5 | 4 | 8 | 9 | 35 |
Seen from Table 2, the use does not contain a pigment dispersion resin ureido F made of pigment paste (Comparative Example 2),
Preparation of cathodic electrophoretic coating bath, the storage stability was poor, indicating that use of a tertiary amino group with primary
And the resulting amine into a urea group, so that the prepared pigment dispersion resin has excellent dispersibility, and thus confer
Bath better storage stability. Examples 7 to 10 containing ≥ 3 using the isocyanate groups of the aromatic polyisocyanate
Cyanate ester resin prepared pigment dispersion, the dispersion is superior to Example 6 containing two isocyanate
An aromatic ester polyisocyanates prepared pigment dispersion resin, the corresponding storage-stable electrophoretic bath
Is also better.
...
Seen from Table 2, the use does not contain a pigment dispersion resin ureido F made of pigment paste (Comparative Example 2),
Preparation of cathodic electrophoretic coating bath, the storage stability was poor, indicating that use of a tertiary amino group with primary
And the resulting amine into a urea group, so that the prepared pigment dispersion resin has excellent dispersibility, and thus confer
Bath better storage stability. Examples 7 to 10 containing ≥ 3 using the isocyanate groups of the aromatic polyisocyanate
Cyanate ester resin prepared pigment dispersion, the dispersion is superior to Example 6 containing two isocyanate
An aromatic ester polyisocyanates prepared pigment dispersion resin, the corresponding storage-stable electrophoretic bath
Is also better.
...
Following the procedure of Example 12 was formulated gray cathodic electrodeposition coating bath, to curing for 48 hours,
At 250 volts, bath temperature 28 ℃, electrophoresis time 3 minutes under the conditions determined by the Ford box
Throwing power, and the results are shown in Table 3.
Table 3 cathodic electrophoretic coating inspection table throwing power
| Examples pigment paste | 6 | 7 | 8 | 9 | 10 | Comparative Example 2 |
| Throwing Power Rating (cm) | 17.5 | 18.2 | 18.5 | 17.8 | 17 | 16.3 |
Seen from Table 3, the use of a primary amine containing a tertiary amino group-containing urea groups prepared pigment dispersion resin,
Pigment paste corresponding electrophoretic coating can improve the throwing power (Examples 6 to 10 were higher than those of Comparative Example 2).
From the results of Tables 1 to 3 show, in the conventional quaternary ammonium salt group-containing pigment dispersion resin, the introduction of the containing
Primary amines of the tertiary amino groups of urea produced, to improve the pigment dispersibility, storage stability and pigment paste electrophoresis tank
Fluid stability achieved significant results, but also improve the throwing power. Therefore, the cathodic electrodeposition coating and its
Has obvious benefits.
Claims (9)
- A method of cathodic electrodeposition coating pigment dispersing resin, characterized in that: it contains a urea group and a quaternary Ammonium salt cationic resin with deionized water three times diluted, 25 ℃ measured pH of 7.0 ± 0.8, electric Conductivity of 2500 ± 500μs/cm; said cation resin is a quaternizing agent with an epoxy resin in a solvent By reaction, both the reaction, the quaternary ammonium active agent is hydrogen and the epoxy group molar ratio of 1 to 1.1:1; said quaternizing agent is an at least two-NCO containing isocyanate groups of an aromatic polyisocyanate Isocyanate, hydroxyl-OH containing one or more alcohols, glycol ethers or mixtures thereof and at least one tertiary amino group-containing ≡ N primary amine adduct, and then the organic acid from the reaction Time-NCO:-OH:-NH ...2A method of cathodic electrodeposition coating pigment dispersing resin, characterized in that: it contains a urea group and a quaternary Ammonium salt cationic resin with deionized water three times diluted, 25 ℃ measured pH of 7.0 ± 0.8, electric Conductivity of 2500 ± 500μs/cm; said cation resin is a quaternizing agent with an epoxy resin in a solvent By reaction, both the reaction, the quaternary ammonium active agent is hydrogen and the epoxy group molar ratio of 1 to 1.1:1; said quaternizing agent is an at least two-NCO containing isocyanate groups of an aromatic polyisocyanate Isocyanate, hydroxyl-OH containing one or more alcohols, glycol ethers or mixtures thereof and at least one tertiary amino group-containing ≡ N primary amine adduct, and then the organic acid from the reaction Time-NCO:-OH:-NH ...
- 2, according to claim 1, wherein the pigment dispersion resin, wherein: said quaternizing agent Preparation, is at least one tertiary amino group containing ≡ N been added to the partial closure of the primary amine of the aromatic polyisocyanate Acid esters.
- 2, according to claim 1, wherein the pigment dispersion resin, wherein: said quaternizing agent Preparation, is at least one tertiary amino group containing ≡ N been added to the partial closure of the primary amine of the aromatic polyisocyanate Acid esters....
- 4, according to claim 1, wherein the pigment dispersion resin, wherein: said quaternizing agent Preparation, the use of alcohol is isopropanol, butanol, isobutanol, octanol, iso-octanol, dimethylaminoethanol, Diethylamino, dimethylamino ethanol or isobutanol; ethers used are ethylene glycol monoethyl ether, ethylene glycol monobutyl Ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol monoethyl ether, propylene glycol monobutyl ether, dipropylene Glycol monoethyl ether, diethylene glycol monobutyl ether or propylene glycol monophenyl ether.
- 5, according to claim 1, wherein the pigment dispersion resin, wherein: said quaternizing agent Preparation, the use of primary amines are ethylamine, propylamine, butylamine, dimethylamino propylamine, diethylamino propylamine or di Ethylamino amylamine.
- 6, according to claim 1, wherein the pigment dispersion resin, wherein: said quaternizing agent Preparation, the use of organic acids are formic acid, acetic acid, propionic acid, butyric acid, lactic acid, adipic acid, alkyl sulfonic acid Or alkyl sulfonic acid.
- 7, according to claim 1, wherein the pigment dispersion resin, characterized by: generating cationic resin When the solvent is ketones, alcohols, ethers or mixtures thereof.
- 8 A pigment dispersion according to claim 1 containing resin cathodic electrophoretic coating pigment paste, characterized in that On: it is a pigment dispersion of claim 1 a resin, at least one pigment, an organic tin catalyst, and to Composed of deionized water, and the pigment of the pigment dispersion resin solids weight ratio of 1:1 to 10 by weight of solids pigment paste 40 to 60%, representing an organic tin catalyst slurry weight of total solids pigment 0.5 to 2%; said pigment slurry Used 1-fold diluted with deionized water, 25 ℃ measured with a pH of 7.0 ± 0.6, conductivity of 1200 ± 500μs/cm.
- 9, according to claim 8, wherein the pigment paste, characterized in that: for the pigment preparation of the pigment paste Is any conventional coloring pigment, extender pigment or a rust-preventive pigment.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 03158229 CN1218000C (en) | 2003-09-10 | 2003-09-10 | Pigment dispersion resin for cathode electrophoresis paint and its pigment paste |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 03158229 CN1218000C (en) | 2003-09-10 | 2003-09-10 | Pigment dispersion resin for cathode electrophoresis paint and its pigment paste |
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| Publication Number | Publication Date |
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| CN1493627A true CN1493627A (en) | 2004-05-05 |
| CN1218000C CN1218000C (en) | 2005-09-07 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 03158229 Expired - Fee Related CN1218000C (en) | 2003-09-10 | 2003-09-10 | Pigment dispersion resin for cathode electrophoresis paint and its pigment paste |
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100410339C (en) * | 2006-10-18 | 2008-08-13 | 江南大学 | Method for preparing cationic water-based pigment colour paste |
| CN101851456B (en) * | 2010-05-13 | 2012-04-18 | 湖南伟邦汽车涂料有限公司 | High-gloss cathodic electrophoretic paint and preparation method thereof |
| CN101583678B (en) * | 2007-01-16 | 2013-07-17 | 株式会社Kcc | A cationic resin for pigment dispersion and an electrodepositable paint composition comprising the same |
| CN103554352A (en) * | 2013-09-29 | 2014-02-05 | 中国海洋石油总公司 | Pigment dispersion resin used for acrylic series cathode electrophoretic coating and pigment slurry thereof |
| CN106700028A (en) * | 2016-11-28 | 2017-05-24 | 中海油常州涂料化工研究院有限公司 | Sulfonium salt type dispersion resin for cathodic electrophoretic paint and preparation method of sulfonium salt type dispersion resin |
| CN109111563A (en) * | 2018-07-19 | 2019-01-01 | 浩力森化学科技（江苏）有限公司 | Pigment dispersing resin and preparation method thereof for bottom surface unification cathode electrophoresis dope |
| CN109679453A (en) * | 2018-12-28 | 2019-04-26 | 尚志造漆(昆山)有限公司 | A kind of preparation method of water-dispersion type cathode epoxy electrophoretic coating |
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2003
- 2003-09-10 CN CN 03158229 patent/CN1218000C/en not_active Expired - Fee Related
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100410339C (en) * | 2006-10-18 | 2008-08-13 | 江南大学 | Method for preparing cationic water-based pigment colour paste |
| CN101583678B (en) * | 2007-01-16 | 2013-07-17 | 株式会社Kcc | A cationic resin for pigment dispersion and an electrodepositable paint composition comprising the same |
| CN101851456B (en) * | 2010-05-13 | 2012-04-18 | 湖南伟邦汽车涂料有限公司 | High-gloss cathodic electrophoretic paint and preparation method thereof |
| CN103554352A (en) * | 2013-09-29 | 2014-02-05 | 中国海洋石油总公司 | Pigment dispersion resin used for acrylic series cathode electrophoretic coating and pigment slurry thereof |
| CN103554352B (en) * | 2013-09-29 | 2016-01-20 | 中国海洋石油总公司 | A kind of Acrylate Cathodic Electrodeposition Coatings pigment dispersing resin and pigment slurry thereof |
| CN106700028A (en) * | 2016-11-28 | 2017-05-24 | 中海油常州涂料化工研究院有限公司 | Sulfonium salt type dispersion resin for cathodic electrophoretic paint and preparation method of sulfonium salt type dispersion resin |
| CN106700028B (en) * | 2016-11-28 | 2019-03-22 | 中海油常州涂料化工研究院有限公司 | A kind of cathode electrophoresis dope sulfosalt type dispersion resin and preparation method thereof |
| CN109111563A (en) * | 2018-07-19 | 2019-01-01 | 浩力森化学科技（江苏）有限公司 | Pigment dispersing resin and preparation method thereof for bottom surface unification cathode electrophoresis dope |
| CN109111563B (en) * | 2018-07-19 | 2021-06-15 | 浩力森化学科技（江苏）有限公司 | Pigment dispersion resin for primer-topcoat cathode electrophoretic coating and preparation method thereof |
| CN109679453A (en) * | 2018-12-28 | 2019-04-26 | 尚志造漆(昆山)有限公司 | A kind of preparation method of water-dispersion type cathode epoxy electrophoretic coating |
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| Publication number | Publication date |
|---|---|
| CN1218000C (en) | 2005-09-07 |
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