CN1047398C - Resin used for cathode electrodeposition paint and its production and application - Google Patents
Resin used for cathode electrodeposition paint and its production and application Download PDFInfo
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- CN1047398C CN1047398C CN94111495A CN94111495A CN1047398C CN 1047398 C CN1047398 C CN 1047398C CN 94111495 A CN94111495 A CN 94111495A CN 94111495 A CN94111495 A CN 94111495A CN 1047398 C CN1047398 C CN 1047398C
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Abstract
The present invention relates to epoxy amine, polyamine, masked isocyanate and preparation and application thereof. Cathodic electrodeposition paint with excellent use property can be made from resin and home-made raw material and has the same product performance as similar products abroad.
Description
The present invention relates to a kind of epoxy amine-polyamines-blocked isocyanate resin and preparation and application of used for cathode electrodeposition paint.
Cathode electrodeposition paint is that the mid-1970s grows up and obtains a kind of novel electrocoating paint of industrial applications rapidly.Because it has advantages such as good non-corrosibility, mechanical property, permeability ratio and automation paint ability, is subjected to the attention of automotive industry very soon, had 91% in the world car ultimate production by 1988 and adopt cathode electrodeposition paint to make priming paint.
In China, succeed in developing the phenol aldehyde modified epoxy polyamine cationic type cathode electrodeposition paint initial stage eighties introduces PPG and Hoechst two big systems in succession from states such as Japan, Austria cathode electrodeposition paint the latter stage seventies voluntarily.
But, because foreign technology is harsh to the raw materials used requirement of preparation coating, the localization rate of parts and components is lower, so be difficult to large-scale popularization, and independently developed phenol aldehyde modified epoxy polyamine cationic pad cathode electrodeposition paint technology, still belong to early stage cathode electrodeposition paint, this product corrosion-resistant, electrophoresis liquid pH value is low, permeability ratio is low.Therefore, along with the development of Domestic Automotive Industry, be badly in need of a kind of on product performance can with external like product quite, the starting material production domesticization, and in aspect good quality production such as operability and usability.
The objective of the invention is with the home products is raw material, and a kind of non-corrosibility of exploitation preparation is good, permeability ratio is high, electrophoresis liquid is near resin used for cathode electrodeposition paint and the preparation and the application of neutrality and galvanic deposit good cycling stability
The method that realizes the object of the invention is epoxy amine-polyamines-blocked isocyanate resin that a kind of suitable electrocoating paint of preparation is used.
This resin constitutes adducts by three kinds of components: component (1) is that the amination degree is 20～70% epoxy amine affixture; Component (2) is the polyamines of ketone sealing; Component (3) is the isocyanic ester with the compound sealing of band reactive hydrogen.Above-mentioned 3 kinds of components are carried out heat by following prescription weighing, mixing, intensification pieces together, (Ge Shi manages 25 ℃ of mensuration to reach predetermined viscosity 3～5 seconds, portions of resin butanols=6: 4) after, be cooled to below 80 ℃, adding lactic acid and glycol ether stir and can make water soluble resin.Prescription
Component 1 epoxy amine affixture 45～55 (weight percentage, down together)
Component 2 polyamines (solids constituent 90 ± 2%) 10～20
Component 3 blocked isocyanates 18～25
Neutralizing agent lactic acid (industrial goods) 1.5～2.5
Solvent glycol ether (industrial goods) 5～9
Wherein the preparation method of 3 kinds of components is:
Component 1 is that Resins, epoxy is added aminating agent by the amination degree, and making it to reflux, to form the amination degree be 20～70% epoxy amine affixture.Used Resins, epoxy can be high molecular weight bisphenol A type Resins, epoxy of different varieties and composition thereof; Used aminating agent can be low molecular weight amine (as, diethylamine, triethylamine, Trimethylamine 99 etc.), hydramine (as, Monoethanolamine MEA BASF, diethanolamine, trolamine etc.) or the mixture of above-mentioned amine.
Component 2 is to be catalyzer with the acids, makes with ketone and the heating of polyphosphazene polymer acid amides, backflow, dehydration, and wherein ketone is acetone, butanone, methylethylketone, methyl iso-butyl ketone (MIBK) etc.; Polymeric amide is the polyamine compounds of dimeracid, trimer acid etc., and the amine value is 315 ± 15mg KOH/g, and acids is a mineral acid, example hydrochloric acid.
Component 3 is in the presence of organotin catalysts, and the encapsulant of isocyanic ester with the band reactive hydrogen heated, and reacts to free isocyanate groups≤2% and makes.Used isocyanic ester is tolylene diisocyanate, diphenylmethanediisocyanate etc.; Encapsulant is the compound of band reactive hydrogens such as the pure ethers of the list of alcohols, dibasic alcohol, polyethers and methyl aceto acetate; Organotin catalysts is a dibutyl tin laurate.
Material fat of the present invention can adopt the existing general production unit of China to be mixed with the coating that is applicable to cathode electrodeposition by following prescription and method: after part resin, pigment, filler and art stir in will fill a prescription (face/base is than＞1.5), be ground to fineness＜30 μ m with triple-roller mill, polishing residual content resin and butanols again, with homogenizer stir well even after, measure solids constituent and transfer to solids constituent 70 ± 2% with distilled water.
(A) red iron oxide base paint formulation
Resin 60.0～65.0 of the present invention (weight percentage, down together)
Red iron oxide 12.0～18.0
Butanols 1.0～2.5
China clay 5.0～8.0
Water 10.0～15.0
(B) black semi-gloss paint
Resin 80.0～90.0 of the present invention (weight percentage, down together)
Carbon black 3.0～6.5
China clay 5.0～8.0
Molybdenum red 1.0～3.0
Butanols 1.0～3.0
Above-mentioned coating is made into electrophoresis liquid, and its solid is divided into 16～20%, and the pH value is 6.0～6.5, and specific conductivity is 1200 ± 400 μ s/cm, adopts conventional electrophoresis method to carry out electrophoretic painting, 150～250 volts of voltages, 23～27 ℃ of electrophoresis groove liquid temperature.
Adopt the electrocoating paint of resin of the present invention preparation to carry out cathode electro-coating, permeability ratio 〉=70%, coulombic efficiency 〉=25mg/c, the gained appearance of film is evenly smooth, and thickness reaches 19～24 μ m, salt spray resistance 〉=600 hour, shock-resistant (square impact) 50cm, elasticity≤3mm.
The present invention compares with original technology (phenol aldehyde modified epoxy polyamine cationic type resin), by child epoxy amine-polyamines of the present invention-blocked isocyanate resin, adopt the superpolyamide class to seal back and epoxy amine addition with ketone, not only improved the mechanical property of filming, and this resin still can be stablized in the electrophoresis liquid of pH6.0～6.5, thereby face, the dispersiveness of filler in electrophoresis liquid also are improved.Like this, utilize the cathode electrodeposition paint of resin preparation of the present invention good non-corrosibility, permeability ratio height, electrophoresis liquid to be arranged near neutrality and galvanic deposit good cycling stability.
In addition, the present invention adopts the isocyanic ester of free isocyanate groups≤2% to make linking agent, and feasible cathode electrodeposition paint system with this resins can adopt inexpensive butanols to make solubility promoter.
The starting material that use for the present invention are home made article, thus reduced cost, and all suitable at aspects such as former lacquer performance, tank liquor performance, use properties and paint film properties with external like product.
Giving an actual example below specifies the present invention, but is not limited to this.
The preparation of example 1 ketone sealing polyamines
(1) prescription name of an article specification dosage (Kg) polymeric amide TY-300 amine value 300 ± 15mg KOH/g
(chemical plant, Yan'an, Tianjin) 510.0 methyl iso-butyl ketone (MIBK) Shanghai solvent factories, industrial goods 180.5 hydrochloric acid industrial goods or reagent 0.08
(2) technology:
In the reactor that thermometer, agitator, reflux water-dividing device are housed, the polyamide resin and the methyl that add formula ratio are butyl ketone, back adding hydrochloric acid and intensification stir, when reaching about 120 ℃, reaction mass begins reflux dewatering, temperature of reaction constantly raises simultaneously, the anhydrous reaction end (during dehydration temperature must not＞230 ℃) that is when deviating from, be cooled to then about 170 ℃, unnecessary methyl iso-butyl ketone (MIBK) is taken out in decompression, then is cooled to 80 ℃ rapidly with in the bottom discharge and the dry closed unit of crossing of packing into stand-by (should keep away water during storage).
The preparation of example 2 blocked isocyanates
(1) prescription
Name of an article specification dosage (Kg)
Tolylene diisocyanate (TDI) 2,4 body burdens 99.8% 290.0
Polyethers N-220 molecular weight 2000 ± 200 130.0
Hydroxyl value 56 ± 4mg KOH/g
(Nanjing plastic factory industry product)
Glycol monomethyl ethanol industry product (Tianjin Chemical Plant) 260.0
Dibutyl tin laurate 10% xylene solution 0.30
(2) technology
In the low-temp reaction still of thermometer, agitator, reflux exchanger and dropping funnel is housed, after adding TDI starts stirring, add dibutyl tin laurate and be warming up to 45 ℃ and begin to drip ethylene glycol monoethyl ether (thermopositive reaction), the control rate of addition remains on below 70 ℃ temperature of reaction, add and be incubated 1 hour again, add polyethers and be warming up to 90 ℃ and be incubated 3 hours, sampling and measuring free isocyanate groups content, treat its value＜2% o'clock, be cooled to 60 ℃ with bottom discharge, be placed in the exsiccant encloses container standby.
The heat of the preparation of example 3 epoxy amine affixtures and bad oxygen amine-polyamines-sealing tolylene diisocyanate resin is pieced together
(1) prescription name of an article specification dosage (Kg) epoxy resin epoxide number 0.12 (Wuxi resin processing plant) 210.0 butanols industrial goods, 70.5 methyl iso-butyl ketone (MIBK) industrial goods (Shanghai solvent factory) 48.5 triethanolamine industrial goods (Lik-Sang chemical plant, Tianjin) 3.05 diethanol amine industrial goods (Lik-Sang chemical plant, Tianjin) 15.5 modified polyamine resins (example 1) 120.0 blocked isocyanates (example 2) 140.5 diglycol industrial goods (Beijing Orient oil plant) 50.6
Lactic acid food grade or industrial goods (Suzhou the 4th pharmaceutical factory) 13.0
(2) technology
Thermometer is being housed, agitator, the Resins, epoxy that adds formula ratio in the reactor of dropping funnel and reflux exchanger, butanols, methyl iso-butyl ketone (MIBK), slowly heat up and treat to begin to stir after the Resins, epoxy fusing evenly, add trolamine and be warming up to reflux temperature, be incubated 1 hour, again diethanolamine is slowly splashed into, reduce to 110 ℃ in the reflux temperature insulation after 1 hour, add modified polyamine resin and blocked isocyanate, be warming up to 120 ℃ and carry out the heat assembly, be incubated viscosimetric after 1 hour, treat that viscosity reaches (25 ℃ of Ge Shi pipe viscosity 3.4～4.6 seconds, portions of resin butanols=6: 4), be cooled to below 80 ℃, add lactic acid and glycol ether, the discharging that stirs is resin of the present invention.
Example 4 red iron oxide base paint formulation and performances
(1) prescription
Name of an article specification dosage (Kg)
The red iron oxide wet method, Shanghai iron oxide red factory 17.0
Butanols industrial goods 1.5
China clay Suzhou produces 7.1
Resin solids of the present invention 70% 65.0
Water distilled water or remove high sub-water 11.0
(2) electrocoating paint solution properties
Solids constituent 16～20% pH6.0～6.5 specific conductivity, 1200 ± 400 μ s/cm
(3) electrophoretic painting characteristic
23～27 ℃ of electrophoresis groove liquid temperature
Electrodeposition time 120～180 seconds
150～250 volts of voltages
170 ℃/30 seconds storing temperature/time
Permeability ratio (steel pipe method) 〉=70%
Coulombic efficiency 〉=25mg/c
(4) film performance
Outward appearance is evenly smooth
Thickness 18～24 μ m
Pencil hardness＞2H
Sticking power (drawing the circle method)≤2 is slow
Elasticity≤3mm
Shock strength (square impact) 50cm
Gloss 45 °＞60%
Anti-40 ℃ of distilled water 〉=1000 hour
Salt spray resistance 〉=720 hour
4 months storage periods (0～30 ℃)
Weight loss on heating ≯ 10%
Claims (10)
1, a kind of epoxy amine-polyamines of used for cathode electrodeposition paint-blocked isocyanate resin, it is characterized in that, this resin is 20～70% epoxy amine affixture 45～55 (weight percentage) by (1) amination degree, (2) with polyamines (solids constituent 90 ± 2%) 10～20 (weight percentage) of ketone sealing, (3) use the adducts of three kinds of components of isocyanic ester of the compound sealing of being with reactive hydrogen to reach (4) organic acid neutralizing agent 1.5～2.5 (weight percentage) and (5) pure ethers organic solvents 5～9 (weight percentage) are formed.
2, according to the described resin of claim 1, it is characterized in that, component 1 is the quantity of determining according to the amination degree, with Resins, epoxy and aminating agent reflux, make it amination 20～70% and make, use therein Resins, epoxy is high molecular weight bisphenol A type Resins, epoxy of different varieties and composition thereof; Aminating agent is low molecular weight amine, hydramine or is the mixture of above-mentioned two kinds of amine.
According to the described resin of claim 2, it is characterized in that 3, the low molecular weight amine in the preparation component 1 used aminating agent is diethylamine, triethylamine or Trimethylamine 99; Hydramine is Monoethanolamine MEA BASF, diethanolamine or trolamine.
According to the described resin of claim 1, it is characterized in that 4, component 2 is to be catalyzer with acid, make with ketone and the heating of polyphosphazene polymer amides, backflow, dehydration.
According to the described resin of claim 4, it is characterized in that 5, preparation component 2 used ketones are acetone, butanone, methylethylketone or methyl iso-butyl ketone (MIBK); Polymeric amide is the polyamine compounds of dimeracid or the polyamine compounds of trimer acid; Acid is mineral acid.
According to the described resin of claim 1, it is characterized in that 6, component 3 is in the presence of organotin catalysts,, react to free isocyanate groups≤2% and make the heating of the compound of isocyanic ester and encapsulant-band reactive hydrogen.
According to the described resin of claim 6, it is characterized in that 7, preparation component 3 used isocyanic ester are tolylene diisocyanate, diphenylmethanediisocyanate or hexamethylene diisocyanate; The compound of encapsulant-band reactive hydrogen is the pure ethers of list, polyethers or the methyl aceto acetate of alcohols, dibasic alcohol; Organic catalyst is a dibutyl tin laurate.
8, according to the preparation method of the described resin of one of claim 1～7, it is characterized in that, formula ratio by claim 1, heat is carried out in the isocyanic ester intensification of epoxy amine affixture, polyamines and sealing pieces together, reached predetermined viscosity 3～5 seconds after (Ge Shi manages viscosity, 25 ℃, portions of resin butanols=6: 4), be cooled to below 80 ℃, adding organic acid neutralizing agent and pure ethers organic solvent stir and get final product.
According to the preparation method of the described resin of claim 8, it is characterized in that 9, used organic acid neutralizing agent is lactic acid, formic acid, acetate or sulfonic acid among this preparation method; Alcohol ethers organic solvent be-diglycol ethylene, ethylene glycol ethyl ether, diethylene glycol monomethyl ether or glycol ether pair butyl ether.
10, supply used for cathode electrodeposition paint according to the described resin of one of claim 1～9, it is characterized in that, this coating takes by weighing resin (part), pigment, filler and water by following prescription (face/base is than＞1.5), be ground to fineness＜30 μ m with three rollers after stirring, add residual content resin and butanols again, with high speed agitator stir well even after, measure solids constituent and transfer to solid and be divided into 70 ± 2% with distilled water
A, iron oxide red primer prescription
Resin 60～65 of the present invention (weight percentage, down together)
Red iron oxide 12～18
Butanols 1.0～2.5
China clay 5～8
Water 10～15
B, black semi-gloss paint
Resin 80～90 of the present invention (weight percentage, down together)
Carbon black 3.0～6.5
China clay 5～8
Molybdenum red 1～3
Butanols 1～3.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN94111495A CN1047398C (en) | 1994-11-02 | 1994-11-02 | Resin used for cathode electrodeposition paint and its production and application |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN94111495A CN1047398C (en) | 1994-11-02 | 1994-11-02 | Resin used for cathode electrodeposition paint and its production and application |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1122353A CN1122353A (en) | 1996-05-15 |
| CN1047398C true CN1047398C (en) | 1999-12-15 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN94111495A Expired - Fee Related CN1047398C (en) | 1994-11-02 | 1994-11-02 | Resin used for cathode electrodeposition paint and its production and application |
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Families Citing this family (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US8062760B2 (en) * | 2008-06-19 | 2011-11-22 | Basf Coatings Gmbh | Electrocoat composition and process |
| CN102924684B (en) * | 2012-10-18 | 2014-04-09 | 铜陵市陵阳化工有限责任公司 | Method for preparing isocyanate cross-linking agent prepolymer |
| CN103146295B (en) * | 2013-03-01 | 2015-06-03 | 广东科德化工实业有限公司 | Matte cathode electrophoresis coating as well as preparation method and use method for same |
| KR101858272B1 (en) * | 2013-05-16 | 2018-05-15 | 주식회사 케이씨씨 | Method for preparing urethane curing agent for electrodeposition paint, a cationic resin composition for electrodeposition paint and an electrodeposition paint composition comprising the same |
| CN104403402A (en) * | 2014-10-31 | 2015-03-11 | 安徽省广德县华林造漆厂 | Cathode electrophoresis paint emulsion tackifier and preparation method thereof |
| CN104592482A (en) * | 2014-10-31 | 2015-05-06 | 安徽省广德县华林造漆厂 | Epoxy resin for producing cathode electrophoresis paint and preparation method thereof |
| CN106009934B (en) * | 2016-05-23 | 2020-01-10 | 潍坊合力水性涂料制造有限公司 | Resin color paste and production process thereof |
| CN109627951B (en) * | 2018-12-18 | 2020-10-30 | 广东科德环保科技股份有限公司 | Modified epoxy resin, preparation method thereof and high-throwing-power cathode electrophoretic coating |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN86108712A (en) * | 1985-11-29 | 1987-11-25 | 巴斯夫漆及染料公司 | Be used as the tackiness agent that the catholyte coating is used |
| CN1045116A (en) * | 1988-12-22 | 1990-09-05 | 美国Basf公司 | The electric clad compositions of polyamine self-condensed epoxy adduct and the coating of making |
| CN1051184A (en) * | 1989-06-07 | 1991-05-08 | 巴斯福拉克和法本股份公司 | Conductive substrate coating method and cationic amine modified epoxy preparation method |
-
1994
- 1994-11-02 CN CN94111495A patent/CN1047398C/en not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN86108712A (en) * | 1985-11-29 | 1987-11-25 | 巴斯夫漆及染料公司 | Be used as the tackiness agent that the catholyte coating is used |
| CN1045116A (en) * | 1988-12-22 | 1990-09-05 | 美国Basf公司 | The electric clad compositions of polyamine self-condensed epoxy adduct and the coating of making |
| CN1051184A (en) * | 1989-06-07 | 1991-05-08 | 巴斯福拉克和法本股份公司 | Conductive substrate coating method and cationic amine modified epoxy preparation method |
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| CN1122353A (en) | 1996-05-15 |
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