CN107674485A - A kind of bottom surface unification cathode electrophoresis dope resin and preparation method thereof - Google Patents
A kind of bottom surface unification cathode electrophoresis dope resin and preparation method thereof Download PDFInfo
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- CN107674485A CN107674485A CN201711113974.0A CN201711113974A CN107674485A CN 107674485 A CN107674485 A CN 107674485A CN 201711113974 A CN201711113974 A CN 201711113974A CN 107674485 A CN107674485 A CN 107674485A
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/44—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes for electrophoretic applications
- C09D5/4419—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes for electrophoretic applications with polymers obtained otherwise than by polymerisation reactions only involving carbon-to-carbon unsaturated bonds
- C09D5/4465—Polyurethanes
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/64—Macromolecular compounds not provided for by groups C08G18/42 - C08G18/63
- C08G18/6415—Macromolecular compounds not provided for by groups C08G18/42 - C08G18/63 having nitrogen
- C08G18/643—Reaction products of epoxy resins with at least equivalent amounts of amines
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/80—Masked polyisocyanates
- C08G18/8061—Masked polyisocyanates masked with compounds having only one group containing active hydrogen
- C08G18/807—Masked polyisocyanates masked with compounds having only one group containing active hydrogen with nitrogen containing compounds
- C08G18/8077—Oximes
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Abstract
The invention discloses a kind of bottom surface to unify cathode electrophoresis dope resin, including following parts by weight of component is prepared：50~70 parts of amination epoxy modified acrylic resin, 20~40 parts of blocked polyisocyanates crosslinking agent, neutralize 1.5~4 parts of acid.Its emulsion can be as the film-forming components of cathode electro-coating, and film has anti-corrosive properties and weatherability effect concurrently, realize bottom surface unification, one time electrophoretic painting can reach protection and cosmetic requirement, reduce painting cost.
Description
Technical field
The present invention relates to chemical field, more particularly, it relates to a kind of bottom surface unification cathode electrophoresis dope resin and its preparation side
Method.
Background technology
Cathode electrophoresis dope is since the seventies in last century occurs, just with its excellent film combination property, high coating
The features such as utilization rate, full-automatic application, it is applied in painting dressing automobiles field rapidly.With the hair of electrophoretic coating technology
Exhibition, electrophoretic painting are used widely in industries such as vehicular traffic, light industry, agricultural machinery, household electrical appliances, military project, building materials.Due to each row
The requirement of industry is different, and the function of mutually tackling electrophoretic coating proposes different requirements.
Cathode electrophoresis dope in the market uses epoxy resin as matrix resin substantially, as primer for automobiles, most
Main effect is protection.Though the cathode electrophoresis dope based on epoxy resin has permanent protective property energy, weatherability is poor, no
With light colour retention is protected, it is not suitable for using as outdoor decorative finish paint.Although existing acrylic resin is with excellent resistance to
Time property and guarantor's light colour retention, but pure acrylic resin chemical resistance, antiseptic property are general, can not meet anticorrosion requirement.
With popularization of the electrophoretic painting in each field, every profession and trade active demand can develop existing suitable antiseptic property has guarantor's light again
The high-decoration electrophoretic coating kind of colour retention, realize that bottom surface is unified, an electrophoretic painting can reach protection and dicoration will
Ask, to reduce painting cost.
The content of the invention
For overcome the deficiencies in the prior art, it is an object of the invention to provide a kind of bottom surface to unify cathode electrophoresis dope tree
Fat, its emulsion can be as the film-forming components of cathode electro-coating, and film has anti-corrosive properties and weatherability effect concurrently, realize bottom surface conjunction
One, one time electrophoretic painting can reach protection and cosmetic requirement, reduce painting cost.
To solve the above problems, the technical solution adopted in the present invention is as follows：
The present invention includes a kind of bottom surface unification cathode electrophoresis dope resin, including following parts by weight of component is prepared：
50~70 parts of amination epoxy modified acrylic resin,
20~40 parts of blocked polyisocyanates crosslinking agent,
Neutralize 1.5~4 parts of acid.
Preferably, the amination epoxy modified acrylic resin is organic secondary with list successively by the epoxide group in epoxy resin
Amine, carboxylic acrylic resin and the acrylic resin reaction completely containing secondary amine and primary amine are made, and single organic secondary, contain
The acrylic resin of carboxyl and acrylic resin and the percent reaction point of epoxy resin epoxide epoxy group group containing secondary amine and primary amine
Wei not 30-60%, 10-20% and 20-60%.
Preferably, the epoxy resin is bisphenol A-type or bisphenol f type epoxy resin, epoxide number 0.1-0.5mol/
100g。
Preferably, single organic secondary is in diethanol amine, methylethanolamine, diethylamine, di-n-propylamine, di-n-butylamine
One or more of mixtures.
Preferably, the carboxylic acrylic resin is by 5-10wt% acrylic acid and/or methacrylic acid, 10-
The acrylic ester monomer of 30wt% hydroxyls and/or the other propylene of the methacrylate-based monomer of hydroxyl, 60-85wt%
Esters of gallic acid monomer and/or the copolymerization of other methacrylate-based monomers and/or unsaturated vinyl monomer form.
Preferably, the acrylic resin containing secondary amine and primary amine is made by following methods：Contracted by 10-20wt% acrylic acid
Water glyceride and/or GMA, the acrylic ester monomer and/or hydroxyl of 10-30wt% hydroxyls
Methacrylate-based monomer, the other acrylic ester monomers of 40-70wt% and/or other methacrylate-based monomers
And/or acrylic resin of the unsaturated vinyl monomer copolymerization containing epoxide group, the acrylic resin containing epoxide group
The single organic secondary of epoxide group reacts 60-80%, and remaining epoxide group reacts with primary amino-compound, its epoxide group and primary
The mol ratio of amine groups is 1：1-2.
Preferably, single organic secondary is in diethanol amine, methylethanolamine, diethylamine, di-n-propylamine, di-n-butylamine
One or more of mixtures；The primary amino-compound is MEA, dimethylaminopropylamine, diethylaminopropylamine or polyethers list
Amine.
Preferably, the blocked polyisocyanates crosslinking agent be in the presence of organotin catalysts, polyisocyanates with
Sealer reaction is prepared；The polyisocyanates is one or more aromatic polyisocyanates, or the more isocyanides of aromatic series
Acid esters and aliphatic polyisocyante and/or the mixture of alicyclic polyisocyanates；The sealer is the alcohol containing active hydrogen
Class, alcohol ethers, phenols work ketoxime class.
Preferably, the neutralization acid is acetic acid, formic acid, lactic acid, alkyl sulfonic acid or tartaric acid.
Present invention additionally comprises a kind of preparation method of bottom surface unification cathode electrophoresis dope resin, including：Amination epoxy is changed
Property acrylic resin be added in container, be heated to 75-85 DEG C, add totally-enclosed polyisocyanates and neutralize fully mixed after acid
Close, produce.
Compared with prior art, the beneficial effects of the present invention are：The present invention provides a kind of bottom surface unification cathode electrophoresis dope
Resin, bottom surface unification is realized, one time electrophoretic painting can reach protection and cosmetic requirement, reduce painting cost.
Embodiment
The present invention is described in further detail with reference to embodiment.
The present invention includes a kind of bottom surface unification cathode electrophoresis dope resin, including following parts by weight of component is prepared：
50~70 parts of amination epoxy modified acrylic resin, 20~40 parts of blocked polyisocyanates crosslinking agent, neutralize 1.5~4 parts of acid.
Preferably, the amination epoxy modified acrylic resin is organic secondary with list successively by the epoxide group in epoxy resin
Amine, carboxylic acrylic resin and the acrylic resin reaction completely containing secondary amine and primary amine are made, and single organic secondary, contain
The acrylic resin of carboxyl and acrylic resin and the percent reaction point of epoxy resin epoxide epoxy group group containing secondary amine and primary amine
Wei not 30-60%, 10-20% and 20-60%.The epoxy resin is bisphenol A-type or bisphenol f type epoxy resin, and epoxide number is
0.1-0.5mol/100g.Single organic secondary is diethanol amine, methylethanolamine, diethylamine, di-n-propylamine, di-n-butylamine
Middle one or more of mixture.The carboxylic acrylic resin be by 5-10wt% acrylic acid and/or methacrylic acid,
The acrylic ester monomer of 10-30wt% hydroxyls and/or the methacrylate-based monomer of hydroxyl, 60-85wt% are other
Acrylic ester monomer and/or the copolymerization of other methacrylate-based monomers and/or unsaturated vinyl monomer form；Wherein,
The acrylic ester monomer of hydroxyl is referred mainly to such as (methyl) hydroxy-ethyl acrylate, (methyl) hydroxypropyl acrylate, (methyl) third
Olefin(e) acid hydroxy butyl ester etc.；Other acrylic ester monomers and/or other methacrylate-based monomers and/or vinyl are unsaturated single
Body is referred mainly to such as (methyl) methyl acrylate, (methyl) ethyl acrylate, (methyl) propyl acrylate, (methyl) acrylic acid fourth
Ester, (methyl) 2-EHA, (methyl) lauryl acid esters, (methyl) acrylic acid borneol base ester, (methyl) third
Olefin(e) acid benzyl ester, (methyl) cyclohexyl acrylate, (methyl) acrylate, styrene, methyl styrene etc..
Preferably, the acrylic resin containing secondary amine and primary amine is made by following methods：Contracted by 10-20wt% acrylic acid
Water glyceride and/or GMA, the acrylic ester monomer and/or hydroxyl of 10-30wt% hydroxyls
Methacrylate-based monomer, the other acrylic ester monomers of 40-70wt% and/or other methacrylate-based monomers
And/or acrylic resin of the unsaturated vinyl monomer copolymerization containing epoxide group, the acrylic resin containing epoxide group
The single organic secondary of epoxide group reacts 60-80%, and remaining epoxide group reacts with primary amino-compound, its epoxide group and primary
The mol ratio of amine groups is 1：1-2.Wherein, the acrylic ester monomer of hydroxyl refer mainly to as (methyl) hydroxy-ethyl acrylate,
(methyl) hydroxypropyl acrylate, (methyl) hy-droxybutyl etc.；Other acrylic ester monomers and/or other methacrylic acids
Esters monomer and/or unsaturated vinyl monomer are referred mainly to such as (methyl) methyl acrylate, (methyl) ethyl acrylate, (methyl)
Propyl acrylate, (methyl) butyl acrylate, (methyl) 2-EHA, (methyl) lauryl acid esters, (first
Base) acrylic acid borneol base ester, (methyl) benzyl acrylate, (methyl) cyclohexyl acrylate, (methyl) acrylate,
Styrene, methyl styrene etc..Single organic secondary is diethanol amine, methylethanolamine, diethylamine, di-n-propylamine, two just
One or more of mixture in butylamine；The primary amino-compound be MEA, dimethylaminopropylamine, diethylaminopropylamine or
Polyether monoamine.
Preferably, the blocked polyisocyanates crosslinking agent be in the presence of organotin catalysts, polyisocyanates with
Sealer reaction is prepared；The polyisocyanates is one or more aromatic polyisocyanates, or the more isocyanides of aromatic series
Acid esters and aliphatic polyisocyante and/or the mixture of alicyclic polyisocyanates；The sealer is the alcohol containing active hydrogen
Class, alcohol ethers, phenols work ketoxime class.
Preferably, the neutralization acid is acetic acid, formic acid, lactic acid, alkyl sulfonic acid or tartaric acid.
Present invention additionally comprises a kind of preparation method of bottom surface unification cathode electrophoresis dope resin, including：By modified acroleic acid
Resin is added in container, is heated to 75-85 DEG C, is added totally-enclosed polyisocyanates and is sufficiently mixed after neutralizing acid, is produced.
Embodiment 1
1.1 prepare carboxylic acrylic resin
The formula table of 1.1 carboxylic acrylic resin of table
With reference to table 1.1, in the dried and clean reactor equipped with thermometer, agitator, reflux condenser and head tank etc.
Component a is added, is warming up to reflux temperature, component b is added dropwise, 2-3h is dripped off, is incubated after dripping off, and component c is added dropwise under reflux temperature,
0.5h or so is dripped off, and is dripped off cooling after 3h is incubated under rear reflux temperature and is obtained acid number 41.5mgKOH/g (solid), non-volatile part
61.2% carboxylic acrylic resin.
1.2 prepare the acrylic resin containing secondary amine and primary amine
The formula table of acrylic resin of the table 1.2 containing secondary amine and primary amine
With reference to table 1.2, in the dried and clean reactor equipped with thermometer, agitator, reflux condenser and head tank etc.
Component d is added, is warming up to reflux temperature, component e is added dropwise, 2-3h is dripped off, is incubated after dripping off, and component f is added dropwise under reflux temperature,
0.5h or so is dripped off, and is dripped off and is cooled to 90 DEG C after 3h is incubated under rear reflux temperature, adds component g, 100 DEG C are incubated 1h, addition group
Divide h, 110 DEG C of insulation 2h, obtain the acrylic resin containing secondary amine and primary amine group of non-volatile part 65.5%.
1.3 prepare amination epoxy modified acrylic resin
The formula table of the amination epoxy modified acrylic resin of table 1.3
| Component | Raw material | Dosage (g) |
| Epoxy resin | EPIKOTE 1001, Tao Shi are produced, epoxide equivalent 480 | 480 |
| Solvent | Butyl glycol ether | 100 |
| Single organic secondary | Diethanol amine | 52.5 |
| Carboxylic acrylic resin | Self-control | 330 |
| Acrylic resin containing secondary amine and primary amine | Self-control | 2000 |
With reference to table 1.3, equipped with thermometer, agitator, reflux condenser dried and clean reactor in add solvent and
Epoxy resin, it is warming up at 90-100 DEG C and is incubated dissolving；Less than 80 DEG C are cooled to, adds single organic secondary, is warming up at 105 DEG C
It is incubated 1h；Carboxylic acrylic resin is added, insulation to acid number is less than 2mgKOH/g at 130-140 DEG C, and addition contains secondary amine
3h is incubated at 120-130 DEG C with the acrylic resin of primary amine, obtains 69% amination epoxy modified acrylic resin of solid point.
1.4 prepare blocked polyisocyanates crosslinking agent
The formula table of the blocked polyisocyanates crosslinking agent of table 1.4
| Component | Raw material | Dosage (g) |
| Polyisocyanates | The tripolymer N-3300 of hexamethylene diisocyanate | 444 |
| Solvent | Methyl iso-butyl ketone (MIBK) | 229 |
| Sealer | Methyl ethyl ketoxime | 327.1 |
| Catalyst | Dibutyl tin laurate | 0.2 |
With reference to table 1.4, more isocyanides are added in the four-hole boiling flask that one is equipped with agitator, condenser pipe, logical nitrogen pipe, thermometer
Acid esters, solvent and catalyst, sealer is added dropwise at 40 DEG C, continues to be incubated 2h at 60 DEG C after being added dropwise, obtained solid is divided into
75% Totally-enclosed-type polyisocyanates.
1.5 prepare bottom surface unification cathode electrophoresis dope resin and its emulsion E-1
The bottom surface of table 1.5 unification cathode electrophoresis dope resin emulsion E-1 formula table
With reference to table 1.5, matrix resin is added to and is equipped with the 1000ml four-hole boiling flasks of agitator, condenser pipe, thermometer,
80 DEG C are heated to, addition crosslinking agent, neutralization acid are sufficiently mixed, and produce bottom surface unification cathode electrophoresis dope resin；Bottom surface unification is cloudy
Pole electrophoretic paint resin adds deionized water, scattered to form emulsion, obtains the resin emulsion E-1 that solid is divided into 26%.
Embodiment 2
1.1 prepare carboxylic acrylic resin
The formula table of 2.1 carboxylic acrylic resin of table
With reference to table 2.1, in the dried and clean reactor equipped with thermometer, agitator, reflux condenser and head tank etc.
Component a is added, is warming up to reflux temperature, component b is added dropwise, 2-3h is dripped off, is incubated after dripping off, and component c is added dropwise under reflux temperature,
0.5h or so is dripped off, and is dripped off cooling after 3h is incubated under rear reflux temperature and is obtained acid number 41.4mgKOH/g (solid), non-volatile part
61.1% carboxylic acrylic resin.
2.2 prepare the acrylic resin containing secondary amine and primary amine
The formula table of acrylic resin of the table 2.2 containing secondary amine and primary amine
With reference to table 2.2, in the dried and clean reactor equipped with thermometer, agitator, reflux condenser and head tank etc.
Component d is added, is warming up to reflux temperature, component e is added dropwise, 2-3h is dripped off, is incubated after dripping off, and component f is added dropwise under reflux temperature,
0.5h or so is dripped off, and is dripped off and is cooled to 90 DEG C after 3h is incubated under rear reflux temperature, adds component g, 100 DEG C are incubated 1h, addition group
Divide h, 110 DEG C of insulation 2h, obtain the acrylic resin containing secondary amine and primary amine group of non-volatile part 65.4%.
2.3 prepare amination epoxy modified acrylic resin
The formula table of the amination epoxy modified acrylic resin of table 2.3
With reference to table 2.3, equipped with thermometer, agitator, reflux condenser dried and clean reactor in add solvent and
Epoxy resin, it is warming up at 90-100 DEG C and is incubated dissolving；Less than 80 DEG C are cooled to, adds single organic secondary, is warming up at 105 DEG C
It is incubated 1h；Carboxylic acrylic resin is added, insulation to acid number is less than 2mgKOH/g at 130-140 DEG C, and addition contains secondary amine
3h is incubated at 120-130 DEG C with the acrylic resin of primary amine, obtains 68.5% amination epoxy modified acrylic resin of solid point.
2.4 prepare blocked polyisocyanates crosslinking agent
The formula table of the blocked polyisocyanates crosslinking agent of table 2.4
| Component | Raw material | Dosage (g) |
| Polyisocyanates | The tripolymer N-3300 of hexamethylene diisocyanate | 444 |
| Solvent | Methyl iso-butyl ketone (MIBK) | 229 |
| Sealer | Methyl ethyl ketoxime | 327.1 |
| Catalyst | Dibutyl tin laurate | 0.2 |
With reference to table 2.4, more isocyanides are added in the four-hole boiling flask that one is equipped with agitator, condenser pipe, logical nitrogen pipe, thermometer
Acid esters, solvent and catalyst, sealer is added dropwise at 40 DEG C, continues to be incubated 2h at 60 DEG C after being added dropwise, obtained solid is divided into
74.8% Totally-enclosed-type polyisocyanates.
2.5 prepare bottom surface unification cathode electrophoresis dope resin and its emulsion E-2
The bottom surface of table 2.5 unification cathode electrophoresis dope resin emulsion E-2 formula table
| Component | Raw material | Dosage (g) |
| Matrix resin | Amination epoxy modified acrylic resin | 290.5 |
| Crosslinking agent | Blocked polyisocyanate | 78.5 |
| Neutralize acid | Formic acid | 8 |
| Deionized water | Deionized water | 619.8 |
With reference to table 2.5, matrix resin is added to and is equipped with the 1000ml four-hole boiling flasks of agitator, condenser pipe, thermometer,
75 DEG C are heated to, addition crosslinking agent, neutralization acid are sufficiently mixed, and produce bottom surface unification cathode electrophoresis dope resin；Bottom surface unification is cloudy
Pole electrophoretic paint resin adds deionized water, scattered to form emulsion, obtains the emulsion E-2 that solid is divided into 25.9%.
Embodiment 3
3.1 prepare carboxylic acrylic resin
The formula table of 3.1 carboxylic acrylic resin of table
With reference to table 3.1, in the dried and clean reactor equipped with thermometer, agitator, reflux condenser and head tank etc.
Component a is added, is warming up to reflux temperature, component b is added dropwise, 2-3h is dripped off, is incubated after dripping off, and component c is added dropwise under reflux temperature,
0.5h or so is dripped off, and is dripped off cooling after 3h is incubated under rear reflux temperature and is obtained acid number 41.5mgKOH/g (solid), non-volatile part
61.3% carboxylic acrylic resin.
3.2 prepare the acrylic resin containing secondary amine and primary amine
The formula table of acrylic resin of the table 3.2 containing secondary amine and primary amine
With reference to table 3.2, in the dried and clean reactor equipped with thermometer, agitator, reflux condenser and head tank etc.
Component d is added, is warming up to reflux temperature, component e is added dropwise, 2-3h is dripped off, is incubated after dripping off, and component f is added dropwise under reflux temperature,
0.5h or so is dripped off, and is dripped off and is cooled to 90 DEG C after 3h is incubated under rear reflux temperature, adds component g, 100 DEG C are incubated 1h, addition group
Divide h, 110 DEG C of insulation 2h, obtain the acrylic resin containing secondary amine and primary amine group of non-volatile part 65.5%.
3.3 prepare amination epoxy modified acrylic resin
The formula table of the amination epoxy modified acrylic resin of table 3.3
With reference to table 3.3, equipped with thermometer, agitator, reflux condenser dried and clean reactor in add solvent and
Epoxy resin, it is warming up at 90-100 DEG C and is incubated dissolving；Less than 80 DEG C are cooled to, adds single organic secondary, is warming up at 105 DEG C
It is incubated 1h；Carboxylic acrylic resin is added, insulation to acid number is less than 2mgKOH/g at 130-140 DEG C, and addition contains secondary amine
3h is incubated at 120-130 DEG C with the acrylic resin of primary amine, obtains 69.1% amination epoxy modified acrylic resin of solid point.
3.4 prepare blocked polyisocyanates crosslinking agent
The formula table of the blocked polyisocyanates crosslinking agent of table 3.4
| Component | Raw material | Dosage (g) |
| Polyisocyanates | The tripolymer N-3300 of hexamethylene diisocyanate | 444 |
| Solvent | Methyl iso-butyl ketone (MIBK) | 229 |
| Sealer | Methyl ethyl ketoxime | 327.1 |
| Catalyst | Dibutyl tin laurate | 0.2 |
With reference to table 3.4, more isocyanides are added in the four-hole boiling flask that one is equipped with agitator, condenser pipe, logical nitrogen pipe, thermometer
Acid esters, solvent and catalyst, sealer is added dropwise at 40 DEG C, continues to be incubated 2h at 60 DEG C after being added dropwise, obtained solid is divided into
75.2% Totally-enclosed-type polyisocyanates.
3.5 prepare bottom surface unification cathode electrophoresis dope resin and its emulsion E-3
The bottom surface of table 3.5 unification cathode electrophoresis dope resin emulsion E-3 formula table
| Component | Raw material | Dosage (g) |
| Matrix resin | Amination epoxy modified acrylic resin R-3 | 280.5 |
| Crosslinking agent | Blocked polyisocyanate C-3 | 91.5 |
| Neutralize acid | Lactic acid | 8.3 |
| Deionized water | Deionized water | 619.8 |
With reference to table 3.5, matrix resin is added to and is equipped with the 1000ml four-hole boiling flasks of agitator, condenser pipe, thermometer,
80 DEG C are heated to, addition crosslinking agent, neutralization acid are sufficiently mixed, and produce bottom surface unification cathode electrophoresis dope resin；Bottom surface unification is cloudy
Pole electrophoretic paint resin adds deionized water, scattered to form emulsion, obtains the resin emulsion E-3 that solid is divided into 26.1%.
Embodiment 4
4.1 prepare carboxylic acrylic resin
The formula table of 4.1 carboxylic acrylic resin of table
With reference to table 4.1, in the dried and clean reactor equipped with thermometer, agitator, reflux condenser and head tank etc.
Component a is added, is warming up to reflux temperature, component b is added dropwise, 2-3h is dripped off, is incubated after dripping off, and component c is added dropwise under reflux temperature,
0.5h or so is dripped off, and is dripped off cooling after 3h is incubated under rear reflux temperature and is obtained acid number 41.6mgKOH/g (solid), non-volatile part
61.3% carboxylic acrylic resin.
4.2 prepare the acrylic resin containing secondary amine and primary amine
The formula table of acrylic resin of the table 4.2 containing secondary amine and primary amine
With reference to table 4.2, in the dried and clean reactor equipped with thermometer, agitator, reflux condenser and head tank etc.
Component d is added, is warming up to reflux temperature, component e is added dropwise, 2-3h is dripped off, is incubated after dripping off, and component f is added dropwise under reflux temperature,
0.5h or so is dripped off, and is dripped off and is cooled to 90 DEG C after 3h is incubated under rear reflux temperature, adds component g, 100 DEG C are incubated 1h, addition group
Divide h, 110 DEG C of insulation 2h, obtain the acrylic resin containing secondary amine and primary amine group of non-volatile part 65.6%.
4.3 prepare amination epoxy modified acrylic resin
The formula table of the amination epoxy modified acrylic resin of table 4.3
With reference to table 4.3, equipped with thermometer, agitator, reflux condenser dried and clean reactor in add solvent and
Epoxy resin, it is warming up at 90-100 DEG C and is incubated dissolving；Less than 80 DEG C are cooled to, adds single organic secondary, is warming up at 105 DEG C
It is incubated 1h；Carboxylic acrylic resin is added, insulation to acid number is less than 2mgKOH/g at 130-140 DEG C, and addition contains secondary amine
3h is incubated at 120-130 DEG C with the acrylic resin of primary amine, obtains 69.2% amination epoxy modified acrylic resin of solid point.
4.4 prepare blocked polyisocyanates crosslinking agent
The formula table of the blocked polyisocyanates crosslinking agent of table 4.4
| Component | Raw material | Dosage (g) |
| Polyisocyanates | The tripolymer N-3300 of hexamethylene diisocyanate | 444 |
| Solvent | Methyl iso-butyl ketone (MIBK) | 229 |
| Sealer | Methyl ethyl ketoxime | 327.1 |
| Catalyst | Dibutyl tin laurate | 0.2 |
With reference to table 4.4, more isocyanides are added in the four-hole boiling flask that one is equipped with agitator, condenser pipe, logical nitrogen pipe, thermometer
Acid esters, solvent and catalyst, sealer is added dropwise at 40 DEG C, continues to be incubated 2h at 60 DEG C after being added dropwise, obtained solid is divided into
75.1% Totally-enclosed-type polyisocyanates.
4.5 prepare bottom surface unification cathode electrophoresis dope resin and its emulsion E-4
The bottom surface of table 4.5 unification cathode electrophoresis dope resin emulsion E-4 formula table
| Component | Raw material | Dosage (g) |
| Matrix resin | Amination epoxy modified acrylic resin R-4 | 291.5 |
| Crosslinking agent | Blocked polyisocyanate C-4 | 80.5 |
| Neutralize acid | Glacial acetic acid | 8.1 |
| Deionized water | Deionized water | 619.8 |
With reference to table 4.5, matrix resin is added to and is equipped with the 1000ml four-hole boiling flasks of agitator, condenser pipe, thermometer,
78 DEG C are heated to, addition crosslinking agent, neutralization acid are sufficiently mixed, and produce bottom surface unification cathode electrophoresis dope resin；Bottom surface unification is cloudy
Pole electrophoretic paint resin adds deionized water, scattered to form emulsion, obtains the resin emulsion E-4 that solid is divided into 26.2%.
Embodiment 5
The cathode electrophoresis dope resin emulsion E-5 for taking commercially available pure acrylic resin solid to be divided into 26.2%.
Embodiment 6
The cathode electrophoresis dope resin emulsion E-6 for taking Commercial epoxy class solid to be divided into 35.1%.
Embodiment 7
Performance detection and contrast
Resin emulsion E-1~E-4 made from embodiment 1-4 is pressed 6 with deionized water and mill base respectively:10:1 ratio is matched somebody with somebody
The pH value that cathode electrophoresis dope T-1~T-4, obtained cathode electrophoresis dope T-1~T-4 is made is 5.3 ± 0.3, and electrical conductivity is
1200±500μs/cm.Wherein mill base be cathode electrophoresis dope general color paste, by quaternary ammonium salt-modified 20 parts of epoxy dispersion resin,
65 parts of 50 parts of kaolin, 8 parts of carbon black, 2 parts of bismuth hydroxide, 15 parts of butyl glycol ether and deionized water, are dispersed through being ground to fineness
≤ 15 μm are made.
The resin emulsion E-5 of embodiment 5 and deionized water and mill base are pressed 6:10:1 ratio is configured to ability cathode electrophoresis painting
Material T-5, the mill base of use are identical with above-mentioned mill base.
The resin emulsion E-6 of embodiment 6 and deionized water and mill base are pressed 4:5:1 ratio is configured to cathode electrophoresis dope
T-6, the mill base of use are identical with above-mentioned mill base.
Cathode electrophoresis dope T-1~T-4 is placed on after curing 48h in electrophoresis tank, in 100 volts of electrophoretic voltage, 28 DEG C of temperature,
Electrophoresis time 2 minutes, gained film toast 30 minutes at 160 DEG C, and it is 22 μm to obtain thickness of dry film, and flat appearance is smooth,
The unilateral expansion erosion that film draws fork position after 500h salt sprays is respectively less than 2mm, and the artificial accelerating ageing experiment through 500h is not
Efflorescence is non-foaming.
Cathode electrophoresis dope T-5 is conventionally subjected to application, film thickness of dry film is 22 μm, flat appearance light
Sliding, the unilateral expansion erosion that film draws fork position after 240h salt sprays reaches 2.1mm, the artificial accelerating ageing experiment nothing through 500h
Efflorescence foaming phenomena.
Cathode electrophoresis dope T-6 is conventionally subjected to application, film thickness of dry film is 20 μm, flat appearance light
Sliding, the unilateral expansion erosion that film draws fork position after 500h salt sprays is 0.8mm, and the artificial accelerating ageing experiment through 200h occurs
Obvious efflorescence foaming phenomena.
Contrasted from above-mentioned detection, the bottom surface unification cathode electrophoresis dope resin prepared in the present invention is pure compared to commercially available
Acrylic resin product has more excellent performance at corrosion-resistant aspect, compared to Commercial epoxy resins product in anti-aging side
Face has excellent performance, can meet the requirement that outdoor decoration uses.And it is used in coating, bottom surface unification is realized, once
Electrophoretic painting can reach protection and cosmetic requirement, reduce painting cost.
It will be apparent to those skilled in the art that technical scheme that can be as described above and design, make other various
Corresponding change and deformation, and all these changes and deformation should all belong to the protection domain of the claims in the present invention
Within.
Claims (10)
1. cathode electrophoresis dope resin is unified in a kind of bottom surface, it is characterised in that is prepared including following parts by weight of component：
50~70 parts of amination epoxy modified acrylic resin,
20~40 parts of blocked polyisocyanates crosslinking agent,
Neutralize 1.5~4 parts of acid.
2. cathode electrophoresis dope resin is unified in bottom surface as claimed in claim 1, it is characterised in that the amination epoxide modified third
Olefin(e) acid resin is by the epoxide group in epoxy resin successively with single organic secondary, carboxylic acrylic resin and containing secondary amine and primary
The reaction completely of the acrylic resin of amine is made, single organic secondary, carboxylic acrylic resin and containing secondary amine and primary amine
Acrylic resin and the percent reaction of epoxy resin epoxide epoxy group group are respectively 30-60%, 10-20% and 20-60%.
3. cathode electrophoresis dope resin is unified in bottom surface as claimed in claim 2, it is characterised in that the epoxy resin is bis-phenol
A types or bisphenol f type epoxy resin, epoxide number 0.1-0.5mol/100g.
4. cathode electrophoresis dope resin is unified in bottom surface as claimed in claim 2, it is characterised in that single organic secondary is two
One or more of mixture in monoethanolamine, methylethanolamine, diethylamine, di-n-propylamine, di-n-butylamine.
5. cathode electrophoresis dope resin is unified in bottom surface as claimed in claim 2, it is characterised in that the carboxylic acrylic acid
Resin be by 5-10wt% acrylic acid and/or methacrylic acid, 10-30wt% hydroxyls acrylic ester monomer and/or contain
The other acrylic ester monomers of methacrylate-based monomer, 60-85wt% and/or other methyl acrylic ester lists of hydroxyl
Body and/or unsaturated vinyl monomer copolymerization form.
6. cathode electrophoresis dope resin is unified in bottom surface as claimed in claim 2, it is characterised in that described containing secondary amine and primary amine
Acrylic resin is made by following methods：By 10-20wt% glycidyl acrylates and/or methyl propenoic acid glycidyl
Ester, the methacrylate-based monomer of the acrylic ester monomer of 10-30wt% hydroxyls and/or hydroxyl, 40-70wt% its
Its acrylic ester monomer and/or other methacrylate-based monomers and/or unsaturated vinyl monomer copolymerization contain ring
The acrylic resin of oxygen groups, the epoxide group of the acrylic resin containing epoxide group reacts 60-80% with single organic secondary, remaining
Under epoxide group and primary amino-compound react, the mol ratio of its epoxide group and primary amine group is 1：1-2.
7. cathode electrophoresis dope resin is unified in bottom surface as claimed in claim 6, it is characterised in that single organic secondary is two
One or more of mixture in monoethanolamine, methylethanolamine, diethylamine, di-n-propylamine, di-n-butylamine；The primary amino-compound
For MEA, dimethylaminopropylamine, diethylaminopropylamine or polyether monoamine.
8. cathode electrophoresis dope resin is unified in bottom surface as claimed in claim 1, it is characterised in that the blocked polyisocyanates
Crosslinking agent is in the presence of organotin catalysts, and polyisocyanates is prepared with sealer reaction；The polyisocyanates
For one or more aromatic polyisocyanates, or aromatic polyisocyanate and aliphatic polyisocyante and/or alicyclic
The mixture of polyisocyanates；The sealer is the alcohols containing active hydrogen, alcohol ethers, phenols work ketoxime class.
9. cathode electrophoresis dope resin is unified in bottom surface as claimed in claim 1, it is characterised in that it is described neutralize acid for acetic acid,
Formic acid, lactic acid, alkyl sulfonic acid or tartaric acid.
10. the preparation method of any one of the claim 1-10 bottom surface unification cathode electrophoresis dope resins, including：By amination ring
Oxygen is acrylic resin modified to be added in container, is heated to 75-85 DEG C, is added after totally-enclosed polyisocyanates and neutralization acid fully
Mixing, is produced.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109294314A (en) * | 2018-09-06 | 2019-02-01 | 中国海洋石油集团有限公司 | A kind of epoxy acrylic cathode electrophoresis dope resin emulsion and preparation method thereof |
| CN107674485B (en) * | 2017-11-13 | 2020-05-22 | 中国海洋石油集团有限公司 | Primer-topcoat cathode electrophoretic coating resin and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN1493633A (en) * | 2003-09-10 | 2004-05-05 | 江苏鸿业涂料科技产业有限公司 | Resin emulsion for high penetrating powder cathod electrophoresis paint |
| CN101100567A (en) * | 2007-07-27 | 2008-01-09 | 湖南工程学院 | Method for preparing bottom surface unification cathode electrophoresis dope |
| CN103333595A (en) * | 2013-06-09 | 2013-10-02 | 广东科德化工实业有限公司 | Cathode electrophoresis paint with combined bottom surfaces and preparation method and application method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN107674485B (en) * | 2017-11-13 | 2020-05-22 | 中国海洋石油集团有限公司 | Primer-topcoat cathode electrophoretic coating resin and preparation method thereof |
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- 2017-11-13 CN CN201711113974.0A patent/CN107674485B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1493633A (en) * | 2003-09-10 | 2004-05-05 | 江苏鸿业涂料科技产业有限公司 | Resin emulsion for high penetrating powder cathod electrophoresis paint |
| CN101100567A (en) * | 2007-07-27 | 2008-01-09 | 湖南工程学院 | Method for preparing bottom surface unification cathode electrophoresis dope |
| CN103333595A (en) * | 2013-06-09 | 2013-10-02 | 广东科德化工实业有限公司 | Cathode electrophoresis paint with combined bottom surfaces and preparation method and application method thereof |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107674485B (en) * | 2017-11-13 | 2020-05-22 | 中国海洋石油集团有限公司 | Primer-topcoat cathode electrophoretic coating resin and preparation method thereof |
| CN109294314A (en) * | 2018-09-06 | 2019-02-01 | 中国海洋石油集团有限公司 | A kind of epoxy acrylic cathode electrophoresis dope resin emulsion and preparation method thereof |
| CN109294314B (en) * | 2018-09-06 | 2020-10-16 | 中国海洋石油集团有限公司 | Epoxy acrylic acid cathodic electrophoretic coating resin emulsion and preparation method thereof |
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