CN111057408A - Cationic modification auxiliary agent of electrophoretic coating and preparation method thereof - Google Patents
Cationic modification auxiliary agent of electrophoretic coating and preparation method thereof Download PDFInfo
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- CN111057408A CN111057408A CN201911230982.2A CN201911230982A CN111057408A CN 111057408 A CN111057408 A CN 111057408A CN 201911230982 A CN201911230982 A CN 201911230982A CN 111057408 A CN111057408 A CN 111057408A
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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
- C09D5/448—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes for electrophoretic applications characterised by the additives used
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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
- C09D5/4488—Cathodic paints
- C09D5/4492—Cathodic paints containing special additives, e.g. grinding agents
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Abstract
The invention discloses a cationic modification auxiliary agent of an electrophoretic coating, which comprises the following components in parts by weight: 80-365 parts of epoxy resin with the molecular weight of less than 1600, 30-300 parts of inert hydroxyl-free solvent, 10-100 parts of small molecular secondary amine, 45-300 parts of polyetheramine with the molecular weight of 400-5000, 30-300 parts of alcohol ether solvent, 25-80 parts of organic acid, 8-37 parts of epoxy resin with the molecular weight of less than 1200 and 191.1-1000 parts of deionized water. The invention also discloses a preparation method thereof, the cationic modified auxiliary agent is obtained by modifying the epoxy resin through the amine neutralized by the organic acid and emulsifying the epoxy resin into the aqueous dispersion, and the cationic modified auxiliary agent can be directly added into the working solution of the electrophoretic coating, so that the conductivity of the electrophoretic coating can be rapidly and effectively improved, the updating time of the conductivity of the bath solution is greatly shortened, and the defects of difficult film coating, reduced coulomb efficiency, reduced throwing power and the like of the electrophoretic coating are avoided.
Description
Technical Field
The invention belongs to the technical field of coatings, and particularly relates to a cationic modification auxiliary agent of an electrophoretic coating and a preparation method thereof.
Background
Conductivity is one of the most common detection indicators for electrophoretic paints. The conductivity is low, so that various defects of difficult film coating of the electrophoretic paint, reduced coulombic efficiency, reduced throwing power and the like can be caused, the performance of a paint film of the electrophoretic paint is influenced, and energy consumption is wasted. In the electrophoretic coating industry, because a working tank body is large (tank liquid is usually from several tons to hundreds of tons), certain updating time is provided, and when the conductivity is low and abnormal, no effective adjusting scheme exists in the industry at present.
Disclosure of Invention
The present invention is directed to solving at least one of the problems of the prior art. Therefore, the invention provides a cationic modification auxiliary agent for an electrophoretic coating and a preparation method thereof, wherein the auxiliary agent can be directly added into an electrophoretic coating working solution, can quickly and effectively improve the conductivity of the electrophoretic coating, and has no other negative effects.
In order to overcome the technical problems, the technical scheme adopted by the invention is as follows: the cationic modification auxiliary agent for the electrophoretic coating comprises the following components in parts by weight:
as a further improvement of the above aspect, the epoxy resin having a molecular weight of less than 1600 includes a 128E epoxy resin. The larger the molecular weight of the epoxy resin is, the higher the equivalent weight is, the smaller the epoxy value is, that is, the smaller the number of epoxy groups per unit weight is, the smaller the density of ionic groups formed after amination and acidification in the main structure is, the lower the conductivity is, and the larger the viscosity of the compounded material is.
As a further refinement of the above scheme, the inert non-hydroxylic solvent comprises at least one of methyl isobutyl ketone, butanone, and cyclohexanone. As a solvent, it plays a role in dissolution. Methyl isobutyl ketone with stronger dissolving capacity is preferred. A preferred value is 80.
As a further improvement of the scheme, the small-molecule secondary amine is selected from at least one of diethylamine, diethanolamine and N-methylethanolamine. The small-fraction secondary amine has a simple structure, high ion density in unit volume or unit weight and higher conductivity. During compounding, secondary amine is utilized to open epoxy rings, a tertiary amine structure is formed, and the structure is neutralized by organic acid to form quaternary ammonium salt, so that the conductivity of the structure can be effectively increased.
As a further improvement of the above scheme, the polyetheramines having molecular weights of 400-5000-beta-molecular weight include polyetheramine D500 and polyetheramine D2000. Both ends of the polyether amine molecule are provided with primary amine, and the primary amine has two active hydrogens and can form a branched chain structure, so that more amine groups capable of forming ions in a single main body molecule are provided. Meanwhile, the smaller the molecular weight, the better the polyetheramine is from the viewpoint of ion density.
As a further improvement of the above aspect, the alcohol ether solvent includes at least one of ethylene glycol butyl ether, diethylene glycol hexyl ether, ethylene glycol hexyl ether, and propylene glycol methyl ether. The alcohol ether solvent is used as a solvent and a cosolvent, so that the hydrophilicity of the main raw material in mixing with water can be increased, and the final product can form a stable aqueous dispersion more easily. Preferably 70.
As a further improvement of the above aspect, the organic acid is at least one selected from the group consisting of formic acid, acetic acid, lactic acid, and sulfamic acid. Preferably sulfamic acid.
A preparation method of a cationic modification auxiliary agent of an electrophoretic coating comprises the following steps:
1) weighing the raw material components according to the raw material proportion of the cationic modification auxiliary agent of the electrophoretic paint for later use;
2) taking an inert hydroxyl-free solvent and epoxy resin with the molecular weight less than 1600, heating to 100 +/-5 ℃, and uniformly stirring until the mixture is clear and transparent;
3) dropwise adding micromolecular secondary amine, and keeping the temperature at 100 +/-5 ℃ for 90-120 min;
4) dripping polyether amine with molecular weight of 400-;
5) cooling to 80 + -5 deg.C, adding organic acid dissolved in deionized water, and keeping the temperature for 60-80 min;
6) adding deionized water, and keeping the temperature at 80 + -5 deg.C for 60-80 min;
7) slowly adding epoxy resin with the molecular weight less than 1200, and preserving the heat at the temperature of 80 +/-5 ℃ for 180 min;
8) adding deionized water, and keeping the temperature at 80 +/-5 ℃ for 160-.
The invention has the beneficial effects that: the invention provides a cationic modification auxiliary agent of an electrophoretic coating, which takes epoxy resin with the molecular weight less than 1600 as a main basic raw material, reacts with inert non-hydroxyl solvent, micromolecular secondary amine, polyether amine with the molecular weight of 400-5000, alcohol ether solvent, organic acid and the like, modifies the epoxy resin through amine neutralized by the organic acid, emulsifies the epoxy resin into aqueous dispersion, thereby obtaining the cationic modification auxiliary agent, can be directly added into an electrophoretic coating working solution, can rapidly and effectively improve the conductivity of the electrophoretic coating, greatly shortens the updating time of the conductivity of a bath solution, avoids the occurrence of various defects of difficult film coating, reduced coulomb efficiency, reduced throwing power and the like of the electrophoretic coating, has high efficiency, simple process flow, low cost and wide application prospect, and can rapidly and effectively improve the conductivity of the electrophoretic coating, without other negative effects.
Detailed Description
The present invention is specifically described below with reference to examples in order to facilitate understanding of the present invention by those skilled in the art. It should be particularly noted that the examples are given solely for the purpose of illustration and are not to be construed as limitations on the scope of the invention, as non-essential improvements and modifications to the invention may occur to those skilled in the art, which fall within the scope of the invention as defined by the appended claims. Meanwhile, the raw materials mentioned below are not specified in detail and are all commercially available products; the process steps or extraction methods not mentioned in detail are all process steps or extraction methods known to the person skilled in the art.
Example 1
Placing 80 parts of methyl isobutyl ketone and 94 parts of epoxy resin 128E in the raw materials in a flask, uniformly stirring, and heating to 100 +/-5 ℃; dripping 53 parts of diethanolamine into the flask by using a dropping funnel, controlling the temperature to be 100 +/-5 ℃ by using an oil bath pan, and preserving the temperature for 90-120 min; slowly dripping 62.5 parts of polyetheramine D500 into the flask by using a dropping funnel, controlling the temperature to be 100 +/-5 ℃ by using an oil bath pot in the dripping process, adding 70 parts of diethylene glycol monobutyl ether after finishing dripping, and keeping the temperature at 100 +/-5 ℃ for 60-80 min; reducing the temperature to 80 +/-5 ℃, adding 40 parts of sulfamic acid dissolved by deionized water into the flask, and keeping the temperature at 80 +/-5 ℃ for 60-80 min; adding deionized water, and keeping the temperature at 80 + -5 deg.C for 60-80 min; slowly adding the remaining 9.4 parts of epoxy resin 128E into the flask, and keeping the temperature at 80 +/-5 ℃ for 160-180 min; adding deionized water, and preserving the temperature at 80 +/-5 ℃ for 160-.
Example 2
Placing 100 parts of methyl isobutyl ketone and 100 parts of epoxy resin 128E in the raw materials in a flask, uniformly stirring, and heating to 100 +/-5 ℃; dropwise adding 68 parts of diethanolamine into the flask by using a dropping funnel, controlling the temperature to be 100 +/-5 ℃ by using an oil bath pan, and preserving the temperature for 90-120 min; slowly dripping 190 parts of polyetheramine D500 into the flask by using a dropping funnel, controlling the temperature to be 100 +/-5 ℃ by using an oil bath pot in the dripping process, adding 100 parts of diethylene glycol butyl ether after finishing dripping, and keeping the temperature at 100 +/-5 ℃ for 60-80 min; reducing the temperature to 80 +/-5 ℃, adding 35 parts of sulfamic acid dissolved by deionized water into the flask, and keeping the temperature at 80 +/-5 ℃ for 60-80 min; adding deionized water, and keeping the temperature at 80 + -5 deg.C for 60-80 min; slowly adding the remaining 8 parts of epoxy resin 128E into the flask, and keeping the temperature at 80 +/-5 ℃ for 160-180 min; adding deionized water, and preserving the temperature at 80 +/-5 ℃ for 160-.
Example 3
Placing 150 parts of methyl isobutyl ketone and 100 parts of epoxy resin 128E in the raw materials in a flask, uniformly stirring, and heating to 100 +/-5 ℃; dripping 87 parts of diethanolamine into the flask by using a dropping funnel, controlling the temperature to be 100 +/-5 ℃ by using an oil bath pan, and preserving the temperature for 90-120 min; slowly dripping 120 parts of polyetheramine D500 into the flask by using a dropping funnel, controlling the temperature to be 100 +/-5 ℃ by using an oil bath pot in the dripping process, adding 40 parts of diethylene glycol butyl ether after finishing dripping, and keeping the temperature at 100 +/-5 ℃ for 60-80 min; reducing the temperature to 80 +/-5 ℃, adding 50 parts of sulfamic acid dissolved by deionized water into the flask, and keeping the temperature at 80 +/-5 ℃ for 60-80 min; adding deionized water, and keeping the temperature at 80 + -5 deg.C for 60-80 min; slowly adding the rest 11 parts of epoxy resin 128E into the flask, and keeping the temperature at 80 +/-5 ℃ for 160-180 min; adding deionized water, and preserving the temperature at 80 +/-5 ℃ for 160-.
Example 4
Placing 80 parts of methyl isobutyl ketone and 94 parts of epoxy resin 128E in the raw materials in a flask, uniformly stirring, and heating to 100 +/-5 ℃; dripping 53 parts of diethanolamine into the flask by using a dropping funnel, controlling the temperature to be 100 +/-5 ℃ by using an oil bath pan, and preserving the temperature for 90-120 min; slowly dripping 62.5 parts of polyetheramine D500 into the flask by using a dropping funnel, controlling the temperature to be 100 +/-5 ℃ by using an oil bath pot in the dripping process, adding 70 parts of diethylene glycol monobutyl ether after finishing dripping, and keeping the temperature at 100 +/-5 ℃ for 60-80 min; reducing the temperature to 80 +/-5 ℃, adding 40 parts of lactic acid dissolved by deionized water into the flask, and keeping the temperature at 80 +/-5 ℃ for 60-80 min; adding deionized water, and keeping the temperature at 80 + -5 deg.C for 60-80 min; slowly adding the remaining 9.4 parts of epoxy resin 128E into the flask, and keeping the temperature at 80 +/-5 ℃ for 160-180 min; adding deionized water, and preserving the temperature at 80 +/-5 ℃ for 160-.
Example 5
The cationic modified assistant finished products 1 to 4 obtained in examples 1 to 4 were subjected to performance tests on nonvolatile content/(105 ℃ 3h), pH/25 ℃, conductivity/25 ℃ and the like, and the obtained test results are shown in table 1 below.
TABLE 1 Performance test of cationic modification assistants 1 to 4 obtained in examples 1 to 4
As can be seen from table 1, the organic acid added in example 4 is lactic acid, and the nonvolatile content/(105 ℃ x 3h), pH value and conductivity/25 ℃ of the cationic modification assistant 4 prepared by the method is lower than that of the finished cationic modification assistant 1-3 prepared by using sulfamic acid as the organic acid. The cationic modified auxiliary agent finished product 1-3 prepared by taking sulfamic acid as organic acid has high conductivity, so that the product has high stability and is more convenient to store for a long time.
Example 6
Adding the finished cationic modification assistant product 1 obtained in the example 1 into the same electrolytic bath solution, and then carrying out conductivity detection, wherein the detection results are shown in the following table 2;
the finished product 4 of the cationic modification assistant obtained in example 4 is added to the same electrolytic bath solution, and then the conductivity is detected, and the detection results are shown in table 3 below.
Wherein, the addition amounts of the finished cationic modification auxiliary agent are respectively 0, 0.05%, 0.1%, 1.5% and 0.2% by weight.
Table 2 detection of conductivity effect of cationic modification assistant finished product 1 of example 1
TABLE 3 detection of conductivity Effect of the cationic modification aid product 4 of example 4
As can be seen from the comparison between tables 2 and 3, the cationic modification assistant obtained by using sulfamic acid has higher conductivity and better conductive effect. The sulfamic acid belongs to strong acid with strong acidity in organic acid, the acidity of the sulfamic acid, formic acid, lactic acid and acetic acid is different, and the acidity can influence parameters such as pH value, conductivity and the like of a final product under the condition that the main structures of the amine modified epoxy resin are the same. From experimental data, equimolar amounts of acid, in the order of sulfamic acid, formic acid, lactic acid, acetic acid, increase in pH and decrease in conductivity, which can correspond to the theoretical acid-base strength of the acid.
It will be obvious to those skilled in the art that many simple derivations or substitutions can be made without inventive effort without departing from the inventive concept. Therefore, simple modifications to the present invention by those skilled in the art according to the present disclosure should be within the scope of the present invention. The above embodiments are preferred embodiments of the present invention, and all similar processes and equivalent variations to those of the present invention should fall within the scope of the present invention.
Claims (10)
1. The cationic modification auxiliary agent for the electrophoretic coating comprises the following components in parts by weight:
2. the cationic modification aid of claim 1, wherein the epoxy resin having a molecular weight of less than 1600 comprises a 128E epoxy resin.
3. A cationic modification aid according to claim 1, wherein the inert non-hydroxylic solvent comprises at least one of methyl isobutyl ketone, butanone, and cyclohexanone.
4. A cationic modification aid according to claim 3, wherein the inert non-hydroxylic solvent is methyl isobutyl ketone.
5. The cationic modification aid of claim 1, wherein the small molecule secondary amine is at least one selected from the group consisting of diethylamine, diethanolamine, and N-methylethanolamine.
6. The cationic modification aid of claim 1, wherein the polyetheramines having molecular weight of 400-5000 comprise polyetheramine D500 and polyetheramine D2000.
7. The cationic modification aid according to claim 1, wherein the alcohol ether solvent comprises at least one of ethylene glycol butyl ether, diethylene glycol butyl ether, ethylene glycol hexyl ether, diethylene glycol hexyl ether, and propylene glycol methyl ether.
8. The cationic modification aid of claim 1, wherein the organic acid is at least one selected from the group consisting of formic acid, acetic acid, lactic acid, and sulfamic acid.
9. The cationic modification aid of claim 8, wherein the organic acid is sulfamic acid.
10. A preparation method of a cationic modification auxiliary agent of an electrophoretic coating is characterized by comprising the following steps:
1) weighing the raw material components according to the raw material proportion of the cationic modification assistant of the electrophoretic paint as claimed in any of claims 1 to 9 for later use;
2) taking an inert hydroxyl-free solvent and epoxy resin with the molecular weight less than 1600, heating to 100 +/-5 ℃, and uniformly stirring;
3) dropwise adding micromolecular secondary amine, and keeping the temperature at 100 +/-5 ℃ for 90-120 min;
4) dripping polyether amine with molecular weight of 400-;
5) cooling to 80 + -5 deg.C, adding organic acid dissolved in deionized water, and keeping the temperature for 60-80 min;
6) adding deionized water, and keeping the temperature at 80 + -5 deg.C for 60-80 min;
7) slowly adding epoxy resin with the molecular weight less than 1200, and preserving the heat at the temperature of 80 +/-5 ℃ for 180 min;
8) adding deionized water, and keeping the temperature at 80 +/-5 ℃ for 160-.
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2019
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