CN114736353A - Special toughening resin for cathode electrophoretic coating and preparation method and application thereof - Google Patents
Special toughening resin for cathode electrophoretic coating and preparation method and application thereof Download PDFInfo
- Publication number
- CN114736353A CN114736353A CN202210200707.1A CN202210200707A CN114736353A CN 114736353 A CN114736353 A CN 114736353A CN 202210200707 A CN202210200707 A CN 202210200707A CN 114736353 A CN114736353 A CN 114736353A
- Authority
- CN
- China
- Prior art keywords
- parts
- electrophoretic coating
- cathode electrophoretic
- special
- resin
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Classifications
-
- 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
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/14—Polycondensates modified by chemical after-treatment
- C08G59/1433—Polycondensates modified by chemical after-treatment with organic low-molecular-weight compounds
- C08G59/1477—Polycondensates modified by chemical after-treatment with organic low-molecular-weight compounds containing nitrogen
-
- 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
- C09D5/443—Polyepoxides
- C09D5/4434—Polyepoxides characterised by the nature of the epoxy binder
-
- 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
- C09D5/443—Polyepoxides
- C09D5/4434—Polyepoxides characterised by the nature of the epoxy binder
- C09D5/4438—Binder based on epoxy/amine adducts, i.e. reaction products of polyepoxides with compounds containing amino groups only
-
- 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
- C09D5/443—Polyepoxides
- C09D5/4457—Polyepoxides containing special additives, e.g. pigments, polymeric particles
-
- 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
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Materials Engineering (AREA)
- Engineering & Computer Science (AREA)
- Molecular Biology (AREA)
- Wood Science & Technology (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Paints Or Removers (AREA)
Abstract
The application relates to the field of cathode electrophoretic coatings, and particularly discloses a special toughening resin for a cathode electrophoretic coating, and a preparation method and application thereof, wherein the special toughening resin for the cathode electrophoretic coating comprises the following raw materials in parts by weight: 2-2.5 parts of bisphenol A type epoxy resin, 1.5-2 parts of polybasic fatty amine, 0.5-1 part of polyether amine, 2-3 parts of alcohol ether solvent, 0.01-0.02 part of organic acid catalyst, 1-1.5 parts of polybasic fatty acid, 4-10 parts of organic acid and 5-10 parts of water. The special toughening resin for the cathode electrophoretic coating obtained by the method is added, so that the adhesion, flexibility, impact strength, pencil hardness and glossiness of the obtained cathode electrophoretic coating are respectively 0 grade, 1 grade, 72 cm.kg, 3.5H and 86%, and the adhesion and mechanical properties of the cathode electrophoretic coating are improved.
Description
Technical Field
The application relates to the field of cathode electrophoretic coatings, in particular to a special toughening resin for a cathode electrophoretic coating, and a preparation method and application thereof.
Background
The electrophoretic paint is divided into anode electrophoretic paint and cathode electrophoretic paint according to the electrode of the workpiece to be coated. The cathodic electrophoretic coating is an electrophoretic coating product which is prepared by neutralizing a polymer containing carboxylic acid or amine with amine or acid to dissolve or disperse water, using a coated workpiece as an anode, and then separating out the polymer on the surface of the coated workpiece through insolubilization by an electrophoresis method. The cathode electrophoretic coating has good film leveling property and high electrophoretic permeability, can be uniformly coated on the surface of a workpiece, is more suitable for coating the workpiece with a complex shape or structure, and can be widely applied to the fields of automobiles, motor vehicles, building materials, household appliances, hardware, artware and the like so as to achieve the purposes of surface corrosion prevention or decoration and the like.
In the related technology, the cathode electrophoretic coating is mainly prepared by taking epoxy resin as a main raw material, adding pigment, deionized water and a mixed auxiliary agent, and carrying out high-temperature mixing reaction. The obtained cathode electrophoretic coating has poor adhesion on the surface of a workpiece, and is easy to drop in a point or block shape on the surface of the coated workpiece.
Disclosure of Invention
In order to improve the adhesion performance of the cathode electrophoretic coating, the application provides a special toughening resin for the cathode electrophoretic coating, and a preparation method and application thereof.
In a first aspect, the application provides a special toughening resin for a cathode electrophoretic coating, which adopts the following technical scheme:
the special toughening resin for the cathode electrophoretic coating comprises the following raw materials in parts by weight: 2-2.5 parts of bisphenol A type epoxy resin, 1.5-2 parts of polybasic fatty amine, 0.5-1 part of polyether amine, 2-3 parts of alcohol ether solvent, 0.01-0.02 part of organic acid catalyst, 1-1.5 parts of polybasic fatty acid, 4-10 parts of organic acid and 5-10 parts of water.
Further, the polybasic aliphatic amine comprises at least one of diethylenetriamine, triethylene tetramine, methyl cyclopentediamine and methyl diphenylamine; the alcohol ether solvent comprises at least one of ethylene glycol methyl ether, ethylene glycol ethyl ether, diethanol propyl ether, diethylene glycol ethyl ether, diethylene glycol butyl ether, diethylene glycol hexyl ether, propylene glycol methyl ether and propylene glycol butyl ether; the organic acid catalyst comprises oxalic acid, salicylic acid, formic acid, acetic acid and p-toluenesulfonic acid; the polybasic fatty acid comprises at least one of sebacic acid, tribasic fatty acid, undecanedioic acid and dodecanedioic acid; the organic acid comprises at least one of sulfamic acid, acetic acid, glycolic acid, formic acid, oxalic acid, citric acid monohydrate and lactic acid.
By adopting the technical scheme, the bisphenol A epoxy resin has good physical and mechanical properties, chemical resistance and electrical insulation, and has strong adhesion to metal and higher adhesion. The poly aliphatic amine has higher chemical resistance, solvent resistance and physical and mechanical properties, and the polyether amine has lower viscosity, can reduce the dosage of alcohol ether solvents, reduces the system viscosity, and has higher toughness and fatigue resistance.
The alcohol ether solvent can keep the leveling property of the coating film, simultaneously avoid the whitening phenomenon caused by the volatilization of the solvent in the cathode electrophoretic coating, and improve the drying speed of the cathode electrophoretic coating. The addition of the organic acid catalyst can maintain high stability of each raw material.
The polybasic fatty acid is added, and can react with the bisphenol A epoxy resin to crosslink and solidify into a film, and a polybasic fatty acid flexible chain segment is introduced into the low-molecular liquid bisphenol A epoxy resin molecules, so that the crosslinking density of the grafted bisphenol A epoxy resin after solidification is reduced, the toughness of the coating is improved, and the adhesive force of the coating to a coated workpiece is improved. And adding organic acid to perform neutralization reaction on the reaction solution to generate a quaternary ammonium salt aqueous solution.
The method comprises the steps of simultaneously adding the polybasic fatty amine, the polyether amine and the polybasic fatty acid, carrying out amine modification on the polybasic fatty acid by using the polybasic fatty amine and the polyether amine, grafting the amine-modified polybasic fatty acid onto the bisphenol A type epoxy resin, providing flexibility and stretchability for the toughened resin by using the polybasic fatty acid and the polybasic fatty amine, and improving the adhesive force of the toughened resin by using the quaternary ammonium salt structure grafted on the bisphenol A type epoxy resin main chain, so that the adhesive force of the cathode electrophoretic coating is further improved.
Preferably, the method comprises the following steps: the special toughening resin for the cathode electrophoretic coating comprises the following raw materials in parts by weight: 2.2-2.4 parts of bisphenol A type epoxy resin, 1.7-1.9 parts of polybasic aliphatic amine, 0.7-0.9 part of polyether amine, 2.4-2.8 parts of alcohol ether solvent, 0.014-0.018 part of organic acid catalyst, 1.2-1.4 parts of polybasic fatty acid, 6-8 parts of organic acid and 7-9 parts of water.
Further, 2.2 parts, 2.2 to 2.3 parts, 2.3 to 2.4 parts, and more preferably 2.4 parts of bisphenol A epoxy resin; the polybasic fatty acid is selected from 1.2 parts, 1.2-1.3 parts, 1.3-1.4 parts, and preferably 1.3 parts.
Preferably, the method comprises the following steps: the special toughening resin for the cathode electrophoretic coating also comprises the following raw materials in parts by weight: 0.2-0.4 part of cyanoethylated alcohol.
By adopting the technical scheme, the addition of the cyanoethylated alcohol can avoid the breakage of ether bonds and reduce the occurrence of side reactions.
Preferably, the method comprises the following steps: the weight ratio of the cyanoethylated alcohol to the polyether amine is 1: (2-4).
By adopting the technical scheme, the flexibility of the toughening resin and the adhesion to a coated workpiece can be further improved by adjusting the weight part ratio of the cyanoethylated alcohol to the polyether amine.
Preferably, the method comprises the following steps: the special toughening resin for the cathode electrophoretic coating also comprises the following raw materials in parts by weight: 1-2 parts of nano lanthanum oxide and 0.3-0.7 part of monoalkoxyl titanate coupling agent.
By adopting the technical scheme, the nano lanthanum oxide can increase the surface area and the surface energy of the coating, and improve the bonding strength of unsaturated bonds of a coating film and a coated workpiece, thereby improving the adhesive force of the cathode electrophoretic coating. One end of the monoalkoxy titanate coupling agent can react with hydroxyl on the surface of metal, and the other end can react with epoxy in epoxy resin, so that a firm covalent bond is formed between the surface of a coated workpiece and the invention, and the adhesive force of the invention is greatly improved. In addition, the addition of the mono-alkoxy titanate coupling agent can also improve the dispersibility of the nano lanthanum oxide in a toughening resin raw material system.
Preferably, the method comprises the following steps: the weight portion ratio of the monoalkoxy titanate coupling agent to the nano lanthanum oxide is 1: (2.5-3.5).
By adopting the technical scheme, the weight part ratio of the monoalkoxy titanate coupling agent to the nano lanthanum oxide is adjusted, and the dispersibility of the nano lanthanum oxide in a toughening resin raw material system is further improved, so that the adhesive force of the cathode electrophoretic coating is improved.
Preferably, the method comprises the following steps: the weight ratio of the polybasic fatty acid to the bisphenol A epoxy resin is 1: (1.5-2).
By adopting the technical scheme, the weight part ratio of the polybasic fatty acid to the bisphenol A epoxy resin is adjusted, so that the grafting effect of the polybasic fatty acid on the bisphenol A epoxy resin can be further improved, and the adhesive force of the cathode electrophoretic coating is further improved.
In a second aspect, the application provides a preparation method of a special toughening resin for a cathode electrophoretic coating, which is specifically realized by the following technical scheme:
a preparation method of special toughening resin for cathode electrophoretic paint comprises the following operation steps:
mixing the polybasic fatty acid, the polyether amine, the polybasic fatty amine, the alcohol ether solvent and other raw materials, heating to the temperature of 200 ℃ and 250 ℃, and dehydrating to obtain amine modified polybasic fatty acid;
mixing amine modified polybasic fatty acid and bisphenol A epoxy resin at 90-120 ℃, preserving heat for 1-4h, cooling to 60 ℃, adding organic acid for neutralization, heating to 80 ℃, preserving heat, adding water for dilution after the acid value is less than 1, and obtaining the special toughening resin for cathode electrophoretic coating.
In a third aspect, the application provides an application of a special toughening resin for a cathode electrophoretic coating in the cathode electrophoretic coating.
In summary, the present application includes at least one of the following beneficial technical effects:
(1) according to the application, the raw material types and the mixing amount of the special toughening resin for the cathode electrophoretic paint are controlled, so that the adhesive force and the flexibility of the cathode electrophoretic paint are respectively 2-grade and 1.5-grade, the impact strength, the pencil hardness and the glossiness are respectively 55 cm-kg, 2H and 63%, and the adhesive force and the mechanical property of the cathode electrophoretic paint are improved.
(2) According to the application, the weight part ratio of the polybasic fatty acid to the bisphenol A epoxy resin in the raw materials of the special toughening resin for the cathode electrophoretic paint is controlled, so that the adhesive force and the flexibility of the cathode electrophoretic paint are respectively 1 grade and 1.5 grades, the impact strength, the pencil hardness and the glossiness are respectively 60 cm-kg, 2H and 68%, and the adhesive force and the mechanical property of the cathode electrophoretic paint are further improved.
(3) The method comprises the steps of adding cyanoethylated alcohol into a raw material of the special toughening resin for the cathode electrophoretic coating, and adjusting the weight part ratio of the cyanoethylated alcohol to the polyether amine, so that the adhesive force and the flexibility of the cathode electrophoretic coating are respectively 1 grade and 1 grade, and the impact strength, the pencil hardness and the glossiness are respectively 64 cm-kg, 3H and 76%.
(4) The raw materials of the special toughening resin for the cathode electrophoretic coating are added with the monoalkoxy titanate coupling agent and the nano lanthanum oxide, and the proportion of the monoalkoxy titanate coupling agent and the nano lanthanum oxide is adjusted, so that the adhesive force and the flexibility of the cathode electrophoretic coating are respectively 1 grade and 1 grade, the impact strength, the pencil hardness and the glossiness are respectively 69 cm-kg, 3H and 84%, and the adhesive force and the mechanical property of the cathode electrophoretic coating are further improved.
(5) According to the application, the raw materials of the special toughening resin for the cathode electrophoretic coating are added with the monoalkoxy titanate coupling agent and the nano lanthanum oxide, and then the cyanoethylated alcohol is added, so that the adhesion and flexibility of the cathode electrophoretic coating are respectively 0 grade and 1 grade, and the impact strength, pencil hardness and glossiness are respectively 72 cm-kg, 3.5H and 86%.
Detailed Description
The present application will be described in further detail with reference to specific examples.
The following raw materials are all commercially available products, and are all sufficient for disclosure of the raw materials in the present application, and should not be construed as limiting the source of the raw materials. The method specifically comprises the following steps: the bisphenol A type epoxy resin is selected from Gallery compliant building materials, Inc., model No. 6101; the polybasic aliphatic amine is selected from Shandong Ruili environmental protection science and technology limited, and the model is triethylene diacid; the polyether amine is selected from Shandong Xin chemical industry Co., Ltd, and the model is CX-JMA; the alcohol ether solvent is selected from chemical industry Limited of Jinnan Guangyu, and the content of effective substances is 99.9 percent; the organic acid catalyst is selected from Guangzhou branch company of the great chemical industry Co., Ltd, which is named as p-toluenesulfonic acid; the polybasic fatty acid is selected from Jun LONG CHEMICAL CORPORATION of Shandong, and has a model of dodecanedioic acid; the organic acid is selected from Sichuan Bo-Xuan chemical industry Co., Ltd, and the type of the organic acid is citric acid monohydrate; the cyanoethylated alcohol is selected from Hefeijian chemical industry Co.Ltd; the nanometer lanthanum oxide is selected from Shanghai Xiao Huan nanometer science and technology limited, and has a particle size of 50 nm; the monoalkoxy titanate coupling agent is selected from the chemical company of Nayayatsu, Inc., and is TM-S.
Example 1
The toughening resin special for the cathode electrophoretic coating of the embodiment 1 is obtained by the following operation steps:
mixing the polybasic fatty acid, the polyether amine, the polybasic fatty amine, the alcohol ether solvent and the organic acid catalyst according to the mixing amount shown in the table 1, heating to 250 ℃, and dehydrating to obtain amine modified polybasic fatty acid;
mixing amine modified polybasic fatty acid and bisphenol A epoxy resin at 120 ℃, preserving heat for 4h, cooling to 60 ℃, adding organic acid for neutralization, heating to 80 ℃, preserving heat, adding water for dilution after the acid value is less than 1, and obtaining the special toughening resin for the cathode electrophoretic coating.
Examples 2 to 5
The toughened resin special for the cathode electrophoretic coating in the embodiments 2 to 5 has the same preparation method and the same types of raw materials as those in the embodiment 1, and is different in the blending amount of each raw material, and the detailed description is shown in table 1.
TABLE 1 EXAMPLES 1-5 blending amounts (unit: kg) of raw materials of toughening resin for cathode electrophoretic coating
| Raw materials | Example 1 | Example 2 | Example 3 | Example 4 | Example 5 |
| Bisphenol A type epoxyResin composition | 2.3 | 2.3 | 2.3 | 2.3 | 2.3 |
| Polybasic fatty amines | 1.5 | 1.7 | 1.8 | 1.9 | 2.0 |
| Polyether amine | 0.5 | 0.7 | 0.8 | 0.9 | 1.0 |
| Alcohol ether solvent | 2 | 2.4 | 2.6 | 2.8 | 3.0 |
| Organic acid catalyst | 0.01 | 0.014 | 0.016 | 0.018 | 0.02 |
| Polybasic fatty acid | 1.3 | 1.3 | 1.3 | 1.3 | 1.3 |
| Organic acids | 4 | 6 | 7 | 8 | 10 |
| Water (I) | 5 | 7 | 8 | 9 | 10 |
Examples 6 to 9
The toughened resin special for the cathode electrophoretic coating in the embodiments 6 to 9 has the same preparation method and the same types of raw materials as those in the embodiment 3, except that the mixing amount of each raw material is different, and the detailed description is shown in table 2.
TABLE 2 EXAMPLES 6-9 blending amounts (unit: kg) of raw materials of toughening resin for cathode electrophoretic paint
| Raw materials | Example 6 | Example 7 | Example 8 | Example 9 |
| Bisphenol A epoxy resin | 2.25 | 2.5 | 2 | 2 |
| Polybasic fatty amines | 1.8 | 1.8 | 1.8 | 1.8 |
| Polyether amine | 0.8 | 0.8 | 0.8 | 0.8 |
| Alcohol ether solvent | 2.6 | 2.6 | 2.6 | 2.6 |
| Organic acid catalyst | 0.016 | 0.016 | 0.016 | 0.016 |
| Polybasic fatty acid | 1.5 | 1.38 | 1 | 1.5 |
| Organic acids | 7 | 7 | 7 | 7 |
| Water (W) | 8 | 8 | 8 | 8 |
Example 10
The toughening resin special for the cathode electrophoretic coating of the embodiment 10 is obtained by the following operation steps:
mixing the polybasic fatty acid, the polyether amine, the polybasic fatty amine, the alcohol ether solvent, the organic acid catalyst and the cyanoethylated alcohol according to the mixing amount shown in the table 3, heating to 250 ℃, and dehydrating to obtain amine modified polybasic fatty acid;
mixing amine modified polybasic fatty acid and bisphenol A epoxy resin at 120 ℃, preserving heat for 4h, cooling to 60 ℃, adding organic acid for neutralization, heating to 80 ℃, preserving heat, adding water for dilution after the acid value is less than 1, and obtaining the special toughening resin for the cathode electrophoretic coating.
Examples 11 to 13
The toughened resin special for the cathode electrophoretic coating in the embodiments 11 to 13 has the same preparation method and the same types of raw materials as those in the embodiment 10, except that the mixing amount of each raw material is different, and the details are shown in table 3.
TABLE 3 EXAMPLES 10-13 blending amounts (unit: kg) of raw materials of toughening resin for cathode electrophoretic coating
| Raw materials | Example 10 | Example 11 | Example 12 | Example 13 |
| Bisphenol A epoxy resin | 2.5 | 2.5 | 2.5 | 2.5 |
| Polybasic fatty amines | 1.8 | 1.8 | 1.8 | 1.8 |
| Polyether amine | 0.8 | 0.6 | 1 | 0.5 |
| Alcohol ether solvent | 2.6 | 2.6 | 2.6 | 2.6 |
| Organic acid catalyst | 0.016 | 0.016 | 0.016 | 0.016 |
| Polybasic fatty acid | 1.38 | 1.38 | 1.38 | 1.38 |
| Organic acids | 7 | 7 | 7 | 7 |
| Water (W) | 8 | 8 | 8 | 8 |
| Cyanoethylated alcohols | 0.4 | 0.2 | 0.25 | 0.33 |
Example 14
The toughening resin special for the cathode electrophoretic coating of the example 14 is obtained by the following operation steps:
according to the mixing amount shown in the table 4, mixing polybasic fatty acid, polyether amine, polybasic fatty amine, alcohol ether solvent, organic acid catalyst, nano lanthanum oxide and monoalkoxyl titanate coupling agent, heating to 250 ℃, and dehydrating to obtain amine modified polybasic fatty acid;
mixing amine modified polybasic fatty acid and bisphenol A epoxy resin at 120 ℃, preserving heat for 4h, cooling to 60 ℃, adding organic acid for neutralization, heating to 80 ℃, preserving heat, adding water for dilution after the acid value is less than 1, and obtaining the special toughening resin for the cathode electrophoretic coating.
Examples 15 to 17
The toughened resin special for the cathode electrophoretic coating in the embodiments 15 to 17 has the same preparation method and the same types of raw materials as those in the embodiment 14, except that the mixing amount of each raw material is different, and the details are shown in table 4.
TABLE 4 examples 14-17 blending amount (unit: kg) of each raw material of the toughening resin for cathode electrophoretic coating
Example 18
The toughening resin special for cathode electrophoretic coating in example 18 is completely the same as the preparation method and raw material type in example 15, except that 0.2kg of cyanoethylated alcohol is added to the raw material of the toughening resin special for cathode electrophoretic coating, and the types and the mixing amount of other raw materials are the same as those in example 15.
Comparative example 1
The toughening resin special for the cathode electrophoretic coating of the comparative example 1 is completely the same as the preparation method of the example 1, and the difference is that: the raw materials of the special toughening resin for the cathode electrophoretic coating are not added with polyether amine, and the other raw materials and the doping amount are the same as those in the embodiment 1.
Comparative example 2
The toughening resin special for the cathode electrophoretic coating of the comparative example 2 is completely the same as the preparation method of the example 1, and the difference is that: the raw materials of the special toughening resin for the cathode electrophoretic coating are not added with the polybasic aliphatic amine, and the other raw materials and the mixing amount are the same as those in the embodiment 1.
Application example 1
12.5kg of the special toughening resin for the cathode electrophoretic coating obtained in the example 1, 22.5kg of color paste, 0.5kg of alkylphenol polyoxyethylene ether and 2.5kg of acrylate dispersant are mixed and stirred uniformly to prepare the cathode electrophoretic coating.
Application examples 2 to 18
The application examples 2 to 18 are the same as the application example 1 in application method, and the difference is that the toughening resins of the examples 2 to 18 are respectively the toughening resins special for the cathode electrophoretic paint.
Application of comparative examples 1 to 2
The application comparative examples 1-2 are the same as the application example 1, except that the toughening resins special for the cathode electrophoretic coating of the comparative examples 1-2 are respectively used as the toughening resins.
Performance detection
The following test standards or methods were used to test the performance of the different application examples 1-18 and comparative examples 1-2, respectively, and the test results are detailed in Table 5.
Adhesion force: the adhesion of the cathodic electrophoretic coating is determined by GB/T9286-1998 test for marking the paint film of the colored paint and the varnish.
Flexibility: the flexibility of the cathode electrophoretic paint was measured by GB/T6742 bending test for paints and varnishes (cylindrical shaft).
Impact strength: the impact strength of the cathode electrophoretic paint is measured by GB/T1732-2020 paint film impact resistance measuring method.
Pencil hardness: GB/T6739 color paint and varnish: pencil hardness of cathode electrophoretic coating was measured by pencil method determination of film hardness.
Gloss: the 60 ℃ gloss of the cathodic electrocoat was determined by GB/T9754-2007 determination of 20 ℃, 60 ℃ and 85 ℃ specular gloss of pigmented paint films in which the paints and varnishes do not contain metallic pigments.
TABLE 5 Performance test results for different cathodic electrophoretic coatings
The detection results in table 5 show that the adhesion and flexibility of the cathode electrophoretic coating prepared from the toughening material obtained in the application are optimally 0-grade and 1-grade respectively, so that the adhesion and flexibility of the cathode electrophoretic coating are improved; meanwhile, the impact strength, pencil hardness and glossiness of the cathode electrophoretic coating obtained by the method are respectively 72 cm-kg, 3.5H and 86% to the maximum, and the method shows that the excellent mechanical property is kept while the adhesive force is improved.
In examples 1-5, the adhesion and flexibility of the cathodic electrophoretic coating in example 3 are respectively 2 grades and 1.5 grades, which are superior to those of examples 1-2 and examples 4-5; further, the impact strength, pencil hardness, and gloss of the cathodic electrodeposition paint of example 3 were 55 cm. multidot.kg, 2H, and 63%, respectively, which were higher than those of examples 1-2 and 4-5. The results show that the raw materials of the cathode electrophoretic paint in example 3 contain proper amounts of the polyhydric aliphatic amine, the polyether amine, the alcohol ether solvent and the organic acid, and the adhesion and the mechanical properties of the cathode electrophoretic paint are improved.
In examples 6-9, the adhesion and flexibility of the cathodic electrodeposition coating of example 7 were respectively 1 grade and 1.5 grades, which were superior to those of examples 6 and 8-9; further, the impact strength, pencil hardness, and gloss of the cathodic electrodeposition paint of example 7 were 60 cm. kg, 2H, and 68%, respectively, which were higher than those of examples 6 and 8 to 9. The raw materials of the special toughening resin for the cathode electrophoretic coating are properly mixed according to the weight ratio of 1:1.8 of the polybasic fatty acid to the bisphenol A epoxy resin, so that the adhesion and the mechanical property of the cathode electrophoretic coating are improved. Probably related to introducing a polybasic fatty acid flexible chain segment into bisphenol A epoxy resin molecules, reducing the crosslinking density of the grafted bisphenol A epoxy resin after curing, improving the toughness of a coating and improving the adhesive force of the coating to a coated workpiece.
In examples 10 to 13, the adhesion and flexibility of the cathodic electrodeposition coating of example 11 were respectively grade 1 and grade 1, which were superior to those of examples 10 and 12 to 13; further, the impact strength, pencil hardness, and gloss of the cathodic electrodeposition paint of example 11 were 64 cm. multidot.kg, 3H, and 76%, respectively, which were higher than those of examples 10 and 12 to 13. The result shows that when the weight ratio of the cyanoethylated alcohol to the polyether amine in the raw materials of the cathode electrophoretic coating is 1:3, the adhesion and the mechanical property of the cathode electrophoretic coating are improved. Possibly in connection with the addition of cyanoethylated alcohols to avoid the cleavage of ether linkages.
In examples 14-17, the adhesion and flexibility of the cathodic electrodeposition coating of example 15 were respectively grade 1 and grade 1, which are superior to those of examples 14 and 16-17; further, the impact strength, pencil hardness, and gloss of the cathodic electrodeposition paint of example 15 were 69 cm. kg, 3H, and 84%, respectively, which were higher than those of examples 14 and 16 to 17. The weight ratio of the monoalkoxy titanate coupling agent to the nano lanthanum oxide in the raw materials of the cathode electrophoretic coating is 1:3, so that the adhesion and the mechanical property of the cathode electrophoretic coating are improved. The method is probably related to the improvement of the adhesive force of the cathode electrophoretic coating by the nano lanthanum oxide and the improvement of the dispersibility of the nano lanthanum oxide in a special toughening resin raw material system for the cathode electrophoretic coating by the mono-alkoxy titanate coupling agent.
Combining example 18 with examples 14-17, it can be seen that the adhesion and flexibility of the cathodic electrocoat of example 18 are respectively 0-grade and 1-grade, which are superior to those of examples 14-17; further, the impact strength, pencil hardness, and gloss of the cathodic electrodeposition paint of example 15 were 72 cm. multidot.kg, 3.5H, and 86%, respectively, which were higher than those of examples 14 to 17. The raw materials of the cathode electrophoretic coating are added with the monoalkoxy titanate coupling agent and the nano lanthanum oxide, and then the cyanoethylated alcohol is added, so that the adhesion and the mechanical property of the cathode electrophoretic coating can be further improved. May be relevant.
The performance detection data of the cathode electrophoretic paint of the comparative examples 1-2 and the example 1 show that the adhesive force and the mechanical property of the cathode electrophoretic paint are improved to different degrees by adding the polyether amine and the multi-element fatty amine into the special toughening resin raw material for the cathode electrophoretic paint.
The present embodiment is only for explaining the present application, and it is not limited to the present application, and those skilled in the art can make modifications of the present embodiment without inventive contribution as needed after reading the present specification, but all of them are protected by patent law within the scope of the claims of the present application.
Claims (9)
1. The special toughening resin for the cathode electrophoretic coating is characterized by comprising the following raw materials in parts by weight: 2-2.5 parts of bisphenol A type epoxy resin, 1.5-2 parts of polybasic fatty amine, 0.5-1 part of polyether amine, 2-3 parts of alcohol ether solvent, 0.01-0.02 part of organic acid catalyst, 1-1.5 parts of polybasic fatty acid, 4-10 parts of organic acid and 5-10 parts of water.
2. The toughening resin special for the cathode electrophoretic coating according to claim 1, which is characterized by comprising the following raw materials in parts by weight: 2.2-2.4 parts of bisphenol A type epoxy resin, 1.7-1.9 parts of polybasic aliphatic amine, 0.7-0.9 part of polyether amine, 2.4-2.8 parts of alcohol ether solvent, 0.014-0.018 part of organic acid catalyst, 1.2-1.4 parts of polybasic fatty acid, 6-8 parts of organic acid and 7-9 parts of water.
3. The special toughening resin for the cathode electrophoretic coating according to claim 1, further comprising the following raw materials in parts by weight: 0.2-0.4 part of cyanoethylated alcohol.
4. The toughening resin special for the cathodic electrophoretic coating according to claim 3, characterized in that: the weight ratio of the cyanoethylated alcohol to the polyether amine is 1: (2-4).
5. The special toughening resin for the cathode electrophoretic coating according to claim 1, further comprising the following raw materials in parts by weight: 1-2 parts of nano lanthanum oxide and 0.3-0.7 part of monoalkoxyl titanate coupling agent.
6. The toughening resin special for the cathode electrophoretic coating according to claim 5, wherein: the weight ratio of the monoalkoxy titanate coupling agent to the nano lanthanum oxide is 1: (2.5-3.5).
7. The toughening resin special for the cathode electrophoretic coating according to claim 1, wherein: the weight ratio of the polybasic fatty acid to the bisphenol A epoxy resin is 1: (1.5-2).
8. A preparation method of the special toughened resin for the cathode electrophoretic coating, which is characterized by comprising the following operation steps:
mixing the polybasic fatty acid, the polyether amine, the polybasic fatty amine, the alcohol ether solvent and other raw materials, heating to the temperature of 200 ℃ and 250 ℃, and dehydrating to obtain amine modified polybasic fatty acid;
mixing amine modified polybasic fatty acid and bisphenol A epoxy resin at 90-120 ℃, preserving heat for 1-4h, cooling to 60 ℃, adding organic acid for neutralization, heating to 80 ℃, preserving heat, adding water for dilution after the acid value is less than 1, and obtaining the special toughening resin for cathode electrophoretic coating.
9. The application of the special toughening resin for the cathode electrophoretic coating of any one of claims 1 to 7 in the cathode electrophoretic coating.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210200707.1A CN114736353A (en) | 2022-03-01 | 2022-03-01 | Special toughening resin for cathode electrophoretic coating and preparation method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210200707.1A CN114736353A (en) | 2022-03-01 | 2022-03-01 | Special toughening resin for cathode electrophoretic coating and preparation method and application thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN114736353A true CN114736353A (en) | 2022-07-12 |
Family
ID=82275820
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202210200707.1A Pending CN114736353A (en) | 2022-03-01 | 2022-03-01 | Special toughening resin for cathode electrophoretic coating and preparation method and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN114736353A (en) |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5576416A (en) * | 1994-12-13 | 1996-11-19 | Air Products And Chemicals, Inc. | Amide-containing self-emulsifying epoxy curing agent |
| JPH08311392A (en) * | 1995-05-23 | 1996-11-26 | Abc Trading Co Ltd | Epoxy resin coating material |
| CN105969056A (en) * | 2016-06-02 | 2016-09-28 | 广德县中银化工有限责任公司 | High-throwing-power cathodic electrophoretic paint |
| CN109608622A (en) * | 2018-12-18 | 2019-04-12 | 江西原石科技有限公司 | A kind of non-ion aqueous polyamide curing agent and preparation method thereof |
| CN109627951A (en) * | 2018-12-18 | 2019-04-16 | 广东科德环保科技股份有限公司 | A kind of modified epoxy and preparation method thereof and high throwing power cathode electrophoresis dope |
-
2022
- 2022-03-01 CN CN202210200707.1A patent/CN114736353A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5576416A (en) * | 1994-12-13 | 1996-11-19 | Air Products And Chemicals, Inc. | Amide-containing self-emulsifying epoxy curing agent |
| JPH08311392A (en) * | 1995-05-23 | 1996-11-26 | Abc Trading Co Ltd | Epoxy resin coating material |
| CN105969056A (en) * | 2016-06-02 | 2016-09-28 | 广德县中银化工有限责任公司 | High-throwing-power cathodic electrophoretic paint |
| CN109608622A (en) * | 2018-12-18 | 2019-04-12 | 江西原石科技有限公司 | A kind of non-ion aqueous polyamide curing agent and preparation method thereof |
| CN109627951A (en) * | 2018-12-18 | 2019-04-16 | 广东科德环保科技股份有限公司 | A kind of modified epoxy and preparation method thereof and high throwing power cathode electrophoresis dope |
Non-Patent Citations (2)
| Title |
|---|
| SHIBATA M, ET AL: "Synthesis of sugar alcohol-derived water-soluble polyamines by the thiolene reaction and their utilization as hardeners of water-soluble bio-based epoxy resins", 《REACTIVE AND FUNCTIONAL POLYMERS》, vol. 118, pages 35 - 41, XP085155510, DOI: 10.1016/j.reactfunctpolym.2017.07.003 * |
| 王思学等: "水性环氧树脂固化剂的研究进展", 《涂料工业》, vol. 48, no. 8, pages 55 - 60 * |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US4432850A (en) | Ungelled polyepoxide-polyoxyalkylenepolyamine resins, aqueous dispersions thereof, and their use in cationic electrodeposition | |
| US4423166A (en) | Ungelled polyepoxide-polyoxyalkylenepolyamine resins, aqueous dispersions thereof, and their use in cationic electrodeposition | |
| US4420574A (en) | Ungelled polyepoxide-polyoxyalkylenepolyamine resins, aqueous dispersions thereof, and their use in cationic electrodeposition | |
| EP0070550A1 (en) | Aqueous dispersions of ungelled polyepoxide-polyoxyalkylenpolyamine resins and cationic resins, the use of such dispersions for electrocoating and articles electrocoated with such dispersions | |
| JPH024826A (en) | Glycidol modified polyepoxide-polyoxyalkylene polyamine adduct | |
| CN109294407B (en) | Water-based anticorrosive paint and preparation method thereof | |
| CN1374991A (en) | Cathodic electrocoating compositions having improved appearance, improved edge converage and reduced craters | |
| CN111073475A (en) | Water-based high-temperature-resistant polyester amino baking coating, preparation method and use method | |
| CN108192437B (en) | Water-based high-temperature metallic paint capable of being used for wet-on-wet floating-free system and construction process thereof | |
| CN106318130A (en) | High-performance epoxy resin heavy anti-corrosion paint | |
| CN107805798A (en) | Graphene prefilming agent and its preparation and application before coated metal | |
| CN106905664B (en) | Functional polyamine modified microgel, preparation method and application thereof | |
| JPH03430B2 (en) | ||
| CN111848878A (en) | Aqueous acrylic acid dispersion and preparation method and application thereof | |
| CN112341856B (en) | Conductive coating composition with corrosion resistance | |
| JP3253764B2 (en) | Electrocoat primer layer containing regenerated radical scavenger | |
| CN114736353A (en) | Special toughening resin for cathode electrophoretic coating and preparation method and application thereof | |
| US4769420A (en) | Binder which is rendered water-dilutable by protonation with an acid, from carboxyl terminated butadiene/acrylonitrile copolymers | |
| CN110791176A (en) | Cation electrophoretic paint main body resin and preparation method thereof | |
| CN112266671A (en) | High-hardness high-gloss environment-friendly coating for metal surface and preparation process thereof | |
| JPH0689275B2 (en) | Coating composition | |
| WO2023056756A1 (en) | Water-based one-component intermediate coating for helmets using electrostatic spraying | |
| CN109294369A (en) | A kind of water soluble acrylic acid baking vanish | |
| EP0125577B1 (en) | Low temperature aminoplast curable cationic electrodepositable coating compositions | |
| CN107083136B (en) | Polyacrylate paint and coating method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination |