CN108473798B - Acrylic copolymer for electrodeposition paint and process for producing the same - Google Patents
Acrylic copolymer for electrodeposition paint and process for producing the same Download PDFInfo
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- CN108473798B CN108473798B CN201680077210.8A CN201680077210A CN108473798B CN 108473798 B CN108473798 B CN 108473798B CN 201680077210 A CN201680077210 A CN 201680077210A CN 108473798 B CN108473798 B CN 108473798B
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/04—Acids; Metal salts or ammonium salts thereof
- C08F220/06—Acrylic acid; Methacrylic acid; Metal salts or ammonium salts thereof
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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
Abstract
The present invention relates to an acrylic copolymer for electrodeposition paint and a method for manufacturing the same, and more particularly to an acrylic copolymer and a method for manufacturing the same, which are capable of suppressing shrinkage cavities and improving the appearance quality of a coating layer by improving resistance to appearance deterioration caused by contaminants when the acrylic copolymer is used for electrodeposition paint.
Description
Technical Field
The present invention relates to an acrylic copolymer for electrodeposition paint and a method for manufacturing the same, and more particularly, to an acrylic copolymer and a method for manufacturing the same, which are capable of suppressing craters (oil components) and improving the appearance quality of a coating layer by improving resistance to appearance deterioration caused by contaminants when used in electrodeposition paint.
Background
U.S. patent No.3,963,663 discloses a cationic electrodeposition coating composition which contains a polyepoxy resin cured with a polyoxyalkylene polyamine and is capable of suppressing the generation of craters. In this patent, a resin obtained by reacting a polyoxypropylene diamine having a molecular weight of about 2,000 or about 400 with a polyepoxide as an intermediate of a binder resin is contained in a coating composition as a crater inhibitor. However, the adhesion of the coating composition using a polyoxypropylene diamine having a molecular weight of about 2,000 to the top coat was significantly reduced, while the removal function of craters was insufficient for the coating composition using a polyoxypropylene diamine having a molecular weight of about 400. That is, the coating composition disclosed in the U.S. patent may not improve both the function of suppressing coating craters and the adhesion of the coating.
In order to impart the anti-cratering property and the anti-oil stain property to the electrodeposition coating, acrylate and polybutene diene have been used in the electrodeposition coating. However, an electrodeposition layer formed by applying the electrodeposition paint has poor adhesion with a subsequently applied layer. In addition, electrodeposition coating compositions containing a depoling agent are unstable if stored at high temperatures for a long period of time. Therefore, if such unstable electrodeposition coating materials are applied, the resistivity, coulombic efficiency and film formation control as electrodeposition properties are insufficient. In addition, if a silicone additive is used to remove shrinkage cavities, defects of poor interlayer adhesion may occur.
U.S. patent No.5,501,779 discloses the addition of homopolymers or copolymers of alkyl vinyl ethers to cationic electrodeposition coatings. However, if such alkyl vinyl ether is applied to a coating, interlayer adhesion may be improved, but wettability to a primer or a topcoat may be reduced, and traces of a cleaning solvent may be left on the coating.
In order to remove the craters, methyl cellulose, ethyl cellulose, polyvinyl butyral, acrylic polymers, and the like are generally used in the electrodeposition coating material. Such a polymer increases the viscosity of the electrodeposition coating composition and suppresses the generation of craters on the coating surface. However, this method can affect the corrosion resistance of the coating.
Disclosure of Invention
Technical problem
An aspect of the present invention provides an acrylic copolymer capable of improving the appearance quality of a coating layer by increasing resistance to appearance deterioration caused by contaminants when the acrylic copolymer is used for an electrodeposition coating material, and a method for manufacturing the same.
Technical scheme
The acrylic copolymer of the present invention contains, as polymerized units, (1) a reaction product of a glycidyl group-containing compound and (meth) acrylic acid, (2) an aryl group-containing monomer, (3) an alkyl-modified acrylic monomer, (4) an amine group-containing acrylic monomer, (5) a silane-modified acrylic monomer, and (6) an alkoxysilane.
The method for producing an acrylic copolymer of the present invention comprises: (1) a step of reacting a glycidyl group-containing compound with (meth) acrylic acid; (2) copolymerizing the reaction product of step (1), an aryl group-containing monomer, an alkyl-modified acrylic monomer, an amine group-containing acrylic monomer, and a silane-modified acrylic monomer; and (3) a step of reacting the reaction product of step (2) with an alkoxysilane.
Advantageous effects
The acrylic copolymer of the present invention, when used in an electrodeposition coating, can suppress cratering and improve the appearance quality of a coating by increasing resistance to appearance deterioration caused by a siloxane-based contaminant having a low surface tension, which is undesirably introduced. In addition, the function of a curing reaction catalyst of the electrodeposition coating material can also be obtained by the tertiary amine group in the copolymer.
Best mode for carrying out the invention
Hereinafter, the present invention will be described in detail.
The term "(meth) acrylic acid" used in the present invention has a concept including acrylic acid, methacrylic acid, or a combination thereof.
The copolymer of the present invention contains a reaction product of a glycidyl group-containing compound and (meth) acrylic acid as a polymerization unit.
The glycidyl group-containing compound binds to an acid and plays a role in controlling a hydroxyl value (OH value), and an epoxy group-containing monomer can be used. Its Molecular Weight (MW) may be 250 to 620 and its glass transition temperature (Tg) may be-80 ℃ to 45 ℃. For example, glycidyl esters of carboxylic acids can be used as the glycidyl group-containing compound. As the glycidyl ester of a carboxylic acid, a glycidyl ester of a carboxylic acid having 9 to 10 carbon atoms (for example, 10 glycidyl versatate, trade name: Cardura E10P) can be used, but is not limited thereto.
The weight ratio of each component used in the reaction of the glycidyl group-containing compound and (meth) acrylic acid may be, for example: the glycidyl group-containing compound (meth) acrylic acid is 9:1 to 5:5, more preferably 7:3 to 6:4, but is not limited thereto.
The amount of the reaction product of the glycidyl group-containing compound and (meth) acrylic acid, which is a polymerized unit included in the copolymer of the present invention, may be, for example, 5 to 15% by weight, based on 100% by weight of the copolymer of the present invention in total, but is not limited thereto. If the amount of polymerized units of the reaction product of the glycidyl group-containing compound and (meth) acrylic acid in the copolymer is too low, unreacted acrylic acid may remain, thereby deteriorating the storage quality of the final reaction product. Conversely, if the amount is too high, the viscosity of the final reaction product may decrease.
The copolymer of the present invention further comprises an aromatic group-containing monomer as a polymerized unit.
The aryl group-containing monomer functions to control the glass transition temperature (Tg) of the resin, and may have a Molecular Weight (MW) of 80 to 120 and a glass transition temperature (Tg) of 25 ℃ to 130 ℃.
The amount of the aryl group-containing monomer, which is a polymerized unit included in the copolymer of the present invention, may be, for example, 10 to 40% by weight, based on the total 100% by weight of the copolymer of the present invention, but is not limited thereto. If the amount of the aromatic group-containing monomer polymerized units in the copolymer is too small, there is a disadvantage that the oil content-lowering effect becomes poor, whereas if it is too large, the viscosity of the final reaction product may increase.
The copolymer of the present invention further comprises an alkyl-modified acrylic monomer as a polymerized unit.
The alkyl-modified acrylic monomer functions to control the glass transition temperature (Tg) of the resin, and may have a Molecular Weight (MW) of 80 to 260 and a glass transition temperature (Tg) of-90 to 130 ℃. For example, the alkyl-modified acrylic monomer may use an alkyl (meth) acrylate, more specifically, one or more alkyl (meth) acrylates having 1 to 6 carbon atoms, such as an alkyl (meth) acrylate selected from the group consisting of methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, propyl acrylate, propyl methacrylate, n-butyl acrylate, n-butyl methacrylate, and combinations thereof, but is not limited thereto.
The amount of the alkyl-modified acrylic monomer, which is a polymerized unit included in the copolymer of the present invention, may be, for example, 30 to 65% by weight, based on the total 100% by weight of the copolymer of the present invention, but is not limited thereto. If the amount of the alkyl-modified acrylic monomer in the copolymer is too small, there is a possibility that a defect that the oil content reducing effect is deteriorated may occur. Conversely, if the amount is too large, the viscosity of the final reaction product may increase.
The copolymer of the present invention further comprises an acrylic monomer containing an amine group as a polymerized unit.
The amine group-containing acrylic monomer functions to control the amine value of the resin, and may have a Molecular Weight (MW) of 50 to 250 and a glass transition temperature (Tg) of-20 to 330 ℃. For example, the amine group-containing acrylic monomer may use a tertiary amine group-containing (meth) acrylic monomer, particularly a dialkylamino (meth) acrylate, more particularly one or more di (alkyl of 1 to 4 carbon atoms) amino (meth) acrylates. For example, one selected from the group consisting of dimethylamino acrylate, dimethylamino methacrylate, diethylamino acrylate, diethylamino methacrylate, dipropylamino acrylate, dipropylamino methacrylate, and a combination thereof may be used, but is not limited thereto.
The amount of the amine group-containing acrylic monomer, which is a polymerized unit included in the copolymer of the present invention, may be, for example, 1 to 10% by weight, based on the total 100% by weight of the copolymer of the present invention, but is not limited thereto. If the amount of the polymerized units of the amino group-containing acrylic monomer in the copolymer is too small, the oil content reducing effect may be deteriorated. Conversely, if the amount is too large, the color of the additive may darken.
The copolymer of the present invention further comprises a silane-modified acrylic monomer as a polymerized unit.
The silane-modified acrylic monomer functions to control the glass transition temperature (Tg) and surface tension of the resin, and may have a Molecular Weight (MW) of 200 to 250, and a glass transition temperature (Tg) of-70 to 80 ℃. For example, the silane-modified acrylic monomer may use an alkoxysilane group-containing (meth) acrylic monomer, particularly a monoalkoxysilane group-containing (meth) acrylate, a dialkoxysilane group-containing (meth) acrylate, or a trialkoxysilane group-containing (meth) acrylate, and more particularly one or more (meth) acrylates containing tri (alkoxy) silane groups of 1 to 3 carbon atoms. For example, one selected from the group consisting of 3- (trimethoxysilyl) propyl acrylate, 3- (trimethoxysilyl) propyl methacrylate, and combinations thereof may be used, but is not limited thereto.
The amount of the silane-modified acrylic monomer, which is a polymerized unit included in the copolymer of the present invention, may be, for example, 1 to 10% by weight, based on the total 100% by weight of the copolymer of the present invention, but is not limited thereto. If the amount of the silane-modified acrylic monomer polymerized units in the copolymer is too small, there is a possibility that a defect that the oil content reducing effect becomes poor may occur. Conversely, if the amount is too large, the viscosity of the final reaction product may increase.
The copolymers of the present invention also comprise alkoxysilanes as polymerized units.
The alkoxysilane functions to control the surface tension of the resin, and alkyltrialkoxysilane, more specifically, one or more selected from (alkyl group of 1 to 3 carbon atoms) tri (alkoxy group of 1 to 3 carbon atoms) silane and a combination thereof may be used. For example, methyltrimethoxysilane (molecular weight (MW): 136.22, boiling point 102 ℃ C.) can be used, but is not limited thereto.
The amount of the alkoxysilane, which is a polymerized unit included in the copolymer of the present invention, may be, for example, 1 to 10% by weight, based on the total 100% by weight of the copolymer of the present invention, but is not limited thereto. If the amount of the alkoxysilane polymerization unit in the copolymer is too small, there is a possibility that a defect that the oil content reducing effect becomes poor may occur. Conversely, if the amount is too large, the viscosity of the final reaction product may increase.
The acrylic copolymer of the present invention can be prepared by a process comprising the steps of: (1) a step of reacting a glycidyl group-containing compound with (meth) acrylic acid; (2) copolymerizing the reaction product of step (1), an aryl group-containing monomer, an alkyl-modified acrylic monomer, an amine group-containing acrylic monomer, and a silane-modified acrylic monomer; and (3) a step of reacting the reaction product of step (2) with an alkoxysilane.
The copolymerization of the above monomer components may be carried out in a water-soluble solvent (e.g., butyl cellosolve, ionized water, etc.) in the presence of an initiator (e.g., benzoyl peroxide).
According to an embodiment of the present invention, the acrylic copolymer thus prepared may have a solid content of 40% to 60%, a viscosity of U-Z3, an acid value of 5mgKOH/g to 30mgKOH/g, and an amine value of 10mgKOH/g to 20mgKOH/g, but is not limited thereto.
Hereinafter, the present invention will be explained in more detail with reference to examples. However, the scope of the present invention is not limited thereto.
[ examples ]
Example 1
To a four-necked flask equipped with a thermometer and a stirring device, 72g of Cardura E10P was placed, and 28g of acrylic acid was added dropwise over 1 hour, and the reaction was continued until the acid value was unchanged.
250g of butyl cellosolve and 250g of ionized water were charged into another four-necked flask, and the temperature was raised to 90 ℃ to 97 ℃ (the temperature being a temperature at which reflux was to be started). Then, a mixture of 28g of the reaction product of Cardug E10P with acrylic acid, 142g of styrene, 24g of diethylamino methacrylate, 149g of n-butyl acrylate, 98g of n-butyl methacrylate, 25g of 3- (trimethoxysilyl) propyl methacrylate and 10g of benzoyl peroxide was added dropwise to the flask uniformly over 4 hours. After the end of the dropwise addition, the mixture was kept at 95 ℃ for 2 hours. When the viscosity was not changed, the reaction product was cooled to 60 ℃ and 25g of methyltrimethoxysilane was added dropwise over 2 hours, followed by cooling to obtain a resin having a solid content of 50%, a viscosity of Z, an acid value of 4mgKOH/g and an amine value of 15 mgKOH/g.
Example 2
To a four-necked flask equipped with a thermometer and a stirring device, 72g of Cardura E10P was placed, and 28g of acrylic acid was added dropwise over 1 hour, and the reaction was continued until the acid value was unchanged.
250g of butyl cellosolve and 250g of ionized water were charged into another four-necked flask, and the temperature was raised to 90 ℃ to 97 ℃ (the temperature being a temperature at which reflux was to be started). Then, a mixture of 51g of the reaction product of Cardug E10P with acrylic acid, 147g of styrene, 24g of diethylamino methacrylate, 239g of n-butyl acrylate, 5g of 3- (trimethoxysilyl) propyl methacrylate and 10g of benzoyl peroxide was added dropwise to the flask uniformly over 4 hours. After the end of the dropwise addition, the mixture was kept at 95 ℃ for 2 hours. When the viscosity was not changed, the reaction product was cooled to 60 ℃ and 25g of methyltrimethoxysilane was added dropwise over 2 hours, followed by cooling to obtain a resin having a solid content of 50%, a viscosity of Z, an acid value of 7mgKOH/g and an amine value of 15 mgKOH/g.
Example 3
To a four-necked flask equipped with a thermometer and a stirring device, 72g of Cardura E10P was placed, and 28g of acrylic acid was added dropwise over 1 hour, and the reaction was continued until the acid value was unchanged.
250g of butyl cellosolve and 250g of ionized water were charged into another four-necked flask, and the temperature was raised to 90 ℃ to 97 ℃ (the temperature being a temperature at which reflux was to be started). Then, a mixture of 28g of the reaction product of Cardug E10P with acrylic acid, 171g of styrene, 24g of diethylamino methacrylate, 120g of n-butyl acrylate, 98g of n-butyl methacrylate, 25g of 3- (trimethoxysilyl) propyl methacrylate and 10g of benzoyl peroxide was added dropwise uniformly to the flask over 4 hours. After the end of the dropwise addition, the mixture was kept at 95 ℃ for 2 hours. When the viscosity was not changed, the reaction product was cooled to 60 ℃ and 25g of methyltrimethoxysilane was added dropwise over 2 hours, followed by cooling to obtain a resin having a solid content of 50%, a viscosity of Z, an acid value of 5mgKOH/g and an amine value of 15 mgKOH/g.
Comparative example 1
To a four-necked flask equipped with a thermometer and a stirring device, 72g of Cardura E10P was placed, and 28g of acrylic acid was added dropwise over 1 hour, and the reaction was continued until the acid value was unchanged.
250g of butyl cellosolve and 250g of ionized water were charged into another four-necked flask, and the temperature was raised to 90 ℃ to 97 ℃ (the temperature being a temperature at which reflux was to be started). Then, a mixture of 28g of the reaction product of Cardug E10P with acrylic acid, 142g of styrene, 24g of diethylamino methacrylate, 149g of n-butyl acrylate, 147g of n-butyl methacrylate and 10g of benzoyl peroxide was added dropwise to the flask uniformly over 4 hours. After the end of the dropwise addition, the mixture was kept at 95 ℃ for 2 hours. The reaction product was cooled to 60 ℃ to obtain a resin having a solid content of 50%, a viscosity of Z, an acid value of 11mgKOH/g and an amine value of 15 mgKOH/g.
Comparative example 2
To a four-necked flask equipped with a thermometer and a stirring device, 72g of Cardura E10P was placed, and 28g of acrylic acid was added dropwise over 1 hour, and the reaction was continued until the acid value was unchanged.
250g of butyl cellosolve and 250g of ionized water were charged into another four-necked flask, and the temperature was raised to 90 ℃ to 97 ℃ (the temperature being a temperature at which reflux was to be started). Then, a mixture of 28g of the reaction product of Cardug E10P with acrylic acid, 142g of styrene, 24g of diethylamino methacrylate, 110g of n-butyl acrylate, 76g of n-butyl methacrylate, 55g of 3- (trimethoxysilyl) propyl methacrylate and 10g of benzoyl peroxide was added dropwise uniformly to the flask over 4 hours. After the end of the dropwise addition, the mixture was kept at 95 ℃ for 2 hours. When the viscosity was not changed, the reaction product was cooled to 60 ℃ and 55g of methyltrimethoxysilane was added dropwise over 2 hours, followed by cooling to obtain a resin having a solid content of 50%, a viscosity of Z, an acid value of 11mgKOH/g and an amine value of 15 mgKOH/g.
Each of the Acrylic Copolymers (ACA) thus obtained (examples 1 to 3 and comparative examples 1 and 2) was applied to an electrodeposition coating material having the composition shown in table 1 below, and the measured physical properties are shown in table 2.
[ Table 1]
The main reagents are as follows: ED2800-A-BLACK (KCC Corp.)
Curing agent: ED2800-B (K) (KCC Co.)
[ Table 2]
Method for evaluating physical properties
1. Oil removal effect
To the electrodeposition paint containing no oily additive (trade name: ED2800) was poured 250ppm of an rust preventive oil and stirred for 30 minutes. The samples were coated with the resulting product at a voltage of 180V. Then, the acrylic copolymer of each example was added in an amount of 0.4% of the bath, followed by stirring for 30 minutes. The samples were then coated with the resulting product. The oil content reduction effect before and after addition of the acrylic copolymer was compared and evaluated.
2. Mechanical Properties
1) The test specimens produced according to the regulations are required to be planar and to be free of foreign matter on the uncoated back of the test specimens to prevent impact absorption.
2) Since the impact characteristics are affected by temperature, it is necessary to set the temperature of the impact tester and the specimen to 21 ± 2 ℃.
3) Confirm whether the dimensions of the bottom of the impact tester and the insert (pludge) are correct, place the test specimen in the bottom position, and let the pendulum with fixed weight fall.
4) If there is no particular regulation, the impact is tested by the front method (front method) in which impact is applied to the coated surface. In special cases, the dimensions of the base and insert are fixed (typically, unless otherwise noted, the insert is 1/2 inches in size).
5) The circular edge portion of the depressed portion caused by the impact was examined to evaluate whether or not a crack was generated.
6) The impact test of the fixed height is repeated two or more times, and if there is no crack, the height is increased and the impact test is repeated.
7) The maximum height (cm) without cracks was taken as the result value.
8) The standard value and the result value are compared.
3. Evaluation of adhesion
1) In the center portion of the sample, 11 parallel lines were drawn in each of the length direction and the width direction at a gap of 1mm or 2mm, respectively, to obtain 100 square lattices in a checkerboard shape (in which the line pitch of the primer was 1mm and the top coat was 2 mm).
2) In drawing these lines, the angle of the front end of the knife used for cutting with respect to the drawing sheet was maintained at a constant angle in the range of 35 ° to 45 °, and the knife was stroked at the same rate of about 0.5 seconds per division while contacting the bottom of the specimen.
3) A nichin tape having a width of 2 inches was firmly attached to the cross-cut portion to discharge air.
4) The tape was grasped by hand and pulled forcefully at an angle of 45 degrees toward the body side.
5) The evaluations were carried out according to the annex regulations, and the adhesion was evaluated by M-1 to M-5, where M-1 corresponds to the best adhesion.
4. Hardness of pencil
1) If not specified, a hardness pencil of Mitsubishi corporation (Japan) is used.
2) Samples that were left for at least 24 hours under the specified curing conditions were used as the dried coating.
3) The pencil lead is rubbed on 1000-mesh abrasive paper at a right angle to enable the arc of the pencil lead to be at a right angle, and then the abrasive paper powder on the pencil lead is removed by using soft cloth.
4) Five parallel lines of 2cm in length were drawn at an angle of 45 degrees to the coating in the direction of the ruler in the upward direction of the body, and a load of about 500g was applied when drawn. In this case, the hexagonal edge of the pencil is rotated slowly so that the pencil lead with the rounded right angle is not used twice.
5) Half of the five parallel lines were gently wiped with an eraser and the pencil was checked for wear of the coating.
6) The above test was repeated using sequentially low to high hardness pencils.
7) If no significant damage was found in three or more of the five parallel lines, it was evaluated as having the same hardness as the pencil grade used.
5. Exfoliation Property
1) The sample and 50g of flying stone (fly' g stone) were placed in a cold-resistant chamber (-40 ℃ C.) for 3 hours.
2) After standing for 3 hours, the test was carried out by the same method as the standard conditions.
3) The finished test specimens were dehumidified and ethylene tape was used to remove pieces of the coating.
4) The samples were examined and rated.
As shown in table 2, examples 1 to 3, which are equivalent to the electrodeposition coating composition comprising the acrylic copolymer of the present invention, were found to exhibit excellent oil removal (anti-cratering) effect and excellent physical properties such as mechanical performance properties and adhesion, as compared to comparative examples 1 and 2. That is, it was found that if the acrylic copolymer of the present invention is used in an electrodeposition paint, oil can be removed and the appearance of the coating can be improved.
Claims (5)
1. An acrylic copolymer comprising as polymerized units:
(1) reaction products of glycidyl group-containing compounds with (meth) acrylic acid,
(2) a monomer containing an aromatic group, wherein the aromatic group is a linear aromatic group,
(3) an alkyl-modified acrylic monomer, wherein the acrylic monomer is a linear or branched acrylic monomer,
(4) an acrylic monomer containing an amino group, wherein,
(5) a silane-modified acrylic monomer, and
(6) an alkoxysilane(s) in a liquid phase comprising at least one alkoxy silane,
wherein the acrylic copolymer comprises, based on 100 wt% total of the copolymer:
5 to 15% by weight of the reaction product of the glycidyl group-containing compound and (meth) acrylic acid,
10 to 40 weight percent of the aryl-containing monomer,
30 to 65 weight percent of the alkyl-modified acrylic monomer,
1 to 10% by weight of the amine group-containing acrylic monomer,
1 to 10% by weight of the silane-modified acrylic monomer, and
1 to 10 weight percent of the alkoxysilane.
2. The acrylic copolymer of claim 1, wherein the weight ratio of the glycidyl group containing compound to the (meth) acrylic acid is from 9:1 to 5: 5.
3. The acrylic copolymer of claim 1 wherein the amine group containing acrylic monomer has a molecular weight of 50 to 250 and a Tg of-20 to 330 ℃.
4. The acrylic copolymer of claim 1, wherein the silane-modified acrylic monomer has a molecular weight of 200 to 250 and a Tg of-70 to 80 ℃.
5. A method for producing an acrylic copolymer, comprising:
(1) a step of reacting a glycidyl group-containing compound with (meth) acrylic acid;
(2) copolymerizing the reaction product of step (1), an aryl group-containing monomer, an alkyl-modified acrylic monomer, an amine group-containing acrylic monomer, and a silane-modified acrylic monomer; and
(3) a step of reacting the reaction product of step (2) with an alkoxysilane,
wherein the acrylic copolymer comprises, based on 100 wt% total of the copolymer:
5 to 15% by weight of the reaction product of the glycidyl group-containing compound and (meth) acrylic acid,
10 to 40 weight percent of the aryl-containing monomer,
30 to 65 weight percent of the alkyl-modified acrylic monomer,
1 to 10% by weight of the amine group-containing acrylic monomer,
1 to 10% by weight of the silane-modified acrylic monomer, and
1 to 10 weight percent of the alkoxysilane.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| KR1020150189553A KR101820581B1 (en) | 2015-12-30 | 2015-12-30 | Acrylic copolymer for electrodeposition paint and method for preparing the same |
| KR10-2015-0189553 | 2015-12-30 | ||
| PCT/KR2016/015479 WO2017116165A1 (en) | 2015-12-30 | 2016-12-29 | Acrylic copolymer for electrodeposition paint and manufacturing method therefor |
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| Publication Number | Publication Date |
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| CN108473798A CN108473798A (en) | 2018-08-31 |
| CN108473798B true CN108473798B (en) | 2020-06-12 |
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| CN201680077210.8A Active CN108473798B (en) | 2015-12-30 | 2016-12-29 | Acrylic copolymer for electrodeposition paint and process for producing the same |
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| Country | Link |
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| KR (1) | KR101820581B1 (en) |
| CN (1) | CN108473798B (en) |
| RU (1) | RU2705954C1 (en) |
| TR (1) | TR201809321T1 (en) |
| WO (1) | WO2017116165A1 (en) |
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| KR102222229B1 (en) * | 2020-12-10 | 2021-03-04 | 윤상훈 | Orgainc-inorganic hybrid asphalt coating agent for repair and reinforcement of asphalt and asphalt coated the same |
| KR102599546B1 (en) * | 2021-04-14 | 2023-11-07 | 주식회사 케이씨씨 | Acrylic composition for electro-deposition coating |
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| US5908910A (en) * | 1996-12-23 | 1999-06-01 | E. I. Du Pont De Nemours And Company | Cathodic electrocoating compositions containing an anticrater agent |
| EP1149876A2 (en) * | 2000-04-24 | 2001-10-31 | Kansai Paint Co., Ltd. | Electrodeposition coating composition |
| CN102388108A (en) * | 2009-03-31 | 2012-03-21 | Ppg工业俄亥俄公司 | Electrocoating composition comprising a crater control additive |
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| JPS61115974A (en) * | 1984-11-09 | 1986-06-03 | Nippon Paint Co Ltd | Composition for cationic electrodeposition coating |
| DE19508544A1 (en) * | 1995-03-10 | 1996-09-12 | Bollig & Kemper | Modified acrylic copolymer |
| JP4126570B2 (en) * | 1996-10-07 | 2008-07-30 | 日本ペイント株式会社 | Cationic electrodeposition coating composition having excellent repellency resistance |
| JP2001064568A (en) | 1999-08-25 | 2001-03-13 | Kansai Paint Co Ltd | Anionic electrodeposition coating composition |
| BR0017309A (en) | 2000-07-31 | 2003-09-30 | Ppg Ind Ohio Inc | Dual cure coating compositions having improved scratch resistance, coated substrates and related methods |
| US7264705B2 (en) * | 2004-10-18 | 2007-09-04 | E. I. Dupont De Nemours And Company | Cathodic electrocoating compositions containing an anti-crater agent |
| US8057592B2 (en) * | 2007-07-20 | 2011-11-15 | Ppg Industries Ohio, Inc. | Cationic electrodepositable coatings comprising rosin |
| KR101477751B1 (en) * | 2008-05-08 | 2014-12-30 | 주식회사 케이씨씨 | Binder composition using modified, chlorinated polyolefin acryl copolymer, process for preparing the same and coating composition comprising the same |
| KR20110112386A (en) * | 2008-12-29 | 2011-10-12 | 바스프 코팅스 게엠베하 | Pyridine group-containing electrocoat resin |
| KR101311759B1 (en) * | 2011-03-23 | 2013-09-26 | 주식회사 케이씨씨 | Acrylic powder coating composition with excellecnt corrosionresistance and adherence |
| BR112014000689A2 (en) * | 2011-07-13 | 2017-02-14 | Nissan Motor | painting composition and method for forming coating film using the same |
-
2015
- 2015-12-30 KR KR1020150189553A patent/KR101820581B1/en active Search and Examination
-
2016
- 2016-12-29 CN CN201680077210.8A patent/CN108473798B/en active Active
- 2016-12-29 WO PCT/KR2016/015479 patent/WO2017116165A1/en active Application Filing
- 2016-12-29 RU RU2018121950A patent/RU2705954C1/en active
- 2016-12-29 TR TR2018/09321T patent/TR201809321T1/en unknown
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5908910A (en) * | 1996-12-23 | 1999-06-01 | E. I. Du Pont De Nemours And Company | Cathodic electrocoating compositions containing an anticrater agent |
| EP1149876A2 (en) * | 2000-04-24 | 2001-10-31 | Kansai Paint Co., Ltd. | Electrodeposition coating composition |
| CN102388108A (en) * | 2009-03-31 | 2012-03-21 | Ppg工业俄亥俄公司 | Electrocoating composition comprising a crater control additive |
Also Published As
| Publication number | Publication date |
|---|---|
| WO2017116165A1 (en) | 2017-07-06 |
| KR20170080769A (en) | 2017-07-11 |
| TR201809321T1 (en) | 2018-07-23 |
| RU2705954C1 (en) | 2019-11-12 |
| KR101820581B1 (en) | 2018-01-22 |
| CN108473798A (en) | 2018-08-31 |
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