JPS6226324B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a novel nitrogen-containing acrylic resin that can be deposited onto a cathode by electrodeposition, a method for producing the same, a coating material made of the resin, and a method for using the same. A coating method in which a coating material is deposited on the surface of an object by electrophoresis using an electrode as an electrode is generally called electrodeposition coating, and is widely used for car body painting and the like. Electrodeposition coating methods are divided into anionic electrodeposition methods in which the object to be coated serves as an anode, and cationic electrodeposition methods in which the object to be coated serves as a cathode. Among these, the latter cationic electrodeposition method uses the metal of the object to be coated as a cathode, so it is a technique that has the great advantage that there is no elution of metal ions. Currently used compositions for cationic electrodeposition include, for example, reacting an epoxy resin with a secondary amine to convert the epoxy group into α-dialkylamino-
A typical example is one converted to a β-hydroxyethyl group. The present inventors have endeavored to develop a new cationic electrodeposition material, that is, a cathodic electrodeposition coating, and as a result, have discovered a novel linear copolymer. That is, the copolymer of the present invention is a linear copolymer containing a repeating unit represented by structural formula (A) and a repeating unit represented by structural formula (B). (Hereinafter abbreviated as "copolymer AB".) [Wherein R ₁ and R ₂ are hydrogen, an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group, an alkenyl group, an aminoalkyl group, an aryl group having 6 to 20 carbon atoms,
or arylalkyl group, R ₃ is hydrogen, methyl group, halogen, carboxymethyl group, acetoxy group, CH ₂ COOR ₅ (R ₅ is hydrogen, carbon number 1 to 10
(alkyl group or arylalkyl group), or an alkoxy group having 1 to 5 carbon atoms, R ₄ is hydrogen, an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group, an alkenyl group, an aryl group having 6 to 20 carbon atoms, Arylalkyl group, carbon number 1 to 12
haloalkyl group, hydroxyalkyl group, alkoxyalkyl group, tetrahydrofurfuryl group,
Glycidyl group, -( _CH2 - _CH2 -O) _{-o R6} ( _R6 is an alkyl group having 1 to 8 carbon atoms, n is an integer of 1 to 30), or dialkylaminoalkyl group having 3 to 20 carbon atoms represents. ] In the above formula, when one of R ₁ and R ₂ is hydrogen, it becomes a copolymer with a secondary amino group in the side chain, and further derivatives can be produced by taking advantage of the reactivity peculiar to the amino group. It was found that it is possible,
It has become clear that this is one of the preferred embodiments. Further, either R ₁ or R ₂ is hydrogen, and the other is preferably an alkyl group having 1 to 20 carbon atoms or an aminoalkyl group, particularly an alkyl group having 2 to 8 carbon atoms or an aminoalkyl group. in particular,
Examples include ethyl group, n-propyl group, isopropyl group, butyl group, and aminoethyl group. Also R ₁ , R ₂
It is also preferable that both are an alkyl group or an aminoalkyl group. Specifically, R ₁ and R ₂ are selected from a methyl group, an ethyl group, and an aminoethyl group. In structural formula (A), the substituted aminoethyl group, which is a side chain substituent, may be bonded to any position with respect to the main chain, but is preferably at the p-position for ease of production. In structural formula (B), R ₃ is generally hydrogen, a methyl group, or an alkoxycarbonylmethyl group, and R ₄ is hydrogen, an alkyl group having 1 to 20 carbon atoms, or a hydroxyalkyl group having 1 to 12 carbon atoms. groups, especially hydroxyethyl. Furthermore, a dialkylaminoalkyl group having 3 to 20 carbon atoms is preferred, and a diethylaminoethyl group is particularly preferred. If a preferred specific combination of R ₃ and R ₄ is expressed in the form (R ₃ , R ₄ ), (H, CH ₃ ), (H, C ₂ H ₅ ), (H, C ₄ H ₉ ) ,
(H, C ₈ H ₁₇ ), (H, CH ₂ CH ₂ OH), (H, H),
(H, CH ₂ CH ₂ N(CH ₃ ) ₂ ), (CH ₃ , CH ₃ ),
(CH ₃ , C ₂ H ₅ ), (CH ₃ , C ₄ H ₉ ), (CH ₃ , C ₈ H ₁₇ ),
(CH ₃ , C ₁₂ H ₂₅ ), (CH ₃ , C ₁₈ H ₃₇ ), (CH ₃ , cyclo
-C ₆ H ₁₁ ), (CH ₃ , H), (CH ₃ , CH ₂ CH ₂ OH),
( _CH3 , _CH2 , _CH2N ( _CH3 ) ₂ ), ( _CH3 ,

[Formula]), (CH ₃ ,

[Formula]) etc. Each of R ₁ , R ₂ , R ₃ and R ₄ is not limited to one type, and mixtures of two or more types are also included in the present invention. There is no restriction on the weight fraction of the moiety represented by structural formula (A) based on the total copolymer, but it is preferably 1 to 90% by weight, more preferably 3 to 80% by weight. As the fraction of the moiety represented by structural formula (A) increased, the specific conductivity in electrodeposition increased. Although there is no restriction on the molecular weight of the copolymer AB of the present invention, it is preferable that the number average molecular weight is 1,000 to 500,000. Furthermore, in the copolymer AB of the present invention, part of the portion represented by the structural formula (B) in its structure can be replaced with a repeating unit structure represented by the following formula (H). In the formula, X is hydrogen, methyl group or halogen, Y
is a phenyl group, a nitrile group,

[expression] or

[Formula] (R is selected from an alkyl group and a halogen). Copolymer AB of the present invention can be obtained by copolymerizing monomers having structures represented by the following formulas (C) and (D). The definitions and preferably examples of R ₁ , R ₂ , R ₃ and R ₄ are as already mentioned. A general method for producing monomer (C) is to convert an amine represented by the following Mizozo formula (E) (hereinafter referred to as "amine E" or simply "amine") into the corresponding alkali metal amide ( It is reacted with divinylbenzene in the coexistence of F). (In the formula, R ₁ and R ₂ have the same meanings as above, and M represents an alkali metal.) In this case, as the alkali metal, lithium is preferable due to its high reactivity and ease of reaction operation. A preferred method for preparing lithium amide is a method in which an amine is reacted with alkyllithium, phenyllithium, aluminum lithium hydride, lithium hydride, etc. Among these, alkyllithium is preferable due to its solubility in solvents, operability, etc. It is particularly preferred to use Lithium amide (F) corresponding to amine E is also simply referred to as "lithium amide" hereinafter. As divinylbenzene, p-divinylbenzene, m-divinylbenzene, or a mixture thereof can be used. Furthermore, although commercially available divinylbenzene contains ethylvinylbenzene as an impurity, such crude divinylbenzene can also be used.
However, when crude divinylbenzene is used as a starting material, a product derived from ethylvinylbenzene may be produced as a by-product. p-Divinylbenzene has a high reaction rate and produces by-products as described below.
(G) is more preferable as a raw material because it is difficult to produce. As the amine, a primary amine or a secondary amine can be used, but methiamine and ammonia have low reactivity and are not preferred. As primary amines, ethylamine, n-propylamine,
Isopropylamine, n-butylamine, sec-
Alkylamines such as butylamine, tert-butylamine, pentylamine, 2-ethylhexylamine, dodecylamine, octadecylamine, cycloalkylamines such as cyclohexylamine, cyclopentylamine, unsaturated amines such as allylamine, benzylamine, aniline, etc., hydrocarbons It is a primary amine having a group. Examples of secondary amines include dialkylamines such as dimethylamine, diethylamine, dipropylamine, dibutylamine, and dioctylamine, dicyclohexylamine,
Secondary amines having a hydrocarbon group include dicycloalkylamines such as dicyclopropylamine, cyclic amines such as ethyleneimine, and unsaturated amines such as diallylamine. Furthermore, diamines or triamines such as ethylenediamine, trimethylenediamine, hexamethylenediamine, octamethylenediamine, dodecamethylenediamine, diethylenetriamine, dipropylenetriamine, N-methylethylenediamine, N-ethylethylenediamine, and N·N'-diethylethylenediamine are also used. be able to. When a primary amino group and a secondary amino group coexist in one molecule, generally the more reactive secondary amino group is selectively added to the double bond of divinylbenzene. Among these, ethylamine, n-propylamine, isopropylamine, butylamine, N-methylethylenediamine, and N-ethylethylenediamine are particularly preferred. In this reaction, lithium amide F performs a catalytic action. This is one of the major features of this reaction. In other words, it is sufficient to use lithium amide F in an equimolar amount or less relative to divinylbenzene, preferably in a molar ratio of 0.01 to 0.5.
Double the amount, more preferably 0.01 to 0.2 times the amount. At this time, it should be kept in mind that the concentration of lithium amide F controls the reaction rate. Since lithium amide is deactivated by reacting with substances containing active hydrogen such as water, alcohol, and acids coexisting in the reaction system, it is preferable to dehydrate and otherwise purify the raw materials and solvents used. When a substance having active hydrogen is mixed, it is desirable to use lithium amide F in a predetermined amount or more. As already mentioned, lithium amides can be easily prepared, for example, by reacting an alkyllithium with an amine. As the alkyl lithium, methyl lithium, ethyl lithium, butyl lithium, etc. can be used, but among these, n-butyl lithium, which is also produced industrially, is particularly preferred from the viewpoint of easy availability. Although the amine causes a stoichiometric reaction with divinylbenzene, the amount used is preferably 0.3 to 2.5 times, more preferably 0.6 to 1.3 times, molar ratio to divinylbenzene. If the amount of amine is too small, the amount produced will naturally decrease. Furthermore, if an excessive amount is used, a product (G) in which amines are added to both vinyl groups may be produced, which is not preferable. There are, for example, the following two methods for reacting the mixture of lithium amide and amine with divinylbenzene. The first method is to add the former mixture to divinylbenzene.
This method has the advantage of suppressing the formation of by-products. A second method, in which divinylbenzene is added to the lithium amide and amine mixture, requires only one reaction vessel.
Advantages include that it only requires a container and that there is no need to transfer the lithium amide solution. This reaction can also be carried out in the presence of an inert solvent. Examples of solvents include aliphatic hydrocarbons such as pentane, hexane, cyclohexane, and octane, aromatic hydrocarbons such as benzene and toluene, ethers such as diethyl ether, dioxane, and tetrahydrofuran, dimethyl sulfoxide, N/N'-dimethylformamide, Liquids that do not react with lithium amide under the reaction conditions can be used, such as aprotic polar solvents such as hexamethylphosphoric triamide. Among these, hexane, cyclohexane, benzene, tetrahydrofuran and the like are more preferred. In particular, when tetrahydrofuran is used, the reaction rate is high and the reaction time can be shortened. Furthermore, aliphatic hydrocarbons such as hexane are commonly used as completely inert solvents. The amount of solvent used is the volume of divinylbenzene.
Preferably 0.1 to 50 times, more preferably 0.5
It is 20 to 20 times larger. The reaction generally slows down as the relative amount of solvent increases. The temperature at which this reaction is carried out is not particularly limited, but is preferably -50°C to 100°C, more preferably -20°C to 50°C. When carrying out the reaction above the boiling point of the amine or solvent, it is necessary to use a pressure vessel. It is also preferred that the reaction mixture be stirred or shaken. The reaction time is not limited, but preferably 1 minute to 24 hours, more preferably 5 minutes to 8 hours.
The reaction rate depends on temperature, type of amine, concentration of raw materials,
The reaction time should be set depending on the conditions, as it is largely controlled by the type of solvent, etc., but during the reaction,
It is recommended to determine the end time of the reaction by sampling over time and quantifying the raw materials and products using gas chromatography, liquid chromatography, etc. To stop the reaction,
It is necessary to deactivate the lithium compound with alcohol such as ethanol or propanol, water, or the like. Monomer C, which is a product, can be isolated by distillation, column chromatography, or by adding hydrochloric acid or hydrogen chloride gas to the reaction mixture to precipitate monomer C as a hydrochloride salt. Isolation operations often become more efficient by adding water to the reaction mixture as a pretreatment and performing extraction and separation. Preferred representative examples of the monomer (C) produced in this way include ethylaminoethylstyrene, isopropylaminoethylstyrene, dimethylaminoethylstyrene, diethylaminoethylstyrene, di(aminoethyl)aminoethylstyrene, N - N-Aminoethylmethylethylstyrene ( _R1 = _CH3 , _R2 = _CH2 - _CH2 - _NH2 ) and the like. Representative examples of the monomer represented by structural formula (D), that is, acrylic acid derivatives, include unsaturated carboxylic acids such as acrylic acid, methacrylic acid, α-chloroacrylic acid, and itaconic acid; methyl acrylate, ethyl acrylate, Alkyl acrylates such as butyl acrylate, octyl acrylate, octadecyl acrylate; Cycloalkyl acrylates such as cyclohexyl acrylate, trimethylcyclohexyl acrylate; Aryl acrylates such as phenyl acrylate, amyl phenyl acrylate; Chlorethyl acrylate, dichloro acrylate Haloalkyl acrylates such as propyl and bromopropyl acrylate; Hydroxyalkyl acrylates such as hydroxyethyl acrylate and bishydroxymethylpentyl acrylate; Alkoxy acrylates such as methoxyethyl acrylate and ethoxypropyl acrylate; glycidyl acrylate and tetrahydrofuric acrylate Acrylic acid esters such as cyclic ether esters of acrylic acid such as Furyl. Alkyl methacrylate or cycloalkyl methacrylate such as methyl methacrylate, ethyl methacrylate, butyl methacrylate, octyl methacrylate, decyl methacrylate, dodecyl methacrylate, stearyl methacrylate, cyclohexyl methacrylate; phenyl methacrylate, butyl phenyl methacrylate, Aryl methacrylates such as naphthyl methacrylate; Aryl alkyl methacrylates such as benzyl methacrylate and triphenylmethyl methacrylate; Haloalkyl methacrylates such as chloromethyl methacrylate, fluoroethyl methacrylate, bromoethyl methacrylate, and chlorocyclohexyl methacrylate; Chlorphenyl methacrylate, methacrylate Haloaryl methacrylates such as tribromphenyl methacrylate; Hydroxyalkyl methacrylates such as hydroxyethyl methacrylate and hydroxypropyl methacrylate; Alkoxyalkyl methacrylates such as ethoxyethyl methacrylate and methoxybutyl methacrylate; Glycidyl methacrylate, tetrahydrofurfuryl methacrylate, etc. Cyclic ether ester of methacrylic acid; methacrylic acid ester such as methoxypolyethylene glycol methacrylate. α-chloroacrylic acid esters such as methyl α-chloroalkylate, α-butyl chloroacrylate, and ethoxyethyl α-chloroacrylate; α-alkoxy acrylates such as ethyl α-acetoxyacrylate and ethyl α-benzoyloxyacrylate Acid esters; itaconate esters such as dimethyl itaconate, dibutyl itaconate, chloroethyl itaconate, and hydroxyethyl itaconate; α-alkoxyacrylic acid esters such as methyl α-methoxyacrylate and cyclohexyl α-ethoxyacrylate. Among these, preferred examples include methyl acrylate, butyl acrylate, 2-ethylhexyl acrylate, acrylic acid, hydroxyethyl acrylate, methyl methacrylate, butyl methacrylate, 2-ethylhexyl methacrylate, methyl methacrylate, and methacrylic acid. Examples include butyl, 2-ethylhexyl methacrylate, methacrylic acid, dimethylaminoethyl methacrylate, and tetrahydrofurfuryl methacrylate. It is also possible to add styrene, vinyl chloride, acrylonitrile, vinylidene chloride, methyl vinyl ketone, vinyl acetate, etc. as other copolymerization components. The polymerization method may be ionic polymerization or radical polymerization, but copolymerization is preferably carried out in the presence of a radical initiator. As for the polymerization operation, any of the general polymerization methods such as bulk polymerization, solution polymerization, suspension polymerization, and emulsion polymerization can be used. As a radical initiator, benzoyl peroxide,
Peroxides such as dilauroyl peroxide, azo compounds such as azobisisobutyronitrile, 2,2'-azobis(2,4-dimethylvaleronitrile), 1,1'-azobiscyclohexane-1-carbonitrile,
Representative examples include hydroperoxides such as cumene hydroperoxide and t-butyl hydroperoxide, and persulfates such as potassium persulfate and ammonium persulfate. Adjustment of the molecular weight of the copolymer can be achieved by adjusting the amount of initiator used or by carrying out solution polymerization in a system in which a solvent or a chain transfer agent is added. Increasing the amount of initiator will decrease the molecular weight. The amount of these initiators used is preferably 0.05 to 10% by weight, more preferably 0.2% based on the monomer.
and 5% by weight. As a solvent or chain transfer agent, toluene,
Examples include aromatic hydrocarbons such as ethylbenzene, cumene, and diphenylmethane, halogenated hydrocarbons such as hydrogen tetrachloride and chloroform, aliphatic alcohols such as n-butanol and isopropanol, and mercaptans such as n-butylmercaptan. The amount of the solvent or chain transfer agent to be used is not particularly limited, but it is preferably 0.1 to 40 times the weight of the monomer, and more preferably the same to 20 times. The polymerization temperature is preferably 0°C to 150°C, and preferably 40°C to 100°C.
C. is more preferred. Various methods known in the art can be used to isolate the copolymer AB obtained by the above method, but in the case of solution polymerization, it can be isolated in a solvent that does not dissolve the copolymer produced. Preferred are a reprecipitation method in which the reaction mixture is charged, and a steam distillation method in which the reaction mixture is heated while blowing steam to distill off the solvent and unreacted monomers. In the case of suspension polymerization, it is recommended that the resulting granular product be separated and thoroughly washed with water to remove suspending agents, suspension aids, etc. adhering to the surface of the product. Common methods such as elemental analysis, infrared absorption spectroscopy, and nuclear magnetic resonance spectroscopy are used to confirm the structure of the obtained copolymer. Furthermore, the composition of the copolymer can be estimated by quantifying unreacted monomers by gas chromatography or liquid chromatography after polymerization. To measure the molecular weight, viscosity method, gel permeation chromatography, light scattering method, osmotic pressure method, vapor pressure osmometry, etc. are used. The copolymer AB of the present invention is useful as a coating component. In other words, it has become clear that the coating film made of copolymer AB exhibits good durability. A coating film can also be obtained by dissolving copolymer AB in a solvent, applying it, and then evaporating the solvent.
AB is reacted with acid HX to convert part or all of the structure represented by formula (A) into formula (A') (In the formula, X represents an acid group.) After replacing the structure with membrane can be obtained. That is, coating film formation is achieved by using the object to be coated as a cathode and passing a direct current between it and the anode. Such a cationic electrodeposition method is the most preferred method for forming a coating film made of the present copolymer. There are no particular restrictions on the acid HX, but examples include hydrochloric acid, sulfuric acid, nitric acid, chromic acid, perchloric acid, phosphoric acid, mineral acids such as carbonic acid, acetic acid, propionic acid, butyric acid,
Aliphatic carboxylic acids such as caproic acid, hydroxycarboxylic acids such as glycolic acid and lactic acid, malonic acid,
Dicarboxylic acids such as adipic acid, aromatic carboxylic acids such as benzoic acid, phthalic acid, and salicylic acid, alkanesulfonic acids such as methanesulfonic acid and ethanesulfonic acid, benzenesulfonic acid, toluesulfonic acid,
There are arylsulfonic acids such as laurylbenzenesulfonic acid, and among these, organic carboxylic acids are preferred, and acetic acid, lactic acid, hydroxyacetic acid, and the like are more preferred because they can keep the electrolyte near neutrality. The amount of acid added is preferably 0.1 to 5 times the amount of nitrogen in the copolymer AB, more preferably 0.3 to 2 times the amount of nitrogen in the copolymer AB. In the neutralization reaction, only the copolymer and the acid may be mixed, but when the acid is solid or when reacting with less than an equivalent amount of the acid, it is recommended to use a solvent. As the solvent, water-soluble organic liquids such as alcohols and ketones are preferred. Among these, lower alcohols such as methanol, ethanol, and propanol, acetone, and methyl ethyl ketone are particularly preferred. The amount of solvent is preferably 10% to 300% by weight, more preferably 20% to 150%, based on the weight of copolymer AB.
The temperature of the neutralization reaction is preferably -20°C to 200°C, more preferably 10°C to 150°C. The amount of water used to prepare the electrolyte is
It is preferably at least 30 times the weight of copolymer A'B, more preferably at least 5 times and at most 20 times the weight.
The pH of the electrolytic solution prepared here is preferably 3 to 8, more preferably 5 to 7. Copolymer A′B has the following structural formula () It can also be produced by copolymerizing a monomer mixture containing the monomer represented by and monomer (D). This monomer is a monomer represented by formula (C) with acid HX
It can be easily produced by neutralizing with In the case of copolymerization of monomers (I) and (D), radical polymerization is preferred, and solution polymerization in a highly polar solvent is recommended. When water is used as a solvent, in addition to water-soluble initiators mentioned above, redox initiators consisting of combinations of persulfate/bisulfite, chlorate/sulfite, etc. can also be used. . Typical examples of this redox initiator are combinations such as potassium persulfate/sodium bisulfite, sodium chlorate/sodium sulfite, and the like. Typical examples of the material for the cathode, that is, the surface to be coated, include zinc phosphate-treated steel sheets, iron phosphate-treated steel sheets, untreated steel sheets, galvanized steel sheets, tin-plated steel sheets, aluminum, copper, and copper alloys. As an anode,
Stainless steel plates, carbon plates, etc. are preferred. There is no limit to the voltage between the poles, but 50V to 500V is preferable.
Particularly preferred is 100V to 400V. Electrodeposition time is 10
The time period is preferably from seconds to 20 minutes, and more preferably from 1 minute to 10 minutes. The temperature of the electrodeposition solution is preferably 0°C to 60°C, more preferably 10°C to 40°C. Examples will be described below, but the present invention is not limited thereto. Note that reference examples are also shown. Reference Example 1 Prepare a stirring device, a thermometer, and a reflux device in a three-necked flask 2 purged with nitrogen, and add 44 ml of purified tetrahydrofuran using a dropping funnel. While stirring, 86 ml of isopropylamine was added, followed by 20 ml of a 2N solution of n-butyllithium, and the color of the solution changed from clear and colorless to pale yellow. This flask was placed in a constant temperature bath at 30°C, and 148 ml of p-divinylbenzene was added while stirring. The reaction mixture is orange and remains
After reacting for an hour, 1 ml of methanol was added, and the mixture was poured into 2 water. Extraction was performed twice with n-hexane, the oil layer was dried over magnesium sulfate overnight, and then distilled. 0.07mm as product
11.8g of a fraction having a boiling point of around 67°C in Hg was obtained.
This product is p-(isopropylaminoethyl)
It was confirmed that it was styrene from the following spectrum data. Proton nuclear magnetic resonance spectrum (100MHz, solvent: deuterated chloroform, reference material TMS), δ value;
0.8 (1H), 0.96 (double line, J=7Hz, 1H), 2.6~
2.9 (multiple line, 5H), 5.1 (double line, J=11Hz,
1H), 5.6 (doublet, J=18Hz, 1H), 6.6 (two sets of doublets, 1H), 7.0-7.35 (multiplet, 4H). Infrared absorption spectrum (liquid film); 3300, 1630,
1510, 1470, 1380, 1080, 990, 910, ^{835cm -1} . Reference Example 2 After putting 80 ml of n-hexane that has been dried and distilled over sodium metal into a stainless steel pressure-resistant reaction device with an internal volume of 200 ml and equipped with a stirring device, the device is sufficiently cooled from the outside with a dry ice-methanol mixture. Did. An ethylamine cylinder (manufactured by Tokyo Kasei Kogyo Co., Ltd.) was connected to the apparatus, and the valve was opened to introduce ethylamine into the reaction apparatus. From the change in the weight of the cylinder before and after introduction, it was confirmed that 6.3g of ethylamine had been introduced. While stirring, 8.4 ml of a 15% n-hexane solution of n-butyllithium was introduced. Next, 18.2 g in 40 ml of dry n-hexane
A solution containing p-divinylbenzene was introduced. The reaction apparatus was placed in a water bath at 25° C., and stirring was continued for 5 hours. 0.5 g of methanol was added to the reaction mixture, and the mixture was poured into 200 ml of water. Extraction was performed twice with n-hexane, the oil layer was dried over magnesium sulfate overnight, and then distilled. 72℃ at 0.31mmHg
14.7g of a fraction having a boiling point of 73°C was obtained. It was confirmed by gas chromatography that it was a single substance. The refractive index of this fraction is 1.538 (Na
D line). The spectroscopic analysis results were as follows. Infrared absorption spectrum; 3280, 1620, 1510,
1120, 985, 900, 820 cm ^-1 . Nuclear magnetic resonance spectrum [100MHz, tetramethylsilane (TMS) standard], δ value: 0.80 (single line,
1H), 1.04 (triple line, J=7.2Hz, 3H), 2.55 (4
Multiplet, J=7.2Hz, 2H), 2.6-2.8 (multiplet,
4H), 5.08 (double line, J = 10.5Hz, 1H), 5.60 (2
double line, J = 17.8Hz, 1H), 6.56 (two sets of double lines,
J=10.5, 17.8Hz, 1H), 6.9-7.3 (multiplet,
4H). Here, J is a coupling constant, and nH is equivalent to n hydrogen atoms. These analytical results indicate that the product is para-(β-ethylaminoethyl)styrene. Reference Example 3 In a four-necked flask equipped with a corrugated condenser, a thermometer, and two dropping funnels, and containing a magnetic rotor, n- was distilled after drying with sodium metal.
100 g of hexane was added, and the mixture was sufficiently cooled from the outside with a methanol and dry ice mixture. After circulating dry ice-methanol in the cooler, a dimethylamino cylinder (manufactured by Tokyo Chemical Industry Co., Ltd.) was connected to the tip of the cooler, and the valve was opened to introduce dimethylamine into the flask. It was confirmed from the change in the weight of the cylinder before and after introduction that 115.4g of dimethylamine had been introduced. While stirring the n-hexane solution of dimethylamine with a magnetic rotor, 77 g of a 15% hexane solution of n-butyllithium was added dropwise from the dropping funnel at such a rate that the temperature of the mixture did not exceed -60°C. The liquid turned pale yellow due to the dropwise addition of n-butyllithium. Next, a liquid mixture of 435 g of dry hexane and 332 g of paradivinylbenzene prepared by the method described below was added dropwise from the second dropping funnel at a rate such that the internal temperature did not exceed -60°C. The reaction solution turned pale colored. After the dropping was completed, stirring was continued for 3 and a half hours, and the internal temperature rose to -20°C. When a portion of the sample was sampled and divinylbenzene was quantitatively determined using a gas chromatograph, it was determined to be 15% of the starting concentration, so 10 ml of methanol was added to terminate the reaction. The reaction mixture was added to the water in Step 1, extracted twice with n-hexane, and then the oil phase was dried over magnesium sulfate overnight, and after separating the magnesium sulfate, distillation was performed under reduced pressure. 75℃ to 80℃ at 0.4mmHg
250 g of a fraction with a boiling point of . Analysis by gas chromatography showed that the purity was over 98%, and although some raw material divinylbenzene was included, the main component was a single peak (filling material: silicon DC-550, column length; 1m, column temperature: 150℃, carrier gas: nitrogen, flow rate: 136
ml/min, retention time: 3.2 minutes). The specific gravity of this fraction is
0.913 at 23℃, refractive index 1.534 at 23℃ (Na D line)
was measured. Analyzes were conducted to confirm the structure using high-purity samples obtained by fractionation using gas chromatography. The results are shown below. Elemental analysis; C: 82.08%, H: 9.86%, N:
8.07% Infrared absorption spectrum; 2920, 2740, 1620,
1500, 1440, 1250, 1130, 1030, 980, 890, 820
cm ^-1 proton nuclear magnetic resonance spectrum; (measurement solvent:
Carbon tetrachloride) δ value (reference material: TMS deuterium chloroform solution) 2.07 (singlet, 6H); 2.2 to 2.7 (4H)
5.00 (double line, J = 11 Hz, 1H); 5.50 (double line, J = 18 Hz, 1H); 6.55 (two sets of double lines, J = 11 Hz and 18 Hz, 1H); 6.8~
7.3 (4H) Here, J indicates the coupling constant,
Also, 1H represents the equivalent of one hydrogen. Reference Example 4 Put 26 g of p-divinylbenzene and 40 ml of cyclohexane into a 200 ml three-necked flask. moreover
Add 40 ml of a cyclohexane solution of an amide/amine mixture prepared from 14.8 g of diethylamine and 0.512 g of butyllithium, and stir at 50°C for 30 minutes.
heated for an hour. Then add 10ml of methanol,
The reaction solution was distilled to obtain 29 g of p-diethylaminoethylstyrene having a boiling point around 84° C. at 1 mmHg. This product gave an infrared absorption spectrum with the following characteristic absorption. 1800, 1620,
1505, 1195, 1060, 980, 895, 820 cm ^-1 , and elemental analysis showed that C: 82.65%, H: 10.58
%, N: 6.80%. Example 1 In a 2-volume separable flask equipped with a stirring bar, a thermometer, and a reflux condenser, 1014 g of toluene, 102.8 g of methyl methacrylate, and the p- synthesized in Reference Example 1 were added.
17.7 g of isopropylaminoethyl styrene, 41.7 g of 2-ethylhexyl methacrylate and 2.
Add 2.5g of 2′-azobisisobutyronitrile,
Stirring was continued at 80°C for 18 hours. After the reaction, the amount of residual monomer was determined by gas chromatography, and it was found that 11.6% of methyl methacrylate and 12.7% of 2-ethylhexyl methacrylate were unreacted, but all p-isopropylaminoethylstyrene was reacted. It became clear. Steam was introduced into the reaction mixture from a steam generator to steam distill the unreacted monomers and toluene. After cooling the obtained copolymer, it was crushed and dried. Yield is 130
Elemental analysis of the produced copolymer showed that C: 65.9%,
H: 9.1%, O: 0.24%, N: 0.9%. In addition, the following characteristic absorption was observed in the infrared absorption spectrum. 2930, 1720, 1450, 1280, 1230,
980, 960, 740 cm ^-1 . The results of the proton nuclear magnetic resonance spectrum were as follows. Solvent; deuterated chloroform, reference material;
TMS, δ value (ppm); 0.8 to 1.2 (J=6Hz), 1.2
~1.7, 1.7~2.3, 2.7~3.1, 3.65, 3.8~4.1, 6.9
~7.3. Furthermore, when the viscosity of the chloroform solution was measured, it was found to be [η]=0.049 at 25°C. Example 2 In a 2-volume separable flask, 1300 g of cumene, 11.3 g of p-isopropylaminoethylstyrene
g, methyl methacrylate 47g, methacrylic acid n-
After adding 93.1 g of octyl and 7.5 g of 2,2'-azobisisobutyronitrile and blowing nitrogen at room temperature for 2 minutes, the mixture was sealed tightly and heated at 80°C for 18 hours, followed by the same procedure as in Example 1. Steam distillation was carried out using the following method. Elemental analysis of the obtained copolymer showed C: 69.6%,
H: 10.2%, O: 19.6%, N: 0.6%. In addition, the intrinsic viscosity [η] measured in chloroform solution is
It was 0.022. The infrared absorption spectrum showed the following absorption. 2940, 1720, 1470, ^{1230, 1150cm -1} . Examples 3 to 5 The solvents and monomers shown in Table 1 were added to a 5-separable flask equipped with a stirring bar, a thermometer, and a reflux condenser, heated, and reacted at 70°C for 15 hours. After the reaction, the residual monomer was quantified by gas chromatography. Gas chromatographic analysis values are shown in Table 2. After the reaction, the reaction product was reprecipitated by adding 3 times the amount of hexane, and the polymer was isolated and dried under reduced pressure. The results of elemental analysis are shown in Table 3.

【table】

【table】

[Table] In the infrared absorption spectrum of Example 4, the following characteristic absorptions were obtained. 2930, 1720, 1480, 1440, 1380, 1230, 1190,
1140, 980, 830, 750 cm ^-1 . The nuclear magnetic resonance spectrum of Example 4 had the following results. Solvent: Deuterated chloroform, Reference material: TMS, δ
Value (ppm); 0.4-1.7, 1.7-2.6, 2.6-3.3,
3.8, 7-7.3. In addition, when the intrinsic viscosity was measured using a chloroform solution, it was found that for Examples 3, 4, and 5, each
They were 0.095, 0.187, and 0.108. Example 6 Partially saponified polyvinyl alcohol (degree of saponification 88%, viscosity of 2% aqueous solution 23CP
), 8 g of sodium chloride and 800 ml of pure water
73.6 g of ethyl methacrylate, 17.7 g of p-n-propylaminoethylethylene, and 69.7 g of 2-ethylhexyl acrylate at 60°C with stirring.
g, 1.6 g of 2,2'-azobis(2,4-dimethylvaleronitrile) is added. While stirring, heating was continued at 60°C for 2 hours, 70°C for 2 hours, and 80°C for 4 hours. After the reaction, the product was thoroughly washed with warm water and dried. Granular copolymer with a diameter of 50 to 400μ
I got 140g. The elemental analysis value of this copolymer is C:
69.0%, H: 9.9%, O: 20.2%, and N: 0.9%. Example 7 In a separable flask equipped with a stirring bar, thermometer, and reflux condenser, 500 g of hexane, 30 g of methyl methacrylate, 56.7 g of p-isopropylaminoethylstyrene, and 2.6 g of 2,2'-azobisisobutyronitrile. g and reacted at 70°C for 18 hours. After the reaction, the liquid was homogeneous, but when it was externally cooled with a dry ice-methanol mixture, a white precipitate was generated. The product was separated using a glass filter in the cooled state. The results of elemental analysis of the dried product are: C: 71.1%, H: 8.92%, O: 15.97%,
N: 4%. Examples 8 to 10 The solvents and monomers shown in Table 4 were added to a separable flask equipped with a stirring bar, a thermometer, and a reflux condenser, heated, and reacted at 70°C for 18 hours.
Steam was introduced into the reaction mixture from a steam generator to steam distill the unreacted monomers and toluene. After cooling the obtained copolymer, it was crushed and dried. The results of elemental analysis of the product are shown in Table 5.

【table】

[Table] Examples 11 to 14 The solvents and monomers listed in Table 6 were added to a separable flask (1) equipped with a stirring bar, thermometer, and reflux condenser, heated, and reacted at 60°C for 20 hours. I did it. Steam was introduced into the reaction mixture from a steam generator to steam distill the unreacted monomers and benzene. After cooling the obtained copolymer, it was crushed and dried. The results of elemental analysis of the product are shown in Table 7.

【table】

[Table] Examples 15 to 16 The mixture shown in Table 8 was placed in a 200 ml glass tube, sealed, and then placed in a water bath maintained at 80°C for 18 hours. Thereafter, the container was opened, and the solvent and unreacted monomers were steam distilled to obtain a product. The results of elemental analysis of the product are shown in Table 9, and the infrared absorption spectrum is shown in Table 10.
Shown in the table.

【table】

【table】

[Table] Example 17 21.5 g of the copolymer obtained in Example 1 was added to 21.5 g of isopropanol, heated to 70° C., and mixed uniformly. 1 g of lactic acid was added to this and stirred until uniform. When 31.7 g of this mixed liquid was dissolved in 98 ml of water, the pH of the liquid was 6.6. When a direct current was passed through this solution using a 4 cm x 10 cm steel plate as a cathode and a stainless steel anode as a counter electrode, electrodeposition was made on the cathode at a voltage of 200V. The specific conductivity of the same liquid was separately measured and found to be 1540 μmho/cm. The resulting coating film had an Erichsen value of 10 mm, cross-cut adhesion (1 mm width cross cut) of 100/100, and Dupont impact strength of 70 cm. Examples 18 to 19 Using the mixed solution listed in Table 11, Example 17
Electrodeposition experiments similar to those were conducted. The results are shown in Table 12.

【table】

[Table] Example 20 10 g of the copolymer obtained in Example 1 was dissolved in 10 g of isopropanol, applied to a zinc phosphate treated steel plate, and dried at 150° C. for 10 minutes. The Erichsen value of this coating is 9 mm, and the grain adhesion is 100/
100, Dupont impact resistance was 65cm.

Claims (1)

[Claims] 1. A linear copolymer consisting of a repeating unit represented by structural formula (A) and a repeating unit represented by structural formula (B). [Wherein R ₁ and R ₂ are hydrogen, an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group, an alkenyl group, an aminoalkyl group, an aryl group having 6 to 20 carbon atoms,
or arylalkyl group, R ₃ is hydrogen, methyl group, halogen, carboxymethyl group, acetoxy group, CH ₂ COOR ₅ (R ₅ is hydrogen, carbon number 1 to 10
(alkyl group or arylalkyl group), or an alkoxy group having 1 to 5 carbon atoms, R ₄ is hydrogen, an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group, an alkenyl group, an aryl group having 6 to 20 carbon atoms, Arylalkyl group, carbon number 1 to 12
haloalkyl group, hydroxyalkyl group, alkoxyalkyl group, tetrahydrofurfuryl group,
Glycidyl group, -( _CH2 - _CH2 -O) _{-o R6} ( _R6 is an alkyl group having 1 to 8 carbon atoms, n is an integer of 1 to 30), or dialkylaminoalkyl group having 3 to 20 carbon atoms represents. 2. The copolymer according to claim 1, wherein one of R ₁ and R ₂ is hydrogen. 3. The copolymer according to claim 2, wherein one of R ₁ and R ₂ is hydrogen and the other is an alkyl group having 1 to 20 carbon atoms. 4. The copolymer according to claim 3, wherein the alkyl group has 2 to 8 carbon atoms. 5. The copolymer according to claim 4, wherein the alkyl group is an ethyl group, an n-propyl group, or an isopropyl group. 6. The copolymer according to claim 1, wherein R ₁ and R ₂ are both alkyl groups. 7. The copolymer according to claim 6, wherein R ₁ and R ₂ are both methyl or ethyl groups. 8 In structural formula (A), claims 1 to 7 in which the main chain and the substituted aminoethyl group are in the p-position
Copolymer described in section. 9. The copolymer according to claims 1 to 8, wherein R ₃ is a methyl group. 10. The copolymer according to claims 1 to 8, wherein R ₃ is hydrogen. 11 Claims 1 to 10, wherein R ₄ is hydrogen or an alkyl group having 1 to 20 carbon atoms.
Copolymer described in section. 12 Claims 1 to 10, wherein R ₄ is a hydroxyalkyl group having 1 to 12 carbon atoms.
Copolymer described in section. 13. The copolymer according to claim 12, wherein R ₄ is a hydroxyethyl group. 14. The copolymer according to claims 1 to 10, wherein R ₄ is a dialkylaminoalkyl group having 3 to 20 carbon atoms. 15. The copolymer according to claim 14, wherein R ₄ is a diethylaminoethyl group. 16. The copolymer according to claims 1 to 15, which contains 1 to 90% by weight of a repeating unit portion represented by structural formula (A). 17. The copolymer according to claims 1 to 16, which has a number average molecular weight of 1,000 to 500,000. 18 A repeating unit represented by structural formula (A) characterized by copolymerizing a monomer mixture containing a monomer represented by structural formula (C) and a monomer represented by structural formula (D). A method for producing a linear copolymer comprising a repeating unit represented by structural formula (B). [Wherein R ₁ and R ₂ are hydrogen, an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group, an alkenyl group, an aminoalkyl group, an aryl group having 6 to 20 carbon atoms,
or arylalkyl group, R ₃ is hydrogen, methyl group, halogen, carboxymethyl group, acetoxy group, CH ₂ COOR ₅ (R ₅ is hydrogen, carbon number 1 to 10
(alkyl group or arylalkyl group), or an alkoxy group having 1 to 5 carbon atoms, R ₄ is hydrogen, an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group, an alkenyl group, an aryl group having 6 to 20 carbon atoms, Arylalkyl group, carbon number 1 to 12
haloalkyl group, hydroxyalkyl group, alkoxyalkyl group, tetrahydrofurfuryl group,
Glycidyl group, -( _CH2 - _CH2 -O) _{-o R6} ( _R6 is an alkyl group having 1 to 8 carbon atoms, n is an integer of 1 to 30), or dialkylaminoalkyl group having 3 to 20 carbon atoms represents. ] 19. The method for producing a copolymer according to claim 18, wherein the copolymerization is carried out in the presence of a radical initiator. 20. The method for producing a copolymer according to claim 19, wherein the copolymerization is carried out in the coexistence of an inert solvent. 21 Repeating unit shown by structural formula (A) and structural formula (B)
A cathodically deposited electrodeposition paint consisting of a linear copolymer containing repeating units represented by: [Wherein R ₁ and R ₂ are hydrogen, an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group, an alkenyl group, an aminoalkyl group, an aryl group having 6 to 20 carbon atoms,
Aryl alkyl group, _R3 is hydrogen, methyl group, halogen, carboxymethyl group, acetoxy group,
CH ₂ COOR ₅ (R ₅ is hydrogen, an alkyl group having 1 to 10 carbon atoms, or an arylalkyl group), or an alkoxy group having 1 to 5 carbon atoms, R ₄ is hydrogen,
Alkyl group having 1 to 20 carbon atoms, cycloalkyl group, alkenyl group, aryl group having 6 to 20 carbon atoms, arylalkyl group, haloalkyl group having 1 to 12 carbon atoms, hydroxyalkyl group, alkoxyalkyl group, tetrahydrofurfuryl group , glycidyl group, -( _CH2 - _CH2 -O) _{-o R6} ( _R6 is an alkyl group having 1 to 8 carbon atoms, n is an integer of 1 to 30), or dialkylaminoalkyl having 3 to 20 carbon atoms represents a group. ] 22 Repeating unit represented by structural formula (A) and structural formula (B)
Acid HX is applied to a copolymer consisting of repeating units shown in
A cationic electrodeposition coating method characterized in that the solution obtained by dissolving or dispersing this in water is applied as an electrodeposition solution. [Wherein R ₁ and R ₂ are hydrogen, an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group, an alkenyl group, an aminoalkyl group, an aryl group having 6 to 20 carbon atoms,
or arylalkyl group, R ₃ is hydrogen, methyl group, halogen, carboxymethyl group, acetoxy group, CH ₂ COOR ₅ (R ₅ is hydrogen, carbon number 1 to 10
(alkyl group or arylalkyl group), or an alkoxy group having 1 to 5 carbon atoms, R ₄ is hydrogen, an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group, an alkenyl group, an aryl group having 6 to 20 carbon atoms, Arylalkyl group, carbon number 1 to 12
haloalkyl group, hydroxyalkyl group, alkoxyalkyl group, tetrahydrofurfuryl group,
Glycidyl group, -( _CH2 - _CH2 -O) _{-o R6} ( _R6 is an alkyl group having 1 to 8 carbon atoms, n is an integer of 1 to 30), or dialkylaminoalkyl group having 3 to 20 carbon atoms represents. ] 23. The coating method according to claim 22, wherein a carboxylic acid is used as the acid. 24 Claim 2 using acetic acid as the acid
Coating method described in Section 3. 25 Claim 2 using lactic acid as the acid
Coating method described in Section 3. 26 The amount of acid is 0.1 relative to the amount of nitrogen in the copolymer.
Claim 2, which is twice the mole to five times the mole
The coating method described in Items 2 to 25.