JPS58160311A - New resin composition, paint therefrom, crosslinked product thereof and paint film formation therewith - Google Patents

Abstract

PURPOSE:A cathode-depositable epoxy resin composition suitable as an electropaint or the like, prepared by mixing a nitrogen-containing acrylic copolymer with an amine-modified epoxy resin and a blocked polyisocyanate. CONSTITUTION:The purpose resin composition is prepared by mixing (A) a nitrogen-containing acrylic linear copolymer containing repeating units of formulaI(wherein R1 and R2 are each H, a 1-20 C alkyl or the like) and repeating units of formula II (wherein R3 is H, methyl or the like and R4 is H, a 1-20 C alkyl or the like) with (B) an amine-modified epoxy resin prepared by replacing part or all of the epoxy groups of an epoxy compound having at least one epoxy group with a structure of formula III (wherein R7 and R8 are each H, a 1-20 C alkyl or the like) and (C) a compound prepared by blocking all or part of the isocyanate group of a polyisocyanate with an alcohol and/or an amine.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a novel epoxy resin composition that can be deposited on a cathode by electrodeposition, which is composed of a nitrogen-containing acrylic copolymer, an amine-modified epoxy resin, and a blocked polyisocyanate. The present invention relates to a paint comprising the composition, a crosslinked product obtained from the composition, and a method for forming a coating film using the composition.

A coating method in which paint is deposited on the surface of the object by electrophoresis using the object as an electrode is generally called electrodeposition coating, and it has the following advantages: it forms a uniform coating film, and it can be applied automatically.
Since the paint can be recovered and reused, it causes less environmental pollution and is economical, so it is widely used for painting automobile bodies.

Initially, an anionic electrodeposition method using the object to be coated as an anode was used, but in recent years, a cationic electrodeposition method using the object to be coated as a cathode has become popular. The main reason for this is that cationic electrodeposition paints have high corrosion resistance.

The present inventors have endeavored to develop new materials for cationic electrodeposition, and as a result, have discovered a novel nitrogen-containing acrylic composition. The composition of the present invention is a linear copolymer (hereinafter referred to as total copolymer AB) containing a repeating unit represented by Structural Formula (A) and a repeating unit represented by Structural Formula (B).
+) A compound in which part or all of the epoxy group of an epoxy compound containing one or more epoxy groups is replaced with a structure represented by formula (C1) (hereinafter, this is referred to as an epoxyamine modified product), and (iii) This is a composition consisting of a compound in which all or part of the isocyanate groups of polyisocyanate are blocked with alcohol and/or amine (hereinafter referred to as blocked polyisocyanate).

R, R2 [wherein R1+R2 is 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 an arylalkyl group, Rsl'j hydrogen, Methyl group, halogen, carboxymethyl group, 1゛nacetoxy group, CHICO
OR, (R6 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, R4 is hydrogen, an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group, alkenyl group, C1-C20 aryl group, arylalkyl group, C1-C12 haloalkyl group, hydroxyalkyl group, alkoxyalkyl group, tetrahydrofurfuryl group, glycidyl group, +CH2-CH, -0÷ (Ra is an alkyl group having 1 to 8 carbon atoms, n is an integer of 1 to 50), or a dialkylaminoalkyl group having 3 to 20 carbon atoms, R7+R11 are each hydrogen, an alkyl group having 1 to 20 carbon atoms, cycloalkyl group, hydroxyalkyl group, aminoalkyl group, H-(-NH-CH, -C
It represents a group selected from H, -)- (m is an integer of 1 to 8), an aryl group having 6 to 15 carbon atoms, and an alkyl group. ] In the above formula, when both or one of R+ and R* is hydrogen, the copolymer has a primary or secondary amine group in the side chain, and this hydrogen reacts with the block polyisocyanate, It has become clear that this is one of the preferred embodiments because the coating film can be more easily cured and a strong coating film can be formed. Further F
Either iRl or R is hydrogen, and the other is preferably an alkyl group having 1 to 20 carbon atoms, or -18- is an aminoalkyl group, particularly an alkyl group having 2 to 8 carbon atoms or an aminoalkyl group. Specifically, they include an ethyl group, a lopropyl group, an isopropyl group, a 5et-butyl group, a cyclohexyl group, an n-hexyl group, an aminoethyl group, and the like. It is also preferable that one or both of R and R is an aminoalkyl group. Specifically, aminoethyl group and aminopropyl group are preferred.

Structural formula (Bl is generally hydrogen, a methyl group or an alkoxycarbonylmethyl group, and R4 is hydrogen or an alkyl group having 1 to 20 carbon atoms or a hydroxyalkyl group having 1 to 12 carbon atoms, Among them, hydroxyethyl is preferred. Furthermore, dialkylaminoalkyl groups having 6 to 20 carbon atoms are preferred, and diethylamineethyl groups are particularly preferred. If a preferred specific combination of R7 and R2 is shown in the form (R3, R4), ( H, CH3), (H, C1Hs), (
H, C41H9), (H.

CB Ht? ), (H, CH, CH, OH), (H
,H), (a , cHt cutN(caa)J, (
CH3, CHa ), (CH,, C, H,), CCHs
, C4H,), (CH3°-19- C3HI7), ("R3+ CItH25), (CH,
,C,5Ha7),(CH,,cyclo-CaHo
), (CH,,H), (CH,,CH,CHtOH)
, (CH,, CH, CH2N, CH+OH290),
etc.

There are various combinations of RI + R2+ R and R1, but preferred combinations include RI for hydrogen and R2 for isopropyl, Jd 5ec-butyl group, cyclohexyl group, n- Hexyl group, R3 is hydrogen or methyl group, R4 is selected from methyl, butyl, 2-ethylhexyl or hydroxyethyl group.

The combination of RI I R2+ R and R4 is not limited to one type, and combinations of two or more types are also included in the present invention.

Preferred in this case is a structural formula (
A copolymer containing two or more types of Bl is preferred.

Furthermore, in the copolymer AB of the present invention, a part of the part represented by the structural formula (Bl) in its structure can be replaced with a repeating unit structure represented by the following formula (D). In this case, the structure The ratio to be replaced in formula (D) is 6 in structural formula (B).
It is preferably 0% by weight or less.

-CH, -C-) [wherein XFi hydrogen, methyl group or halogen, Y is selected from halogen, phenyl group, nitrile group, and halogen. ). ] Here, X is preferably hydrogen or a methyl group, and more preferably hydrogen. Also Y
Preferable examples thereof include norogen, phenyl group, and nitrile group.

There is no restriction on the weight fraction of the moiety represented by the structural formula (Al) based on the total copolymer, but it is preferably 1 to 90% by weight, more preferably 3 to 80% by weight, and furthermore 5% by weight.
30 to 30% by weight is preferred.

There is no limit to the molecular weight of the copolymer AB of the present invention, but the number average molecular weight should be from 1,000 to 100,000.
- is preferred, and more preferably 2,000 to 30,000.

According to the present inventors, copolymers AB having a glass transition point of 140 DEG C. to 80 DEG C. are preferred as paints, and those having a glass transition point of 140 DEG C. to 50 DEG C. are more preferred.

R1 is hydrogen, R2 is isopropyl group, 5ec-butyl group, cyclohexyl group, or n-hexyl group, and R
8 is hydrogen or methyl group, R4 is methyl, butyl 1.2
- R1. selected from ethylhexyl or hydroxyethyl group. It has been found that copolymers containing two or more types of structure (B) consisting of R4 and having a glass transition point within the above range are particularly preferable as paints.

The copolymer AH of the present invention can be obtained by copolymerizing monomers having structures represented by the following formulas (K) and (L).

The definitions and preferred examples of R, R2, R, and R6 have already been described.

-22- R, R2 Monomer represented by structural formula (K) (hereinafter referred to as monomer)
A typical manufacturing method is to react romethylstyrene represented by the structural formula (M) with an amine represented by the structural formula (group) (hereinafter referred to as amine N), and is represented by the following formula.

Hat here refers to nitrogen, but bromine or chlorine is preferable. The reaction can be carried out without a solvent or in a solvent, but it is preferable to use the amine N consisting of HNR,R, in an excess amount relative to the halomethylstyrene. Furthermore, it is also preferable to add an aqueous alkali solution such as sodium hydrogen carbonate, sodium carbonate, sodium hydroxide, potassium hydroxide, or the like.

Typical examples of monomers represented by structural formula (L) (hereinafter referred to as monomers), that is, acrylic acid derivatives, include:
Unsaturated carboxylic acids such as acrylic acid, methacrylic acid, α-chloroacrylic acid, and itaconic acid; Alkyl acrylates such as methyl acrylate, ethyl acrylate, butyl acrylate, octyl acrylate, and octadecyl acrylate; cyclohexyl acrylate, acrylic acid Cycloalkyl acrylates such as trimethylcyclohexyl; aryl acrylates such as phenyl acrylate and amyl phenyl acrylate;
Haloalkyl acrylates such as chloroethyl acrylate, dichloroglobyl acrylate, and bromopropyl acrylate; hydroxyalkyl acrylates such as hydroxyethyl acrylate and bishydroxymethylpentyl acrylate;
Alkoxy acrylates such as methoxyethyl acrylate and ethoxyglopyl acrylate; acrylic acid esters such as cyclic ether esters of acrylic acid such as glycidyl acrylate and tetrahydrofurfuryl acrylate; methyl methacrylate, ethyl methacrylate, butyl methacrylate, and methacrylate. Alkyl methacrylate or cycloalkyl methacrylate such as octyl acid, decyl methacrylate, dodecyl methacrylate, stearyl methacrylate, cyclohexyl methacrylate; Aryl methacrylate such as phenyl methacrylate, phthylphenyl methacrylate, naphthyl methacrylate; benzyl methacrylate, methacrylate Arylalkyl methacrylates such as triphenylmethyl methacrylate; Haloalkyl methacrylates such as chloromethyl methacrylate, fluoroethyl methacrylate, bromethyl methacrylate, and chlorocyclohexyl methacrylate; Haloaryl methacrylates such as chlorphenyl methacrylate and tribromphenyl methacrylate; Hydroxy methacrylate Hydroxyalkyl methacrylates such as ethyl and hydroxyglobyl methacrylate; Alkoxyalkyl methacrylates such as ethyl methacrylate and methoxybutyl methacrylate; cyclic ether esters of methacrylic acid such as glycidyl methacrylate and tetrahydrofurfuryl methacrylate; methacrylic acid Methacrylic acid esters such as methoxypolyethylene glycol, α-methyl chloroacrylate, (α-chloroacrylic esters such as χ-butyl chloroacrylate, α-ethoxyethyl chloroacrylate, etc.; α-acetoxyethyl acrylate, α-benzoyl α-Alkoxyacrylic acid esters such as ethyl oxyacrylate; itaconic esters such as dimethyl itaconate, dibutyl itaconate, chloroethyl itaconate, hydroxyethyl itaconate; α-methyl α-methoxyacrylate, cyclohexyl α-ethoxyacrylate, etc. Alcoquine acrylate esters are mentioned. Among these, preferred examples include 1, methyl acrylate, butyl acrylate, 2-ethylhexyl acrylate, hydroxyethyl acrylate, methyl methacrylate, 2-ethylhexyl methacrylate, hydroxy methacrylate. There are ethyl etc.

Other copolymerization components include styrene and vinyl chloride 26
- vinyl, acrylonitrile, vinylidene chloride, methyl vinyl,
It is also possible to add luketone, vinyl acetate, etc.

Among these, styrene and acrylonitrile are particularly preferred.

The polymerization method may be ionic polymerization or radical polymerization, but
Preferably, the copolymerization is 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, peroxides such as benzoyl peroxide and dilauroyl peroxide, azobisisobutyronitrile 24/-azobis(2,4-dimethylvaleronitrile), 1,1'-azobiscyclohexane-1- Carbonitrile, 2,2'-azobis(2-amidinopropane)
Azo compounds such as dihydrochloride, cumene hydroperoxide,
Representative examples include hydroperoxides such as 1-butyl hydroperoxide, and persulfates such as potassium persulfate and ammonium persulfate.

The molecular weight of the copolymer can be adjusted by adjusting the amount of initiator used,
This is achieved by 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 Oj to 5% by weight based on the monomer.

As the solvent or chain transfer agent, aromatic hydrocarbons such as toluene, ethylbenzene, cumene, and diphenylmethane; halogenated hydrocarbons such as carbon tetrachloride and chloroform;
Examples include ketones such as methyl ethyl ketone and methyl isobutyl ketone, aliphatic alcohols such as n-butanol and ingropanol, and mercaptans such as n-butyl mercaptan and dodecyl mercaptan. The amount of the solvent or chain transfer agent to be used is not particularly limited, but it is preferably o, i times to 40 times the weight ratio of the monomer, and more preferably the same amount to 2 times the weight of the monomer.
0 times the amount is preferred. The polymerization temperature is preferably 0°C to 150°C, more preferably 40°C to 100°C.

The copolymers disclosed in this invention can also be obtained by reacting copolymers of halomethylstyrene and one or more monomers with amine N. The method for producing this copolymer and examples of monomers are the same as those already shown, and the reaction between the copolymer and amine N is carried out by dissolving the copolymer in a solvent in which the copolymer is dissolved, and then reacting with the amine N. It is preferable to react with N. The solvent is preferably used in an amount equal to to 100 times the amount of the copolymer, more preferably 5 times to 20 times. There is no limit to the reaction temperature, but it is preferably -20°C to 200°C, and K is 20°C to 100°C. The amount of amine to be used is required to be at least equimolar to the no-romethylstyrene structure in the copolymer, preferably from 5 times to 50 times by mole. Also, sodium bicarbonate,
It is also preferable to add an alkali such as sodium carbonate, sodium hydroxide, potassium hydroxide alone, or as an aqueous solution.

One of the most important means of controlling the properties of the composition disclosed in the present invention is the selection of RI and R1. For example, when a long-chain alkyl group is used as R1, the glass transition point of copolymer AB is lowered by -29- and the flexibility of the composition is improved. [7 or 1~,)・
In the method of reacting methylstyrene and amine N to prepare monomer K and obtain copolymers A and B, when R1 has a large molecular weight, the monomer has a high boiling point, making purification difficult. There are some drawbacks. In that case, as described herein, a copolymer is prepared using halomethylstyrene as a monomer,
By using the method of reacting with amine N, the copolymer AB can be easily purified by simply removing excess amine N after the reaction.
can be obtained.

The method for isolating the copolymer AH obtained by the above method is as follows:
Various methods known in the art can be used, but in the case of solution polymerization, a method of distilling the solvent under reduced pressure, a reprecipitation method, and a steam distillation method are preferred.

In the case of suspension polymerization, it is recommended that the obtained granular product be taken from house to house and thoroughly washed with water to remove the suspending agent, suspension aid, etc. adhering to the surface of the product.

As means for confirming the structure of the obtained copolymer, general methods such as elemental analysis, infrared absorption spectroscopy, and nuclear magnetic resonance spectroscopy are used. Furthermore, the composition of the copolymer can be estimated by quantifying unreacted monomers by gas chromatography or liquid chromatography after polymerization. For the measurement of molecular weight, viscosity method, Kervermeation chromatography, light scattering method, osmotic pressure method, vapor pressure method, etc. are used.

Further, the nitrogen content in the copolymer AB is an important parameter, and can be accurately determined by elemental analysis, titration, etc. Titration is with copolymer AB.

It is preferable to dissolve it in a water-soluble organic solvent such as acetone or ethanol, titrate it with hydrochloric acid or the like, and monitor the change in pH.

To design a copolymer with a given glass transition temperature,
It is preferable to use the following formula.

The glass transition point (Tg
c) is expressed by the following formula.

Here, Tgi represents the glass transition point of the homopolymer of the first monomer, and Wl represents the weight fraction of the i-th monomer. The glass transition point of polymers and copolymers can be measured by differential thermal analysis (DTA) or differential scanning calorimetry (DSC). In addition, the glass transition point of many polymers is known, for example, as described in "Polymer Handbook" co-authored by J. Brandrup and E. H. Immergut.
2nd edition (1975) III-139 pages ~ll'i-1
It is also described on page 92.

This copolymer is preferably dissolved in a suitable solvent and used as a paint raw material. As a solvent, ethanol,
Lower fatty alcohols such as propatool, butanol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol motsubutyl ether, ethylene glycol motsubutyl ether, ethylene glycol motsubutyl ether, diethylene glycol monomethyl ethyl ether, diethylene glycol hexaethyl Examples include ethers, ether alcohols such as diethylene glycol motsubutyl ether and propylene glycol monomethyl ether, and ketones such as diacetone alcohol, methyl isobutyl lactone and methyl ethyl lactone.

The epoxy compound that is the raw material for the "epoxyamine modified product" which is the second component of the composition of the present invention may be any substance that has one or more epoxy groups, but especially has two or more epoxy groups. Preferably, these include the following:

1.) Compound (E) represented by the structural formula (E) (In the formula, 2 represents hydrogen or halogen, and p represents an integer from 0 to 60.) Among these, compounds where 2 is hydrogen are so-called bisphenol A diglycidyl. This is a typical example of Ebor 53-oxy resin called ether. Preferred examples included in this group are tetrachlorobisphenol A diclycidyl ether and tetrabromobusphenol A diglycidyl ether.

2.) A compound represented by the structural formula (Fl (in the formula, R11 represents hydrogen or an alkyl group having 1 to 1 carbon atoms, and q represents an integer of 1 to 15). Typical examples included in this group are phenol novolacs. Epoxy resin,
Examples include alkylphenol novolak glycidyl ether such as 0-talesol novolac glycidyl ether, bisphenol F diglycidyl ether, and these are preferred.

6.) Compound represented by the structural formula (G) -34= (wherein, W is an r-valent aliphatic hydrocarbon group having 1 to 15 carbon atoms, or an r-valent aromatic hydrocarbon group having 6 to 12 carbon atoms) (r represents an integer of 2 to 4.) Preferred examples of compounds included in this group include aliphatic diglycidyl esters such as diglycidyl hexahydrophthalate and diglycidyl adipate, and aromatic diglycidyl esters such as diglycidyl phthalate. They are glycidyl esters.

4.) A compound represented by the structural formula (H) (wherein ■ is an S-valent aromatic hydrocarbon group having 6 to 715 carbon atoms, an S-valent aliphatic hydrocarbon group having 2 to 12 carbon atoms, or a carbon An aryl-substituted aliphatic hydrocarbon group having an S value of 7 to 20, where S represents an integer of 2 to 5.) Preferred representative examples include aliphatic hydrocarbon groups such as butanediol diglycidyl ether, glycerin triglycidyl ether, pentaglycidyl pentaerythritol, etc. Polyglycidyl ethers, bisphenol F diglycidyl ether, resorcinol diglycidyl ether, hydroquinone diglycidyl ether, catechol diglycidyl ether,
Tetraphenylethane tetraglycidyl ether, 1,
Examples include 1,5,5-tetraphenylpentane tetraglycidyl ether.

5.) A compound represented by the structural formula (Jl (in the formula, R1° is hydrogen or a methyl group, t is 0 to 2
Represents an integer of 0. ) Representative examples of the compounds included here include ethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, 1,4-butylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, diglycidyl ether, etc. be.

6.) The next group is compounds with an aliphatic structure having 4 to 20 carbon atoms, and representative compounds belonging to this group include:
Non-EJ type aliphatic polyoxides such as butadiene jepoxide, loamy aliphatic dioxides such as dicyclopentadiene dioxide, vinylcyclohexene dioxide, limonene dioxide, trivinylcyclohexane trioxide, divinylbenzene dioxide, etc. Examples of polyepoxy compounds include copolymers of diphenolic acid diglycidyl ether, diglycidyl phenol, glycidyl methacrylate with other monomers (e.g., styrene, methyl methacrylate, vinyl chloride, acrylonitrile, vinyl acetate, acrylamide). combination, tetraglycidyl aminodiphenylmethane, triglycidyl isocyanurate),
Examples include nitrogen-containing polyglycidyl compounds such as N,N-diglycidylaniline.

7.) Another group contains one epoxy group and includes butyl glycidyl ether, phenylene glycidyl ether, allyl glycidyl ether, talesyl glycidyl ether, glycidyl methacrylate, t-butyl glycidyl benzoate. , octylene oxide, styrene oxide, cyclohexene vinyl monoxide, dipentene monoxide, α-pinene monoxide, etc.

The epoxyamine modified product used in the present invention is an epoxy compound in which all or part of the epoxy group is replaced with a structure represented by the formula (C1), and R7 and R8 are as follows:
Preferred is an alkyl group or hydroxyalkyl group having 1 to 1 o carbon atoms, and more preferred is an ethyl group, propyl group, hydroxyethyl group, hydroxyalkyl group, and the like.

The epoxyamine modified product is an epoxy compound and the following formula (
It can be obtained by reacting the amine represented by P).

-38- Examples of amines include methylamine, ethylamine, butylamine, hexylamine, dodecylamine, octadecylamine, diethylamine, dipropylamine, mono- and dialkylamines, ethanolamine, glopanolamine, octatoolamine, Mono- and dialkanolamines such as jetanolamine and dibrobanolamine, fatty amines such as cyclohexylamine, pyrrolidine, and morpholine, ethylenediamine, hexamethylenediamine, dodecamethylenediamine, diethylenetriamine, triethylenepentamine, tetraethylenepentamine, These include alkylene polyamines such as propylene diamine, dipropylene triamine, and butylene diamine, and aromatic amines such as aniline, N-methylaniline, toluidine, benzylamine, metaphenylene diamine, and 4,4'-diaminodiphenylmethane.

Among these, dialkylamine and dialkanolamine are preferred, and diethylamine, jetanolamine,
More preferred is dibrobanolamine.

The epoxy compound and the amine need only be mixed together, and the reaction is accelerated by heating. The temperature is between 40℃ and 1
80°C is preferred, and 60°C to 150°C is more preferred. The amount of amine is 0.2 times less than the epoxy ring.
It is preferably 1.2 times, and more preferably 0.4 to 1.0 times. At this time, a solvent can also be used. Recommended solvents include alcohols such as ingropanol, butanol, ethylene glycol 7-ethyl ether, diethylene glycol 7-ethyl ether, esters such as ethyl acetate, cellosolve acetate, and ketones such as methyl ethyl ketone, methyl imbutyl ketone, and diacetone alcohol. . When the epoxyamine modified product is used as a raw material for a paint, it can also be used in a form containing these solvents.

The polyisocyanates that serve as raw materials for the block polyisocyanate, which is the third component of the composition of the present invention, include the following.

Trimethylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate, 1,2
-Diisocyanatopropane, 1,2-diisocyanatobutane, 1,3-diisocyanatobutane, decamethylene diisocyanate, 2,2,4-trimethylhexamethylene diinkana-1, etc. with 4 carbon atoms to 20 polyisocyanatoalkanes, 1,4-diisocyanatocyclohexane, 1,6-cyincyanatocyclopentane, 1.
2-dicyanatocyclohexane 7.2.4-diisocyanatomethylcyclohexane, 4.4'-diynecyanatodicyclohexylmethane, inphorone diisocyana-1.
Polyincyanatocycloalkanes having 5 to 18 carbon atoms; / diisocyanate, xylylene diisocyanate, 1,5-naphthylene diisocyanate, 1,4-menthylene diisocyanate-1-54,4
'-biphenylene diisocyanate, triisocyanatobenzene, triynecyanatotoluene, 3,3'-dimethyl-4,4'-dimethyl-41-4,4'-diphenylene diisocyanate, etc. with 8 carbon atoms
4 to 20 polyisocyanato aromatic hydrocarbons;
4'-diinocyanatodiphenylmethane, 4,4',
4"-triisocyanatotriphenylmethane, 4.4
'-Diphenyldimethylmethane 2, 2', 5, 5
Typical examples include polyphenylalkane polyisocyanates having 14 to 30 carbon atoms such as '-tetraisocyanate, among which polyincyanato alkanes having 4 to 20 carbon atoms, aromatic polyisocyanates having 8 to 20 carbon atoms Hydrocarbons are preferred, and niha-xamethylene diisocyanate and L-lylene diisocyanate are particularly preferred. These polyincyanates can be used alone or in a mixture of two or more. Blocked polyisocyanates are compounds in which all or part of the isone anato of these polyisocyanates are blocked with alcohol and/or amine, but monoalcohols or polyols can be used as the alcohol,
It preferably has 1 to 20 carbon atoms and is selected from aliphatic alcohols, aryl-substituted aliphatic alcohols, and phenols. For example, R
,, When using a monoalcohol with a structure of -OH, the isocyanate group of polyisocyanate (-N=C=
0) is converted to the type of urethane bond (-COORt+). The strained amine is preferably a primary or secondary amine, preferably having 1 to 20 carbon atoms, and any type of aliphatic amine, aromatic amine, monoamine or polyamine can be used. For example, if an amine R,2-NH-R, is used as a blocking agent, it will be blocked.

Blocked polyisocyanate is also called capped polyisocyanate, and is prepared by reacting polyisocyanate with alcohol and/or amine.

Examples of alcohols include methanol, ethanol,
Aliphatic monoalcohols such as phthanol, hexanol, 2-ethylhexyl alcohol, dodecanol, and octadecyl alcohol; hydroxyl 6-ary amines such as dimethylaminoethanol and diethylaminoethanol; alkoxymonoalcohols such as ethylene glycol monoethyl ether and ethylene glycol monobutyl ether; ethylene glycol; glycerin, trimethylolpropane,
Pentaerythritol, 1,2.6-) Aliphatic polyols such as IJ hydroxyhexane, polyalkylene glycols such as polyethylene glycol and polypropylene glycol, cycloalkanols such as cyclohexanol and cyclooctatool, phenols such as phenol, cresol, and naphthol, benzyl alcohol, There are phenyl alkyl alcohols such as phenethyl alcohol, and oximes such as methyl ethyl ketone oxime, acetone oxime, and cyclohexane oxime. As amine i1% diethylamine, dipropylamine, inpropylamine,
Butylamine etc.

There are various types of block polyisocyanates. First, there is a group of compounds obtained by reacting an incyanato group with an equivalent or more amount of monoalcohol.

The second group is blocked isocyanates with increased molecular weight obtained by reacting polyalcohols with partially blocked polyisocyanates obtained by reacting isocyanate groups with monoalcohols under @precursor. be. The third group includes blocked isocyanates consisting of the above partially blocked polyisocyanate-1 and an epoxyamine-modified compound.

Each group will be explained using all concrete examples. First, among those belonging to the first group, there are those in which tolylene diisocyanate or Hegi-cho methylene diisocyanate is reacted with twice the mole of alcohol such as butanol or octatool. As for those belonging to the second group, for example, 3 moles of tolylene diisocyanate and 3 moles of 2-ethylhegysyl alcohol are reacted to prepare semi-blocked diisocyanate-45-, and then 1 mole of trimethylolpropane is prepared. Examples include those made by reacting with. Examples of the third group include those made by reacting a reaction mixture of bisphenol diglycidyl ether and diethylamine with the semi-block polyisocyanate described above.

Such blocked polyisocyanates are stable at room temperature, but at high temperatures (approximately 100C to 500C), any block polyisocyanate may be used as long as it is reactive with active hydrogen such as hydroxyl groups and amine groups. It is also recommended to incorporate into the composition a catalyst to accelerate this reaction. As the catalyst, any known catalyst for producing urethane can be used. for example,
Tertiary amines such as triethylamine, triethylenediamine, iron acetylacetonate, tin acetate tri-n-butyltin acetate, moro-butyltin dichloride, di-n
There are metal salts such as -butyltin dilaurate, and tin compounds are particularly preferred. The amount used is preferably from 0.5 to 5% by weight, based on the composition of the invention.

In preparing the 46-block polyisocyanate, a solvent inert to the isocyanate can be used in order to lower the viscosity of the reaction product and prevent gelation. Examples include ethyl acetate, butyl acetate, cellosolve acetate, methyl isobutyl ketone, diethylene glycol dimethyl ether, and the like. In order to facilitate handling of the reaction product, it is also recommended to add a solvent such as alcohol to the reaction product to make it homogeneous after the blocking reaction is completed.

Examples of solvents include isopropanol, butanol, ethylene glycol monoethyl ether, and the like. By adding an excess of the blocking agent, it is also possible to use a portion of it as a solvent.

Although there is no limit to the mixing ratio of each component in the composition in the present invention, the weight ratio of block polyisocyanate to copolymer AB is preferably 0.1 to 10 times, and 0.3 to 4 times. is even more preferable.

The weight ratio of the amine-modified epoxy compound to copolymer AB is preferably 0.2 to 8 times, more preferably 0.4 to 3 times.

The composition of the present invention can be converted into a three-dimensional crosslinked product by reacting the blocked polyisocyanate, which is a component thereof, with other components, and the crosslinked product is useful as a molded article or a coating film. In this reaction, a new urethane bond or urea bond is formed by reacting the blocked isocyanate group with active hydrogen such as a hydroxyl group or an amine group in the copolymer AB and/or the epoxyamine modified product. It is presumed that it becomes a three-dimensional crosslinked product. The composition of the present invention and its crosslinked product are particularly useful as coating films. The coating method may be one in which the entire composition is dissolved in a suitable solvent, applied, and the solvent is evaporated, but the most preferred method is cationic electrodeposition. The cationic electrodeposition method will be described below. That is, the present composition is mixed with acid HA.
After reacting with water, it is dissolved or dispersed in water, and this is used as an electrodeposition liquid, the object to be coated is used as a cathode, and a direct current is applied between it and the counter electrode.
M. The present composition is deposited on the object to be coated by passing the flow through it.

There are no particular restrictions on acids II A, but five examples include mineral acids such as hydrochloric acid, sulfuric acid, nitric acid, chromic acid, perchloric acid, phosphoric acid, and carbonic acid, and aliphatic carboxylic acids such as acetic acid, propionic acid, butyric acid, and caproic acid. acids, hydroxycarboxylic acids such as glycolic acid and lactic acid, dicarboxylic acids such as malonic acid and adipic acid, aromatic carboxylic acids such as benzoic acid, phthalic acid and salicylic acid, ylucansulfonic acids such as methanesulfonic acid and ethanesulfonic acid, Among them, organic carboxylic acids are preferred, and acetic acid,
Lactic acid, hydroxyacetic acid, and the like are more preferred because they can keep the electrodeposition solution close to neutral. The amount of acid added is 0.1 to 5 times the amount of basic nitrogen in the composition.
The amount is preferably twice the molar amount, and more preferably 0.3 times to the same molar amount.

When acid HA is added to the composition, copolymer AB in the composition
, and structural formulas in epoxyamine modified products) and (
All or part of the moiety represented by C1 is converted into the following structural formulas (A') and (0), and the copolymer obtained here is referred to as copolymer A'B.

-49= (In the formula, RI + R2+ R7+ R8 is already defined.) In preparing the electrodeposition solution, each component of the composition can also be used in the form of a solution. As the solvent, those already mentioned in the explanation of each component of the composition are preferable, and the concentration of the total solid content in the obtained composition solution is preferably 50% by weight to 95% by weight.
%, more preferably 60% to 90%. The amount of water used in preparing the electrodeposition solution is preferably at least 30 times the weight of the present composition, more preferably at least 5 times and no more than 20 times the weight of the present composition. It is desirable to add water gradually while stirring the composition and acid mixture.

Copolymer A'B can also be produced by copolymerizing a monomer mixture containing a monomer represented by the following structural formula (Q+ -50- CH2=CH 1 2 and monomer (I5)). I can do it.

This monomer can be easily produced by neutralizing the monomer represented by the formula (C1) with an acid HA.In the case of copolymerization of the monomer (Q+ and (I), Polymerization is preferable, and solution polymerization in a highly polar solvent is recommended.When using water as a solvent, in addition to the water-soluble initiators listed above, persulfate/hydrogen sulfite, chlorine, etc. Redox initiators consisting of combinations of acid salts/sulfites, etc. can also be used. Typical examples of these redox initiators are combinations such as potassium persulfate/sodium hydrogen sulfite, sodium chlorate/thorium sulfite, etc. .

What is the amount of water used to make vM electrolyte?

The amount is preferably equal to or more than 30 times the total solid content, more preferably 5 times or more and 20 times or less.

The pH of the electrolytic solution prepared here is preferably 5 to 8, more preferably 5.5 to 7.5.

The material of the cathode, that is, the surface to be coated, includes zinc phosphate treated steel plate, iron phosphate treated steel plate, untreated steel plate, galvanized steel plate,
Typical examples include tin-plated steel sheets, aluminium, copper, and copper alloys. As the anode, a stainless steel plate, a carbon plate, etc. are preferable. There is no limit to the voltage between the poles, but 50V or 5
00■ is preferred, and 100■ to 400■ is particularly preferred.

The electrodeposition time is preferably 10 seconds to 20 minutes, more preferably 1 minute to 10 minutes. The temperature of the electrodeposition solution is OC to 6
0C is preferred, more preferably 10[ to 40C
It is.

The composition of the present invention may be used by adding a pigment thereto.

Examples of pigments include pen color, titanium oxide, carbon black, Merck, clay, iron oxide, lead oxide, zinc oxide, strontium chromate, barium imitate, molybdenum orange, cadmium yellow, cadmium red, nickel titanium yellow, and chromium. Yellow, etc. Kale.

Dissolve the composition in a solvent and apply it, then remove the solvent, or
Alternatively, a coating film formed by cationic electrodeposition can function as a coating film even in the T-form, but a better coating film can be obtained by converting it into a three-dimensional crosslinked product. be able to. Although there are no restrictions on the method of curing the coating film, heating is preferred. The heating temperature is preferably 100C to 250C, more preferably 150C to 220C.

The coating film obtained in this way has good chemical resistance strength,
It showed flexibility and weather resistance. In particular, it showed remarkable performance in resistance to salt spray. -! A molded article can be obtained by placing the composition of the present invention in a mold and causing a crosslinking reaction by heating or the like.

Examples will be described below, but the present invention is not limited thereto. Note that reference examples are also shown.

53- Reference fl11 1 equipped with a stirrer, thermometer, dropping funnel, and reflux condenser
2BOm of chloroporum in a 000-volume four-day flask.
1, isopropylamine 3547 was added thereto, and while stirring at 40C, 91.57 of cool methyl styrene (m-form, p-temperature mixture) was added dropwise from the dropping funnel over 3 hours.

After further stirring for 2 hours after the dropwise addition, the reaction solution was concentrated using an evaporator. - Place the number of lines in a separation liquid q -) and add 1N hydrochloric acid 100rn/! was added and thoroughly shaken to separate the chloroform layer.

Next, the aqueous layer was washed with 1001 Lt of chloroform, 25-N of 5N sodium hydroxide solution was added to the aqueous layer, and 50-N of hexane was added to perform liquid separation. After further extraction by adding 50 parts of hexane to the aqueous layer, the oil layers from both regions were combined and concentrated using an evaporator to obtain 257 g of oil at around -30 C per 0.05 mm.

Acid titration of this oil revealed that it had a purity of 98% and a pKa of 8.9.

Acid titration involves dissolving the oil in a mixture of attenuate and water to obtain a titration of 0.1
It was titrated with 100 liters of hydrochloric acid.

54- Further, the infrared absorption spectrum showed fifth-order characteristic absorption.

1630, 1600, 1470, 140IJ, 1380
゜1170.1000,910,830,800,72
0071b-' Furthermore, the nuclear magnetic resonance spectrum showed the following pattern.

δ value (splitting type, relative proton number) 1. L12 (double line.

6), 13 (single line, 1), 2.84 (septad line, 1)
, 5, B (single line, 1), 5.26 (2 sets of double edges, 1), 5.8 (2 silk 2M edges, 1), 6.8 (multiple lines, 1), 7 .2 to 7.5 (multiple line, 4) From these data, it was confirmed that this compound was N-isopropylamine methylstyrene.

Reference Example 2 In a 500-capacity separable flask equipped with a stirrer, thermometer, and reflux condenser, 150 liters of ethylbenzene was added.

Improvohylamide synthesized in Reference Example 11, trimethylstyrene 13,9ii', 2-hydroxyethyl acrylate 107, methyl methacrylate 27.4F, butyl acrylate 48,7? , 2.2'-Azobiisof thionitrile 37 was added, and stirring was continued at 701C for 2 hours, at 80C for 4 hours, and further at 85C for 4 hours. After that, 100+++7 with the vacuum lid! Ethylbenzene and the like were distilled off, and the copolymer mixture was poured into 2 tons of cold hexane to obtain a pale yellow viscous solid. ao this thing
It was vacuum dried at C. The obtained copolymer is called C-2, and its elemental analysis values are: C: 65.5%, H: 8
, 2%, 0: 25, 5%, N: 1.0%. The intrinsic viscosity was measured at 30C using chloroform as a solvent.
It was 0.09.

Moreover, the glass transition point was determined to be -80.

Reference Example 5 In a 600-capacity four-day flask equipped with a stirrer, thermometer, and reflux condenser, 602 toluene and 10 butyl methacrylate were added.
1. Isopropylaminomethylstyrene synthesized in Reference Example 1 was added with 17.5 f, 0.27 r of azobisisobutyronitrile, and the internal temperature was maintained at 80C with thorough stirring. The reaction was completed in 16 hours, and unreacted monomers were quantified using gas chromatography, and it was confirmed that 92% of butyl methacrylate and 98% of isopropylamine methylstyrene were polymerized. Steam was blown into the reaction mixture to distill off the solvent and unreacted monomers. When the obtained polymer was vacuum dried, a pale yellow monomer was obtained. The elemental analysis value of this polymer is C; 76.
0%, H: 9.2%, N: 5.9%. Moreover, the infrared absorption spectrum showed the following absorption. 172
0, 1460, 1250, 1150, 760I
IL-1 This copolymer, hereinafter referred to as C-2, had a glass transition point of 25C.

Reference Example 4 In a pressure-resistant glass sealed tube with a capacity of 200 rnl, 50 d of ethylbenzene and 7 ml of isopropylamine methylstyrene were added. , 2-ethylhexyl methacrylate 24v, 2-hydroxyethyl acrylate 51. After adding 142% of butyl methacrylate and 1.57% of azobisisobutyronitrile and mixing well,
The sealed tube was melt-sealed and continued shaking at 90C for 7 hours. Thereafter, the package was opened, poured into a glass Petri dish, and vacuum-dried using aoC in a vacuum dryer. The glass transition point -57- of the obtained copolymer C-4 was 8C.

Reference Example 5 Diethylamine methylstyrene 10? was synthesized in the same manner as Example 1 in a 200-volume flask. , butyl acrylate 301, 2-hydroxyethyl methacrylate 52,
Methyl methacrylate 52.1.1'-Azobiscyclohexanecarbonitrile 0.59 and cumene 509 were added and reaction was carried out at 70C for 10 hours with magnetic stirring. After the reaction, the solvent and unreacted mixture were removed by steam evaporation, and a copolymer was obtained by vacuum drying. Obtained copolymer C
The glass transition temperature of -5 was -5'c.

Reference Example 6 In a 1-4-day flask equipped with a stirrer, a reflux condenser, and a thermometer, 100-V toluene and 30 V chloromethylstyrene were added. of butyl acrylate, 207 of 2-ethylhexyl methacrylate, and 1v of benzoyl peroxide were added, stirred at 70C for 5 hours, and further heated at 90p for 5 hours.
After reacting for an hour, the internal temperature was lowered to 40C, and 300y of isopropylene 58-pylamine was added at once, followed by stirring for 8 hours.

After the reaction, isopropylamine and toluene were capped using an evaporator, and the reaction solution was poured into -50 petroleum ether, and the white precipitate formed was dried. The glass transition point of the obtained polymer C-6 was -5.

Reference Example 7 Into the four-day flask used in Reference Example 6, add 1 oor of ethylbenzene and 20 f of chloromethylstyrene.

40? of butyl acrylate, 10v of hydroxyethyl acrylate, 2Of styrene, 2f of 2,z-azobisisobutyronitrile are added and stirring is continued at 80C for 4 hours and then at 90C for 4 hours.

Next, the internal temperature was lowered to 60'Q, and n-hexylamine 652 was added dropwise over 30 minutes. Thereafter, the temperature was further raised to 80C and stirring was continued for 4 hours. Next, 50
- After preparing the liquid, cool it to room temperature. On the other hand, -2
3 tons of OC n-hexane was prepared and poured into the above reaction mixture with stirring, and the resulting precipitate was separated from P and dried. The copolymer C-7 had a glass transition point of -17C.

Sangoro? 118 Into a 3-day flask with a capacity of 1, equipped with a stirrer, a temperature side, and a dropping funnel, add bisphenol A diglycidyl ether type epoxy resin (AEII-661 manufactured by Asahi Kasei Corporation; epoxy volume: 450 to 50 mouths) as an epoxy compound. 2
852 and 1471 ethylene glycol monoethyl ether were added as a solvent and stirred until homogeneous. 56.77 jetanolamine was added dropwise as an amine while maintaining the temperature at 8 oc, and stirring was continued for 3 hours after the dropwise addition. The amine-modified epoxy compound obtained here is called C-8.

Reference Example 9 Add 105y phenylcricidyl ether% 44.6 ff ethylene glycol monoethyl ether to the flask used in Reference Example 2, heat with stirring,
When the temperature reached 0C, dropwise addition of 73.59 jetanolamine was started. The internal temperature rose, and it was added over 1 hour while adjusting it so that it did not exceed 80C, and then for 4 hours.
Stirring was continued at 80c. The amine-modified epoxy compound obtained here is called C-9.

Reference Example +o-17 An epoxyamine-modified glaze was prepared in the same manner as in Reference Example 8. The charging composition is shown in Table 1.

Table 1 -61- The obtained epoxyamine modified products were classified into C-10 to C-10, respectively.
-17.

(Note 1 *IAER357; Bisphenol A diglycidyl ether type epoxy resin manufactured by Asahi Kasei Corporation, epoxy equivalent 225-280 *2AER66
4; Same as above, epoxy equivalent 900-1000 *5 AER7
71; Tetrabromo bisphenol A diglycidyl ether type epoxy resin manufactured by Asahi Kasei Corporation, epoxy equivalent 445-520, bromine content 21% *4 DEN431; Phenol novolak type epoxy resin manufactured by Dow Chemical Company, epoxy equivalent 172-179 *5 DER732 ; Dow Chemical Company split polypropylene glycol diglycidyl ether, epoxy equivalent; 605 to 335 Reference Example 18 Tolylene diiso-62-cyaner) (20% 2,is, 80% 2,4 mixture) was added to the same 60 flask as in Reference Example 8. ) 174r and heat at 30 to 40C while stirring.
Of 2-ethylhexyl alcohol was added dropwise over 1 hour, and the mixture was stirred for an additional 2 hours, and the infrared absorption spectrum of the reaction mixture was measured.

It was confirmed that the absorption peculiar to the isocyanate group of 2240 to 227UQs-' disappeared. Next, 44.7 f of trimethylolpropane was added dropwise, stirring was continued for 30 minutes at 80C, 1 drop of dibutyltin dilaurate was added, and 6 f.
The mixture was stirred for 0 minutes, and 87.2f of ethylene glycol monoethyl ether was processed into a uniform bath solution. This blocked polyisocyanate is hereinafter referred to as C-18.

Reference Example 19 50-row three-loaf flask 1C equipped with a stirring bar and thermometer
2.4-) lylene diisocyanate of 1009 was added, and while maintaining the temperature at 80C, chidylua and alcohol were added dropwise to 2-ethyl 160f as a blocking agent. Stir 2 more times
The disappearance of incyanato groups was confirmed by infrared absorption spectrum. Thereafter, Improper Tool 1107 was added as a solvent to form a homogeneous solution. The obtained product is C-1
It is called 9.

Reference Example 20 Various blocked polyisocyanates were prepared using the same apparatus and operation as in Reference Example 19. Tani raw materials and amounts are shown in Table 2. The obtained block polyisocyanates were each C-
20 to C-24.

Example 1 In a separable flask with a capacity of 1 cm equipped with a stirrer and a water inlet tube, 8 f of ethylene glycol monoethyl ether and 5 l of ethylene glycol monoethyl ether were added as a copolymer and 30 v1 of C-2 as a solvent, and the mixture was heated to 80 C. After stirring to homogenize and lowering the temperature to 50C, C-18 was mixed at 28.8F as a block polyincyanate, and C-8 was mixed at 67.1F as an amine-modified epoxy compound. The mixture was added and stirred until uniform. Next, 2.3 l of acetic acid as an acid and 3 v of dibutyltin dilaurate as a catalyst were added.

While stirring, water 5001 was added dropwise from the water inlet pipe at a constant rate over 45 minutes, and then water 3402 was added over 15 minutes. The specific conductivity of this liquid is 1480 μmoh/4. pH
was 6.2.

Transfer this mixed solution to a 2-ton flask, and add a zinc phosphate-treated steel plate (manufactured by Nippon Test Piece Co., Ltd., 150 m
/mX) Lo m/mX Lo, 8m/m)
, and a stainless steel plate was used as an anode, and a direct current was passed for 3 minutes at a voltage of 250 V between the electrodes. During this time, the electrolytic solution continued to be magnetically stirred, and the solution temperature was 30 to 53 C. A uniform coating film was formed on the steel plate. After thoroughly washing the coated plate with water, air-drying it, and heating it at 175°C for 20 minutes, a uniform, glossy, transparent coating was obtained, which was rubbed strongly with gauze containing methyl isobutyl ketone. However, no changes such as dissolution of coating film turbidity, reduction in gloss, or friction scratches were observed. Membrane burial is 20μ, Erichsen value is 7.8m
/m, and in the DuPont impact test, no peeling cracks were observed in the coating even when a load of IQ was dropped from a height of 50 degrees. Further, the electrolytic hardness was 3H, and the cross-cut test was 100/100. Examples 2 to 17 Electrodeposition was performed in the same manner as in Example 1 in a continuous system. Table 3 shows the copolymer used to prepare the electrolyte, its solvent, block polyisocyanate, amine-modified epoxy compound, type and amount of acid, amount of water, and liquid properties of the obtained electrolyte.
summarized in. Electrodeposition was carried out in the same manner as in Example 1, and the resulting coating film was heated at 175C for 20 minutes. In both cases, a uniform coating film was formed. The film thickness, Erichsen value, and Empi hardness are summarized in Table 4. In addition, the DuPont impact test -66
- It was carried out under the conditions of % inch
Also, the first test is 10 for all sample files.
0/10L] was passed.

-67- 68- (Note) Solvent A: Ethylene glycol monoethyl ether B: Isoglopanol C: Diethylene glycol monoethyl ether D: Diethylene glycol monobutyl ether E: Ethylene glycol 7-hexyl ether F Ni-diethylene glycol 7-methyl needle G: Methyl isobutyl ketone catalyst X Nidibutyltin dilaurate Y: Tri-n-butyltin acetate 2: Tin acetate W: Di-n-n-butyltin chloride Table 4 -71- 89-

Claims (1)

[Claims] 1. (i) The repeating unit shown in the structural formula and the structural formula (
B) A linear copolymer containing repeating units represented by (f
i A compound in which part or all of the epoxy groups of an epoxy compound containing 11 or more epoxy groups are replaced with a structure represented by formula (C), and (ii+) polyisocyanate-1.
A novel resin composition comprising a compound in which all or part of the isocyanate groups of are blocked with alcohol and/or amine. R, Rt H [wherein, R1+R2 is 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, mfc is an arylalkyl group, and R3 is hydrogen, methyl group, halogen,
Carboxymethyl group, acetoxy group, CH, COOR,
(RI+ 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, R4 is aqueous, an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group, an alkenyl group, Aryl group having 6 to 20 carbon atoms, arylalkyl group, 1 carbon number
to 12 haloalkyl groups, hydroxyalkyl groups,
Alkoxyalkyl group, tetrahydrofurfuryl group, glycidyl group, + CHt CHt o-)-rlRs
(Re is an alkyl group having 1 to 8 carbon atoms, n is an integer of 1 to 30), or a dialkylaminoalkyl group having 5 to 20 carbon atoms, and R71R11 is hydrogen, an argyl group having 1 to 20 carbon atoms, a cyclo Alkyl group, hydroxyargyl group, aminoalkyl group, H+
NH-CH2CH2% (m is an integer from 1 to 8),
Represents a group selected from aryl groups and arylalkyl groups having 6 to 15 carbon atoms. 2. The composition according to claim 1, wherein one of R and Rt is hydrogen. 3. The composition according to claim 2, wherein one of R, t or R2 is hydrogen and the other is an alkyl group. 4. The composition according to claim 6, wherein the alkyl group has 2 to 8 carbon atoms. 5. The composition according to claim 4, wherein the alkyl group is an isopropyl group. 6. Claims 1 to 5, wherein R8 is hydrogen or a methyl group. 7. Claims, wherein R1 is hydrogen or an alkyl group having 1 to 20 carbon atoms. The composition according to claims 1 to 6. 8. The composition according to claims 1 to 6, wherein R4 is a hydroxyalkyl group having 1 to 12 carbon atoms. 9. R6 is a hydroxyethyl group. 10. The composition according to claim 8, wherein R is a dialkylaminoalkyl group having 3 to 20 carbon atoms. 11. R4 is a diethylaminoethyl group. 12. The composition according to claim 10, in which a part of the structure represented by the structural formula (B) is a diethylaminoethyl group.
) The composition according to any one of claims 1 to 12, wherein the repeating unit structure is replaced by a repeating unit structure represented by: -C)I, -C-) (In the formula, X represents a group selected from hydrogen and a methyl group, and Y represents a group selected from a phenyl group, a nitrile group, and a halogen.) 13. As an epoxy compound 7 Claims 1 to 3 use a compound containing two or more epoxy groups. 13. The composition according to item 12. 14.Special d'"Scope of market demand for the group described in item 13 (
In the formula, 2 represents hydrogen or halogen, and p represents an integer from 1 to 60. ) 15. The composition according to claim 14, wherein X is hydrogen. 16. The composition according to claim 13, which uses a compound represented by structural formula (F) as the epoxy compound. = 5- (In the formula, R represents dihydrogen or an alkyl group having 1 to 6 carbon atoms, and q represents an integer of 1 to 15.) 17. Claims using a compound represented by formula (G) as an epoxy compound A composition according to scope item 15. (In the formula, W represents a monovalent aliphatic hydrocarbon group having 1 to 15 carbon atoms or a monovalent aromatic hydrocarbon group having 6 to 12 carbon atoms, and r represents an integer of 2 to 4.) 18. Epoxy 17. The composition according to claim 16, which uses a compound represented by formula (6) as the compound. (CH, -CM-CH, -0-)-V\/5(Hl (wherein, St is an integer from 2 to 5, and ■ is a carbon number of 6-6
= represents a group selected from a pentavalent aromatic hydrocarbon group having 1 to 15 carbon atoms, a pentavalent aliphatic hydrocarbon group having 2 to 20 carbon atoms, and a pentavalent aryl-substituted aliphatic hydrocarbon group having 7 to 20 carbon atoms . 19. The composition according to claim 13, which uses a compound represented by formula (J) as the epoxy compound. (In the formula, RIO is hydrogen or a methyl group, t is 0 to 2
Represents an integer of 0. ) 20, Using a compound with a structure in which the number of carbon atoms is replaced with 4 to 220 as an epoxy compound 41! The composition according to claim 13, amended by I'. 21. The composition according to claims 1 to 20, in which each of R7 and R8 is an argyl group having 1 to 10 carbon atoms. 22. The composition according to claim 21, wherein R7, R, and R are all ethyl groups. Claims 1 to 2, wherein both 25-R71Ra are hydroxyalkyl groups having 1 to 10 carbon atoms.
Composition according to item 0. 24, R7, R, must be either a hydroxyethyl group or a hydroxyalkyl group %π "M range 2nd
The composition according to item 3. 25. The composition according to claims 1 to 24, wherein the polyisocyanate is a polyisocyanate aromatic hydrocarbon having 8 to 20 carbon atoms. 26, polyisocyanate aromatic hydrocarbon (tolylene diisoanor)? %♂f--The composition according to claim I81 paragraph 25. 27. Blocking agent for polyisocyanate 2. The composition according to claims 1 to 26, in which an aliphatic monoalcohol having 1 to 220 carbon atoms and a polyol having 2 to 20 carbon atoms are used in combination. 28. (i)? S formula (a linear copolymer that refers to repeating units represented by A+ (~ unit and +jlJ repeating unit represented by formula (B), and If) epoxy groups of epoxy compounds containing 11761 or more epoxy groups A compound in which part of EE fl is completely substituted with the structure represented by formula (C), and (
iii) A paint made of a resin composition made of a compound in which all or part of the incyanate groups of polyisocyanate are blocked with alcohol and/or amine. H [wherein R1 and Rt are hydrogen, an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group, an alknyl group, an aminoalkyl group, an aryl group having 6 to 20 carbon atoms, or an arylalkyl group, R1 is hydrogen, methyl group, halogen, carboxymethyl group, acetoxy group, CH2C00Rs
(Ra Vi hydrogen, alkyl group having 1 to 10 carbon atoms,
fc is an 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, an arylalkyl group having 1 to 12 carbon atoms;
loalkyl group, hydroxyalkyl group, alkoxyalkyl group, tetrahydrofurfuryl group, glycidyl group, +
CH2CHt O+-nRa (R6 is an alkyl group having 1 to 8 carbon atoms, n is an integer of 1 to 30), dialkylaminoalkyl group having 3 to 20 carbon atoms, R
,,R81d each hydrogen, alkyl group having 1 to 20 carbon atoms, cycloargyl group, hydroxyalkyl group, aminoalkyl group, H-j-NH-CH, -CH,-)m
(m is an integer of 1 to 8), an aryl group having 6 to 15 carbon atoms, and an arylalkyl group. [29] The paint according to claim 28, wherein the paint is an electrodeposition paint. ac+, (1) a linear copolymer containing a repeating unit represented by the structural formula (A) and a repeating unit represented by the structural formula (Bl), and (ii) an epoxy compound epoxy compound containing one or more epoxy groups 10 - Reaction of a compound in which one or all of the Si groups are substituted with a structure represented by formula (C), and (iii) a compound in which all or part of the incyanate groups of polyisocyanate are blocked with alcohol and/or amine. R, R. H [In the formula, R11R2 is hydrogen, an alkyl group having 1 to 2 o carbon atoms, a cycloalkyl group, an alkenyl group, an aminoargyl group, an aryl group having 6 to 20 carbon atoms, is an arylalkyl group, R3 is hydrogen, methyl group, halogen, carboxymethyl group, acetoxy group, CH, C00RII
(R is hydrogen, an alkyl group having 1 to 10 carbon atoms, or an arylalkyl group), or an alkoxy group having 1 to 75 carbon atoms, R4 is hydrogen, an alkyl group having 1 to 20 carbon atoms, a 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, -(-cH2cH', 0-)-Re
(R6 is an alkyl group having 1 to 8 carbon atoms, n is an integer of 1 to 60), or a dialkylaminoalkyl group having 3 to 20 carbon atoms, R7lR4 is hydrogen, an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group, Hydroxyargyl group, aminoalkyl group, H-4NH-CH2-
It represents a group selected from CH, -)- (m is an integer of 1 to 8), an aryl group having 6 to 15 carbon atoms, and an arylalkyl group. ] 51. The crosslinked product according to claim 30, which has a film-like shape. 32, (1) A linear copolymer containing a repeating unit represented by structural formula (A) and a repeating unit represented by structural formula (B), and an epoxy group of an epoxy compound containing one or more epoxy groups. A coating of a resin composition consisting of a compound partially or entirely substituted with the structure represented by formula (C), and (iii) a compound in which all or a portion of the incyanato groups of polyisocyanate are blocked with alcohol and/or amine. Forming a coating film by forming on the surface to be coated and then curing R1H [wherein RI and R1 are hydrogen, an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group, an alkenyl group, aminoalkyl group, aryl group having 6 to 20 carbon atoms, arylalkyl group, R3 is hydrogen, methyl-13-yl group, halogen, carboxymethyl group, acetoxy group,
CH2C00Rs (Rs is hydrogen, carbon number 1 to 10
or arylalkyl group) or an alkoxy group having 1 to 5 carbon atoms, R4 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, an arylalkyl group group, C1-C12 haloalkyl group, hydroxyalkyl group, alkoxyalkyl group, tetrahydrofurfuryl group, glycidyl M, + cl(, -CH, -
0-)-, R6 (R6 is an alkyl group having 1 to 8 carbon atoms, n is an integer of 1 to 30) or 3 to 20 carbon atoms
dialkylaminoalkyl group, R7lR11 is hydrogen, alkyl group having 1 to 20 carbon atoms, cycloalkyl group, hydroxyalkyl group, aminoalkyl group, H
+NH-CH, -CH, ÷ (m is an integer from 1 to 8)
, an aryl group having 6 to 15 carbon atoms, and an arylalkyl group. ] -14- 33. Claim 32, in which an acid is added to the composition and then dissolved or dispersed in water to form an electrodeposition liquid, and a film is formed by cathodophoresis on the surface to be coated.
Coating film forming method described in section. 64, Claim 3 using carboxylic acid as the acid
The method for forming a quasi-film according to item 3. 35. The coating film forming method according to claims 32 to 34, wherein the coating is cured by heating. 36. The coating film forming method according to claim 35, wherein the coating film is heated at a temperature of 36° to 100°C and 250°C or less.