JPH03160061A - Amic acid modified resin - Google Patents

Abstract

PURPOSE:To prepare an amic acid-modified resin which is suitable for a water- base coating material and gives a coating film excellent in the resistance to corrosion and water by introducing a specific amic acid residue capable of thermally forming an imide ring into terminal groups and(or) side chains of the molecule of a base resin. CONSTITUTION:The title resin has at least one amic acid residue of the formula (wherein R is an optionally substd. 2-4C alkylene group, an alkenylene group, or a di- or trivalent alicyclic or arom, hydrocarbon group; and n is 1 or 2) introduced into a terminal group and(or) side chain of the molecule of a base resin. The amic acid residue cyclizes thermally to form an imide ring. The title resin is prepd., e.g. by reacting a dicarboxylic acid anhydride (e.g. maleic anhydride) with amino groups of the base resin having amino groups (e.g. an amino resin or polyamide resin) and introducing amic acid residues into terminal groups and(or) side chains of the molecule of the base resin.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to novel film-forming modified resins primarily for use in water-based paints and electrodeposition paints. The invention also relates to a method for producing the modified resin and a coating composition containing the modified resin.

In the case of water-based paints, the resin itself is made water-soluble or water-dispersible, and in the case of anionic electrodeposition paints, it is necessary to give the resin the negative charge necessary for electrodeposition. has a base. Such carboxyl group-containing resins are used in combination with curing agents such as melamine resins and blocked polyisocyanates, and are baked and cured after painting. However, the carboxyl groups contained in such resins do not react with the curing agent and remain in the coating film, significantly reducing the durability of the coating film, especially its water resistance due to its hydrophilic nature.

Therefore, the present invention provides for dissolving or dispersing in an aqueous medium,
Alternatively, to provide a film-forming resin that contains a carboxyl group in order to provide a negative charge necessary as an electrodeposition resin, but has a modified group that does not leave any carboxyl group functionality in the coating film after curing. The task is to In the present invention, four raw ILG columns have at least one of the formula -NH-C-R-{-C○OH), 110 (wherein R represents a substituent) at the terminal and/or side chain of the base resin molecule. C2-C4 alkylene or alkenylene groups or divalent or trivalent alicyclic or aromatic hydrocarbon groups, n is 1 or 2), and by heating the Provided is an amic acid-modified resin characterized by having the property of generating an imide ring by cyclization of an amic acid residue.

The amic acid residue of the above formula forms an idando ring as shown below by heating.

(Left below) 1N H - C - R+- C O O H )1
; O Therefore, at least one carboxyl group functionality bonded to the terminal and/or side chain of the base resin disappears,
The properties of cured coatings formed from the modified resin are improved.

The amic acid-modified resin of the present invention can be produced by the following method.

In other words, when the base resin itself has an amino group, such as amino resin, polyamide resin, amino group-containing polyurethane resin, polyethylene ξene resin, amino group-containing polybutadiene resin, and amino group-containing silicone resin, A terminal and/or side chain hairamic acid residue of the base resin can be introduced by reacting with an amino group or tricarboxylic acid anhydride. In addition, when the base resin has an oxirane ring, such as epoxy resin, glycidyl group-containing acrylic resin, eboxidized polybutadiene resin, and glycidyl group-containing fluororesin, the oxirane ring can be opened by reaction with diamine. Using the remaining amino group of the bound diamine, a terminal and/or side chain hairamide acid residue of the base resin can be introduced by reaction with di- or tri-carboxylic acid anhydride in the same manner as described above.

In any of the above cases, the di- or tricarboxylic acid anhydride used has a 4-membered ring or a 5-membered amic acid residue.
The two carboxyl groups must be attached to the same carbon atom, or each must be attached to two adjacent carbon atoms, so as to form a membered imide ring.

The amide acid-modified resin of the present invention can be dissolved or dispersed in an aqueous medium containing a neutralizing agent for the amide-modified resin in combination with a curing agent such as a melamine resin or a blocked polyisocyanate compound, or can be used in conventional paints. It can be dissolved or dispersed in an organic solvent to form a coating composition.

These coatings can be applied by spraying, brushing, dipping,
It can be applied to objects such as metals by electrodeposition or the like. Thereafter, when the coating film is baked, it is cured by a crosslinking reaction between a functional group such as a hydroxyl group in the modified resin and a curing agent, and at the same time, the amic acid residue is cyclized to form an imide ring. Therefore, the obtained cured coating film is superior to cured coating films formed from conventional carboxyl group-containing resins in properties such as durability, adhesion, corrosion resistance, and water resistance.

Niratoyo Hoshi a removal ■. Amino group-containing base resin The amino group-containing base resin can be made into an amic acid-modified resin by directly reacting with di- or tricarboxylic acid anhydride.

As the amino resin, etherified amino resins obtained by addition condensation of melamine, guanagon, urea, their derivatives, etc. with formaldehyde, and further denaturation with alcohol can be preferably used. Specifically, methylated melamine Good examples include resins, butylated melamine resins, methylated butylated melamine resins, penzoguanamine resins, and the like. Commercially available products include melamine resin rJ-820-60 (number average molecular weight 12) manufactured by Dainippon Ink and Chemicals.
40), same rJ-830-60,+ (number average molecular weight 1120) and guanamon resin rBL manufactured by Sanwa Chemical ■
-60 J (acid value 0.5 or less), rBX-3900
J (acid value 0.5 or less) etc. are suitable. Amino groups in these resins can be used to introduce amic acid residues. Further, the molecular weight is not particularly limited, but it is preferable to use a number average molecular weight of about 400 to 100,000.

As the polyamide resin, the following general formula: fcOR'
-CONHR'' -NH?- (wherein R' and R'' are each independently a functional group-substituted or unsubstituted alkylene group having 1 to 20 carbon atoms, an alkenylene group, an alkynylene group,
It represents a cycloalkylene group or an arylene group, and n represents a positive integer of 2 or more. ) can be exemplified. As a commercially available product, for example, Nomex J manufactured by DuPont, etc. can be preferably used. Amino groups in these resins can be used to introduce amic acid residues. Further, the molecular weight is preferably about 400 to 100,000, but may be outside this range.

Examples of amino group-containing polyurethane resins include polyurea resins and polyurethane resins with terminal urea bonds.

As the polyethyleneimine resin, for example, those represented by the following general formula: a = 1 to 100, b = 1 to 100) can be used, and the amine value of the primary and secondary amines is 5 or more. And, the molecular weight is 600~
It is preferable to use a material with a strength of about 10,000. Commercially available products include "Evomin SP-103J" manufactured by Nippon Shokubai Chemical Industry ■.
(molecular weight 250), “Evomin sp-200J (molecular weight 10,000),” “Epo ξn P-1000 J (molecular weight 70,000),” “Evomin SP-018J (molecular weight 180
0) etc. can be exemplified.

The amino group-containing polyptadiene resin is 1, 4 type or 1 type.
, 2 type polybutadiene (the content of each structure is arbitrary) can be preferably used, and at least one terminal group must be an amino group. As a commercially available product, for example, borobutadiene with an amino terminal group manufactured by Idemitsu Petrochemical (1) can be used. It is preferable to use a number average molecular weight of about 400 to 50,000.

As the amino group-containing silicone resin, for example, the general formula: group or arylene group, and X1 to X4 are each independently hydrogen, an aryloxy group, an alkoxy group having 1 to 20 carbon atoms, an aryl group, or a group having 1 to 400 carbon atoms that may contain an ester bond, a urethane bond, or a carboxylic acid. represents an alkyl group, and n represents a positive integer of 2 or more.) Silicone resins having amino groups at both ends (or one end may be used) can be preferably used.

Here, the terminal amino group can be used to introduce an amic acid residue. Regarding the molecular weight, it is preferable that the number average molecular weight is about 400 to 100,000.

■． Introduction of oxirane ring-containing base resin and amino group The oxirane ring-containing resin is prepared by opening the oxirane ring with a diamine to form -CH-CH-NH-R' -NH. ○H (In the formula, R゜ represents a divalent organic group.) The same modification method as applied to the amino group-containing base resin by using the remaining axon group of the diamine bonded to the base resin. By,
A ξ-adoic acid residue can be introduced.

Typical examples of oxirane ring-containing resins include epoxy resins, but acrylic resins containing glycidyl groups,
Eboxidized polybutadiene or glycidyl group-containing fluororesin can also be used as the base resin.

As the epoxy resin, known epoxy resins can be used.

Particularly useful polyepoxy resins are glycidyl ethers of polyhydric phenols.

Such epoxy resins are derived from epihalohydrins and dihydric phenols and have epoxide equivalent weights of about 100 to about 5000. As the epihalohydrin, shrimp chlorohydrin is preferred.

Examples of dihydric phenols include resorcinol, hydroquinone, p,p'-dihydroxydiphenylpropane (commonly referred to as bisphenol A), P,p''-dihydroxybenzophenone, p,p'-monodihydroxybiphenyl, p,p'-dihydroxy diphenylethane,
Examples include bis(2-hydroxynaphthyl)methane and 1,5-dihydroxynaphthylene, with bisphenol A being preferred. These epoxy resins are well known in the art and can be prepared by reacting epihalohydrins and dihydric phenols in various ratios, or by reacting dihydric phenols with low molecular weight epoxides. It is formed into. A particularly preferred epoxy resin is a bisphenol A type epoxy resin.

Other useful epoxy resins are similarly made from novolac resins or similar phenolic resins.

Ethylene glycol, diethylene glycol, triethylene glycol, 1,2-propylene glycol, 1.
Similar to polyhydric alcohols derived from polyhydric alcohols such as 4-propylene glycol, 1,5-pentanediol, 1,2,6-hexanetriol, glycerol, bis(4-hydroxycyclohexyl)2,2-brovane, etc. Also suitable are glycidyl ethers. Glycidyl esters of polycarboxylic acids may also be used; such esters can be used to synthesize shrimp chlorohydrin or similar epoxy compounds, such as oxalic acid, succinic acid, glutaric acid, terephthalic acid, 2,6-naphthalene dicarboxylic acid, dimerized It is produced by reacting it with an aliphatic or aromatic polycarboxylic acid such as linolenic acid. Examples of these are glycidyl adipate and glycidyl phthalate. Also useful are polyeboxides derived by epoxidation of olefinically unsaturated alicyclic compounds. This includes diepoxides that partially contain one or more monoepoxides. These polyepoxides are non-phenolic and are obtained by eboxidizing alicyclic olefins.

For example, it can be obtained with oxygen and the selected catalyst, with perbenzoic acid, with acetaldehyde monoperacetate or with peracetic acid. Among such polyepoxides are the epoxy cycloaliphatic ethers and esters well known in the art.

Other epoxy derivatives include bisimide-containing diepoxides, heterocyclic N,N'-diglycidyl compounds, 1,3
．． 5-}liglycidyl uric acid isocyanate and other known epoxy group-containing resins.

The epoxy equivalent of the polyepoxy resin used in the present invention is 100 to 5000, preferably 250 to 200.
It is 0. The above-mentioned epoxy resin includes those whose chains are extended with aliphatic polyols, aromatic polyols, polybutadiene polyols, polyester polyols, polyether polyols, and polycabrolactone polyols having at least two primary alcoholic hydroxyl groups. .

The acrylic resin containing a glycidyl group can be any acrylate ester (for example, methyl acrylate, ethyl acrylate, n-butyl acrylate, etc.), methacrylate ester (for example, methyl methacrylate, ethyl methacrylate, n-methacrylate, etc.). butyl, etc.), or acrylic acid,
Acrylic monomers such as acids or amides such as methacrylic acid, itaconic acid, acrylamide, methacrylamide, diacetone acrylamide, or any polymerizable monomer such as styrene or vinylstyrene, and acrylic monomers containing epoxy groups such as glycidyl methacrylate. Examples include copolymers with monomers. The molecular weight of these resins is suitably about 400 to 100,000, but is not limited to this.

As the fluororesin, fluorinated acrylic ester, fluorinated methacrylic ester (for example, 2,2.2-1
-Refluoroethyl acrylate, 1.1,1,3,3
．． 3-hexafluoroisoprobyl acrylate, 2,
2.2-trifluoroethyl methacrylate, etc.) or fluorinated styrene (2,3,4,5.6-pentafluorostyrene, etc.), and an epoxy group-containing acrylic acid/methacrylic acid ester monomer. Copolymers of and the like can be preferably used.

The ratio of the above fluorinated modified monomer to other acrylic monomers is 1-9 9/9 9-1, and the molecular weight is 4
It is preferable that it is about 000,000 to 100,000.

Eboxidized polybutadiene is obtained by adding oxygen to some of the carbon-carbon double bonds of polybutazine, and contains an oxirane ring. Such an epoxidized polybutadiene resin can also be used as a base resin in the same way as an epoxy resin. The molecular weight of these is preferably about 400 to 50,000.

To open the oxirane ring of the oxirane ring-containing base resin,
Various diamines having two primary agono groups NH, can be used. Examples include aliphatic diamines such as diethylenetriamine, trimethylenetetramine, tetraethylenepentamine, polymethyleneamines, polyetherdiamines, N,N'-diaminoethylpiperazine, isophoronediamine, 1.3- Diaminoxyhexane, 3,9-bis(3-aminopropyl-2
,4,8.10-tetrabiro(5,5)undecane,
Lamilon C-2 60 (BASF), Wondermin (New Japan Chemical), 1.3-BAC (Mitsubishi Gas Chemical)
Alicyclic diamines such as o-, m- or p-phenylenediamine, diaminodiphenylmethane, diaminodiphenylsulfone, 2.4-diaminoanizole, 2.4
-1-lylene diamine, xylylene diamine, 2,4-
There are aromatic diamines such as diaminobiphenyl and diaminodixylyl sulfone.

A diamine compound represented by the general formula HzN R' NHz (wherein R゜ is a divalent organic group), such as 4,4゜-bis(4
-aminophenoxy)biphenyl, 4,4'-diaminodiphenylsulfone, 3,3'-diaminodiphenylsulfone, bis(4-(4-aminophenoxy)phenyl)sulfone, bis(4-(3-aminophenoxy)phenyl) Sulfone, bis(4-(2-aminophenoxy)
phenyl]sulfone, 1.4-bis(4-aminophenoxy)benzene, 1.3-bis(4-aminophenoxy)benzene, 1. 3-bis(3-aminophenoxy)benzene, 1,4-bis(4-aminophenyl)benzene, bis(4-(4-aminophenoxy)phenyl)
Ether, bis(3-ethyl-4-aminophenyl)methane, bis(3-methyl-4-aminophenyl)methane, bis(3-chloro-4-aminophenyl)methane, 4
．． 4'-diaminodiphenyl sulfide, 3.3'-
Diaminodiphenyl ether, 3,4'-diaminodiphenyl ether, 4,4'-diaminodiphenyl ether, 4,4°-diaminodiphenylmethane, 2,2-
Bis(4-(4-aminophenoxy)phenyl)propane, 2,2-bis(4-(4-aminophenoxy)phenyl)hexafluoropropane, 2,2-bis(4-
aminophenyl)propane, 2,2-bis(4-aminophenyl)hexafluoropropane, 2,2-bis(3
-Hydroxy4-aminophenyl)broban, 2,2-
Bis(3-hydroxy-4-acunophenyl)hexafluoropropane, 9,9-bis(4-aminophenyl)
-10-hydroanthracene, orthotolidine sulfone, and 3.3'. It is also possible to partially use polyvalent amine compounds such as 4.4°-biphenyltetraamine, 3,3''-4.4''-tetraaminodiphenyl ether.

In order to prevent the two primary amino groups of the diamine from participating in the ring-opening reaction of the oxirane ring at the same time, one of the two primary amino groups of the diamine is
The adanino group may be regenerated by reacting the class amine with a ketone to form a blocked ketimine, opening the oxirane ring, and then hydrolyzing the ketimine.

■． Introduction of atomic acid residue Amino groups directly bonded to the base resin and amino groups introduced to the base resin by ring-opening reaction of oxirane ring with diamine are reacted with di- or tri-carboxylic acid anhydride. to form an amic acid residue.

The two carboxyl groups of the 1I 0 di- or tricarboxylic anhydride must be attached to the same carbon atom or each must be attached to two adjacent carbon atoms.

Examples of such acid anhydrides include dicarboxylic anhydrides such as succinic anhydride, dodecenyl succinic anhydride, maleic anhydride, phthalic anhydride, tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, and endomethylenetetrahydrophthalic anhydride. , methylendomethylenetetrahydrophthalic anhydride, methylbutenyltetraphthalic anhydride, hexahydrophthalic anhydride, methylhexahydrophthalic acid, chlorendoic anhydride, tetrabromophthalic anhydride, tetrachlorophthalic anhydride, etc. Tricarboxylic acid anhydride includes trimellitic anhydride.

The ratio of the acid anhydride to the amino-containing base resin, and the ratio of the diamine and acid anhydride to the oxirane ring-containing base resin are such that the acid value of the amic acid-modified resin to be used is 20 to 400. It is preferable.

■． Coated bottom material The amic acid-modified resin of the present invention can be combined with a curing agent to form a coated bottom material. As the curing agent, amino resins typified by melamine resins or blocked polyisocyanate compounds can be used.

Suitable amino resins are reaction products of melamine, guanamine, urea and their derivatives with aldehydes, optionally further etherified with alcohols. Examples of amino resin compounds include urea, ethylene urea, thiourea, melamine, penzoguanamine, and acetoguanamine. Aldehydes include formaldehyde, acetaldehyde, and propionaldehyde. Although the amino resin may be used in the alkylol form, it is preferred that the etherifying agent is used in the ether form, which is a monohydric alcohol containing from 1 to about 8 carbon atoms. If a blocked polyisocyanate is used, any suitable organic polyisocyanate may be used.

Typical examples include trimethylene diisocyanate,
Tetramethylene diisocyanate, pentamethylene diisocyanate, hexamethylene diisocyanate, 1,
2-propylene diisocyanate, 1.2-butylene diisocyanate, 2.3-butylene diisocyanate,
Aliphatic diisocyanates such as 1,3-butylene diisocyanate, phenylene diisocyanate, 4,4°-
diphenyl diisocyanate, 1. Aromatic diisocyanates such as 4-naphthalene diisocyanate, 4,4'-diphenylmethane diisocyanate, 2,4- or 2,6-tolylene diisocyanate or mixtures thereof, 4,4"-toluidine diisocyanate, 1,4-xylene diisocyanate, Triphenylmethane-4
, 4'-4'' triisocyanate, 1,3,5-triisocyanate benzene, 2,4,6-triisocyanate toluene, 4,4'-diphenyldimethylmethane-2,2', 5 Tetraisocyanates such as 5°-tetraisocyanate, tolylene diisocyanate dimers and trimers, 2 to 3 NCOs.
Examples include polymerized polyisocyanates such as polymethylene polyphenylene polyisocyanate having functional groups.

Furthermore, organic polyisocyanates include glycols such as ethylene glycol and propylene glycol, glycerol, trimethylolpropane, hexanetriol,
Other polyols such as pentaerythritol, diethylene glycol, tripropylene glycol, and prepolymers derived from polyether polyols and polyisocyanates may be used. Alkylene oxides used in the addition reaction to form polyethers include ethylene oxide, propylene oxide, butylene oxide, styrene oxide, and the like. These may be either linear or branched. Particularly useful polyols are ethylene glycol, diethylene glycol, triethylene glycol, 1,4-butylene glycol, 1,3-butylene glycol, 1,6-hexanediol and mixtures thereof, trimethylolethane, trimethylolpropane, 1,2 ．． Other polyols such as 6-hexanetriol, pentaerythritol, dipentaerythritol, tripentaerythritol, polypentaerythritol, sorbitol, methyl glucoside, sucrose etc., ethylene oxide, propylene oxide,
They are derived by reacting with alkylene oxides such as mixtures thereof.

Blocking agents include methyl alcohol, ethyl alcohol, chloroethyl alcohol, proyl alcohol,
Butyl alcohol, amyl alcohol, hexyl alcohol, hebutyl alcohol, octyl alcohol, nonyl alcohol, 3,3.5-trimethylhexanol,
Alcohols such as decyl alcohol, lauryl alcohol, phenyl carbinol, methylphenyl carbinol, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, and substituted phenols may be used. Examples of substituted phenols include cresol, nitrophenol, chlorophenol, and t-butylphenol. Other blocking agents include amines such as diethylethanolamine, oximes such as methyl ethyl ketoxime, acetone oxime, cyclohexanone oxime, and cabrolacune. A preferred oxime is methyl-n-amylketoxime.

The blocked polyisocyanate is prepared by reacting a sufficient amount of blocking agent with the polyisocyanate under reaction conditions conventionally employed in the art such that no free isocyanate groups are present upon completion of the reaction. It is expressed by this.

The amic acid-modified resin and its curing agent are dissolved or dispersed in a commonly used organic solvent for coatings.

At least 20% of the carboxyl groups of the amic acid-modified resin should be used as a water-based paint or an electrodeposition paint.
is dissolved or dispersed in an aqueous medium containing a sufficient amount of base to neutralize the

Bases that neutralize the resin include ammonia, diethanolamine, triethanolamine, methylethanolamine, N,N-dimethylethanolamine, diethylamine, triethylamine, morpholine, potassium hydroxide, and the like.

The aqueous medium is water, but may contain an organic solvent to reduce viscosity or facilitate dispersion.

Examples of such solvents include ethyl cellosolve, probyl cellosolve, butyl cellosolve, methanol, ethanol, isopropyl alcohol, n-butanol, isobutanol, ethylene glycol dimethyl ether, diacetone alcohol, 4-methoxy-4-methylpentanone. -2, water-miscible organic solvents such as acetone, methyl ethyl ketone, methoxybutanol, dioxane, ethylene glycol monomethyl ether acetate, xylene, toluene, methyl isobutyl ketone, hexane, carbon tetrachloride, 2-ethylhexanol, isophorone, cyclohexane, benzene , toluene, and other water-miscible organic solvents.

The coating compositions of the present invention may contain conventional coating additives and pigments. Examples of pigments include color pigments such as titanium dioxide, red iron oxide, carbon black, extender pigments such as aluminum silicate, precipitated barium sulfate, and aluminum phosphomolybdate, strontium chromate, basic lead silicate, and chromic acid. There are rust-preventing pigments such as lead, hydrotalcite, and kaolin.

In the case of a water-based paint, the coating composition of the present invention has a non-volatile content of 1
It can be adjusted to about 0 to 30%, coated or electrodeposited to a dry film thickness of 15 to 30 microns, and then thermally cured at a temperature of, for example, 100 to 180'C.

Examples and comparative examples of the present invention are shown below. Parts and percentages in these examples are by weight.

Example 1 70.4 g of diaminodiphenylmethane and 3 g of dioxane were placed in a reaction vessel equipped with a stirrer, a reflux condenser, and a nitrogen inlet tube.
3. 9 g was added, and the temperature was raised to 80°C under a nitrogen atmosphere. Furthermore, 80.0 g of bisphenol A type epoxy resin (epoxy equivalent: 450) was added to dioxane 3 4.
This solution was added dropwise into the reaction vessel little by little while paying attention to the temperature inside the reaction vessel. The reaction was continued while maintaining the temperature at 80°C, and the end point of the reaction was determined by measuring the epoxy group concentration using the hydrochloric acid-dioxane method, and the reaction was continued until the epoxy group completely disappeared.

After the reaction is completed, it is cooled, unreacted diaminodiphenylmethane is removed, and Intermediate A having an axon group at both ends of the molecule is obtained.
I got it.

Furthermore, 70.0 g (solid content) of this intermediate A, 3 dioxane 7. Weigh out 0 g into another reaction container and heat at 50°C.
6. Raise the temperature to phthalic anhydride. 0 g was added and reacted to obtain modified resin (I). The properties of the obtained modified resin are: acid value 70.4, non-volatile content 70.3%, molecular weight 1600.
Met.

Example 2 Using intermediate A obtained in Example 1, maleic anhydride 10. React using 6 g,
A modified resin (n) was obtained.

The properties of the obtained modified resin include an acid value of 75.2 and a non-volatile content of 7.
0.9%, molecular t1500.

Example 3 Polyepsilon prolactone polyol (Mn:
500) and 160.0 g of bisphenol A type epoxy resin (epoxy equivalent: 450) were weighed, and dimethylbenzylamine 0.0 g was weighed. 04g was added and reacted at 150°C to obtain a polyepsilon caprolactone modified epoxy resin.

80g of this polyibsilon caprolactone modified epoxy
18.4 g of a ketimine derivative obtained by reacting diethylene triamine and methyl isobutyl ketone was added to the mixture, and the mixture was reacted until the epoxy group disappeared.

Thereafter, ion-exchanged water was added and hydrolyzed to obtain an intermediate B having amino groups at both ends of the molecule. This intermediate 87
0g (solid content), additionally 14.6g of anhydrous phthalate #3 and dioxane 6. 3 g was added and reacted to obtain a modified resin (1).

The properties of the obtained modified resin include an acid value of 33.6 and a non-volatile content of 6.
It was 9.4% and the molecular weight was 3,200.

Example 4 Intermediate B obtained in Example 3 was reacted with 9.8 g of maleic anhydride in place of phthalic anhydride to obtain modified resin (IV).

The properties of the obtained modified resin include an acid value of 37.0 and a non-volatile content of 7.
It was 0.0% and the molecular weight was 3000.

Example 5 Bisphenol A type epoxy resin (epoxy equivalent: 200
Intermediate C was obtained in the same manner as in Example 1 from 80.0 g of 0) and 3.6 g of ethylenediamine.

70.0 g (solid content) of this intermediate was reacted with 6.5 g of trimellitic anhydride to obtain a modified resin (V).

The properties of the obtained modified resin include an acid value of 47.3 and a non-volatile content of 7.
It was 0.6% and the molecular weight was 5,000.

Example 6 Bisphenol A type epoxy resin (epoxy 1190
) 80.0g, diaminodiphenylsulfone 2 0 9
．． Intermediate D was obtained from 0 g in the same manner as in Example 1.

70.0 g (solid content) of this intermediate and 2 ml of tetrahydrophthalic anhydride 4. 3 g was reacted, and the modified resin (VI)
I got it.

The properties of the obtained modified resin include an acid value of 95.0 and a non-volatile content of 7.
0.2, and the molecular weight was 1200.

Example 7 Hexahydrophthalic acid diglycidyl ester (epoxy equivalent weight 19B) 80.0 g, diagonodiphenylmethane 1
Intermediate E was obtained from 60.0 g in the same manner as in Example 1.

70.0 g (solid content) of this intermediate and 50.0 g of tetrachlorophthalic anhydride. 5 g was reacted to obtain a modified resin (■).

The properties of the obtained modified resin include an acid value of 80.2 and a non-volatile content of 6.
It was 9.0% and the molecular weight was 1500.

Example 8 Bis A type epoxy resin (epoxy equivalent: 450)/polytetramethylene glycol (molecule itl000) = 4/2
Addendum 8 0. Intermediate D was obtained in the same manner as in Example 3 from 0 g and 7.1 g of Kechikun obtained by reacting diethylenetriamine with methyl isobutyl ketone.

70.0 g (solid content) of this intermediate was reacted with 6.6 g of hexahydrophthalic anhydride to obtain a modified resin (■).

The properties of the obtained modified resin include an acid value of 31.0 and a non-volatile content of 7.
It was 1.0% and the molecular weight was 7,600.

Example 9 Adduct of 1,4-butanediol diglycidyl ether and diaminodiphenylsulfone (epoxy equivalent: 300
Intermediate F was obtained in the same manner as in Example 1 from 80.0 g of 0) and 4.6 g of hexamethylene diamine.

70.0 g (solid content) of this intermediate was reacted with 3.3 g of trimellitic anhydride to obtain a modified resin (IX). The properties of the obtained modified resin include an acid value of 26.2 and a non-volatile content of 70.9.
%, and the molecular weight was 9,500.

Example IO Cardura-10 (epoxy equivalent weight 250) 80.0 g,
Ethylene diane 3 8. Intermediate G was obtained from 4 g in the same manner as in Example 1.

70.0 g (solid content) of this intermediate was mixed with 22 ml of maleic anhydride.
．． 1 g was reacted to obtain a modified resin (X).

The properties of the obtained modified resin are as follows: acid value: 1 3 8. O, non-volatile content was 70.2%, and molecular weight was 400.

Comparative Example 1 According to Example 1, 70.0 g of bisphenol type epoxy resin (epoxy equivalent: 250) was mixed with 3.
4 g was directly reacted to obtain a modified resin (A).

The properties of the obtained modified resin include an acid value of 88.0 and a non-volatile content of 7.
It was 0.3% and the molecular weight was 1300.

Example 11 Bisphenol A type epoxy citrus (epoxy equivalent: 4
50) Add 90.0 g of toluene and 22.5 g of toluene and raise the temperature to 80°C under a nitrogen atmosphere.
2 g was added and reacted for 30 min. Furthermore, 4
．． 1.6 g of 4''-diaminodiphenylmethane 3 was added and reacted at 70°C. The reaction was monitored by the hydrochloric acid-dioxane method until the epoxy equivalent reached 15,000 or more.

After the reaction is completed, dioxane 6 4. The reactant was cooled to room temperature, and 24.1 g of hexahydrophthalic anhydride M was added little by little while paying attention to the temperature in the reaction vessel to obtain a modified resin (XI).

The properties of the obtained modified resin are as follows: acid value: 60.2. Non-volatile content 7 7 0. 4%, molecular weight: 1500.

Example 12 214 g of the modified resin obtained in Example It was half-blocked with isophorone diisocyanate (NV: 70%)65. 8 g was reacted at 40°C to obtain modified resin X■.

The properties of the obtained modified resin are: acid value: 45.3, non-volatile content: 70. 3%, molecule 1:2000.

Example 13 100% of 1,4-butanediol diglycidyl ether was added to a reaction vessel equipped with a stirrer, a reflux condenser, and a nitrogen inlet tube.
Weigh out g and silicone diamine (X-2 2-1
6 1 As Amine equivalent 450 Shin-Etsu Chemical) 900
g was added thereto, and the reaction was carried out at 80°C.

The mixture was cooled to room temperature, 148 g of phthalic anhydride was added, and the mixture was reacted at a reaction temperature of 40°C to obtain modified resin X■.

The properties of the obtained resin are as follows: acid value: 4B. 9, non-volatile content = 9
8%, molecular weight: 2300.

Example 14 Polyethyleneimine resin (Evomin SP-2 00
Molecular weight 10000 Nippon Shokubai Chemical) 100g, N
- Weigh out 106 g of methylpyrrolidone, add 6.2 g of hexahydrophthalic anhydride at room temperature, and add modified resin XIV.
I got it.

The properties of the obtained resin are: acid value: 22.0, non-volatile content: 5
0%, molecular weight: 10,000.

Example 15 An acrylic resin consisting of styrene/2-hydroxyethyl methacrylate/methyl methacrylate/glycidyl methacrylate (Molecular Dong 8000, Epeq: 2000, N
V: 50%, manufactured by Nippon Paint Co., Ltd.) Weighed out 200 g,
15.0 g of dioxane and 10.0 g of 4,4''-diaminodiphenylmethane were added, and the mixture was reacted at 80'C until the epoxy group disappeared. After cooling to room temperature, further:
Add 5.0 g of maleic anhydride and react to form modified resin
I got V.

The properties of the obtained resin were as follows: acid value: 24.4. Non-volatile content: 5
0%, molecular weight: 9200.

Comparative Example 2 Comparative resin B was obtained by using methacrylic acid instead of the glycidyl methacrylate of the acrylic resin used in Example 15.

The properties of the obtained resin are: acid value: 27.5, hydroxyl value: 7
0, nonvolatile content: 50%, molecular weight: 8,500.

Coating Notes Examples I6 to 30 and Comparative Examples 3 to 4 The modified resin was prepared by adding melamine resin and blocked isocyanate curing agent as a curing agent, and using the solution as it was, or
The solvent was removed, a base was added to neutralize the carboxyl groups, the paint was diluted with water, and the paint was evaluated.

In the present invention, a mixed alkoxylated melamine resin Cymail 267 (manufactured by Mitsui Toatsu Co., Ltd.) or a 2-ethylhexyl alcohol block of tolylene diisocyanate is used as a curing agent in a ratio of 95/5 to 5/95, and the catalyst is It was made into a paint.

Baking conditions are mixed alkoxylated melan resin (MF)
When a block isocyanate curing agent (Bl) was used, the temperature was 160°C for 30 minutes, and when a blocked isocyanate curing agent (Bl) was used, the temperature was 170°C for 30 minutes.

As a catalyst, in the case of curing melamine resin, P-toluenesulfonic acid 0. 5 wt%/solids, dibutyltin oxide 0.0% for flocked isocyanate curing.
5 wt%/solids was used.

The results are shown in Table-1 and Table-2.

(Margin below)

Claims (1)

[Claims] There is at least one formula ▲ mathematical formula, chemical formula, table, etc. ▼ at the terminal and/or side chain of the base resin molecule (wherein R may have a substituent, C_2 to C_
4 alkylene or alkenylene group or divalent or trivalent alicyclic or aromatic hydrocarbon group, n is 1 or 2. ), and has a property of generating an imide ring by cyclizing the amic acid residue when heated.