JP5162744B2 - OH-modified polyamideimide resin and method for producing the same - Google Patents

Description

The present invention relates to an OH-modified polyamide-imide resin having improved adhesion to various substrates without impairing the excellent heat resistance, mechanical strength, and chemical resistance of the polyamide-imide resin, and a method for producing the same. .

Polyamideimide resins have excellent heat resistance, mechanical strength, and chemical resistance, and are therefore widely used as coating agents or heat resistant paints for electronic parts and various base materials such as electric wires. However, the aromatic ring-containing polyamide-imide resin having a particularly high rigidity is excellent in various properties but has insufficient adhesion to the base material, which causes problems such as peeling from the base material.
Conventionally, in order to improve the processability of the polyamideimide resin, a polyamideimide resin composition in which a polyamideimide resin having a specific repeating structure is mixed with a polyester resin and a phosphoric ester compound having good processability has been proposed. (Patent Document 1). However, the addition of the polyester resin may decrease the heat resistance of the polyamideimide resin, and may further impair mechanical strength and chemical resistance due to insufficient compatibility between the polyamideimide resin and the polyester resin.
In addition, in order to impart adhesion and flexibility to the polyamide-imide resin, the polyamide-imide resin obtained by reacting a dicarboxylic acid having a specific alkyl chain, a trivalent carboxylic acid and an aromatic polyisocyanate is heterogeneous. A resin composition containing a cyclic mercaptan has been proposed (Patent Document 2). In the invention described above, flexibility is imparted by introducing a specific alkyl chain into a polyamideimide resin, and adhesion to a substrate is improved by mixing a heterocyclic mercaptan. However, the above method still does not provide sufficient adhesion, and the odor of the heterocyclic mercaptan is also a problem. In addition, since the dicarboxylic acid having an alkyl chain has various functional groups in the side chain, it has some effect of improving the adhesion to the base material. Introducing into the chain skeleton may impair heat resistance.
JP 07-207157 A JP-A-2005-120135

An object of the present invention is to provide an OH-modified polyamideimide resin having improved adhesion to a substrate without impairing various physical properties such as heat resistance, mechanical strength, and chemical resistance of the polyamideimide resin, and a method for producing the same. Is to provide.
Another object of the present invention is to provide a resin composition containing the OH-modified polyamideimide resin.

According to the present invention, an OH-modified polyamideimide resin obtained by OH-modifying an aromatic ring-containing polyamideimide resin, wherein at least a part of the side chain of the aromatic ring-containing polyamideimide resin contains the aromatic ring A amide bond is formed between the nitrogen atom of the —NH— group of the polyamideimide resin and the carboxyl group derived from the polyvalent carboxylic acid compound, and the carboxyl group not formed with the amide bond derived from the polyvalent carboxylic acid compound and a primary alcohol By reacting a non-halogen polyhydric alcohol compound having at least two OH groups derived from or a non-halogen alcoholic epoxy compound having a terminal epoxy group with an OH group derived from a primary alcohol, the polyhydric alcohol or alcoholic hydroxyl group-containing modifying group derived from an epoxy compound becomes coupled, and 1mgKO / OH-modified polyamideimide resin, characterized in that g has the above hydroxyl value is provided.

In addition, according to the present invention, an unmodified aromatic ring-containing polyamide-imide resin is reacted with a polyvalent carboxylic acid, whereby a nitrogen atom of the —NH— group present in the polyamide-imide resin is bonded via an amide bond. A COOH-modified polyamideimide resin by introducing a modified group derived from a monovalent carboxylic acid,
Next, a non-halogen polyhydric alcohol compound having at least two OH groups derived from a primary alcohol or a non-halogen alcohol-based epoxy compound having an OH group and a terminal epoxy group derived from a primary alcohol is used as a modifier. By mixing and heating the modifier with the COOH-modified polyamideimide resin, the modifier is reacted with a carboxyl group in the modified group introduced into the COOH-modified polyamideimide resin, and the polyhydric alcohol or There is provided a method for producing an OH-modified polyamideimide resin, wherein an OH-containing group derived from an alcoholic epoxy compound is introduced into the modifying group.
In the present invention, the COOH-modified polyamideimide resin preferably has an acid value of 1 mgKOH / g or more.

  According to the present invention, the OH-modified polyamideimide resin, and a COOH-modified polyamideimide resin in which a carboxyl group-containing group is introduced via an amide bond to the nitrogen atom of the —NH— group present in the polyamideimide resin; A resin composition containing a polyisocyanate compound is provided. In this resin composition, the COOH-modified polyamideimide resin is preferably contained in an amount of 10 to 1000 parts by weight per 100 parts by weight of the OH-modified polyamideimide resin.

In the OH-modified polyamideimide resin of the present invention, it is remarkable that a non-halogen-based hydroxyl group-containing modifying group is introduced into at least a part of the polyamideimide resin having a repeating structure containing an aromatic ring via an amide bond. It is a special feature. That is, since such a hydroxyl group-containing modifying group is introduced, adhesion to various base materials and metals is remarkably improved without impairing excellent heat resistance and mechanical properties.

<OH-modified polyamideimide resin>
The OH-modified polyamideimide resin of the present invention has a non-halogen-based hydroxyl group-containing modified group bonded to at least a part of the aromatic ring-containing polyamideimide resin via an amide bond, and has a hydroxyl value of 1 or more. doing.
The aromatic ring-containing polyamideimide resin used in the present invention is produced by a method known per se. For example, (1) a method in which a polycarboxylic acid having a valence of 3 or more or a derivative thereof and a polyisocyanate are reacted in a solvent ( 2) A method of reacting a tricarboxylic or higher polycarboxylic acid or derivative thereof with a diamine in a solvent.

Examples of the trivalent or higher polycarboxylic acid used in the method (1) include trimellitic anhydrides such as trimellitic anhydride and naphthalene-1,2,4-tricarboxylic anhydride; pyromellitic dianhydride, Benzophenone-3,3 ′, 4,4′-tetracarboxylic dianhydride, diphenyl ether-3,3 ′, 4,4′-tetracarboxylic dianhydride, benzene-1,2,3,4-tetracarboxylic Acid dianhydride, biphenyl-3,3'4,4'-tetracarboxylic dianhydride, biphenyl-2,2'3,3'-tetracarboxylic dianhydride, naphthalene-2,3,6,7 -Tetracarboxylic dianhydride, naphthalene-1,2,4,5-tetracarboxylic dianhydride, naphthalene-1,4,5,8-tetracarboxylic dianhydride, decahydronaphthalene-1,4 5,8- Tracarboxylic dianhydride, 4,8-dimethyl-1,2,3,5,6,7-hexahydronaphthalene-1,2,5,6-tetracarboxylic dianhydride, 2,6-dichloronaphthalene -1,4,5,8-tetracarboxylic dianhydride, 2,7-dichloronaphthalene-1,4,5,8-tetracarboxylic dianhydride, 2,3,6,7-tetrachloronaphthalene- 1,4,5,8-tetracarboxylic dianhydride, fetentylene-1,3,9,10-tetracarboxylic dianhydride, berylene-3,4,9,10-tetracarboxylic dianhydride, bis (2,3-dicarboxyphenyl) methane dianhydride, bis (3,4-dicarboxyphenyl) methane dianhydride, 1,1-bis (2,3-dicarboxyphenyl) ethane dianhydride, 1, 11 One screw (3,4-dicarboki Phenyl) ethane dianhydride, 2,2-bis (2,3-dicarboxyphenyl) propane dianhydride, 2,3-bis (3,4-dicarboxyphenyl) propane dianhydride, bis (3,4 -Use an aromatic acid anhydride such as a tetracarboxylic acid having an aromatic organic group in the molecule such as dicarboxyphenyl) sulfone dianhydride or bis (3,4-dicarboxyphenyl) ether dianhydride. This is preferable in that the reactivity at the time of synthesizing the polyamideimide is good and the physical properties such as heat resistance and mechanical strength of the synthesized resin are good.

Examples of polyisocyanates include isophorone diisocyanate, hexamethylene diisocyanate, 4,4'-dicyclohexylmethane diisocyanate, hydrogenated xylene diisocyanate, norbornylene diisocyanate, lysine diisocyanate, and other aliphatic and alicyclic isocyanates, and p-phenylene diisocyanate. M-phenylene diisocyanate, p-xylene diisocyanate, m-xylene diisocyanate, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, 3'-diphenylmethane diisocyanate, 4,4'-diphenylmethane diisocyanate, 3,3′-dimethyldiphenyl-4,4′-diisocyanate, 3,3′-diethyldiphenyl-4,4′-diisocyanate, m-xylene Examples include isocyanate, p-xylene diisocyanate, naphthalene diisocyanate, biphenyl-3,4'-diisocyanate, 2,2'-diethylbiphenyl-4,4'-diisocyanate, and the like. It is preferable to use an aromatic diisocyanate having good mechanical strength.

In the method (2), examples of the trivalent or higher polycarboxylic acid include those described above, and it is preferable to use an aromatic acid anhydride as described above. Examples of polyamines include diaminobutane, hexamethylenediamine, trimethylhexamethylenediamine, m-xylidinediamine, p-phenylenediamine, m-phenylenediamine, toluylenediamine, xylylenediamine, 4,4'-diaminodiphenylmethane, 4,4'-diaminodiphenylpropane, 4,4'-diaminodiaminobenzophenone, 4,4'-diaminodiphenyl ether, 3,4'-diaminodiphenyl ether, 4,4'-diaminobiphenyl, 3,3'-dimethyl-4 , 4'-diaminobiphenyl, 4,4'-diaminodiphenyl sulfide, 2,6-diaminonaphthalene, 4,4'-bis (p-aminophenoxy) diphenyl sulfone, 4,4'-bis (m-aminophenoxy) Diphenylsulfone 4,4'-bis (p-aminophenoxy) benzophenophene, 4,4'-bis (m-aminophenoxy) benzophenophene, 4,4'-bis (p-aminophenylmercapto) benzophenone, 4,4 '-Bis (p-aminophenylmercapto) diphenylsulfone, 4,4', 4 "-triaminotriphenylmethane, etc. are mentioned, but the heat resistance and mechanical strength of the produced polyamideimide resin are improved. Above, it is preferable to use an aromatic-containing diamine.

The aromatic ring-containing polyamideimide resin used in the present invention has a GPC number average molecular weight of 1,000 to 1,000,000, particularly 10,000 to 500,000, particularly preferably about 50,000 to 150,000.

In the OH-modified polyamideimide resin of the present invention, the hydroxyl group-containing modifying group is bonded to the polyamideimide resin via an amide bond.
In the present invention, the bonding of the hydroxyl group-containing modified group to the polyamideimide resin is such that a carboxyl group-containing group is introduced via an amide bond to the nitrogen atom of the -NH- group in the unmodified polyamideimide resin. It is preferable that a hydroxyl group-containing group that has an ester bond with the introduced carboxyl group is introduced.

As the compound (COOH modifier) for introducing a carboxyl group-containing group, maleic acid, fumaric acid, succinic acid, adipic acid, phthalic acid, isophthalic acid, hexahydrophthalic acid, tetrahydrophthalic acid, dimer acid, sebacic acid , Azelaic acid, 5-Na sulfoisophthalic acid, itaconic acid, citraconic acid, norbornene dicarboxylic acid, bicyclo [2,2,1] hept-2-ene-5,6-dicarboxylic acid, and acid anhydrides thereof A polyvalent carboxylic acid compound can be exemplified, and maleic acid or maleic anhydride is particularly preferred in terms of reactivity.

In addition, as the compound for introducing a hydroxyl group-containing group (OH modifier), a non-halogen compound is used. When a halogen-containing OH modifier is used, halogen is introduced into the polyamide-imide resin, and adhesion may be impaired. The OH modifier used in the present invention is a non-halogen polyhydric alcohol having at least two OH groups derived from primary alcohol, or a non-halogen alcohol having an OH group derived from primary alcohol and a terminal epoxy group. Epoxy compounds are preferably used.

Among these, non-halogen alcoholic epoxy compounds are more preferably used in that gelation is less likely to occur when an OH modifier is introduced, and further, the reactivity with a carboxyl group is good and the reaction rate is high. In the non-halogen alcoholic epoxy compound, the OH group derived from the primary alcohol and the terminal epoxy group are more reactive with the polyamideimide resin, and bind to the polyamideimide resin at the epoxy group site. For this reason, free OH groups are introduced into the polyamideimide resin.

Examples of the non-halogen polyhydric alcohol compound include, but are not limited to, ethylene glycol, propylene glycol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,8-octanediol, 3-ethoxy-1,2-dihydroxypropane, 3-n-octoxy-1,2-dihydroxypropane, 3-lauroxy-1,2-dihydroxypropane, 3-propoxy-1,2- Dihydroxypropane, 3- (2-n-butyl) ethoxy-1,2-dihydroxypropane, 3- (3,3-dimethoxybutyl) oxy-1,2-dihydroxypropane, 3- (n-butyl) -1, 2-dihydroxypropane, 3- (n-hexyl) -1,2-dihydroxypropane, 1,4-bis (1,2 Dihydroxypropyl)-n-butane or the like can be exemplified.
Examples of the non-halogen alcoholic epoxy compound include 2,3-epoxy-1-propanol, 3,4-epoxy-1-butanol, 4,5-epoxy-1-pentanol, and 5,6-epoxy- Examples thereof include 1-hexanol.

The hydroxyl group value of the OH-modified polyamidoimide resin of the present invention is 1 mgKOH / g or more, preferably in the range of 10 to 100 mgKOH / g, particularly preferably in the range of 20 to 90 mgKOH / g. By introducing hydroxyl groups in such an amount, high adhesion to metals and various substrates can be secured without impairing the superheat resistance of the polyamideimide resin. That is, if the hydroxyl value is less than the above range, the adhesion is impaired, and if the hydroxyl value is excessively higher than the above range, gelation occurs during OH modification, making it difficult to produce stably. Workability at the time of film formation also deteriorates.

<Manufacture of OH-modified polyamideimide resin>
The OH-modified polyamideimide resin of the present invention can be obtained by modifying an unmodified polyamideimide resin in two stages of COOH modification and OH modification.
As the unmodified polyamideimide resin used in the present invention, the above-mentioned polyamideimide resin is used.
In the present invention, first, the above-mentioned unmodified polyamideimide resin is COOH-modified using a COOH modifier.
This COOH modification is performed by dissolving an unmodified polyamideimide resin in a solvent to prepare a polyamideimide resin solution, and mixing and reacting with a COOH modifier. As the solvent in this case, N, N-dimethylacetamide, N, N-dimethylformamide, dimethylsulfoxide, N-methyl-2-pyrrolidone and the like can be used, and N, N-dimethylacetamide is particularly preferable. Polyamideimide resin is commercially available in the form of a solution dissolved in the above solvent.

As the COOH modifier, those described above can be used. Such a COOH modifier is usually used in an amount of 0.5 parts by weight or more, preferably 3 to 15 parts by weight per 100 parts by weight of the raw material polyamideimide resin, and the resulting COOH-modified polyamideimide resin has an acid value of 1 mgKOH. / G or more, particularly 10 to 100 mgKOH / g. That is, when the amount of the COOH modifier used is small, the acid value of the obtained COOH-modified polyamideimide resin is small, which makes it difficult to introduce a predetermined OH group. In addition, if an unnecessarily large amount of COOH modifier is used and the acid value of the resulting COOH-modified polyamideimide resin becomes unnecessarily large, the amount of unreacted substances generated in the OH modification step described later increases. Further, there is a risk that the adhesiveness is deteriorated and the properties such as heat resistance and wear resistance inherent in the polyamide-imide resin are impaired.
In addition, the reaction with the COOH modifier is usually preferably performed in an inert gas atmosphere such as a nitrogen atmosphere in order to suppress side reactions and the like, and is performed at a temperature of about 50 to 150 ° C. under heating and reflux. Is preferred.

As described above, a COOH-modified polyamideimide resin having an appropriate acid value can be obtained. In this COOH-modified polyamideimide resin, at least one carboxyl group of the COOH modifier was amide-bonded to the nitrogen of the —NH— group in the unmodified polyamideimide resin during the reaction, and free COOH groups that were not involved in the bond Is introduced into the polyamide-imide resin.

In the present invention, the modifier used for OH modification is a non-halogen polyhydric alcohol having at least two primary alcohol-derived OH groups and / or a non-halogen having a primary alcohol-derived OH group and a terminal epoxy group. Alcoholic epoxy compounds are used.
As the non-halogen OH modifier, those described above can be used. Further, non-halogen alcoholic epoxy compounds are more preferably used in that gelation is less likely to occur when an OH modifier is introduced, and the reactivity with the COOH group is high and the reaction rate is high. In the non-halogen alcoholic epoxy compound, since the terminal epoxy group is involved in the reaction with the polyamideimide resin, a free OH group is introduced into the polyamideimide resin.

Such an OH modifier may be used in an amount of 0.1 to 10 equivalents, preferably 0.5 to 5 equivalents, based on COOH groups, for example, 1.0 weight per 100 parts by weight of the raw material polyamideimide. It is preferably used in an amount of at least 3 parts, in particular 3 to 15 parts by weight. The reaction using such an OH modifier is preferably performed under heating and refluxing at a temperature of 50 to 150 ° C. in an inert atmosphere as in the case of the COOH modification described above.
By such a reaction, the OH group and / or epoxy group derived from the primary alcohol reacts with the carboxyl group in the COOH-modified group to form an ester bond, whereby a predetermined amount of hydroxyl group is introduced and the desired OH-modified A polyamide-imide resin is obtained.

The OH-modified polyamideimide resin introduced with a hydroxyl group in this way should have a hydroxyl value of 1 mgKOH / g or more, preferably 10 to 100 mgKOH / g, more preferably 20 to 90 mgKOH / g. . By introducing hydroxyl groups in such an amount, high adhesion to metals and various resins can be ensured without impairing the properties such as heat resistance, mechanical strength, and chemical resistance inherent to the polyamide-imide resin. . That is, if the hydroxyl value is less than the above range, the adhesiveness is impaired, and if the hydroxyl value is excessively higher than the above range, gelation occurs during OH modification, making it difficult to produce stably. Thus, workability at the time of forming the coating film also deteriorates.

Since the above-described OH-modified polyamideimide resin of the present invention is obtained in a solution state, it is usually used as it is. For example, it is coated on the surface of a molded product made of metal or various resins, and dried by heating to form a cured film. By forming, it is applied to various uses such as, for example, a wire coating, as a super heat resistant protective film.

<Resin composition>
In addition, the OH-modified polyamideimide resin of the present invention can be used for applications such as the formation of a protective film as a resin composition in which a COOH-modified polyamideimide resin and a polyisocyanate compound are mixed. That is, this OH-modified polyamideimide resin is highly compatible with the COOH-modified polyamideimide resin, and when used in combination with the COOH-modified polyamideimide resin, the COOH group of the COOH-modified polyamideimide resin and the OH group of the OH-modified polyamideimide resin Since it reacts and cures during the formation of the coating film, a three-dimensional cross-linking structure is introduced, and heat resistance, mechanical strength, and the like are further improved. In addition, the polyisocyanate compound is urethane-bonded with the OH-modified polyamideimide resin, and a crosslinked structure due to the urethane bond is introduced into the polyamideimide resin to form a partially urethanized polyamideimide resin. This makes it possible to form a dense and high-hardness film in which the heat resistance and mechanical strength of the polyamideimide resin are further improved.

In the resin composition, as the COOH-modified polyamideimide resin to be used, those having an acid value in the above-mentioned range are particularly suitable from the viewpoint of compatibility with the OH-modified polyamideimide resin, and usually, the OH-modified polyamideimide resin. It may be used in an amount of 10 to 1000 parts by weight, especially 30 to 300 parts by weight per 100 parts by weight. That is, if a larger amount of COOH-modified polyamideimide resin is used than necessary, the adhesion by the OH-modified polyamideimide resin may be impaired, and if the amount of COOH-modified polyamideimide resin used is too small, the heat resistance due to the formation of a crosslinked structure This is because merits such as improvement of mechanical strength are diminished.

Moreover, as a polyisocyanate compound, although not limited to this, tolylene diisocyanate, xylylene diisocyanate, 4,4'-diphenylmethane diisocyanate, 1,5-naphthalene diisocyanate, 3,3'-dimethyl-4, Aromatic diisocyanates such as 4'-diphenylmethane diisocyanate, 1,6-hexamethylene diisocyanate, isophorone diisocyanate, 4,4'-dicyclohexylmethane diisocyanate, 1,3-bis (isocyanatomethyl) cyclohexane, trimethylhexamethylene diisocyanate, etc. Examples thereof include aliphatic diisocyanates and alcohol adducts thereof such as trimethylolpropane. In particular, aromatic diisocyanates are suitable from the viewpoint of compatibility with OH-modified polyamideimide resin and heat resistance.

Such a polyisocyanate compound is usually used in an amount of 0.1 to 20 parts by weight, particularly 1 to 10 parts by weight, per 100 parts by weight of the OH-modified polyamideimide resin. In other words, using a polyisocyanate compound in an amount larger than necessary has no technical merit, but rather disadvantageous economically, and if it is too small, curing is insufficient and improvement in coating film performance due to crosslinking cannot be expected. There is a fear.

In order to mix the COOH-modified polyamideimide resin and the polyisocyanate compound with the OH-modified polyamideimide resin, it is preferable to use the above-mentioned solvent for the polyamideimide resin. In addition, the resin composition has an amount in a range that does not impair the properties of the OH-modified polyamideimide resin, and various additives known per se, for example, coloring agents such as dyes and pigments, antistatic agents, fillers, plasticizers, A dispersing agent etc. can be mix | blended suitably.

The raw material polyamideimide resin used in the following Examples and Comparative Examples, the types of OH modifiers and the evaluation of the materials are as follows.
Raw material polyamide-imide: 15% N-methyl-2-pyrrolidone solution of polyamide-imide (Viromax (registered trademark) HR-16NN manufactured by Toyobo Co., Ltd.)
OH modifier:
(A) 1,4-butanediol (b) ethylene glycol (c) 2,3-epoxy-1-propanol (d) 2,2,3,3-tetrafluoro-1,4-butanediol

[Adhesion]
It was evaluated by a cross cut test method (JIS K5400).
That is, a sample was applied on an aluminum plate so that the thickness of the coating film after drying was 10 μm, dried at 150 ° C. for 10 minutes, and then heat-treated at 200 ° C. for 1 hour to form a coating film. . Make a scratch with a width of 1 mm on the coating film in a grid pattern (100 squares), and then apply cellophane tape to this coating film. After attaching it, peel off the cellophane tape, and then remove the cellophane tape. Adhesion was evaluated according to the criteria.
A: 100/100
○: 90 to 99/100
Δ: 80-89 / 100
X: 0 to 79/100

[Heat-resistant]
A sample was applied on an aluminum plate so that the thickness of the coating film after drying was 10 μm, dried at 150 ° C. for 10 minutes, and then heat-treated at 200 ° C. for 1 hour to form a coating film. The formed coating film was heated at 400 ° C. for 1 hour, and the heat resistance was evaluated by the change in weight of the coating film before and after heating.
○: Change in weight is within 10% ×: Change in weight is greater than 10%

(Production Example 1) 670 parts by weight of the polyamideimide resin solution (100 parts by weight of polyamideimide resin), maleic anhydride in a flask equipped with a COOH-modified polyamideimide resin stirring device, a nitrogen gas inlet pipe, a thermometer, and a reflux condenser (COOH modifier) 5 parts by weight were charged, and the contents in the flask were heated to 95 ° C. while stirring in the flask, and reacted while maintaining the temperature at 95 ° C. as it was. After the reaction, the reaction mixture was cooled to room temperature to obtain a COOH-modified polyamideimide resin (A-1).
The obtained COOH-modified polyamideimide resin (A-1) had a number average molecular weight of 30,000 and an acid value of 20 mgKOH / g.

(Production Example 2) COOH-modified polyamideimide resin A COOH-modified polyamideimide resin (A-2) was obtained in the same manner as in Production Example 1 except that the amount of maleic anhydride was changed to 0.1 parts by weight.
The obtained COOH-modified polyamideimide resin (A-2) had a number average molecular weight of 30,000 and an acid value of 0.3 mgKOH / g.

Example 1
In the flask containing the COOH-modified polyamideimide resin (A-1) obtained in Production Example 1,
5 parts by weight of OH modifier (a) [1,4-butanediol] was added, and nitrogen substitution was performed by stirring for 30 minutes while introducing nitrogen gas into the flask.
Next, the contents in the flask were heated to 95 ° C. and reacted for 3 hours while maintaining the temperature at 95 ° C. as it was. After the reaction, it was cooled to room temperature to obtain a solution of OH-modified polyamideimide resin (B-1).
The resulting OH-modified polyamideimide resin had a hydroxyl value of 20 mgKOH / g.
Further, using this OH-modified polyamideimide resin (B-1) solution, the adhesion and heat resistance were evaluated according to the methods described above, and the results are shown in Table 1.

(Example 2)
A solution of the OH-modified polyamideimide resin (B-2) was obtained in the same manner as in Example 1 except that the OH modifier (b) [ethylene glycol] was used instead of the OH modifier (a).
With respect to the obtained OH-modified polyamideimide resin (B-2), the hydroxyl value, adhesion and heat resistance were measured in the same manner as in Example 1, and the results are shown in Table 1.

(Example 3)
An OH-modified polyamideimide resin (B-3) was prepared in the same manner as in Example 1 except that the OH modifier (c) [2,3-epoxy-1-propanol] was used instead of the OH modifier (a). A solution was obtained.
With respect to the obtained OH-modified resin (B-3), the hydroxyl value, adhesion and heat resistance were measured in the same manner as in Example 1, and the results are shown in Table 1.

(Comparative Example 1)
A solution of OH-modified polyamideimide resin (B-4) was obtained in the same manner as in Example 1 except that the amount of the OH-modifying agent (a) was changed to 0.1 parts by weight.
The obtained OH-modified resin (B-4) was measured for hydroxyl value, adhesion and heat resistance in the same manner as in Example 1, and the results are shown in Table 1.

(Comparative Example 2)
A solution of OH-modified polyamideimide resin (B-5) was obtained in the same manner as in Example 1 except that the amount of the OH-modifying agent (c) was changed to 0.1 parts by weight.
For the obtained OH-modified resin (B-5), the hydroxyl value, adhesion, and heat resistance were measured in the same manner as in Example 1, and the results are shown in Table 1.

(Comparative Example 3)
Except for using the COOH-modified polyamideimide resin (A-2) obtained in Production Example 2 instead of the COOH-modified polyamideimide resin (A-1) obtained in Production Example 1, the procedure was the same as in Example 1. A solution of OH-modified polyamide resin (B-6) was obtained.
For the obtained OH-modified resin (B-6), the hydroxyl value, adhesion and heat resistance were measured in the same manner as in Example 1, and the results are shown in Table 1.

(Comparative Example 4)
OH in the same manner as in Example 3 except that the COOH-modified polyamideimide resin (A-2) obtained in Production Example 2 was used instead of the COOH-modified polyamideimide resin (A-1) obtained in Production Example 1. A solution of the modified polyamide resin (B-7) was obtained.
For the obtained OH-modified resin (B-7), the hydroxyl value, adhesion, and heat resistance were measured in the same manner as in Example 1, and the results are shown in Table 1.

(Comparative Example 5)
OH-modified polyamide in the same manner as in Example 1 except that the OH modifier (d) [2,2,3,3-tetrafluoro-1,4-butanediol] was used instead of the OH modifier (a). A solution of an imide resin (B-8) was obtained.
For the obtained OH-modified resin (B-8), the hydroxyl value, adhesion, and heat resistance were measured in the same manner as in Example 1, and the results are shown in Table 1.

(Comparative Example 6)
Adhesion and heat resistance were evaluated in the same manner as in Example 1 using the unmodified polyamideimide resin solution used as a raw material, and the results are shown in Table 1.

(Application 1)
A resin obtained by mixing a polyisocyanate compound (tolylene diisocyanate) in an amount of 5 parts by weight per 100 parts by weight of the OH-modified polyamideimide resin (B-1) obtained in Example 1 A composition was prepared. About this resin composition, adhesiveness and heat resistance were evaluated similarly to Example 1, and the result was shown in Table 2.

(Application example 2)
A resin composition was prepared and evaluated in the same manner as in Application Example 1 except that the solution of the OH-modified polyamideimide resin (B-3) obtained in Example 3 was used. The results are shown in Table 2.

(Application example 3)
The COOH-modified polyamideimide resin prepared in Production Example 1 (100 parts by weight per 100 parts by weight of OH-modified polyamideimide resin) was added to the solution of the OH-modified polyamideimide resin (B-1) obtained in Example 1. A-1) was mixed to prepare a resin composition. The adhesiveness and heat resistance of this resin composition were evaluated in the same manner as in Application Example 1, and the results are shown in Table 2.

(Application 4)
A resin composition was prepared and evaluated in the same manner as in Application Example 3 except that the OH-modified polyamideimide resin (B-3) solution obtained in Example 3 was used. The results are shown in Table 2.

(Application example 5)
The resin composition prepared in Application Example 3 is further mixed with a polyisocyanate compound (tolylene diisocyanate) in an amount of 5 parts by weight per 100 parts by weight of the OH-modified polyamideimide resin (B-1). Was prepared. The resin composition was evaluated for adhesion and heat resistance, and the results are shown in Table 2.

(Application example 6)
The resin composition prepared in Application Example 4 is further mixed with a polyisocyanate compound (tolylene diisocyanate) in an amount of 5 parts by weight per 100 parts by weight of the OH-modified polyamideimide resin (B-3). Was prepared. The resin composition was evaluated for adhesion and heat resistance, and the results are shown in Table 2.

(Application example 7)
A resin composition was prepared in the same manner as in Application Example 1 except that the solution of the OH-modified polyamideimide resin (B-4) prepared in Comparative Example 1 was used, and the adhesion and heat resistance were evaluated. The results are shown in Table 2.

(Application 8)
A resin composition was prepared in the same manner as in Application Example 3 except that the solution of the OH-modified polyamideimide resin (B-4) prepared in Comparative Example 1 was used, and the adhesion and heat resistance were evaluated. The results are shown in Table 2.

(Application example 9)
A resin composition was prepared in the same manner as in Application Example 5 except that the solution of the OH-modified polyamideimide resin (B-4) prepared in Comparative Example 1 was used, and the adhesion and heat resistance were evaluated. The results are shown in Table 2.

(Application example 10)
Without using any OH-modified polyamideimide resin, 5 parts by weight per 100 parts by weight of the COOH-modified polyamideimide resin (A-1) solution prepared in Production Example 1 and the COOH-modified polyamideimide resin (A-1) A polyisocyanate compound (tolylene diisocyanate) was mixed to prepare a resin composition. The resin composition was evaluated for adhesion and heat resistance. The results are shown in Table 2.

(Application Example 11)
A resin composition was prepared in the same manner as in Application Example 3 except that the amount of the COOH-modified polyamideimide resin (A-1) was 2500 parts by weight, and the adhesion and heat resistance were evaluated. The results are shown in Table 2. Show.

(Application 12)
A resin composition was prepared in the same manner as in Application Example 3 except that the amount of the COOH-modified polyamideimide resin (A-1) was 5000 parts by weight, and the adhesion and heat resistance were evaluated. The results are shown in Table 2.

Claims (6)

An OH-modified polyamideimide resin obtained by OH-modifying an aromatic ring-containing polyamideimide resin,
At least a part of the side chain of the aromatic ring-containing polyamideimide resin has an amide bond between the nitrogen atom of the —NH— group of the aromatic ring-containing polyamideimide resin and the carboxyl group derived from the polyvalent carboxylic acid compound. ,
Non-halogen polyhydric alcohol compound having at least two OH groups derived from a primary alcohol and a non-halogen polyhydric alcohol compound derived from the polyhydric carboxylic acid compound and an OH group and a terminal epoxy group A hydroxyl group-containing modifying group derived from the polyhydric alcohol or alcoholic epoxy compound is bonded by a reaction with a non-halogen alcoholic epoxy compound having
And an OH-modified polyamide-imide resin having a hydroxyl value of 1 mgKOH / g or more. By reacting an aromatic ring-containing polyamideimide resin with a polyvalent carboxylic acid, a modification group derived from the polyvalent carboxylic acid is bonded to the nitrogen atom of the —NH— group via an amide bond on the side of the aromatic ring-containing polyamideimide resin. Introducing into the chain to adjust the COOH-modified polyamideimide resin,
Next, a non-halogen polyhydric alcohol compound having at least two OH groups derived from a primary alcohol or a non-halogen alcohol-based epoxy compound having an OH group and a terminal epoxy group derived from a primary alcohol is used as a modifier. By mixing and heating the modifier with the COOH-modified polyamideimide resin, the modifier is reacted with a carboxyl group in the modified group introduced into the COOH-modified polyamideimide resin, and the polyhydric alcohol or A method for producing an OH-modified polyamideimide resin, wherein an OH-containing group derived from an alcoholic epoxy compound is introduced into the modifying group. The method for producing an OH-modified polyamideimide resin according to claim 2, wherein the COOH-modified polyamideimide resin has an acid value of 1 mgKOH / g or more. An OH-modified polyamideimide resin according to claim 1 , a COOH-modified polyamideimide resin in which a carboxyl group-containing group is introduced through an amide bond to a nitrogen atom of a -NH- group present in an unmodified polyamideimide resin, A resin composition containing an isocyanate compound. The resin composition according to claim 4 , comprising the COOH-modified polyamideimide resin in an amount of 10 to 1000 parts by weight per 100 parts by weight of the OH-modified polyamideimide resin. A partially urethane-cured resin obtained by heating the resin composition according to claim 4 or 5 and reacting an OH group in the OH-modified polyamideimide resin with an isocyanate group in the polyisocyanate compound.