KR101713996B1 - Polyamide-imide resin, thermosetting resin composition, method for producing cured product of thermosetting resin composition and polyamide-imide resin - Google Patents

Abstract

(X₁는 탄소수가 24∼48인 다이머산 유래의 지방족 디아민(a)의 잔기, X₂는 카르복시기를 갖는 방향족 디아민(b)의 잔기, Y는 각각 독립하여 시클로헥산환 또는 방향환이다)An object of the present invention is to provide a polyamideimide resin which can be a component of a thermosetting resin composition capable of forming a cured product having an appropriate alkali solubility and an excellent dielectric property.
In order to solve such a problem, there is provided a polyamideimide resin characterized by having a structure represented by the following general formula (1) and a structure represented by the following general formula (2).

(X ₁ is a moiety having a carbon number of the ring, Y are each independently a cyclohexane ring or a direction of the 24-48 residues of an aliphatic diamine (a) of the dimer acid-derived, X ₂ is an aromatic diamine (b) having a carboxyl group)

Description

TECHNICAL FIELD [0001] The present invention relates to a polyamide-imide resin, a polyamide-imide resin, a thermosetting resin composition, a cured product of the thermosetting resin composition and a process for producing a polyamide-

The present invention relates to a polyamideimide resin, a process for producing the polyamideimide resin, a thermosetting resin composition and a cured product of the thermosetting resin composition.

There is a demand for a resin material that can be used for an insulating material, an adhesive, a resin for a film raw material, and the like as a resin material excellent in solubility in an alkali solution in various fields centering on the electric and electronic industry.

Patent Document 1 discloses, as a material capable of meeting such a demand, at least (A1) an A agent containing a compound having a carboxyl group and a photosensitive group, (B1) an epoxy resin, and (B2) an oxime ester photopolymerization initiator. Wherein the epoxy resin (b1) is present as a solid at room temperature (25 占 폚) in the agent B. The photosensitive resin composition according to claim 1, The (a1) compound having a carboxyl group and a photosensitive group in the document is a compound having at least one kind of a carboxyl group and a photosensitive group selected from the group consisting of epoxy acrylate, urethane acrylate and acrylated acrylate.

In recent years, a demand for an alkali-soluble resin has been advanced, and in particular, improvement in mechanical properties and heat resistance has been demanded. It is difficult for an epoxy acrylate type or urethane acrylate type resin as disclosed in Patent Document 1 to meet this demand.

With respect to this point, Patent Document 2 discloses an alkali-soluble resin having a Tg of 200 ° C or higher, a dissolution time of 5% by weight aqueous sodium hydroxide solution of 10 minutes or less, and a light transmittance of 350 nm of 5% have. The polyamide-imide resin disclosed in Patent Document 2 can meet the above-mentioned demand for improvement in mechanical properties and heat resistance.

Japanese Patent Application Publication No. 2012-98470 Japanese Patent Application Laid-Open No. 2002-88154

However, the polyamide-imide resin disclosed in Patent Document 2 has the following problems from the viewpoint of alkali solubility. That is, the conventional alkali-soluble resin containing a resin such as epoxy acrylate or urethane acrylate as disclosed in Patent Document 1 has sufficient solubility in a weakly alkaline aqueous solution of about 1.0% by mass aqueous solution of sodium carbonate. On the other hand, in the polyamide-imide resin disclosed in Patent Document 2, it is necessary to use a strong alkaline aqueous solution such as 5 mass% aqueous sodium hydroxide solution as a developer, as shown in the examples.

Therefore, when the alkali soluble resin according to the prior art and the alkali soluble resin disclosed in the patent document 2 are to be used separately in accordance with the product and the application, the developer is mixed with an aqueous solution of a strong alkali from an aqueous solution of weak alkaline, Or vice versa, so that the productivity is remarkably lowered. Further, when the developing solution is changed from a slightly alkaline aqueous solution to a strong alkaline aqueous solution, the waste liquid treatment corresponding to the weak alkaline aqueous solution must be changed correspondingly to the strong alkaline aqueous solution. The change of the waste liquid treatment may cause a decrease in industrial productivity in which a large amount of equipment investment is required and the running cost is increased.

Therefore, from the viewpoint of securing industrial productivity, it is desired that the alkali-soluble resin has sufficient solubility in a weakly alkaline aqueous solution such as 1.0% by weight aqueous sodium carbonate solution.

When applied to the field of the electrical and electronics industry, the cured product of the curable resin composition containing an alkali soluble resin is preferably one having excellent dielectric properties (specifically, one having a low dielectric constant and a low dielectric loss) .

The present invention relates to a thermosetting resin composition which can be dissolved even when an aqueous solution of 1.0% by mass of sodium carbonate is used as an alkali solution, that is, a polyamide capable of being a component of a thermosetting resin composition capable of forming a cured product having appropriate alkali solubility, And a process for producing the polyamide-imide resin. The present invention also provides a thermosetting resin composition containing the above-described polyamideimide resin, and a cured product obtained by curing the thermosetting resin composition.

In order to solve the above problems, the present invention is as follows.

[1] A polyamideimide resin having a structure represented by the following general formula (1) and a structure represented by the following general formula (2).

(X ₁ is a moiety having a carbon number of the ring, Y are each independently a cyclohexane ring or a direction of the 24-48 residues of an aliphatic diamine (a) of the dimer acid-derived, X ₂ is an aromatic diamine (b) having a carboxyl group)

[2] The polyamideimide resin according to the above [1], wherein the acid value is 30 mgKOH / g or more and 150 mgKOH / g or less.

[3] The polyamideimide resin according to [1] or [2], wherein the content of the aliphatic diamine (a) derived from dimeric acid having 24 to 48 carbon atoms is 20 to 60% by weight.

[4] Any one or two selected from a cyclohexane ring and an aromatic ring represented by Y in the general formulas (1) and (2) (except when Y is an aromatic ring) The polyamideimide resin according to any one of [1] to [3], wherein the molar ratio of the cyclohexane ring content to the aromatic ring content is 85 / 15-100 / 0.

[5] The aromatic diamine (b) having a carboxyl group is at least one selected from the group consisting of 3,5-diaminobenzoic acid and 5,5'-methylenebis (anthranilic acid). Is a polyamideimide resin according to any one of [4] to [4].

[6] A thermosetting resin composition comprising the polyamide-imide resin and the thermosetting material according to any one of [1] to [5].

[7] The thermosetting resin composition according to the above [6], wherein the thermosetting material is an epoxy resin.

[8] The thermosetting resin composition according to the above [6] or [7], further comprising a thermosetting accelerator.

[9] A cured product of the thermosetting resin composition according to any one of [6] to [8].

[10] A process for producing an aliphatic diamine compound (a), which comprises reacting an aliphatic diamine (a) derived from a dimer acid having a carbon number of 24 to 48, an aromatic diamine (b) having a carboxy group and a cyclohexane-1,2,4-tricarboxylic acid- An imidization step of reacting one or two selected from the group consisting of trimellitic anhydride (d) to obtain an imide (A), and a step of adding an imide (A) And a diisocyanate compound (e) are reacted with each other to obtain a polyamide-imide resin represented by the following general formula (3).

(Wherein X is each independently a diamine residue, Y is independently a cyclohexane ring or an aromatic ring, Z is a residue of a diisocyanate compound (e), and n is a natural number)

[11] The process for producing a polyamide-imide resin according to the above [10], wherein the polyamide-imide resin obtained by the amideimidation step has an acid value of 30 mgKOH / g or more and 150 mgKOH / g or less.

[12] The amount of the aliphatic diamine (a) derived from dimeric acid having 24 to 48 carbon atoms is preferably such that the content of the aliphatic diamine (a) derived from dimeric acid having 24 to 48 carbon atoms is 20 to 60 wt% The method for producing a polyamide-imide resin according to the above [10] or [11].

[13] The method for producing a polymer according to [13], wherein the amount of the cyclohexane-1,2,4-tricarboxylic acid-1,2-anhydride (c) used is in the range of from 85/15 to 100/0 with respect to the amount of the trimellitic anhydride (d) 10] to [12], wherein the polyamide-imide resin is a polyamide-imide resin.

[14] The aromatic diamine (b) having a carboxyl group is at least one selected from the group consisting of 3,5-diaminobenzoic acid and 5,5'-methylenebis (anthranilic acid). [13] A process for producing a polyamide-imide resin as described in any one of [1] to [13].

[15] The process for producing a polyamide-imide resin according to any one of [10] to [14], wherein the diisocyanate compound (e) is an aliphatic isocyanate compound.

According to the present invention, there is provided a polyamide-imide resin capable of dissolving even when a mild alkaline solution such as 1.0% by mass aqueous sodium carbonate solution is used and a method for producing the same.

Further, the present invention provides a thermosetting resin composition which can dissolve even when a mild alkaline solution such as 1.0% by mass aqueous sodium carbonate solution is used. Further, according to the present invention, a cured product having excellent dielectric properties is provided as a cured product of the above-mentioned thermosetting resin composition.

Hereinafter, an embodiment of the present invention will be described.

The polyamideimide resin according to one embodiment of the present invention has a structure represented by the following general formula (1) and a structure represented by the following general formula (2).

Here, X ₁ is a residue of an aliphatic diamine (a) derived from a dimer acid having 24 to 48 carbon atoms (also referred to as "dimer diamine (a)" in this specification). X ₂ is a residue of an aromatic diamine (b) having a carboxyl group (also referred to as "carboxyl group-containing diamine (b)" in this specification). Y are each independently cyclohexane or an aromatic ring.

By including the structure represented by the general formula (1) and the structure represented by the general formula (2), even when a mild alkali solution such as 1.0% by mass aqueous sodium carbonate solution is used, the alkali solubility An excellent polyamideimide resin can be obtained. In addition, the cured product of the thermosetting resin composition containing such a polyamideimide resin can have excellent dielectric properties.

The dimer diamine (a) can be obtained by reductive amination of a carboxyl group in a dimer of an aliphatic unsaturated carboxylic acid having 12 to 24 carbon atoms. Namely, the dimer diamine (a), which is an aliphatic diamine derived from dimer acid, is obtained by polymerizing an unsaturated fatty acid such as oleic acid or linolic acid into a dimer acid, reducing it and then aminating it. As such an aliphatic diamine, for example, a commercially available product such as PRIAMINE 1073, 1074, 1075 (trade name, manufactured by Kuroda Japan Co., Ltd.), which is a diamine having a skeleton of 36 carbon atoms, can be used. The dimer diamine (a) is preferably derived from a dimer acid having a carbon number of 28 to 44, and more preferably a dimer acid derived from a dimer acid having a carbon number of 32 to 40.

Specific examples of the carboxyl group-containing diamine (b) include 3,5-diaminobenzoic acid, 3,4-diaminobenzoic acid, 5,5'-methylenebis (anthranilic acid), benzidine-3,3'-dicarboxylic acid, . The carboxyl group-containing diamine (b) may be composed of one kind of compound or a plurality of kinds of compounds. From the viewpoint of raw material availability, it is preferable that the carboxyl group-containing diamine (b) contains 3,5-diaminobenzoic acid and 5,5'-methylenebis (anthranilic acid).

The relationship between the content of the structure represented by the general formula (1) and the content of the structure represented by the general formula (2) in the polyamideimide resin according to one embodiment of the present invention is not limited. (Unit:% by weight) of the dimer diamine (a) from the viewpoint of improving the balance between the alkali solubility of the polyamide-imide resin and other characteristics such as the mechanical properties of the cured product of the thermosetting resin composition including the polyamide- Is preferably 20 to 60% by weight, and more preferably 30 to 50% by weight. In the present specification, the "content of dimer diamine (a)" means the amount of dimer diamine (a) introduced as one of the raw materials in the production of polyamideimide resin by the weight of the polyamideimide resin . Here, the " weight of the produced polyamideimide resin " means the weight of water (H ₂ O) generated in the imidization and the carbon dioxide gas (CO ₂ ) generated in the amidation from the amounts of all raw materials for producing the polyamide- Is the value obtained by subtracting the theoretical amount of.

From the standpoint of improving the balance between the alkali solubility of the polyamide-imide resin and other characteristics such as the mechanical properties of the cured product of the thermosetting resin composition including the polyamide-imide resin, the polyamide- The acid value (solid acid value) is preferably 30 mgKOH / g or more, more preferably 30 mgKOH / g or more and 150 mgKOH / g or less, still more preferably 50 mgKOH / g or more and 120 mgKOH / g or less Is particularly preferable.

From the viewpoint of enhancing the alkali solubility of the polyamide-imide resin, the moiety represented by Y in the general formula (1) and the general formula (2) preferably has a cyclohexane ring. From the viewpoint of improving the balance between the alkali solubility of the polyamide-imide resin and other characteristics such as the mechanical properties of the cured product of the thermosetting resin composition including the polyamide-imide resin, it is preferable that the aromatic ring and the cyclo The molar ratio of the content of the cyclohexane ring to the content of the aromatic ring is preferably 85/15 to 100/0, more preferably 90/10 to 99/1, and most preferably 90/10 to 98/1, / 2 is more preferable.

The polyamideimide resin according to one embodiment of the present invention may further have a partial structure represented by the following general formula (i).

Here, X ₃ is a residue of a diamine (f) other than the dimer diamine (a) and the diamine (b) containing a carboxyl group (also referred to as "other diamine (f)" in this specification) Are each independently an aromatic ring or a cyclohexane ring as in the formulas (1) and (2). The other diamine (f) may be composed of one kind of compound or a plurality of kinds of compounds.

Specific examples of other diamines (f) include bis [4- (4-aminophenoxy) phenyl] propane, bis [4- (4-aminophenoxy) phenyl] methane, 4,4'-bis (aminophenoxy) phenyl] sulfone, 2,2- Bis (4-aminophenoxy) phenyl] ether, bis [4- (4-aminophenoxy) phenyl] ketone, (4-aminophenoxy) benzene, 2,2'-dimethylbiphenyl-4,4'-diamine, 2,2'-bis (trifluoromethyl) biphenyl- 4,4'-diamine, 2,6,2 ', 6'-tetramethyl-4,4'-diamine, 5,5'-dimethyl-2,2'-sulfonyl- Diamine, 3,3'-dihydroxybiphenyl-4,4'-diamine, (4,4'-diamino) diphenyl ether, (4,4'-diamino) diphenylsulfone, (Diamino) benzophenone, (3,3'-diamino) benzophenone, (4,4'-diamino) diphenylmethane, (4,4'-diamino) '- Dia Aromatic diamines such as hexamethylenediamine, octamethylenediamine, decamethylenediamine, dodecamethylenediamine, octadecamethylenediamine, 4,4'-methylenebis (cyclohexylamine), iso Aliphatic diamines such as phthalic anhydride, peronediamine, 1,4-cyclohexanediamine and norbornenediamine.

The polyamideimide resin according to one embodiment of the present invention may have a structure represented by the following general formula (ii).

Here, Z may be an aliphatic or aromatic containing moiety. When it is an aliphatic group, it may contain an alicyclic group such as a cyclohexane ring. According to the production method described later, Z is a residue of the diisocyanate compound (e).

The method for producing the polyamide-imide resin according to one embodiment of the present invention is not limited. When the following production method is employed, it is possible to efficiently produce the polyamide-imide resin according to one embodiment of the present invention.

A process for producing a polyamideimide resin according to an embodiment of the present invention comprises an imidization process and an amidimidation process.

In the imide process, a group consisting of dimer diamine (a), a carboxyl group-containing diamine (b), cyclohexane-1,2,4-tricarboxylic acid-1,2-anhydride (c) and trimellitic anhydride Is reacted to obtain an imide (A).

The amount of the dimer diamine (a) is preferably such that the content of the dimer diamine (a) is 20 to 60 wt%, and the content of the dimer diamine (a) is more preferably 30 to 50 wt%. The definition of the content of the dimer diamine (a) is as described above.

If necessary, other diamine (f) may be used together with the dimer diamine (a) and the carboxyl group-containing diamine (b).

From the viewpoint of enhancing the alkali solubility of the polyamide-imide resin, it is preferable to use cyclohexane-1,2,4-tricarboxylic acid-1,2-anhydride (c) in the imidation step. The molar ratio of the amount of the cyclohexane-1,2,4-tricarboxylic acid-1,2-anhydride (c) to the amount of the anhydrous trimellitic acid (d) used is preferably 85/15 to 100/0, More preferably 90/10 to 99/1, and even more preferably 90/10 to 98/2.

Means diamine compound (B) (specifically, dimer diamine (a) and carboxyl group-containing diamine (b) used for obtaining imide cargo (A) and other diamine (f) (C) (specifically, one or two selected from the group consisting of cyclohexane-1,2,4-tricarboxylic acid-1,2-anhydride (c) and anhydrous trimellitic acid ) Is not limited. The amount of the acid anhydride (C) to be used is preferably such that the molar ratio with respect to the amount of the diamine compound (B) is 2.0 or more and 2.4 or less, more preferably 2.0 or more and 2.2 or less.

The reaction temperature at which the diamine compound (B) and the acid anhydride (c) are reacted to obtain the imide cargo (A) is not limited. It is usually preferred to be in the range of 120 to 200 DEG C, and more preferably in the range of 140 to 180 DEG C.

The reaction solvent for obtaining the imide cargo (A) is not limited. Specific examples of such reaction solvents include γ-butyrolactone, cyclohexanone, dimethylacetamide (DMAC), dimethylformamide (DMF), dimethylsulfoxide, N-methyl-2-pyrrolidone Propane, cyclopentane, diglyme, triglyme, and the like. The reaction solvent for obtaining the imide cargo (A) may be composed of one kind of compound, or two or more kinds of compounds may be combined and used as a reaction solvent. Among them, the step of producing the imide cargo (A) requires a high reaction temperature, so that the boiling point is high, the solubility of the resulting polymer is relatively good, and the γ- It is preferable to use at least one member selected from the group consisting of lactone, cyclohexanone, triglyme, diglyme and cyclopentanone as a reaction solvent for obtaining the imide (A).

In the imidization reaction, water is produced. Therefore, when the reaction for obtaining the imide (A) is carried out, it is preferable that an aromatic hydrocarbon capable of being azeotropic with water generated in the imidization reaction is present. Examples of such aromatic hydrocarbons include benzene, toluene, xylene, ethylbenzene, and mesitylene. Among them, toluene is preferable because it is relatively low in toxicity and low in boiling point, and therefore, it is easy to remove by distillation.

In the amideimidation step, the diisocyanate compound (e) is reacted with the imide (A) obtained by the imidation process described above to obtain a polyamideimide containing a substance having a structure represented by the following general formula (3) A resin is obtained.

The specific kind of the diisocyanate compound (e) is not limited. The diisocyanate compound (e) may be composed of one kind of compound or plural kinds of compounds.

Specific examples of the diisocyanate compound (e) include 4,4'-diphenylmethane diisocyanate, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, naphthalene-1,5-diisocyanate, Aromatic diisocyanates such as randy isocyanate, m-xylylene diisocyanate, and 2,4-tolylene dimer; And aliphatic diisocyanates such as hexamethylene diisocyanate, trimethylhexamethylene diisocyanate, dicyclohexylmethane diisocyanate, isophorone diisocyanate, and norbornene diisocyanate. From the viewpoint of improving the alkali solubility of the polyamide-imide resin and the light transmittance of the polyamide-imide resin, the diisocyanate compound (e) preferably contains an aliphatic isocyanate and the diisocyanate compound (e) is an aliphatic isocyanate More preferable.

The amount of the diisocyanate compound (h) used in the amideimidation step is not limited. The amount of the diisocyanate compound (h) to be used is preferably from 0.3 to 1.0 (molar ratio) to the amount of the diamine compound (B) used for obtaining the imide compound (A) from the viewpoint of imparting appropriate alkali solubility to the polyamide- Or less, more preferably 0.4 or more and 0.95 or less, and particularly preferably 0.50 or more and 0.90 or less.

The reaction temperature of the amideimidation reaction in the amideimidation step is not limited. In one specific example of the reaction temperature of the amideimidation reaction, the reaction is preferably carried out in the range of 130 占 폚 to 200 占 폚, and in the range of 150 占 폚 to 180 占 폚.

For the amidimidation reaction in the amideimidation step, a catalyst can be used if necessary. Specific examples of the catalyst that can be used include amines such as triethylamine, lutidine, picoline, and triethylenediamine; Compounds of alkali metals or alkaline earth metals such as lithium methylate, sodium methylate, lithium ethylate, sodium ethylate, magnesium ethylate, potassium butoxide, potassium fluoride, and sodium fluoride; Cobalt, titanium, tin, and zinc, and the like.

The polyamideimide resin produced by the above production method includes a substance having a structure represented by the following general formula (3).

In the general formula (3), X is independently a diamine residue (residue of the diamine compound (B)), Y is independently an aromatic ring or cyclohexane ring, and Z is a residue of the diisocyanate compound (e). n is a natural number.

The polyamideimide resin produced by the above production method contains a carboxyl group. From the viewpoint of enhancing the alkali solubility of the polyamide-imide resin, the acid value is preferably 50 mgKOH / g or more. From the viewpoint of enhancing the alkali solubility of the polyamide-imide resin, the upper limit of the acid value is not limited. From the viewpoint of improving the balance between the other properties such as the mechanical properties of the cured product of the thermosetting resin composition including the polyamide-imide resin and the alkali solubility of the polyamide-imide resin, it is preferable that the acid value is 150 mgKOH / g or less And more preferably 120 mgKOH / g or less.

Next, the thermosetting resin composition using the polyamide-imide resin according to one embodiment of the present invention will be described. Since the polyamide-imide resin according to one embodiment of the present invention has a carboxyl group, it is possible to cause the polymerization reaction (curing reaction) to take place using the carboxyl group as a reaction site by using an appropriate thermosetting material. Therefore, the thermosetting resin composition according to one embodiment of the present invention contains the polyamideimide resin and the thermosetting material according to one embodiment of the present invention. The thermosetting material may be composed of one kind of material or may be composed of a plurality of kinds of materials.

The thermosetting material is a material capable of reacting with a carboxyl group possessed by the polyamideimide resin according to one embodiment of the present invention by heat. As such a material, a compound having an epoxy group, a compound having an isocyanate group, and the like are exemplified. Any compound preferably has a plurality of functional groups (also referred to as " reactive functional groups " in the present specification) capable of reacting with a carboxyl group.

As an example of the compound having an epoxy group, an epoxy resin can be mentioned. Examples of the epoxy resin include bisphenol type epoxy resins such as bisphenol A type epoxy resin, bisphenol F type epoxy resin and bisphenol S type epoxy resin; Novolak type epoxy resins such as phenol novolak epoxy resin, cresol novolac epoxy resin, and bisphenol A novolak type epoxy resin; An epoxide of a dicyclopentadiene type phenolic resin obtained by reacting dicyclopentadiene with a phenol; Biphenyl type epoxy resins such as epoxy compounds of 2,2 ', 6,6'-tetramethylbiphenol; An epoxy resin having a naphthalene skeleton; Aromatic epoxy resins such as epoxy resins having a fluorene skeleton, hydrogenated products of these aromatic epoxy resins; Aliphatic epoxy resins such as ethylene glycol diglycidyl ether, diethylene glycol diglycidyl ether, neopentyl glycol diglycidyl ether, and 1,6-hexanediol diglycidyl ether; Alicyclic epoxy resins such as 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate and bis- (3,4-epoxycyclohexyl) adipate; And heterocycle-containing epoxy resins such as triglycidyl isocyanurate.

From the viewpoint of enhancing the heat resistance and mechanical properties of the cured product of the thermosetting resin composition according to one embodiment of the present invention, when the thermosetting material contains an epoxy resin, it is preferable to use an epoxy resin containing at least one of a bisphenol- .

The relationship between the amount of the polyamide-imide resin contained in the thermosetting resin composition according to one embodiment of the present invention and the amount of the thermosetting material such as epoxy resin is not limited. From the viewpoint of enhancing the mechanical properties, heat resistance and the like of the cured product of the thermosetting resin composition according to one embodiment of the present invention, it is preferable that the ratio of the carboxyl group equivalent of the polyamideimide resin (which can be calculated from the acid value of the polyamideimide resin) Epoxy equivalent and the like is preferably 0.6 or more and 1.3 or less, more preferably 0.8 or more and 1.2 or less.

The thermosetting resin composition according to one embodiment of the present invention may contain a curing accelerator. That is, the thermosetting resin composition according to one embodiment of the present invention may contain a polyamideimide resin, an epoxy resin and a curing accelerator according to one embodiment of the present invention.

When the thermosetting resin composition according to one embodiment of the present invention contains a curing accelerator, the kind of the curing accelerator is not limited. The curing accelerator may be composed of one kind of material or a plurality of kinds of materials.

Examples of the case where the curing accelerator is a material promoting thermosetting include tertiary amine compounds, quaternary ammonium salts, imidazoles, phosphine compounds, and phosphonium salts. More specifically, there may be mentioned triethylamine, triethylenediamine, benzyldimethylamine, 2,4,6-tris (dimethylaminomethyl) phenol, 1,8-diazabicyclo Of a tertiary amine compound; Imidazoles such as 2-methylimidazole, 2,4-dimethylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole and 2-phenyl-4-methylimidazole; Phosphine compounds such as triphenylphosphine, tributylphosphine, tri (p-methylphenyl) phosphine, and tri (nonylphenyl) phosphine; Phosphonium salts such as tetraphenylphosphonium tetraphenylborate and tetraphenylphosphonium tetranaphthoateborate; Triphenylphosphonoformate, triphenylphosphonium phenolate, and a reaction product of benzoquinone and triphenylphosphine.

When the thermosetting resin composition according to one embodiment of the present invention contains a thermosetting material, the thermosetting resin composition can be cured by heating the thermosetting resin composition according to one embodiment of the present invention. The curing conditions such as the curing temperature and the curing time may be appropriately set depending on the components contained in the thermosetting resin composition. As an example of the curing condition, a curing temperature of 80 ° C or more and 300 ° C or less and a curing time of 30 minutes to 6 hours can be cited.

The above-described embodiments are described for the purpose of facilitating understanding of the present invention, and are not described for limiting the present invention. Therefore, each element disclosed in the above embodiment is intended to include all design modifications and equivalents falling within the technical scope of the present invention.

[Example]

Hereinafter, the present invention will be described more specifically by way of examples, but the present invention is not limited thereto.

(Example 1)

28.01 g (0.052 mol) of an aliphatic diamine (product name: PRIAMINE 1075, manufactured by Kuroda Japan Co., Ltd.) derived from dimer acid having a carbon number of 36 as dimer diamine (a) was added to four 300 ml flasks equipped with a stirrer, , 4.26 g (0.028 mol) of 3,5-diaminobenzoic acid as a carboxyl group-containing diamine (b) and 85.8 g of? -Butyrolactone were added and dissolved at room temperature.

Next, 30.12 g (0.152 mol) of cyclohexane-1,2,4-tricarboxylic acid anhydride (c) and 3.07 g (0.016 mol) of anhydrous trimellitic acid (d) were added and kept at room temperature for 30 minutes. 30 g of toluene was further charged, the temperature was raised to 160 캜, water produced together with toluene was removed, and the mixture was maintained for 3 hours and cooled to room temperature to obtain a solution containing the imide.

14.30 g (0.068 mol) of trimethylhexamethylene diisocyanate as a diisocyanate compound (e) was added to a solution containing the obtained imide compound, and the solution was kept at 160 캜 for 32 hours and diluted with 21.4 g of cyclohexanone Thereby obtaining a solution (A-1) containing a polyamide-imide resin. The polyamide-imide resin thus obtained had a weight average molecular weight Mw of 5250, a solid content of 41.5% by mass, an acid value of 63 mgKOH / g and a content of dimer diamine (a) of 40.0% by weight.

(Example 2)

29.49 g (0.054 mol) of an aliphatic diamine (product name: PRIAMINE 1075, manufactured by Kuroda Japan Co., Ltd.) derived from a dimer acid having a carbon number of 36 as a dimer diamine (a) was added to four 300 ml flasks equipped with a stirrer, , 4.02 g (0.026 mol) of 3,5-diaminobenzoic acid as the carboxyl group-containing diamine (b) and 73.5 g of? -Butyrolactone were added and dissolved at room temperature.

Next, 31.71 g (0.160 mol) of cyclohexane-1,2,4-tricarboxylic acid anhydride (c) and 1.54 g (0.008 mol) of anhydrous trimellitic acid (d) were added and kept at room temperature for 30 minutes. 30 g of toluene was further charged, the temperature was raised to 160 캜, water produced together with toluene was removed, and the mixture was maintained for 3 hours and cooled to room temperature to obtain a solution containing the imide.

6.90 g (0.033 mol) of trimethylhexamethylene diisocyanate and 8.61 g (0.033 mol) of dicyclohexylmethane diisocyanate as a diisocyanate compound (e) were fed into a solution containing the obtained imide cargo, , And the solution was diluted with 36.8 g of cyclohexanone to obtain a solution (A-2) containing the polyamideimide resin. The polyamide-imide resin thus obtained had a weight average molecular weight Mw of 5840, a solid content of 40.4% by weight, an acid value of 62 mgKOH / g and a content of dimer diamine (a) of 40.1% by weight.

(Example 3)

29.49 g (0.054 mol) of an aliphatic diamine (product name: PRIAMINE 1075, manufactured by Kuroda Japan Co., Ltd.) derived from a dimer acid having a carbon number of 36 as a dimer diamine (a) was added to four 300 ml flasks equipped with a stirrer, , 4.02 g (0.026 mol) of 3,5-diaminobenzoic acid as the carboxyl group-containing diamine (b) and 75.0 g of? -Butyrolactone were added and dissolved at room temperature.

Next, 33.29 g (0.168 mol) of cyclohexane-1,2,4-tricarboxylic acid anhydride (c) was added and kept at room temperature for 30 minutes. 30 g of toluene was further charged, the temperature was raised to 160 캜, water produced together with toluene was removed, and the mixture was maintained for 3 hours and cooled to room temperature to obtain a solution containing the imide.

16.79 g (0.064 mol) of dicyclohexylmethane diisocyanate as the diisocyanate compound (e) was added to a solution containing the imide compound obtained, and the solution was kept at 160 ° C for 32 hours, diluted with 37.5 g of cyclohexanone To obtain a solution (A-3) containing a polyamideimide resin. The polyamide-imide resin thus obtained had a weight average molecular weight Mw of 6430, a solid content of 41.2% by mass, an acid value of 63 mgKOH / g and a content of dimer diamine (a) of 39.3% by weight.

(Example 4)

33.01 g (0.060 mol) of an aliphatic diamine (product name: PRIAMINE 1075, manufactured by Kuroda Japan Co., Ltd.) derived from a dimer acid having a carbon number of 36 as a dimer diamine (a) was added to four 300 ml flasks equipped with a stirrer, 5.73 g (0.020 mol) of 5,5'-methylenebis (anthranilic acid) as a carboxyl group-containing diamine (b) and 95.4 g of? -Butyrolactone were added and dissolved at room temperature.

Next, 31.71 g (0.160 mol) of cyclohexane-1,2,4-tricarboxylic acid anhydride (c) and 1.54 g (0.008 mol) of anhydrous trimellitic acid (d) were added and kept at room temperature for 30 minutes. 30 g of toluene was further charged, the temperature was raised to 160 캜, water produced together with toluene was removed, and the mixture was maintained for 3 hours and cooled to room temperature to obtain a solution containing the imide.

7.40 g (0.035 mol) of trimethylhexamethylene diisocyanate as a diisocyanate compound (e) and 9.23 g (0.035 mol) of dicyclohexylmethane diisocyanate were fed into a solution containing the obtained imide compound at a temperature of 160 ° C. The solution was kept for 32 hours and diluted with 23.9 g of cyclohexanone to obtain a solution (A-4) containing the polyamideimide resin. The polyamide-imide resin thus obtained had a weight average molecular weight Mw of 8310, a solid content of 41.3% by mass, an acid value of 70 mgKOH / g and a content of dimer diamine (a) of 41.5% by weight.

(Example 5)

33.01 g (0.060 mol) of an aliphatic diamine (product name: PRIAMINE 1075, manufactured by Kuroda Japan Co., Ltd.) derived from a dimer acid having a carbon number of 36 as a dimer diamine (a) was added to four 300 ml flasks equipped with a stirrer, 5.73 g (0.020 mol) of 5,5'-methylenebis (anthranilic acid) as a carboxyl group-containing diamine (b) and 96.5 g of? -Butyrolactone were added and dissolved at room temperature.

Next, 31.71 g (0.160 mol) of cyclohexane-1,2,4-tricarboxylic acid anhydride (c) and 1.54 g (0.008 mol) of anhydrous trimellitic acid (d) were added and kept at room temperature for 30 minutes. 30 g of toluene was further charged, the temperature was raised to 160 캜, water produced together with toluene was removed, and the mixture was maintained for 3 hours and cooled to room temperature to obtain a solution containing the imide.

3.70 g (0.018 mol) of trimethylhexamethylene diisocyanate as a diisocyanate compound (e) and 13.85 g (0.053 mol) of dicyclohexylmethane diisocyanate were fed into a solution containing the obtained imide compound at a temperature of 160 ° C. The solution was kept for 32 hours and diluted with 24.1 g of cyclohexanone to obtain a solution (A-5) containing the polyamideimide resin. The polyamide-imide resin thus obtained had a weight average molecular weight Mw of 8900, a solid content of 41.0% by mass, an acid value of 69 mgKOH / g and a content of dimer diamine (a) of 41.0% by weight.

(Comparative Example 1)

In a four-necked 300 ml flask equipped with a nitrogen gas introducing tube, a thermometer and a stirrer, 6.98 g of 2,2'-bis [4- (4-aminophenoxy) phenyl] propane, 3.80 g of 3,5-diaminobenzoic acid, , 8.21 g of etherdiamine (product name: Erastamine RT1000, molecular weight 1025.64) and 86.49 g of? -Butyrolactone were added and dissolved at room temperature.

Next, 17.84 g of cyclohexane-1,2,4-tricarboxylic acid-1,2-anhydride and 2.88 g of trimellitic anhydride were added and kept at room temperature for 30 minutes. 30 g of toluene was further charged, the temperature was raised to 160 캜, water produced together with toluene was removed, and the mixture was maintained for 3 hours and cooled to room temperature to obtain an imide freed solution.

9.61 g of trimellitic anhydride and 17.45 g of trimethylhexamethylene diisocyanate were added to the resulting imide cargo solution, and the mixture was kept at 160 ° C for 32 hours. Thus, a polyamideimide resin solution (B-1) containing a carboxyl group was obtained. The solid content was 40.1% by mass and the acid value was 83 mgKOH / g.

(Comparative Example 2)

Diaminobenzoic acid, 4.05 g of a modified silicone oil (product name: X-22-9409, amine equivalent: 680 g / eq, manufactured by Shin-Etsu Chemical Co., Ltd.) was placed in a four-necked 300 ml flask equipped with a stirrer, And 76.72 g of? -Butyrolactone were added and dissolved at room temperature.

Then, 20.11 g of cyclohexane-1,2,4-tricarboxylic anhydride and 2.69 g of trimellitic anhydride were added and kept at room temperature for 30 minutes. 30 g of toluene was further charged, the temperature was raised to 160 캜, water produced together with toluene was removed, and the mixture was maintained for 3 hours and cooled to room temperature to obtain an imide freed solution.

0.94 g of trimellitic anhydride, 1.80 g of cyclohexane-1,2,4-tricarboxylic acid anhydride and 13.77 g of dicyclohexylmethane-4,4'-diisocyanate were added to the obtained imide cargo solution, And maintained at a temperature for 32 hours to obtain a polyamide-imide resin solution (B-2) containing a carboxyl group. The solid content was 52.0 mass% and the acid value was 65 mg KOH / g.

(Comparative Example 3)

In a four-necked 300 ml flask equipped with a nitrogen gas introducing tube, a thermometer and a stirrer, 10.26 g of 2,2'-bis [4- (4-aminophenoxy) phenyl] propane, 3.80 g of 3,5- -Butyrolactone were added and dissolved at room temperature.

Next, 17.84 g of cyclohexane-1,2,4-tricarboxylic anhydride and 2.88 g of trimellitic anhydride were added and kept at room temperature for 30 minutes. Further, 30 g of toluene was added, the temperature was raised to 160 캜, water produced together with toluene was removed, and the mixture was kept for 3 hours and cooled to room temperature to obtain an imidodicarboxylic acid solution.

To the obtained imidodicarboxylic acid solution, 9.61 g of trimellitic anhydride and 17.87 g of trimethylhexamethylene diisocyanate were charged and maintained at 160 ° C for 32 hours to obtain a polyamideimide resin solution (B-3) containing a carboxyl group. The solid content was 40.2% by mass and the acid value was 90 mgKOH / g.

(Examples 6 to 10)

1-benzyl-2-phenylimidazole (product name: 1B2PZ, manufactured by Shikoku Chemicals) as a curing accelerator, and bisphenol A-type liquid epoxy resin as a thermosetting resin (product name: JER828, epoxy equivalent: 185 g / eq; manufactured by Mitsubishi Chemical Corporation) A thermosetting resin composition containing any one of the polyamide-imide resins of Examples 1 to 5 as a varnish of a polyamide-imide resin containing the structure represented by the formula (1) and the structure represented by the formula (2) (Examples 6 to 10). In all of the thermosetting resin compositions 1 to 5, the equivalent ratio of the carboxyl group equivalent of the polyamide resin to the epoxy equivalent of the epoxy resin calculated on the basis of the acid value of the polyamideimide resin was 1/1, and the curing accelerator per 100 parts by mass of the polyamide- Was contained in an amount of 1 part by mass.

(Comparative Examples 4 to 6)

1-benzyl-2-phenylimidazole (product name: 1B2PZ, manufactured by Shikoku Chemicals) as a curing accelerator, and bisphenol A-type liquid epoxy resin as a thermosetting resin (product name: JER828, epoxy equivalent: 185 g / eq; manufactured by Mitsubishi Chemical Corporation) Any one of the polyamide-imide resins of Comparative Examples 1 to 3 as a varnish of polyamide-imide resin which does not contain any one of the structure represented by the formula (1) and the structure represented by the formula (2) (Comparative Examples 4 to 6). All of the comparative thermosetting resin compositions 1 to 3 were prepared in the same manner as in Example 1 except that the equivalent ratio of the carboxyl group equivalent of the polyamide resin to the epoxy equivalent of the epoxy resin calculated on the basis of the acid value of the polyamideimide resin was 1/1, And 1 part by mass of an accelerator.

[Test Example 1] Evaluation of alkali solubility of polyamide-imide resin

The thermosetting resin compositions of Examples 5 to 8 and the comparative thermosetting resin compositions of Comparative Examples 4 to 6 thus prepared were each applied to a copper foil so as to have a dry film thickness of 25 占 퐉 and dried at 90 占 폚 for 30 minutes And dried to obtain a dried film. The dried film thus obtained was dissolved in an alkali developing machine DV-40L manufactured by Alps Engineering Co., Ltd. at a temperature of 30 DEG C and a spray pressure of 0.2 MPa using a 1 mass% sodium carbonate aqueous solution and the state of the dried film was observed. The alkali solubility as a composition was evaluated.

A: What could be dissolved within 60 seconds

B: What was dissolved within 120 seconds

C: What was able to dissolve within 180 seconds

D: What could not be dissolved within 180 seconds

[Test Example 2] Measurement of tensile modulus, tensile strength and elongation

The thermosetting resin compositions of Examples 5 to 8 and Comparative Examples 4 to 6 prepared with the composition shown in Table 1 were applied to polyethylene terephthalate (PET), dried in an oven at a temperature of 90 DEG C for 30 minutes, Cured for 60 minutes, peeled from PET to prepare a cured film having a thickness of 80 mu m, and the cured film was cut into a predetermined size to obtain a sample for measurement.

Measuring instrument: manufactured by Shimadzu Corporation, product name Autograph AG-Xplus

Tensile speed: 5 mm / min.

Sample size: 10 mm x 150 mm

[Test Example 3] Measurement of glass transition temperature, 5% weight reduction temperature

The cured film produced by the method described in Test Example 2 was cut out and put into the following measuring container and measured.

Measuring instrument: manufactured by Hitachi Hi-Tech Co., Ltd. Product name TG / DTA7220

Atmosphere: In the air

Measuring temperature: 25 to 400 DEG C

[Test Example 4] Evaluation of dielectric properties (dielectric constant, dielectric tangent)

The cured film produced by the method described in Test Example 2 was cut out, and measurement was carried out using the following measuring instrument.

Measuring instrument: manufactured by Gisite Technologies, Ltd. Product name Network analyzer E5071C

Kanto Denshi Yogai Hearts Co., Ltd. Cavity resonator Pulsating method Permittivity measuring device

Frequency: 1 GHz

Sample dimensions: width 2 mm x length 100 mm x thickness 0.080 mm

[Table 1]

The thermosetting compositions of Examples 6 to 10 containing the polyamide-imide resin solutions of Examples 1 to 5 were all excellent in alkali solubility and dielectric properties.

On the other hand, the thermosetting compositions of Comparative Examples 4 to 6 containing the polyamide-imide resin solution of Comparative Examples 1 to 3 were inferior in dielectric properties and in alkali solubility as compared with the thermosetting compositions of Examples 6 to 10.

The polyamideimide resin provided by the present invention is a carboxyl group-containing polyamideimide resin having excellent alkali solubility.

The thermosetting resin composition provided by the present invention is a composition capable of giving a cured product excellent in alkali solubility, mechanical properties and heat resistance, and a concrete example is a thermosetting resin composition containing an epoxy resin.

The cured product of the thermosetting resin composition containing the polyamideimide resin of the present invention is excellent in mechanical properties, heat resistance and dielectric properties. In this respect, the polyamide-imide resin of the present invention can be used as an insulating material for a flexible printed wiring board, an adhesive, a resin for a film raw material, and the like. Since the polyamide-imide resin of the present invention is excellent in alkali solubility, it can be used as a photosensitive film or an adhesive by mixing the polyamide-imide resin of the present invention with a photoreactive material. In this case, It is also useful as a coating material or the like.

Claims (15)

A polyamideimide resin characterized by having a structure represented by the following general formula (1) and a structure represented by the following general formula (2).

(X ₁ is a moiety having a carbon number of the ring, Y are each independently a cyclohexane ring or a direction of the 24-48 residues of an aliphatic diamine (a) of the dimer acid-derived, X ₂ is an aromatic diamine (b) having a carboxyl group) The method according to claim 1,
Wherein the acid value is not less than 30 mgKOH / g and not more than 150 mgKOH / g. 3. The method according to claim 1 or 2,
Wherein the content of the aliphatic diamine (a) derived from a dimer acid having a carbon number of 24 to 48 is 20 to 60% by weight. 3. The method according to claim 1 or 2,
Any one or two selected from a cyclohexane ring and an aromatic ring represented by Y in the general formula (1) and the general formula (2) (except when Y is an aromatic ring) may be a cyclohexane ring Wherein the molar ratio of the content of aromatic rings to the content of aromatic rings is 85 / 15-100 / 0. 3. The method according to claim 1 or 2,
The aromatic diamine (b) having a carboxyl group includes at least one selected from the group consisting of 3,5-diaminobenzoic acid and 5,5'-methylenebis (anthranilic acid). A thermosetting resin composition comprising the polyamide-imide resin and the thermosetting material according to claim 1 or 2. The method according to claim 6,
Wherein the thermosetting material is an epoxy resin. The method according to claim 6,
A thermosetting resin composition further comprising a thermosetting accelerator. A cured product of the thermosetting resin composition according to claim 6. An aliphatic diamine (a) derived from a dimer acid having 24 to 48 carbon atoms, an aromatic diamine (b) having a carboxyl group, and cyclohexane-1,2,4-tricarboxylic acid-1,2-anhydride (c) (D), to obtain an imide compound (A), and a step of reacting the imide compound
And an amideimidation step of reacting the imide compound (A) obtained by the imidation step with a diisocyanate compound (e) to obtain a polyamideimide resin represented by the following general formula (3) By weight based on the total weight of the polyamide-imide resin.

(Wherein X is each independently a diamine residue, Y is independently a cyclohexane ring or an aromatic ring, Z is a residue of a diisocyanate compound (e), and n is a natural number) 11. The method of claim 10,
Wherein the polyamide-imide resin obtained by the amidimidation step has an acid value of 30 mgKOH / g or more and 150 mgKOH / g or less. The method according to claim 10 or 11,
The amount of the aliphatic diamine (a) derived from the dimeric acid having 24 to 48 carbon atoms is preferably such that the content of the aliphatic diamine (a) derived from dimeric acid having 24 to 48 carbon atoms is 20 to 60 wt% A method for producing a resin. The method according to claim 10 or 11,
The amount of the cyclohexane-1,2,4-tricarboxylic acid-1,2-anhydride (c) to be used is in the range of from 85/15 to 100/0 in terms of the amount of the trimellitic anhydride (d) Gt; The method according to claim 10 or 11,
Wherein the aromatic diamine (b) having a carboxyl group comprises at least one member selected from the group consisting of 3,5-diaminobenzoic acid and 5,5'-methylenebis (anthranilic acid). The method according to claim 10 or 11,
Wherein the diisocyanate compound (e) is an aliphatic isocyanate compound.