JP2016020471A - Polyamide-imide resin and manufacturing method of polyamide-imide resin, thermosetting resin composition and cured article of the thermosetting resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an alkali soluble resin capable of being dissolved even when 1.0 mass% of sodium carbonate solution is used as an alkali solution and a manufacturing method of the alkali soluble resin.SOLUTION: There is provided a polyamide-imide resin obtained by reacting a reaction raw material (α) containing an imidized compound (A) and a diisocyanate compound (h), the imidized compound (A) is obtained by reacting a diamine compound (B) and acid anhydride (C), the diamine compound (B) contains polysiloxanediamine having an aromatic ring (a) and carboxyl group-containing diamine (b), the acid anhydride (C) for obtaining the imidized compound (A) contains cyclohexane-1,2,4-tricarboxylic acid anhydride (e), the polyamide-imide resin contains a carboxylic group and a solid content acid value is 30 mgKOH/g or more.SELECTED DRAWING: None

Description

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

  Resin material that has light transmissivity and excellent solubility in alkaline solutions in various fields, mainly in the electrical and electronics industry, and can be used as insulating materials, adhesives, resin for film raw materials, etc. There is a need for materials.

  As materials that can meet such demands, Patent Document 1 discloses at least (a1) an agent A containing a compound having a carboxyl group and a photosensitive group, (b1) an epoxy resin, and (b2) an oxime ester-based light. A photosensitive resin composition comprising a B agent containing a polymerization initiator, wherein the (b1) epoxy resin is present in a solid at room temperature (25 ° C.) in the B agent. The photosensitive resin composition characterized by this is disclosed. The compound (a1) having a carboxyl group and a photosensitive group in this document is a compound having at least one carboxyl group and a photosensitive group selected from the group consisting of epoxy acrylate, urethane acrylate and acrylated acrylate.

  In recent years, demands for alkali-soluble resins have been advanced, and in particular, improvement of mechanical properties and heat resistance has been demanded. Epoxy acrylate and urethane acrylate resins as disclosed in Patent Document 1 are difficult to meet this requirement.

  In this regard, Patent Document 2 discloses that alkali solubility is characterized in that the Tg is 200 ° C. or higher and the dissolution time in a 5 wt% sodium hydroxide aqueous solution is within 10 minutes, and the light transmittance at 350 nm is 5% or more. A resin is disclosed. The polyamide-imide resin disclosed in Patent Document 2 can meet the above-described demands for improving mechanical properties and heat resistance.

JP 2012-98470 A JP 2002-88154 A

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

  For this reason, whenever it tries to use the alkali-soluble resin which concerns on a prior art, and the alkali-soluble resin disclosed by patent document 2 according to a product or a use, a developing solution is used for the aqueous solution of weak alkali each time. Therefore, the work of exchanging from an aqueous solution of strong alkali to an aqueous solution of strong alkali or vice versa is required, and the productivity is significantly reduced. Further, when the developing solution is changed from the weak alkaline aqueous solution to the strong alkaline aqueous solution, the waste liquid treatment corresponding to the weak alkaline aqueous solution must be changed to be compatible with the strong alkaline aqueous solution. This change in waste liquid treatment may lead to a decrease in industrial productivity, such as requiring large capital investment and increasing running costs.

  Therefore, from the viewpoint of ensuring industrial productivity, the alkali-soluble resin should have sufficient solubility in a weakly alkaline aqueous solution such as a 1.0 wt% sodium carbonate aqueous solution as before. Is desired.

  The present invention provides an alkali-soluble polyamideimide resin that can be dissolved even when a 1.0% by mass sodium carbonate aqueous solution is used as an alkali solution, and a method for producing the alkali-soluble polyamideimide resin. Objective. The present invention also relates to an alkali-soluble resin that can be dissolved even when a 1.0% by mass aqueous sodium carbonate solution is used as an alkaline solution, and a cured product obtained by curing the composition. It aims at providing the thermosetting resin composition which can have the outstanding mechanical characteristic and heat resistance. Furthermore, this invention aims at providing the hardened | cured material of a thermosetting resin composition provided with this outstanding characteristic.

The present invention provided to solve the above-described problems is as follows.
(1) A polyamide-imide resin obtained by reacting an imidized product (A) and a reaction raw material (α) containing a diisocyanate compound (h), the imidized product (A) comprising a diamine compound (B) and an acid anhydride The diamine compound (B) includes a polysiloxane diamine (a) represented by the following general formula (1) and a carboxyl group-containing diamine (b). The acid anhydride (C) for obtaining the imidized product (A) contains cyclohexane-1,2,4-tricarboxylic acid-1,2-anhydride (e), and the polyamideimide resin contains a carboxyl group. And a polyamideimide resin having a solid content acid value of 30 mgKOH / g or more.
Here, in the general formula (1), a represents an integer of 1 or more, and b represents an integer of 0 or more. R ₁ and R ₂ are each independently an alkylene group having 1 to 5 carbon atoms.

(2) The polyamideimide resin according to (1), wherein the acid anhydride (C) further contains trimellitic anhydride (d).

(3) The amount of trimellitic anhydride (d) used is such that the molar ratio to the amount of cyclohexane-1,2,4-tricarboxylic acid-1,2-anhydride (e) used is 4 or less. The polyamide-imide resin according to (2) above.

(4) The polyamideimide resin according to any one of (1) to (3), wherein the amine equivalent of the polysiloxane diamine (a) is 300 g / eq or more and 2500 g / eq or less.

(5) The diamine compound (B) according to any one of (1) to (4), including a diamine (c) other than the polysiloxane diamine (a) and the carboxyl group-containing diamine (b). Polyamideimide resin.

(6) The polyamideimide resin according to any one of (1) to (5), wherein the diisocyanate compound (h) is an aliphatic diisocyanate.

(7) The polyamideimide resin according to any one of (1) to (6), wherein the reaction raw material (α) further includes an acid anhydride (β).

(8) The acid anhydride (β) includes at least one of trimellitic anhydride (f) and cyclohexane-1,2,4-tricarboxylic acid-1,2-anhydride (g). The polyamideimide resin described in 1.

(9) A method for producing a polyamideimide resin described in any one of (1) to (6) above, wherein a reaction raw material (α) containing an imidized product (A) and a diisocyanate compound (h) is reacted. And a step of obtaining a polyamideimide resin as a reaction product, wherein the imidized product (A) is obtained by reacting a diamine compound (B) with an acid anhydride (C), and the diamine compound ( B) includes the polysiloxane diamine (a) represented by the general formula (1) of the above (1) and the carboxyl group-containing diamine (b), and the acid anhydride (C) is cyclohexane-1,2,4- A polyamic acid characterized by comprising a tricarboxylic acid-1,2-anhydride (e), wherein the polyamideimide resin contains a carboxyl group and has a solid content acid value of 30 mgKOH / g or more. Manufacturing method of de resin.

(10) The method for producing a polyamideimide resin according to (9), wherein the reaction raw material (α) further contains an acid anhydride (β).

(11) The acid anhydride (β) includes at least one of trimellitic anhydride (f) and cyclohexane-1,2,4-tricarboxylic acid-1,2-anhydride (g). The manufacturing method of the polyamide-imide resin as described in 2.

(12) The use amount of the diamine compound (B) is described in (10) or (11) above, wherein the molar ratio with respect to the use amount of the acid anhydride (β) is ¼ or more and 4 or less. The manufacturing method of the polyamide-imide resin.

(13) A thermosetting resin composition comprising the polyamideimide resin described in any of (1) to (8) above and a thermosetting material.

(14) The thermosetting resin composition according to (13), wherein the thermosetting material is an epoxy resin.

(15) The thermosetting resin composition according to (13) or (14), further including a thermosetting accelerator.

(16) A cured product of the thermosetting resin composition described in any one of (13) to (15) above.

  The present invention provides an alkali-soluble resin that can be dissolved even when a mild alkaline solution such as a 1.0 mass% sodium carbonate aqueous solution is used, and a method for producing the alkali-soluble resin.

  Further, according to the present invention, there is provided a thermosetting resin composition that can be dissolved even when a mild alkaline solution such as a 1.0% by mass sodium carbonate aqueous solution is used, which has mechanical properties and heat resistance. There is provided a thermosetting resin composition capable of forming a cured product. Furthermore, the present invention provides a cured product of the above thermosetting resin composition.

Hereinafter, embodiments of the present invention will be described.
The polyamide-imide resin according to one embodiment of the present invention is a reaction product obtained by reacting a reaction raw material (α) containing an imidized product (A) and a diisocyanate compound (h).

  The polyamide-imide resin according to an embodiment of the present invention contains a carboxyl group and has a solid content acid value of 30 mgKOH / g or more. Alkali solubility of polyamideimide resin and light transmittance of polyamideimide resin (the ability to transmit light in the wavelength range of about 250 nm to about 450 nm is given as a specific example of light transmittance), polyamideimide resin The solid content acid value of the polyamideimide resin according to an embodiment of the present invention is 30 mgKOH / g or more and 150 mgKOH from the viewpoint of improving the balance with other characteristics such as mechanical characteristics of the cured product of the curable resin composition containing / G or less, more preferably 50 mgKOH / g or more and 120 mgKOH / g or less.

  The imidized product (A) according to one embodiment of the present invention is obtained by reacting the diamine compound (B) and the acid anhydride (C).

The diamine compound (B) includes a polysiloxane diamine (a) that is a polysiloxane diamine having an aromatic ring represented by the following general formula (1).

In the general formula (1), a represents an integer of 1 or more, and b represents an integer of 0 or more. R ₁ and R ₂ are each independently an alkylene group having 1 to 5 carbon atoms.

  The polysiloxane diamine (a) may be composed of one type of compound, or may be composed of a plurality of compounds satisfying the general formula (1). Specifically, the polysiloxane diamine (a) may be composed of a plurality of types of polysiloxane diamines having different siloxane skeletons. The amine equivalent of polysiloxane diamine (a) is preferably about 300 g / eq or more and 2500 g / eq or less. As such polysiloxane diamine having an aromatic ring, it can be appropriately selected from commercially available ones. As such commercially available diamines, modified silicone oils manufactured by Shin-Etsu Chemical Co., Ltd., X-22-9409 (amine equivalent of about 700 g / eq), X-22-1660B-3 (amine equivalent of about 2200 g / eq) and the like.

  From the viewpoint of improving the balance between the alkali solubility of the polyamideimide resin, the light transmittance of the polyamideimide resin, and other properties such as the mechanical properties of the cured product of the curable resin composition containing the polyamideimide resin, The amine equivalent of (a) is preferably from 300 g / eq to 2500 g / eq, more preferably from 500 g / eq to 1500 g / eq.

  The amount of polysiloxane diamine (a) used in the reaction for obtaining the imidized product (A) is not limited. From the viewpoint of improving the balance between the alkali solubility of the polyamide-imide resin, the light transmittance of the polyamide-imide resin, and other properties such as the mechanical properties of the cured product of the curable resin composition containing the polyamide-imide resin, The polysiloxane diamine is such that the ratio of the component skeleton based on the polysiloxane diamine (a) contained in the polyamide-imide resin obtained according to the embodiment to the polyamide-imide resin is in the range of 5% by mass to 70% by mass. It is preferable to set the usage amount of the amount of (a), and it is particularly preferable to set the usage amount of the polysiloxane diamine (a) so that the above ratio is in the range of 15% by mass to 50% by mass. preferable.

  The diamine compound (B) contains a carboxyl group-containing diamine (b). Specific examples of the carboxyl group-containing diamine (b) include 3,5-diaminobenzoic acid, 3,4-diaminobenzoic acid, 4,4-methylenebisanthranilic acid, benzidine-3,3-dicarboxylic acid, and the like. . The carboxyl group-containing diamine (b) may be composed of one type of compound or may be composed of a plurality of types of compounds. From the viewpoint of raw material availability, the carboxyl group-containing diamine (b) preferably contains 3,5-diaminobenzoic acid.

  The amount of the carboxyl group-containing diamine (b) used in the reaction for obtaining the imidized product (A) is not limited. From the viewpoint of improving the balance between the alkali solubility of the polyamide-imide resin, the light transmittance of the polyamide-imide resin, and other properties such as the mechanical properties of the cured product of the curable resin composition containing the polyamide-imide resin, The amount of the carboxyl group-containing diamine (b) is preferably set so that the solid content acid value of the polyamideimide resin obtained according to one embodiment is 30 mgKOH / g or more and 150 mgKOH / g or less. It is particularly preferable to set the amount of the carboxyl group-containing diamine (b) so that the value is 50 mgKOH / g or more and 120 mgKOH / g or less.

  The diamine compound (B) may contain a diamine (c) other than the polysiloxane diamine (a) and the carboxyl group-containing diamine (b) (also referred to as “other diamine (c)” in the present specification). Other diamine (c) may be comprised from one type of compound, and may be comprised from the multiple types of compound.

  Specific examples of the other diamine (c) include 2,2-bis [4- (4-aminophenoxy) phenyl] propane, bis [4- (3-aminophenoxy) phenyl] sulfone, and bis [4- (4 -Aminophenoxy) phenyl] sulfone, 2,2-bis [4- (4-aminophenoxy) phenyl] hexafluoropropane, bis [4- (4-aminophenoxy) phenyl] methane, 4,4'-bis (4 -Aminophenoxy) biphenyl, bis [4- (4-aminophenoxy) phenyl] ether, bis [4- (4-aminophenoxy) phenyl] ketone, 1,3-bis (4-aminophenoxy) benzene, 1,4 -Bis (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-biphenyl-4,4'- Diamine, 3,3′-dihydroxybiphenyl-4,4′-diamine, (4,4′-diamino) diphenyl ether, (4,4′-diamino) diphenylsulfone, (4,4′-diamino) benzophenone, (3 , 3′-diamino) benzophenone, (4,4′-diamino) diphenylmethane, (4,4′-diamino) diphenyl ether, (3,3′-diamino) diphenyl ether and the like, and hexamethylenediamine, Octamethylenediamine, decamethylenediamine, dodecamethylenediamine, octadecamethylenediamine, 4,4-methyl Nbisu (hexylamine cyclohexane), isophorone diamine, hexane diamine 1,4-cyclohexylene, include aliphatic diamines such as norbornene diamine.

  From the viewpoint of improving the balance between the alkali solubility of the polyamideimide resin, the light transmittance of the polyamideimide resin, the mechanical properties of the cured product of the curable resin composition containing the polyamideimide resin, and other diamines. (C) preferably contains 2,2-bis [4- (4-aminophenoxy) phenyl] propane (BAPP).

  When the diamine compound (B) contains another diamine (c), the amount of the other diamine (c) used in the reaction for obtaining the imidized product (A) is not limited. It is preferable to set the amount of use so that the mass ratio of the polysiloxane diamine (a) contained in the polyamideimide resin obtained by one embodiment of the present invention and the acid value of the polyamideimide resin fall within the above-mentioned range.

  The acid anhydride (C) to be reacted with the diamine compound (B) to obtain the imide compound (A) is a compound having at least three carboxyl groups, two of which are anhydrous. An acid anhydride is roughly classified into an aromatic compound and an aliphatic compound. The acid anhydride (C) is an aliphatic compound such as cyclohexane-1,2,4-tricarboxylic acid-1,2-anhydride ( e). The acid anhydride (C) may be composed of cyclohexane-1,2,4-tricarboxylic acid-1,2-anhydride (e), or may contain other acid anhydrides. Examples of other acid anhydrides contained in such an acid anhydride (C) include trimellitic anhydride (d) which is an aromatic compound.

  When the acid anhydride (C) contains cyclohexane-1,2,4-tricarboxylic acid-1,2-anhydride (e) and trimellitic anhydride (d), the relationship between these contents is not limited. . From the viewpoint of improving the balance between the alkali solubility of the polyamideimide resin and other properties such as the light transmission property of the polyamideimide resin, the amount of trimellitic anhydride (d) used is cyclohexane-1,2,4- The molar ratio to the amount of tricarboxylic acid-1,2-anhydride (e) used is preferably 4 or less, more preferably 1 or less, more preferably 0.5 or less. It is particularly preferable that the amount is as follows. The molar ratio may be zero.

  The relationship between the amount of the diamine compound (B) used to obtain the imidized product (A) and the amount of the acid anhydride (C) is not limited. It is preferable that the usage-amount of an acid anhydride (C) is a quantity from which the molar ratio with respect to the usage-amount of a diamine compound (B) will be 2.0 or more and 2.3 or less, and the said molar ratio is 2.0 or more and 2. The amount is more preferably 1 or less.

  The reaction temperature at which the diamine compound (B) and the acid anhydride (C) are reacted to obtain the imidized product (A) is not limited. Usually, it is preferably in the range of 120 ° C. to 200 ° C., more preferably in the range of 140 ° C. to 180 ° C.

  The reaction solvent for obtaining the imidized product (A) is not limited. Specific examples of such reaction solvents include dimethylacetamide (DMAC), dimethylformamide (DMF), dimethyl sulfoxide, N-methyl-2-pyrrolidone (NMP), γ-butyrolactone, sulfolane, cyclohexanone, cyclopentanone, diglyme, triglyme, etc. Is mentioned. The reaction solvent for obtaining the imidized product (A) may be composed of one kind of compound, or two or more kinds of compounds may be used in combination as a reaction solvent. Above all, the process of generating imidized product (A) requires a high reaction temperature, so the boiling point is high, the solubility of the resulting polymer is relatively good, and strict humidity control is not necessary when using the polymer solution. It is preferable to use one or more selected from the group consisting of γ-butyrolactone, triglyme, diglyme, cyclohexanone and cyclopentanone as a reaction solvent for obtaining the imidized product (A).

  Since water is generated in the imidization reaction, when a reaction for obtaining the imidized product (A) is performed, it is preferable that an aromatic hydrocarbon azeotropic with water generated in the imidization reaction is present. Examples of such aromatic hydrocarbons include benzene, toluene, xylene, ethylbenzene, mesitylene and the like. Of these, toluene is preferred because of its relatively low toxicity and low boiling point, which makes it easy to distill off.

The specific kind of diisocyanate compound (h) contained in the reaction raw material (α) for the polyamideimide resin according to one embodiment of the present invention is not limited. The diisocyanate compound (h) may be composed of one type of compound or may be composed of a plurality of types of compounds.

  Specific examples of the diisocyanate compound (h) include 4,4′-diphenylmethane diisocyanate, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, naphthalene-1,5-diisocyanate, o-xylylene diisocyanate, m -Aromatic diisocyanates such as xylylene diisocyanate and 2,4-tolylene dimer; aliphatic diisocyanates such as hexamethylene diisocyanate, trimethylhexamethylene diisocyanate, 4,4-methylenebis (cyclohexyl isocyanate), isophorone diisocyanate, norbornene diisocyanate, etc. It is done. From the viewpoint of improving the balance between the alkali solubility of the polyamideimide resin, the light transmittance of the polyamideimide resin, and other properties such as the mechanical properties of the cured product of the curable resin composition containing the polyamideimide resin, h) preferably contains an aliphatic isocyanate, and the diisocyanate compound (h) is more preferably an aliphatic isocyanate.

  The reaction raw material (α) for the polyamideimide resin according to one embodiment of the present invention may further contain an acid anhydride (β) in addition to the imidized product (A) and the diisocyanate compound (h). As long as the acid anhydride (β) is a compound having at least three carboxyl groups and two of them are anhydrous, like the acid anhydride (C), the type of the acid anhydride (β) is It is not limited. The acid anhydride which consists of an aliphatic compound may be sufficient, and the acid anhydride which consists of an aromatic compound may be sufficient. Specific examples of the acid anhydride (β) include cyclohexane-1,2,4-tricarboxylic acid-1,2-anhydride (g) which is an aliphatic compound and trimellitic anhydride (f) which is an aromatic compound. Can be mentioned.

  When the reaction raw material (α) contains an acid anhydride (β), the content of the acid anhydride (β) in the reaction raw material (α) is not limited. From the viewpoint of improving the balance between the alkali solubility of the polyamideimide resin, the light transmittance of the polyamideimide resin, and other properties such as the mechanical properties of the cured product of the curable resin composition containing the polyamideimide resin, The molar ratio of the amount of the acid anhydride (β) contained in the reaction raw material (α) to the amount of the diamine compound (B) used to obtain the imide compound (A) contained in α) was 0. It is preferably 25 or more and 4 or less, more preferably 0.5 or more and 2 or less, and particularly preferably 0.6 or more and 1.5 or less.

  The content of the diisocyanate compound (h) in the reaction raw material (α) is not limited. From the viewpoint of improving the balance between the alkali solubility of the polyamideimide resin, the light transmittance of the polyamideimide resin, and other properties such as the mechanical properties of the cured product of the curable resin composition containing the polyamideimide resin, The amount of the diisocyanate compound (h) contained in α) is determined depending on the amount of the diamine compound (B) used for obtaining the imide compound (A) contained in the reaction raw material (α) and the reaction raw material (α ) Is preferably 0.3 or more and 1.0 or less, more preferably 0.4 or more and 0.95 or less, with respect to the total amount of acid anhydride (β) contained in It is particularly preferable to set the value to 50 or more and 0.90 or less.

  The reaction temperature of the amidimidization reaction with the reaction raw material (α) is not limited. What is necessary is just to set suitably according to the characteristic of the component contained in the reaction raw material ((alpha)). As a specific example of such a reaction temperature, it may be preferable that the reaction is performed within a range of 130 ° C. or higher and 200 ° C. or lower and within a range of 150 ° C. or higher and 180 ° C. or lower.

  A catalyst can be used in the amidimidization reaction with the reaction raw material (α) as necessary. Specific examples of the catalyst that can be used include amines such as triethylamine, lutidine, picoline, and triethylenediamine; lithium methylate, sodium methylate, lithium ethylate, sodium ethylate, magnesium ethylate, potassium butoxide, fluoride, and the like. Examples include alkali metal or alkaline earth metal compounds such as potassium fluoride and sodium fluoride; and metal or metalloid compounds such as cobalt, titanium, tin, and zinc.

  If the polyamideimide resin obtained by one embodiment of the present invention is estimated based on the composition of the reaction raw material (α), there is a possibility that it can be represented by a chemical formula such as the following general formula (2).

  In the general formula (2), n = 0 to 50, m = 0 to 50, and l = 0 to 30, X represents a diamine residue, Y represents an aromatic ring or a cyclohexane ring, and Z represents an isocyanate residue.

  As described above, the polyamideimide resin according to one embodiment of the present invention is obtained by reacting the reaction raw material (α) containing the imidized product (A) and the diisocyanate compound (h), and using the polyamideimide resin as a reaction product. A obtaining step. Here, the imidized product (A) is obtained by reacting the diamine compound (B) and the acid anhydride (C), and the diamine compound (B) is represented by the general formula (1). A polysiloxane diamine (a) and a carboxyl group-containing diamine (b) are included. The acid anhydride (C) includes cyclohexane-1,2,4-tricarboxylic acid-1,2-anhydride (e).

  The polyamideimide resin according to one embodiment of the present invention thus obtained contains a carboxyl group and has a solid content acid value of 30 mgKOH / g or more. From the viewpoint of increasing the alkali solubility of the polyamideimide resin, the solid content acid value is preferably 50 mgKOH / g or more. From the viewpoint of increasing the alkali solubility of the polyamideimide resin, the upper limit of the solid content acid value is not limited. From the viewpoint of improving the balance between the light transmittance of the polyamideimide resin, the mechanical properties of the cured product of the curable resin composition containing the polyamideimide resin, and the alkali solubility of the polyamideimide resin, the above solid The partial acid value is preferably 150 mgKOH / g or less, and more preferably 120 mgKOH / g or less.

  Next, the curable resin composition using the polyamideimide resin according to an embodiment of the present invention will be described. Since the polyamide-imide resin according to an embodiment of the present invention has a carboxyl group, it is possible to cause a polymerization reaction (curing reaction) to be performed using this carboxyl group as a reactive site by using an appropriate curable material. . Therefore, the curable resin composition which concerns on one Embodiment of this invention is a thermosetting resin composition containing the polyamide-imide resin which concerns on one Embodiment of this invention, and a thermosetting material.

  The thermosetting material is a material that can react with the polyamide-imide resin by heat. Such a thermosetting material may be composed of one kind of substance or may be composed of a plurality of kinds of substances.

  A specific example of the thermosetting material is a material capable of reacting with the carboxyl group of the polyamide-imide resin according to an embodiment of the present invention by heat. Examples of such materials include compounds having an epoxy group, compounds having an isocyanate group, and the like. Any compound preferably has a plurality of functional groups capable of reacting with a carboxyl group (also referred to as “reactive functional groups” in this specification).

  An example of the compound having an epoxy group is an epoxy resin. 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; novolaks such as phenol novolac epoxy resin, cresol novolac epoxy resin and bisphenol A novolak type epoxy resin. Type epoxy resin; epoxidized product of dicyclopentadiene type phenolic resin obtained by reacting dicyclopentadiene with phenol; biphenyl type epoxy resin such as epoxidized product of 2,2 ′, 6,6′-tetramethylbiphenol; naphthalene Epoxy resins having a skeleton; aromatic epoxy resins such as epoxy resins having a fluorene skeleton, and hydrogenated products of these aromatic epoxy resins; ethylene glycol diglycidyl ether, Aliphatic epoxy resins such as ethylene glycol diglycidyl ether, neopentyl glycol diglycidyl ether, 1,6-hexanediol diglycidyl ether; 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate, bis- ( 3,4-epoxycyclohexyl) adipate and other alicyclic epoxy resins; and triglycidyl isocyanurate and other heterocyclic ring-containing epoxy resins.

  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, a bisphenol type epoxy resin and a biphenyl type epoxy are used. It is preferable to contain at least one of the resins.

  The relationship between the amount of polyamideimide resin contained in the thermosetting resin composition according to one embodiment of the present invention and the amount of thermosetting material such as epoxy resin is not limited. From the viewpoint of enhancing the mechanical properties, heat resistance, etc. of the cured product of the thermosetting resin composition according to one embodiment of the present invention, the acid value (carboxyl group equivalent) of the polyamideimide resin and the thermosetting material such as an epoxy resin The ratio of the reactive functional group equivalent is preferably 0.6 or more and 1.3 or less, and 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 thermosetting accelerator. That is, the thermosetting resin composition according to an embodiment of the present invention may contain a polyamideimide resin, an epoxy resin, and a thermosetting accelerator according to an embodiment of the present invention.

  In the case where the thermosetting resin composition according to one embodiment of the present invention contains a thermosetting accelerator, the type of the thermosetting accelerator is not limited. The thermosetting accelerator may be composed of one kind of substance, or may be composed of a plurality of kinds of substances.

  Specific examples of the thermosetting accelerator include tertiary amine compounds, quaternary ammonium salts, imidazoles, phosphine compounds, phosphonium salts and the like. More specifically, tertiary amine compounds such as triethylamine, triethylenediamine, benzyldimethylamine, 2,4,6-tris (dimethylaminomethyl) phenol, 1,8-diazabicyclo (5,4,0) undecene-7 Imidazoles such as 2-methylimidazole, 2,4-dimethylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole; triphenylphosphine, tributylphosphine, tri (p Phosphine compounds such as -methylphenyl) phosphine and tri (nonylphenyl) phosphine; phosphonium salts such as tetraphenylphosphonium tetraphenylborate and tetraphenylphosphonium tetranaphthoate borate; triphenylphosphoniophenola DOO, such betaine-like organic phosphorus compound in the reaction products of benzoquinone and triphenyl phosphine and the like.

  What is necessary is just to set suitably the hardening conditions (hardening temperature, hardening time, etc.) of the thermosetting resin composition which concerns on one Embodiment of this invention according to the component contained in a thermosetting resin composition. As an example of the curing conditions, the curing temperature may be 80 ° C. or more and 300 ° C. or less, and the curing time may be 30 minutes to 6 hours.

  The embodiment described above is described for facilitating understanding of the present invention, and is not described for limiting the present invention. Therefore, each element disclosed in the above embodiment is intended to include all design changes and equivalents belonging to the technical scope of the present invention.

  The present invention will be described more specifically with reference to the following examples. However, the present invention is not limited to these examples.

(Synthesis Example 1)
In a four-necked 300 mL flask equipped with a nitrogen gas inlet tube, a thermometer, and a stirrer, 3.65 g of 3,5-diaminobenzoic acid, modified silicone oil (manufactured by Shin-Etsu Chemical Co., Ltd., product name “X-22-9409”, Amine equivalent 680 g / eq) 18.36 g and γ-butyrolactone 76.80 g were charged and dissolved at room temperature.

  Next, 13.38 g of cyclohexane-1,2,4-tricarboxylic acid-1,2-anhydride and 2.16 g of trimellitic anhydride were charged and kept at room temperature for 30 minutes. Furthermore, 30 g of toluene was added, the temperature was raised to 160 ° C., water generated together with toluene was removed, and the mixture was kept for 3 hours and cooled to room temperature to obtain an imidized product solution.

  The obtained imidized product solution was charged with 7.20 g of trimellitic anhydride and 13.41 g of trimethylhexamethylene diisocyanate, and kept at a temperature of 160 ° C. for 32 hours. Thus, a polyamideimide resin solution (A-1) containing a carboxyl group was obtained. The solid content was 41.5% and the solid content acid value was 80.5 mgKOH / g.

(Synthesis Example 2)
In a four-necked 300 mL flask equipped with a nitrogen gas inlet tube, a thermometer, and a stirrer, 2.44 g of 3,5-diaminobenzoic acid, modified silicone oil (manufactured by Shin-Etsu Chemical Co., Ltd., product name “X-22-9409”, Amine equivalent 680 g / eq) 23.59 g and γ-butyrolactone 80.86 g were charged and dissolved at room temperature.

Next, 11.90 g of cyclohexane-1,2,4-tricarboxylic acid-1,2-anhydride and 1.92 g of trimellitic anhydride were charged and held at room temperature for 30 minutes. Furthermore, 30 g of toluene was added, the temperature was raised to 160 ° C., water generated together with toluene was removed, and the mixture was kept for 3 hours and cooled to room temperature to obtain an imidized product solution.

  To the obtained imidized product solution, 1.92 g of trimellitic anhydride, 4.63 g of cyclohexane-1,2,4-tricarboxylic acid-1,2-anhydride and dicyclohexylmethane-4,4′-diisocyanate 13. 12 g was charged and kept at a temperature of 160 ° C. for 32 hours. Thus, a polyamideimide resin solution (A-2) containing a carboxyl group was obtained. The solid content was 42.0%, and the solid content acid value was 80.2 mgKOH / g.

(Synthesis Example 3)
In a four-necked 300 mL flask equipped with a nitrogen gas inlet tube, a thermometer, and a stirrer, 2.85 g of 3,5-diaminobenzoic acid, modified silicone oil (manufactured by Shin-Etsu Chemical Co., Ltd., product name “X-22-9409”, Amine equivalent 680 g / eq) 18.36 g, 2,2-bis [4- (4-aminophenoxy) phenyl] propane (hereinafter referred to as “BAPP”) 2.16 g and γ-butyrolactone 80.86 g were charged at room temperature. Dissolved.

  Next, 13.38 g of cyclohexane-1,2,4-tricarboxylic acid-1,2-anhydride and 2.16 g of trimellitic anhydride were charged and kept at room temperature for 30 minutes. Furthermore, 30 g of toluene was added, the temperature was raised to 160 ° C., water generated together with toluene was removed, and the mixture was kept for 3 hours and cooled to room temperature to obtain an imidized product solution.

  The obtained imidized product solution was charged with 7.20 g of trimellitic anhydride and 13.12 g of trimethylhexamethylene diisocyanate, and kept at a temperature of 160 ° C. for 32 hours. In this way, a carboxyl group-containing polyamideimide resin solution (A-3) was obtained. The solid content was 43.4%, and the solid content acid value was 71.2 mgKOH / g.

(Synthesis Example 4)
In a four-necked 300 mL flask equipped with a nitrogen gas inlet tube, a thermometer, and a stirrer, 1.64 g of 3,5-diaminobenzoic acid, modified silicone oil (manufactured by Shin-Etsu Chemical Co., Ltd., product name “X-22-9409”, Amine equivalent 680 g / eq) 26.11 g and γ-butyrolactone 79.24 g were charged and dissolved at room temperature.

  Next, 10.11 g of cyclohexane-1,2,4-tricarboxylic acid-1,2-anhydride and 2.31 g of trimellitic anhydride were charged and kept at room temperature for 30 minutes. Furthermore, 30 g of toluene was added, the temperature was raised to 160 ° C., water generated together with toluene was removed, and the mixture was kept for 3 hours and cooled to room temperature to obtain an imidized product solution.

  To the obtained imidized product solution, 1.73 g of trimellitic anhydride, 4.16 g of cyclohexane-1,2,4-tricarboxylic acid-1,2-anhydride and dicyclohexylmethane-4,4′-diisocyanate were added. 81 g was charged and kept at a temperature of 160 ° C. for 32 hours. In this way, a carboxyl group-containing polyamideimide resin solution (A-4) was obtained. The solid content was 45.0% and the solid content acid value was 64.1 mgKOH / g.

(Synthesis Example 5)
In a four-necked 300 mL flask equipped with a nitrogen gas inlet tube, a thermometer, and a stirrer, 1.83 g of 3,5-diaminobenzoic acid, modified silicone oil (manufactured by Shin-Etsu Chemical Co., Ltd., product name “X-22-9409”, Amine equivalent 680 g / eq) 24.48 g and γ-butyrolactone 84.54 g were charged and dissolved at room temperature.

  Next, 21.40 g of cyclohexane-1,2,4-tricarboxylic acid-1,2-anhydride and 3.46 g of trimellitic anhydride were charged and held at room temperature for 30 minutes. Furthermore, 30 g of toluene was added, the temperature was raised to 160 ° C., water generated together with toluene was removed, and the mixture was kept for 3 hours and cooled to room temperature to obtain an imidized product solution.

  9.44 g of dicyclohexylmethane-4,4′-diisocyanate was charged into the imidized product solution obtained and kept at a temperature of 160 ° C. for 32 hours to obtain a carboxyl group-containing polyamideimide resin solution (A-5). . The solid content was 42.2%, and the solid content acid value was 74.3 mgKOH / g.

(Comparative Synthesis Example 1)
BAPP 10.26 g, 3.5-diaminobenzoic acid 3.80 g and γ-butyrolactone 79.48 g were charged and dissolved in a four-necked 300 mL flask equipped with a nitrogen gas inlet tube, a thermometer and a stirrer 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 charged and held at room temperature for 30 minutes. Furthermore, 30 g of toluene was added, the temperature was raised to 160 ° C., water generated together with toluene was removed, and the mixture was kept for 3 hours and cooled to room temperature to obtain an imidized product solution.

  The obtained imidized product solution was charged with 9.61 g of trimellitic anhydride and 17.87 g of trimethylhexamethylene diisocyanate, and kept at a temperature of 160 ° C. for 32 hours. In this way, a carboxyl group-containing polyamideimide resin solution (B-1) was obtained. The solid content was 40.2%, and the solid content acid value was 89.8 mgKOH / g.

(Comparative Synthesis Example 2)
In a four-necked 300 mL flask equipped with a nitrogen gas inlet tube, a thermometer, and a stirrer, 3,5-diaminobenzoic acid 2.19 g, modified silicone oil (manufactured by Shin-Etsu Chemical Co., Ltd., product name “X-22-9409”, Amine equivalent 680 g / eq) 21.22 g and N-methylpyrrolidone 72.06 g were charged and dissolved at room temperature.

  Next, 12.10 g of trimellitic anhydride was charged and held at room temperature for 30 minutes. Furthermore, 30 g of toluene was added, the temperature was raised to 160 ° C., water generated together with toluene was removed, and the mixture was kept for 3 hours and cooled to room temperature to obtain an imidized product solution.

  The obtained imidized product solution was charged with 5.76 g of trimellitic anhydride and 11.102 g of dicyclohexylmethane-4,4'-diisocyanate and kept at a temperature of 160 ° C. for 32 hours. In this way, a carboxyl group-containing polyamideimide resin solution (B-2) was obtained. The solid content was 41.4%, and the solid content acid value was 79.7 mgKOH / g.

[Test Example 1] Evaluation of Alkali Solubility of Polyamideimide Resin The polyamideimide resin solution obtained in the above synthesis examples and comparative synthesis examples was applied to a glass plate, dried at 180 ° C. for 30 minutes, and cooled to room temperature. The film on the glass plate thus obtained was immersed in a 1% by mass aqueous sodium carbonate solution and a 1% by mass aqueous sodium hydroxide solution together with the glass plate. The state of the film after being immersed in each aqueous solution was observed and judged according to the following criteria. The determination results are shown in Table 1.
A: Dissolved within 30 minutes.
B: Dissolved within 60 minutes.
C: Dissolved within 2 hours.
D: Not dissolved.

[Test Example 2] Measurement of light transmittance Obtained by diluting the polyamideimide resin solution obtained in the above synthesis examples and comparative synthesis examples with γ-butyrolactone so that the resin content is 0.25% by mass. About the diluted solution, the transmittance | permeability of the wavelength of 365 nm and 405 nm was measured using Shimadzu Corporation ultraviolet-visible spectrophotometer UV-1800. The measurement results are shown in Table 1.

Test Example 3 Evaluation of Alkali Solubility of Thermosetting Resin Composition Polyamideimide resin varnish composed of a polyamideimide resin solution obtained by the above synthesis examples and comparative synthesis examples, bisphenol A type liquid epoxy resin (manufactured by Mitsubishi Chemical Corporation) It contains a thermosetting material consisting of “jER (registered trademark) 828”, an epoxy equivalent of 185 g / eq), and a thermosetting accelerator (“TPP-MK” (registered trademark) manufactured by Hokuko Chemical Co., Ltd.). A thermosetting resin composition comprising a mixture having the following composition was prepared.

The obtained thermosetting resin composition is applied to a copper foil so that the dry film thickness is 25 μm, and dried at a temperature of 90 ° C. for 30 minutes, whereby a dry film of the thermosetting resin composition is formed on the copper foil. Got. This dry film was developed using an alkaline developing machine ("DV-40L" manufactured by Alps Engineering Co., Ltd.) using a 1 mass% sodium carbonate aqueous solution at a temperature of 30 ° C and a spray pressure of 0.2 MPa. Evaluation was made according to the following criteria, and the alkali solubility of the thermosetting resin composition was evaluated.
A: Development was possible within 60 seconds.
B: Development was possible within 90 seconds.
C: Development was possible within 180 seconds.
D: Development was not possible.
The evaluation results are shown in Table 2.

Test Example 4 Measurement of Tensile Elastic Modulus, Tensile Strength, and Elongation Rate of Cured Product A thermosetting resin composition prepared with the composition shown in Table 2 was applied to the glossy surface of copper foil, and a temperature of 90 ° C. in an oven. For 30 minutes to obtain a dry film. Subsequently, the dried film was heated at 180 ° C. for 60 minutes to cure the thermosetting resin composition in the dried film to obtain a cured product. The obtained cured product was peeled from the copper foil to produce a 50 μm cured film. This cured film was cut into a size of 10 mm × 150 mm, and used as a sample (test piece type 2) for measuring the properties of the cured product.

Various mechanical properties of the samples were measured. The measuring apparatus, measurement conditions, etc. were as follows.
The measurement results are shown in Table 2.
Measuring equipment: “Autograph AG-Xplus” manufactured by Shimadzu Corporation
Tensile speed: 2.5 mm / min Table 2 shows the measurement results.

[Test Example 5] Measurement of glass transition temperature A cured film was prepared in the same manner as in Test Example 2, and then cut into a size of 5 mm x 15 mm to obtain a sample for measuring the glass transition temperature. The glass transition temperature of this sample was measured. The measuring apparatus, measurement conditions, etc. were as follows. The measurement results are shown in Table 2.
Measuring instrument: “TMA8310evo” manufactured by Rigaku Corporation
Atmosphere: In nitrogen Measurement temperature: 25-250 ° C

[Test Example 6] Measurement of 5% weight reduction temperature A cured film produced by the same method as in Test Example 1 was cut out to obtain a sample for measuring the 5% weight reduction temperature. The obtained sample was charged into a measurement container, and its 5% weight loss temperature was measured. The measuring apparatus, measurement conditions, etc. were as follows. The measurement results are shown in Table 2.
Measuring instrument: Rigaku TG8120
Atmosphere: In air Measurement temperature: 25-400 ° C

  Polyamideimide resins according to the examples (Examples 1-1 to 1-5) are excellent in alkali solubility. Moreover, the thermosetting resin composition (Example 2-1 to 2-5) which concerns on an Example is excellent in alkali solubility. The cured product (Examples 2-1 to 2-5) of the thermosetting resin composition according to the examples is excellent in mechanical properties and heat resistance. On the other hand, the polyamideimide resin according to Comparative Example 1-1 that did not use the modified silicone oil had poor alkali solubility. Polyamideimide resin according to Comparative Example 1-2 in which cyclohexane-1,2,4-tricarboxylic acid-1,2-anhydride (e) was not used is poor in both alkali solubility and light transmittance. Met. The thermosetting resin composition using the polyamide-imide resin according to these comparative examples was inferior in alkali solubility (Comparative Examples 2-1 and 2-2).

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

  The thermosetting resin composition provided by the present invention is a composition that can give a cured product excellent in alkali solubility, mechanical properties and heat resistance, and in one specific example, a thermosetting resin containing an epoxy resin. It is an adhesive resin composition.

  Since the cured product of the thermosetting resin composition containing the polyamideimide resin of the present invention is excellent in mechanical properties and heat resistance, the polyamideimide resin of the present invention is an insulating material, an adhesive, and a film of a flexible printed wiring board. It can be used as a raw material resin, a circuit board coating material, and the like.

Claims (16)

A polyamide-imide resin obtained by reacting an imidized product (A) and a reaction raw material (α) containing a diisocyanate compound (h),
The imidized product (A) is obtained by reacting the diamine compound (B) with the acid anhydride (C),
The diamine compound (B) includes a polysiloxane diamine (a) represented by the following general formula (1) and a carboxyl group-containing diamine (b),
The acid anhydride (C) for obtaining the imidized product (A) includes cyclohexane-1,2,4-tricarboxylic acid-1,2-anhydride (e),
The polyamide-imide resin contains a carboxyl group and has a solid content acid value of 30 mgKOH / g or more.
Here, in the general formula (1), a represents an integer of 1 or more, and b represents an integer of 0 or more. R ₁ and R ₂ are each independently an alkylene group having 1 to 5 carbon atoms.   The polyamideimide resin according to claim 1, wherein the acid anhydride (C) further contains trimellitic anhydride (d).   The amount of trimellitic anhydride (d) used is such that the molar ratio to the amount of cyclohexane-1,2,4-tricarboxylic acid-1,2-anhydride (e) used is 4 or less. Item 3. Polyamideimide resin according to Item 2.   The polyamidoimide resin as described in any one of Claim 1 to 3 whose amine equivalent of the said polysiloxane diamine (a) is 300 g / eq or more and 2500 g / eq or less.   The polyamide imide resin according to any one of claims 1 to 4, wherein the diamine compound (B) includes a diamine (c) other than the polysiloxane diamine (a) and the carboxyl group-containing diamine (b).   The polyamideimide resin according to any one of claims 1 to 5, wherein the diisocyanate compound (h) is an aliphatic diisocyanate.   The polyamideimide resin according to any one of claims 1 to 6, wherein the reaction raw material (α) further contains an acid anhydride (β). The polyamide according to claim 7, wherein the acid anhydride (β) includes at least one of trimellitic anhydride (f) and cyclohexane-1,2,4-tricarboxylic acid-1,2-anhydride (g). Imide resin. A method for producing a polyamide-imide resin according to any one of claims 1 to 6,
A reaction raw material (α) containing an imidized product (A) and a diisocyanate compound (h) is reacted to obtain a polyamideimide resin as a reaction product,
The imidized product (A) is obtained by reacting the diamine compound (B) with the acid anhydride (C),
The diamine compound (B) includes a polysiloxane diamine (a) represented by the general formula (1) of claim 1 and a carboxyl group-containing diamine (b),
The acid anhydride (C) includes cyclohexane-1,2,4-tricarboxylic acid-1,2-anhydride (e),
The method for producing a polyamide-imide resin, wherein the polyamide-imide resin contains a carboxyl group and has a solid content acid value of 30 mgKOH / g or more.   The method for producing a polyamide-imide resin according to claim 9, wherein the reaction raw material (α) further contains an acid anhydride (β).   The polyamide according to claim 10, wherein the acid anhydride (β) comprises at least one of trimellitic anhydride (f) and cyclohexane-1,2,4-tricarboxylic acid-1,2-anhydride (g). Manufacturing method of imide resin.   The production amount of the polyamide-imide resin according to claim 10 or 11, wherein the diamine compound (B) is used in an amount such that a molar ratio to a use amount of the acid anhydride (β) is ¼ or more and 4 or less. Method.   A thermosetting resin composition comprising the polyamideimide resin according to any one of claims 1 to 8 and a thermosetting material.   The thermosetting resin composition according to claim 13, wherein the thermosetting material is an epoxy resin.   The thermosetting resin composition according to claim 13 or 14, further comprising a thermosetting accelerator.   Hardened | cured material of the thermosetting resin composition as described in any one of Claim 13 to 15.