JP5722951B2 - Method for producing polyimide derivative - Google Patents

Description

  The present invention relates to a method for producing a polyimide derivative composed of polyamideimide (PAI), polyesterimide (PEI) and polyesteramideimide (PEAI), and the reaction product contains secondary substances such as water, lower alcohol, carbon dioxide and other volatile low molecular compounds. Since there is no raw material, it is possible to produce film moldings and heat compression moldings with excellent mechanical strength and heat resistance by eliminating the occurrence of craters and voids, and thermocompression bonding adhesives with excellent adhesive strength Provide what you can.

Polyimide (PI) is widely used in aerospace materials, automotive parts materials, heat-resistant materials, electronic materials, etc. because of its excellent properties such as heat resistance, mechanical strength, chemical resistance, and insulation. On the contrary, the point which is excellent in heat resistance and heat resistance becomes a bottleneck, and there is a disadvantage that it is insoluble in a solvent, is infusible thermally, and is inferior in moldability.
For this reason, in order to produce a polyimide molded body for practical use, in most cases, first, a polyamic acid precursor is produced by reacting an aromatic or aliphatic tetracarboxylic acid with an aromatic or aliphatic diamine. The precursor solution is cast on a support to form a film, the solvent is evaporated, and a polyimide film is produced by thermal imidization by heating or chemical imidation reaction based on the dehydrating action of acetic anhydride. However, since these have polyamic acid as an intermediate, it cannot be avoided that defects such as voids occur in the film accompanied by desorption of water molecules.
Also, in other molding methods that use a polyamic acid as a precursor and do not involve a solvent, such as thermal compression molding, the imidization reaction via the polyamic acid itself is a condensation reaction that involves elimination of water molecules. There are harmful effects such as creating voids.

On the other hand, when an amide bond or an ester bond is introduced into the polymer main chain of polyimide, the heat resistance is slightly inferior, but it is known that the insolubility and infusibility which are disadvantages of polyimide are improved. The polyamidoimide has a decomposition start temperature of 362 ° C., a 10% weight loss temperature of 410 ° C., and has practically sufficient heat resistance and solvent solubility.
The production method of polyamideimide (PAI) is roughly classified into “acid chloride method” and “isocyanate method”. In “acid chloride method”, for example, trimellitic acid chloride and diaminodiphenylmethane are reacted to obtain polyamic acid, This is dehydrated by heating and cyclized imidized to synthesize PAI (see, for example, JP 2000-0663520 A). In the “isocyanate method”, for example, PAI is synthesized by reacting trimellitic anhydride and diphenylmethane diisocyanate.
All of these are characterized by a polycondensation reaction, and water is generated and by-produced in the “acid chloride method” and carbon dioxide gas is generated as a by-product in the “isocyanate method” when an imide bond is formed.

Accordingly, a conventional technique for producing polyimide derivatives such as PAI and PEI will be described with reference to the publication as follows.
For example, in Patent Document 1, aromatic tetracarboxylic acid and bisoxazoline are polymerized to obtain a solvent solution of polyester amic acid (Claim 1), and this polyester amic acid solution is heated or other methods (solution casting) The polyester imide (PEI) film is manufactured by imidizing by the method etc., and bridge | crosslinking (Claim 8, Paragraphs 22, 31, and 17).
The characteristic of the above reaction lies in the generation of PEI by an imidization reaction via a polyester amide acid (see paragraph 22), which is considered to be based on a polycondensation reaction. A suitable example of the aromatic tetracarboxylic acid is biphenyltetracarboxylic acid (see paragraph 26), and examples of other tetracarboxylic acids used as part of the aromatic tetracarboxylic acid component include dianhydride. (See paragraph 29).

  In Patent Document 2, an aromatic polyamideimide precursor is produced by a reaction of an aromatic amide with an aromatic carboxylic acid anhydride and an aromatic carboxylic acid anhydride substituted with a phenylethynyl group, and the precursor belonging to polyamic acid. The body is heated as a solid, or heated in a solution, or chemically dehydrated and closed using a dehydrating agent to produce an aromatic polyamideimide (PAI) (paragraphs 24 to 25 and paragraphs 29 to 30). .

In Patent Document 3, a tetracarboxylic dianhydride having an ester bond and an amide bond is reacted with an aromatic or aliphatic diamine to produce a polyamic acid as a precursor, and the polyamic acid is heated with a dehydrating imide. Polyamide amideimide (PEAI) is produced by simultaneously introducing an amide group and an ester group into the polymer main chain of the polyimide by forming or chemically imidizing.

As described above, the conventional production methods that disclose or propose polyimide derivatives such as PAI and PEI that are excellent in heat resistance and molding processability are both based on the polycondensation method.
When PAI and PEI are produced by the polycondensation method, when a molded body is obtained by heat compression molding or transfer molding, the released low molecular weight compound is not discharged from the molded body, and molding defects such as voids and surface roughness and mechanical This causes a decrease in the mechanical strength and causes a bonding failure when applied to a thermocompression bonding adhesive.
In addition, there is a method of preparing a varnish in which a polyamide amide acid precursor that gives PAI or polyester amide acid that gives PEI is dissolved in a solvent, casting this, and thermal imidizing to obtain a film. Therefore, at the time of rapid thermal imidization or film thickness film formation, pinholes and crater-like bubble traces are generated due to volatilization of the detached low molecular weight compound, resulting in poor appearance.
When manufacturing PAI and PEI, the polymer itself, which has completed imidation reaction and high molecular weight, can be used as a varnish by dissolving it in a solvent. There is a limit to it.

JP 2007-262367 A JP 2005-239838 A JP 2010-111783 A

  The present invention is not a polycondensation reaction, but another method that does not involve the by-product of a volatile low molecular weight compound, and has no molding defects such as voids and surface roughness, and has improved mechanical strength and heat resistance. Development of a new method capable of producing various polyimide derivatives of polyester imide or polyester amide imide is a technical issue.

The present inventor conceived a new production method based on a polyaddition reaction without using a polycondensation reaction attributed to elimination of water molecules and the like, and as a result of repeated earnest research to solve the conventional problems, It was found that a polyaddition reaction proceeds smoothly between tetracarboxylic dianhydride and a cyclic amidine compound and / or a cyclic imino ether compound.
In the polymerization reaction, polyamide imide, polyester imide, or polyester amide imide in which imide bonds that maintain physical properties such as heat resistance and mechanical strength are incorporated in the polymer main chain at as high a concentration as possible can be produced. The present invention was completed by discovering that a molded film free from voids and surface roughness, or a thermocompression bonding adhesive free from adhesion failure can be produced as much as low molecular weight compounds such as the above are eliminated.

That is, the present invention 1 includes (A) tetracarboxylic dianhydride,
(B) a polyaddition reaction with at least one amidine compound selected from the group consisting of bis or tris type 2-substituted-2-imidazolines and bis or tris type 2-substituted-2-tetrahydropyrimidines; A method for producing a polyimide derivative, characterized by producing polyamideimide (PAI).

In the present invention 2, compound (A) is tetracarboxylic dianhydride,
Compound (C) is at least one iminoether compound selected from the group consisting of bis or tris type 2-substituted-2-oxazolines, bis or tris type 2-substituted-2-oxazines,
A first step of subjecting the compound (A) and the compound (C) to a prepolyaddition reaction in the presence of a solvent to obtain a liquid composition of an intermediate polymer; and in the presence or absence of a small amount of solvent. It is a method for producing a polyimide derivative, comprising a second step of obtaining a film-formed product or a molded product by imidation rearrangement reaction of the intermediate polymer .

Invention 3 comprises (A) tetracarboxylic dianhydride;
(B) at least one amidine compound selected from the group consisting of bis or tris type 2-substituted-2-imidazolines, bis or tris type 2-substituted-2-tetrahydropyrimidines;
(C) a polyaddition reaction with at least one iminoether compound selected from the group consisting of bis or tris type 2-substituted-2-oxazolines and bis or tris type 2-substituted-2-oxazines; A method for producing a polyimide derivative, comprising producing a polyesteramidoimide (PEAI).

The present invention 4 is the invention 1, wherein the compound (A) in the presence of a solvent,
At least one amidine compound (B) selected from the group consisting of bis or tris type 2-substituted-2-imidazolines and bis or tris type 2-substituted-2-tetrahydropyrimidines;
A method for producing a polyimide derivative, characterized in that a liquid composition is obtained by a polyaddition reaction .

Invention 5 provides the compound (A) according to the invention 1 described above in the presence of a solvent,
At least one amidine compound (B) selected from the group consisting of bis or tris type 2-substituted-2-imidazolines and bis or tris type 2-substituted-2-tetrahydropyrimidines;
A first step of pre-addition reaction to obtain a liquid composition of the intermediate polymer;
It is a method for producing a polyimide derivative, comprising a second step of obtaining a film-formed product or a molded product by subjecting the intermediate polymer to an imidation rearrangement reaction in the presence of a small amount of solvent or in the absence of a solvent .

The present invention 6 relates to the present invention 1, 3, 4 or 5, wherein the bis-type imidazolines (B) are 2,2'-bi (2-imidazoline), 2,2 '-(ethylene) bis (2 -Imidazoline), 2,2 '-(tetraethylene) bis (2-imidazoline), 2,2'-(1,3-phenylene) bis (2-imidazoline), 2,2 '-(1,4-phenylene) ) Bis (2-imidazoline), 2,2 '(1,3-phenylene) bis (1-methyl-2-imidazoline), 2,2' (1,3-phenylene) bis (1-ethyl-2-imidazoline) ), 2,2 '(1,4-phenylene) bis (1-methyl-2-imidazoline), 2,2' (1,4-phenylene) bis (1-ethyl-2-imidazoline) At least one kind
Tris-type imidazolines (B) are 1,3,5-tris (2-imidazolin-2-yl) benzene, 1,3,5-tris (1-methyl-2-imidazolin-2-yl) benzene, 1,3,5-tris (1-ethyl-2-imidazolin-2-yl) benzene is at least one selected from the group consisting of tris-type tetrahydropyrimidines (B) A method for producing a polyimide derivative, which is (1,4,5,6-tetrahydropyrimidin-2-yl) benzene.

The present invention 7 relates to the present invention 2 or 3, wherein the bis-type oxazoline (C) is 2,2 '-(1,3-phenylene) bis (2-oxazoline), 2,2'-(1, And at least one selected from the group consisting of 4-phenylene) bis (2-oxazoline) ,
A method for producing a polyimide derivative, wherein the tris-type oxazoline (C) is 1,3,5-tris (2-oxazolin-2-yl) benzene .

Invention 8 relates to any one of Inventions 1 to 5 , wherein the tetracarboxylic dianhydride (A) is bicyclo [2,2,2] oct-7-ene-2,3,5,6-tetra. Carboxylic dianhydride, pyromellitic dianhydride, 3,3 ', 4,4'-benzophenone tetracarboxylic dianhydride, 3,3'4,4'-biphenyltetracarboxylic dianhydride, bis ( 3,4-dicarboxyphenyl) ether dianhydride, 9,9-bis [4- (3,4-dicarboxyphenyl) phenyl] fluorene dianhydride , a polyimide oligomer having a succinic anhydride group at the end, A polyimide derivative characterized in that it is at least one selected from the group consisting of a polyimide oligomer having a phthalic anhydride group, a polyamideimide oligomer having a succinic anhydride group at the end, and a polyamideimide oligomer having a phthalic anhydride group at the end Is a manufacturing method of .

Polyamideimide without the elimination of low molecular weight compounds such as water and lower alcohols, because tetracarboxylic dianhydride and a specific cyclic amidine compound or cyclic imino ether compound are selected and polyadded to the reaction product. Polyimide derivatives made of polyester imide or polyester amide imide can be produced smoothly.
In the polyaddition reaction of the present invention, unlike the conventional polycondensation method such as Patent Document 1, a volatile low molecular weight compound is not by-produced. Thus, it is possible to easily produce a film molded body having a smooth surface without the defects of the air bubble trace. In heat compression molding or transfer molding, it is possible to produce a molded article that is free from voids and surface roughness and has no reduction in mechanical strength or heat resistance.
Moreover, since there is no defect of the bubble trace, a thermocompression bonding adhesive having no adhesion failure can be produced.

In the polyaddition reaction of the present invention, a series of reactions are allowed to proceed in a solution, and the product can be used as it is as a liquid composition (varnish) for coatings or the like. After obtaining a liquid composition of an intermediate polymer The film can also be formed by imidizing dislocation by performing a heat treatment after film formation by a casting method.
In this case, when an oligomer having a terminal acid anhydride group is used for the compound (A), there is an advantage that a varnish having an appropriate viscosity can be efficiently produced, and a tris-type compound (B ) And / or (C) to be imidized has the advantage that the mechanical properties and chemical resistance of the polyimide derivative can be improved by introducing a crosslinked structure.

In the present invention, first, (A) a tetracarboxylic dianhydride and (B) a bis- or tris-type 5-membered or 6-membered amidine compound are subjected to a polyaddition reaction to produce a polyamideimide (PAI). Second, the component (A) is subjected to a polyaddition reaction between the component (A) and (C) a bis or tris type 5-membered or 6-membered iminoether compound , This is a method for producing a polyesterimide (PEI) by a two-stage reaction method in which the intermediate polymer obtained in the preliminary reaction is subjected to imidation rearrangement (see the present invention 2), and thirdly, the component (A), This is a method for producing a polyesteramidoimide (PEAI) by subjecting component (B) and component (C) to a polyaddition reaction (see Invention 3).
That is, the present invention 2 is a polyaddition reaction by the above two-stage method (corresponding to the second embodiment described later), but the present invention 1 or 3 does not have such a restriction.
The polyimide derivative of the present invention is a superordinate concept including the above PAI, PEI and PEAI. PAI is a polymer repeating unit in which imide bond units are essential and amide bond units coexist, PEI is an ester bond unit coexisting, PEAI is an ester bond unit and amide bond unit coexisting Say.

In the present invention 1, the cyclic amidine compound (B) is a cyclic compound in which one carbon atom has one double atom and one single bond has one nitrogen atom, and is bis or tris type 5 It is selected from membered or six-membered amidine compounds. The 5-membered amidine compound (B) is an imidazoline belonging to a 5-membered heterocyclic compound containing two nitrogen atoms , and the 6-membered amidine compound (B) is a 6-membered heterocyclic compound containing two nitrogen atoms. tetrahydronaphthyl pyrimidines belonging to the compound.
In the second aspect of the present invention, the cyclic iminoether compound (C) is a cyclic compound in which one carbon atom has one double atom and one oxygen atom has a single bond, and is bis or tris. Selected from five-membered or six-membered ring iminoether compounds of the type. The 5-membered ring iminoether compound (C) is an oxazoline belonging to a 5-membered heterocyclic compound containing one nitrogen atom and one oxygen atom , and the 6-membered ring iminoether compound (C) is composed of one nitrogen atom and a belonging oxazines to 6-membered ring heterocyclic compound containing one oxygen atom.

  The cyclic amidine compound (B) or the cyclic imino ether compound (C) of the present invention can be represented by the following general formula (I).

In general formula (I), R does not exist, is a linear, branched or alicyclic alkyl group having 1 to 10 carbon atoms, or an aromatic hydrocarbon group having 6 to 25 carbon atoms, or an alkyl-substituted aromatic. Group hydrocarbon group. Here, the absence of R means that the left and right cyclic structures of the general formula (I) are directly bonded without R.
In addition, the alkyl group and the aromatic hydrocarbon group are directly or independently bonded to each other, or a methylene group (—CH ₂ —), a dimethylmethylene group (—C (CH ₃ ) ₂ —), di (trifluoro) Methylene group (—C (CF ₃ ) ₂ —), ether group (—O—), carbonyl group (—CO—), sulfone group (—SO ₂ —), amide group (—NH (CO) —), ester It may be bonded via one or more groups (—COO—) and one or more groups.
X in the cyclic structure represents an amino group residue represented by NR ₁ or O (oxygen atom). Here, R ₁ is H (hydrogen atom), a linear, branched or alicyclic alkyl group having 1 to 8 carbon atoms represented by R ′, or an aromatic hydrocarbon having 6 to 9 carbon atoms. Group or an alkyl-substituted aromatic hydrocarbon group.
R ₂ , R ₃ , R ₄ and R ₅ bonded to the cyclic structure are each independently H (hydrogen atom), a linear, branched or alicyclic alkyl group having 1 to 8 carbon atoms, or carbon number 6-9 aromatic hydrocarbon groups or alkyl-substituted aromatic hydrocarbon groups, wherein one of R ₂ and R ₃ and one of R ₄ and R ₅ are bonded to each other at an arbitrary position. A cyclic structure of a saturated or unsaturated hydrocarbon having 5 to 7 members may be formed.
M and n are each an integer of 1 or 2, and m and n take the same numerical value, and m = n. p is an integer of 1 or 2. The compound represented by the general formula (I) is a bis form when p = 1 and a tris form when p = 2. When m = n = 1, the cyclic structure is a 5-membered ring, and when m = n = 2, it is a 6-membered ring.

In the present invention, for example, in the case of the bis type 5-membered ring amidine compound (B), the carbon atom position of the imino group is the 2-position of the 5-membered ring, and the position of the bis substitution is also the 5-membered ring. Of these, the bis-type compound (B) is limited to a 2-substituted-2-5-membered amidine compound.
The point that the position of the imino group and the position of bis-substitution are limited is the same as in the case of the bis-type six-membered amidine compound (B). The position is limited to the compound at the 2-position, and the tris-type 5-membered or 6-membered amidine compound (B) is similarly limited to the 2-position compound.
As for the position of the carbon atom of the imino group and the position of bis substitution, in the case of the bis or tris type 5-membered ring or 6-membered ring imino ether compound (C), the imino group (B) is similar to the imino group. Both the position of the carbon atom and the position of the bis substitution are limited to compounds at the 2-position of the 5-membered ring or 6-membered ring.

The 5-membered imidazolines (X = NR ₁ , m = n = 1 in the above formula (I)) include 2,2′-bi (2-imidazoline), 2,2′-bi (4- Methyl-2-imidazoline), 2,2'-bi (5-methyl-2-imidazoline), 2,2 '-(ethylene) bis- (2-imidazoline), 2,2'-(tetramethylene) bis- (2-imidazoline), 2,2 '-(hexamethylene) bis- (2-imidazoline), 2,2'-(octamethylene) bis- (2-imidazoline), 2,2 '-(1,4- Cyclohexylene) bis- (2-imidazoline), 2,2 '(1,2-phenylene) bis (2-imidazoline), 2,2' (1,3-phenylene) bis (2-imidazoline), 2, 2 '(1,4-phenylene) bis (2-imidazoline), 2,2' (1,3-phenylene) bis (4-methyl-2-imidazoline), 2,2 '(1,3-phenylene) bis (5-methyl-2-imidazoline), 2,2 '(1,4-phenylene) bis (4-methyl-2-imidazoline), 2,2' (1,4-pheny ) Bis (5-methyl-2-imidazoline), 2,2 '(1,3-phenylene) bis (1-methyl-2-imidazoline), 2,2' (1,3-phenylene) bis (1- Ethyl-2-imidazoline), 2,2 '(1,3-phenylene) bis (1-phenyl-2-imidazoline), 2,2' (1,4-phenylene) bis (1-methyl-2-imidazoline) 2,2 '(1,4-phenylene) bis (1-ethyl-2-imidazoline), 2,2' (1,4-phenylene) bis (1-phenyl-2-imidazoline), 2,2 '( 1,3-phenylene) bis (1-methyl-5-methyl-2-imidazoline), 2,2 '(1,4-phenylene) bis (1-methyl-5-methyl-2-imidazoline), 2,2 '(1,3-phenylene) bis (1-methyl-4,5-diphenyl-2-imidazoline), 2,2' (1,4-phenylene) bis (1-methyl-4,5-diphenyl-2-) Imidazoline), 2,2 '-(1,3-phenylene) bis (1H-benzimidazole), 2,2'-(1,4-phenylene) bis (1H-benzimidazole), 1,3,5-to (2-imidazolin-2-yl) benzene, 1,3,5-tris (1-methyl-2-imidazolin-2-yl) benzene, 1,3,5-tris (1-ethyl-2-imidazoline- 2-yl) benzene.
Of these, 2,2'-bi (2-imidazoline), 2,2 '-(ethylene) bis- (2-imidazoline), 2,2'-(tetramethylene) bis- (2-imidazoline), 2, 2 '(1,3-phenylene) bis (2-imidazoline), 2,2' (1,4-phenylene) bis (2-imidazoline), 2,2 '(1,3-phenylene) bis (5-methyl) -2-imidazoline), 2,2 '(1,4-phenylene) bis (5-methyl-2-imidazoline), 2,2' (1,3-phenylene) bis (1-methyl-2-imidazoline), 2,2 '(1,3-phenylene) bis (1-ethyl-2-imidazoline), 2,2' (1,4-phenylene) bis (1-methyl-2-imidazoline), 2,2 '(1 , 4-Phenylene) bis (1-ethyl-2-imidazoline) 1,3,5-tris (2-imidazolin-2-yl) benzene, 1,3,5-tris (1-methyl-2-imidazoline-2 -Yl) benzene, 1,3,5-tris (1-ethyl-2-imidazolin-2-yl) benzene are preferred.

The above 6-membered tetrahydropyrimidines (in the above formula (I), X = NR ₁ , m = n = 2) include 2,2′-bi [1,4,5,6-tetrahydropyrimidine], 2 2,2'-bi [4-methyl-1,4,5,6-tetrahydropyrimidine], 2,2'-bi [5-methyl-1,4,5,6-tetrahydropyrimidine], 2,2'- (Ethylene) bis (1,4,5,6-tetrahydropyrimidine) 2,2 '-(tetramethylene) bis (1,4,5,6-tetrahydropyrimidine), 2,2'-(hexamethylene) bis ( 1,4,5,6-tetrahydropyrimidine), 2,2 '-(octamethylene) bis (1,4,5,6-tetrahydropyrimidine), 2,2'-(1,4-cyclohexylene) bis (1,4,5,6-tetrahydropyrimidine), 2,2 '-(1,3-phenylene) bis (1,4,5,6-tetrahydropyrimidine), 2,2'-(1,4-phenylene ) Bis (1,4,5,6-tetrahydropyrimidine), 2,2 ′-(1,3-phenylene) bis (4-methyl-1,4,5,6-tetrahydropyrimidine), 2,2 '-(1,3-phenylene) bis (5-methyl-1,4,5,6-tetrahydropyrimidine), 2,2'-(1,3-phenylene) bis (6-methyl-1, 4,5,6-tetrahydropyrimidine), 2,2 '-(1,4-phenylene) bis (4-methyl-1,4,5,6-tetrahydropyrimidine), 2,2'-(1,4 -Phenylene) bis (5-methyl-1,4,5,6-tetrahydropyrimidine), 2,2 '-(1,4-phenylene) bis (6-methyl-1,4,5,6-tetrahydropyrimidine) 2,2 '-(1,3-phenylene) bis (1-methyl-1,4,5,6-tetrahydropyrimidine), 2,2'-(1,4-phenylene) bis (1-methyl-1) , 4,5,6-tetrahydropyrimidine), 1,3,5-tris (1,4,5,6-tetrahydropyrimidin-2-yl) benzene and the like.
Of these, 2,2 '-(1,3-phenylene) bis (1,4,5,6-tetrahydropyrimidine), 2,2'-(1,4-phenylene) bis (1,4,5,6 -Tetrahydropyrimidine), 2,2 '-(1,3-phenylene) bis (1-methyl-1,4,5,6-tetrahydropyrimidine), 2,2'-(1,4-phenylene) bis (1 -Methyl-1,4,5,6-tetrahydropyrimidine), 1,3,5-tris (1,4,5,6-tetrahydropyrimidin-2-yl) benzene are preferred.

The 5-membered oxazolines (X = O, m = n = 1 in the above formula (I)) include 2,2'-bi (2-oxazoline), 2,2'-bi (4-methyl -2-oxazoline), 2,2'-bi (5-methyl-2-oxazoline), 2,2 '-(ethylene) bis (2-oxazoline), 2,2'-(tetramethylene) bis (2- Oxazoline), 2,2 '-(hexamethylene) bis (2-oxazoline), 2,2'-(octamethylene) bis (2-oxazoline), 2,2 '-(1,4-cyclohexylene) bis- (2-oxazoline), 2,2 '-(1,2-phenylene) bis (2-oxazoline), 2,2'-(1,3-phenylene) bis (2-oxazoline), 2,2 '-( 1,4-phenylene) bis (2-oxazoline), 2,2 '-(1,3-phenylene) bis (4-methyl-2-oxazoline), 2,2'-(1,3-phenylene) bis ( 5-methyl-2-oxazoline), 2,2 '-(1,4-phenylene) bis (4-methyl-2-oxazoline), 2,2'-(1,4-phenylene) bis (5-methyl- 2- Xazoline), 2,2 '-(1,2-phenylene) bis (2-benzoxazole), 2,2'-(1,3-phenylene) bis (2-benzoxazole), 2,2 '-(1 , 4-phenylene) bis (2-benzoxazole), 1,3,5-tris (2-oxazolin-2-yl) benzene and the like.
Of these, 2,2 '-(ethylene) bis (2-oxazoline), 2,2'-(tetramethylene) bis (2-oxazoline), 2,2 '-(1,3-phenylene) bis (2- Oxazoline), 2,2 '-(1,4-phenylene) bis (2-oxazoline), and 1,3,5-tris (2-oxazolin-2-yl) benzene are preferred.

The 6-membered ring oxazines (in the above formula (I), X = O, m = n = 2) include 5,5 ', 6,6'-tetrahydro-2,2'-bi [4H-1 , 3-oxazine], 4-methyl-5,5 ′, 6,6′-tetrahydro-2,2′-bi [4H-1,3-oxazine], 5-methyl-5,5 ′, 6,6 '-Tetrahydro-2,2'-bi [4H-1,3-oxazine], 6-methyl-5,5', 6,6'-tetrahydro-2,2'-bi [4H-1,3-oxazine ], 2,2 '-(ethylene) bis (5,6-dihydro-4H-1,3 oxazine), 2,2'-(tetramethylene) bis (5,6-dihydro-4H-1,3 oxazine) 2,2 '-(hexamethylene) bis (5,6-dihydro-4H-1,3oxazine), 2,2'-(1,4-cyclohexylene) bis (5,6-dihydro-4H- 1,3oxazine), 2,2 '-(1,3-phenylene) bis (5,6-dihydro-4H-1,3oxazine), 2,2'-(1,4-phenylene) bis (5, 6-dihydro-4H-1,3 oxazine), 2,2 '-(1,3-phenylene) bis (4-methyl-5,6-dihydro-4H-1,3 oxazine), 2,2'-( 1,3-F Nylene) bis (5-methyl-5,6-dihydro-4H-1,3oxazine), 2,2 '-(1,3-phenylene) bis (6-methyl-5,6-dihydro-4H-1, 3oxazine), 2,2 '-(1,4-phenylene) bis (4-methyl-5,6-dihydro-4H-1,3oxazine), 2,2'-(1,4-phenylene) bis ( 5-methyl-5,6-dihydro-4H-1,3 oxazine), 2,2 '-(1,4-phenylene) bis (6-methyl-5,6-dihydro-4H-1,3 oxazine) Can be mentioned.
Of these, 2,2 '-(tetramethylene) bis (5,6-dihydro-4H-1,3oxazine) 2,2'-(1,3-phenylene) bis (5,6-dihydro-4H-1 , 3 oxazine), 2,2 '-(1,4-phenylene) bis (5,6-dihydro-4H-1,3 oxazine).

Therefore, the specific compounds listed above will be described based on the compounds represented by the general formula (I).
(1) In the general formula (I), when X = NH, R is absent, m = n = 1, p = 1, R2, R3, R4, R5 is hydrogen, the compound of the above formula (I) is a 5-membered ring 2,2'-bi (2-imidazoline) of the formula

  (2) In the general formula (I), when X = NCH3, R = 1,3-phenylene group, m = n = 1, p = 1, R2, R3, R4, R5 is hydrogen, the above formula (I) This compound is a 5-membered 2,2 '(1,3-phenylene) bis (1-methyl-2-imidazoline) and is represented by the following formula (see Example 1 described later).

  (3) In the general formula (I), when X = NH, R = 1,4-phenylene group, m = n = 1, p = 1, R2, R3, R4 and R5 are hydrogen, the above formula (I) This compound is a 5-membered 2,2 '(1,4-phenylene) bis (2-imidazoline) and is represented by the following formula (see Example 4 described later).

  (4) In general formula (I), when X = NCH 3, R = 1,3,5-trisubstituted phenyl group, m = n = 1, p = 2, R 2, R 3, R 4 and R 5 are hydrogen, The compound of the formula (I) is 5-membered 1,3,5-tris (1-methyl-2-imidazolin-2-yl) benzene and is represented by the following formula (see Example 5 described later).

  (5) In the general formula (I), when X = NCH3, R = 1,4-phenylene group, m = n = 2, p = 1, R2, R3, R4, R5 is hydrogen, the above formula (I) This compound is 6-membered 2,2 '-(1,4-phenylene) bis (1-methyl-1,4,5,6-tetrahydropyrimidine) and is represented by the following formula (Examples described later). 5).

  (5) In the general formula (I), when X = O, R = 1,3-phenylene group, m = n = 1, p = 1, R2, R3, R4 and R5 are hydrogen, the above formula (I) This compound is a 5-membered 2,2 '(1,3-phenylene) bis (2-oxazoline) and is represented by the following formula (see Example 6 described later).

  (6) In the general formula (I), when X = O, R = 1,3-phenylene group, m = n = 2, p = 1, R2, R3, R4 and R5 are hydrogen, the above formula (I) This compound is 6-membered 2,2 '-(1,3-phenylene) bis (5,6-dihydro-4H-1,3oxazine) and is represented by the following formula.

The tetracarboxylic dianhydride (A) used in the present invention can be selected from aliphatic, alicyclic, or aromatic tetracarboxylic dianhydrides. However, this tetracarboxylic dianhydride (A) means vicinal, that is, an anhydride between carboxyl groups bonded to two adjacent carbon atoms.
The compound (A) includes a polymer having a succinic anhydride group or a phthalic anhydride group at its terminal, specifically, a polyimide oligomer having a terminal succinic anhydride group or a phthalic anhydride group, a succinic anhydride group, or A polyamideimide oligomer having a phthalic anhydride group at the terminal can also be selected .
Examples of the aliphatic or alicyclic tetracarboxylic dianhydride include ethylene tetracarboxylic dianhydride, 1,2,3,4-butanetetracarboxylic dianhydride, 1,2,3,4-cyclobutane. Tetracarboxylic dianhydride, 1,2,4,5-cyclopentanetetracarboxylic dianhydride, bicyclo [2.2.2] oct-7-ene-2,3,5,6-tetracarboxylic dianhydride Bicyclo [2.2.2] oct-7-ene-2,3,5,6-tetracarboxylic dianhydride is preferred from the viewpoint of heat resistance and solvent solubility of the varnish.
Aromatic tetracarboxylic dianhydrides include pyromellitic dianhydride, benzene-1,2,3,4-tetracarboxylic dianhydride, 3,3 ', 4,4'-benzophenyltetracarboxylic acid Dianhydride, 2,2 ', 3,3'-benzophenyltetracarboxylic dianhydride, 3,3'4,4'-biphenyltetracarboxylic dianhydride, 2,2', 3,3'- Biphenyltetracarboxylic dianhydride, 2,2-bis (3,4-dicarboxyphenyl) propane dianhydride, 2,2-bis (1,2-dicarboxyphenyl) propane dianhydride, bis (3, 4-dicarboxyphenyl) ether dianhydride, bis (3,4-dicarboxyphenyl) sulfone dianhydride, 1,1-bis (2,3-dicarboxyphenylethane dianhydride, 1,1-bis ( 3,4-dicarboxyphenyl) methane dianhydride, 2,3,6,7-naphthalenetetracarboxylic dianhydride, 1,4,5,8-naphthalenetetracarboxylic dianhydride, 1,2,5 , 6-Naph Talentetracarboxylic dianhydride, perylene-3,4,9,10-tetracarboxylic dianhydride, 2,3,6,7-anthracene tetracarboxylic dianhydride, 1,2,7,8-phenanthrene Tetracarboxylic dianhydride, 9,9-bis [4- (3,4-dicarboxyphenyl) phenyl] fluorene dianhydride, 9,9-bis (4-hydroxyphenyl) fluorene bis (anhydro trimellitate) ), 2,2-bis (3,4-dicarboxyphenyl) hexafluoropropane dianhydride, 4,4′-bis (3,4-dicarboxyphenoxy) octafluorobiphenyl dianhydride, and the like.
Of these, pyromellitic dianhydride, 3,3 ′, 4,4′-benzophenonetetracarboxylic dianhydride, 3,3′4,4′-biphenyltetrahydride are preferred from the viewpoint of heat resistance and mechanical properties. Carboxylic acid dianhydride, bis (3,4-dicarboxyphenyl) ether dianhydride is preferred, and from the viewpoint of solvent solubility of the varnish, 9,9-bis [4- (3,4-dicarboxyphenyl) Phenyl] fluorene dianhydride is preferred.

For example, pyromellitic dianhydride (PMDA) is represented by the following formula (see Examples 1, 3, 6 and the like described later).

3,3 ′, 4,4′-benzophenyltetracarboxylic dianhydride is represented by the following formula (see Example 5 described later).

Among the compounds (A), the polymer having a succinic anhydride group or a phthalic anhydride group at the terminal is composed of an imide bond, an amide bond, or an ester bond in the polymer main chain, and at least one of them. A relatively low molecular weight polymer having a succinic anhydride group or a phthalic anhydride group at the end, that is, an oligomer is meant, but an oligomer having a succinic anhydride group or a phthalic anhydride group at both ends is preferred.
In the case of this terminal acid anhydride group oligomer, even if one end is a succinic anhydride group and the other end is a carboxyl group (not an anhydride structure), bisimidazoline and bisoxazoline are Since it can react to form amide amides and amide esters, it is a polymer that always generates imide bonds with bisimidazolines and bisoxazolines even if it is an acid anhydride group oligomer of one end type rather than both ends. The main chain can be extended to produce a polyimide derivative.
An oligomer having a succinic anhydride group (or phthalic anhydride group) at a terminal preferably used in the present invention is a terminal succinic anhydride (or phthalic anhydride group) polyimide oligomer having a polymer main chain formed of an imide bond. Or a terminal succinic anhydride (or phthalic anhydride group) polyamide-imide oligomer composed of an amide bond and an imide bond and having a molecular weight of 500 to 50,000, preferably 1000 to 30,000 It is.
The terminal succinic anhydride (or phthalic anhydride group) polyimide oligomer can be produced by a known method. For example, tetracarboxylic dianhydride can be obtained by imidation reaction with a diamine compound in an excess molar ratio. it can. The terminal succinic anhydride (or phthalic anhydride group) polyamideimide oligomer can be obtained, for example, by a decarboxyamidimide reaction with a diisocyanate compound at a molar ratio of trimellitic anhydride excess.
As described above, the oligomer is preferably a polymer having acid anhydride groups at both ends. In this case, for example, in order to ensure that both ends are acid anhydride groups, in the first stage reaction, diisocyanate is used. React with trimellitic anhydride in excess to obtain polyamideimide with isocyanate groups at both ends, and in the second stage reaction, react both isocyanate groups with tetracarboxylic dianhydride to acid anhydrides at both ends. It is desirable to introduce a group.

A feature of the present invention is that a tetracarboxylic dianhydride (A) and a specific cyclic amidine compound (B) and / or a cyclic imino ether compound (C) are used as a reaction product to produce polyamideimide (PAI), polyesterimide ( PEI) or a polyester derivative of polyesteramide imide (PEAI) is produced by a polyaddition reaction, and the polymerization method is fundamentally different from the above-mentioned Patent Document 1 in which PEI is obtained through polyesteramido acid.
Therefore, taking the reaction of polymerizing PEI from a tetracarboxylic acid component and bisoxazoline as a representative example, the present invention and Patent Document 1 mentioned above will be compared and considered from the viewpoint of stoichiometry.
First, with respect to Patent Document 1, a specific example is a case where the tetracarboxylic acid component is a free acid type pyromellitic acid and the bisoxazoline is 2,2 ′-(1,3-phenylene) bis (2-oxazoline). The following polymerization reaction is shown.

The molecular formula of one pyromellitic acid (free acid form) of the reactant is nC10H6O8, and the other 2,2 '-(1,3-phenylene) bis (2-oxazoline) of the reactant is nC12H12N2O2, and the product PEI Is (C22H14N2O8) n.
For this reason, looking at the stoichiometry of the reactant and the product, the stoichiometry does not match with the product unless 2n H2O molecules are added to the reactant. It is confirmed that this is a polycondensation reaction in which H 2 O molecules are eliminated upon rearrangement to PEI.

  On the other hand, in the present invention, the case where the tetracarboxylic acid component is pyromellitic dianhydride (PMDA) and the bisoxazoline is 2,2 ′-(1,3-phenylene) bis (2-oxazoline) is a specific example. From the viewpoint of stoichiometry, the molecular formula of one PMDA of the reaction product is nC10H2O6, and the other 2,2 '-(1,3-phenylene) bis (2-oxazoline) is nC12H12N2O2. Since the PEI of (C22H14N2O8) n matches the stoichiometry of the reaction product and the product, it can be judged that the reaction of the present invention is a polyaddition reaction without elimination of H2O molecules.

Therefore, in order to further clarify the difference in the polymerization reaction between the present invention and Patent Document 1 in addition to the above-mentioned stoichiometry, the following will be compared and considered from the viewpoint of the reaction mechanism.
However, the reaction mechanism of the present invention is still unclear, and there are many points that must be estimated, but this intermediate polymer undergoes imidation rearrangement via a certain intermediate polymer, resulting in a polyimide derivative. Can be estimated.
In addition, since the chemical formula of polyester amide acid is not specifically disclosed in Patent Document 1, the reaction mechanism must be estimated.

First, the estimated reaction mechanism of the present invention is as follows.
In the following formula, P is a polymer residue whose terminal is a succinic anhydride group obtained by polyaddition of the compound (A) and the compound (B) or (C), and P ′ is produced similarly. The terminal is a polymer residue having a cyclic amidine group or a cyclic imino ether group.

First, considering the case where X = O in the general formula (I) (that is, the general formula (I) is a bis-type oxazoline compound), in the polyaddition reaction,
(1) The lone pair of nitrogen atoms (as an electric child) of the oxazoline compound (C) nucleophilically attacks the carbon atom of the carbonyl group of the tetracarboxylic dianhydride (A), and the anhydrous compound (A) The product structure is opened, and a 1,3-oxazepine intermediate polymer (II) having a 7-membered ring structure is formed between the nitrogen atom of the oxazoline compound (C) and the adjacent carbon atom.
(2) The nitrogen atom loan pair of the oxazepine intermediate polymer (II) attacks the carbon of the carbonyl group derived from the anhydride structure located on the diagonal side of the seven-membered ring structure to form part of the intermediate While the 7-membered ring structure is rearranged to an imide group structure, the C2-N3 bond derived from the oxazoline ring is cleaved along with this imidization rearrangement reaction, and an ester bond is formed on the opposite side of the imide group. ) Can be estimated.

Next, considering the case of X = NH in the above general formula (I) (for example, when the general formula (I) is a bis-type imidazoline compound), in the polyaddition reaction,
(1) The nitrogen atom loan pair of the imidazoline compound (B) nucleophilically attacks the carbon atom of the carbonyl group of the tetracarboxylic dianhydride (A), and the anhydride structure of the compound (A) opens, and the same structure The carbonyl group located on one side of the imidazoline compound (B) is bonded to the nitrogen atom to form an amide group, and the other carbon side of the anhydride structure becomes a carboxyl group to form a cyclic amidinoamic acid intermediate polymer (III ) Is generated.
(2) The lone pair of the 1st nitrogen atom derived from the imidazoline ring of the cyclic amidinoamidic acid intermediate polymer (III) attacks the carbonyl carbon of the carboxyl group produced from the compound (A) to form an imide group. Accompanying this, simultaneously with the cleavage of the N 1 -C 2 bond of the imidazoline ring, the OH group of the carboxyl group moves to C 2 of the imidazoline ring to form an imidazole group, which then isomerizes and eventually opposes the imide group. It can be presumed that an amide bond is formed in the resulting product to produce polyamideimide (V).

The specific reaction mechanism when PEI is produced by polyaddition is shown. For example, the compound (A) is tetracarboxylic dianhydride, and the bis-type 5-membered ring imino ether compound (C) is 2,2 When ′-(1,3-phenylenene) bis (2-oxazoline) (in the general formula (I), X = O, m = 1, R2 = R3 = R4 = R5 = H), the reaction route is As shown in the following formula, this intermediate undergoes the intramolecular rearrangement described above through the oxazepine intermediate polymer represented by (II-1) to produce polyesterimide (IV-1).
Thus, in the reaction process shown in (Chemical Formula 12) or (Chemical Formula 13), all atoms constituting the reactant are transferred to the product, and low molecular compounds such as water are not eliminated.
For this reason, it turns out that the reaction form of this invention is not a polycondensation reaction but a polyaddition reaction.

On the other hand, in Patent Document 1 described above, an aromatic polyester amide acid is obtained by reacting an aromatic tetracarboxylic acid and an aromatic bisoxazoline (claim 1, paragraph 22), and an aromatic polyester is obtained by imidization reaction. This is a method for producing an imide (claim 8, paragraph 22, paragraph 31).
Although the chemical formula of the aromatic polyester amide acid is not specifically disclosed in the same document 1, since the transition form of imidization rearrangement from the polyester amide acid is specified, it is disclosed in the above-mentioned Patent Document 3. Referring to the structure of the polyamic acid (see claim 3), the reaction route from the polyester amic acid to the final product polyester imide is presumed to be as shown in the following formula.

According to this reaction route, water molecules are eliminated from the OH of the carboxyl group of the polyester amic acid (VI) and the hydrogen atom of the amide group, and an imide ring is formed from two carbonyl carbons and one nitrogen atom. Imide (IV-1) is formed. That is, in the production of polyesterimide in Patent Document 1, it is found that the elimination of one molecule of water is indispensable for each repeating unit of polyester amide acid, and the reaction form is a polycondensation reaction.
Therefore, although the present invention and Patent Document 1 are common in the point of producing a polyimide derivative, Patent Document 1 is a polycondensation reaction, whereas the present invention is a polyaddition reaction that does not involve elimination of a low-molecular compound. In some respects, the reaction forms are fundamentally different.

As described above, the polyaddition reaction between the compound (A) of the present invention and the compounds (B) and / or (C) is basically composed of two processes, ie, an intermediate polymer formation process and an imidation rearrangement process. .
In this case, at a temperature of 150 ° C. or lower, first, a 1,3-oxazepine intermediate polymer (II) or a cyclic amidinoamidic acid intermediate polymer (III) is formed, and these are further heated to at least 160 ° C. or higher. Preferably, the intermediate polymer undergoes an intramolecular rearrangement reaction (imidation rearrangement reaction) to an imide group by heating at a temperature of 180 ° C. or higher, more preferably 200 to 350 ° C., and an imide bond is generated. Then, an amide bond and / or an ester bond is formed, and various polymers of polyamideimide (PAI), polyesterimide (PEI), or polyesteramideimide (PEAI) are formed.
In addition, the rearrangement reaction from the intermediate polymer to PAI or PEI is not necessarily quantitative, and the required physical properties such as heat resistance, mechanical properties and chemical resistance of the obtained PAI and PEI are retained. As long as possible, unrearranged 1,3-oxazepine structure (II) and cyclic amidinoamidic acid structure (III) may be left in the main chain.

In the present invention 3, PEAI is produced by polyaddition of the compound (A), the compound (B) and the compound (C), and the product has an imide bond unit as an essential component in the repeating unit of the polymer. A bond unit and an amide bond unit coexist.
However, in the present invention 1, it is fundamental to obtain PAI by polyadding the compound (A) and the compound (B) which are essential components, and in this case, the compound (C) is further used in combination with the compound (B). The product requires an imide bond unit in the repeating unit of the polymer, and an amide bond unit may coexist with a smaller amount of an ester bond unit.
This point is the same in the case of the present invention 2 based on the fact that PEI is obtained by polyaddition of the compound (A) and the compound (C), and in this case, the combined use of the compound (B) is not excluded. In the product, the imide bond unit is essential in the repeating unit of the polymer, and a smaller amount of the amide bond unit may be present together with the ester bond unit.
That is, the present invention 3 is based on the production of PEAI, whereas the present invention 1 based on the production of PAI coexists with ester bond units in the polymer main chain, and is based on the production of PEI. The present invention 2 does not exclude the presence of amide bond units.

The polyaddition reaction of the present invention is performed in the presence or absence of a solvent depending on the embodiment.
That is, when the polyimide derivative obtained by the polyaddition reaction of the present invention is used as a liquid composition (varnish), the imidation rearrangement reaction is performed in the presence of a solvent (see the present invention 4 ). When the polyimide derivative is used as a cast film or a molded product, the intermediate polymer in the former stage is produced in the presence of a solvent, and the imidation rearrangement reaction in the latter stage is carried out in the presence of a very small amount of solvent or not. The reaction is carried out under a solvent (see Inventions 2 and 5 ).
The above solvents include N-methyl-2-pyrrolidone (NMP), N, N-dimethylacetamide (DMAc), N, N-dimethylformamide (DMF), N, N-diethylacetamide, N, N-dimethylmethoxyacetamide Amide solvents such as 1,3-dimethyl-2-imidazolidinone (DMI), tetramethylurea, N-methylcaprolactam, butyrolactam, sulfur-containing solvents such as dimethylsulfoxide (DMSO), dimethylsulfone, hexamethylphospho Phosphorus amide solvents such as luamide, amine solvents such as pyridine and picoline, ester solvents such as γ-butyrolactone and γ-valerolactone, 1,2-dimethoxyethane, bis (2-methoxyethyl) ether, 1, Ether-based solvents such as 2-bis (2-methoxyethoxy) ethane, diethylene glycol dimethyl ether, and triethylene glycol dimethyl ether , Ketone solvents such as methyl ethyl ketone, cyclohexanone, methylcyclohexanone, o-cresol, m-cresol, p-cresol, o-chlorophenol, m-chlorophenol, p-chlorophenol, 2,3-xylenol, 3,4- Phenolic solvents such as xylenol and 2,5-xylenol are listed.
Among these, from the viewpoint of solubility and inertness, N-methyl-2-pyrrolidone, N, N-dimethylacetamide, 1,3-dimethyl-2-imidazolidinone, N, N-dimethylformamide, dimethyl sulfoxide, γ-Butyrolactone and cyclohexanone are preferred.

In this case, the formation reaction and imidation rearrangement reaction of the oxazepine intermediate polymer or cyclic amidinoamidic acid intermediate polymer proceed smoothly even in the absence of a special catalyst, but based on the compounds (A) to (C). The catalyst may be used at a ratio of 0.03 to 2 mol.
Examples of the catalyst include trimethylamine, triethylamine, tripropylamine, tributylamine, N, N-dimethylaniline, N, N-diethylaniline, pyridine, quinoline, isoquinoline, α-picoline, β-picoline, 2,4-lutidine, Basic catalysts such as 2,6-lutidine, diazabicyclooctane, diazabicycloundecene, acidic acids such as formic acid, acetic acid, propionic acid, butyric acid, crotonic acid, benzenesulfonic acid, p-toluenesulfonic acid, naphthalenesulfonic acid A catalyst is mentioned.

In the present invention, it has been described above that the polyimide derivative is produced in different embodiments depending on the presence or absence of the solvent. Hereinafter, this point is roughly divided into three embodiments (a) to (c). Describe.
(A) In the first embodiment, a series of reactions are allowed to proceed in a solution, and the resulting mixture can be used as it is as a coating composition or a liquid composition (varnish) for paint (see the present invention 4 ). .
In the polymerization reaction, tetracarboxylic dianhydride (A), cyclic amidine (B) and / or cyclic iminoether (C) are dissolved in a common solvent, and the reaction is carried out in a nitrogen atmosphere (the subsequent imidization rearrangement step). Then, this can be achieved by reacting at a temperature of at least 160 ° C. for 7 to 24 hours.
In this first embodiment, the ratio of the total number of moles of cyclic amidine or cyclic imino ether per mole of tetracarboxylic dianhydride is 0.95 to 0.995 or 1.005 to 1.05, preferably Is carried out at a ratio of 0.96 to 0.995 or 1.005 to 1.04, that is, the number of moles of either reaction substrate is slightly less than equimolar.
When the ratio of the number of moles is less than 0.95 or more than 1.05, the resulting polyamideimide (PAI), polyesterimide (PEI) or polyesteramideimide (PEAI) has a low molecular weight and mechanical properties. Tends to be small and is not practical. On the other hand, when the molar ratio is in the range of more than 0.995 and less than 1.005, the molecular weight tends to be too high and the viscosity becomes high, and the operability tends to deteriorate or become insoluble.
The reaction solution of the solvent-soluble polyimide derivative obtained by the polymerization reaction can be used as it is as a varnish for known applications such as insulating coating materials, heat-resistant coating materials, paints and the like.

(B) In the second embodiment, the production method is divided into a first process and a second process (see the present invention 5), and the present invention 2 belongs to the second embodiment. .
In the first step, tetracarboxylic dianhydride (A) and cyclic amidine (B) and / or cyclic iminoether (C) are polyadded in a common solvent to obtain a liquid composition of an intermediate polymer. .
Next, in the second step, this liquid composition is applied to a heat-resistant support such as metal, heat-resistant plastic, or ceramic, and gradually gradually in an oven or a hot plate under an inert atmosphere such as nitrogen. By raising the temperature and finally heating to a temperature of 250 ° C. or higher, the intermediate polymer undergoes imidation rearrangement, and the solvent is evaporated to obtain a film-like molded product.
In this case, the first step has two roles, one of which is to obtain an appropriate solution viscosity necessary for uniform application to the support in the second step, and the other is the formation of an intermediate polymer. It is for reducing the burden of a 2nd process by implementing until.
In the second form, as described above, a polyimide oligomer having a succinic anhydride group (or phthalic anhydride group) at the terminal or a polyamideimide oligomer can be used as the tetracarboxylic dianhydride (A). . About the use time of the oligomer which has this specific terminal group, there is no restriction | limiting in particular, It can be used from a 1st process, However , In this case, by using an oligomer as (A) component, the viscosity provision of a 1st process and Since the purpose of reducing the polymerization reaction load has already been achieved, the operation of polyaddition can be omitted from this aspect.

In the first step of the second embodiment, a solvent solution of the component (A) and (B) and / or (C) is reacted in advance at a temperature of, for example, 80 to 220 ° C. for 5 to 20 hours, and at least The polyaddition is performed up to the previous stage of the imidization rearrangement.
However, if necessary, it may be pre-reacted up to the stage of the partial imidation rearrangement reaction and then supplied to the second step.
In the present invention, such a polyaddition liquid composition that does not reach the imidization rearrangement or a liquid composition that is partially imidized rearrangement reaction is referred to as an intermediate polymer composition.
In the second embodiment, the total molar ratio of the compound (A) to the compounds (B) and / or (C) is 0.95 to 1.05, preferably 0.96 to 1.04. If the molar ratio is less than 0.95 or exceeds 1.05, the molecular weight of the resulting polyimide derivative becomes too small, and physical properties such as mechanical strength and chemical resistance may be lowered.
The total content of the compound (A) and the compounds (B) and / or (C) is 5 to 35% by weight, preferably 8 to 25% by weight, in the liquid composition. If the content is less than 5% by weight, it is not economical in terms of solvent cost, and if it exceeds 35% by weight, the viscosity of the liquid composition increases, so that operations such as uniform coating may be difficult in the second step. is there.
In this second embodiment, the imidization rearrangement reaction mainly occurs in the second step, but for its completion, it is substantially 180 ° C. or higher, preferably 200 to 350 ° C., more preferably 230 to 310 ° C. Heating is required. When the processing is finished at a temperature lower than 180 ° C, the solvent does not completely evaporate, or the imidization rearrangement reaction is incomplete, resulting in insufficient mechanical properties and chemical resistance of the resulting polyimide derivative become. Moreover, it is economically disadvantageous when the processing temperature exceeds 350 ° C.

On the other hand, in the second embodiment, the tris-type cyclic amidine compound (B) and / or the imino ether compound (C) is added during the first step or before the second step, thereby Mechanical properties and chemical resistance can be increased.
In the present invention, a linear polymer is basically produced in the polymerization reaction between the compound (A) and the bis-type compound (B) and / or (C), so there is an advantage of solvent solubility, but chemical resistance. However, the tris-type compound (B) and / or (C) is added during or after the first step to render the polyimide derivative insoluble and infusible by a crosslinking reaction. Chemical properties can be improved. However, if it is added from the initial stage of the first step, gelation occurs during the polymerization due to crosslinking and it becomes difficult to produce a liquid composition. Therefore, the addition is limited to the middle of the first step or after that.
As described above, the tris-type (trifunctional) compound (B) or (C) is represented by p = 2 in the above formula (I), and the amount of the compound (B) and / or (C) added is The content is 0.1 to 10% by weight, preferably 0.5 to 5% by weight, based on the solid content.
Trifunctional cyclic amidine compounds (B) include 1,3,5-tris (2-imidazolin-2-yl) benzene and 1,3,5-tris (1-methyl-2-imidazolin-2-yl) benzene. 1,3,5-tris (1-ethyl-2-imidazolin-2-yl) benzene, 1,3,5-tris (1,4,5,6-tetrahydropyrimidin-2-yl) benzene are preferred, As the trifunctional cyclic imino ether compound (C), 1,3,5-tris (2-oxazolin-2-yl) benzene is preferable.

(C) The third embodiment is thermoplastic molding.
This is a solid powder obtained by separation and purification from the reactant solution of the first embodiment by means such as reprecipitation, or the 1,3-oxazepine intermediate polymer solution obtained in the first step of the second embodiment. The solid powder obtained by separation and purification by reprecipitation is heated and compression-molded by, for example, hot pressing, and the imidization rearrangement reaction is completed at the same time to obtain a molded body.
As another molding method, it can also be applied to transfer molding using the same solid powder.

  Hereinafter, examples of the method for producing a polyimide derivative of the present invention will be sequentially described. It should be noted that the present invention is not limited to the following embodiments, and can of course be modified arbitrarily within the scope of the technical idea of the present invention.

<< Examples of production of polyimide derivatives >>
Of the following Examples 1 to 9, Example 1 is a polyaddition of pyromellitic dianhydride (PMDA) and a bisimidazoline compound. One embodiment example) and Example 2 are examples in which the intermediate polymer of Example 1 was subjected to imidization rearrangement on a hot plate.
Example 3 is an example in which PMDA and a bisimidazoline compound different from Example 1 are reacted in the second embodiment, and Example 4 is a tetracarboxylic dianhydride that is different from PMDA and a bisimidazole compound that is different from the above example. An example of reacting an imidazoline compound in the second embodiment, Example 5 is a second step in which a tetracarboxylic dianhydride and a tetrahydropyrimidine compound different from the above example are reacted in the second embodiment. This is an example in which a tris-type imidazoline compound is added before the step.
Example 6 is an example in which PMDA and a bisoxazoline compound are reacted in the second embodiment, Example 7 is a tetracarboxylic dianhydride different from PMDA, and a bisoxazoline compound different from Example 6 is used in the second embodiment. It is the example made to react in embodiment of this.
Example 8 is an example in which a phthalic anhydride group polyamideimide oligo was used for compound (A) and reacted with a bisimidazoline compound in the second embodiment, and Example 9 was compound (A). In this example, both ends of phthalic anhydride group polyimide oligo were used and reacted with a bisimidazoline compound different from Example 8 in the second embodiment.
Example 10 is an example in which the oligomer of Example 9 above, a bisimidazoline compound, and a bisoxazoline compound were reacted in the second embodiment.
Examples 1 to 5 and Examples 8 to 9 are production examples of polyamideimide, Examples 6 to 7 are production examples of polyesterimide, and Example 10 is a production example of polyesteramide imide.

  On the other hand, Comparative Example 1 is an example based on Patent Document 1 described above, in which a polyesterimide was produced via a polyester amic acid obtained by a reaction between pyromellitic acid as a free acid and a bisoxazoline compound. is there. In Comparative Example 2, hexacarboxylic dianhydride and a bisimidazoline compound were reacted in place of tetracarboxylic dianhydride. Comparative Example 3 is an example in which hexacarboxylic dianhydride and a bisimidazoline compound were reacted in place of tetracarboxylic dianhydride.

  In the following Examples and Comparative Examples, IR was measured by the KBr tablet method using a Fourier transform infrared spectrophotometer FTIR-8400 manufactured by Shimadzu Corporation. 1H-NMR was measured by NMR JEOL-JNM-EX400 manufactured by JEOL Ltd. The viscosity of the liquid composition was measured by an E-type viscometer (Tuning Fork Vibration Viscometer SV-1A manufactured by A & D Co., Ltd.). Further, when the liquid composition was heated to form a film, a digital hot plate ND-1 program hot plate manufactured by AS ONE Co., Ltd. was used.

(1) Example 1
In a 100 mL four-necked flask equipped with a thermometer, stirrer, and nitrogen inlet tube, 40.0 g of 1,3-dimethyl-2-imidazolidinone dehydrated with molecular sieve and 5.456 g of pyromellitic dianhydride (25 0.02) and 2,2 ′ (1,3-phenylene) bis (1-methyl-2-imidazoline) 6.002 g (24.8 mmol), and the system was replaced with nitrogen gas and stirred. The solution was dissolved while warming.
Subsequently, the temperature in the system was raised to 150 ° C. and kept at this temperature for 5 hours. A part of the reaction liquid at this stage was collected as an intermediate polymer composition (A), and then heated to 220 ° C. and reacted for 10 hours to obtain a brown transparent reaction product liquid.
The viscosity (20 ° C.) of the product liquid was 231 mPa · s. A part of this reaction solution was precipitated in diethyl ether, and the yield of the product calculated from the yield of the powder obtained by drying under reduced pressure was 99.3%.
The generated liquid can be used as it is as a coating material or paint component.

[Identification of Polyamideimide]
FIG. 1 is an infrared absorption spectrum of the powder.
According to the absorption spectrum, characteristic absorption of imide groups was confirmed at wave numbers = 1772 cm-1, 1715 cm-1, 1395 cm-1, and 737 cm-1, and amide I absorption of a tertiary amide was observed at 1622 cm-1. It was.
Therefore, after an excess amount of isobutylamine is reacted with succinic anhydride groups at both ends of the polyamideimide to convert to amic acid with a part of the product liquid, DMSO of isobutylimide polyamideimide at both ends is obtained by thermal imidization reaction. 1H-NMR measured at 20 ° C in -d6, protons of aromatic nucleus were observed at 6.8 to 8.4 ppm, alkyl protons at 2.7 to 4.2 ppm, and isobutyl methyl proton peaks at 0.86 ppm. It was done.
The number average molecular weight Mn of the product calculated from the area ratio of alkyl group protons to isobutyl methyl protons was 40,600.
For this reason, it was confirmed that the product obtained by the above reaction was a polyamideimide of Mn = 40,600 represented by the formula (VII) of (Chemical Formula 15).

(2) Example 2
0.881 g of the intermediate polymer composition (A) (concentration 22.3%) collected during the reaction of Example 1 above was cast on an aluminum dish having a diameter of 4.5 cm and placed on a hot plate to have a space capacity of 600 ml. Cover the glass and raise the temperature while flowing nitrogen at a rate of 30 ml / min. Steps of 80 ° C x 30 minutes, 140 ° C x 30 minutes, 200 ° C x 1 hour, 230 ° C x 1 hour, 260 ° C x 2 hours As a result, a film having a smooth surface and no defects such as pinholes and crater-like bubble traces and a thickness of 86 μm was obtained.
In the FT-IR of this film, characteristic absorption of imide groups and tertiary amide groups was observed in the same absorption band as in Example 1, and it was confirmed that the intermediate polymer was rearranged to polyamideimide.

(3) Example 3
In the same reaction vessel as in Example 1, 36.0 g of dehydrated N-methyl-2-pyrrolidone, 2.183 g of pyromellitic dianhydride (10.0 mmol), 2,2 ′-(1,3-phenylene) Bis (2-imidazoline) 2.161 g (10.1 mmol) and 0.12 g (2 mmol) of acetic acid as a catalyst were charged, and the system was dissolved by heating while replacing the inside with nitrogen gas.
Next, the temperature in the system was raised to 150 ° C. and the reaction was continued for 7 hours, and then the temperature was raised to 200 ° C. and the reaction was further continued for 7 hours to obtain an intermediate polymer composition (B). The viscosity (20 ° C.) of the intermediate polymer composition (B) was 15.3 mPa · s, and the yield of the intermediate polymer by reprecipitation with diethyl ether was 99.9%.
1.663 g of the intermediate polymer composition (B) was cast on an aluminum dish having a diameter of 4.5 cm, and 80 ° C. × 30 minutes, 140 ° C. × 30 minutes, 200 ° C. × 30 minutes on the same hot plate as in Example 2. When heated in steps of 230 ° C x 1 hour, 260 ° C x 1 hour, 300 ° C x 1 hour, a film with a smooth surface and no defects such as pinholes and crater-like bubble traces was obtained. .

[Identification of Polyamideimide]
FIG. 2 is an FT-IR absorption spectrum of the obtained product.
According to the absorption spectrum, wavenumbers = 1773 cm-1, 1712 cm-1, 1385 cm-1, and 729 cm-1 are characteristic absorptions based on imide groups, amide I of secondary amide is 1643 cm-1, and secondary amide is 1538 cm-1. II. Absorption of secondary amide III was observed at 1298 cm-1.
Therefore, it was confirmed that the intermediate polymer composition (B) was rearranged to the polyamideimide represented by the formula (VIII) of (Chemical Formula 16).
This polyamideimide was soluble in NMP, DMAc, DMF, DMI and DMSO, but was insoluble in methanol, ethyl acetate and benzene.

(4) Example 4
The following change process was performed based on the above Example 3, and the other conditions were the same as in Example 3.
That is, in Example 4, tetracarboxylic dianhydride is converted from pyromellitic dianhydride to bicyclo [2.2.2] oct-7-ene-2,3,5,6-tetracarboxylic dianhydride. 482 g (10.0 mmol) and bisimidazoline was changed from 2,2 '-(1,3-phenylene) bis (2-imidazoline) to 2,2'-(1,4-phenylene) bis (2 -Imidazoline) to 2.129 g (9.9 mmol) to obtain an intermediate polymer composition (C).
Next, 2.030 g of the intermediate polymer composition (C) was heated on a hot plate under the same conditions as in Example 3 to obtain a smooth surface with no defects such as pinholes and crater-like bubble traces. A 101 μm film was obtained.

[Identification of Polyamideimide]
In the FT-IR absorption spectrum of the above product, characteristic absorption of imide groups was observed at wave numbers = 1768 cm-1, 1701 cm-1, 1406 cm-1, and 727 cm-1, and the absorption of amide I of the secondary amide was 1647 cm-1. In addition, absorption of amide II was observed at 1539 cm-1, and absorption of amide III was observed at 1290 cm-1.
For this reason, it was confirmed that the intermediate polymer composition (C) was rearranged to the polyamideimide represented by the formula (IX) in (Chemical Formula 17).
This polyamideimide was soluble in NMP, DMAc, DMF, DMI and DMSO, but was insoluble in methanol, ethyl acetate and benzene.

(5) Example 5
In the same reaction vessel as in Example 1 above, 30.0 g of N-methyl-2-pyrrolidone, 2.942 g (10.0 mmol) of 3,3′4,4′-biphenyltetracarboxylic dianhydride, 2,2 Charge 2.625 g (9.7 mmol) of ′-(1,4-phenylene) bis (1-methyl-1,4,5,6-tetrahydropyrimidine) and dissolve by heating while replacing the system with nitrogen gas did.
Subsequently, the temperature in the system was raised to 150 ° C. and reacted for 7 hours to obtain an intermediate polymer composition (D). To this intermediate polymer composition was added 0.220 g (0.7 mmol; 4.0 wt% / solid) of 1,3,5-tris (1-methyl-2-imidazolin-2-yl) benzene at room temperature. And dissolved uniformly.
0.851g was collected from this homogeneous solution, cast on an aluminum dish, and heated on a hot plate under a nitrogen stream of 30ml / min, 80 ℃ × 30min, 140 ℃ × 30min, 200 ℃ × 30min, 230 ℃ Heating was performed in steps of × 1 hour, 260 ° C. × 1 hour, and 280 ° C. × 1 hour to obtain a smooth film having a thickness of 61 μm without pinholes or crater-like bubble traces.

[Identification of Polyamideimide]
In the FT-IR absorption spectrum of the above product, the absorption of imide groups is observed at wave numbers = 1769 cm-1, 1711 cm-1, 1377 cm-1, and 737 cm-1, and the characteristic absorption of tertiary amide amide I at 1644 cm-1. Was observed, and was insoluble in any solvent of NMP, DMAc, DMF, DMI, DMSO, methanol, ethyl acetate, and benzene, so that the repeating unit of the main chain was represented by the formula (X) in (Chemical Formula 18). It was confirmed to be a crosslinked product of the represented polyamideimide.

(6) Example 6
In the same reactor as in Example 1 above, pyromellitic dianhydride 5.455 g (25.0 mmol), 2,2 '-(1,3-phenylene) bis (2-oxazoline) 5.375 g (24. 9 mmol), and 42.0 g of dehydrated N-methyl-2-pyrrolidone and 0.40 g (5.1 mmol) of pyridine were charged, and the system was purged with nitrogen. Thereafter, the reaction mixture was dissolved by heating and reacted at 150 ° C. for 10 hours to obtain an intermediate polymer composition (E) having a concentration of 20.5%.
The viscosity of the intermediate polymer composition (E) was 98.2 mPa · s. Moreover, when the calculation based on the yield obtained by reprecipitating a part of the reaction solution in diethyl ether, the yield of the intermediate polymer (E) was 97.2%.
Next, 0.863 g of the intermediate polymer composition (E) was cast on an aluminum dish and heated on a hot plate under a nitrogen stream of 30 ml / min at 80 ° C. × 30 minutes, 140 ° C. × 30 minutes, 200 ° C. × 1 hour. The film was heated in steps of 230 ° C. × 1 hour and 260 ° C. × 2 hours to obtain a smooth film having a film thickness of 78 μm without pinholes or crater-like bubble traces.

[Identification of polyesterimide]
FIG. 3 is an FT-IR absorption spectrum of the above product.
In the above absorption spectrum, absorptions of imide groups were observed at wave numbers = 1775 cm-1, 1387 cm-1, and 729 cm-1, and characteristic absorptions based on imide groups and ester groups were observed at 1715 cm-1, respectively. Was confirmed to be a polyesterimide represented by the formula (XI) in (Chemical Formula 19).
This polyesterimide was insoluble in NMP, DMAc, DMF, DMI, DMSO, methanol, ethyl acetate and benzene.

(7) Example 7
In the same reaction vessel as in Example 1 above, 40.0 g of dehydrated 1,3-dimethyl-2-imidazolidinone, 7.358 g of 3,3′4,4′-biphenyltetracarboxylic dianhydride (25.0 mmol) ), 2.370 g (24.8 mmol) of 2,2 ′-(1,4-phenylene) bis (2-oxazoline), and 0.40 g (5.1 mmol) of pyridine, and the system was purged with nitrogen. The temperature was raised to 150 ° C. with stirring. After maintaining at this temperature for 5 hours, the temperature was further raised to 220 ° C., and the reaction was continued for 10 hours to obtain a dark brown transparent reaction product liquid.
The viscosity of this product solution was 249 mPa · s at 20 ° C.

[Identification of polyesterimide]
In the FT-IR absorption spectrum of the product obtained by reprecipitation of the above product in diethyl ether, characteristic absorption of imide groups was observed at wave numbers = 1778cm-1, 1392cm-1, and 735cm-1, and imide groups and esters were observed at 1713cm-1. Characteristic absorption based on groups was observed respectively.
For this reason, it was confirmed that the said product is the polyesterimide represented by the formula (XII) of (Chemical Formula 20). The yield of polyesterimide calculated from the yield of the reprecipitated product was 99.8%.
The reaction solution containing this polyesterimide can be used as it is as a coating material or paint component.

(8) Example 8
[Synthesis of polyamideimide oligomers having acid anhydride groups at both ends]
In a 200 ml four-necked flask equipped with a thermometer, reflux condenser, stirrer and nitrogen inlet tube, 5.765 g (30.0 mmol) of trimellitic anhydride and 15.013 g (60.0 mmol) of diphenylmethane diisocyanate And 95.0 g of dehydrated N-methyl-2-pyrrolidone were charged and dissolved at room temperature. Nitrogen gas was introduced at a rate of 20 ml / min, and the effluent gas was passed through a calcium chloride drying tube and then bubbled into an aqueous Ca (OH) ₂ solution.
When the flask was heated and the temperature was raised to 80 ° C., the generation of carbon dioxide gas due to the reaction was confirmed by the cloudiness of Ca (OH) ₂ water. The reaction temperature was gradually raised from 80 ° C. to 120 ° C. over 3 hours and held at 120 ° C. for 5 hours. During this time, the degree of white turbidity of Ca (OH) ₂ water gradually decreased, and was almost not observed after 5 hours at 120 ° C.
The reaction solution was once cooled to room temperature, 9.819 g (45 mmol) of pyromellitic dianhydride was added, and the mixture was heated to 80 ° C. and dissolved. The reaction temperature was raised from 80 ° C. to 140 ° C. over 3 hours. In this process, white turbidity of Ca (OH) ₂ water was observed again. The reaction temperature was maintained at 140 ° C., and the reaction was continued until no cloudiness of Ca (OH) 2 water was observed after 5 hours, followed by cooling and N-terminal succinic anhydride group polyamideimide oligomer having a number average molecular weight of 1665. 119.1 g of a methyl-2-pyrrolidone solution (G) was obtained.
This solution contains 21.3% by weight of the oligomer and contains phthalic anhydride groups at a rate of 0.252 mmol / g.

[Synthesis of Polyamideimide]
In the same reaction vessel as in Example 1, 25.0 g of the above-mentioned phthalic anhydride group polyamideimide oligomer solution (G) and 25.0 g of dehydrated N-methyl-2-pyrrolidone were charged and heated to 50 ° C. with stirring. Then, 2.676 g of 2,2 '(1,3-phenylene) bis (2-imidazoline) (1/2 mol with respect to the phthalic anhydride group) was added to this mixture, and stirring was continued for 2.5 hours at the same temperature until uniform. Liquid composition (H) was obtained.
Place 1.517 g of this liquid composition (H) in an aluminum dish and place it on a hot plate under a nitrogen stream of 30 ml / min at 80 ° C x 30 minutes, 140 ° C x 30 minutes, 200 ° C x 30 minutes, 260 ° C x 2 The reaction was carried out in steps of 300 ° C. for 1 hour for a time to obtain a film having a thickness of 80 μm having no defects such as pinholes and crater-like bubble traces.

[Identification of Polyamideimide]
In the FT-IR absorption spectrum of the above product, the absorption intensity corresponding to the absorption of amide I of the secondary amide is increased from that of the original polyamideimide oligomer, and the amideimide group is incorporated. It was observed that
For this reason, it was confirmed that the product was a polyamideimide represented by the formula (XIII) of (Chemical Formula 21). P1 in the above formula (XIII) is a polyamideimide oligomer residue.

(9) Example 9
[Synthesis of polyimide oligomer having acid anhydride groups at both ends]
In a 200 ml three-necked flask equipped with a Dean-Stark divide pipe connected to a thermometer, stirrer and reflux condenser, N-methyl-2-pyrrolidone 80 g, m-xylene 30 g, and pyromellitic dianhydride 13.090 g (60.0 mmol) was charged and dissolved. To this solution, 3.604 g (18.0 mmol) of p-diaminodiphenyl ether and 6.271 g (18.0 mmol) of 9,9-bis (4-aminophenyl) fluorene were added at room temperature.
After replacing the system with nitrogen gas, the mixture was stirred at room temperature for 2 hours, then heated to 60 ° C. and stirred at this temperature for 2 hours. Thereafter, when the temperature was raised to 170 ° C., water liberated by the imidization reaction began to be separated by a water separator. The reaction was terminated at 170 ° C. for 7 hours. The reaction was terminated when no new water was observed. After distilling off m-xylene, the product was cooled and cooled at both ends with a number average molecular weight of 913. 100.70 g of oligomer solution (I) was obtained.
This solution contains the oligomer at a rate of 21.1% by weight and contains phthalic anhydride groups at a rate of 0.478 mmol / g.

[Synthesis of Polyamideimide]
To 25.0 g of the phthalic anhydride group polyimide oligomer solution (I) at both ends, 1.618 g of 2,2 ′-(1,4-phenylene) bis (1-ethyl-2-imidazoline) (based on the phthalic anhydride group) 1 /
2 mol) was added and stirred and dissolved at room temperature to obtain a uniform liquid composition (J).
Cast 0.902 g of the liquid composition (J) onto an aluminum dish, place it on a hot plate, and 80 ° C. × 30 minutes, 140 ° C. × 30 minutes, 200 ° C. × 30 minutes under a nitrogen stream of 30 ml / min. The film was heated at 260 ° C. for 2 hours to obtain a 102 μm thick film having no defects such as pinholes and crater-like bubble traces.

[Identification of Polyamideimide]
FIG. 4 is an FT-IR absorption spectrum of the above product.
In this absorption spectrum, in addition to the absorption of imide groups of wave numbers = 1774cm-1, 1718cm-1, 1371cm-1, and 725cm-1 that were in the original polyimide oligomer, the amide I absorption of a tertiary amide is observed at 1630cm-1. It was clearly seen that an amidoimide group was incorporated.
Therefore, it was confirmed that the product was a polyamideimide represented by the formula (XIV) in (Chemical Formula 22). In the above formula (XIV), P2 is a polyimide oligomer residue.

(10) Example 10
[Synthesis of Polyesteramideimide]
In Example 9 above, the amount of 2,2 ′-(1,4-phenylene) bis (1-ethyl-2-imidazoline) used per 25.0 g of the phthalic anhydride group polyimide oligomer solution (I) at both ends Is changed to 0.809 g of ½ amount (1/4 mol with respect to phthalic anhydride group) and 0.645 g of 2,2 ′-(1,3-phenylene) bis (2-oxazoline) is newly added ( The film was processed under the same conditions as in Example 9 except that 1/4 mole relative to phthalic anhydride was used, and a tough film having a thickness of 97 μm free from pinholes and crater-like defects was obtained.
In the FT-IR spectrum of the above product, in addition to the absorption of wave numbers 1774cm-1, 1718cm-1, 1371cm-1, and 725cm-1 that were in the original polyimide oligomer, the amide I absorption of tertiary amide at 1630cm-1 It was observed that a new absorption of ester C—O stretching vibration appeared at 1221 cm-1 and an amide bond and an ester bond were incorporated.
For this reason, it was confirmed that the product was a polyesteramidoimide (PEAI) represented by the formula (XV) in (Chemical Formula 23). In the above formula (XV), P2 is a polyimide oligomer residue. “*” Indicates that the polymer main chain is continuous.

(11) Comparative Example 1
In this example, pyromellitic acid as a free acid and bisoxazoline were reacted to synthesize polyesterimide (PEI) via polyesteramic acid.
That is, in the same manner as in Patent Document 1, pyromellitic acid (free acid type) 6.355 g (25.0 mmol), 2, 2 '-(1,3-phenylene) bis (2-oxazoline) 5 .379 g (24.9 mmol) and 45.5 g of dehydrated N-methyl-2-pyrrolidone were charged and reacted at 70 ° C. for 7 hours to obtain a polyesteramic acid solution (F) having a concentration of 20.50%.
0.871 g of this polyester amic acid solution (F) was cast on an aluminum dish and heat-treated under the same conditions as in Example 6 to obtain a 69 μm thick PEI film.
When this film was visually observed, 14 pinholes with a diameter of less than 0.5 mm and 5 traces of crater-like bubbles with a diameter of 1 to 2 mm were found, which are caused by desorption of water molecules. It can be judged that the synthesis is a polycondensation reaction.
This polyesterimide was insoluble in various solvents such as NMP, DMAc, DMF, DMI, DMSO, methanol, ethyl acetate and benzene.

(12) Comparative Example 2
On the basis of Example 1, instead of tetracarboxylic dianhydride (PMDA), hexacarboxylic dianhydride and a bisimidazoline compound were reacted according to the first embodiment, and the gelation of the solution progressed. As a result, the polymerization reaction could not be carried out any more, and the reaction was stopped midway.
This is presumed that it was difficult to produce an intermediate polymer solution because gelation proceeded through a crosslinking reaction due to the reaction of a trifunctional hexacarboxylic dianhydride and a bifunctional bisimidazoline compound.

(13) Comparative Example 3
Based on Example 1, instead of tetracarboxylic dianhydride (PMDA), a hexacarboxylic dianhydride and a bisimidazoline compound were reacted according to the first embodiment. Could not be carried out anymore and the reaction was stopped.
In hexacarboxylic dianhydride, a free carboxyl group also acts as a functional group, so that it becomes tetrafunctional in the polyaddition reaction, and gelation due to crosslinking is inevitable. In addition, when a free carboxyl group and an imidazoline (or oxazoline) undergo an addition reaction, an amide group or an ester group is generated instead of an imide group, resulting in a disadvantage that the heat resistance is lowered.

<< Comprehensive evaluation based on Examples and Comparative Examples >>
In Comparative Example 1 based on Patent Document 1 described above, polyesterimide (PEI) was synthesized through polyester amic acid. However, many pinholes and craters were generated in the obtained PEI film, and water molecules were removed. It is clear that the synthesis of PEI is due to the polycondensation reaction because the traces of bubbles due to separation and volatilization are remarkable. For this reason, the polyimide derivative obtained in Comparative Example 1 has problems such as molding defects such as voids and surface roughness, a decrease in mechanical strength and heat resistance, and adhesion failure.
On the other hand, in Examples 1 to 10, the production of polyamideimide (PAI), polyesterimide (PEI), or polyesteramideimide (PEAI) can be confirmed from the IR absorption spectrum. Since there is no trace of bubbles such as craters, it is supported that the synthesis of PAI, PEI, or PEAI is based on a polyaddition reaction without water molecule elimination, and a smooth film free from voids and surface roughness can be formed. Can improve mechanical strength and heat resistance. Moreover, when the product by polyaddition is applied to an adhesive application, a thermocompression adhesive without adhesion failure can be produced.

When a polyimide derivative is produced by the polyaddition reaction of the present invention, a series of reactions are allowed to proceed in solution as in Example 1 (see the first embodiment), and the resulting liquid composition (varnish) is obtained. Can be used as a main component of coating agents and paints as they are.
On the other hand, as in the second embodiment (for example, Example 3), a liquid composition of an intermediate polymer is obtained by a polyaddition reaction (first step), and this solution is applied to a support and heated. Then, it can be formed into a film by a method (cast method) in which imidization rearrangement is performed to evaporate the solvent (second step).
In the production of the polyimide derivative of the present invention, as shown in Examples 8 to 10, by using a terminal acid anhydride group oligomer in tetracarboxylic dianhydride (A), the load of polymerization operation is reduced and efficient. Viscosity can be imparted or heat resistance can be improved, and as shown in Example 5, a tris-type cyclic amidine or imino ether compound is added before or during the second step of the second embodiment. Thus, the mechanical properties and chemical resistance of the polyimide derivative can be enhanced by introducing a crosslinked structure.

On the other hand, an example will be described in comparison with Comparative Examples 2 to 3 above. In the light of the synthesis results of Comparative Examples 2 to 3, in the polyaddition reaction with the amidine compound (B) (or imino ether compound (C)). It can be judged that the carboxylic acid anhydride component capable of producing an appropriate polyimide derivative without gelation is limited to tetracarboxylic dianhydride.
In addition, it is well-known in the above-mentioned patent document 3 and Unexamined-Japanese-Patent No. 2007-169392 that a tetracarboxylic acid anhydride component (A) and a diamine can be made to produce a polyimide via a polyamic acid. However, since this reaction is a polycondensation reaction and has the detrimental effect of elimination of low molecular weight compounds such as H 2 O, tetracarboxylic dianhydride (A) can be used to properly produce a polyimide derivative by polyaddition reaction. Is limited to a specific amidine compound (B) (or imino ether compound (C)).

2 is an IR absorption spectrum of the product of Example 1. 2 is an IR absorption spectrum of the product of Example 3. 7 is an IR absorption spectrum of the product of Example 6. 4 is an IR absorption spectrum of the product of Example 9.

Claims (8)

(A) tetracarboxylic dianhydride;
(B) a polyaddition reaction with at least one amidine compound selected from the group consisting of bis or tris type 2-substituted-2-imidazolines and bis or tris type 2-substituted-2-tetrahydropyrimidines; A method for producing a polyimide derivative, characterized by producing polyamideimide (PAI). Compound (A) is tetracarboxylic dianhydride,
Compound (C) is at least one iminoether compound selected from the group consisting of bis or tris type 2-substituted-2-oxazolines, bis or tris type 2-substituted-2-oxazines,
A first step of subjecting the compound (A) and the compound (C) to a prepolyaddition reaction in the presence of a solvent to obtain a liquid composition of an intermediate polymer; and in the presence or absence of a small amount of solvent. A method for producing a polyimide derivative, comprising: a second step of obtaining a film-formed product or a molded product by causing the intermediate polymer to undergo an imidization rearrangement reaction . (A) tetracarboxylic dianhydride;
(B) at least one amidine compound selected from the group consisting of bis or tris type 2-substituted-2-imidazolines, bis or tris type 2-substituted-2-tetrahydropyrimidines;
(C) a polyaddition reaction with at least one iminoether compound selected from the group consisting of bis or tris type 2-substituted-2-oxazolines and bis or tris type 2-substituted-2-oxazines; The manufacturing method of the polyimide derivative characterized by manufacturing a polyesteramide imide (PEAI). Compound (A) in the presence of a solvent;
At least one amidine compound (B) selected from the group consisting of bis or tris type 2-substituted-2-imidazolines and bis or tris type 2-substituted-2-tetrahydropyrimidines;
The method for producing a polyimide derivative according to claim 1 , wherein a liquid composition is obtained by polyaddition reaction . Compound (A) in the presence of a solvent;
At least one amidine compound (B) selected from the group consisting of bis or tris type 2-substituted-2-imidazolines and bis or tris type 2-substituted-2-tetrahydropyrimidines;
A first step of pre-addition reaction to obtain a liquid composition of the intermediate polymer;
The polyimide derivative according to claim 1 , comprising a second step of obtaining a film-formed product or a molded product by causing the intermediate polymer to undergo an imidization rearrangement reaction in the presence of a small amount of solvent or in the absence of a solvent . Production method. Bis-type imidazolines (B) are 2,2'-bi (2-imidazoline), 2,2 '-(ethylene) bis (2-imidazoline), 2,2'-(tetraethylene) bis (2- Imidazoline), 2,2 '-(1,3-phenylene) bis (2-imidazoline), 2,2'-(1,4-phenylene) bis (2-imidazoline), 2,2 '(1,3- Phenylene) bis (1-methyl-2-imidazoline), 2,2 '(1,3-phenylene) bis (1-ethyl-2-imidazoline), 2,2' (1,4-phenylene) bis (1- Methyl-2-imidazoline), 2,2 ′ (1,4-phenylene) bis (1-ethyl-2-imidazoline) , and at least one selected from the group consisting of
Tris-type imidazolines (B) are 1,3,5-tris (2-imidazolin-2-yl) benzene, 1,3,5-tris (1-methyl-2-imidazolin-2-yl) benzene, 1,3,5-tris (1-ethyl-2-imidazolin-2-yl) benzene is at least one selected from the group consisting of tris-type tetrahydropyrimidines (B) 6. The method for producing a polyimide derivative according to claim 1, 3, 4, or 5 , wherein it is (1,4,5,6-tetrahydropyrimidin-2-yl) benzene. The bis-type oxazolines (C) are composed of 2,2 '-(1,3-phenylene) bis (2-oxazoline) and 2,2'-(1,4-phenylene) bis (2-oxazoline) It is at least one selected from the group consisting of,
The method for producing a polyimide derivative according to claim 2 or 3 , wherein the tris-type oxazoline (C) is 1,3,5-tris (2-oxazolin-2-yl) benzene . Tetracarboxylic dianhydride (A) is bicyclo [2,2,2] oct-7-ene-2,3,5,6-tetracarboxylic dianhydride, pyromellitic dianhydride, 3,3 ′, 4,4′-benzophenone tetracarboxylic dianhydride, 3,3′4,4′-biphenyltetracarboxylic dianhydride, bis (3,4-dicarboxyphenyl) ether dianhydride, 9,9 -Bis [4- (3,4-dicarboxyphenyl) phenyl] fluorene dianhydride , a polyimide oligomer having a succinic anhydride group at the end, a polyimide oligomer having a phthalic anhydride group at the end, and a succinic anhydride group at the end The method for producing a polyimide derivative according to any one of claims 1 to 5, wherein the polyamide derivative is at least one selected from the group consisting of a polyamideimide oligomer having a terminal and a polyamideimide oligomer having a phthalic anhydride group at a terminal. .

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