KR20120104145A - Polyimide soluble in organic solvent and comprising pmda, dade da and bis(amino-4-hydroxyphenyl)sulfone component, and process for production thereof - Google Patents

Abstract

The present invention provides a carboxylic acid dianhydride containing (1) pyromellitic acid dianhydride (PMDA), (2) biphenyltetracarboxylic acid dianhydride (BPDA) or benzophenonetetracarboxylic acid dianhydride (BTDA) It relates to a heat resistant polyimide obtained by polymerizing DA), (3) diaminodiphenyl ether (DADE), and (4) bis (3-amino-4-hydroxyphenyl) sulfone (HOABSO ₂ ). Advantageous Effects of Invention The present invention can provide a polyimide that is excellent in heat resistance and soluble in an organic solvent, and a method for producing the same.

Description

POLYIMIDE SOLUBLE IN ORGANIC SOLVENT AND COMPRISING PMDA, DADE DA AND BIS (AMINO-) containing a polyimide containing PDMA, DDA, DA, bis (amino-4-hydroxyphenyl) sulfone component soluble in an organic solvent 4-HYDROXYPHENYL) SULFONE COMPONENT, AND PROCESS FOR PRODUCTION THEREOF}

The present invention relates to a polyimide soluble in an organic solvent and a method for producing the same. More specifically, the present invention relates to a superheat resistant polyimide containing bis (3-amino-4-hydroxyphenyl) sulfone (hereinafter also referred to as "HOABSO ₂ "), PMDA, DADE, and DA components.

Conventionally, insoluble and insoluble polyimide is known as a superheat-resistant polyimide as a two-component system, such as KAPTON (registered trademark) and Upilex (registered trademark). Kapton was first manufactured by DuPont in 1960 and synthesized from pyromellitic acid dianhydride (hereinafter also referred to as "PMDA") and 1,4-diaminodiphenylether.

This polyimide is a polymer having a glass transition temperature (Tg) of 420 ° C and a thermal decomposition initiation temperature (Tm) of 500 ° C or more, and excellent in electrical insulation, mechanical strength, and chemical resistance. It is widely used as an electric component, a material for semiconductors, etc. (nonpatent literature 1: polyimides; D. Wilson, HD Steinberger, RM Morgenrother; Blackie, New York (1990)).

Eupyrex is a polyimide film produced by Ube Heungsan Co., Ltd. in 1980 and is synthesized from biphenyltetracarboxylic acid dianhydride (hereinafter also referred to as "BPDA") and 1,4-diaminobenzene. This polyimide has heat resistance of Tg> 500 degreeC and Tm> 550 degreeC (nonpatent literature 1).

Since their development, to date no other heat resistant polyimide films comparable to Kapton or Eupyrex have been manufactured and sold. No tetracarboxylic acid dianhydrides have been developed in place of the raw materials PMDA and BPDA.

Since Kapton and Eupyrex are poorly soluble in organic solvents, polycarboxylic condensates of tetracarboxylic dianhydrides and aromatic amines in polar organic solvents synthesize a high molecular weight polyamic acid, followed by casting and heating (400 占 폚 or more). ) It is obtained by making an imidation reaction, making it an organic solvent. That is, the conventional polyimide was obtained by forming a coating film from a polyamic-acid solution, and performing an imidation reaction and film formation simultaneously.

However, polyamic acid is easy to decompose into water, and even if cryopreserved, the quality is maintained for about 3 months. In addition, since the exchange reaction is likely to occur in the solution, the polyamic acid becomes a random copolymer by the exchange reaction when other components are added. It is difficult to make a random copolymer high performance by modification.

As mentioned above, the method of synthesizing a polyimide while removing an organic solvent from a polyamic-acid solution was not a method suitable enough for industrial production.

On the other hand, the method of producing a polyimide from polyamic acid in a solution is known. For example, Patent Document 1 (International Publication No. 2008/120398 pamphlet) and Patent Document 2 (International Publication No. 2008/155811 pamphlet) include biphenyltetracarboxylic acid dianhydride (BPDA), 4,4'- A heat resistant polyimide copolymer soluble in organic polar solvents based on diaminodiphenyl ether (DADE), pyromellitic acid dianhydride (PMDA), 2,4-diaminotoluene (DAT) and the like is disclosed. This polyimide is a first step of obtaining an oligomer having an amino group at both ends obtained by reacting DADE at both ends of BPDA, and reacting the oligomer with 2 molar equivalents of PMDA and 1 molar equivalent of DAT so that both ends thereof are PMDA. It is manufactured through the 2nd step of obtaining the oligomer which is an derived acid anhydride group, and the 3rd step of reacting and polymerizing this oligomer and DAT. Conventionally, when PMDA and BPDA which are acid anhydride components are used together, there exists a problem that an insoluble matter generate | occur | produces during the synthesis | combination of a polyimide. This reason was inferred that PMDA-DADE-PMDA segment or DADE-PMDA-DADE segment in polyimide was poorly soluble in an organic solvent. However, according to the method described in this document, a polyimide which does not contain such a segment can be synthesized, so that a polyimide soluble in an organic solvent is obtained.

Moreover, the method of producing | generating a polyimide from polyamic acid in a solution using a catalyst is known (patent document 3: A. Berger, US Patent No. 401297 (1993), and Patent Document 4: US Patent No. 4359572) (1983)). For example, a method using toluenesulfonic acid or phosphoric acid as a catalyst is known. However, in the polyimide obtained as described above, the catalyst remains in the solution, and therefore, deterioration of the catalyst may occur when the film is formed. Therefore, it is necessary to remove a catalyst from a solution. As a catalyst which can be easily removed from the solution, γ-valerolactone and pyridine or a mixture of γ-valerolactone and N-methylmorpholine is known (Patent Document 5: Y. Oie, H. Itatani, US Patent No. 5502142 Specification (1996). As shown below, this catalyst becomes an acidic ionic species and a basic ionic species in the presence of water, and when water is removed, an equilibrium reaction with lactone and a base is caused.

[Formula 1]

〔산〕⁺〔염기〕^- [Γ-valerolactone] + [pyridine] + [water]

[Acid] ⁺ [base] ^-

That is, when acid dianhydride and diamine are reacted in the presence of this catalyst, the reaction system is 160? When it heats and stirred at 200 degreeC, water produces | generates by condensation reaction in a system. Therefore, the equilibrium of this catalyst is inclined to the right, so that the catalytic activity is improved and the imidization reaction can be promoted. On the other hand, a small amount of toluene is usually added to the reaction system, and water generated by the reaction is removed out of the system by toluene azeotropy. In addition, when the imidation reaction is terminated, the reaction system becomes close to anhydrous state. Then, the equilibrium is inclined to the left to produce γ-valerolactone and pyridine, and the acidic ionic species as a catalyst disappears. By using such a catalyst, a high purity polyimide copolymer is obtained.

International Publication No. 2008/120398 Brochure International Publication No. 2008/155811 Pamphlet US Patent No. 401297 U.S. Pat.No.4359572 U.S. Patent No. 5502142 US Patent No. 6890621

 Polyimides; D. Wilson, H. D. Steinberger, R. M. Morgenrother; Blackie, New York (1990)

The polyimide soluble in an organic solvent is expected to be a new use such as a high heat resistant adhesive or a coating agent. However, polyimide, as represented by further improvement in heat resistance, requires higher functionalization. In order to meet this demand, it is necessary to obtain novel polyimide using the raw material which gives such a function. However, as already mentioned, when a different compound is used as a raw material, there exists a possibility that the solubility with respect to the organic solvent of a polyimide may fall. That is, although the polyimide which is excellent in heat resistance and soluble in an organic solvent is calculated | required, such a polyimide did not exist yet.

In view of such circumstances, an object of the present invention is to provide a polyimide excellent in heat resistance and soluble in an organic solvent, and a method for producing the same.

The inventors solved the above problem by using a specific aromatic diamine. That is, the present invention,

(1) pyromellitic dianhydride (PMDA),

(2) carboxylic acid dianhydrides (DA) containing biphenyltetracarboxylic acid anhydride (BPDA) or benzophenonetetracarboxylic acid dianhydride (BTDA),

(3) diaminodiphenyl ether (DADE), and

(4) A polyimide soluble in an organic solvent obtained by polymerizing bis (3-amino-4-hydroxyphenyl) sulfone (HOABSO ₂ ) is provided.

It is preferable that the said polyimide has a repeating unit represented by general formula (I).

-[PMDA]-[HOABSO ₂ ]-[PMDA]-[DADE]-[DA]-[DADE]-[PMDA]-[HOABSO ₂ ]-[PMDA] -U _1- (Ⅰ)

In formula, [PMDA] is the said pyromellitic-acid dianhydride residue,

[HOABSO ₂ ] is the bis (3-amino-4-hydroxyphenyl) sulphone residue,

[DADE] is the diaminodiphenylether residue,

[DA] is the carboxylic acid dianhydride residue,

U ₁ is a group represented by X ₁ or X _1- [DA] -X ₁ ,

Wherein X ₁ represents a phenylenediamine residue, an alkyl substituted phenylenediamine residue, a diaminodiphenylsulfone residue, a bis (aminophenoxy) benzene residue, or the bis (3-amino-4-hydroxyphenyl) sulfone Residues)

[DADE] and [DA], and the bond of [DADE] and [PMDA] are imide bonds,

The bond of [PMDA] and [HOABSO ₂ ] is a bond represented by the general formula (i) or (ii),

[Formula 2]

(Wherein α represents part of [PMDA], β represents part of [HOABSO ₂ ], and R represents a hydrogen atom or a carboxyl group)

Binding of [PMDA] and U ₁ is, in the case where X ₁ of U _1, bis (3-amino-4-hydroxyphenyl) sulfone moiety, and the bond shown by the general formula (ⅰ) or (ⅱ), the In other cases, it is an imide bond.)｝

In addition, the polyimide may be a polyimide having a repeating unit represented by General Formula (II).

-[DADE]-[DA]-[DADE]-[PMDA]-[HOABSO ₂ ]-[PMDA]-[DADE]-[DA]-[DADE] -U _2- (II)

In formula, [PMDA] is the said pyromellitic-acid dianhydride residue,

[HOABSO ₂ ] is the bis (3-amino-4-hydroxyphenyl) sulphone residue,

[DADE] is the diaminodiphenylether residue,

[DA] is the carboxylic acid dianhydride residue,

U ₂ is a group represented by [DA] or [DA] -X _2- [DA],

Wherein X ₂ is a phenylenediamine residue, an alkyl substituted phenylenediamine residue, a diaminodiphenylsulfone residue, a 1,3-bis (4-aminophenoxy) benzene residue, or the bis (3-amino-4 Hydroxyphenyl) sulfone residues)

[DADE] and [DA], [DADE] and [PMDA], and [DADE] and U ₂ are imide bonds,

A bond of [HOABSO ₂ ] and [PMDA] is a bond represented by the general formula (i) or (ii).

In addition, the polyimide may be a polyimide having a repeating unit represented by General Formula (III).

-[PMDA] -X _3- [PMDA]-[DADE]-[DA]-[DADE]-[PMDA] -X _3- [PMDA] -U _3- (III)

In formula, [PMDA] is the said pyromellitic-acid dianhydride residue,

[DADE] is the diaminodiphenylether residue,

[DA] is the carboxylic acid dianhydride residue,

X ₃ is a phenylenediamine residue, an alkyl substituted phenylenediamine residue, a diaminodiphenylsulfone residue, or a bis (aminophenoxy) benzene residue,

U ₃ is a group represented by [HOABSO ₂ ], [HOABSO ₂ ]-[DA]-[HOABSO ₂ ], [HOABSO ₂ ]-[DA] -X ₃ , or X _3- [DA]-[HOABSO ₂ ] Wherein [HOABSO ₂ ] is the bis (3-amino-4-hydroxyphenyl) sulphone residue and [DA], X ₃ is defined as above),

[DADE] and [DA], [DADE] and [PMDA], [PMDA] and X ₃ are imide bonds,

[HOABSO ₂ ] and [PMDA], and [HOABSO ₂ ] Bond of [DA] is a bond represented by the said general formula (i) or (ii).

Preferred embodiment of this invention is a polyimide containing the repeating unit represented by General formula (1).

(3)

[Wherein Q is a single bond or a carbonyl group,

R is independently a hydrogen atom or a carboxyl group,

a? h represents the position of a carbon atom, and when carbon of a, c, e, g couple | bonds with R, it shows that carbon of b, d, f, h couple | bonds with an oxazole group,

Y ₁ is a general formula (11)? It is group represented by (13),

[Formula 4]

(R ₁₀ represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, Ar ₁ is a group represented by the general formulas (11) to (13) independently, and Q is defined as above)

* Indicates that a phenylene group and an imide group are bonded.]

Another preferable embodiment of this invention is polyimide containing the repeating unit represented by General formula (2).

[Chemical Formula 5]

[Wherein Q is a single bond or a carbonyl group,

R is independently a hydrogen atom or a carboxyl group,

a? d represents the position of a carbon atom, and when carbon of a and c couple | bonds with R, it shows that carbon of b and d couple | bonds with an oxazole group,

Y ₂ is a group represented by General Formula (21), (22) or (23),

[Formula 6]

In formula, Q and R are defined as above,

e? h is a? defined as d,

Ar ₁ is a general formula (11)? It is group represented by (13),

[Formula 7]

(In General formula (11), R <_10> represents a hydrogen atom or a C1-C3 alkyl group.)

* Indicates that a phenylene group and an imide group are bonded.]

Another preferable embodiment of this invention is a polyimide containing the repeating unit represented by General formula (3-1).

[Formula 8]

[Wherein Q is a single bond or a carbonyl group,

R is independently a hydrogen atom or a carboxyl group,

a? d represents the position of a carbon atom, and when carbon of a and c couple | bonds with R, it shows that carbon of b and d couple | bonds with an oxazole group,

Ar ₁ is independently a general formula (11)? It is group represented by (13),

[Chemical Formula 9]

(R ₁₀ represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms.)

Y ₃ is a single bond or a group represented by formula (31),

[Formula 10]

(Wherein R ₁ independently represents a hydrogen atom or a carboxyl group, Q is defined as above, and e? H are defined in the same manner as a? D)

* Indicates that a phenylene group and an imide group are bonded.]

Another preferable embodiment of this invention is polyimide containing the repeating unit represented by General formula (3-2).

[Formula 11]

[Wherein Q is a single bond or a carbonyl group,

R is independently a hydrogen atom or a carboxyl group,

a? d represents the position of a carbon atom, and when carbon of a and c couple | bonds with R, it shows that carbon of b and d couple | bonds with an oxazole group,

Ar ₁ is independently a general formula (11)? It is group represented by (13),

[Chemical Formula 12]

(R ₁₀ represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms.)

* Indicates that a phenylene group and an imide group are bonded.]

According to the present invention, (A1) 1 molar equivalent of carboxylic acid dianhydride (DA) containing biphenyltetracarboxylic acid anhydride (BPDA) or benzophenone tetracarboxylic acid anhydride (BTDA) and 2 molar equivalents Reacting diaminodiphenyl ether (DADE) to obtain an oligomer whose both ends are an amino group derived from DADE,

(A2) The oligomer obtained in the step A1 is reacted with 4 molar equivalents of pyromellitic acid dianhydride (PMDA) and 2 molar equivalents of bis (3-amino-4-hydroxyphenyl) sulfone (HOABSO ₂ ) to react both. The process of obtaining the oligomer which is this PMDA derived acid anhydride group, and

(A3) carboxylic acid dianhydride (BDA) containing an oligomer obtained in the step A2 and one mole equivalent of an aromatic diamine or biphenyl tetracarboxylic dianhydride (BPDA) or benzophenone tetracarboxylic dianhydride And a step of reacting 1 molar equivalent of (DA) and 2 molar equivalents of aromatic diamine to obtain a polymer.

In addition, according to the present invention, (B1) 2 molar equivalents of pyromellitic acid dianhydride (PMDA) and 1 molar equivalent of bis (3-amino-4-hydroxyphenyl) sulfone (HOABSO ₂ ) are reacted to both terminals. The process of obtaining the oligomer which is this PMDA derived acid anhydride group,

(B2) 2 molar equivalents of the carboxylic acid dianhydride (DA) containing the oligomer obtained by the B1 process and biphenyl tetracarboxylic dianhydride (BPDA) or benzophenone tetracarboxylic dianhydride (BTDA), 4 A step of reacting a molar equivalent of diaminodiphenyl ether (DADE) to obtain an oligomer whose both ends are an amino group derived from DADE, and

(B3) 1 mol equivalent of the carboxylic acid dianhydride (DA) containing the oligomer obtained by the B2 process, and a biphenyl tetracarboxylic dianhydride (BPDA) or benzophenone tetracarboxylic dianhydride (BTDA), or A method for producing a polyimide is provided, including a step of reacting 2 molar equivalents of the carboxylic acid dianhydride (DA) with 1 molar equivalent of an aromatic diamine to obtain a polymer.

Moreover, according to this invention, 1 molar equivalent of carboxylic acid di-anhydride (DA) containing (C1) biphenyl tetracarboxylic dianhydride (BPDA) or benzophenone tetracarboxylic dianhydride (BTDA), and 2 A step of reacting a molar equivalent of diaminodiphenyl ether (DADE) to obtain an oligomer whose both ends are an amino group derived from DADE,

(C2) a step of reacting the oligomer obtained in the step C1 with 4 molar equivalents of pyromellitic acid dianhydride (PMDA) and 2 molar equivalents of aromatic diamine to obtain an oligomer whose both ends are PMDA-derived acid anhydride groups, and

(C3) oligomer obtained in step C2 and 1 molar equivalent of bis (3-amino-4-hydroxyphenyl) sulfone (HOABSO ₂ ) or biphenyltetracarboxylic acid anhydride (BPDA) or benzophenonetetracarb 1 molar equivalent of carboxylic acid dianhydride (DA) containing acid dianhydride (BTDA), 1 molar equivalent of bis (3-amino-4-hydroxyphenyl) sulfone (HOABSO ₂ ), and 1 molar equivalent A method for producing a polyimide is provided that includes a step of reacting an aromatic diamine to obtain a polymer.

It is preferable that reaction in the manufacturing method of said polyimide is performed in presence of (gamma) -valerolactone and pyridine, or (gamma) -valerolactone and N-methylmorpholine.

According to this invention, the composite material containing the film obtained from the polyimide of this invention can be provided.

Moreover, according to this invention, the electrodeposition paint containing the polyimide of this invention is also provided.

Moreover, according to this invention, the process of preparing the solution containing the polyimide of this invention and an organic solvent,

Forming a film by casting or applying the solution onto a substrate, and

There is provided a method for producing a composite material comprising the step of drying the film.

It is preferable that the drying process in the manufacturing method of the said composite material is performed at 300 degrees C or less.

Advantageous Effects of Invention The present invention can provide a polyimide that is excellent in heat resistance and soluble in an organic solvent, and a method for producing the same.

1. Polyimide of the present invention

The polyimide of the present invention,

(1) pyromellitic dianhydride (PMDA),

(2) carboxylic acid dianhydrides (DA) containing biphenyltetracarboxylic acid anhydride (BPDA) or benzophenonetetracarboxylic acid dianhydride (BTDA),

(3) diaminodiphenyl ether (DADE), and

4-bis (3-amino-4-hydroxyphenyl) sulfone is obtained by polymerizing a (HOABSO _2).

(1) PMDA

Pyromellitic acid dianhydride (PMDA) is a compound represented by general formula (m1).

[Chemical Formula 13]

(2) DA

Biphenyltetracarboxylic acid dianhydride (BPDA) is a compound in which two acid anhydride groups are bonded to biphenyl. In this invention, the compound represented by general formula (m2-1) is preferable at the point of the availability.

[Formula 14]

Benzophenonetetracarboxylic acid dianhydride (BTDA) is a compound in which two acid anhydride groups are bonded to benzophenone. In this invention, the compound represented by general formula (m2-2) is preferable at the point of the availability.

[Formula 15]

The polyimide of the present invention is a carboxylic acid dianhydride (DA) containing biphenyltetracarboxylic acid anhydride (BPDA) or benzophenone tetracarboxylic acid anhydride (BTDA) as a raw material, but BPDA alone It is preferable to use. It is because the polyimide containing a BPDA derived component is higher in glass transition temperature (Tg).

(3) DADE

Diaminodiphenyl ether (DADE) is a compound in which an amino group is bonded to the benzene ring of diphenyl ether one by one. Examples thereof include 4,4'-diaminodiphenyl ether and 3,4'-diaminodiphenyl ether. In this invention, 4,4'- diamino diphenyl ether is preferable. It is because the polyimide which uses this as a raw material is more excellent in heat resistance. 4,4'- diamino diphenyl ether is represented by general formula (m3).

[Chemical Formula 16]

(4) HOABSO ₂

Bis (3-amino-4-hydroxyphenyl) sulfone (HOABSO ₂ ) is a compound represented by chemical formula (m4). This compound is a dihydroxydiamine having a sulfonyl group, two amino groups, and two hydroxyl groups in the molecule.

[Chemical Formula 17]

In addition, the polyimide of this invention may use aromatic diamine of that excepting the above as a raw material. Aromatic diamine is a compound in which two amino groups are couple | bonded with an aromatic group. Preferred examples thereof include phenylenediamine, alkyl substituted phenylenediamine, diaminodiphenylsulfone, and 1,3-bis (4-aminophenoxy) benzene. Preferable examples of the alkyl substituted phenylenediamine include toluenediamine. These aromatic diamines also include isomers such as p-form, m-form, 4,4'-form and 3,4'-form.

(5) Characteristics of the polyimide of the present invention

The polyimide of the present invention is soluble in an organic solvent, preferably a polar organic solvent. Examples of such polar organic solvents include N-methylpyrrolidone, N, N'-dimethylacetamide, and N, N'-dimethylformamide. The amount of the polyimide dissolved in the organic solvent is 10? To 100 parts by mass of the aforementioned organic solvent. 15 parts by mass is preferred. In the present invention, the symbol "?" Includes the values of both ends thereof. It is because the polyimide which has such solubility is excellent in the handleability at the time of using as a polyimide solution. What is necessary is just to select an organic solvent suitably according to the solubility degree of a polyimide.

The polyimide of this invention is excellent in heat resistance. Heat resistance is evaluated by decomposition start temperature (Tm) or glass transition temperature (Tg). The polyimide of the present invention has a high Tm. This is considered to be because it has an oxazole group in a molecule | numerator as demonstrated later. Tm of the polyimide of this invention is 500? 560 degreeC is preferable and 540? 560 degreeC is more preferable. Moreover, Tg of the polyimide of this invention is 300? 400 ° C. is preferred. The polyimide which has Tm and Tg of such a range is applicable to the use which requires very high heat resistance.

The polyimide of this invention is derived from (3-amino-4-hydroxyphenyl) sulfone (HOABSO ₂ ), and will have an oxazole group or carboxyl group which is a polar group in a principal chain as mentioned later. For this reason, the polyimide of this invention is excellent in adhesiveness with another material. Moreover, the polyimide of this invention also has the photosensitivity characteristic that a -N = C- bond of an oxazoline ring will be cleaved and the molecular chain of this part will be cut | disconnected if light is irradiated (patent document 6). Moreover, the polyimide of this invention also has electrodeposition characteristics by ionizing a carboxyl group.

(6) Structure of the polyimide of the present invention

It is preferable that the polyimide of this invention has a repeating unit of the following general formula (I), (II), or (III).

-[PMDA]-[HOABSO ₂ ]-[PMDA]-[DADE]-[DA]-[DADE]-[PMDA]-[HOABSO ₂ ]-[PMDA] -U _1- (Ⅰ)

-[DADE]-[DA]-[DADE]-[PMDA]-[HOABSO ₂ ]-[PMDA]-[DADE]-[DA]-[DADE] -U _2- (II)

-[PMDA] -X _3- [PMDA]-[DADE]-[DA]-[DADE]-[PMDA] -X _3- [PMDA] -U _3- (III)

Repeating unit of (I)

-[PMDA]-[HOABSO ₂ ]-[PMDA]-[DADE]-[DA]-[DADE]-[PMDA]-[HOABSO ₂ ]-[PMDA] -U _1- (Ⅰ)

In the formula, [PMDA] is the pyromellitic acid dianhydride residue. [HOABSO ₂ ] is the bis (3-amino-4-hydroxyphenyl) sulphone residue. [DADE] is the diaminodiphenyl ether residue. [DA] is the carboxylic acid dianhydride residue. A residue is a partial structure in a polymer and means structures other than a chemical bond. For example, in general formula (I), [DADE], ie, a diaminodiphenyl ether residue, is a divalent diphenyl ether group.

U ₁ is a group represented by X ₁ or X _1- [DA] -X ₁ . X ₁ is a phenylenediamine residue, an alkyl substituted phenylenediamine residue, a diaminodiphenyl sulfone residue, a bis (aminophenoxy) benzene residue, or a bis (3-amino-4-hydroxyphenyl) sulfone residue.

Especially, as X <_1> , a phenylenediamine residue or a toluenediamine residue is preferable. This is because such polyimide has high solubility in organic solvents.

[DADE] and [DA], and the bond of [DADE] and [PMDA] are imide bonds. That is, the bond is an imide bond formed by reaction of an amino group derived from diaminodiphenyl ether (DADE) and an acid anhydride group derived from an acid dianhydride.

In addition, the bond of [HOABSO ₂ ] and [PMDA] is a bond represented by general formula (i) or (ii).

[Chemical Formula 18]

The bond represented by general formula (VII) is a bond through an oxazole group, and is also referred to as "oxazole bond" in the present invention. R is a hydrogen atom or a carboxyl group. α represents part of [PMDA] and β represents part of [HOABSO ₂ ].

An oxazole bond is formed by reacting the amino group and the hydroxyl group of HOABSO ₂ , which is a dihydroxydiamine, with an acid anhydride group derived from PMDA (scheme 1).

[Formula 19]

Of the two carboxyl groups generated from one acid anhydride group, one carboxyl group remains since it cannot participate in this reaction (L-2). When this carboxyl group is heated at 410 degreeC or more, it will detach | desorb by decarboxylation reaction (L-3). This is also supported by thermal analysis of the polyimide of the present invention, in which mass reduction can be observed at around 410 ° C. Therefore, R in Formula (i) becomes a hydrogen atom or a carboxyl group.

In addition, the bond represented by general formula (ii) is an imide bond in which a hydroxyl group exists in the vicinity of an imide group.

[Chemical Formula 20]

These bonds are produced by reaction of an amino group of HOABSO ₂ with an acid anhydride group such as PMDA. At that time, the hydroxyl group of HOABSO ₂ does not participate in the reaction and remains (L-4 in Scheme 2). However, this imide group and hydroxyl group are displaced to stable oxazole bond by heating at 150 degreeC or more and less than 400 degreeC (L-2).

[Chemical Formula 21]

[HOABSO _2] and, like binding of [PMDA], a combination of the case where X ₁ of U _1, bis (3-amino-4-hydroxyphenyl) sulfone moiety, [PMDA] and U ₁ is the general formula (I) or (ii). Otherwise, the bond of [PMDA] and U ₁ is an imide bond.

Since the polyimide of this invention contains the structure which [PMDA] and [DADE] couple | bonded, it is excellent in heat resistance and water resistance. However, as mentioned later, the polyimide containing the structure in which [PMDA] and [DADE] couple | bonded three or more like [PMDA]-[DADE]-[PMDA] falls in the solubility with respect to an organic solvent. Although this cause is not certain, it is inferred that the said structure may be because the density of the imide group is high. As described above, since the polyimide of the present invention also contains a specific structure such as [HOABSO ₂ ] while controlling the bond of [PMDA] and [DADE], it is excellent in heat resistance and water resistance and has various functions.

In the case where the polyimide of the present invention has a structure of L-2 or L-4, that is, an oxazole group, a hydroxyl group or a carboxyl group, the adhesion with other materials is particularly excellent. Moreover, when the polyimide of this invention has a structure of L-2 or L-3 in a coupling part, ie, it has an oxazole group and a carboxyl group, it is excellent in adhesiveness and excellent in heat resistance. In particular, when the polyimide of this invention has many structures of L-3 in a coupling part, it is excellent in heat resistance.

By at least, di-hydroxy diamine of HOABSO ₂ and the structure of the combination of the acid anhydride selected appropriately, can exhibit a variety of poly-functional polyimide of the present invention. However, the bond is preferably a bond represented by L-2 or L-3. This is because such polyimide is excellent in heat resistance.

Therefore, it is preferable that the repeating unit of (I) in the polyimide of this invention is represented by General formula (1).

Repeating unit of (1)

[Formula 22]

This repeating structure is characterized in that HOABSO ₂ bonds oxazole with acid dianhydride.

In the formulas, * indicates that a phenylene group and an imide group are bonded.

Q is a single bond or a carbonyl group. In the case of using biphenyltetracarboxylic acid dianhydride (BPDA) as the carboxylic acid dianhydride (DA), Q is a single bond, and in the case of using benzophenonetetracarboxylic acid anhydride (BTDA), a carbonyl group to be. The single bond means that the benzene rings are directly bonded to each other to form a biphenyl skeleton. In the present invention, Q is preferably a single bond. It is because the polyimide whose Q is a single bond is more excellent in heat resistance.

Y ₁ is equivalent to U ₁ in General Formula (I) and is a group represented by General Formula (11), (12), (13), or (14).

(23)

That is, general formula (11)? (13) is a specific structure in the case where U <_1> of General formula (I) is represented by X <_{1>, and} is an aromatic diamine residue. R <_10> in General formula (11) is a hydrogen atom or C1-C? Although it is an alkyl group of 3, a hydrogen atom or a methyl group is preferable. This is because such polyimide has higher solubility in organic solvents.

General formula (14) is a specific structure in the case where U <_1> of general formula (I) is represented by X <_1> -[DA] -X <_1> . Ar ₁ in General formula (14) is independently the said General formula (11)? It is group represented by (13). Q is a single bond or a carbonyl group. As described above, Q is preferably a single bond.

As Y <_1>, group represented by General formula (11) is preferable. This is because such polyimide is more excellent in heat resistance.

Repeating units of (II)

-[DADE]-[DA]-[DADE]-[PMDA]-[HOABSO ₂ ]-[PMDA]-[DADE]-[DA]-[DADE] -U _2- (II)

This repeating structure is characterized in that HOABSO ₂ can bond oxazole with acid dianhydride.

In formula, [PMDA] etc. are as having demonstrated by Formula (I).

U ₂ is a group represented by [DA] or [DA] -X _2- [DA]. X ₂ is a phenylenediamine residue, an alkyl substituted phenylenediamine residue, a diaminodiphenylsulfone residue, 1,3-bis (4-aminophenoxy) benzene, or the bis (3-amino-4-hydroxyphenyl) Sulfone residues. Among these, a phenylenediamine residue or a toluenediamine residue is preferable. This is because such polyimide has high solubility in organic solvents.

The bond of [DADE] and [DA], [DADE] and [PMDA], and U ₂ and [DADE] is an imide bond.

As explained in Formula (I), it is preferable that the oxazole bond in the polyimide of this invention is a bond represented by L-2 or L-3. Therefore, it is preferable that the repeating unit of (II) in the polyimide of this invention is represented by General formula (2).

(2) repeat unit

&Lt; EMI ID =

In the formula, Q is a single bond or a carbonyl group. In the present invention, Q is preferably a single bond. It is because the polyimide whose Q is a single bond is more excellent in heat resistance.

Y ₂ is a group corresponding to U ₂ in General Formula (II). Y ₂ is represented by General Formula (21), (22), or (23).

(25)

Formula (21) is a concrete structure of a case showing a U ₂ in the general formula (Ⅱ) to X _2, it is a di-carboxylic acid anhydride residue.

Formula (22), (23) is a U ₂ in the general formula _{(Ⅱ) [DA] -X 2} - is the detailed structure of the case shown in [DA]. Formula (23) is a structure in the case where X ₂ is HOABSO _2, formula (22) is a structure in the case where X ₂ is an aromatic diamine other than HOABSO _2. Q is defined as above and a single bond is preferable for the reason mentioned above. Ar ₁ represents the general formula (11) described above; Although it is (13), the group of General formula (11) is preferable for the reason mentioned above.

R, a? d and * are defined similarly to general formula (1).

As Y <_2>, group represented by General formula (22) is preferable. This is because such polyimide is more excellent in heat resistance.

Repeat units of (III)

-[PMDA] -X _3- [PMDA]-[DADE]-[DA]-[DADE]-[PMDA] -X _3- [PMDA] -U _3- (III)

In formula, [PMDA] etc. are as having demonstrated in Formula (I) and (II).

X ₃ is a phenylenediamine residue, an alkyl substituted phenylenediamine residue, a diaminodiphenylsulfone residue, or a bis (aminophenoxy) benzene residue. Among these, X ₃ is preferably a phenylenediamine residue or a toluenediamine residue. This is because such polyimide is excellent in solubility in an organic solvent.

U ₃ is [HOABSO ₂ ], [HOABSO ₂ ]-[DA]-[HOABSO ₂ ], [HOABSO ₂ ]-[DA] -X ₃ , or X _3- [DA]-[HOABSO ₂ ].

The bond of [DADE] and [DA], [DADE] and [PMDA], [PMDA] and X ₃ is an imide bond.

The combination of [HOABSO ₂ ] and [PMDA], and the combination of [HOABSO ₂ ] and [DA] is a bond represented by the above general formula (i) or (ii).

As mentioned above, it is preferable that the oxazole bond in the polyimide of this invention is a bond represented by L-2 or L-3. Therefore, it is preferable that the repeating unit of (III) in the polyimide of this invention is represented by General formula (3-1) or (3-2).

Repeat unit of (3-1)

(26)

In formula, Q is a single bond or a carbonyl group, A single bond is preferable as mentioned above.

Ar ₁ corresponds to the aromatic diamine residue X ₃ of General Formula (III) and is represented by General Formula (11), (12), or (13).

Y ₃ is a group represented by a group derived from the formula U ₃ (Ⅲ), or a single bond, or a group represented by the formula (31).

(27)

That is, in the general formula (III), when U ₃ is [HOABSO ₂ ], Y ₃ is a single bond. In the general formula (III), when U ₃ is [HOABSO ₂ ]-[DA]-[HOABSO ₂ ], Y ₃ becomes the structure of general formula (31).

In General Formulas (3-1) and (31), R, R ₁ , Q, * and a? h is defined similarly to General formula (1), (2).

Repeat unit of (3-2)

(28)

This repeating unit is a specific structure in the case where U ₃ is [HOABSO ₂ ]-[DA] -X ₃ in General Formula (III).

Wherein Q, Ar ₁ , R, R ₁ , Q, * and a? d is defined similarly to General formula (3-1).

In addition, the following structure may be sufficient as the repeating structure of the polyimide of this invention.

-[PMDA]-[DADE]-[DA]-[DADE]-[PMDA]-[HOABSO ₂ ] _- [PMDA] -U _1- (I ')

-[PMDA]-[DADE]-[DA]-[DADE]-[PMDA] -X _3- [PMDA] -U _3- (III ')

In these structures, [PMDA] etc. are represented by Formula (I)? It is as described in (III).

2. Manufacturing method of polyimide of the present invention

Carboxylic acid dianhydride (DA) of this invention has one acid anhydride group in one benzene ring. On the other hand, pyromellitic-acid dianhydride (PMDA) has two acid anhydride groups in one benzene ring. That is, since the close degree of the acid anhydride groups which exist in 1 molecule differs by the difference in the structure of an acid di-anhydride, the reactivity of an imidation reaction also differs significantly.

For example, when polymerizing a polyimide using biphenyltetracarboxylic acid dianhydride (BPDA) as a raw material, the molecular weight of the polymer decreases with the passage of the reaction time. In short, plotting the molecular weight of the polymer produced with time as the horizontal axis yields a parabolic curve.

On the other hand, when polymerizing a polyimide using pyromellitic acid dianhydride (PMDA) as a raw material, the molecular weight of the polymer produced | generated with time increases rapidly, unlike this. In short, a hyperbolic curve is obtained by plotting the molecular weight of a polymer produced with time as the horizontal axis. When the molecular weight increases sharply, a gelled product is formed and the solubility of the polyimide in the organic solvent is lowered. The rapid increase in molecular weight is thought to be due to the intermolecular crosslinking reaction of the polyamic acid produced as a precursor (Scheme 3).

[Formula 29]

In this invention, PMDA and DA are used together as an acid di-anhydride, and the polyimide soluble in an organic solvent is synthesize | combined. Therefore, the difference of the reactivity of PMDA and DA, control of molecular weight, and determination of the end point of reaction become important.

As mentioned above, it is preferable that the polyimide of this invention is manufactured by the method characterized by the following points.

1) A three-stage sequential polymerization method in which sequential polymerization is performed in three stages is adopted.

2) In the first and second steps, oligomers having amino groups at both ends or oligomers having acid anhydride groups at both ends are obtained.

3) In the third step, the oligomer obtained in the previous step is polymerized to obtain a high molecular weight polyimide.

4) In the same process, diaminodiphenyl ether (DADE) and pyromellitic acid anhydride (PMDA) are not present at the same time, and [PMDA]-[DADE]-[PMDA] or [components which are poorly soluble in an organic solvent. The oligomers represented by DADE]-[PMDA]-[DADE] are either not produced during manufacture or these structures are not formed in the polymer.

Specifically, it is preferable that the polyimide of this invention is manufactured by the method of the following A, B or C.

(1) Production method A

Manufacturing method A,

(A1) 1 molar equivalent of carboxylic acid dianhydride (DA) containing biphenyl tetracarboxylic dianhydride (BPDA) or benzophenone tetracarboxylic dianhydride (BTDA), and diamino diphenyl ether (DADE) Reacting 2 molar equivalents to obtain an oligomer whose both ends are an amino group derived from DADE,

(A2) The oligomer obtained in step A1 is reacted with 4 molar equivalents of pyromellitic acid dianhydride (PMDA) and 2 molar equivalents of bis (3-amino-4-hydroxyphenyl) sulfone (HOABSO ₂ ), and both ends thereof are PMDA. A step of obtaining an oligomer which is a derived acid anhydride group, and

(A3) 1 molar equivalent of the oligomer obtained by the A2 process and aromatic diamine, or

(DA) containing biphenyltetracarboxylic dianhydride (BPDA) or benzophenonetetracarboxylic dianhydride (BTDA) in an amount of 1 mole equivalent of an oligomer obtained in the step A2 and 2 moles of an aromatic diamine In an equivalent amount to obtain a polymer.

The aromatic diamine in the present production method is not limited as long as it is a compound in which two amino groups are bonded to an aromatic group. However, phenylenediamine, toluenediamine, diaminodiphenylsulfone, bis (4-aminophenoxy) benzene, or bis (3-amino-4-hydroxyphenyl) sulfone are preferred. This is because these aromatic amines can be obtained easily and can give polyimide excellent in solubility. These aromatic amines also include their isomers. Among these, a phenylenediamine residue or a toluenediamine residue is preferable. This is because such polyimide has higher solubility in organic solvents.

In order to simplify description below, biphenyltetracarboxylic-acid dianhydride (BPDA) is used as carboxylic acid di-anhydride (DA), and 2,4'- diaminotoluene (DAT) is used as aromatic diamine. The case where 1 mol equivalent of BPDA and 2 mol equivalent of DAT are made to react in A3 process is demonstrated. This reaction is represented by the following scheme A.

(30)

1) A1 process

In this step, one acid anhydride group of BPDA and one amino group of DADE react, and the other acid anhydride group of BPDA reacts with one amino group of DADE of another molecule. As a result, oligomer (a1) whose terminal is an amino group is produced. Since this oligomer is stable and soluble in an organic solvent, an oligomer does not precipitate in a reaction liquid.

This step is preferably carried out under an inert gas stream and under a polar organic solvent. Examples of inert gases include nitrogen and argon. Examples of polar organic solvents include NMP, DMAc, and DMF.

It is preferable to use γ-valerolactone and pyridine or γ-valerolactone and N-methylmorpholine as a catalyst. γ-valerolactone is 10? 15 mmol equivalent, pyridine, or N-methylmorpholine is 20? It is preferred that it is 30 millimolar equivalents.

Moreover, in order to remove the water produced | generated by reaction out of the system, it is preferable to use together solvents, such as toluene which can be azeotropic with water.

What is necessary is just to determine reaction temperature in consideration of the balance of reaction rate, degradation of a raw material, etc. In the present invention, the reaction temperature is 150? About 200 degreeC is preferable.

Moreover, what is necessary is just to determine reaction time suitably according to the progress of reaction.

2) A2 process

This step adds 4 molar equivalents of pyromellitic acid dianhydride (PMDA) and 2 molar equivalents of bis (3-amino-4-hydroxyphenyl) sulfone (HOABSO ₂ ) to react with the oligomer obtained in the previous step. Although the reaction mechanism is not limited, it is inferred as follows.

i) One amino group of HOABSO ₂ and one acid anhydride group of PMDA react, and the other amino group of HOABSO ₂ and one acid anhydride group of PMDA of another molecule react. As a result, 2 mol equivalents of the oligomer represented by [PMDA]-[HOABSO ₂ ]-[PMDA] are produced.

ii) The amino group at one terminal of the oligomer (a1) produced in the previous step and the acid anhydride group present at one terminal of [PMDA]-[HOABSO ₂ ]-[PMDA] react.

iii) The amino group of one terminal of the oligomer (a1) and the acid anhydride group of one terminal of another [PMDA]-[HOABSO ₂ ]-[PMDA] react. As a result, oligomer (a2) whose terminal is an acid anhydride group is produced.

In this method, as described above, oligomers represented by [PMDA]-[DADE]-[PMDA] or [DADE]-[PMDA]-[DADE] which are poorly soluble in an organic solvent are not produced. However, oligomers which have not existed conventionally are generated, such as [PMDA]-[HOABSO ₂ ]-[PMDA]. Although the oligomer containing the compound which was not used conventionally as a raw material of a polyimide is often insoluble in an organic solvent, the oligomer represented by [PMDA]-[HOABSO ₂ ]-[PMDA] is soluble in an organic solvent. Therefore, the oligomer (a2) which contains this structure in a molecule | numerator is also soluble in an organic solvent. This is inferred to be because HOABSO ₂ has a hydroxyl group and a sulfonyl group which are polar groups in the molecule.

It is preferable to perform A2 process also in inert gas airflow similarly to A1 process. Moreover, reaction temperature and reaction time may also be the same as that of A1 process.

3) A3 process

This step adds 1 molar equivalent of biphenyltetracarboxylic acid anhydride (BPDA) and 2 molar equivalents of 2,4'-diaminotoluene (DAT) to obtain an oligomer obtained in the previous step, and 1 molar equivalent of BPDA. And 2 molar equivalents of DAT are reacted to obtain a polymer.

Although this reaction mechanism is not limited, it is inferred as follows.

i) One acid anhydride group of BPDA and one amino group of DAT react, and the other acid anhydride group of BPDA and one amino group of DAT of another molecule react. As a result, 1 mol equivalent of the oligomer represented by [DAT]-[BPDA]-[DAT] is produced.

ii) The acid anhydride of one terminal of the oligomer (a2) produced | generated in the previous process, and the amino group which exists in one terminal of [DAT]-[BPDA]-[DAT] react, and [ An oligomer having DAT]-[BPDA]-[DAT] bound is generated.

iii) Since this oligomer has an amino group at one end and an acid anhydride group at the other end, it polymerizes and produces | generates high molecular weight polyimide (a3).

This polyimide is a polyimide which has a repeating unit of General formula (1). Also in this process, the oligomer represented by [PMDA]-[DADE]-[PMDA] or [DADE]-[PMDA]-[DADE] which is poorly soluble in an organic solvent is not produced | generated. Therefore, a component does not precipitate in a reaction system during a process, and the obtained polyimide (a3) is also soluble in an organic solvent.

It is preferable that A3 process is also performed under inert gas airflow similarly to A1 process. Moreover, reaction temperature and reaction time may also be the same as that of A1 process. It is preferable to add a solvent because the viscosity of the system increases as the polymer becomes high molecular weight. Although the addition amount of a solvent may be adjusted suitably, in consideration of the handleability of a reaction solution, etc., the reaction liquid contains 10? It is preferable to adjust so that it may contain about 20 mass%.

In the above, 1) a three-stage sequential polymerization method is employed, 2) an oligomer having an amino group at both ends in the first step is obtained, an oligomer having an acid anhydride group at both ends in the second step, and 3) a high molecular weight at the third step. The polyimide which is soluble in a solvent is obtained by this manufacturing method which has the characteristics similar to obtaining the polyimide of 4, and not producing the oligomer shown by 4) [PMDA]-[DADE]-[PMDA].

In the polyimide represented by general formula (a3), the bond of PMDA and DADE represented by V, and the bond of DADE and BPDA are imide bonds. It is preferable that an imide bond arises in A1 and A2 process. That is, it is preferable that an imide bond is produced | generated instead of an amide bond between DADE and BPDA in A1 process, and similarly, an imide bond is produced between PMDA and DADE in A2 process. This is because the exchange reaction proceeds in solution if DADE and BPDA are unstable amide bonds. Since the polyimide of this invention is soluble in an organic solvent even if an imide bond is formed, there exists an advantage that exchange reaction hardly arises in solution.

In addition, although some intermolecular crosslinking reaction may have occurred in the polyimide of the present invention, since the bonds generated by intermolecular crosslinking are relatively weak, even if intermolecular crosslinking has occurred, they can be cleaved by a bond releasing agent. have.

In the general formula (a3), the bond between PMDA and HOABSO _{2 in} the portion represented by W may have various bonds as described above. However, A1? A3 process is 150 ℃? It carries out at 200 degreeC and reaction of A3 process is 3? Since it is preferable to carry out about 6 hours, the part of W is a bond mainly interposed through an oxazole group, and it is thought that a carboxyl group exists in the vicinity of an oxazole group (structure of L-2 mentioned above). Therefore, in the process of A3, it is 400 degreeC? 500 ° C., preferably 410 ° C.? When polyimide is heated at 450 degreeC, the part of W is a bond which interposed the oxazole group, and it is thought that it becomes a bond (the structure of L-3 mentioned above) which does not exist in the vicinity of an oxazole group. However, the reaction system containing the solvent is 400 ℃? Heating at 500 ° C may impair the physical properties of the polyimide with decomposition of the solvent and the like. Therefore, A3 process is 150 ℃? It carries out at 200 degreeC, and after this process, a solvent is removed and 400 degreeC? You may form the process of heating a polyimide at 500 degreeC.

In the above step, the method of reacting 1 molar equivalent of carboxylic acid dianhydride and 2 molar equivalent of aromatic amine in the A3 step is described, but only 1 molar equivalent of aromatic diamine may be reacted.

(2) Manufacturing Method B

Manufacturing method B,

(B1) 2 molar equivalents of pyromellitic acid dianhydride (PMDA) and 1 molar equivalent of bis (3-amino-4-hydroxyphenyl) sulfone (HOABSO ₂ ) are reacted to obtain an oligomer whose both ends are PMDA-derived acid anhydride groups. fair,

(B2) 2 molar equivalents of the carboxylic acid dianhydride (DA) containing the oligomer obtained by the B1 process, biphenyl tetracarboxylic dianhydride (BPDA), or benzophenone tetracarboxylic dianhydride (BTDA), and dia Reacting 4 molar equivalents of minodiphenylether (DADE) to obtain an oligomer whose both ends are an amino group derived from DADE, and

(B3) 1 mol equivalent of the carboxylic acid dianhydride (DA) containing the oligomer obtained by the B3 process, and biphenyl tetracarboxylic dianhydride (BPDA) or benzophenone tetracarboxylic dianhydride (BTDA), or

It is a method including the process of making the polymer by making the oligomer obtained by the B3 process, 2 mol equivalent of the said carboxylic acid di-anhydride (DA), and 1 mol equivalent of aromatic diamine react.

The aromatic diamine is preferably a compound as described in Production Method A.

In order to simplify the explanation, hereinafter, biphenyl tetracarboxylic dianhydride (BPDA) is used as the carboxylic acid dianhydride (DA), DAT is used as the aromatic diamine, and 2 molar equivalents of BPDA 1 molar equivalent of DAT is reacted. This reaction is represented by the following scheme B.

(31)

In B1 process, the oligomer (b1) whose terminal is an acid anhydride group is produced. Since this oligomer is soluble in an organic solvent, oligomer does not precipitate in a reaction liquid.

In the step B2, 2 molar equivalents of BPDA and 4 molar equivalents of DADE are added to react with the oligomer obtained in the previous step. The oligomer produced in this reaction contains a HOABSO ₂ derived skeleton in the molecule, and the terminal is an amino group. This oligomer is soluble and does not precipitate in the reaction solution.

B3 process adds 2 mol equivalent of BPDA and 1 mol equivalent of DAT, and makes it react with the oligomer obtained in the previous process, and obtains high molecular weight polyimide (b3). This polyimide has a repeating unit of General formula (2), and is soluble in an organic solvent.

What is necessary is just to make the conditions of each process the same as the manufacturing method A. In addition, after B3 process, it is 400 degreeC? 500 ° C., preferably 410 ° C.? You may form the process of heating a polyimide at 450 degreeC. Moreover, the reaction mechanism of this method can be inferred similarly to the manufacturing method A.

Although the above described the method for reacting 2 molar equivalents of carboxylic acid dianhydride and 1 molar equivalent of aromatic amine in the B3 step, only 1 molar equivalent of aromatic diamine may be reacted.

(3) Manufacturing Method C

Manufacturing method C,

(C1) 1 molar equivalent of carboxylic acid dianhydride (DA) containing biphenyl tetracarboxylic dianhydride (BPDA) or benzophenone tetracarboxylic dianhydride (BTDA), and diamino diphenyl ether (DADE) Reacting 2 molar equivalents to obtain an oligomer whose both ends are an amino group derived from DADE,

(C2) a step of reacting the oligomer obtained in the previous step with 4 molar equivalents of pyromellitic acid dianhydride (PMDA) and 2 molar equivalents of aromatic diamine to obtain an oligomer whose both ends are PMDA-derived acid anhydride groups, and

(C3) 1 molar equivalent of oligomer and bis (3-amino-4-hydroxyphenyl) sulfone (HOABSO ₂ ) obtained in the previous step, or

1 mol equivalent of carboxylic acid dianhydride (DA) containing the oligomer obtained by the previous process, biphenyl tetracarboxylic dianhydride (BPDA), or benzophenone tetracarboxylic dianhydride (BTDA), and bis (3- amino-4-hydroxyphenyl) sulfone (HOABSO ₂₎ and 1 molar equivalent, by reacting one molar equivalent of an aromatic diamine which comprises the step of obtaining the polymer.

Aromatic diamine in this way, preferably in the aromatic diamine other than HOABSO _2, and phenylene diamine, toluene diamine, diaminodiphenyl sulfone, or 1,3-bis (4-aminophenoxy) benzene is preferred over the Do. This is because these aromatic amines can be obtained easily and can give polyimide excellent in solubility. Among these, a phenylenediamine residue or a toluenediamine residue is preferable. Such polyimide has higher solubility in organic solvents.

For the sake of simplicity, the following is a description of the case where biphenyltetracarboxylic acid dianhydride (BPDA) is used as the carboxylic acid dianhydride (DA) and 2,4'-diaminotoluene (DAT) is used as the aromatic diamine. Explain. The scheme of this reaction is shown below.

(32)

In C1 process, the oligomer (c1) whose terminal is an amino group is produced. Since this oligomer is soluble in an organic solvent, oligomer does not precipitate in a reaction liquid.

The C2 process adds 4 molar equivalents of pyromellitic acid dianhydride (PMDA) and 2 molar equivalents of aromatic diamine to react with the oligomer obtained in the previous step. The oligomer produced in this reaction is an acid anhydride group at the end (c2).

The C3 process comprises one molar equivalent of biphenyltetracarboxylic acid anhydride (BPDA), one molar equivalent of 2,4'-diaminotoluene (DAT), and one molar equivalent of bis (3-amino-4-hydroxy Phenyl) sulfone (HOABSO ₂ ) is reacted with the oligomer obtained in the C2 step to obtain a polymer (c3). This polyimide is soluble in an organic solvent, and has a repeating unit of general formula (3-2).

What is necessary is just to make the conditions of each process the same as the manufacturing method A. In addition, after C3 process, 400 degreeC? 500 ° C., preferably 410 ° C.? You may form the process of heating a polyimide at 450 degreeC. The reaction mechanism of this method can be estimated similarly to the manufacturing method A.

Although the above described a method for reacting 1 molar equivalent of carboxylic acid dianhydride with 1 molar equivalent of HOABSO ₂ , and 1 molar equivalent of aromatic amine in the C3 process, 1 molar equivalent of HOABSO ₂ Only one reaction may be carried out, or one molar equivalent of carboxylic acid dianhydride and two molar equivalents of HOABSO ₂ may be reacted. In this case, the polyimide which has a repeating unit represented by General formula (3-1) is obtained.

3. Use of the polyimide of the present invention

(1) composite materials

The polyimide of this invention can be used as a composite material composited with another material. In particular, the composite material obtained by laminating | stacking the film obtained from the polyimide of this invention on a base material is preferable. As mentioned above, since the polyimide of this invention has the outstanding heat resistance and adhesiveness, the composite material of high heat resistance and high strength is obtained. Such a composite material can be used as an aerospace material, a vehicle material for transport, and a semiconductor material.

Such a composite material,

1) preparing a solution containing the polyimide of the present invention and an organic solvent,

2) a step of forming a film by casting or applying the solution on a substrate, and

3) It is preferable to manufacture by the method including the process of drying the said film | membrane.

Since the polyimide of this invention is soluble in an organic solvent, a solution can be easily prepared. What is necessary is just to carry out preparation of a solution as well as a well-known polar solvent as an organic solvent. Examples of the polar solvent include NMP, DMAc, DMF, and the like. Although the concentration of the solution is not limited, it is excellent in handleability and the like. 20 mass% is preferable.

What is necessary is just to carry out the process of cast | flow_spreading or apply | coating this solution on a base material, and forming a film | membrane as well-known. For example, this step may be performed using a device such as a spin coater, knife coater, roll coater, or the like. A well-known thing may be used for a base material, For example, glass, a metal, Preferably a copper plate, a ceramic, etc. are contained.

The film is then dried, which condition may be determined in accordance with the properties to be obtained. For example, if it is the use which requires high adhesiveness, Preferably it is 300 degrees C or less, More preferably, it is 200 degreeC? The membrane is dried at 300 ° C. When the film is dried at such a temperature, high adhesion is obtained because polar groups such as carboxyl groups exist in the molecule. On the other hand, if it is the application which requires high heat resistance, especially high thermal decomposition property, it is 400 degreeC? 500 ° C., in particular 410 ° C.? It is preferable to dry the film at 450 ° C. When the film is dried at such a temperature, very high heat resistance is obtained because the carboxyl group is detached.

(2) photosensitive material

As described above, the polyimide of the present invention has photosensitivity because it has an oxazole group in its molecule. Therefore, it is useful as a positive resist material. Generally, since a positive resist can draw a very fine pattern, it can be used as a next-generation semiconductor material.

(3) paints, adhesives

Since the polyimide of this invention is soluble in an organic solvent, and the solution is stable and excellent in adhesiveness, it can be used as a coating agent, a coating material, or an adhesive agent. In particular, it can be used for medical materials, building materials, household high heat-resistant materials (iron flooring, pot lining materials), flame retardant curtains, coatings as polytetrafluoroethylene substitutes. Moreover, when the polyimide of this invention has a carboxyl group in a molecule | numerator, it can be used also as an electrodeposition paint which can be electrodeposition-coated.

What is necessary is just to prepare a coating agent, a coating material, or an adhesive agent by a well-known method.

Example

In an embodiment, for example, 1 molar equivalent of carboxylic acid dianhydride (DA) and 2 molar equivalents of DADE are reacted in a first step, and 4 molar equivalents of PMDA and 2 molar equivalents of HOABSO are reacted in a second step. _{When 2 is made} to react and 1 mol equivalent of DA and 2 mol equivalent of aromatic diamine (X) are reacted in a 3rd process, the reaction process is shown as follows.

(DA + 2DADE) (4PMDA + 2HOABSO ₂ ) (DA + 2X)

In the examples, 4,4'-diaminodiphenyl ether was particularly denoted as DADE, and 3,4'-diaminodiphenyl ether was denoted as mDADE.

The most important process in the manufacturing method of the polyimide of this invention is a 2nd process. Normally, this step simply adds a reagent to the reaction system, but there are cases where a restriction occurs in the order of adding the reagent or the time for adding the reagent. Therefore, a 2nd process can be changed suitably as needed and can be performed. Thus, changing and implementing a 2nd process suitably is effective at the time of performing an experiment for the first time. For example, in the second step, 1) a container different from the reaction container is prepared, the reagent added in the second step is heated as necessary, and dissolved in advance, and 2) the uniform solution thus obtained is added to the reaction container. What is necessary is just to make it the process of adding. Moreover, you may add such a change also to a 3rd process as needed.

Example 1

(BPDA + 2DADE) (4PMDA + 2HOABSO ₂ ) (BPDA + 2DAT)

The glass-separable flask was equipped with the stirring apparatus provided with the anchor type stirring blade (made of stainless steel), the water separation trap (Dinstock trap), and the reflux condenser. The flask was immersed in a silicon bath while flowing nitrogen gas into the flask.

1) 2.94 g (10 mmol) of 3,4,3 ', 4'-biphenyltetracarboxylic acid anhydride (BPDA), 4.00 g (20 mmol) of 4,4'-diaminodiphenylether (DADE), 1.2 g (12 mmol) of gamma-valerolactone, 2.0 g (25 mmol) of pyridine, 80 g of N-methylpyrrolidone (NMP), and 25 g of toluene were charged to a flask. The reaction was carried out by heating and stirring for 40 minutes under conditions of 180 rpm and a silicon bath temperature of 180 ° C. under a nitrogen gas stream. Thereafter, the reaction mixture was air cooled for 20 minutes while stirring.

2) Next, 8.73 g (40 mmol) of pyromellitic acid dianhydride (PMDA), followed by 5.60 g (20 mmol) of bis (3-amino-4-hydroxyphenyl) sulfone (HOABSO ₂ ) and 100 g of NMP Charged in. The flask was immersed in a 180 degreeC silicon bath, and it stirred for 20 minutes at 180 rpm, and reaction was performed. Thereafter, the reaction mixture was air cooled for 20 minutes while stirring.

3) Subsequently, 2.94 g (10 mmol) of BPDA, 2.44 g (20 mmol) of 2,4-diaminotoluene (DAT), and 115 g of NMP were charged into the flask in this order. The flask was immersed in a 180 degreeC silicone bath, and the polymerization reaction was performed at 180 rpm. After carrying out the reaction for 4 hours, the reaction mixture was air cooled to stop the reaction. Thus, 12 mass% polyimide solution was obtained.

A part of the solution was taken and polyethylene conversion molecular weight and molecular weight distribution were measured by high performance liquid chromatography (GPC: HLCP-8320 manufactured by Tosoh Corporation). As a result, Mn = 29160, Mw = 60919, Mz = 93437, Mw / Mn = 2.09, and Mz / Mw = 1.53.

4) The obtained solution was apply | coated to the glass plate surface, and it dried at 150 degreeC under air ventilation. The dried coating film was liberated from a glass plate and affixed to a metal frame. In this state, it heated further at 300 degreeC for 1 hour, and obtained the polyimide film. The thermal decomposition start temperature (Tm) and the primary loss temperature and glass transition temperature (Tg), which are the decomposition temperatures first observed in the Tm measurement, were measured using a TG-DTA analyzer manufactured by Mac Science. Measurement conditions are temperature increase rate: 10 degree-C / min, measurement temperature: Room temperature? It was made into 600 degreeC and nitrogen gas airflow. As a result, it was Tm = 555 degreeC, primary weight loss temperature = 418 degreeC, and Tg = 388 degreeC.

In addition, regarding the process of 2), the polyimide was synthesize | combined using the following other methods.

PMDA 8.73 g, HOABSO ₂ 5.60 g and NMP 100 g were collected in another flask, and occasionally heated while stirring at room temperature to obtain a uniform solution. After adding this liquid to the reaction mixture obtained at the process of 1), and stirring for 20 minutes, it stirred for 20 minutes on 180 degreeC and 180 rpm conditions. Thereafter, the reaction mixture was air cooled with stirring for 20 minutes.

[Example 2]

(BPDA + 2DADE) (4PMDA + 2HOABSO ₂ ) (BPDA + DAT + mTPE)

A 10 mass% polyimide solution was obtained in the same manner as in Example 1 except for the following changes.

1.0g of gamma-valerolactone was used in the process of 1).

The amount of NMP added in the process of 2) was 140 g.

The raw material added in the process of 3) is made into 2.92 g of BPDA 2.94 g (10 mmol), DAT 1.22 g (10 mmol), and 1, 3-bis (4-aminophenoxy) benzene (mTPE), and to add The amount of NMP was 80 g. Moreover, reaction time was 6 hours.

The molecular weight and heat resistance of the obtained polyimide are shown in Table 1.

[Example 3]

(BPDA + 2DADE) (4PMDA + 2HOABSO ₂ ) (BTDA + DAT + HOABSO ₂ )

Except the following change point, it carried out similarly to Example 1, and obtained the polyimide solution.

1.0g of gamma-valerolactone was used in the process of 1).

The amount of NMP added in the process of 2) was 140 g.

3.22 g (10 mmol) of benzophenonetetracarboxylic-acid dianhydride (BTDA), 1.22 g (10 mmol) of DAT, 2.48 g of 4,4'- diamino diphenyl sulfones 10 mmol) and the reaction time was 6.5 hours.

The molecular weight and heat resistance of the obtained polyimide are shown in Table 1.

Example 4

(BPDA + 2DADE) (3PMDA + HOABSO ₂ ) (BTDA + 2DAT)

Except the following change point, it carried out similarly to Example 1, and obtained the polyimide solution.

1.2 g of pyridine was used in the process of 1).

The raw material to be added in the step of 2), PMDA 6.64 g (30 mmol), HOABSO 2 It was 2.80 g (10 mmol) and the amount of NMP added was 60 g.

The amount of NMP added in the process of 3) was 80 g, and reaction time was 4.75 hours.

The molecular weight and heat resistance of the obtained polyimide are shown in Table 1.

[Example 5]

(2PMDA + HOABSO ₂ ) (2BPDA + 4DADE) (2BPDA + mPD)

The flask similar to Example 1 was prepared, and it immersed in the silicon bath.

1) PMDA 4.36 g (20 mmol), HOABSO ₂ 2.80 g (10 mmol), gamma -valerolactone 1.2 g (12 mmol), pyridine 2.0 g (25 mmol), N-methylpyrrolidone (NMP) 100 g and toluene 25 g were charged to the flask.

The reaction was carried out by heating and stirring for 40 minutes under conditions of 180 rpm and a silicon bath temperature of 180 ° C. under a nitrogen gas stream. Thereafter, the reaction mixture was air cooled for 20 minutes while stirring.

2) Subsequently, 8.0 g (40 mmol) of DADE, then 5.88 g (20 mmol) of BPDA, and 60 g of NMP were charged to the flask in this order. The flask was immersed in a 180 degreeC silicon bath, and it stirred for 40 minutes at 180 rpm, and reaction was performed. Thereafter, the reaction mixture was air cooled for 20 minutes while stirring.

3) Subsequently, 5.88 g (20 mmol) of BPDA, then 1.00 g (10 mmol) of m-phenylenediamine (mPD) and 80 g of NMP were charged into a flask. The flask was immersed in a 180 degreeC silicone bath, and the polymerization reaction was performed at 180 rpm. After carrying out the reaction for 4.5 hours, the reaction mixture was air cooled to stop the reaction. Thus, 12 mass% polyimide solution was obtained. In the same manner as in Example 1, the molecular weight and heat resistance of the polyimide were measured. The results are shown in Table 1.

In addition, regarding the process of 2), the polyimide was synthesize | combined using the following other methods.

8.0 g of DADE, 5.88 g (20 mmol) of BPDA, and 60 g of NMP were collected in another flask, and occasionally heated while stirring at room temperature to obtain a uniform solution. This solution was added to the reaction mixture obtained in the step 1) and stirred for 20 minutes, followed by stirring for 40 minutes under conditions of 180 ° C and 180 rpm. Thereafter, the reaction mixture was air cooled with stirring for 20 minutes.

[Example 6]

(2PMDA + HOABSO ₂ ) (2BPDA + 4DADE) (2BPDA + HOABSO ₂ )

Except the following change point, it carried out similarly to Example 5, and obtained the polyimide solution.

In the step 1), 2.4 g of pyridine and 80 g of NMP were used, and the reaction time was 50 minutes.

The raw material to be added in the step of 3) was 5.88 g (20 mmol) of BPDA, followed by 2.80 g (10 mmol) of HOABSO ₂ , and the amount of NMP to be added was 60 g, and the reaction time was 2.75 hours. It was.

After the process of 3), NMP100g was further added to the reaction mixture, and the 10 mass% polyimide solution was obtained.

The molecular weight and heat resistance of the obtained polyimide are shown in Table 1.

[Example 7]

(2PMDA + HOABSO ₂ ) (2BPDA + 4DADE) (2BTDA + HOABSO ₂ )

Except the following change point, it carried out similarly to Example 5, and obtained the polyimide solution.

The raw material to be added in the step of 3), BTDA 6.46 g (20 mmol), HOABSO 2 It was 2.80 g (10 mmol) and reaction time was 4 hours. In addition, 60 hours of NMP was added when reaction passed 2 hours.

After the process of 3), NMP40g was further added to the reaction mixture, and the 10 mass% polyimide solution was obtained.

The obtained polyimide solution was apply | coated to the glass plate surface, and it dried for 30 minutes at 150 degreeC under air ventilation. The dried coating film was liberated from a glass plate and affixed to a metal frame. In this state, it heated further at 250 degreeC for 1 hour, and obtained the polyimide film.

The molecular weight and heat resistance of the obtained polyimide are shown in Table 1.

[Example 8]

(2PMDA + HOABSO ₂ ) (2BPDA + 4mDADE) (2BTDA + mTPE)

Except the following change point, it carried out similarly to Example 5, and obtained the polyimide solution.

The raw material added in the process of 2) was made into 8.00 g (40 mmol) of 3,4'- diamino diphenyl ether (mDADE), and 5.88 g (20 mmol) of BPDA.

The raw materials to be added in the step 3) were 6.46 g (20 mmol) of BTDA, 2.92 g (10 mmol) of 1,3-bis (4-aminophenoxy) benzene (mTPE), and the amount of NMP added was It was 50 g. The reaction time was 4 hours and 20 minutes, but when the reaction was passed for 3 hours, 50 g of NMP was added.

After the process of 3), NMP100g was further added to the reaction mixture, and the 10 mass% polyimide solution was obtained.

The molecular weight and heat resistance of the obtained polyimide are shown in Table 1.

[Example 9]

(BPDA + 2DADE) (4PMDA + 2DAT) (BPDA + DAT + HOABSO ₂ )

The flask similar to Example 1 was prepared, and it immersed in the silicon bath.

1) 4.12 g (14 mmol) of BPDA, 5.6 g (28 mmol) of DADE, 1.3 g of gamma-valerolactone, 2.6 g of pyridine, 126 g of NMP, and 30 g of toluene were charged to a flask. The reaction was carried out by heating and stirring for 50 minutes under a condition of 180 rpm and a silicon bath temperature of 180 ° C. under a nitrogen gas stream. Thereafter, the reaction mixture was air cooled for 20 minutes while stirring.

2) Then 12.2 g (56 mmol) of PMDA, 3.42 g (28 mmol) of DAT and 50 g of NMP were charged to the flask at intervals. The flask was immersed in a 180 degreeC silicon bath, and it stirred for 20 minutes at 180 rpm, and reaction was performed. Thereafter, the reaction mixture was air cooled for 20 minutes while stirring.

3) Then 4.12 g (14 mmol) of BPDA, 1.71 g (14 mmol) of DAT, HOABSO ₂ 3.93 g (14 mmol) and NMP 80 g were charged into the flask. The flask was immersed in a 180 degreeC silicone bath, and the polymerization reaction was performed at 180 rpm. After carrying out the reaction for 4 hours and 20 minutes, the reaction mixture was air cooled to stop the reaction. Thus, 14 mass% polyimide solution was obtained.

The obtained polyimide was evaluated similarly to Example 1. The results are shown in Table 1.

[Example 10]

(BPDA + 2DADE) (4PMDA + 2DAT) (BTDA + DAT + HOABSO ₂ )

Except the following change point, it carried out similarly to Example 9, and obtained the polyimide solution.

1) The reaction time in the step was 40 minutes, and the subsequent air cooling time was 40 minutes.

2) The amount of NMP added in the step was 70 g.

3) The raw materials added in the process were 4.51 g (14 mmol) of BTDA, 1.71 g (14 mmol) of DAT, and HOABSO ₂ It was 3.93 g (14 mmol), and the quantity of NMP to add was 58 g. Moreover, reaction time of this process was made into 5 hours. Thus, 14 mass% polyimide solution was obtained.

The obtained polyimide was evaluated similarly to Example 1. The results are shown in Table 1.

[Example 11]

(BPDA + 2DADE) (4PMDA + 2DAT) (HOABSO ₂ )

Except the following change point, it carried out similarly to Example 9, and obtained the polyimide solution.

The raw material added at the process of 1) was 2.94 g (10 mmol) of BPDA, 4.00 g (20 mmol) of DADE, 0.9 g of gamma-valerolactone, 1.8 g of pyridine, 100 g of NMP, and 35 g of toluene. Moreover, reaction time was made into 1 hour and further air cooling time was made into 15 minutes.

PMDA 8.72g (40 mmol) and DAT 2.44g (20mmol) were used as the raw material added in the process of 2), and the quantity of NMP to add was 44g. The air cooling time after reaction was made into 30 minutes.

3) The raw material to be added in the step of HOABSO ₂ It was 2.80 g (10 mmol) and the amount of NMP added was 44 g. Moreover, reaction time of this process was made into 3.5 hours. In this way, a 10 mass% polyimide solution was obtained.

The obtained polyimide was evaluated similarly to Example 1. The results are shown in Table 1.

[Example 12]

(BPDA + 2DADE) (3PMDA) (2DAT + HOABSO ₂ + BPDA)

Except the following change point, it carried out similarly to Example 9, and obtained the polyimide solution.

The cooling time after reaction in the process of 1) was made into 50 minutes.

The raw material added in the process of 2) was 9.15 g (42 mmol) in PMDA, and the quantity of NMP added was 50 g. The air cooling time after reaction was made into 25 minutes.

In the process of 3), 3.42 g (28 mmol) DAT, HOABSO ₂ 3.93 g (14 mmol) was added, followed by 4.12 g (14 mmol) of BPDA and 80 g of NMP after stirring. The obtained polyimide was evaluated similarly to Example 1. The results are shown in Table 1.

[Example 13]

(BPDA + 2DADE) (3PMDA + DAT) (BTDA + HOABSO ₂ + SO ₂ AB)

Except the following change point, it carried out similarly to Example 9, and obtained the polyimide solution.

PMDA 9.15g (42 mmol) and DAT 1.71g (14mmol) were used for the raw material added in the process of 2), and the quantity of NMP to add was 60g.

3) The raw material to be added in the step of HOABSO ₂ 3.93 g (14 mmol) and SO ₂ AB 3.48 g (14 mmol) were used, and the amount of NMP added was 80 g. Moreover, after performing reaction for 20 minutes at room temperature, this process required 11 hours and 45 minutes at 180 degreeC further. In this way, a 10 mass% polyimide solution was obtained. The obtained polyimide was evaluated similarly to Example 1. The results are shown in Table 1.

Example 14

(BPDA + 2DADE) (3PMDA + BPDA + mPD) (HOABSO ₂ )

Except the following change point, it carried out similarly to Example 9, and obtained the polyimide solution.

The raw material added in the process of 1) was 2.94 g (10 mmol) of BPDA, 4.00 g (20 mmol) of DADE, 1.2 g of gamma-valerolactone, 2.0 g of pyridine, 80 g of NMP, and 25 g of toluene.

PMDA 4.36 g (20 mmol), BPDA 2.94g (10 mmol), mPD 1.00g (10 mmol) were made into the raw material added in the process of 2), and the quantity of NMP added was 60 g. After adding these, the mixture was stirred at room temperature for 30 minutes, and then reacted at 180 ° C. for 20 minutes.

3) The raw material to be added in the step of HOABSO ₂ 2.80 g (10 mmol) and the amount of NMP added were 40 g. The reaction time of this step was 4 hours and 40 minutes. In this way, a 10 mass% polyimide solution was obtained. The obtained polyimide was evaluated similarly to Example 1. The results are shown in Table 1.

Comparative Example 1

(BPDA + 2DADE) (4PMDA + 2DAT) (BPDA + 2DAT)

The same apparatus as in Example 1 was prepared.

5.88 g (20 mmol) of BPDA, 8.01 g (40 mmol) of DADE, 1.5 g (15 mmol) of γ-valerolactone, 3.5 g (44 mmol) of pyridine, 150 g of NMP, and 45 g of toluene were charged to the apparatus. The nitrogen bath was heated and stirred for 1 hour at a rotation speed of 180 ° C and 180 rpm in a silicon bath temperature. 20 ml of water-toluene fraction was removed.

It air-cooled and stirred at 180 rpm for 1 hour. Then 17.45 g (80 mmol) of PMDA, then 4.88 g (40 mmol) of DAT were added, and 250 g of NMP was further added, and stirred at 180 rpm while passing nitrogen for 20 minutes at room temperature.

Next, BPDA 5.88 g (20 mmol), DAT 4.88 g (40 mmol), NMP 120 g, and toluene 30 g were added, stirred at 230 rpm for 30 minutes, heated in a silicon bath at 180 ° C, and stirred at 180 rpm. It was. 20 ml of toluene was removed. It reacted at 180 degreeC and 180 rpm for 5 hours and 10 minutes, and obtained the 10 mass% polyimide solution.

A part of the reaction solution was diluted with dimethylformamide, and the molecular weight was measured in the same manner as in Example 1.

A part of dry polyimide film was taken, and the thermal decomposition start temperature (Tm) was measured with the thermal analysis apparatus Thermo Plus Tg 8120 of Rigaku Electric Corporation. The conditions were the temperature increase rate of 10 degreeC / 1 minute, and the temperature rising to 600 degreeC. Tm was 512.5 degreeC.

The glass transition temperature (Tg) was measured using a Perkin Elmer Pyrid Diameter DSC. The conditions were raised to 400 degreeC by the temperature increase rate of 10 degreeC / 1 minute, After that, it cooled by air and heated up to 430 degreeC by 10 degreeC / 1 minute again. Tg was not observed.

The polyimide of the present invention has a thermal decomposition start temperature (Tm) of 500? It has very high heat resistance at 560 ° C. It is considered that this is because the oxazole group rich in thermal stability is included in the molecule.

Claims (16)

(1) pyromellitic dianhydride (PMDA),
(2) carboxylic acid dianhydrides (DA) containing biphenyltetracarboxylic acid anhydride (BPDA) or benzophenonetetracarboxylic acid dianhydride (BTDA),
(3) diaminodiphenyl ether (DADE), and
(4) A polyimide soluble in an organic solvent obtained by polymerizing bis (3-amino-4-hydroxyphenyl) sulfone (HOABSO ₂ ). The method of claim 1,
Polyimide which has a repeating unit represented by general formula (I).
-[PMDA]-[HOABSO ₂ ]-[PMDA]-[DADE]-[DA]-[DADE]-[PMDA]-[HOABSO ₂ ]-[PMDA] -U _1- (Ⅰ)
In formula, [PMDA] is the said pyromellitic-acid dianhydride residue,
[HOABSO ₂ ] is the bis (3-amino-4-hydroxyphenyl) sulphone residue,
[DADE] is the diaminodiphenylether residue,
[DA] is the carboxylic acid dianhydride residue,
U ₁ is a group represented by X ₁ or X _1- [DA] -X ₁ ,
Wherein X ₁ represents a phenylenediamine residue, an alkyl substituted phenylenediamine residue, a diaminodiphenylsulfone residue, a bis (aminophenoxy) benzene residue, or the bis (3-amino-4-hydroxyphenyl) sulfone Residues)
[DADE] and [DA], and the bond of [DADE] and [PMDA] are imide bonds,
The bond of [PMDA] and [HOABSO ₂ ] is a bond represented by the general formula (i) or (ii),
[Formula 1]

(Wherein α represents part of [PMDA], β represents part of [HOABSO ₂ ], and R represents a hydrogen atom or a carboxyl group)
Binding of [PMDA] and U ₁ is, in the case where X ₁ of U _1, bis (3-amino-4-hydroxyphenyl) sulfone moiety, and the bond shown by the general formula (ⅰ) or (ⅱ), the In other cases, it is an imide bond.)｝ The method of claim 1,
Polyimide which has a repeating unit represented by general formula (II).
-[DADE]-[DA]-[DADE]-[PMDA]-[HOABSO ₂ ]-[PMDA]-[DADE]-[DA]-[DADE] -U _2- (II)
In formula, [PMDA] is the said pyromellitic-acid dianhydride residue,
[HOABSO ₂ ] is the bis (3-amino-4-hydroxyphenyl) sulphone residue,
[DADE] is the diaminodiphenylether residue,
[DA] is the carboxylic acid dianhydride residue,
U ₂ is a group represented by [DA] or [DA] -X _2- [DA],
Wherein X ₂ represents a phenylenediamine residue, an alkyl substituted phenylenediamine residue, a diaminodiphenylsulfone residue, a bis (aminophenoxy) benzene residue, or the bis (3-amino-4-hydroxyphenyl) sulfone Residues)
[DADE] and [DA], [DADE] and [PMDA], and [DADE] and U ₂ are imide bonds,
The combination of [HOABSO ₂ ] and [PMDA] is represented by the general formula (i) or (ii).
(2)

(Wherein α represents a part of [PMDA], β represents a part of [HOABSO ₂ ], and R represents a hydrogen atom or a carboxyl group). The method of claim 1,
Polyimide which has a repeating unit represented by general formula (III).
-[PMDA] -X _3- [PMDA]-[DADE]-[DA]-[DADE]-[PMDA] -X _3- [PMDA] -U _3- (III)
In formula, [PMDA] is the said pyromellitic-acid dianhydride residue,
[DADE] is the diaminodiphenylether residue,
[DA] is the carboxylic acid dianhydride residue,
X ₃ is a phenylenediamine residue, an alkyl substituted phenylenediamine residue, a diaminodiphenylsulfone residue, or a bis (aminophenoxy) benzene residue,
U ₃ is [HOABSO ₂ ],
[HOABSO ₂ ]-[DA]-[HOABSO ₂ ],
[HOABSO ₂ ] - [DA] -X ₃ , or
X _3- [DA]-[HOABSO ₂ ] is a group represented by
Wherein [HOABSO ₂ ] is the bis (3-amino-4-hydroxyphenyl) sulphone residue and [DA], X ₃ is defined as above),
[DADE] and [DA], [DADE] and [PMDA], [PMDA] and X ₃ are imide bonds,
[HOABSO ₂ ] and [PMDA], and [HOABSO ₂ ] The bond of [DA] is represented by general formula (i) or (ii).
(3)

(Wherein α represents a part of [PMDA] or [DA], and β represents a part of [HOABSO ₂ ], and R represents a hydrogen atom or a carboxyl group). The method of claim 2,
Polyimide containing the repeating unit represented by General formula (1).
[Chemical Formula 4]

[Wherein Q is a single bond or a carbonyl group,
R is independently a hydrogen atom or a carboxyl group,
a? h represents the position of a carbon atom, and when carbon of a, c, e, g couple | bonds with R, it shows that carbon of b, d, f, h couple | bonds with an oxazole group,
Y ₁ is a general formula (11)? It is group represented by (13),
[Chemical Formula 5]

(R ₁₀ represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, Ar ₁ is a group represented by the general formulas (11) to (13) independently, and Q is defined as above)
* Indicates that a phenylene group and an imide group are bonded.] The method of claim 3, wherein
Polyimide containing the repeating unit represented by General formula (2).
[Chemical Formula 6]

[Wherein Q is a single bond or a carbonyl group,
R is independently a hydrogen atom or a carboxyl group,
a? d represents the position of a carbon atom, and when carbon of a and c couple | bonds with R, it shows that carbon of b and d couple | bonds with an oxazole group,
Y ₂ is a group represented by General Formula (21), (22) or (23),
(7)

In formula, Q and R are defined as above,
e? h is a? defined as d,
Ar ₁ is a general formula (11)? It is group represented by (13),
[Chemical Formula 8]

(In General formula (11), R <_10> is a hydrogen atom or a C1-C3 alkyl group.),
* Indicates that a phenylene group and an imide group are bonded.] The method of claim 4, wherein
Polyimide containing the repeating unit represented by General formula (3-1).
[Chemical Formula 9]

[Wherein Q is a single bond or a carbonyl group,
R is independently a hydrogen atom or a carboxyl group,
a? d represents the position of a carbon atom, and when carbon of a and c couple | bonds with R, it shows that carbon of b and d couple | bonds with an oxazole group,
Ar ₁ is independently a general formula (11)? It is group represented by (13),
[Formula 10]

(R ₁₀ represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms.)
Y ₃ is a single bond or a group represented by formula (31),
(11)

(Wherein R ₁ independently represents a hydrogen atom or a carboxyl group, Q is defined as above, and e? H are defined in the same manner as a? D)
* Indicates that a phenylene group and an imide group are bonded.] The method of claim 4, wherein
Polyimide containing the repeating unit represented by General formula (3-2).
[Chemical Formula 12]

[Wherein Q is a single bond or a carbonyl group,
R is independently a hydrogen atom or a carboxyl group,
a? d represents the position of a carbon atom, and when carbon of a and c couple | bonds with R, it shows that carbon of b and d couple | bonds with an oxazole group,
Ar ₁ is independently a general formula (11)? It is group represented by (13),
[Chemical Formula 13]

(R ₁₀ represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms.)
* Indicates that a phenylene group and an imide group are bonded.] The method of claim 1,
(A1) 1 molar equivalent of carboxylic acid dianhydride (DA) containing biphenyl tetracarboxylic dianhydride (BPDA) or benzophenone tetracarboxylic dianhydride (BTDA), and diamino diphenyl ether (DADE) Reacting 2 molar equivalents to obtain an oligomer whose both ends are an amino group derived from DADE,
(A2) The oligomer obtained in step A1 is reacted with 4 molar equivalents of pyromellitic acid dianhydride (PMDA) and 2 molar equivalents of bis (3-amino-4-hydroxyphenyl) sulfone (HOABSO ₂ ), and both ends thereof are PMDA. A step of obtaining an oligomer which is a derived acid anhydride group, and
(A3) an oligomer obtained in the A2 step,
1 molar equivalent of aromatic diamine, or 1 molar equivalent of carboxylic acid dianhydride (DA) containing biphenyltetracarboxylic acid anhydride (BPDA) or benzophenonetetracarboxylic acid dianhydride (BTDA) and 2 moles of aromatic diamine A method for producing a polyimide comprising the step of reacting an equivalent to obtain a polymer. The method of claim 1,
(B1) 2 molar equivalents of pyromellitic acid dianhydride (PMDA) and 1 molar equivalent of bis (3-amino-4-hydroxyphenyl) sulfone (HOABSO ₂ ) are reacted to obtain an oligomer whose both ends are PMDA-derived acid anhydride groups. fair,
(B2) 2 molar equivalents of the carboxylic acid dianhydride (DA) containing the oligomer obtained by the B1 process, biphenyl tetracarboxylic dianhydride (BPDA), or benzophenone tetracarboxylic dianhydride (BTDA), and dia Reacting 4 molar equivalents of minodiphenylether (DADE) to obtain an oligomer whose both ends are an amino group derived from DADE, and
(B3) oligomers obtained in the B2 process,
1 molar equivalent of carboxylic acid dianhydride (DA) containing biphenyl tetracarboxylic dianhydride (BPDA) or benzophenone tetracarboxylic dianhydride (BTDA), or the said carboxylic acid dianhydride (DA) 2 A method for producing a polyimide comprising the step of reacting a molar equivalent with 1 molar equivalent of an aromatic diamine to obtain a polymer. The method of claim 1,
(C1) 1 molar equivalent of carboxylic acid dianhydride (DA) containing biphenyl tetracarboxylic dianhydride (BPDA) or benzophenone tetracarboxylic dianhydride (BTDA), and diamino diphenyl ether (DADE) Reacting 2 molar equivalents to obtain an oligomer whose both ends are an amino group derived from DADE,
(C2) a step of reacting the oligomer obtained in the step C1 with 4 molar equivalents of pyromellitic acid dianhydride (PMDA) and 2 molar equivalents of aromatic diamine to obtain an oligomer whose both ends are PMDA-derived acid anhydride groups, and
(C3) oligomer obtained in the previous step,
1 molar equivalent of bis (3-amino-4-hydroxyphenyl) sulfone (HOABSO ₂ ), or a car containing biphenyltetracarboxylic acid anhydride (BPDA) or benzophenonetetracarboxylic acid anhydride (BTDA) A polyimide comprising a step of reacting 1 molar equivalent of acid dianhydride (DA) with 1 molar equivalent of bis (3-amino-4-hydroxyphenyl) sulfone (HOABSO ₂ ) and 1 molar equivalent of aromatic diamine to obtain a polymer Method of preparation. 12. The method according to any one of claims 9 to 11,
The reaction in the production method is carried out in the presence of γ-valerolactone and pyridine or γ-valerolactone and N-methylmorpholine. Composite material containing the film obtained from the polyimide of Claim 1. Electrodeposition paint containing the polyimide of Claim 1. The method of claim 13,
The process of preparing the solution containing the polyimide and organic solvent of Claim 1,
Casting or applying the solution onto a substrate to form a film, and
A method for producing a composite material comprising the step of drying the film. The method of claim 15,
The said drying process is a manufacturing method of the composite material which is 300 degrees C or less.