KR20210146921A - Polyamic acid composition, polyimide composition, and polyimide molded article - Google Patents

Abstract

[일반식 (A) 중,
R^A 및 R^B 는, 각각 독립적으로, 수소 원자 또는 메틸기이며,
R^C 는, 수소 원자, 탄소 원자수 1 ∼ 20 의 알킬기 또는 탄소 원자수 2 ∼ 10 의 알케닐기이며,
B^A 는, 2 가의 유기기이며,
B³ 및 B⁴ 는, 각각 독립적으로, -C(=O)- 또는 -CH₂- 이며,
G¹ 및 G² 는, 각각 독립적으로, 지방족 고리 및 방향족 고리로 이루어지는 군에서 선택되는 적어도 1 개의 고리를 포함하거나, 또는 직사슬형의 탄소 원자수 4 ∼ 10 의 알칸트리일기이며, 고리가 2 이상인 경우, 고리는 축합 고리이다]
로 나타내는 반복 단위를 포함하는 폴리아믹산이, 용매 중에 용해 또는 분산되어 이루어진다.The polyamic acid composition of the present invention has the following general formula (A):

[In general formula (A),
R ^A and R ^B are each independently a hydrogen atom or a methyl group,
R ^C is a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, or an alkenyl group having 2 to 10 carbon atoms;
B ^A is a divalent organic group,
B ³ and B ⁴ are each independently -C(=O)- or -CH ₂ -,
G ¹ and G ² each independently represent at least one ring selected from the group consisting of an aliphatic ring and an aromatic ring, or a linear alkanetriyl group having 4 to 10 carbon atoms, and the ring is 2 or more, the ring is a condensed ring]
A polyamic acid containing a repeating unit represented by is dissolved or dispersed in a solvent.

Description

Polyamic acid composition, polyimide composition, and polyimide molded article

The present invention relates to a polymer compound having transparency and UV durability.

The present invention preferably relates to a polyimide molded article having excellent heat resistance, and in particular, a material for forming a product or member that requires high heat resistance, transparency and UV durability along with heat resistance (e.g., replacement of display device glass) etc.), which can be preferably used as a transparent polyimide film. Moreover, this invention relates to the polyamic-acid composition and polyimide composition for manufacturing such a polyimide molded object.

Conventionally, the polyimide obtained by polycondensation of tetracarboxylic dianhydride and a diamine compound is excellent in heat resistance, a physical characteristic, and chemical-resistance, and is known as a polymer with a low dielectric constant. From such a property, polyimide is used for various uses, and in particular, in the field|area of electric and electronic materials, it is widely used as a protective material, an insulating material, etc. (patent document 1).

However, the conventional wholly aromatic polyimide composed of aromatic tetracarboxylic dianhydride and a diamine compound has excellent mechanical properties and durability, but is often colored from yellow to brown, and has not been used for display substrates requiring transparency. .

As a polyimide which has transparency, the polyimide containing the repeating unit derived from, for example, an aliphatic monomer, a fluorine-containing monomer, or a monomer which has a bulk substituent in a molecular side chain is proposed (patent document 2). However, although transparency is improved, the polyimide containing the repeating unit derived from these monomers may fall significantly in mechanical strength and durability.

Then, it is excellent in transparency, and the polyimide excellent in the mechanical strength and durability as a display base material is calculated|required, for example. That is, it is calculated|required by polyimide to make mutually opposing characteristics (excellent transparency, mechanical strength, and durability) compatible. Moreover, the polyamic-acid composition and polyimide composition for manufacturing such a polyimide are also calculated|required.

Japanese Patent Laid-Open No. 2007-152932 Japanese Laid-Open Patent Publication No. 2004-111152

This invention was made in view of the said subject, and the objective of this invention is to provide the polyimide molded object (for example, transparent polyimide film etc.) which had the outstanding transparency, mechanical strength, and durability. Another object of the present invention is to provide a polyamic acid composition and a polyimide composition for producing the polyimide molded article as described above.

In order to solve the above problems, the present inventors have studied intensively, and a specific portion of the polyimide molded body (for example, a chromophore having a specific light absorption band (aromatic ring, etc.)) is close to each other, so that intermolecular and intramolecular charge transfer (CT) ) complex was formed and the transparency was reduced. Based on this focus, in order to suppress formation of a CT complex, it discovered that the distance between molecular chains in the polyamic-acid composition for manufacturing a polyimide molded object, and a polyimide composition was made distant by predetermined distance.

On the other hand, in a polyimide molded article comprising a repeating unit derived from a monomer having a bulk group in the molecular side chain, the bulk group functions as a spacer, thereby extending the distance between molecular chains, and the ordered arrangement of the molecular chains It was disturbed, and as a result, it was noted that the mechanical strength and durability were lowered. Based on this point of view, in order to maintain an ordered molecular chain arrangement to a certain extent, it was found that the distance between the molecular chains in the polyamic acid composition for manufacturing a polyimide molded body and the polyimide composition is brought close to a predetermined distance. .

As a result of a new study by the present inventors, a steroid structure having lipophilic cohesiveness while acting as a spacer between molecular chains is introduced into the main chain in the repeating unit of polyamic acid and polyimide, thereby having transparency, mechanical strength and durability The present invention has been envisioned having both. That is, the present invention includes the following embodiments.

The polyamic acid composition according to an embodiment of the present invention has the following general formula (A):

[Formula 1]

[In general formula (A),

R ^A and R ^B are each independently a hydrogen atom or a methyl group,

R ^C is a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, or an alkenyl group having 2 to 10 carbon atoms;

B ^A is a divalent organic group,

B ³ and B ⁴ are each independently -C(=O)- or -CH ₂ -,

G ¹ and G ² each independently represent at least one ring selected from the group consisting of an aliphatic ring and an aromatic ring, or a linear alkanetriyl group having 4 to 10 carbon atoms, and the ring is 2 or more, the ring is a condensed ring]

A polyamic acid containing a repeating unit represented by is dissolved or dispersed in a solvent.

The polyimide molded object which concerns on another embodiment of this invention apply|coats the said polyamic-acid composition on a base material, performs solvent distillation and imidation reaction by heating, and is manufactured.

The polyimide composition according to another embodiment of the present invention has the following general formula (B):

[Formula 2]

[Of general formula (B),

R ^D and R ^E are each independently a hydrogen atom or a methyl group,

R ^F is a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, or an alkenyl group having 2 to 10 carbon atoms;

B ^D is a divalent organic group,

B ⁵ and B ⁶ are each independently -C(=O)- or -CH ₂ -,

G ³ and G ⁴ each independently represent at least one ring selected from the group consisting of an aliphatic ring and an aromatic ring, or a linear alkanetriyl group having 4 to 10 carbon atoms, and the ring is 2 or more, the ring is a condensed ring]

A polyimide containing a repeating unit represented by is dissolved or dispersed in a solvent.

The polyimide molded object which concerns on another embodiment of this invention apply|coats the said polyimide composition on a base material, performs solvent distillation by heating, and is manufactured.

ADVANTAGE OF THE INVENTION According to this invention, the polyimide molded object which has the outstanding transparency, mechanical strength, and durability can be provided. In addition, it is possible to provide a polyamic acid composition and a polyimide composition for producing the polyimide molded article as described above.

EMBODIMENT OF THE INVENTION Hereinafter, embodiment (a polyamic-acid composition, a polyimide composition, and a polyimide molded object) of this invention is demonstrated in detail. However, this invention is not limited at all to the following embodiment, This invention can be implemented by adding a change suitably within the range which this invention aims at. In addition, although description may abbreviate|omit suitably the point where description overlaps, the summary of invention is not limited.

<Definition>

Hereinafter, a C1-C20 alkyl group, a C1-C10 alkyl group, a C1-C3 alkyl group, a C2-C10 alkenyl group, a C1-C3 alkoxy group, carbon A halogenated alkyl group having 1 to 3 atoms, a halogen atom, an alkylene group having 1 to 3 carbon atoms, a cycloalkanediyl group having 5 to 7 carbon atoms, an arylene group, a cycloalkane ring having 5 to 7 carbon atoms, straight chain The type alkanetriyl group having 4 to 10 carbon atoms, the linear alkanetriyl group having 4 to 6 carbon atoms, and the alcohol having 4 or less carbon atoms are not prescribed at all, and have the following meanings, respectively.

The C1-C20 alkyl group is linear or branched, and is unsubstituted. Examples of the alkyl group having 1 to 20 carbon atoms include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a sec-butyl group, a tert-butyl group, a pentyl group, an isopentyl group, neopentyl group, n-hexyl group, n-heptyl group, n-octyl group, -CH(CH ₃ )(CH ₂ ) ₃ CH(CH ₃ ) ₂ , n-nonyl group, n-decyl group, n-unde Sil group, n-dodecyl group, n-tridecyl group, n-tetradecyl group, n-pentadecyl group, n-hexadecyl group, n-heptadecyl group, n-octadecyl group, n-nonadecyl group, and and n-icosyl group.

The C1-C10 alkyl group is linear or branched, and is unsubstituted. Examples of the alkyl group having 1 to 10 carbon atoms include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a sec-butyl group, a tert-butyl group, a pentyl group, an isopentyl group, neopentyl group, n-hexyl group, n-heptyl group, n-octyl group, -CH(CH ₃ )(CH ₂ ) ₃ CH(CH ₃ ) ₂ , n-nonyl group, and n-decyl group. have.

The C1-C3 alkyl group is linear or branched, and is unsubstituted. As a C1-C3 alkyl group, a methyl group, an ethyl group, n-propyl group, and an isopropyl group are mentioned, for example.

The C2-C10 alkenyl group is linear or branched, and is unsubstituted. Examples of the alkenyl group having 2 to 10 carbon atoms include an ethenyl group, a propenyl group, a butenyl group, and —CH(CH ₃ )(CH ₂ ) ₂ CH=C(CH ₃ ) ₂ .

The alkoxy group having 1 to 3 carbon atoms is a linear or branched, unsubstituted alkoxy group having 1 to 3 carbon atoms, for example, a methoxy group, an ethoxy group, an n-propoxy group, and an isopropane group. bombardment can be heard.

The halogenated alkyl group having 1 to 3 carbon atoms is linear or branched and is unsubstituted. The halogenated alkyl group having 1 to 3 carbon atoms is a group in which one or more hydrogen atoms in the alkyl group having 1 to 3 carbon atoms are substituted with one or more halogen atoms, for example, a trifluoromethyl group. have.

Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom.

The C1-C3 alkylene group is linear or branched, and is unsubstituted. As a C1-C3 alkylene group, a methylene group, an ethylene group, n-propylene group, and an isopropylene group are mentioned, for example.

The cycloalkylene group (cycloalkanediyl group) having 5 to 7 carbon atoms is cyclic and unsubstituted. Examples of the cycloalkylene group having 5 to 7 carbon atoms include a cyclopentanediyl group, a cyclohexanediyl group, and a cycloheptadiyl group (more specifically, a 1,4-cyclohexanediyl group, and 1; 3-cyclohexanediyl group, etc.) are mentioned.

The arylene group (arenediyl group) is cyclic and unsubstituted. As an arylene group, a C6-C14 monocyclic or polycyclic arylene group is mentioned, for example. As a C6-C14 monocyclic arylene group, a phenylene group (more specifically, p-phenylene group etc.) is mentioned, for example. Examples of the polycyclic arylene group include a bicyclic arylene group (more specifically, a naphthylene group (naphthalenediyl group, and indenediyl group, etc.), a tricyclic arylene group (more specifically, anthracenedi). diary, phenantrendiyl group, acenaphthylenediyl group, and indasenediyl group).

The cycloalkane ring having 5 to 7 carbon atoms is cyclic and unsubstituted. Examples of the cycloalkane ring having 5 to 7 carbon atoms include a cyclopentane ring, a cyclohexane ring, and a cyclohepta ring.

The linear C4-C10 alkanetriyl group is unsubstituted. Examples of the linear alkanetriyl group having 4 to 10 carbon atoms include n-butanetriyl group, n-pentanetriyl group, n-hexanetriyl group, n-heptanetriyl group, and n-octanetriyl group. , n-nonantriyl group, and n-decanetriyl group.

The linear C4-C6 alkanetriyl group is unsubstituted. As a linear C4-C6 alkanetriyl group, n-butanetriyl group, n-pentanetriyl group, and n-hexanetriyl group are mentioned, for example.

The C4 or less alcohol is linear or branched, and is unsubstituted. The alcohol having 4 or less carbon atoms is an alcohol having 1 to 4 carbon atoms. Examples of the alcohol having 1 to 4 carbon atoms include methanol, ethanol, n-propanol, and isopropanol.

<First embodiment: polyamic acid composition>

[Polyamic Acid]

The polyamic acid composition which concerns on 1st Embodiment of this invention contains a polyamic acid and a solvent. The polyamic acid composition (hereinafter, may be referred to as "polyamic acid composition (A)") has the following general formula (A):

[Formula 3]

[In general formula (A),

R ^A , and R ^B are each independently a hydrogen atom or a methyl group,

R ^C is a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, or an alkenyl group having 2 to 10 carbon atoms;

B ^A is a divalent organic group,

B ³ and B ⁴ are each independently -C(=O)- or -CH ₂ -,

G ¹ and G ² each independently represent at least one ring selected from the group consisting of an aliphatic ring and an aromatic ring, or a linear alkanetriyl group having 4 to 10 carbon atoms, and the ring is 2 or more, the ring is a condensed ring]

A polyamic acid (hereinafter, sometimes referred to as “polyamic acid (A)”) containing a repeating unit represented by become made

In general formula (A), R ^A and R ^B are preferably a methyl group.

R ^C is preferably an alkyl group having 1 to 10 carbon atoms or an alkenyl group having 2 to 10 carbon atoms, more preferably -CH(CH ₃ )(CH ₂ ) ₃ CH(CH ₃ ) ₂ or - CH(CH ₃ )(CH ₂ ) ₂ CH=C(CH ₃ ) ₂ , and more preferably —CH(CH ₃ )(CH ₂ ) ₃ CH(CH ₃ ) ₂ .

B ^A is preferably a divalent organic group containing at least one ring selected from the group consisting of an aliphatic ring and an aromatic ring, and more preferably a general formula (A-1):

-B ^A1 -(Y ¹ -B ^A1 ) _n1 - ... (A-1)

[of general formula (A-1),

B ^A1 is an arylene group or a divalent aliphatic ring group,

Y ¹ is a single bond, a hetero atom such as an oxygen atom and a sulfur atom, a carbonyl group (-C(=O)-), or a sulfonyl group (-S(=O) ₂ -),

n1 is an integer of 0 to 2,

When n1 is an integer of 1 or more, a plurality of B ^A1 may be the same or different from each other,

When n1 is an integer of 2 or more, a plurality of Y ¹ may be the same or different from each other]

It is a divalent organic group represented by .

Examples of the divalent aliphatic ring group include monocyclic or polycyclic divalent aliphatic ring groups. Examples of the monocyclic divalent aliphatic group include a cycloalkylene group having 5 to 7 carbon atoms. Examples of the polycyclic divalent aliphatic ring group include a bivalent divalent aliphatic ring group and a trivalent or more divalent aliphatic ring group. As a divalent aliphatic group of a bicyclic ring, for example, a bivalent group in which two monocyclic aliphatic rings are condensed (more specifically, a bicyclo [4.4.0] decanediyl group (decalindiyl group), bi A cyclo[2.2.1]heptadiyl group (norbornanediyl group, etc.) and a divalent group obtained by condensing a monocyclic aliphatic ring of 3 (more specifically, a tricyclo[5.2.1.0 ^2,6 ]decanediyl group etc.) can be mentioned.

When n1 represents an integer of 1 or more and X represents a single bond, two B ^A bonded through a single bond may be directly bonded to each other by a ring member atom other than the ring member atom forming the single bond, and carbon You may couple|bond indirectly through an alkylene group of 1 to 3 atoms. In this case, B ^A1 is, for example, a biphenylenediyl group and a fluorenediyl group.

The arylene group or the divalent aliphatic ring group represented by ^{B A1 may further have one or more substituents.} As such a substituent, a C1-C3 alkyl group, a C1-C3 halogenated alkyl group, and a C1-C3 alkoxy group are mentioned, for example. Among these substituents, it is preferably a methyl group.

B ³ and B ⁴ may be the same as or different from each other.

The ^{linear alkanetriyl group having 4 to 10 carbon atoms represented by G 1} and G ² is preferably a linear alkanetriyl group having 4 to 6 carbon atoms. The linear C4-C10 alkanetriyl group is a trivalent substituent. Among the 4-10 carbon atoms which a linear C4-C10 alkanetriyl group has, the carbon atom couple|bonded with the carboxyl group and the carbon atom couple|bonded with the carbonyl group are directly couple|bonded with the single bond.

Examples of the aliphatic ring represented by G ¹ and G ² include a monocyclic or polycyclic aliphatic ring. As a monocyclic aliphatic ring, a C5-C7 cycloalkane ring is mentioned, for example. As the polycyclic aliphatic ring, for example, a ring in which two monocyclic aliphatic rings are condensed (more specifically, a bicyclo[4.4.0]decane ring, a bicyclo[2.2.1]hepta ring, etc.) , and a divalent group in which three monocyclic aliphatic rings are condensed (more specifically, a tricyclo[5.2.1.0 ^2,6 ]decane ring or the like).

Examples of the aromatic ring represented by G ¹ and G ^{2 include} a ring having 6 to 14 monocarbon atoms or a polycyclic aromatic ring. As a C6-C14 monocyclic aromatic ring, a benzene ring is mentioned, for example. Examples of the polycyclic aromatic ring having 6 to 14 carbon atoms include a 2-ring naphthalene ring, a 3-ring anthracene ring, a phenanthrene ring, and an acenaphthylene ring.

G ¹ and G ² are preferably, each independently, at least one ring selected from the group consisting of an aliphatic ring and an aromatic ring, more preferably a monocyclic aliphatic ring or a monocyclic aromatic ring, further Preferably it is a cyclohexane ring or a benzene ring. In addition, G ¹ and G ² may be the same as or different from each other.

B ^A1 is preferably a monocyclic arylene group having 6 to 14 carbon atoms or a cycloalkylene group having 5 to 7 carbon atoms, more preferably a phenylene group or a cyclohexanediyl group, still more preferably p- It is a phenylene group or a 1, 4- cyclohexanediyl group, Especially preferably, it is a p-phenylene group.

n1 is preferably 0 or 1.

Y ¹ is preferably a single bond, an alkylene group having 1 to 3 carbon atoms, or a hetero atom such as an oxygen atom and a sulfur atom, more preferably a single bond, a methylene group, or an oxygen atom, still more preferably is a single bond or an oxygen atom.

Since the polyamic acid in the polyamic acid composition which concerns on 1st Embodiment contains a repeating unit (A), it has excellent transparency, mechanical strength, and durability. The reason is considered as follows.

The repeating unit (A) has a steroid structure derived from a steroiddiol represented by the general formula (C) described later. The steroid structure has a structure in which four aliphatic rings are trans-condensed in a chair-type conformational configuration. Since the repeating unit (A) has such a bulk steroid structure in the main chain, it functions as a spacer between polyamic acids in which linear molecular chains are arranged in parallel. For this reason, the repeating unit (A) can keep a predetermined distance apart between molecular chains, and can disturb the ordered arrangement of molecular chains to some extent. For this reason, it is thought that the overlapping of specific parts (for example, the chromophore (aromatic ring, etc.) which has a specific light absorption band) in the molecular chain of a polyamic acid is suppressed. For this reason, it is difficult to form an intermolecular and intramolecular charge transfer (CT) complex having a light absorption band in the visible region. Moreover, the steroid structure is a condensed ring of an aliphatic ring, and does not have a polycyclic structure in which a condensed ring of an aromatic ring such as fluorene or an aromatic ring such as bisphenol A are connected via carbon or oxygen atoms. Therefore, the steroid structure does not form an intramolecular CT complex like an aromatic ring, and the polyamic acid composition according to the first embodiment is excellent in transparency.

On the other hand, the steroid structure is bulky and more lipophilic than the amide bond and the carboxyl group in the repeating unit (A). For this reason, the steroid structure part has cohesiveness, and when the steroid structure between different molecular chains attracts each other, between molecular chains of a polyamic acid can be made close to a predetermined distance, and can be maintained. Therefore, since the molecular chains of a polyamic acid are mutually ordered to some extent and can be arranged, the polyamic acid composition which concerns on 1st Embodiment is excellent in mechanical strength and durability.

Thus, since the polyamic acid which concerns on 1st Embodiment can keep between molecular chains of a polyamic acid at an appropriate distance by a steroid structure, transparency which are mutually opposing characteristics, mechanical strength, and durability can be combined.

The repeating unit (A) preferably has the following general formula (I):

[Formula 4]

[of general formula (I),

R ¹ and R ² are each independently a hydrogen atom or a methyl group,

R ³ is a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, or an alkenyl group having 2 to 10 carbon atoms;

B ¹ is a divalent organic group],

The general formula (II):

[Formula 5]

[of general formula (II),

R ¹¹ and R ¹² are each independently a hydrogen atom or a methyl group,

R ¹³ is a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, or an alkenyl group having 2 to 10 carbon atoms;

B11 is a divalent organic group];

The general formula (III):

[Formula 6]

[In general formula (III),

R ²¹ and R ²² are each independently a hydrogen atom or a methyl group,

R ²³ is a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, or an alkenyl group having 2 to 10 carbon atoms;

B ²¹ is a divalent organic group], and

The general formula (IV):

[Formula 7]

[of general formula (IV),

R ³¹ and R ³² are each independently a hydrogen atom or a methyl group,

R ³³ is a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, or an alkenyl group having 2 to 10 carbon atoms;

B ³¹ is a divalent organic group]

A repeating unit selected from the group consisting of (hereinafter referred to as "polyamic acid (I)", "polyamic acid (II)", "polyamic acid (III)" and It may be described as "polyamic acid (IV)").

In general formula (I), R ¹ and R ² are preferably a methyl group. In general formula (I), R ³ is preferably an alkyl group having 1 to 10 carbon atoms or an alkenyl group having 2 to 10 carbon atoms, more preferably -CH(CH ₃ )(CH ₂ ) ₃ CH(CH ₃ ) ₂ or —CH(CH ₃ )(CH ₂ ) ₂ CH=C(CH ₃ ) ₂ . In general formula (I), B ^{1 has the same meaning as B A} in general formula (A), and is preferably a p-phenylene group or -C ₆ H ₄ -OC ₆ H ₄ -.

As polyamic acid (I), for example, formula (I-2):

[Formula 8]

and formula (I-3):

[Formula 9]

polyamic acid (hereinafter, may be described as "polyamic acid (I-2)" and "polyamic acid (I-3)", respectively) containing a repeating unit represented by .

In general formula (II), R ¹¹ and R ¹² are preferably a methyl group. In general formula (II), R ¹³ is preferably an alkyl group having 1 to 10 carbon atoms or an alkenyl group having 2 to 10 carbon atoms, more preferably -CH(CH ₃ )(CH ₂ ) ₃ CH(CH ₃ ) ₂ or —CH(CH ₃ )(CH ₂ ) ₂ CH=C(CH ₃ ) ₂ . In general formula (II), B ^{11 has the same meaning as B A} in general formula (A), and is preferably a p-phenylene group or -C ₆ H ₄ -OC ₆ H ₄ -.

As polyamic acid (II), for example, formula (II-2):

[Formula 10]

and formula (II-3):

[Formula 11]

and polyamic acids (hereinafter, may be described as "polyamic acid (II-2)" and "polyamic acid (II-3)", respectively) containing a repeating unit represented by .

In general formula (III), R ²¹ and R ²² are preferably a methyl group. In general formula (III), R23 is preferably an alkyl group having 1 to 10 carbon atoms or an alkenyl group having 2 to 10 carbon atoms, more preferably -CH(CH ₃ )(CH ₂ ) ₃ CH( CH ₃ ) ₂ or —CH(CH ₃ )(CH ₂ ) ₂ CH=C(CH ₃ ) ₂ . In general formula (III), B ^{21 has the same meaning as B A} in general formula (A), and is preferably a p-phenylene group or -C ₆ H ₄ -OC ₆ H ₄ -.

In general formula (IV), R ³¹ and R ³² are preferably a methyl group. In formula (IV), R ³³ is preferably an alkyl group having 1 to 10 carbon atoms or an alkenyl group having 2 to 10 carbon atoms, more preferably -CH(CH ₃ )(CH ₂ ) ₃ CH( CH ₃ ) ₂ or —CH(CH ₃ )(CH ₂ ) ₂ CH=C(CH ₃ ) ₂ . In general formula (IV), B ^{31 has the same meaning as B A} in general formula (A), and is preferably a p-phenylene group or -C ₆ H ₄ -OC ₆ H ₄ -.

The polyamic acid (A) is preferably a polyamic acid containing at least one of the repeating units (I) to (IV), and more preferably a repeating unit selected from the group consisting of the repeating units (I) and (II). It is a polyamic acid containing at least one unit, More preferably, it is a polyamic acid containing repeating unit (I) or (II), Especially preferably, it is polyamic acid (I-2), (I-3), (II-2) or (II-3).

(Terminal structure of polyamic acid)

The polyamic acid (A) can select arbitrarily any one terminal group of an acid anhydride group and an amino group. The terminal group can be selected, for example, by using excessively either one of the acid dianhydride and the diamine compound at the time of the synthetic reaction mentioned later (that is, making one injection amount excessive). When the terminal group is an acid anhydride group, the terminal structure may remain an acid anhydride group, hydrolyze to form carboxylic acid, or use an alcohol having 4 or less carbon atoms to form an ester.

When tetracarboxylic dianhydride is used excessively with respect to a diamine compound at the time of the synthesis reaction of a polyamic acid (A), a monofunctional diamine compound may be added further and the acid anhydride group at the terminal may be sealed with a monofunctional amine compound. . Examples of the monofunctional amine compound include aniline, methylaniline, dimethylaniline, trimethylaniline, ethylaniline, diethylaniline, triethylaniline, aminophenol, methoxyaniline, aminobenzoic acid, biphenylamine, and naphthyl. amines, and primary amines such as cyclohexylamine.

When a diamine compound is used excessively with respect to an acid anhydride after a synthesis reaction, a monofunctional acid anhydride may be further added and the amino group at the terminal may be sealed with a monofunctional acid anhydride. The monofunctional acid anhydride can be used without any particular limitation as long as it is a monofunctional acid anhydride that becomes dicarboxylic acid or tricarboxylic acid upon hydrolysis. As such monofunctional acid anhydride, for example, maleic anhydride, methyl maleic anhydride, dimethyl maleic anhydride, succinic anhydride, norbornene dicarboxylic acid anhydride, 4-(phenylethynyl) phthalic anhydride, 4ethynylphthalic anhydride, phthalic anhydride, methylphthalic anhydride, dimethylphthalic anhydride, trimellitic anhydride, naphthalenedicarboxylic anhydride, 7oxabicyclo[2.2.1]heptane2,3-dicarboxylic anhydride, bicyclo [2.2.1]heptane-2,3-dicarboxylic acid anhydride, bicyclo[2.2.2]octa-5-ene-2,3-dicarboxylic acid anhydride, octahydro-1,3-dioxoiso Benzofuran-5-carboxylic acid anhydride, hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, dimethylcyclohexanedicarboxylic anhydride, 1,2,3,6 tetrahydrophthalic anhydride, and methyl-4-cyclohexene- 1,2-dicarboxylic acid anhydride.

The polyamic acid (A) is preferably a polyamic acid (A) (more specifically, a polyamic acid containing at least one selected from the group consisting of repeating units (I) to (IV)) at the molecular terminus of tetra It is substantially free of dicarbon structures derived from carboxylic acids.

In this specification, "derived from tetracarboxylic acid" may originate not only from tetracarboxylic acid, but also from the derivative|guide_body of tetracarboxylic acid (for example, tetracarboxylic dianhydride). "It does not contain substantially" is the whole molecular terminal of polyamic acid (A). WHEREIN: Preferably 95 % or more, More preferably, it is 98 % or more, More preferably, it is 99 % or more, Especially preferably, it is 100 %. It means that it does not have a dicarboxylic acid structure in a ratio of .

The polyamic acid (A) more preferably contains the amino group derived from diamine in the molecular terminal of the polyamic acid (A), More preferably _{, the ratio of the amino group (-NH 2} ) in the polyamic acid (terminal amino group concentration) is 0.001 -0.1 mol/kg.

The terminal amino group density|concentration of a polyamic acid (A) is the following formula (C)

(Terminal amino group concentration) = 17 × (ΣXB - ΣXA - 0.5 × ΣXC) / (WB × PB) + Σ (WA × PA) ... (C)

[In formula (C),

WB is the injection amount (g) of the diamine compound,

MB is the molecular weight of the diamine compound,

PB is the purity (%) of the diamine compound,

XB is the injection molar amount of the diamine compound, the following formula (C-1):

XB = (WB × PB)/(100 × MB) ... is calculated by (C-1),

WA is the injection amount (g) of tetracarboxylic acid,

MA is the molecular weight of tetracarboxylic acid,

PA is the purity (%) of tetracarboxylic acid,

XA is the injection molar amount of tetracarboxylic acid, following formula (C-2):

XA = (WA × PA)/(100 × MA) ... is calculated by (C-2),

WC is the injection amount (g) of the monofunctional carboxylic acid anhydride mentioned later,

MC is the molecular weight of the monofunctional carboxylic acid anhydride,

PC is the purity (%) of a monofunctional carboxylic acid anhydride,

XC is the injection molar amount of the monofunctional carboxylic acid anhydride, the following formula (C-3):

XC = (WC × PC)/(100 × MC) ... is calculated by (C-3)]

can be calculated by

Although the terminal amino group density|concentration of a polyamic acid (A) is computable from the mass of the reactant of a polyamic acid (A), etc. as above-mentioned, it is computable also from the polyamic acid composition of a finished product. For example, when polyamic acid is dissolved in a water-soluble solvent, it can be measured by titrating an inorganic acid such as hydrochloric acid.

[Method for producing polyamic acid composition]

An example of the manufacturing method of a polyamic-acid composition is demonstrated. The polyamic-acid composition (A) can be obtained by making the tetracarboxylic-acid compound and diamine compound which have a steroid structure react, for example. More specifically, the polyamic acid (A) is a reaction represented by the reaction formulas (R-1) and (R-2) (hereinafter referred to as “reaction (R-1)” and “reaction (R-2)”, respectively. In some cases):

[Formula 12]

[Formula 13]

[In reactions (R-1) and (R-2),

Formula (C) and in formula ^{(E) R A, R B} , and R ^C is represented by the general formula (A) is in the R ^A, R ^B, and R ^C, respectively as defined,

G in the general formula (D) has the same meaning as at least one ^{of G 1} and G ^{2 in the general formula (A),}

In the formula (E) G ¹ and G ² is represented by the general formula (A) are each as defined in G ¹ and G ^2,

B ³ and B ⁴ in the general formula (E), the general formula (A) is as defined in B ³ and B ^4,

Z in the general formula (D) is -CH ₂ X (methyl halide group) or -C(=O)X, X is a halogen atom, preferably a chlorine atom or a bromine atom, more preferably chlorine is an atom,

when B ³ and B ⁴ are -CH ₂ -, Z is -CH ₂ X , when B ³ and B ⁴ are -C(=O)-, Z is -C(=O)X;

m is the number of repeating units (degree of polymerization)]

It is synthesized according to or by a method equivalent thereto. In reaction (R-1), tetracarboxylic dianhydride which has a steroid structure is synthesize|combined, and in reaction (R-2), a polyamic acid (A) is synthesize|combined.

(reaction (R-1))

In the reaction (R-1), 1 equivalent of a steroiddiol represented by the general formula (C) (hereinafter sometimes referred to as "steroiddiol (C)") and 2 equivalents of a carboxyl represented by the general formula (D) An acid anhydride (hereinafter, sometimes referred to as "carboxylic acid anhydride (D)") is reacted, and 1 equivalent of tetracarboxylic dianhydride represented by the general formula (E) (hereinafter, "tetracarboxylic acid 2") is reacted. anhydride (E)") is obtained.

Hereinafter, B ³ and B ⁴ are divided into two cases and described.

(when B ³ and B ⁴ are -CH ₂ -)

Reaction (R-1) is an etherification reaction.

Z is -CH ₂ X .

As steroiddiol (C), for example, steroiddiol represented by formulas (C-1) and (C-2) (hereinafter, “steroiddiol (C-1)” and “steroiddiol (C-2)”, respectively) ) may be mentioned.

[Formula 14]

As the carboxylic acid anhydride (D), for example, a carboxylic acid anhydride represented by the general formula (D-1) (3-halogenated methylphthalic anhydride: hereinafter referred to as "carboxylic acid anhydride (D-1)" ) or a carboxylic acid anhydride represented by the general formula (D-2) (1-halogenated methylcyclohexanedicarboxylic acid anhydride: hereinafter may be referred to as “carboxylic acid anhydride (D-2)”) ) can be mentioned.

[Formula 15]

[In general formulas (D-1) and (D-2), X is a chlorine atom or a bromine atom.]

The carboxylic acid anhydride (D-1) is preferably 3-chloromethylphthalic anhydride and 3-brominated methylphthalic anhydride. The carboxylic acid anhydride (D-2) is preferably 1-methyl-chloride-3,4-cyclohexanedicarboxylic acid anhydride and 1-methyl-bromide-3,4-cyclohexanedicarboxylic acid anhydride.

In the etherification reaction, for example, a carboxylic acid anhydride (D) is subjected to a dehydrohalogenation reaction in a solvent in the presence of a basic catalyst, and then reacted with a steroiddiol (C) to form a tetracarboxylic acid having a steroid structure ( intermediate product). This intermediate product is then dehydrated to convert the two carboxyl groups into the anhydrous dicarboxylic acid structure. Thereby, tetracarboxylic dianhydride (E) is obtained.

Examples of the solvent used for the etherification reaction include aromatic hydrocarbons such as toluene and benzene; ethers such as diethyl ether, methyl ethyl ether, methyl butyl ether, tetrahydrofuran, and dioxane; In addition, acetone, water, etc. are mentioned.

Examples of the basic catalyst used in the ether reaction include hydroxides of alkali metals such as sodium hydroxide and potassium hydroxide, and carbonates of alkali metals such as potassium carbonate.

The reaction temperature of the etherification reaction is usually -50 to 250°C, preferably 0 to 200°C. The reaction time of the etherification reaction is 0.1 to 20 hours normally, Preferably it is 0.5 to 10 hours.

For dehydration of the intermediate product, it is preferable to reduce the intermediate product in a dehydration catalyst such as acetic anhydride.

After dehydration of the intermediate product, tetracarboxylic dianhydride having a steroid structure can be purified. As such a purification method, recrystallization and sublimation are mentioned, for example. It is preferable that the solvent used for recrystallization here is a good solvent which performs ring-opening of an acid anhydride structure at the time of heating, becomes the poor solvent at the time of cooling, and does not deteriorate by recrystallization operation. As such a solvent, For example, ketone solvents like acetone and methyl ethyl ketone; And an acetic anhydride solvent is mentioned.

By etherification, for example, formula (E-2):

[Formula 16]

and formula (E-3):

[Formula 17]

The tetracarboxylic dianhydride (Hereinafter, it may describe as "tetracarboxylic dianhydride (E-2)" and "tetracarboxylic dianhydride (E-3)", respectively) represented by is obtained.

(when B ³ and B ⁴ are -C(=O)-)

Reaction (R-1) is an esterification reaction.

Z is -C(=O)X.

As steroiddiol (C), steroiddiol (C-1) and (C-2) are mentioned, for example.

As carboxylic acid anhydride (D), for example, formula (D-3) carboxylic acid anhydride (3-halogenated methylphthalic anhydride: Hereinafter, it may describe as "carboxylic acid anhydride (D-3)". ) or a carboxylic acid anhydride represented by the general formula (D-4) (1-halogenated methylcyclohexanedicarboxylic acid anhydride: hereinafter may be referred to as “carboxylic acid anhydride (D-4)”):

[Formula 18]

can be heard

In the general formulas (D-3) and (D-4), X is preferably a chlorine atom or a bromine atom.

Carboxylic anhydride (D-3), Preferably they are trimellitic anhydride chloride and anhydrous trimellitic acid broride.

In the esterification reaction, for example, a carboxylic acid anhydride (D) is made to react in a solvent under an acidic catalyst or under a basic catalyst, and the tetracarboxylic acid (intermediate product) which has a steroid structure is obtained. Then, this intermediate product is dehydrated to convert the two carboxyl groups into anhydrous carboxylic acid structure. Thereby, tetracarboxylic dianhydride (E) is obtained.

The solvent used for the esterification reaction is capable of dissolving the reactants (more specifically, steroiddiol (C) and carboxylic acid anhydride (D)) and intermediate products (tetracarboxylic acid (E) having a steroid structure). Also, a solvent in which the solvent itself does not change during the reaction can be preferably used.

As a solvent used for esterification, For example, Aromatic hydrocarbons like benzene and toluene; ethers such as diethyl ether, tetrahydrofuran, dioxane, 1,2-dimethoxyethane, anisole, ethylene glycol dimethyl ether, and ethylene glycol diethyl ether; And water, etc. are mentioned. These solvents may be used individually by 1 type, and may be used in combination of 2 or more type.

As the catalyst used for the esterification reaction, an acid catalyst or a base catalyst usually used as a catalyst for the esterification reaction can be used. The kind of catalyst is suitably selected according to the kind of carboxylic anhydride (C). Examples of the acid catalyst include hydrochloric acid, sulfuric acid, trifluoroacetic anhydride, methanesulfonic acid, p-toluenesulfonic acid, boron trifluoride diethyl ether complex, and boron trifluoride dibutyl ether complex. Further, examples of the base catalyst include triethylamine, tributylamine, pyridine, picoline, lutidine, dimethylaniline, 1,4-diazabicyclo[2.2.2]octane, 1,8-diazabi cyclo[5.4.0]undecene, tetramethylurea, sodium hydroxide, potassium hydroxide, sodium carbonate, and potassium carbonate.

The catalyst is used in an appropriate amount depending on the type of catalyst. A catalyst is 0.001-5.0 mol with respect to 1 mol of carboxylic anhydride (D) normally, Preferably it is used in the substance amount of the range of 0.1-2.5 mol.

Esterification reaction temperature is -50-250 degreeC normally, Preferably it is 0-200 degreeC. Reaction time is 0.1 to 20 hours normally, Preferably it is 0.5 to 10 hours.

For dehydration of the intermediate product, it is preferable to reduce the intermediate product in a dehydration catalyst such as acetic anhydride.

After dehydration of the intermediate product, tetracarboxylic dianhydride having a steroid structure can be purified. As such a purification method, recrystallization and sublimation are mentioned, for example. It is preferable that the solvent used for recrystallization here is a good solvent which performs ring-opening of an acid anhydride structure at the time of heating, becomes the poor solvent at the time of cooling, and does not change in quality by recrystallization operation. As such a solvent, For example, ketone type solvents like acetone and methyl ethyl ketone; And an acetic anhydride solvent is mentioned.

By esterification, for example, formula (E-4):

[Formula 19]

and formula (E-5):

[Formula 20]

The tetracarboxylic dianhydride (Hereinafter, it may describe as "tetracarboxylic dianhydride (E-4)" and "tetracarboxylic dianhydride (E-5)", respectively) represented by is obtained.

(reaction (R-2))

In reaction (R-2), 1 equivalent of tetracarboxylic dianhydride (E) and the diamine compound represented by 1 equivalent of General formula (F) (henceforth "diamine compound (F)" may be described. ) to obtain a polyamic acid (A). ^{B A} in general formula (F) has the same meaning as ^{B A} in general formula (A).

(diamine compound)

The diamine compound (F) is preferably a compound in which two amine groups are bonded to a divalent organic group containing at least one ring selected from the group consisting of an aliphatic ring and an aromatic ring, More preferably, the general formula (F-2 ) :

H ₂ NB ^A2 -(Y ² -B ^A2 ) _n2 -NH ₂ ... (F-2)

[In general formula (F-2), B ^A2 , Y ^{2 , and n2 have the same meaning as B A1} , Y ¹ , and n1 in general formula (A-2), respectively]

It is a diamine compound represented by

In general formula (F-2), B ^A2 is preferably a monocyclic arylene group having 6 to 14 carbon atoms and a cycloalkylene group having 5 to 7 carbon atoms, more preferably a phenylene group and cyclohexane. A diyl group, more preferably a p-phenylene group and a 1,4-cyclohexanediyl group, and particularly preferably a p-phenylene group.

In general formula (F-2), n2 becomes like this. Preferably it is an integer of 0-2, More preferably, it is 0 or 1.

In general formula (F-2), Y ² is preferably a single bond, an alkyl group having 1 to 3 carbon atoms, and a hetero atom, more preferably a single bond, a methyl group, and an oxygen atom, still more preferably is an oxygen atom.

In general formula (F-2), ^{the substituent which B A2} may have is preferably an alkyl group having 1 to 3 carbon atoms and a halogenated alkyl group having 1 to 3 carbon atoms, more preferably a methyl group and a methyl halide group. and more preferably a methyl group and a trifluoromethyl group.

As a diamine compound (F), aromatic diamine and aliphatic diamine are mentioned, for example.

Aromatic diamine has at least 1 aromatic ring. Examples of the aromatic diamine include 1,3-phenylenediamine, 1,4-phenylenediamine (p-phenylenediamine (PDA)), 2,4-diaminotoluene, and 2,6-diaminotoluene. , 3,4-diaminotoluene, 4,5-dimethyl-1,2-phenylenediamine, 2,5-dimethyl-1,4-phenylenediamine, 2,6-dimethyl-1,4-phenylenediamine , 2,3,5,6-tetramethyl-1,4-phenylenediamine, 3-aminobenzylamine, m-xylylenediamine, p-xylylenediamine, 1,5-diaminonaphthalene, 2,2' -Dimethylbiphenyl-4,4'-diamine, 2,2'-bis(trifluoromethyl)benzidine, 3,3'-dimethoxybenzidine, 4,4'-diaminooctafluorobiphenyl, 3,3 '-diaminodiphenylmethane, 3,4'-diaminodiphenylmethane, 4,4'-diaminodiphenylmethane, 4,4'-methylenebis(2,6-diethylaniline), 4,4 '-methylenebis (2-ethyl-6-methylaniline), 4,4'-ethylenedianiline, 4,4'-diaminodiphenyl ether (ODA), 3,4'-diaminodiphenyl ether, 3 ,3'-diaminodiphenyl ether, 4,4'-diaminodiphenyl ether, 2,2'-bis(trifluoromethyl)-4,4'-diaminodiphenyl ether, 1,3-bis (4-aminophenoxy)benzene, 1,3-bis(3-aminophenoxy)benzene, 1,4-bis(4-aminophenoxy)benzene, 1,4-bis(4-amino-2-tri Fluoromethylphenoxy)benzene, 4,4'-bis(4-aminophenoxy)biphenyl, 4,4'-diamino-3,3'-dimethyldiphenylmethane, bis[4-(4-amino) Phenoxy)phenyl]sulfone, bis[4-(3-aminophenoxy)phenyl]sulfone, 2,2-bis(4-aminophenyl)hexafluoropropane, 2,2-bis(3-aminophenyl)hexa Fluoropropane, 2,2'-bis[4-(4-aminophenoxy)phenyl]propane, 2,2'-bis[4-(4-aminophenoxy)phenyl]hexafluoropropane, 2,2 -bis(3-amino-4-methylphenyl)hexafluoropropane, α,α′-bis(4-aminophenyl)-1,4-diisopropylbenzene, bis(2-aminophenyl)sulfide, bis( 4-aminophenyl)sulfide, 3,3'-diaminodiphenylsulfone, 4,4'-diaminodiphenylsulfone, 4,4'-diaminodiphenylsulfide, 4,4'-diaminobenzo phenone, 3,3'-diaminobenzophenone, 4,4'-diaminobenzanilide, 1,4-bis(4-aminophenoxy)benzene, bis(4-aminophenyl)terephthalate, 2,7-diaminofluorene, and 9,9-bis( 4-aminophenyl) fluorene is mentioned.

Examples of the aliphatic diamine include 1,3-diaminocyclohexane, 1,4-diaminocyclohexane, 1,3-bis(aminomethyl)cyclohexane, and 1,1-bis(4-aminophenyl). Cyclohexane, 4,4'-diaminodicyclohexylmethane, 4,4'-methylenebis(2-methylcyclohexylamine), 4,4'-methylenebis(2,6-dimethylcyclohexylamine), 4 ,4'-diaminodicyclohexylpropane, bicyclo[2.2.1]heptane-2,3-diamine, bicyclo[2.2.1]heptane-2,5-diamine, bicyclo[2.2.1]heptane- 2,6-diamine, bicyclo[2.2.1]heptane-2,7-diamine, 2,3-bis(aminomethyl)-bicyclo[2.2.1]heptane, 2,5-bis(aminomethyl)- Bicyclo[2.2.1]heptane, 2,6-bis(aminomethyl)-bicyclo[2.2.1]heptane, and 3(4),8(9)-bis(aminomethyl)tricyclo[5.2.1.0 (2,6)]decane.

A diamine compound (F) may be used individually by 1 type, and may combine 2 or more types.

The diamine compound (E) is, among the above diamine compounds, preferably p-phenylenediamine, 2,2'-dimethylbiphenyl-4,4'-diamine, and 2,2'-bis(trifluoromethyl) benzidine, 2,2'-bis(trifluoromethyl)-4,4'-diaminodiphenylether, and 1,4-bis(4-amino-2-trifluoromethylphenoxy)benzene, and 4 Aromatic diamines such as ,4'-diaminodiphenyl ether, 1,4-diaminocyclohexane, 4,4'-diaminodicyclohexylmethane, 4,4'-methylenebis(2-methylcyclohexylamine) Aliphatic diamines such as (4,4'-methylenebis(2,6-dimethylcyclohexylamine)) and combinations thereof, more preferably p-phenylenediamine, 4,4'-diaminodiphenyl ether , and combinations thereof.

(Tetracarboxylic acid compound)

The polyamic acid (A) may have a repeating unit derived from tetracarboxylic dianhydride other than tetracarboxylic dianhydride (E) which has a steroid structure. Since tetracarboxylic dianhydride does not generate a reaction by-product in such tetracarboxylic acid anhydride (it may describe hereafter as "tetracarboxylic dianhydride (EX)"), polyamic acid (A) It is preferably used in the synthesis of

Tetracarboxylic dianhydride (EX) is an acid dianhydride conventionally used for manufacture of a polyimide on condition that the polyamic acid (A) obtained shows the effect of this invention, For example, aromatic acid 2 Anhydride, aliphatic acid dianhydride, and aliphatic ester type acid dianhydride are mentioned.

As aromatic acid dianhydride, For example, pyromellitic dianhydride, 1,2,3,4-benzenetetracarboxylic dianhydride, 3,3',4,4'- biphenyl tetracarboxylic acid dianhydride, 2,3,3'4'-biphenyltetracarboxylic dianhydride, 2,3,2',3'-biphenyltetracarboxylic dianhydride, 3,3',4,4'- Diphenylmethanetetracarboxylic dianhydride, 2,3,3',4'-diphenylmethanetetracarboxylic dianhydride, 3,3',4,4'-benzophenonetetracarboxylic dianhydride, 2 ,3,3',4'-benzophenonetetracarboxylic dianhydride, 2,3,2',3'-benzophenonetetracarboxylic dianhydride, 3,4'-oxydiphthalic dianhydride, 4, 4'-oxydiphthalic dianhydride, 3,3'-oxydiphthalic dianhydride, diphenylsulfone-3,4,3',4'-tetracarboxylic dianhydride, diphenylsulfone-2,3,3 ',4'-tetracarboxylic dianhydride, diphenylsulfone-2,3,2',3'-tetracarboxylic dianhydride, 4,4'-[isopropylidenebis[(1,4-phenyl) Ren)oxy]]diphthalic dianhydride, 5,5'-isopropylidenebis(phthalic anhydride), 3,5'-isopropylidenebis(phthalic anhydride), 3,3'-isopropylidenebis(phthalic anhydride) ), 4,4'-(1,4-phenylenebisoxy)bisphthalic dianhydride, 4,4'-(1,3-phenylenebisoxy)bisphthalic dianhydride, 5,5'-[oxybis (4,1-phenyleneoxy)]bisphthalic dianhydride and 5,5'-[sulfonylbis(4,1-phenyleneoxy)]bisphthalic dianhydride are mentioned.

Moreover, what has a silicon atom, a fluorine atom, an ester structure, or a fluorene cardo structure is contained as aromatic acid dianhydride. More specifically, as silicon-containing acid dianhydride, for example, 4,4'-(dimethylsilylene)bis(phthalic acid) 1,2:1',2'-2 anhydride, 4,4'-( Methylethylsilylene)bis(phthalic acid) 1,2: 1',2'-2 anhydride, 4,4'-[phenyl (methyl)silylene]bisphthalic acid 1,2: 1',2'-2 anhydride, 4,4'-diphenyl, and silylenebisphthalic acid 1,2:1',2'-2 anhydride.

As the fluorine-containing acid dianhydride, 4,4'-(2,2-hexafluoroisopropylidene)diphthalic dianhydride, 3,4'-(2,2-hexafluoroisopropylidene)diphthalic acid 2 Anhydride, 3,3'-(2,2-hexafluoroisopropylidene)diphthalic acid dianhydride, 4,4'-[2,2-hexafluoroisopropylidenebis[(1,4-phenylene) oxy]] diphthalic dianhydride. As the fluorene cardo structural acid dianhydride, 5,5'-[9H-fluorene-9,9-diylbis(4,1-phenyleneoxy)]bis(isobenzofuran-1,3-dione) , and 5,5'-[9H-fluorene-9,9-diylbis(1,1'-biphenyl-5,2-diyloxy)]bis(isobenzofuran-1,3-dione) can be heard

Examples of the ester-based acid dianhydride include ethylene glycol-bis(trimellitate anhydride), 1,4-phenylenebis(trimellitate anhydride), 1,3-phenylenebis(trimellitate anhydride), 1,2-phenylenebis(trimellitate anhydride), bis(1,3-dihydro-1,3-dioxoisobenzofuran-5-carboxylic acid)-2-acetoxypropane-1,3- Diyl, 5,5'-[ethylenebis(oxy)]bis(isobenzofuran-1,3-dione), bis(1,3-dihydro-1,3-dioxo-5-isobenzofurancarboxyl acid) oxybis(methyleneoxymethylene), and 4,4'-[isopropylidenebis(4,1-phenyleneoxycarbonyl)]bisphthalic dianhydride.

As an aliphatic acid dianhydride, tetracarboxylic dianhydride containing an aliphatic ring is mentioned, for example. The aliphatic ring may be condensed with an aromatic ring. As such an aliphatic acid dianhydride, 1,1'-bicyclohexane-3,3',4,4'-tetracarboxylic dianhydride, 1,1'-bicyclohexane-2 ,3,3'4'-tetracarboxylic dianhydride, 1,1'-bicyclohexane-2,3,2'3'-tetracarboxylic dianhydride, cyclohexane-1,2,4,5 -tetracarboxylic dianhydride, 1,2,3,4-tetracarboxylic dianhydride, 1,3,3a,4,5,9b-hexahydro-5 (tetrahydro-2,5-dioxo- 3-furanyl) naphtho [1,2-c] furan-1,3-dione, 1,2,3,4-butanetetracarboxylic dianhydride, 1,2,3,4-cyclobutanetetracar acid dianhydride (CHDA), 1,2,3,4-cyclopentanetetracarboxylic dianhydride, 5-(2,5-dioxotetrahydrofuryl)-3-methyl-3-cyclohexene-1, 2-dicarboxylic acid anhydride, bicyclo[2.2.2]octo-7-ene-2,3,5,6-tetracarboxylic dianhydride, bicyclo[2.2.2]octane-2,3,5 ,6-tetracarboxylic acid-2,3:5,6-2 anhydride, bicyclo[2.2.1]heptane-2,3,5,6-tetracarboxylic acid-2,3:5,6-2 anhydride, and hexadecahydro-3a, 11a-(2,5-dioxotetrahydrofuran-3,4-diyl)phenanthro[9,10-c]furan-1,3-dione.

As the aliphatic ester acid dianhydride, for example, bis(1,3-dioxo-1,3,3a,4,5,6,7,7a-octahydroisobenzofuran-5-carboxylic acid) Biphenyl-4,4'-diyl, bis(1,3-dioxo-1,3,3a,4,5,6,7,7a-octahydroisobenzofuran-5-carboxylic acid)1,4 -phenylene, and bis(1,3-dioxo-1,3,3a,4,5,6,7,7a-octahydroisobenzofuran-5-carboxylic acid)-2-methyl-1,4 -Phenylene is mentioned.

Tetracarboxylic dianhydride (E-X) may be used individually by 1 type of anhydride for these tetracarboxylic acid, and may be used in combination of 2 or more type.

Among these, tetracarboxylic dianhydride (E-X) suppresses formation of intramolecular and intermolecular CT complex, From a viewpoint of improving transparency of a polyimide, Preferably, an aromatic ring is not included. Moreover, from a viewpoint of improving the mechanical strength of a polyimide, tetracarboxylic dianhydride (E-X), Preferably it has a cyclic structure which is not linear or branched.

That is, from a viewpoint of improving transparency, durability, and mechanical strength of a polyimide in this way, tetracarboxylic dianhydride (EX), Preferably it is tetracarboxylic acid 2 which does not contain an aromatic ring but contains an aliphatic ring. It is anhydrous. More specifically, tetracarboxylic dianhydride (EX), Preferably 1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,2,4,5-cyclopentanetetracarboxylic acid dianhydride, 1,2,4,5-cyclohexanetetracarboxylic dianhydride, bicyclo[2,2,1]heptane-2,3,5,6-tetracarboxylic dianhydride, bicyclo[2 ,2,2]octane-2,3,5,6-tetracarboxylic dianhydride, 3,3',4,4'-bicyclohexyltetracarboxylic dianhydride, and 1,2,4-cyclo hexanetricarboxylic acid anhydride, more preferably 1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,2,4,5-cyclohexanetetracarboxylic dianhydride, and 3,3 ',4,4'-bicyclohexyltetracarboxylic dianhydride.

Synthesis of polyamic acid (A) WHEREIN: When using tetracarboxylic acid anhydride (EX), the ratio of tetracarboxylic acid anhydride (E) and tetracarboxylic acid anhydride (EX) can be selected suitably, for example For example, the ratio "tetracarboxylic anhydride (E): tetracarboxylic anhydride (EX)" (molar ratio) may be in the range of 40:60 to 100:0, preferably 50:50 to 100:0. range, and more preferably 80:20 to 100:0.

The usage ratio (ratio of addition amount) of the tetracarboxylic acid compound (E) and diamine compound (F) used for the synthesis|combination of a polyamic acid (A) is tetracarboxylic with respect to 1 equivalent of amino groups contained in a diamine compound (F). The ratio used as 0.5-1.5 equivalent is preferable and, as for the acid-anhydride group of an acid compound (E), the ratio used as 0.8-1 equivalent is more preferable. Moreover, it is preferable to make the said ratio into 0.5-0.9 equivalent from a viewpoint of making the molecular terminal of a polyamic acid (A) contain the amino group derived from a diamine compound (F).

In addition, the said ratio demonstrated the case where tetracarboxylic dianhydride (E-X) was not included. When tetracarboxylic dianhydride (EX) is included, the said ratio is the sum total of the addition amount of tetracarboxylic dianhydride (E) and tetracarboxylic dianhydride (EX), and addition amount of a diamine compound (F) is the ratio of

The reaction temperature in the reaction (R-2) is preferably -20 to 150°C, more preferably 0 to 100°C. Reaction time becomes like this. Preferably it is 0.2 to 120 hours, More preferably, it is 0.5 to 72 hours. Moreover, in the synthesis|combination of a polyamic acid (A), Preferably it can advance in a solvent. Such a solvent is not particularly limited as long as it can dissolve or disperse the polyamic acid to be synthesized in the solvent, and for example, N-methyl-2-pyrrolidone, N,N-dimethylacetamide, N,N -Aprotic polar solvents such as dimethylformamide, dimethylsulfoxide, γ-butyrolactone, tetramethylurea, and hexamethylphosphotriamide; and phenolic solvents such as m-cresol, xylenol, phenol, and halogenated phenol. In addition, as for the usage-amount of a solvent (a: However, when using together a good solvent and the poor solvent mentioned later, those total amounts), the total amount (b) of tetracarboxylic anhydride (E) and a diamine compound (F) is , it is preferable that it is an amount used as 0.1 to 30% by weight with respect to the total amount (a+b) of the reaction solution.

As a solvent used for the synthesis|combination of a polyamic acid (A), alcohol, a ketone, ester, ether, and halogenated hydrocarbon, a hydrocarbon are mentioned, for example. These solvents may be used individually by 1 type, and may be used in combination of 2 or more type. These solvents are the solvents recognized as the poor solvent of the conventional polyamic acid and polyimide. These solvents can be used in the range in which a polyamic acid (A) does not precipitate. Specifically, it can be used as a mixed solvent in which a good solvent is mixed with a poor solvent. To [ the ratio of a poor solvent / the sum total of a good solvent and a poor solvent ], Preferably it is 25 weight% or less, More preferably, it is 10 weight% or less. Moreover, as a good solvent of a polyamic acid and a polyimide, dimethylacetamide, N-methyl- 2-pyrrolidone (NMP), and formaldehyde are mentioned normally.

Examples of the alcohol include monohydric alcohols such as methanol, ethanol, isopropanol, cyclohexanol, and ethylene glycol monomethyl ether; and polyhydric alcohols such as ethylene glycol, propylene glycol, 1,4-butanediol, and triethylene glycol.

Examples of the ketone include acetone, methyl ethyl ketone, methyl isobutyl ketone, diisobutyl ketone, and cyclohexanone.

As the ester, for example, ethyl lactate, butyl lactate, methyl acetate, ethyl acetate, butyl acetate, methyl methoxypropionate, ethyl ethoxypropionate, and diethyl oxalate, diethyl malonate, isoamylpropio nate, and isoamylisobutyrate.

Examples of the ether include tetrahydrofuran, diethyl ether, diisopentyl ether, ethylene glycol methyl ether, ethylene glycol ethyl ether, ethylene glycol-n-propyl ether, ethylene glycol-i-propyl ether, ethylene glycol- n-Butyl ether, ethylene glycol dimethyl ether, ethylene glycol ethyl ether acetate, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monomethyl ether acetate and diethylene glycol monoethyl ether acetate.

Halogenated hydrocarbons include, for example, halogenated aliphatic hydrocarbons such as dichloromethane, 1,2-dichloroethane, 1,4-dichlorobutane, trichloroethane, and halogenated aromatic hydrocarbons such as chlorbenzene, and o-dichlorobenzene. can be heard

Examples of the hydrocarbon include aliphatic hydrocarbons such as hexane, heptane, and octane, and aromatic hydrocarbons such as benzene, toluene, and xylene.

As mentioned above, the reaction solution formed by melt|dissolving or dispersing (preferably melt|dissolving) a polyamic acid is obtained.

This reaction solution may be provided to a polyamic-acid composition as it is, and after isolating the polyamic acid contained in a reaction solution, you may provide for preparation of a polyamic-acid composition.

Isolation of the polyamic acid can be carried out by pouring the reaction solution into a large amount of poor solvent to obtain a precipitate, and drying the precipitate under reduced pressure, or by distilling off the solvent in the reaction solution under reduced pressure with an evaporator. have. Moreover, a polyamic acid can be refine|purified by the method of melt|dissolving this polyamic acid in a solvent again, then making it precipitate with a poor solvent, or the method of performing the process of depressurizingly distilling off with an evaporator once or several times. .

(menstruum)

Examples of the solvent contained in the polyamic acid composition include sulfoxide solvents such as dimethyl sulfoxide and diethyl sulfoxide; formamide-based solvents such as N,N-dimethylformamide and N,N-diethylformamide; acetamide-based solvents such as N,N-dimethylacetamide and N,N-diethylacetamide; pyrrolidone solvents such as N-methyl-2-pyrrolidone and N-vinyl-2-pyrrolidone; phenolic solvents such as phenol, o-, m- or p-cresol, xylenol, halogenated phenol, and catechol; etheric solvents such as tetrahydrofuran, dioxane, and dioxolane; alcohol solvents such as methanol, ethanol, and butanol; cellosolve solvents such as butyl cellosolve; carbonate ester solvents such as ethylene carbonate and propylene carbonate; carboxylate ester solvents such as γ-butyrolactone; aromatic hydrocarbons such as toluene and xylene; an aqueous solvent such as water or a mixed solvent of water and a low molecular weight alcohol (more specifically, methanol, ethanol, ethylenediol, and glycerin); and other solvents such as 1,3-dimethyl-2-imidazolidinone and hexamethylphosphoric triamide. These solvents may be used individually by 1 type, and may be used in combination of 2 or more type.

Since the energy required for solvent drying can be reduced when a solvent is an aqueous solvent, a solvent can be distilled off easily and a polyimide molded object can be manufactured from a polyamic-acid composition.

Moreover, the aqueous solvent may further contain a tertiary amine. When the solvent is an aqueous tertiary amine solution, an amine salt is formed between the carboxyl group and the tertiary amine contained in the repeating unit, and thus the polyamic acid is dissolved in the aqueous solvent. Examples of the tertiary amine compound include morpholine compounds such as triethylamine, an imidazole compound, methylmorpholine, ethylmorpholine, and phenylmorpholine.

Of these solvents, most solvents were generally known as poor solvents for polyamic acids. Conventionally, as for the solvent which can be used for a polyamic acid, although the solvent like N-methyl- 2-pyrrolidone was known typically, the kind of solvent was limited. For this reason, there existed a big restriction|limiting in the handling of a polyamic acid (for example, the synthesis|combination of a polyamic acid, preparation of a polyamic-acid composition, etc.).

On the other hand, in order to melt|dissolve or disperse|distribute a polyamic acid (A) at the density|concentration of 1 weight% - 30 weight% in the said various types of solvent, the polyamic-acid composition which concerns on 1st Embodiment is excellent in workability.

The quantity of the tertiary amine added to an aqueous solvent can be suitably selected in the range of 0.5-2 equivalent with respect to 1 equivalent of the carboxyl group in a polyamic acid. When the amount of the tertiary amine is in the range of 0.5 to 2 equivalents, the polyamic acid is dissolved in an aqueous solvent, and it is difficult to cause thickening and gelation over time due to a decrease in stability of the polyamic acid composition.

Among these solvents, preferably, an aqueous solvent, a formamide solvent, an acetamide solvent, a pyrrolidone solvent, a carbonate ester solvent, a carboxylic acid ester solvent, and combinations thereof, and more preferably a tertiary Aqueous amine solution, N,N-diethylformamide, N,N-diethylacetamide, N,N-dimethylacetamide, N,N-dimethylformamide, N-methyl-2-pyrrolidone, ethylene carbonate, at least one solvent selected from propylene carbonate and γ-butyrolactone.

The viscosity of a polyamic-acid composition (A) is the density|concentration of 10 weight% of polyamic acids. From a viewpoint of improving mechanical strength, Preferably they are 10 mPa*s - 10,000 mPa*s. The viscosity of a polyamic-acid composition (A) is measured at 22.0 degreeC using an E-type viscometer.

The content of the polyamic acid in the polyamic acid composition (A) is not particularly limited, but the polyamic acid (A) may be in the range of 1 wt% to 30 wt% as solid content in the polyamic acid composition (A), Preferably it is the range of 1 weight% - 25 weight%, It can adjust with the ratio of a solvent suitably.

<Second embodiment: polyimide composition>

The polyimide composition which concerns on 2nd Embodiment of this invention contains a polyimide and a solvent. The polyimide composition has the following general formula (B):

[Formula 21]

[Of general formula (B),

R ^D and R ^E are each independently a hydrogen atom or a methyl group,

R ^F is a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, or an alkenyl group having 2 to 10 carbon atoms;

B ^D is a divalent organic group,

B ⁵ and B ⁶ are each independently -C(=O)- or -CH ₂ -,

G ³ and G ⁴ each independently represent at least one ring selected from the group consisting of an aliphatic ring and an aromatic ring, or a linear alkanetriyl group having 4 to 10 carbon atoms, and the ring is 2 or more, the ring is a condensed ring]

A polyimide (hereinafter, sometimes referred to as “polyimide (B)”) containing a repeating unit represented by become made

In the general formula (B), R ^D, R ^E and R ^F are, respectively, the general formula (A) is the same as defined in R ^A, R ^B and R ^C. G ³ and G ⁴ have the same meanings as ^{G 1} and G ² in the general formula (A), respectively. B ^D has the same meaning as ^{B A} in the general formula (A).

B ^D is preferably a divalent organic group containing at least one ring selected from the group consisting of an aliphatic ring and an aromatic ring, and more preferably a general formula (B-1):

-B ^A3 -(Y ³ -B ^A3 ) _n3 - ... (B-1)

[B ^A3 , Y ³ , and n3 in the general formula (B-1) have the same meaning as ^{B A1} , Y ^{1 , and n1 in the general formula (A-1), respectively]}

It is a divalent organic group represented by .

B ^A3 is preferably a monocyclic arylene group having 6 to 14 carbon atoms or a cycloalkylene group having 5 to 7 carbon atoms, more preferably a phenylene group or a cyclohexanediyl group, still more preferably p- It is a phenylene group or a 1, 4- cyclohexanediyl group, Especially preferably, it is a p-phenylene group.

n3 preferably represents 0 or 1.

Y ³ is preferably a single bond, an alkylene group having 1 to 3 carbon atoms, or a hetero atom such as an oxygen atom and a sulfur atom, more preferably a single bond, a methylene group, or an oxygen atom, still more preferably is an oxygen atom.

Since the polyimide in the polyimide composition which concerns on 2nd Embodiment contains a repeating unit (B), similarly to the above-mentioned polyamic acid (A), for the reason shown below, excellent transparency, mechanical strength, and durability. Since polyimide (B) has a bulk steroid structure, it is thought that it is difficult to form the intermolecular and intramolecular CT complex which has a light absorption band in a visible region. Since it is difficult to form an intermolecular and intramolecular CT complex in this way, it is difficult to cause light absorption that causes deterioration of the polyimide (B). Moreover, a polyimide (B) can arrange the molecular chains of a polyimide (B) mutually in order to some extent by the cohesiveness of a steroid structure part.

The repeating unit (B) is preferably the following general formula (V):

[Formula 22]

[In general formula (V),

R ⁴ and R ⁵ are each independently a hydrogen atom or a methyl group,

R ⁶ is a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, or an alkenyl group having 2 to 10 carbon atoms;

B ² is a divalent organic group];

The general formula (VI):

[Formula 23]

[of general formula (VI),

R ¹⁴ and R ¹⁵ are each independently a hydrogen atom or a methyl group,

R ¹⁶ is a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, or an alkenyl group having 2 to 10 carbon atoms;

B ¹² is a divalent organic group];

The general formula (VII):

[Formula 24]

[In general formula (VII),

R ²⁴ and R ²⁵ are each independently a hydrogen atom or a methyl group,

R ²⁶ is a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, or an alkenyl group having 2 to 10 carbon atoms;

B ²² is a divalent organic group], and

The general formula (VIII):

[Formula 25]

[of general formula (VIII),

R ³⁴ and R ³⁵ are each independently a hydrogen atom or a methyl group,

R ³⁶ is a hydrogen atom or an alkyl group having 1 to 20 carbon atoms;

B ³² is a divalent organic group]

A repeating unit selected from the group consisting of (hereinafter referred to as "polyimide (V)", "polypolyimide (VI)", "polypolyimide (VII)" ' and "polypolyimide (VIII)" in some cases).

In general formula (V), R ⁴ and R ⁵ are preferably a methyl group. In general formula (V), R ⁶ is preferably an alkyl group having 1 to 10 carbon atoms or an alkenyl group having 2 to 10 carbon atoms, more preferably -CH(CH ₃ )(CH ₂ ) ₃ CH(CH ₃ ) ₂ or —CH(CH ₃ )(CH ₂ ) ₂ CH=C(CH ₃ ) ₂ . In general formula (V), B ² is preferably a p-phenylene group or —C ₆ H ₄ -OC ₆ H ₄ —.

As the polyimide (V), for example, the following formula (V-2):

[Formula 26]

and the formula (V-3):

[Formula 27]

and polyimides (hereinafter, sometimes referred to as "polyimide (V-2)" and "polyimide (V-3)", respectively) containing a repeating unit represented by .

In general formula (VI), R ¹⁴ and R ¹⁵ preferably represent a methyl group. In general formula (VI), R ¹⁶ is preferably an alkyl group having 1 to 10 carbon atoms or an alkenyl group having 2 to 10 carbon atoms, more preferably -CH(CH ₃ )(CH ₂ ) ₃ CH(CH ₃ ) ₂ or —CH(CH ₃ )(CH ₂ ) ₂ CH=C(CH ₃ ) ₂ . In general formula (VI), B ¹² is preferably a p-phenylene group or —C ₆ H ₄ -OC ₆ H ₄ —.

As the polyimide containing the repeating unit represented by the general formula (VI), for example, the following general formula (VI-2):

[Formula 28]

and the formula (VI-3):

[Formula 29]

and polyimides containing a repeating unit represented by

In general formula (VII), R ²⁴ and R ²⁵ are preferably a methyl group. In general formula (VII), R ²⁶ is preferably an alkyl group having 1 to 10 carbon atoms or an alkenyl group having 2 to 10 carbon atoms, more preferably -CH(CH ₃ )(CH ₂ ) ₃ CH (CH ₃ ) ₂ or —CH(CH ₃ )(CH ₂ ) ₂ CH=C(CH ₃ ) ₂ . In general formula (VII), B ²² is preferably a p-phenylene group or -C ₆ H ₄ -OC ₆ H ₄ -.

In general formula (VIII), R ³⁴ and R ³⁵ are preferably a methyl group. In general formula (VIII), R ³⁶ is preferably an alkyl group having 1 to 10 carbon atoms or an alkenyl group having 2 to 10 carbon atoms, more preferably -CH(CH ₃ )(CH ₂ ) ₃ CH(CH ₃ ) ₂ or —CH(CH ₃ )(CH ₂ ) ₂ CH=C(CH ₃ ) ₂ . In general formula (VIII), B ³² is preferably a p-phenylene group or -C ₆ H ₄ -OC ₆ H ₄ -.

The polyimide (B) is preferably a polyimide containing at least one of repeating units selected from the group consisting of repeating units (V) to (VIII), and more preferably repeating units (V) and (VI). ), and more preferably a polyimide containing at least one of repeating units (V-2) and (VI-2).

(Terminal structure of polyimide)

The terminal group of a polyimide (B) can select any one of the amino group derived from the acid anhydride group and diamine compound (F) derived from tetracarboxylic dianhydride (E) arbitrarily. The terminal group of the polyimide (B) is, for example, by excessively using either one of the tetracarboxylic dianhydride (E) and the diamine compound (F) in the synthesis of the polyamic acid (A) (that is, Excessive one injection amount) can be selected.

In addition, the terminal amino group density|concentration of a polyimide (B) can be calculated|required by the method similar to the terminal amino group density|concentration of the polyamic acid (A) mentioned above.

From the viewpoint of improving the solubility or dispersibility of the polyimide (B) in the solvent, the polyimide (B) is preferably a polyimide (B) (for example, polyimides (V) to (VIII)). It does not contain a dicarboxylic acid structure derived from tetracarboxylic acid at the molecular terminus. In short, the polyimide (B) preferably contains an amino group derived from diamine at the molecular terminal of the polyimide (B), _{and the ratio of amino groups (-NH 2} ) in the polyimide (B) (terminal amino group concentration) is, It is in the range of 0.001-0.1 mol/kg.

[Synthesis method of polyimide composition]

An example of the manufacturing method of a polyimide composition is demonstrated. A polyimide composition (B) is obtained by dehydrating and imidating the polyamic acid (A) in a polyamic-acid composition (A), for example. More specifically, the polyimide (B) is a reaction represented by the reaction formula (R-3) (hereinafter referred to as “reaction (R-3)” in some cases):

[Formula 30]

[In Reaction Scheme (R-3),

Common in the formula (A) and (B) R ^A, R ^B, R ^C, B ^A in, B ^3, B ^4, G ^1, G ^2, and m is a reaction scheme (R-2) ^{R A} , R ^B , R ^C , B ^A , B ³ , B ⁴ , G ¹ , G ² , and m have the same meaning as in formula (A)]

It is synthesized according to or by a method equivalent thereto.

Moreover, the manufacturing method of a polyimide composition (B) is obtained also by making polyimide (B) (more specifically, polyimide (V)-(VIII)) melt|dissolve or disperse|distribute (preferably melt|dissolve) in a solvent. lose

Hereinafter, the imidation reaction of the polyamic acid (A) in a polyamic-acid composition is demonstrated in detail. As such imidation reaction, the thermal imidation reaction which heats a polyamic-acid composition (A), and the chemical imidation reaction which adds a catalyst and a dehydrating agent are mentioned, for example.

(thermal imidization reaction)

Thermal imidation reaction is performed by heating the solution of a polyamic acid (A) and using it for dehydration imidation reaction. In thermal imidation reaction, Preferably, reaction temperature is the temperature range of about 100 degreeC normally 250 degreeC, and reaction time becomes like this. Preferably it is 1 to 100 hours. It is also possible to use the polyamic-acid composition (A) mentioned above as a solution of a polyamic-acid (A) as it is for the reactant (reactant) of thermal imidation reaction, for example.

(Chemical imidization reaction)

Chemical imidation reaction is performed by heating a polyamic-acid composition (A) in presence of a catalyst and a dehydrating agent, and subjecting it to dehydration imidation reaction. A polyimide composition can be obtained by performing chemical imidation reaction by the method similar to thermal imidation reaction, after adding a catalyst and a dehydrating agent to the solution of a polyamic acid (A), for example. In chemical imidation reaction, Preferably, it is preferable that reaction temperature is the temperature range of about 150 degreeC from normal temperature normally, and it is preferable that reaction time is 1-20 hours.

As a dehydrating agent in chemical imidation reaction, an organic acid anhydride is mentioned, for example. Examples of the organic acid anhydride include an aliphatic acid anhydride, an aromatic acid anhydride, an alicyclic acid anhydride, a heterocyclic acid anhydride, and a mixture of two or more thereof. As an aliphatic acid anhydride, acetic anhydride is mentioned, for example. The usage-amount of a dehydrating agent becomes like this. Preferably it is 0.01-20 mol with respect to 1 mol of repeating units of a polyamic acid (A).

As a catalyst in chemical imidation reaction, triethylamine, a pyridine, a picoline, and a quinoline are mentioned, for example. The amount of the catalyst to be used is preferably 0.01 to 10 moles with respect to 1 mole of the dehydrating agent to be used.

As a solvent used for chemical imidation reaction, the solvent illustrated as what is used for the synthesis|combination of a polyamic acid (A) is mentioned.

(partial imidization reaction)

Moreover, in addition to a repeating unit (B), a polyimide (B) may contain the repeating unit different from the repeating unit (A). As a different repeating unit, repeating unit (A) is mentioned, for example. In other words, the polyimide (B) may be a polyamic acid-polyimide copolymer. A polyamic acid - a polyimide copolymer is obtained by adjusting the catalyst amount used for the chemical imidation reaction of the ratio which converts a polyamic acid into a polyimide. Specifically, the polyamic acid residue is substantially converted into a polyimide by reacting 1 equivalent of a catalyst such as pyridine and a dehydrating agent such as acetic anhydride with respect to 1 equivalent of the polyamic acid residue. That is, in the chemical imidation reaction of a polyamic acid, the polyamic acid-polyimide copolymer in which the polyimide structure and the polyamic acid structure contain substantially molar equivalent by making the quantity of a catalyst and a dehydrating agent each 0.5 equivalent is obtained. In addition, the imidation reaction is reaction conditions (reaction temperature, reaction time) similar to the chemical imidation reaction mentioned above.

The polyimide resin having a molecular structure insolubilized in a solvent by imidization can be solubilized in a solvent by partial imidization, or coatability can be improved.

In the present specification, when the polyimide (B) has a repeating unit (A) in addition to the repeating unit (B), the ratio of the number of moles of the repeating unit (B) to the total number of moles of the repeating units (A) and (B) ( Molar ratio) 80 % or more of polyamic acid - polyimide copolymer is called polyimide (B). In addition, in such a case, the polyamic acid-polyimide copolymer whose molar ratio is less than 80 % is called polyamic acid (A) (in this way, a polyamic acid (A) has a repeating unit (B) in addition to a repeating unit (A), also). This molar ratio is computable with an infrared spectrophotometer.

<Third embodiment: polyimide molded article>

The polyimide molded article according to the third embodiment of the present invention is obtained by molding the polyamic acid composition according to the first embodiment or the polyimide composition according to the second embodiment. That is, the polyimide molded object which concerns on 3rd Embodiment consists of polyimide (B) (For example, polyimide (V) - (VIII)).

Examples of the polyimide molded article include a liquid crystal aligning film, a passivation film, an electric wire coating material, an adhesive film, a flexible electronic substrate film, a copper clad laminate film, a laminate film, an electrical insulation film, a porous film for fuel cells, a separation film, a heat-resistant film. , IC package, resist film, planarization film, lens such as micro lens array film, optical fiber coating film, display base, optical waveguide, optical filter, optical filter, adhesive sheet, interphase insulating film, semiconductor insulation protective film, TFT liquid crystal insulating film, solar Films and sheets usable for electronic materials such as battery protective films, antireflection films, and flexible display substrates and circuit boards, and belts for electrophotographic image forming apparatuses (more specifically, intermediate transfer belts, transfer belts, fixing belts) , and conveying belts, etc.).

The polyimide molded body is preferably a display base, an optical fiber, an optical waveguide, an optical filter, a lens, an optical filter, an adhesive sheet, an interphase insulating film, a semiconductor insulating protective film, a TFT liquid crystal insulating film, a liquid crystal aligning film, a protective film for solar cells, an antireflection film, and It is suitable for applications such as films or sheets that can be used in electronic materials such as flexible display substrates or circuit boards.

Moreover, when using as a polyimide film, it is good that transparency (for example, transmittance|permeability) is high, and a thing with high mechanical strength (for example, pencil hardness) is good. In addition, it is excellent in durability (the pencil hardness after ultraviolet irradiation is the same as before ultraviolet irradiation, or may be reduced by one step), and also maintains transparency (transmittance after ultraviolet irradiation is 10% or less from the transmittance before ultraviolet irradiation) What is necessary is just a reduction rate of 7% or less).

[Method for Producing Polyimide Molded Body]

The polyimide molded body according to the third embodiment can be produced by heat-treating the polyamic acid composition according to the first embodiment or the polyimide composition according to the second embodiment and molding the polyimide composition according to the second embodiment.

The manufacturing method of a polyimide molded object performs solvent distillation and imidation reaction with a polyamic-acid composition (A) and heating, and is manufactured. Or the manufacturing method of a polyimide molded object apply|coats a polyimide composition (B) on a base material, performs solvent distillation, and is manufactured. More specifically, in the method for producing a polyimide molded article, the polyamic acid composition (A) or the polyimide composition (B) is applied on a substrate to form a coating film (hereinafter referred to as “coating film formation process” in some cases. ) and a step of heat-treating the coating film to form a polyimide molded body (hereinafter referred to as a “heating step” in some cases).

(coating film formation process)

In a coating-film formation process, a polyamic-acid composition (A) or a polyimide composition (B) is apply|coated on a base material, and a coating film is formed.

First, the substrate is prepared. A base material is selected according to the use of the polyimide molded object to manufacture.

Specifically, when manufacturing a polyimide molded body as a liquid crystal aligning film, as a base material, the base material applied to a liquid crystal element is mentioned, For example, a silicon substrate, a glass substrate, or a board|substrate in which the metal film or alloy film was formed on these surfaces. can be heard

Moreover, when manufacturing a polyimide molded object as a passivation film, as a base material, the semiconductor substrate with an integrated circuit, the wiring board with wiring, and the printed circuit board with an electronic component and wiring are mentioned, for example.

Further, when the polyimide molded body is manufactured as an electric wire covering material, as the base material, for example, various electric wires (more specifically, copper wire, hard copper, oxygen-free copper, chrome ore, aluminum such as metal or alloy wire rods and bars) , and plate materials, etc.). Moreover, when a polyimide molded object is shape|molded and processed into tape shape, and this is used as a tape-shaped electric wire covering material wound around an electric wire, as a base material, various flat board|substrates or a cylindrical base are mentioned, for example.

Moreover, when manufacturing an adhesive film as a polyimide molded object, as a base material, various molded objects used as an adhesion object (more specifically, various electrical components, such as a semiconductor chip and a printed circuit board, etc.) are mentioned, for example.

Next, a polyamic-acid composition (A) or a polyimide composition (B) is apply|coated to the target base material, and the coating film of a polyamic-acid composition or a polyimide composition is formed.

There is no restriction|limiting in particular as a coating method with respect to the base material of a polyamic-acid composition (A) or a polyimide composition (B), For example, a polyamic-acid composition (A) or a polyimide composition (B) is applied to the viscosity etc. Accordingly, known methods such as spray coating, spin coating, roll coating, bar coating, slit die coating, inkjet coating, spin coating, dipping, and casting can be exemplified.

The film thickness of the coating film can be appropriately selected according to the type and use of the substrate.

(heating process)

In a heating process, a coating film is heat-processed and a polyimide molded object is formed.

Specifically, first, the coating film of the polyamic acid composition (A) or the polyimide composition (B) is subjected to a drying treatment. By this drying process, a dry film is formed. In addition, in the dry film of the polyamic-acid composition (A) coating film, polyamic-acid (A) was not imidated.

A normal heat-drying furnace can be used for the drying process of a coating film. Examples of the atmosphere in the drying furnace include air, an inert gas (more specifically, nitrogen, argon, etc.), and a vacuum. Although drying temperature can be suitably selected according to the boiling point of the solvent in which the polyamic-acid composition (A) or polyimide composition (B) was dissolved, Usually 80-350 degreeC, Preferably it is 100-320 degreeC, More preferably It is 120-270 degreeC. What is necessary is just to select suitably dry time according to thickness, a density|concentration, and the kind of solvent, For example, it is about 1 second - 360 minutes. In addition, it is also effective to receive hot air during heating. When heating, the temperature may be raised stepwise or may be raised without changing the speed of the hot air.

Next, the dried film is subjected to heat treatment. Thereby, a polyimide molded object is formed. The heating temperature is, for example, 150°C to 400°C, preferably 200°C to 300°C. The heating time is, for example, from 20 minutes to 60 minutes. In the case of heat treatment, it is preferable to heat by gradually increasing the temperature stepwise or at a constant rate before reaching the final temperature of the heating. In addition, as for the coating film of a polyamic acid (A), imidation reaction arises by heat processing.

Through the above steps, a polyimide molded body is formed. In this way, for example, the product which has a polyimide molded object as a film is obtained.

Moreover, in the manufacturing method of a polyimide molded object, a polyimide molded object is taken out from a base material as needed, and a post-processing is performed. For example, it can also be obtained as a film by isolate|separating the film of a polyimide molded object from a base material.

Moreover, when obtaining a polyimide molded object using a metal mold|die, after injecting a predetermined amount of a polyamic acid composition (A) or a polyimide composition (B) into a metal mold|die (especially a rotating mold is preferable), shaping|molding of a film etc. A molded article can be obtained by drying at the same temperature and time as the conditions.

Example

Hereinafter, the present invention will be described in more detail with reference to Examples, but the present invention is not limited to these Examples.

[Synthesis of monomers]

(Synthesis Example 1: Synthesis of tetracarboxylic dianhydride having a steroid structure)

To a dry 10-liter separable flask (reaction vessel), 405 g (1.0 mol) of 3,6-cholestanediol and 463.26 g (2.2 mol) of trimellitic anhydride chloride were added and dissolved in 5000 g of tetrahydrofuran. . Then, 174.02 g (2.2 mol) of pyridine was added dropwise into the reaction vessel while stirring under ice cooling. After completion|finish of dripping, the reaction liquid was stirred at room temperature (25 degreeC) for 5 hours. A precipitate was obtained in the contents. After the precipitate was separated by filtration, a large amount of the reaction solution was poured into water, and the precipitate was separated by filtration. The obtained solid was washed well with water, and further, it refluxed in 5000 g of acetic anhydride for 5 hours. After distilling off the solvent component, recrystallization was performed from methyl ethyl ketone. White crystal tetracarboxylic dianhydride A (hereinafter, may be referred to as "ChTA-A") was obtained. The obtained ChTA-A was used for the following production examples (Examples).

¹ H-NMR spectrum of the synthesized ChTA-A was measured using a proton nuclear magnetic resonance spectrometer (“JMM-A400” manufactured by Nippon Electronics Co., Ltd.) (solvent: CDCl ₃ , internal standard sample: tetramethylsilane). The chemical shift values of ChTA-A are shown below.

ChTA-A: ^1H- NMR (CDCl ₃ )δ = 0.8 - 2.4 (44H), 5.5 (2H), 6.6 - 7.8 (6H).

Further, the infrared absorption spectrum of the synthesized ChTA-A was measured using a Fourier transform infrared spectrometer ("Nicolet iS50" manufactured by Thermo Fisher Scientific) (sample preparation method: potassium bromide purification method). The peak in the infrared spectrum of ChTA-A is shown below.

ChTA-A: IR (cm ^-1 ) 3000 - 2840 cm ^-1 , 1780 cm ^-1

From the obtained chemical shift value and the peak of an infrared absorption spectrum, it confirmed that ChTA-A was tetracarboxylic dianhydride represented by General formula (E-4).

(Synthesis Example 2 Synthesis of tetracarboxylic dianhydride having a steroid structure)

The reaction was carried out in the same manner as in Synthesis Example 1 except that 476.67 g (2.2 mol) of 4-chloroformyl-1,2-cyclohexanedicarboxylic acid anhydride was used instead of 463.26 g (2.2 mol) of trimellitic anhydride chloride. It performed to obtain white crystal tetracarboxylic dianhydride B (it may be described as ChTA-B hereafter). The obtained ChTA-B was used for the following production examples (Examples).

¹ H-NMR spectrum and infrared absorption spectrum of ChTA-B were measured in the same manner as for ChTA-A, and from the chemical shift value and the peak of the infrared absorption spectrum, ChTA-B is a tetracaride represented by the formula (E-5) It confirmed that it was acid dianhydride.

[Synthesis of polyamic acid and preparation of polyamic acid composition]

(Preparation Example 1: polyamic acid PAA-1 and polyamic acid composition PAA-1)

71.28 g (0.097 mol) of ChTA-A obtained in Synthesis Example 1 and 20.04 g (0.1 mol) of 4,4'-diaminodiphenyl ether were mixed with N-methyl-2-pyrrolidone (hereinafter referred to as NMP) under a nitrogen stream. ) was dissolved in 365.32 g (equivalent to 20% of solid content) to prepare a reaction solution. Then, the reaction liquid was hold|maintained at 60 degreeC for 24 hours, and the polymerization reaction was performed. The solution of polyamic acid PAA-1 was obtained. Then, NMP was added to the obtained solution, solid content was adjusted to 10 weight%, and polyamic-acid composition PAA-1 which has a repeating unit represented by general formula (I-2) was obtained.

The obtained polyamic acid composition PAA-1 was used for Examples 1-3. Table 1 shows the components used in the production examples and the components in the composition.

Table 1 shows the components used in Production Example 1 and the components in the composition. In Table 1, PAA represents a polyamic acid, and PI represents a polyimide, respectively. Moreover, ChTAH-A shows the tetracarboxylic dianhydride compound A (molecular weight 734.87) synthesize|combined by the synthesis example 1. ChTAH-B represents the tetracarboxylic dianhydride compound B (molecular weight 747.19) synthesize|combined by the synthesis example 2. ODA represents 4,4'-diaminodiphenyl ether (molecular weight 200.4). PDA represents p-phenylenediamine (molecular weight 108.12). NMP represents N-methyl-2-pyrrolidone. These notations are the same also in Tables 2-5.

(Preparation Example 3: polyamic acid PAA-2 and polyamic acid composition PAA-2)

Preparation Example except that the tetracarboxylic acid compound was changed from 71.28 g (0.097 mol) of ChTA-A to 72.48 g (0.097 mol) of ChTA-B obtained in Synthesis Example 2, and the mass of NMP was changed from 365.32 g to 370.07 g. It carried out similarly to 1, and obtained polyamic-acid PAA-2 and polyamic-acid composition PAA-2.

From the peak of the chemical shift value and infrared absorption spectrum obtained by carrying out similarly to polyamic acid PAA- ^{1, and measuring the <1>} H-NMR spectrum and infrared absorption spectrum of polyamic acid PAA-2, polyamic acid PAA-2 is general formula (II- It was confirmed that it was a polyamic acid which has a repeating unit represented by 2).

The obtained polyamic acid composition PAA-2 was used for Examples 7-9. Table 1 shows the components used in Production Example 3 and the components in the composition.

(Production Examples 5, 7, 9, 11, 13, 15, 17, 19: polyamic acid PAA-3 to 10 and polyamic acid composition PAA-3 to 10)

Polyamic acid PAA-, respectively, according to manufacture example 1 except having changed the kind and addition amount of tetracarboxylic dianhydride, the kind and addition amount of diamine compound, and the kind and addition amount of a solvent as described in Table 1 and Table 2 3-10 and polyamic-acid composition PAA-3-10 were obtained.

It carried out similarly to polyamic acid PAA-1 of manufacture example 1, ^{and measured the <1>} H-NMR spectrum and the infrared absorption spectrum. As a result, it was confirmed that polyamic acids PAA-3-6 and PAA-8-10 are polyamic acids containing the repeating unit represented by general formula (I-2). It was confirmed that polyamic acid PAA-7 was a polyamic acid containing the repeating unit represented by general formula (I-3). It was confirmed that polyamic acid PAA-8 further includes a repeating unit derived from 1,2,3,4-cyclobutanetetracarboxylic acid in addition to the repeating unit represented by the general formula (I-2). It was confirmed that polyamic acid PAA-9 contained the repeating unit represented by the formula (I-3) in addition to the repeating unit represented by the formula (I-2).

Each obtained polyamic-acid composition PAA-3-10 was used for the Example. The components used for manufacture and the components in a composition are shown in Table 1 and Table 2.

In Table 2, PMDA represents pyromellitic anhydride (molecular weight 218.12). CHDA represents 1,2,3,4-cyclobutanetetracarboxylic dianhydride (molecular weight 196.11).

(Preparation Example 21: polyamic acid PAA-11 and polyamic acid composition PAA-11)

Polyamic acid PAA-11 according to Production Example 1 except that the tetracarboxylic acid compound was changed from 71.28 g (0.097 mol) of ChTA-A to 21.16 g (0.097 mol) of pyromellitic anhydride (PMDA) having no steroid structure And polyamic acid composition PAA-11 was obtained.

Each obtained polyamic-acid composition PAA-11 was used for the comparative example. The components used for manufacture and the components in a composition are shown in Table 2.

(Preparation Example 23: Polyamic acid PAA-12 and polyamic acid composition PAA-12 that do not have a steroid structure)

The tetracarboxylic acid compound was changed from 71.28 g (0.097 mol) of ChTA-A to 19.61 g (0.1 mol) of 1,2,3,4-cyclobutanetetracarboxylic dianhydride (CHDA) having no steroid structure, Except having changed the mass of NMP into 158.52 g from 365.32 g, according to manufacture example 1, polyamic-acid PAA-12 and polyamic-acid composition PAA-12 were obtained.

Each obtained polyamic-acid composition PAA-12 was used for the comparative example. The components used for manufacture and the components in a composition are shown in Table 2.

[Synthesis of polyimide and preparation of polyimide composition]

(Preparation Example 2: Polyimide PI-1 and Polyimide Composition PI-1)

According to Preparation Example 1, a polyamic acid composition PAA-1 was prepared separately. NMP 456.65g (10% of solid content equivalent) was added to polyamic-acid composition PAA-1, Furthermore, 15.84g (0.2 mol) of pyridines as a catalyst, and 20.43 g (0.2 mol) of acetic anhydride as a dehydrating agent were added, and the reaction liquid was prepared . The reaction liquid was hold|maintained at 100 degreeC under nitrogen stream for 6 hours, and imidation reaction was performed. A solution of polyimide PI-1 was obtained. After the reaction, pyridine, acetic anhydride, and acetic acid were distilled off at a temperature of 100 DEG C and a pressure of 10 mmHg in the reaction vessel. Thereafter, NMP was added to the reaction vessel to adjust the solid content to 10% by weight to obtain a polyimide composition PI-1 containing a polyimide having a repeating unit represented by the general formula (V-2). The obtained polyimide composition PI-1 was used for Examples 4-6.

(Preparation Example 4: polyimide PI-2 and polyimide composition PI-2)

Except for the following changes, according to manufacture example 2, polyimide PI-2 and polyimide composition PI-2 were obtained. The polyamic acid PAA-1 separately prepared according to Preparation Example 1 was changed to the polyamic acid composition PAA-2 separately prepared according to Preparation Example 3. The mass of NMP was changed from 456.65 g (corresponding to 10% of solid content) to 462.59 g (corresponding to 10% of solid content). 15.84 g (0.2 mol) of pyridine and 20.43 g (0.2 mol) of acetic anhydride were replaced with 15.84 g (0.2 mol) of pyridine and 20.43 g (0.2 mol) of acetic anhydride.

From the peak of the chemical shift value and infrared absorption spectrum obtained by carrying out similarly to polyimide PI-1, measuring the 1H-NMR spectrum and infrared absorption spectrum of polyimide PI-2, polyimide PI-2 is Formula (VI-2) It was confirmed that it is a polyimide which has a repeating unit represented by ).

The obtained polyimide composition PI-2 was used for Examples 10-12. Table 1 shows the components used in Production Example 4 and the components in the composition.

(Production Examples 6, 8, 10, 12, 14, 16, 18, 20: polyimide PI-3 to 10 and polyimide composition PI-3 to 10)

Manufacture example 2 except having changed the polyamic acid composition PAA-1 obtained in manufacture example 1 into polyamic acid composition PAA-3-10 obtained by manufacture examples 5, 7, 9, 11, 13, 15, 17, 19, respectively Thus, polyimide PI-3-10 and polyimide composition PI-3-10 were obtained, respectively.

It carried out similarly to polyimidic acid PI-1 of manufacture example 2, and measured the <1>H-NMR spectrum and the infrared absorption spectrum. As a result, it was confirmed that polyimide acids PI-3 to 6 and PI-8 to 10 contained the repeating unit represented by the general formula (V-2). It was confirmed that the polyimide PI-7 contained the repeating unit represented by the general formula (V-3). It was confirmed that polyimide PI-8 further includes a repeating unit derived from 1,2,3,4-cyclobutanetetracarboxylic acid in addition to the repeating unit represented by the general formula (V-2). It was confirmed that polyimide PI-9 contains a repeating unit represented by the formula (V-3) in addition to the repeating unit represented by the formula (V-2).

Each obtained polyimide composition was used for the Example. The components used for manufacture and the components in a composition are shown in Table 1 or Table 2.

(Preparation Example 22: polyimide PI-11 and polyimide composition PI-11)

Except having changed the polyamic acid composition PAA-1 obtained in manufacture example 1 into the polyamic acid composition PAA-11 obtained in manufacture example 21, according to manufacture example 2, polyimide PI-11 and polyimide composition PI-11 were respectively obtained . As for the obtained polyimide composition, the produced|generated polyimide has precipitated.

(Preparation Example 24: Polyimide PI-12 and Polyimide Composition PI-12 that do not have a steroid structure)

According to Preparation 23, a polyamic acid composition PAA-12 was separately prepared. Next, the reaction was carried out according to Production Example 2 except that NMP was 198.15 g (equivalent to 10% solid content), pyridine 15.84 g (0.2 mol), and acetic anhydride 20.43 g (0.2 mol), but the resulting polyimide resin was precipitated abandoned

[Production of polyimide molded article]

(Example 1: Preparation of polyimide film (polyimide molded article) PAA-1)

The polyamic acid composition PAA-1 was apply|coated on the Pyrex (trademark) glass plate using the applicator so that it might become an application|coating thickness of 500 micrometers. After drying for 10 minutes on a 100 degreeC hotplate, it baked in 250 degreeC oven for 30 minutes. The obtained polyimide film was uniform with a film thickness of 50 micrometers, and there was no defect. Each physical property of the film was measured by the method described below. A result is shown in Table 3.

[Measurement method and evaluation method]

(Measurement of solubility of polyamic acid)

The produced polyamic-acid solution was added to methanol, and polyamic-acid resin was reprecipitated. After separation by filtration with a G3 glass filter, it was dried at 30°C under a reduced pressure of 10 mmHg for 24 hours to obtain a polyamic acid resin sample.

Next, a fixed amount of the polyamic acid resin sample was weighed in a sample bottle, the good solvent/poor solvent mixture was added so that solid content might be 10 weight%, and it stirred with a wave rotor for 24 hours, and tried to melt|dissolve. Moreover, NMP was used as a good solvent, and butyl cellosolve was used as a poor solvent.

The external appearance of the obtained mixed solution was observed visually, and the presence or absence of precipitation of resin was confirmed. From the observation result by visual observation, the solubility and dispersibility of a polyamic acid were evaluated based on the following evaluation criteria. It was judged that A and B were dissolved or dispersed. Table 6 shows the results of solubility.

(Evaluation standard)

A (very good): It has the same appearance compared to only the mixed solvent

B (Good): It is slightly cloudy compared to only the mixed solvent.

C (bad): Precipitation of polyamic acid is observed

※ The mixed solvent in the evaluation criteria is a mixed solvent consisting of only a good solvent and a poor solvent.

(Measurement of transmittance and evaluation of transparency)

The transmittance at 550 nm of the polyimide film was measured with a visible light spectrophotometer (absorbance 550 nm). Table 3 shows the measurement results.

Moreover, based on the following evaluation criteria, transparency of the polyimide film was evaluated from the obtained transmittance|permeability. Table 3 shows the evaluation results. Those whose evaluation results were A or B, that is, the polyimide film which has 85% or more of transmittance|permeability was made into pass.

(Criteria for evaluation of transparency)

A (very good): transmittance is 95% or more

B (good): transmittance is 85% or more and less than 95%

C (bad): transmittance is less than 85%

The transmittance|permeability of polyimide film PAA-1 was 98.0 %, the evaluation result was A, and it was very transparent.

(Measurement of pencil hardness and evaluation of mechanical strength)

The pencil hardness of the polyimide film was measured according to JISK5400. Table 3 shows the measurement results.

Moreover, the mechanical strength of a polyimide film was evaluated based on the following evaluation criteria from the obtained pencil hardness. Table 3 shows the evaluation results. A polyimide film having an evaluation result of A or B, that is, a pencil hardness of H or more (more specifically, any of H, 2H, and 3H, etc.) was set as the pass.

(Evaluation criteria for mechanical strength)

A (very good): Pencil hardness is 3H or more (more specifically, any of 3H, 4H, 6H, etc.).

B (good): The pencil hardness is H or 2H.

C (bad): Pencil hardness is HB or less (more specifically, any of HB, B, 2B, 3B, etc.).

Pencil hardness of polyimide film PAA-1 was hardness of 3H, and the evaluation result was A.

(Evaluation of film physical properties (durability) after UV treatment)

The polyimide film was subjected to ultraviolet treatment. Specifically, the polyimide film was irradiated with ultraviolet rays at 1.5 kV for 10 minutes using an ultraviolet irradiation device ECS1511-U manufactured by Eye Graphic. The transmittance and pencil hardness of the polyimide film after UV irradiation were measured. The results of transmittance and pencil hardness before and after UV treatment were compared, respectively. In the comparison of transmittance, the difference in transmittance (= transmittance before ultraviolet irradiation - transmittance after ultraviolet irradiation) was calculated. In the comparison of pencil hardness, the change with respect to the result of the pencil hardness before ultraviolet irradiation (how many stages the evaluation result of pencil hardness fell: For example, when HB changes to B, it is evaluated that it fell by 1 stage) was computed. . From the comparison result, durability of the polyimide film was evaluated based on the following evaluation criteria. Table 3 shows the evaluation results.

(Evaluation criteria of the durability)

A (very good): the difference in transmittance is less than 1, and also the change in the result of pencil hardness is 0 level

B (good): The difference in transmittance is 1 or more and less than 7, or the change in the result of pencil hardness is 0 level

C (bad): The difference in transmittance is 7 or more, or the change to the result of pencil hardness is 0 or more

The transmittance|permeability of polyimide film PAA-1 after ultraviolet irradiation was 97.8 %, and pencil hardness was 3H. For this reason, the difference of the transmittance|permeability before and behind ultraviolet irradiation of polyimide film PAA-1 was 0.2 %, the change of pencil hardness became 0 stage, and the evaluation result of durability was A. In short, almost no change was seen from before UV irradiation.

(Examples 2-24, Comparative Examples 1-8: Preparation of polyimide film (polyimide molded object) 2-24 and C1-C8)

Except having changed into the kind of polyamic-acid composition and polyimide composition of Tables 3-5, and baking conditions, according to Example 1, the polyimide film was produced. The permeability, mechanical strength, and durability of the obtained polyimide film were evaluated. The obtained result is shown to Tables 3-5.

Moreover, in Comparative Examples 7-8, since polyimide precipitated in polyimide compositions PI-11-12, a polyimide film could not be produced and it was not able to evaluate.

As shown in Table 6, even if polyamic-acid PAA-1 changed the weight ratio (NMP:butyl cellosolve) of the good solvent in a mixed solvent, and a poor solvent, a change in solubility was not seen. As polyamic acid PAA-11 increased the ratio of the poor solvent in a mixed solvent, an evaluation result changed from A to C, and it was confirmed that solubility falls. Therefore, it was confirmed that polyamic acid PAA-1 could melt|dissolve in the solvent with high poor solvent fraction compared with polyamic acid PAA-11.

As shown in Tables 1-4, in Examples 1-24, polyamic-acid composition PAA-1-9 contains polyamic-acid PAA-1-9 which has a repeating unit represented by general formula (A), and a solvent, was made up Polyamic acids PAA-1 to 9 were melt|dissolved or disperse|distributed in the said solvent.

Moreover, polyimide compositions PI-1-9 were comprised including polyimide PI-1-9 which have a repeating unit represented by general formula (B), and a solvent. Polyimides PI-1 to 9 were dissolved or dispersed in the solvent.

As shown in Tables 3 - 4, in Examples 1-24, the polyimide films 1-24 were produced from any of polyamic-acid compositions PAA-1-9 and polyimide compositions PI-1-9. As for the polyimide films 1-24, the evaluation results of permeability|transmittance, mechanical strength, and durability were all A (very good) or B (good). In other words, the polyimide films 1 to 24 have high transmittance and pencil hardness, and even after UV irradiation, the transmittance of the film hardly decreases, and the pencil hardness is almost maintained, and has excellent transmittance, mechanical strength and durability. was doing

As shown in Table 2 and Table 5, in Comparative Examples 1-6, the polyamic-acid compositions 11-12 consisted including polyamic-acid PAA-11-12 and a solvent. Polyamic acids PAA-11-12 did not contain the repeating unit represented by General formula (A).

In Comparative Examples 7-8, polyimide compositions PI-11-12 were comprised including polyimide PI-11-12 and a solvent. Polyimides PI-11 to 12 did not include the repeating unit represented by the general formula (B). In polyimide compositions PI-11-12, polyimide PI-11-12 precipitated and did not melt|dissolve or disperse|distribute in a solvent.

As shown in Table 5, in Comparative Examples 1-6, polyimide films C1-C6 were produced from either of polyamic-acid composition PAA-11 and PAA-12. Polyimide films C1-C6 had at least 1 or more of C (bad) among the evaluation results of permeability|transmittance, mechanical strength, and durability. That is, polyimide films C1-C6 had shown at least one among the fall of the low transmittance|permeability, low mechanical strength, and the transmittance|permeability after ultraviolet irradiation, and the fall of mechanical strength. Therefore, the polyimide films C1-C6 were not compatible with the outstanding permeability|transmittance, mechanical strength, and durability.

Moreover, in Comparative Examples 7-8, since polyimide PI-11-12 precipitated as above-mentioned, a polyimide film was not able to be produced from a polyimide composition. Moreover, evaluation of a polyimide film was not able to be performed.

From the above, it is clear that the polyimide film of Examples 1-24 has the outstanding permeability, mechanical strength, and durability compared with the polyimide film of Comparative Examples 1-6.

Claims (12)

The following general formula (A):

[In the above general formula (A),
R ^A and R ^B are each independently a hydrogen atom or a methyl group,
R ^C is a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, or an alkenyl group having 2 to 10 carbon atoms;
B ^A is a divalent organic group,
B ³ and B ⁴ are each independently -C(=O)- or -CH ₂ -,
G ¹ and G ² each independently represent at least one ring selected from the group consisting of an aliphatic ring and an aromatic ring, or a linear alkanetriyl group having 4 to 10 carbon atoms, wherein the ring is If 2 or more, the ring is a condensed ring]
The polyamic acid composition in which the polyamic acid containing the repeating unit represented by is melt|dissolved or disperse|distributed in a solvent. The method of claim 1,
In the general formula (A), G ¹ and G ² each independently represent at least one ring selected from the group consisting of an aliphatic ring and an aromatic ring. 3. The method according to claim 1 or 2,
The repeating unit represented by the general formula (A) has the following general formula (I):

[In the above general formula (I),
R ¹ and R ² are each independently a hydrogen atom or a methyl group,
R ³ is a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, or an alkenyl group having 2 to 10 carbon atoms;
B ¹ is a divalent organic group],
The general formula (II):

[In the above general formula (II),
R ¹¹ and R ¹² are each independently a hydrogen atom or a methyl group,
R ¹³ is a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, or an alkenyl group having 2 to 10 carbon atoms;
B ¹¹ is a divalent organic group],
The general formula (III):

[In the general formula (III),
R ²¹ and R ²² are each independently a hydrogen atom or a methyl group,
R ²³ is a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, or an alkenyl group having 2 to 10 carbon atoms;
B ²¹ is a divalent organic group], and
The general formula (IV):

[In the above general formula (IV),
R ³¹ and R ³² are each independently a hydrogen atom or a methyl group,
R ³³ is a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, or an alkenyl group having 2 to 10 carbon atoms;
B ³¹ is a divalent organic group]
A polyamic acid composition comprising at least one repeating unit selected from the group consisting of 4. The method according to any one of claims 1 to 3,
The polyamic acid composition which does not contain the dicarboxylic acid structure derived from tetracarboxylic acid in the molecular terminal of the polyamic acid containing the repeating unit represented by the said General formula (A). 5. The method according to any one of claims 1 to 4,
An amino group derived from diamine is included at the molecular terminal of the polyamic acid containing the repeating unit represented by the general formula (A),
The ratio of the amino group (-NH ₂₎ of the polyamic acid, in the range of 0.001 to 0.1 mol / ㎏, the polyamic acid composition. The polyimide molded object produced by apply|coating the polyamic acid composition in any one of Claims 1-5 on a base material, performing solvent distillation and imidation reaction by heating. The following general formula (B):

[In the general formula (B),
R ^D and R ^E are each independently a hydrogen atom or a methyl group,
R ^F is a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, or an alkenyl group having 2 to 10 carbon atoms;
B ^D is a divalent organic group,
B ⁵ and B ⁶ are each independently -C(=O)- or -CH ₂ -,
G ³ and G ⁴ each independently represent at least one ring selected from the group consisting of an aliphatic ring and an aromatic ring, or a linear alkanetriyl group having 4 to 10 carbon atoms, wherein the ring is 2 or more, the ring is a condensed ring]
The polyimide composition in which the polyamic acid containing the repeating unit represented by is melt|dissolved or disperse|distributed in a solvent. 8. The method of claim 7,
In the general formula (B), G ³ and G ⁴ each independently represent at least one ring selected from the group consisting of an aliphatic ring and an aromatic ring. 9. The method according to claim 7 or 8,
The repeating unit represented by the general formula (B) has the following general formula (V):

[In the above general formula (V),
R ⁴ and R ⁵ are each independently a hydrogen atom or a methyl group,
R ⁶ is a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, or an alkenyl group having 2 to 10 carbon atoms;
B ² is a divalent organic group],
The general formula (VI):

[In the above general formula (VI),
R ¹⁴ and R ¹⁵ are each independently a hydrogen atom or a methyl group,
R ¹⁶ is a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, or an alkenyl group having 2 to 10 carbon atoms;
B ¹² is a divalent organic group];
The general formula (VII):

[In the above general formula (VII),
R ²⁴ and R ²⁵ are each independently a hydrogen atom or a methyl group,
R ²⁶ is a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, or an alkenyl group having 2 to 10 carbon atoms;
B ²² is a divalent organic group], and
The general formula (VIII):

[In the general formula (VIII),
R ³⁴ and R ³⁵ are each independently a hydrogen atom or a methyl group,
R ³⁶ is a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, or an alkenyl group having 2 to 10 carbon atoms;
B ³² is a divalent organic group]
A polyimide composition comprising at least one repeating unit selected from the group consisting of 10. The method according to any one of claims 7 to 9,
The polyimide composition which does not contain the dicarboxylic acid structure derived from tetracarboxylic acid in the molecular terminal of the polyimide containing the repeating unit represented by the said General formula (B). 11. The method according to any one of claims 7 to 10,
An amino group derived from diamine is included at the molecular terminal of the polyimide containing the repeating unit represented by the general formula (B);
The ratio of the amino group (-NH ₂₎ of the polyimide, in the range of 0.001 to 0.1 mol / ㎏, polyimide composition. A polyimide molded product produced by applying the polyimide composition according to any one of claims 7 to 11 on a substrate, and performing solvent distillation by heating.