JP4667856B2 - Method for producing polybenzazole complex and polybenzazole complex - Google Patents

Description

The present invention, which has excellent anisotropy function by molecular chains are highly oriented, a manufacturing method and a polybenzazole complex of polybenzazole complex physical properties thereof are improved.

  In recent years, films formed from polybenzazole have high strength and high elastic modulus, and are excellent in heat resistance and flame retardancy, such as magnetic tape, insulating films for electrical and electronic parts, liquid crystal alignment films, etc. Much research is being done for new applications. For example, Patent Document 1 discloses a film-shaped polybenzazole molded body having a specific surface roughness excellent in smoothness. Patent Document 2 discloses a film-like polybenzazole molded body having specific elongation and Young's modulus suitable for a magnetic recording medium. Furthermore, Patent Document 3 discloses a method for producing a polyparaphenylene benzobisthiazole film, and Patent Document 4 discloses a polybenzazole molded body in the form of a film that is biaxially stretched and oriented in the stretching direction. ing. For the purpose of further improving mechanical strength, Patent Document 5 discloses a polymer composite having a rigid polymer having a three-dimensional network chain structure. Patent Document 6 discloses a polymer blend composite having excellent mechanical strength and the like by dispersing a rigid polymer in a matrix polymer at a molecular level.

  However, as the characteristics required for semiconductor package materials that have recently been accelerating downsizing and thinning and materials for electronic devices that are becoming more functional and high performance, the high strength of conventional polybenzazole moldings, In addition to high elastic modulus and high heat resistance, new characteristics are required. That is, in the polybenzazole molded body, various properties such as optical properties, magnetic properties, mechanical properties, thermal properties, electrical properties and the like are particularly enhanced in a specific direction of the molded product, so-called An anisotropic function is required. However, in the conventional mechanical stretching method and the method using shear flow, the molecular chain of polybenzazole is a rigid rod, so the molecular chain of polybenzazole is oriented along the surface of the molded body. Only thing was obtained. Therefore, in the film-like molded body, it is impossible to align molecular chains in the thickness direction and develop an anisotropic function in the direction in the above prior art.

Recently, semiconductor devices that operate at high speed have come to be used in small electronic devices. This high-speed operating semiconductor device generates a large amount of heat and is coupled with the state of high-density mounting. The problem is whether to improve the sex. However, many polymer materials including polyimide have low thermal conductivity and insufficient heat dissipation. Attempts have also been made to form a metal base substrate using a metal foil with good heat conductivity as part of the base material, or to obtain a device material with improved thermal conductivity by adding metal fine powder to a polymer material. It has been broken. However, these means for improving thermal conductivity are accompanied by an increase in electrical conductivity, that is, a decrease in electrical insulation, and thus are not preferable for applications such as flexible wiring boards. Therefore, in such applications, development of a polybenzazole molded body having an anisotropic function particularly excellent in thermal conductivity is expected.
Japanese Patent Laid-Open No. 11-171993 JP 2000-273214 A JP-A-63-74612 JP-T 6-503521 JP 2001-11189 A JP 9-157522 A

  However, in the case of forming a molded body in which the molecular chain is highly oriented in a certain direction with polybenzazole alone, the resulting molded body has thermal conductivity, linear expansion coefficient, dielectric constant, light transmittance, gas permeability. It exhibits excellent anisotropy function in properties such as conductivity, liquid permeability, electrical conductivity, and ionic conductivity, but the polybenzazole molecular chain is rigid, so it has poor flexibility, especially molecular chain The mechanical strength in the direction perpendicular to the orientation direction was weak and tended to be brittle. Patent Documents 5 and 6 disclose polymer composites with improved mechanical strength, but methods for imparting the above anisotropic functions to these polymer composites are suggested. There wasn't.

The present invention has been made paying attention to the problems existing in the prior art as described above. The purpose of the polybenzazole composite is to have excellent anisotropic functions and improved physical properties such as flexibility and mechanical strength by highly oriented molecular chains in a certain direction. It is in providing the manufacturing method of a body, and a polybenzazole complex .

In order to solve the above problems, the invention described in claim 1 is a method for producing a polybenzazole composite comprising polybenzazole and at least one physical property modifier, wherein The azole has at least one of the repeating units represented by the following general formulas (1) to (4),

上記式中、Ｘはイオウ原子、酸素原子又はイミノ基を表し、Ａｒ_１及びＡｒ_２は芳香族炭化水素基をそれぞれ表し、ｎは１０〜５００の整数であり、
下記式（ｉ）によって求められるポリベンズアゾールおよび物性調整材の分子鎖の配向度Ａが０．６以上１．０未満の範囲であり、
配向度Ａ＝（１８０−ΔＢ）／１８０・・・（ｉ）
（式中、ΔＢは該成形体のＸ線回折測定によるピーク散乱角を固定して、方位角方向の０〜３６０°までの強度分布における半値幅を表す）
前記物性調整材は、
ポリオレフィン系化合物、ポリエステル系化合物、ポリアクリル系化合物、ポリメタクリル系化合物、ポリビニル系化合物、ポリスチレン系化合物、ポリウレタン系化合物、ポリエーテルアミド系化合物、ポリエステルアミド系化合物、芳香族系ポリマー、フルオロアルキル高分子、液晶性高分子、ビスフェノールＡ型エポキシ樹脂、フェノール・ノボラック型エポキシ樹脂、クレゾール・ノボラック型エポキシ樹脂、グリシジルアミン型エポキシ樹脂、ナフタレン型エポキシ樹脂、トリフェノールアルカン型エポキシ樹脂、ビフェニル型エポキシ樹脂、及び液晶性エポキシ樹脂から選ばれるものであり、
該方法が、
前記ポリベンズアゾールと少なくとも１種の物性調整材とを含み、前記ポリベンズアゾールのリオトロピック液晶性を発現し得る混合溶液を調製する工程と、
前記リオトロピック液晶性を発現させた混合溶液に一定方向の磁場または電場を印加することにより、同混合溶液中のポリベンズアゾールおよび物性調整材の分子鎖を一定方向に配向させる工程と、
そのポリベンズアゾールおよび物性調整材の分子鎖の配向状態を維持したまま、前記混合溶液を凝固させて、ポリベンズアゾールの分子鎖の間に前記物性調整材が含浸された複合基体を形成する工程と、
前記複合基体を硬化させる工程とを含むことを要旨とする。

In the above formula, X represents a sulfur atom, an oxygen atom or an imino group, Ar ₁ and Ar ₂ each represent an aromatic hydrocarbon group, n is an integer of 10 to 500,
The degree of orientation A of the molecular chain of the polybenzazole and the physical property modifier determined by the following formula (i) is in the range of 0.6 to less than 1.0,
Orientation degree A = (180−ΔB) / 180 (i)
(In the formula, ΔB represents the half-value width in the intensity distribution from 0 to 360 ° in the azimuth direction with the peak scattering angle measured by X-ray diffraction measurement of the molded body fixed)
The physical property adjusting material is
Polyolefin compounds, polyester compounds, polyacrylic compounds, polymethacrylic compounds, polyvinyl compounds, polystyrene compounds, polyurethane compounds, polyetheramide compounds, polyesteramide compounds, aromatic polymers, fluoroalkyl polymers , Liquid crystalline polymer, bisphenol A type epoxy resin, phenol novolac type epoxy resin, cresol novolac type epoxy resin, glycidylamine type epoxy resin, naphthalene type epoxy resin, triphenolalkane type epoxy resin, biphenyl type epoxy resin, and It is chosen from liquid crystalline epoxy resins,
The method is
A step of said polybenzazole and saw including at least one physical property adjusting material to prepare a mixed solution capable of expressing a lyotropic liquid crystal of said polybenzazole,
Applying a magnetic field or an electric field in a certain direction to the mixed solution exhibiting the lyotropic liquid crystallinity, thereby orienting molecular chains of the polybenzazole and the physical property adjusting material in the mixed solution in a certain direction;
A step of solidifying the mixed solution while maintaining the alignment state of the molecular chains of the polybenzazole and the physical property adjusting material to form a composite substrate in which the physical property adjusting material is impregnated between the molecular chains of the polybenzazole. When,
And a step of curing the composite substrate.

The invention according to claim 2 is a method for producing a polybenzazole complex comprising polybenzazole and first and second physical property modifiers, wherein the polybenzazole has the following general formula ( Having at least one of the repeating units represented by 1) to (4),

上記式中、Ｘはイオウ原子、酸素原子又はイミノ基を表し、Ａｒ_１及びＡｒ_２は芳香族炭化水素基をそれぞれ表し、ｎは１０〜５００の整数であり、
下記式（ｉ）によって求められるポリベンズアゾールおよび第１の物性調整材の分子鎖の配向度Ａが０．６以上１．０未満の範囲であり、
配向度Ａ＝（１８０−ΔＢ）／１８０・・・（ｉ）
（式中、ΔＢは該成形体のＸ線回折測定によるピーク散乱角を固定して、方位角方向の０〜３６０°までの強度分布における半値幅を表す）
前記第１及び第２の物性調整材は、
ポリオレフィン系化合物、ポリエステル系化合物、ポリアクリル系化合物、ポリメタクリル系化合物、ポリビニル系化合物、ポリスチレン系化合物、ポリウレタン系化合物、ポリエーテルアミド系化合物、ポリエステルアミド系化合物、芳香族系ポリマー、フルオロアルキル高分子、液晶性高分子、ビスフェノールＡ型エポキシ樹脂、フェノール・ノボラック型エポキシ樹脂、クレゾール・ノボラック型エポキシ樹脂、グリシジルアミン型エポキシ樹脂、ナフタレン型エポキシ樹脂、トリフェノールアルカン型エポキシ樹脂、ビフェニル型エポキシ樹脂、及び液晶性エポキシ樹脂から選ばれるものであり、
該方法が、
前記ポリベンズアゾールと第１の物性調整材とを含み、前記ポリベンズアゾールのリオトロピック液晶性を発現し得る混合溶液を調製する工程と、
前記リオトロピック液晶性を発現させた混合溶液に一定方向の磁場または電場を印加することにより、同混合溶液中のポリベンズアゾールおよび第１の物性調整材の分子鎖を一定方向に配向させる工程と、
そのポリベンズアゾールおよび第１の物性調整材の分子鎖の配向状態を維持したまま、前記混合溶液を凝固させて、ポリベンズアゾールと第１の物性調整材との複合基体を形成する工程と、
前記複合基体の分子鎖の間に第２の物性調整材を含浸させる工程と、
前記第２の物性調整材を含浸させた複合基体を硬化させる工程とを有することを要旨とする。
請求項３に記載の発明は、ポリベンズアゾールと、少なくとも１種類の物性調整材とを含む、ポリベンズアゾール複合体であって、前記ポリベンズアゾールは、下記一般式（１）〜（４）で示される繰り返し単位のうちの少なくともいずれかを有し、

上記式中、Ｘはイオウ原子、酸素原子又はイミノ基を表し、Ａｒ_１及びＡｒ_２は芳香族炭化水素基を表し、ｎは１０〜５００の整数であり、
前記物性調整材は、ポリイミドであり、該複合体は、前記ポリベンズアゾールと前記ポリイミドとを含む混合溶液から得られることで前記ポリベンズアゾールの分子鎖の間に前記ポリイミドが含浸されており、前記ポリイミドの分子鎖が、前記ポリベンズアゾールの分子鎖と共に一定方向に配向されており、下記式（ｉ）によって求められる前記ポリベンズアゾールおよび前記ポリイミドの分子鎖の配向度Ａが０．６以上１．０未満の範囲であることを要旨とする。
配向度Ａ＝（１８０−ΔＢ）／１８０ ・・・ （ｉ）
（式中、ΔＢは該成形体のＸ線回折測定によるピーク散乱角を固定して、方位角方向の０〜３６０°までの強度分布における半値幅を表す）
請求項４に記載の発明は、ポリベンズアゾールと、少なくとも１種類の物性調整材とを含む、ポリベンズアゾール複合体であって、前記ポリベンズアゾールは、上記一般式（１）〜（４）で示される繰り返し単位のうちの少なくともいずれかを有し、上記式中、Ｘはイオウ原子、酸素原子又はイミノ基を表し、Ａｒ _１ 及びＡｒ _２ は芳香族炭化水素基を表し、ｎは１０〜５００の整数であり、前記物性調整材は、ポリイミドであり、該複合体は、前記ポリベンズアゾールと前記ポリイミドとを含む混合溶液から得られることで前記ポリベンズアゾールの分子鎖の間に前記ポリイミドが含浸されており、前記ポリイミドの分子鎖が、前記ポリベンズアゾールの分子鎖と共に一定方向に配向されたポリベンズアゾール複合基体にエポキシ樹脂が含浸されており、上記式（ｉ）によって求められる前記ポリベンズアゾールおよび前記ポリイミドおよび前記エポキシ樹脂の分子鎖の配向度Ａが０．６以上１．０未満の範囲であることを要旨とする。
請求項５に記載の発明は、請求項４に記載のポリベンズアゾール複合体において、前記ポリベンズアゾール複合基体がフィルム状であることを要旨とする。

In the above formula, X represents a sulfur atom, an oxygen atom or an imino group, Ar ₁ and Ar ₂ each represent an aromatic hydrocarbon group, n is an integer of 10 to 500,
The degree of orientation A of the molecular chain of the polybenzazole and the first physical property modifier determined by the following formula (i) is in the range of 0.6 or more and less than 1.0,
Orientation degree A = (180−ΔB) / 180 (i)
(In the formula, ΔB represents the half-value width in the intensity distribution from 0 to 360 ° in the azimuth direction with the peak scattering angle measured by X-ray diffraction measurement of the molded body fixed)
The first and second property adjusting materials are:
Polyolefin compounds, polyester compounds, polyacrylic compounds, polymethacrylic compounds, polyvinyl compounds, polystyrene compounds, polyurethane compounds, polyetheramide compounds, polyesteramide compounds, aromatic polymers, fluoroalkyl polymers , Liquid crystalline polymer, bisphenol A type epoxy resin, phenol novolac type epoxy resin, cresol novolac type epoxy resin, glycidylamine type epoxy resin, naphthalene type epoxy resin, triphenolalkane type epoxy resin, biphenyl type epoxy resin, and It is chosen from liquid crystalline epoxy resins,
The method is
A step of said polybenzazole and saw including a first physical property adjusting material to prepare a mixed solution capable of expressing a lyotropic liquid crystal of said polybenzazole,
Applying a magnetic field or electric field in a certain direction to the mixed solution in which the lyotropic liquid crystal properties are expressed, thereby orienting molecular chains of the polybenzazole and the first physical property adjusting material in the mixed solution in a certain direction;
Maintaining the orientation state of the molecular chains of the polybenzazole and the first physical property modifier, solidifying the mixed solution to form a composite substrate of the polybenzazole and the first physical property modifier,
Impregnating a second physical property adjusting material between the molecular chains of the composite substrate;
And a step of curing the composite substrate impregnated with the second physical property adjusting material.
The invention according to claim 3 is a polybenzazole complex including polybenzazole and at least one physical property modifier, wherein the polybenzazole has the following general formulas (1) to (4). Having at least one of the repeating units represented by

In the above formulas, X represents a sulfur atom, an oxygen atom or an imino group, Ar ₁ and Ar ₂ represents an aromatic hydrocarbon group, n is an integer of 10 to 500,
The physical property adjusting material is a polyimide, the complex, the polyimide during the molecular chains of the polybenzazole by obtained from a mixed solution containing said said polybenzazole polyimide is impregnated, The molecular chain of the polyimide is oriented in a certain direction together with the molecular chain of the polybenzazole , and the degree of orientation A of the molecular chain of the polybenzazole and the polyimide determined by the following formula (i) is 0.6 or more The gist is that it is less than 1.0.
Orientation degree A = (180−ΔB) / 180 (i)
(In the formula, ΔB represents the half-value width in the intensity distribution from 0 to 360 ° in the azimuth direction with the peak scattering angle measured by X-ray diffraction measurement of the molded body fixed )
The invention according to claim 4 is a polybenzazole complex including polybenzazole and at least one physical property modifier, wherein the polybenzazole is represented by the general formulas (1) to (4). In the above formula, X represents a sulfur atom, an oxygen atom or an imino group, Ar ₁ and Ar ₂ represent an aromatic hydrocarbon group, and n represents 10 to 10 The physical property adjusting material is polyimide, and the composite is obtained from a mixed solution containing the polybenzazole and the polyimide, whereby the polyimide is interposed between the molecular chains of the polybenzazole. The polybenzazole composite substrate in which the molecular chain of the polyimide is oriented in a certain direction together with the molecular chain of the polybenzazole is impregnated with an epoxy resin. It is, and summarized in that the orientation degree A of molecular chains of said polybenzazole and the polyimide and the epoxy resin obtained by the above formula (i) is in a range of 0.6 or more and less than 1.0.
The gist of the invention described in claim 5 is that, in the polybenzazole complex according to claim 4 , the polybenzazole composite substrate is in the form of a film.

Since this invention is comprised as mentioned above, there exist the following effects .

According to the method for producing a polybenzazole complex according to claim 1 , it is possible to easily produce a polybenzazole complex in which the molecular chains of the polybenzazole and the physical property modifier are oriented in a certain direction. Further, since the molecular chains of polybenzazole are aligned by a magnetic field or an electric field, the alignment direction can be freely controlled.

According to the method for producing a polybenzazole complex according to claim 2, the polybenzazole and the first physical property adjusting material are aligned in a certain direction, and the second physical property adjusting material is further combined. A benzazole complex can be easily produced. Further, since the molecular chains of polybenzazole are aligned by a magnetic field or an electric field, the alignment direction can be freely controlled.
According to the polybenzazole complex of claim 3, by aligning both the polybenzazole and the physical property modifier in a certain direction, a more excellent anisotropic function can be exhibited in the orientation direction. it can. Furthermore, by conjugating the polyimide rigid polybenzazole can improve the flexibility and mechanical strength of the composite.
According to the polybenzazole complex according to claims 4 and 5, in addition to the effect of claim 3, by combining epoxy resin, to improve the flexibility and mechanical strength of the composite Can do.

Hereinafter, embodiments of the polybenzazole complex of the present invention will be described.
FIG. 1 shows an embodiment in which the polybenzazole composite of the present invention is embodied as a polybenzazole composite film 1. The polybenzazole composite film 1 is a polybenzazole compounded with a physical property adjusting material, and the physical property adjusting material imparts characteristics such as flexibility (flexibility) and folding resistance to the film. .

  In the polybenzazole composite film 1 of the first embodiment, the molecular chains of polybenzazole are highly oriented along a certain direction, for example, the X-axis direction, the Y-axis direction, or the Z-axis direction in FIG. A benzazole substrate is formed. The polybenzazole base and the polybenzazole molecular chain are impregnated with the physical property adjusting material, so that the polybenzazole and the physical property adjusting material are combined. The degree of orientation A of the polybenzazole molecular chain is in the range of 0.6 or more and less than 1.0.

  In the polybenzazole composite film 1 of the second embodiment, the molecular chain of the physical property adjusting material is in a certain direction together with the molecular chain of the polybenzazole, for example, the X-axis direction, the Y-axis direction, or the Z-axis direction in FIG. By being highly oriented, polybenzazole and a physical property adjusting material are combined. The degree of orientation of the molecular chain of the physical property modifier and the mixed molecular chain of polybenzazole is in the range of 0.6 or more and less than 1.0.

  In the polybenzazole composite film 1 according to the third embodiment, the molecular chain of the polybenzazole and the first physical property adjusting material are in a certain direction along with the molecular chain of the polybenzazole, for example, FIG. The polybenzazole composite substrate is formed by being highly oriented in the X-axis direction, Y-axis direction, or Z-axis direction. This polybenzazole composite substrate, that is, a polybenzazole and a physical property modifier are combined by further impregnating a second physical property modifier between the molecular chains of the oriented polybenzazole and the physical property modifier. Has been. The degree of orientation of the mixed molecular chain of the first physical property adjusting material and polybenzazole is in the range of 0.6 or more and less than 1.0. The first physical property adjusting material and the second physical property adjusting material may be the same material or different materials.

  In the polybenzazole composite film 1 of the first to third embodiments, a molecular chain of polybenzazole or a mixed molecular chain of polybenzazole and a physical property modifier (hereinafter referred to as “mixed molecular chain containing polybenzazole”). ) Are oriented in a certain direction. Thereby, it has an anisotropic function with enhanced properties such as optical properties, magnetic properties, mechanical properties, thermal properties, physical properties and electrical properties in that direction. Furthermore, the physical property of the polybenzazole composite film 1 is improved by adding a physical property adjusting material to the polybenzazole having a rigid structure. For example, the polybenzazole composite film 1 has moderate flexibility and excellent folding strength. In the second embodiment, since the physical property adjusting material is oriented in a certain direction together with polybenzazole, the physical properties of the composite material can be improved particularly in the orientation direction. In the third embodiment, since the first physical property adjusting material is oriented in a certain direction together with polybenzazole, the physical property of the composite material is improved particularly in the orientation direction. Furthermore, since the second physical property adjusting material does not have a specific orientation, it improves the physical properties of the composite material in directions other than the orientation direction. Therefore, according to the third embodiment, physical properties such as flexibility and mechanical strength can be further improved.

  In the present invention, polybenzazole refers to a polymer containing at least one selected from polybenzoxazole (PBO), polybenzothiazole (PBT), and polybenzimidazole (PBI). Examples of such polybenzazoles include homopolymers composed of any one of PBO, PBT, and PBI, mixtures of two or more selected from PBO, PBT, and PBI, block copolymers, or random copolymers, and PBO, PBT, or PBI. Among them, a copolymer containing at least one of them can be mentioned.

  PBO refers to a polymer composed of a repeating unit having at least one oxazole ring bonded to an aromatic group, and includes, for example, poly (phenylenebenzobisoxazole). PBT refers to a polymer composed of a repeating unit having at least one thiazole ring bonded to an aromatic group, and includes, for example, poly (phenylenebenzobisthiazole). PBI refers to a polymer composed of a repeating unit having at least one imidazole ring bonded to an aromatic group, and includes, for example, poly (phenylenebenzbisimidazole).

  Specifically, the polybenzazole complex of the present invention includes polybenzazole having at least one of repeating units represented by the following general formulas (1) to (4).

上記式中、Ｘはイオウ原子、酸素原子又はイミノ基を表し、Ａｒ_１及びＡｒ_２は芳香族炭化水素基をそれぞれ表し、ｎは１０〜５００の整数である。

In the above formula, X represents a sulfur atom, an oxygen atom or an imino group, Ar ₁ and Ar ₂ each represents an aromatic hydrocarbon group, and n is an integer of 10 to 500.

Specific examples of Ar ₁ include those represented by the following general formulas (I) to (IV).

Ａｒ_２の具体例としては、下記一般式（Ｖ）〜（ＶＩＩＩ）で示すものが挙げられる。

Specific examples of Ar ₂ include those represented by the following general formulas (V) to (VIII).

上記一般式（Ｉ）〜（ＶＩＩＩ）中のＺは、それぞれ酸素原子、イオウ原子、ＳＯ_２、ＣＯ、ＣＨ_２、Ｃ（ＣＨ_３）_２、ＣＦ_２又はＣ（ＣＦ_３）_２のいずれかを表すか、または、隣り合うベンゼン環中の炭素同士の直接結合を表す。また、上記一般式（Ｉ）〜（ＶＩＩＩ）中のベンゼン環において、各炭素原子と結合している水素原子は低級アルキル基、低級アルコキシル基、ハロゲン原子又はトリフルオロメチル等のハロゲン化アルキル基、ニトロ基、スルホン酸基、ホスホン酸基等に置換されていてもよい。この置換反応は、重縮合反応前に対応する上記部分を含む原材料において行なわれてもよいし、または重縮合反応後のポリベンズアゾールの対応する部分について行なわれてもよい。

Z in the general formulas (I) to (VIII) represents an oxygen atom, a sulfur atom, SO ₂ , CO, CH ₂ , C (CH ₃ ) ₂ , CF _2, or C (CF ₃ ) ₂ , respectively. Or a direct bond between carbons in adjacent benzene rings. In the benzene rings in the above general formulas (I) to (VIII), the hydrogen atom bonded to each carbon atom is a lower alkyl group, a lower alkoxyl group, a halogen atom or a halogenated alkyl group such as trifluoromethyl, It may be substituted with a nitro group, a sulfonic acid group, a phosphonic acid group, or the like. This substitution reaction may be performed on the raw material containing the corresponding part before the polycondensation reaction, or may be performed on the corresponding part of the polybenzazole after the polycondensation reaction.

The polybenzazole complex of the present invention is most preferably a polybenzazole having at least one repeating unit of the above general formulas (1) and (2), wherein X is an oxygen atom , Ar ₁ and Ar ₂ are formed from polybenzazoles in which in formulas (I) to (VIII), Z represents an oxygen atom or a direct bond. By having such a structure, the polybenzazole molecular chain becomes more linear, and a higher degree of anisotropic function is expressed by being oriented in a certain direction.

  In addition to the repeating units represented by the above general formulas (1) to (4), the polybenzazole of the present invention is an unreacted product represented by the following formulas (IX) and (X) generated in the production process. It may contain a repeating unit having a ring-opening moiety.

上記一般式（１）〜（４）で示される繰り返し単位を有するポリベンズアゾールは、溶媒に溶解すると所定の濃度範囲において光学異方性を示し、特に限られた濃度範囲においてはリオトロピック液晶性を示す。このようにポリベンズアゾールが光学異方性を示す状態、すなわちポリベンズアゾール分子鎖が一定の規則性を有している状態において、磁場または電場の印加などの手段により、ポリベンズアゾールの分子鎖をさらに所望の一定方向に配向させることによって、ポリベンズアゾールの分子鎖がより高度に配向した複合体を得ることができる。このように、本発明のポリベンズアゾール複合体は、ポリベンズアゾールの分子鎖が一定方向に配向されることにより、異方性機能を発現するように構成されている。

The polybenzazole having the repeating units represented by the general formulas (1) to (4) exhibits optical anisotropy in a predetermined concentration range when dissolved in a solvent, and exhibits lyotropic liquid crystallinity particularly in a limited concentration range. Show. Thus, in the state where polybenzazole exhibits optical anisotropy, that is, in the state where the polybenzazole molecular chain has a certain regularity, the molecular chain of polybenzazole is applied by means such as application of a magnetic field or an electric field. Is further oriented in a desired constant direction to obtain a complex in which the molecular chains of polybenzazole are more highly oriented. Thus, the polybenzazole complex of the present invention is configured to exhibit an anisotropic function by aligning the molecular chain of polybenzazole in a certain direction.

  In the second and third embodiments, the molecular chains of the physical property adjusting material are oriented together with the polybenzazole. In this case, it is preferable that a mixed solution obtained by dissolving polybenzazole and a physical property modifier in a solvent exhibits optical anisotropy in a predetermined concentration range, and particularly exhibits lyotropic liquid crystallinity in a limited concentration range.

  The orientation of the molecular chain containing polybenzazole is such that when the polybenzazole complex has a predetermined light transmittance, optical anisotropy (phase difference, birefringence using two polarizers or a polarizing microscope) is used. ) Measurement or a polarized infrared absorption spectrum analysis method. Further, it can be confirmed by a polarized Raman spectrum method, a method by X-ray diffraction analysis, a method by electron beam diffraction analysis, a method of observation by an electron microscope, and the like.

In the polybenzazole complex of the present invention, the characteristic that anisotropy is manifested is at least one selected from optical properties, magnetic properties, mechanical properties, thermal properties, physical properties, and electrical properties. Useful. More specifically, characteristics such as thermal conductivity, linear expansion coefficient, dielectric constant, light permeability, gas permeability, liquid permeability, electrical conductivity, and ionic conductivity can be mentioned. For example, a polybenzazole molecular chain oriented in a certain direction in a polybenzazole complex or a mixed molecular chain containing polybenzazole acts as a π-electron conjugated molecule, and the π-electron conjugated system extends in a certain orientation direction. Thus, the composite can exhibit an anisotropic function in magnetic properties. In general, heat conduction in an insulator such as a polymer material is caused by phonon scattering, and it is considered that this phonon is likely to be scattered along the longitudinal direction of the molecular chain. Therefore, when the polybenzazole molecular chain or the mixed molecular chain containing polybenzazole is oriented in a certain direction in the composite, the thermal conductivity λ in that direction is improved, and excellent thermal conductivity is exhibited. It becomes possible.

  In the first to third embodiments, the polybenzazole molecular chain obtained by the following formula (i) in which the polybenzazole molecular chain or the mixed molecular chain containing polybenzazole is oriented in a certain direction in the complex. Or the orientation degree A of the mixed molecular chain containing polybenzazole is in the range of 0.6 or more and less than 1.0.

Orientation degree A = (180−ΔB) / 180 (i)
The degree of orientation A of the polybenzazole molecular chain or the mixed molecular chain containing polybenzazole can be obtained by performing wide-angle X-ray diffraction measurement (transmission) of the polybenzazole complex.

  In order to obtain the orientation degree A, wide angle X-ray diffraction measurement is performed on the polybenzazole complex. In an X-ray diffractometer, when a sample is irradiated with X-rays, a concentric arc-shaped diffraction pattern (Debye ring) is obtained when the particles (molecular chains) contained in the sample are oriented. First, a diffraction pattern showing an X-ray diffraction intensity distribution in the radial direction from the center of the Debye ring is obtained for the composite sample (see FIG. 2). In this diffraction pattern, the horizontal axis represents the X-ray diffraction angle 2θ, and the peak confirmed at a specific position on the horizontal axis is considered to represent the distance between molecular chains. By fixing the angle (peak scattering angle) at which this diffraction peak was obtained and measuring the X-ray diffraction intensity distribution from 0 ° to 360 ° in the azimuth angle direction (circumferential direction of the Debye ring), FIG. An X-ray diffraction intensity distribution in the azimuth direction as shown is obtained. The steeper peak in the intensity distribution indicates that polybenzazole or a mixed molecular chain containing polybenzazole is highly oriented in a certain direction. Therefore, in the intensity distribution in the azimuth angle direction, a width at half the peak height (half-value width ΔB) is obtained, and this half-value width ΔB is substituted into the above formula (i), whereby the polybenzazole molecular chain or The degree of orientation A between the mixed molecular chains containing polybenzazole can be calculated. For example, in the case of the intensity distribution in the azimuth direction shown in FIG. 3, the degree of orientation A is 0.8.

  The orientation degree A in the polybenzazole complex of the present invention is preferably in the range of 0.6 or more and less than 1.0, more preferably 0.65 or more and less than 1.0, and most preferably 0.7 or more and less than 1.0. It is in. When the degree of orientation A is less than 0.6, the polybenzazole molecular chain or the mixed molecular chain containing polybenzazole is not sufficiently oriented in the complex. Therefore, for example, when the expected anisotropic characteristic is thermal conductivity, the thermal conductivity λ in a specific direction of the composite is low, and sufficient thermal conductivity cannot be obtained. On the other hand, an orientation degree A of 1.0 or more cannot be taken from the above formula (i) because the full width at half maximum ΔB always shows a positive value. When the range of the orientation degree A is 0.6 or more and less than 1.0, the polybenzazole molecular chain or the mixed molecular chain containing polybenzazole is sufficiently oriented in the polybenzazole complex, and the complex Can exhibit an excellent anisotropic function, for example, excellent thermal conductivity, in the orientation direction of a polybenzazole molecular chain or a mixed molecular chain containing polybenzazole.

  The polybenzazole composite of the present invention includes a semiconductor insulating film, a wiring board material, a sealant, a display alignment film, a polarizing film film base, a magnetic recording film base, a capacitor film, a solar cell, and a planar shape. Use in applications that require anisotropy in heating elements, electromagnetic wave prevention films, sensors, actuators, battery materials, mounting materials, gas barrier materials, laminated films, filters, separation membranes, ion exchange membranes, etc. Can do.

Polybenzazole composite film 1 formed by forming a polybenzazole composite into a film shape
In this case, the thickness of the film 1 is preferably 1 μm or more and 2 mm or less. If the thickness of the film 1 is less than 1 μm, defects such as breakage tend to occur in the composite. On the other hand, when the thickness of the film 1 exceeds 2 mm, it becomes difficult to form the film 1 and the manufacturing cost tends to increase.

  In general, there are two methods for synthesizing polybenzazole, an indirect polycondensation method and a direct polycondensation method. In the indirect polycondensation method, the polybenzazole precursor is heat-treated through a polybenzazole precursor to close the nitrogen-containing ring-forming portion of the precursor to obtain the target polybenzazole. In the direct polycondensation method, the target polybenzazole is obtained by ring-closing the nitrogen-containing ring-forming part by directly reacting the raw materials without going through the polybenzazole precursor. The polybenzazole used in the present invention is preferably synthesized by a direct polycondensation method. In a polybenzazole obtained by heat-treating a polybenzazole precursor by the indirect polycondensation method, rearrangement of the polybenzazole molecules occurs during heating, which becomes a factor that hinders molecular chain orientation.

  The polybenzazole used in the present invention includes a dicarboxylic acid represented by the following general formula (5) or an amide-forming derivative thereof (hereinafter referred to as “acid component”), the following general formula (6) or (7 ) Or an aminobenzene acid derivative represented by the following general formula (8) or (9).

上記式中、Ｘはイオウ原子、酸素原子又はイミノ基を表す。Ａｒ_１及びＡｒ_２は芳香族炭化水素基をそれぞれ表す。

In the above formula, X represents a sulfur atom, an oxygen atom or an imino group. Ar ₁ and Ar ₂ each represent an aromatic hydrocarbon group.

Specific examples of Ar _{2 in} the general formula (5) include those represented by the following general formulas (V) to (VIII) as in the definitions in the formulas (1) to (4).

また、上記一般式（６）又は（７）中のＡｒ_１の具体例としては、式（１）〜（４）における定義と同様に、下記一般式（Ｉ）〜（ＩＶ）で示すものが挙げられる。

In addition, specific examples of Ar _{1 in} the general formula (6) or (7) include those represented by the following general formulas (I) to (IV) as in the definitions in the formulas (1) to (4). Can be mentioned.

上記一般式（Ｉ）〜（ＩＶ）中のＺは、それぞれ酸素原子、イオウ原子、ＳＯ_２、ＣＯ、ＣＨ_２、Ｃ（ＣＨ_３）_２、ＣＦ_２又はＣ（ＣＦ_３）_２のいずれかを表すか、または、隣り合うベンゼン環中の炭素同士の直接結合を表す。また、上記一般式（Ｉ）〜（ＩＶ）中のベンゼン環において、各炭素原子と結合している水素原子を低級アルキル基、低級アルコキシル基、ハロゲン原子又はトリフルオロメチル等のハロゲン化アルキル基、ニトロ基、スルホン酸基、ホスホン酸基等に置換してもよい。

Z in the general formulas (I) to (IV) represents oxygen atom, sulfur atom, SO ₂ , CO, CH ₂ , C (CH ₃ ) ₂ , CF ₂ or C (CF ₃ ) ₂ , respectively. Or a direct bond between carbons in adjacent benzene rings. In the benzene rings in the general formulas (I) to (IV), a hydrogen atom bonded to each carbon atom is a lower alkyl group, a lower alkoxyl group, a halogen atom or a halogenated alkyl group such as trifluoromethyl, A nitro group, a sulfonic acid group, a phosphonic acid group, or the like may be substituted.

Specific examples of the dicarboxylic acid represented by the general formula (5) include phthalic acid, isophthalic acid, terephthalic acid, 3,3'-dicarboxydiphenyl ether, 3,4'-dicarboxydiphenyl ether, 4,4'-di Carboxydiphenyl ether, 3,3′-dicarboxydiphenylmethane, 3,4′-dicarboxydiphenylmethane, 4,4′-dicarboxydiphenylmethane, 3,3′-dicarboxydiphenyldifluoromethane, 3,4′-dicarboxydiphenyldifluoro Methane, 4,4′-dicarboxydiphenyldifluoromethane, 3,3′-dicarboxydiphenylsulfone, 3,4′-dicarboxydiphenylsulfone, 4,4′-dicarboxydiphenylsulfone, 3,3′-dicarboxy Diphenyl sulfide, 3,4'-dicarboxydi Phenyl sulfide, 4,4′-dicarboxydiphenyl sulfide, 3,3′-dicarboxydiphenyl ketone, 3,4′-dicarboxydiphenyl ketone, 4,4′-dicarboxydiphenyl ketone, 2,2-bis (3 -Carboxylphenyl) propane, 2,2- (3,4'-dicarboxyldiphenyl) propane, 2,2-bis (4-carboxylphenyl) propane, 2,2-bis (3-carboxylphenyl) hexafluoropropane, 2,2- (3,4'-dicarboxyldiphenyl) hexafluoropropane, 2,2-bis (4-carboxyldiphenyl) hexafluoropropane, 1,3-bis (3-carboxylphenoxy) benzene, 1,4- Bis (3-carboxylphenoxy) benzene, 1,4-bis (4-carboxylphenyl) Enoxy) benzene, 3,3 ′-[1,4-phenylenebis (1-methylethylidene)] bisbenzoic acid, 3,4 ′-[1,4-phenylenebis (1-methylethylidene)] bisbenzoic acid, 4,4 ′-[1,4-phenylenebis (1-methylethylidene)] bisbenzoic acid, bis [4- (3-carboxylphenoxy) phenyl] sulfide, bis [4- (4-carboxylphenoxy) phenyl] sulfide Bis [4- (3-carboxylphenoxy) phenyl] sulfone, bis [4- (4-carboxylphenoxy) phenyl] sulfone, 2,5-dicarboxybenzenesulfonic acid, 3,5-dicarboxybenzenesulfonic acid Sulfonic acid-containing dicarboxylic acids such as 4,6-dicarboxy-1,3-disulfonic acid, and derivatives thereof; 5-dicarboxylate benzene phosphonic acid, 3,5-dicarboxybenzenesulfonic acid, 2,5-bis phosphono terephthalic acid, aromatic dicarboxylic acids such as phosphonic acid-containing dicarboxylic acids and derivatives thereof, such as. The carboxylate (COO ⁻ ) group of the dicarboxylic acid may form a salt with an alkali metal such as sodium or potassium, an alkaline earth metal such as magnesium or calcium, ammonia or an amine. These ionic group-containing dicarboxylic acids may be used alone or in combination of two or more.

  Specific examples of the amide-forming derivative of the dicarboxylic acid represented by the general formula (5) include acid halides such as dichloride and dibromide of the dicarboxylic acid represented by the general formula (5), dimethyl ester, diethyl ester, etc. And dialkyl esters. These acid components may be used alone or in combination of two or more. The acid component may also be configured as the dihalide.

  Specific examples of the amino basic component represented by the general formula (6) or (7) include 3,4-diamino-1,5-benzenediol, 3,3′-dihydroxy-4,4-diaminobiphenyl, 3,3′-diamino-4,4′-dihydroxybiphenyl, 2,2′-bis (3-amino-4-hydroxyphenyl) ketone, 2,2′-bis (3-amino-4-hydroxyphenyl) sulfide 2,2′-bis (3-amino-4-hydroxyphenyl) ether, 2,2′-bis (3-hydroxy-4-aminophenyl) sulfone, 2,2-bis (3-amino-4-hydroxy) Phenyl) propane, 2,2-bis (3-hydroxy-4-aminophenyl) propane, 2,2-bis (3-hydroxy-4-aminophenyl) methane, 2,2-bis (3-a No-4-hydroxyphenyl) hexafluoropropane, 2,2-bis (3-hydroxy-4-aminophenyl) hexafluoropropane, 2,2-bis (3-amino-4-hydroxyphenyl) difluoropropane and the like. It is done. These amino basic components may be used alone or in combination of two or more.

  In order to synthesize the polybenzazole used in the present invention, first, the above acid component and amino basic component are respectively dissolved in an anhydrous acid having no oxidizing action as a reaction solvent under an inert atmosphere. Prepare the solution. Next, the reaction solution is heated stepwise from 70 ° C. to 200 ° C. with vigorous stirring or shearing, and reacted to obtain polybenzazole. At this time, the reaction between the acid component and the amino basic component is preferably performed in equimolar or almost equimolar amounts, and the order of addition of the components is not limited. When dihalide is used as the acid component, the reaction is preferably performed in the presence of a hydrogen halide trapping agent. Specific examples of the hydrogen halide trapping agent include tertiary amines such as pyridine, triethylamine and dimethylaniline.

  Specific examples of the reaction solvent include polyphosphoric acid, methanesulfonic acid, cresol, and high-concentration sulfuric acid. As the reaction solvent, these substances may be used alone, or two or more kinds may be mixed and used. Among these substances, as the reaction solvent, polyphosphoric acid, methanesulfonic acid, and a mixture thereof are particularly preferable, and polyphosphoric acid is most preferable.

  In the present invention, the physical property adjusting material is a substance that can adjust the physical properties of the resulting polybenzazole complex, for example, mechanical strength, flexibility and flexibility, by combining with the polybenzazole. Point to.

  Such physical property modifiers include thermoplastic or thermo / photo curable polymers, or ultimately thermo / photoreactive monomers that form polymers. More specifically, polyolefin compounds, polyester compounds, polyacryl compounds, polymethacryl compounds, polyvinyl compounds, polystyrene compounds, polyurethane compounds, polyether amide compounds, polyester amide compounds, polysulfones, poly Ether sulfone, polyether ether sulfone, polyaryl sulfone, polyaryl ether sulfone, polyphenyl sulfone, polyphenylene sulfone, polyamide, polyimide, polyetherimide, polyphenylene oxide, polyphenylene sulfoxide, polyphenylene sulfide, polyphenylene sulfide sulfone, polyparaphenylene, poly Phenylquinoxaline, polyaryl ketone, polyether ketone, polyether ether ketone, poly -Aromatic polymers such as terketone ketone, polyether ether ketone ketone, polyether ketone ether ketone ketone, polyvinylidene fluoride, polytetrafluoroethylene, vinylidene fluoride-trifluoroethylene copolymer, vinylidene fluoride-hexafluoro Fluoroalkyl polymer typified by propylene copolymer, polytetrafluoroethylene-ethylene copolymer, and liquid crystal having biphenylene group, biphenyl group, etc. having rigidity in polymer main chain and / or polymer side chain Polymer, bisphenol A type epoxy resin, phenol novolak type epoxy resin, cresol novolac type epoxy resin, glycidylamine type epoxy resin, naphthalene type epoxy resin, triphenolalkane type epoxy resin, bife Le epoxy resins, such as liquid crystalline epoxy resin. These physical property adjusting materials may be used alone or in combination of several kinds.

  When the obtained polybenzazole composite material is used for applications exposed to high temperatures such as when applied to members that generate high temperatures such as electronic device parts, the physical property adjusting material has a heat resistance of at least 100 ° C or higher. It is preferable to have.

  The polybenzazole content in the polybenzazole complex is preferably 50% by weight or more and less than 100% by weight, more preferably 70% by weight or more and less than 100% by weight, based on the entire polybenzazole complex. When the polybenzazole content is less than 50% by weight of the entire polybenzazole complex, the polybenzazole concentration is lowered, and the properties attributable to the polybenzazole such as thermal conductivity are sufficiently obtained. There is no tendency.

Next, a method for producing a polybenzazole complex will be described.
The method for producing the polybenzazole composite film 1 according to the first embodiment includes a step of preparing a polybenzazole solution, and applying a magnetic field or an electric field to the polybenzazole solution, thereby fixing the polybenzazole molecular chain. A step of orienting in a direction, a step of solidifying the polybenzazole solution while maintaining the orientation state of the polybenzazole molecular chain, and forming a polybenzazole substrate; and a physical property adjusting material on the polybenzazole substrate. An impregnation step and a step of curing the polybenzazole substrate impregnated with the physical property adjusting material. By these steps, the polybenzazole composite film 1 in which the physical property adjusting material is filled between the polybenzazole molecular chains oriented in a certain direction is obtained.

  The method for producing the polybenzazole composite film 1 of the second embodiment includes a step of preparing a mixed solution containing a polybenzazole and a physical property adjusting material, and applying a magnetic field or an electric field to the mixed solution, thereby producing a polybenzazole. And a step of orienting the molecular chains of the physical property adjusting material in a certain direction, and solidifying the mixed solution while maintaining the alignment state of the molecular chains of the polybenzazole and the physical property adjusting material, so that the polybenzazole and the physical property adjusting material Forming a composite substrate and a step of curing the composite substrate. By these steps, the polybenzazole composite film 1 in which the polybenzazole and the physical property adjusting material are combined in a certain direction is obtained.

  The method for producing the polybenzazole composite film 1 according to the third embodiment includes a step of preparing a mixed solution containing polybenzazole and the first physical property adjusting material, and applying a magnetic field or an electric field to the mixed solution. A step of orienting the molecular chains of the polybenzazole and the first physical property adjusting material in a certain direction, and solidifying the mixed solution while maintaining the alignment state of the molecular chains of the polybenzazole and the first physical property adjusting material A step of forming a composite substrate of polybenzazole and the first physical property modifier, a step of impregnating the composite substrate with a second physical property modifier, and a composite impregnated with the second physical property modifier Curing the substrate. By these steps, the polybenzazole compound in which the molecular chains of the polybenzazole and the first physical property modifier are oriented in a certain direction and the second physical property modifier is filled between the molecular chains. Film 1 is obtained.

  In the method for producing the polybenzazole film of the first to third embodiments, the polybenzazole solution and the mixed solution containing the polybenzazole and the physical property modifier have at least partially liquid crystal properties. It is preferable that the liquid crystallinity is expressed. Thereby, the polybenzazole molecular chain, or in addition to that, the molecular chain of the physical property modifier can be more highly oriented.

  As a method of mixing the polybenzazole and the physical property adjusting material, both of them can be dissolved and mixed in an appropriate solvent, melt-kneaded, pulverized and mixed, etc., but are not limited thereto. It is not a thing. Among these mixing methods, a method in which polybenzazole and a physical property modifier are dissolved in a solvent is preferable, and a solution in which both polybenzazole and a physical property modifier are dissolved may be mixed, or both may be mixed at once. May be mixed and dissolved.

As a solvent for preparing a polybenzazole solution, and a mixed solution of a polybenzazole and a physical property modifier adjusting material (hereinafter, the solution and the mixed solution are collectively referred to as a “polybenzazole-containing solution”), N, Examples include aprotic polar solvents such as N-dimethylacetamide, N, N-dimethylformamide, dimethyl sulfoxide, N-methylpyrrolidone, hexamethylphosphortriamide, polyphosphoric acid, methanesulfonic acid, cresol, and high-concentration sulfuric acid. These solvents may be used alone or in combination of two or more. Of these substances, polyphosphoric acid, methanesulfonic acid, and a mixture thereof are particularly preferable, and polyphosphoric acid is most preferable. Furthermore, a Lewis acid such as lithium bromide, lithium chloride, or aluminum chloride may be added to the solvent as a means for improving the solubility of both. If necessary, the polybenzazole may be purified by a conventional method such as reprecipitation before preparing the polybenzazole-containing solution.

  The polybenzazole concentration in the polybenzazole-containing solution is preferably sufficiently high so that the polybenzazole exhibits liquid crystallinity in the polybenzazole-containing solution. In order to easily orient a polybenzazole molecular chain or a mixed molecular chain containing polybenzazole, the polybenzazole concentration in the polybenzazole-containing solution is preferably 2 to 30% by weight, more preferably 5%. -25% by weight, more preferably 5-20% by weight.

  The maximum concentration of polybenzazole in a polybenzazole-containing solution is mainly limited by physical factors such as the solubility of the polybenzazole, and in some cases, the property modifier in the solvent, and the viscosity of the polybenzazole-containing solution. . When the concentration of polybenzazole in the polybenzazole-containing solution exceeds 30% by weight, the viscosity of the solution is too high and the molecular chains of polybenzazole or the mixed molecular chains of polybenzazole and the physical property modifier are difficult to be oriented. Further, when the polybenzazole concentration in the polybenzazole-containing solution is less than 2% by weight, the polybenzazole-containing solution cannot exhibit liquid crystallinity because the polybenzazole concentration is low. Therefore, since the effect of promoting the orientation of the polybenzazole molecular chain or the mixed molecular chain of the polybenzazole and the physical property modifier by applying a magnetic field is low, a sufficient anisotropic function cannot be obtained in the polybenzazole complex. There is.

  The intrinsic viscosity of the polybenzazole that can be used in the present invention is measured by an Ostwald viscometer using methanesulfonic acid as a solvent at 25 ° C. (according to American Society for Testing and Materials standard ASTM D2857-95), preferably 0.5 It is -30 dl / g, More preferably, it is 0.5-20 dl / g, More preferably, it is 0.5-15 dl / g. When the intrinsic viscosity of a polybenzazole is less than 0.5 dl / g, such polybenzazole generally has a low molecular weight and is difficult to mold. On the other hand, when the intrinsic viscosity of the polybenzazole exceeds 30 dl / g, when a polybenzazole-containing solution is prepared from the polybenzazole, the viscosity is too high and the polybenzazole molecular chain or the mixed molecule containing the polybenzazole is contained. The chain is difficult to be oriented.

  Polybenzazole-containing solutions include glass fibers and other reinforcing materials, various fillers, pigments, dyes, fluorescent brighteners, dispersants, stabilizers, UV absorbers, antistatic agents, antioxidants, thermal stabilizers, A small amount of a lubricant, a plasticizer or the like may be added.

  As a method for forming a polybenzazole substrate or a composite substrate from a polybenzazole-containing solution, a polybenzazole-containing solution is produced by casting a polybenzazole-containing solution onto a substrate from a die, for example, a slit die, or a casting method. There is a method for applying the solution on the substrate, but the method is not limited thereto. At this time, as shown in FIG. 5, the polybenzazole-containing solution is cast from the slit die onto the lower substrate 3, and another substrate 3 is stacked on the cast polybenzazole-containing solution. The polybenzazole solution may be sandwiched between two substrates 3. By sandwiching the polybenzazole-containing solution between the two substrates 3 in this manner, it is possible to prevent the polybenzazole-containing solution from being deteriorated by contact with air.

The substrate 3 is not particularly limited, but it is preferable to use a closed loop endless belt, an endless drum, an endless film, or the like in order to obtain a long uniform film-like polybenzoazole composite. Moreover, it is also possible to use plate-shaped objects, such as a glass plate and a resin film, as a board | substrate. The substrate may be made of metal, and stainless steel, hastelloy alloy, tantalum, etc. are particularly preferable.

  When the polybenzazole-containing solution has lyotropic liquid crystallinity, the development of liquid crystallinity depends on both the concentration and temperature conditions of the solution. Therefore, before or during the alignment step, the polybenzazole-containing solution may be heated, if necessary, in order to develop liquid crystallinity of the polybenzazole-containing solution. Specifically, the polybenzazole-containing solution cast on the support surface is heated to a temperature range where the solution exhibits liquid crystallinity. Alternatively, the polybenzazole-containing solution is heated to a temperature range in which the solution does not have liquid crystallinity, and once the polybenzazole-containing solution is transferred to a uniform non-liquid crystal state, the solution exhibits liquid crystallinity. The temperature may be gradually lowered to the temperature range. Thereby, the liquid crystal phase grown larger can be obtained. Or you may use together temperature rising and temperature falling as mentioned above sequentially. The heating is usually performed in a temperature range of 40 to 250 ° C, preferably 40 to 200 ° C, and most preferably 60 to 150 ° C. The heating means is not particularly limited, and examples thereof include a method of applying high-temperature humidified air to the intermediate, a method of irradiating ultraviolet rays from an ultraviolet lamp, and a method of dielectric heating.

  As a method for orienting the polybenzazole molecular chain or the mixed molecular chain containing polybenzazole, it is preferable to apply a magnetic field to the polybenzazole-containing solution so that the magnetic lines of force are parallel to the desired orientation direction. The magnetic flux density of the magnetic field is preferably 1 to 30 Tesla (T), more preferably 2 to 25 T, and still more preferably 3 to 20 T. When the magnetic field is less than 1 T, the orientation of the polybenzazole molecular chain or the mixed molecular chain containing polybenzazole may be insufficient. On the other hand, when the magnetic flux density exceeds 30T, the cost for improving the magnetic flux density of the magnetic field increases.

  The polybenzazole-containing solution can be coagulated by mere evaporation of the solvent, but is preferably performed by using a coagulation solution. This coagulation liquid is a substance that is compatible with the solvent of the polybenzazole-containing solution and does not dissolve the polybenzazole and the physical property modifier. By bringing this coagulation liquid into contact with the polybenzazole-containing solution, only the solvent in the polybenzazole-containing solution is dissolved in the coagulation liquid, and as a result, polybenzazole or polybenzazole and a property modifier are precipitated. To solidify. Thereby, a polybenzazole substrate or a composite substrate of polybenzazole and a physical property adjusting material is obtained. According to the method using the coagulating liquid, polybenzazole can be coagulated more easily without requiring a heating device for evaporating the solvent or a device for collecting the evaporated solvent. In addition, when a strong acid such as polyphosphoric acid is used as a solvent, such a strong acid can be diluted by using a coagulating liquid, which is preferable in terms of safety.

  Substances that can be used as the coagulation liquid include water, phosphoric acid aqueous solution, sulfuric acid aqueous solution, sodium hydroxide aqueous solution, methanol, ethanol, acetone, ethylene glycol, and the like. You may mix and use. Further, during this coagulation step, a magnetic field may be continuously applied in order to maintain the orientation of the polybenzazole molecular chain or the mixed molecular chain containing polybenzazole. It is particularly preferable to use a 10 to 70% by weight phosphoric acid aqueous solution or a lower alcohol as the coagulating liquid since the exchange of the coagulating liquid with the solvent of the polybenzazole solution is gentle and the roughness of the film surface can be suppressed.

  The temperature of the coagulation liquid is preferably −60 to 60 ° C., more preferably −30 to 30 ° C., and most preferably 0 to 10 ° C. When the temperature of the coagulation liquid exceeds 60 ° C, the surface of the molded body may be rough, or the density may be different between the front and back of the molded body. Sexuality decreases.

The polybenzazole substrate obtained by coagulation of the polybenzazole-containing solution or the composite substrate of the polybenzazole and the physical property modifier is preferably washed before curing. Cleaning is performed, for example, by running a substrate that supports the polybenzazole substrate or the composite substrate in a cleaning solution, or by spraying the cleaning solution onto the substrate or the composite substrate. Water is usually used as the cleaning liquid, but warm water may be used as necessary. First, the polybenzazole substrate or composite substrate may be neutralized and washed with an aqueous alkali solution such as sodium hydroxide or lithium hydroxide, and then washed with water or the like. The concentration of the acid component, amino basic component and inorganic salt in the polybenzazole substrate or composite substrate after washing is preferably 500 ppm or less. When the concentration of the acid component, amino basic component, and inorganic salt after washing exceeds 500 ppm, the polybenzazole substrate or the composite substrate containing polybenzazole may be deteriorated (decomposed), and finally obtained polybenz Since the properties of the azole complex may be impaired, it is not preferable.

  When the polybenzazole complex is used by directly forming a film on a substrate such as a semiconductor insulating film, a sealing agent, a display alignment film, etc., first, the physical property adjusting material was impregnated on the substrate. A polybenzazole substrate, a composite substrate of polybenzazole and the first physical property adjusting material, or a composite substrate impregnated with the second physical property adjusting material is formed. The composite substrate impregnated with the second physical property adjusting material is dried in a standing state or in a stretched state to obtain a polybenzazole composite film formed on the substrate.

  Examples of a method for impregnating a polybenzazole substrate with a first physical property adjusting material and a method for impregnating a composite substrate of a polybenzazole and a first physical property adjusting material with a second physical property adjusting material include a polybenzazole substrate and Before the composite substrate is cured, the substrate or the composite substrate may be immersed in a solution or melt of the second physical property adjusting material, but is not limited thereto. The second physical property adjusting material may be the same as or different from the first physical property adjusting material previously oriented in a certain direction together with the polybenzazole. In addition, each physical property adjusting material may be used by mixing a plurality of types among the materials listed above.

  In the impregnation step, it is preferable to prepare a solution of the physical property modifier by dissolving the physical property modifier in a solvent and impregnate the polybenzazole substrate or the composite substrate with the solution. Examples of such solvents include aprotic polar solvents such as N, N-dimethylacetamide, N, N-dimethylformamide, dimethyl sulfoxide, N-methylpyrrolidone, hexamethylphosphortriamide, polyphosphoric acid, methanesulfonic acid, cresol, and the like. Examples include high-concentration sulfuric acid. These solvents may be used alone or in combination of two or more. Among these substances, polyphosphoric acid, methanesulfonic acid, and a mixture thereof are particularly preferable, and polyphosphoric acid is most preferable. Furthermore, a Lewis acid such as lithium bromide, lithium chloride, or aluminum chloride may be added to the solvent as a means for improving the solubility of both. In this case, the maximum solute concentration of the physical property modifier in the solvent solution is mainly limited by physical factors such as the solubility of the physical property modifier in the solvent and the viscosity of the physical property modifier.

  When the polybenzazole composite is used as a base film such as a film for a flexible printed wiring board or a magnetic recording film base, the polybenzazole base or composite base formed on the base is cured. A film-like polybenzazole complex can be obtained by peeling from the substrate later. Alternatively, the solidified polybenzazole substrate or composite substrate may be peeled off from the substrate before curing and cured after peeling to obtain a film-shaped polybenzazole complex.

  The method for curing the solidified polybenzazole substrate or the composite substrate is not particularly limited, but a method using a heated gas such as air, nitrogen or argon, a method using radiant heat such as an electric heater or an infrared lamp, and a dielectric Examples thereof include drying by heating such as a heating method. In the case where polybenzazole or a mixed molecule containing polybenzazole contains a photocrosslinkable molecule, a crosslinking reaction by light irradiation may be mentioned.

  When curing a polybenzazole substrate or composite substrate, the outer edge of the polybenzazole substrate or composite substrate may be constrained to limit its shrinkage. The temperature for curing the polybenzazole substrate or the composite substrate is preferably 100 to 500 ° C, more preferably 100 to 400 ° C, and most preferably 100 to 200 ° C. When the temperature is lower than 100 ° C., the polybenzazole substrate or the composite substrate is difficult to be cured, which is not preferable.

  In the present invention, the molding step and the subsequent steps such as heating, magnetic field orientation, solidification, washing, impregnation, and curing may be performed continuously, or all or some of these steps may be performed intermittently, that is, You may go batch-wise.

Hereinafter, according to FIG.4 and FIG.5, the manufacturing method of embodiment which actualized the polybenzazole composite of this invention as the polybenzazole composite film 1 is demonstrated in detail.
As a first embodiment, a polybenzazole molecular chain or a mixed molecular chain containing polybenzazole is oriented in the thickness direction of the polybenzazole composite film 1 (Z-axis direction in FIG. 1), so that thermal conductivity in that direction is obtained. A method for producing a polybenzazole complex having anisotropy in characteristics such as the above will be described. First, a polybenzazole-containing solution containing polybenzazole or polybenzazole used for the present invention and a physical property adjusting material is prepared. The polybenzazole-containing solution is preferably in a concentration range in which the polybenzazole has a liquid crystal state. Next, the solution is cast on a lower substrate 3 from a slit die (not shown), another substrate 3 is overlaid on the cast solution, and the solution is separated into two sheets. By sandwiching between the base materials 3, the film intermediate body 2 in which the solution is formed into a film shape having a certain thickness is formed.

  Next, as shown in FIG. 4, a magnetic field is applied to the film intermediate 2 by disposing a pair of permanent magnets 4 as a magnetic field generator above and below the base material 3. The pair of permanent magnets 4 are arranged such that the N pole and the S pole face each other so that the lines of magnetic force 5 are along the thickness direction of the film intermediate body 2 formed into a film shape.

  Thereby, the polybenzazole molecular chain in the film intermediate 2 or the mixed molecular chain containing polybenzazole is oriented in the thickness direction of the film intermediate 2. At this time, a heating device (not shown) is provided on both sides of the substrate 3, and the film intermediate 2 is maintained in a temperature range in which the solution exhibits a liquid crystal state. While maintaining this orientation, the film intermediate 2 is solidified to form a polybenzazole substrate or a composite substrate of a polybenzazole and a physical property adjusting material. Thereafter, the polybenzazole substrate or composite substrate is impregnated with a physical property adjusting agent as necessary, and then cured, so that a polybenzazole molecular chain or a mixed molecular chain containing polybenzazole in the thickness direction of the film is obtained. Can be obtained, and a polybenzazole composite film 1 having an excellent anisotropic function in that direction can be obtained.

  As a second embodiment, a polybenzazole molecular chain or a mixed molecular chain containing polybenzazole is oriented in a direction along the surface of the polybenzazole composite film 1 (X-axis direction or Y-axis direction in FIG. 1), and the direction A method for producing a polybenzazole composite having anisotropy in characteristics such as thermal conductivity will be described. In this embodiment, as shown in FIG. 5, the film intermediate body 2 having the pair of permanent magnets 4 sandwiched between the base materials 3 so that the lines of magnetic force 5 coincide with the direction along the surface of the film intermediate body 2. The method is the same as that of the first aspect except that the magnetic field is applied by arranging them on the left and right. Thereby, the polybenzazole molecular chain or the mixed molecular chain containing polybenzazole is oriented in the direction along the surface of the film, and the polybenzazole composite film 1 having an excellent anisotropic function in that direction can be obtained. .

The above embodiment can be modified as follows.
In the method for producing the polybenzazole complex of the first and second aspects, the polybenzazole-containing solution is a polybenzazole melt or a mixed melt of a polybenzazole and a physical property modifier (both together, It may be prepared as a “polybenzazole-containing melt”. In that case, the temperature at which the polybenzazole-containing melt can maintain its molten state through the preparation process of the polybenzazole-containing melt, the molding process, and the orientation process of the polybenzazole molecular chain or the mixed molecular chain containing polybenzazole. Has been heated. Such a temperature range is 100 to 450 ° C, more preferably 200 to 400 ° C.

-In the manufacturing method of the polybenzazole complex of the 1st and 2nd aspect, you may arrange | position the permanent magnet 4 only to the one side of the base material 3. FIG. Further, the magnetic field lines 5 may be curved.
-In the manufacturing method of the polybenzazole complex of the 1st and 2nd aspect, you may change a permanent magnet into an electromagnet, a superconducting magnet, a coil, etc. Moreover, you may change a permanent magnet into the electric field generator provided with the electrode, the slider, etc. When configured in this manner, the polybenzazole molecular chain in the polybenzazole complex or the mixed molecular chain containing polybenzazole is oriented in the electric field direction and exhibits an excellent anisotropic function in that direction.

  -The molded body of the present invention may be a laminated film. As a method of stacking, there are known methods such as stacking in a die base, or forming one layer and forming another layer thereon.

Next, the embodiment will be described more specifically with reference examples, examples, and comparative examples.
( Reference Example 1, Examples 2 to 9)
In Reference Example 1, polybenzoxazole in which Ar ₁ and Ar ₂ are both a benzene ring and X is an oxygen atom in the formula (1) was synthesized as polybenzazole. First, in a reaction vessel equipped with a stirrer, a nitrogen introduction tube, and a dryer, 300 g of polyphosphoric acid (H ₃ PO ₄ equivalent 115%), 5 g of 4,6-diaminoresorcinol dihydrochloride (23.4 mmol), terephthalic acid dichloride 4.76 g (23.4 mmol) and a predetermined amount of benzoyl chloride were charged and stirred at 70 ° C. for 16 hours. Further, while stirring the solution, the temperature was increased stepwise in the order of 5 hours at 90 ° C, 3 hours at 130 ° C, 16 hours at 150 ° C, 3 hours at 170 ° C, 3 hours at 185 ° C, 48 hours at 200 ° C. The solution was reacted by warming and maintaining the temperature at each stage for a certain time to obtain a crude polybenzoxazole solution. Next, the crude polybenzoxazole solution was reprecipitated with methanol, acetone and water to obtain polybenzoxazole having an intrinsic viscosity of about 10 dl / g. Polyphosphoric acid was added to the obtained polybenzoxazole to prepare a polybenzoxazole solution having a final concentration of 9 wt%. Here, the polybenzoxazole solution was observed using a polarizing microscope, and it was confirmed that the polybenzoxazole solution exhibited liquid crystallinity.

  As shown in FIG. 4, the polybenzoxazole solution was apply | coated between the two base materials 3, and the film intermediate body 2 was shape | molded. Next, a pair of magnets 4 were arranged above and below the base material 3 so that the lines of magnetic force 5 were parallel to the thickness direction of the film intermediate 2. Thereby, while applying a magnetic field of 10 T to the film intermediate 2, it was heated at 120 ° C. for 20 minutes, further allowed to cool naturally to room temperature, and left still.

Thereafter, the film intermediate 2 sandwiched between the base materials 3 was taken out and immersed in a mixed solution of methanol and water. In the mixed solution, one of the substrates 3 was removed, and the film intermediate 2 was solidified to obtain a polybenzoxazole substrate. The polybenzoxazole substrate was immersed in the same mixed solution for 1 hour as it was, then immersed in water for 1 hour and further in acetone for 1 hour. Thereafter, as shown in Table 1, as a physical property adjusting material, a mixture (molar ratio) of an epoxy resin “EPICLON EXA-4850-150” manufactured by Dainippon Ink & Chemicals, Inc. and a curing agent “D-400” manufactured by Mitsui Chemical Fine Co., Ltd. = 2: 1) impregnated the mixture onto a polybenzoxazole substrate. This polybenzoxazole composite was dried at 100 ° C. for 1 hour and 150 ° C. for 2 hours to obtain a polybenzoxazole composite film 1 having an epoxy resin content of about 60% by weight and a thickness of about 100 μm. Here, the magnetic field application direction coincides with the Z-axis direction shown in FIG. 1 with respect to the polybenzoxazole composite film spreading on the substrate.

In Example 2, polybenzoxazole (PBO) having the same intrinsic viscosity of about 10 dl / g as that of Reference Example 1 as polybenzazole and polyimide “P84” manufactured by Toyobo Co., Ltd. as a physical property adjusting material has a weight ratio of 7: 3 was dissolved in polyphosphoric acid to prepare a mixed solution containing 12 wt% polybenzoxazole as the final concentration. Here, the polybenzoxazole solution was observed using a polarizing microscope, and it was confirmed that the polybenzoxazole mixed solution exhibited liquid crystallinity. The polybenzoxazole mixed solution was applied between two substrates 3 to form a film intermediate 2. Next, the magnetic field lines 5 were arranged between the pair of magnets 4 on the top and bottom of the base material 3 so as to be parallel to the thickness direction of the film intermediate 2. Thereby, while applying a magnetic field of 10 T to the film intermediate 2, it was heated at 120 ° C. for 20 minutes, further allowed to cool naturally to room temperature, and left still. Thereafter, the film intermediate 2 sandwiched between the substrates 3 was taken out and immersed in a mixed solution of methanol and water. In the mixed solution, one of the substrates 3 was removed, and the film intermediate 2 was solidified to obtain a composite substrate of polybenzoxazole and polyimide. The composite substrate was immersed in the same mixed solution for 1 hour, then immersed in water for 1 hour, and then dried at 110 ° C. for 2 hours to obtain a polybenzoxazole composite film 1 having a thickness of about 100 m.

In Example 3, the polybenzoxazole composite film 1 was obtained by the same method as Example 2 except having changed into the weight ratio of Table 1.
In Example 4 and Example 5, as a physical property adjusting material, polyimide was changed from polyimide “P84” manufactured by Toyobo to polyimide “Rika Coat SN-20” manufactured by Shin Nippon Chemical Co., Ltd., and the weight ratio shown in Table 1 was changed. Except for the above, a polybenzoxazole composite film 1 was obtained in the same manner as in Examples 2 to 4.

  In Example 6, a composite substrate of polybenzoxazole and polyimide was obtained in the same manner as in Example 2 using the same polybenzazole and polyimide (physical property adjusting material) as in Example 2 with the same composition. . The composite substrate was immersed in the mixed solution for 1 hour as it was, then immersed in water for 1 hour and further in acetone for 1 hour. Thereafter, as shown in Table 1, as a physical property adjusting material to be impregnated (second physical property adjusting material), an epoxy resin “EPICLON EXA-4850-150” manufactured by Dainippon Ink & Chemicals, Inc. and a curing agent “Mitsui Chemical Fine Co., Ltd.” The polybenzoxazole composite substrate was impregnated with the mixture by dipping in a mixture with D-400 "(molar ratio = 2: 1). This polybenzoxazole composite was dried at 100 ° C. for 1 hour and 150 ° C. for 2 hours to obtain a polybenzoxazole composite film 1 having an epoxy resin content of about 60% by weight and a thickness of about 100 μm.

  In Example 7, the physical property adjusting material to be impregnated (second physical property adjusting material) was an epoxy resin “EPICLON EXA-4850-150” manufactured by Dainippon Ink & Chemicals, Inc. and a curing agent “D-400 manufactured by Mitsui Chemical Fine Co., Ltd. The polybenzoxazole composite film 1 was obtained by the same method as in Example 6 except that the mixture was changed from a mixture with a polyimide (P84) 5 wt% dimethylacetamide solution to Toyobo (molar ratio = 2: 1).

In Example 8, as shown in FIG. 5, after applying the polybenzoxazole solution to the base material 3 to form the film intermediate 2, the surface of the film intermediate 2 is parallel to the magnetic force lines 5. A polybenzoxazole composite film 1 was obtained in the same manner as in Reference Example 1 except that the substrate 3 was disposed between the magnets 4. Here, the magnetic field application direction coincides with the X-axis direction shown in FIG. 1 with respect to the polybenzoxazole film spreading on the substrate.

In Example 9, as shown in FIG. 5, after applying the polybenzoxazole mixed solution to the base material 3 to obtain the film intermediate 2, the surface of the film intermediate 2 is parallel to the magnetic force lines 5. Thus, the polybenzoxazole composite film 1 was obtained by the same method as Example 2 except having arrange | positioned the base material 3 between the magnets 4 in this way. Here, the magnetic field application direction coincides with the X-axis direction shown in FIG. 1 with respect to the polybenzoxazole composite film spreading on the substrate.
(Comparative Examples 1-9)
In Comparative Example 1, the same 9 wt% polybenzoxazole solution as in Reference Example 1 was applied onto a substrate to form a film intermediate 2 and then heated at 120 ° C. for 20 minutes without applying a magnetic field. Cooled naturally to room temperature. Thereafter, the film intermediate 2 sandwiched between the substrates 3 is immersed in a mixed solution of methanol and water, one of the substrates 3 is removed, the film intermediate 2 is solidified, and polybenzo An oxazole substrate was obtained. The polybenzoxazole substrate was peeled from the substrate and immersed in a mixed solution of methanol and water for 1 hour, then immersed in water for 1 hour and further in acetone for 1 hour. Thereafter, as shown in Table 2, as a physical property adjusting material, a mixture (molar ratio) of an epoxy resin “EPICLON EXA-4850-150” manufactured by Dainippon Ink & Chemicals, Inc. and a curing agent “D-400” manufactured by Mitsui Chemical Fine Co., Ltd. = 2: 1) so that the polybenzoxazole substrate was impregnated with the mixture. This polybenzoxazole composite was dried at 110 ° C. for 1 hour and 150 ° C. for 2 hours to obtain a polybenzoxazole composite film having an epoxy resin content of about 65% and a thickness of about 100 μm.

  In Comparative Example 2, the same polybenzoxazole as in Example 2 and polyimide “P84” manufactured by Toyobo Co., Ltd. as a physical property adjusting material were dissolved in polyphosphoric acid so that the weight ratio was 7: 3, and the final concentration As a mixed solution containing 12 wt% polybenzoxazole. Here, the polybenzoxazole mixed solution was observed using a polarizing microscope, and it was confirmed that the polybenzoxazole mixed solution exhibited liquid crystallinity. The polybenzoxazole mixed solution was applied between two substrates 3 to form a film intermediate 2. This film intermediate 2 was heated at 120 ° C. for 20 minutes without applying a magnetic field, and then naturally cooled to room temperature. Thereafter, the film intermediate 2 sandwiched between the base materials 3 was taken out and immersed in a mixed solution of methanol and water. In the mixed solution, one of the substrates 3 was removed, and the film intermediate 2 was solidified to obtain a polybenzoxazole composite substrate. The polybenzoxazole composite substrate was immersed in the same mixed solution as it was for 1 hour, then immersed in water for 1 hour, and then dried at 110 ° C. for 2 hours to obtain a polybenzoxazole composite film 1 having a thickness of about 100 m.

In Comparative Example 3, a polybenzoxazole composite film 1 was obtained by the same method as in Comparative Example 2 except that the weight ratios were changed to those shown in Table 2.
In Comparative Example 4 and Comparative Example 5, polyimide was changed from Toyobo polyimide “P84” to Shin Nippon Rika Co., Ltd. “Rika Coat SN-20” as a physical property adjusting material, and the weight ratios shown in Table 2 were changed. Except for the above, each polybenzoxazole composite film was obtained by the same method as in Comparative Examples 2 to 4.

In Comparative Example 6, a composite substrate of polybenzoxazole and polyimide was obtained in the same manner as in Comparative Example 2 using the same polybenzazole and polyimide (material property adjusting material) as in Comparative Example 2 with the same composition. . The composite substrate was immersed in the mixed solution for 1 hour as it was, then immersed in water for 1 hour and further in acetone for 1 hour. Thereafter, as shown in Table 2, as a physical property adjusting material to be impregnated (second physical property adjusting material), an epoxy resin “EPICLON EXA-4850-150” manufactured by Dainippon Ink & Chemicals, Inc. and a curing agent “Mitsui Chemical Fine Co., Ltd.” The polybenzoxazole composite substrate was impregnated with the mixture by dipping in a mixture with D-400 "(molar ratio = 2: 1). This polybenzoxazole composite was dried at 100 ° C. for 1 hour and 150 ° C. for 2 hours to obtain a polybenzoxazole composite film 1 having an epoxy resin content of about 60% by weight and a thickness of about 80 μm.

  In Comparative Example 7, the physical property adjusting material to be impregnated (second physical property adjusting material) was an epoxy resin “EPICLON EXA-4850-150” manufactured by Dainippon Ink & Chemicals, Inc. and a curing agent “D-400 manufactured by Mitsui Chemical Fine Co., Ltd. The polybenzoxazole composite film 1 was obtained by the same method as in Comparative Example 6 except that the mixture was changed from a mixture with a polyimide (P84) 5 wt% dimethylacetamide solution to Toyobo (molar ratio = 2: 1).

In Comparative Example 8, polybenzoxazole having the same intrinsic viscosity of about 10 dl / g as in Reference Example 1, Examples 2 to 9 and Comparative Examples 1 to 7 was dissolved in polyphosphoric acid, and the final concentration was about 9 wt%. A polybenzoxazole solution was obtained. As shown in FIG. 4, this about 9 wt% polybenzoxazole solution was applied between two substrates 3 to form a film intermediate 2. Next, the magnetic field lines 5 were arranged between the pair of magnets 4 on the top and bottom of the base material 3 so as to be parallel to the thickness direction of the film intermediate 2. Thereby, while applying a 10 T magnetic field to the film intermediate 2, it was heated at 120 ° C. for 20 minutes, and further naturally cooled to room temperature. Thereafter, the film intermediate 2 sandwiched between the base materials 3 was taken out and immersed in a mixed solution of methanol and water. In the mixed solution, one of the substrates 3 was removed, and the film intermediate 2 was solidified to obtain a polybenzoxazole substrate. The polybenzoxazole substrate was immersed in the same mixed solution for 1 hour and then in water for 1 hour, and then dried at 120 ° C. for 2 hours to obtain a polybenzoxazole film having a thickness of about 100 μm. Here, the magnetic field application direction coincides with the Z-axis direction shown in FIG. 1 with respect to the polybenzoxazole film spreading on the substrate.

Comparative Example 9 shows a polyimide film (PI) having a thickness of 75 μm (trade name “Kapton”; manufactured by DuPont).
In each of the obtained films shown in Tables 1 and 2, the thickness direction (Z-axis direction) in Reference Example 1, Examples 2 to 7 and Comparative Examples 1 to 8, and the surface of film 1 in Examples 8 to 9 A thermal diffusivity α and a thermal conductivity λ are shown as characteristics that exhibit the degree of orientation A and anisotropy in the direction along the X-axis. The thermal diffusivity in the X-axis direction is α _X , and the thermal diffusivity in the Z-axis direction is α _Z. The thermal conductivity of the X-axis direction indicated by the thermal conductivity lambda _X, showing the thermal conductivity in the Z-axis direction by the thermal conductivity lambda _Z. In addition, the direction (X-axis direction) along the surface of the film 1 coincides with the application direction of the polybenzazole solution or the mixed solution on the substrate 3 when the film is formed.

  The degree of orientation A of the polybenzoxazole composite film is determined by using an X-ray diffractometer (“RINT-RAPID” manufactured by Rigaku Corporation) and the X-ray diffraction intensity in the azimuth direction of each obtained polybenzoxazole composite film. It was calculated by the formula (i) from the half-value width ΔB of the peak in the distribution. As an example, for the polybenzoxazole composite film of Example 4, FIG. 2 shows a diffraction pattern in the equator direction by X-ray diffraction measurement, and FIG. 3 shows an X-ray diffraction intensity in the azimuth direction at a diffraction peak angle 2θ = about 26 °. Show the distribution. Further, for the polybenzoxazole composite film of Comparative Example 4, FIG. 6 shows a diffraction pattern in the equator direction by X-ray diffraction measurement, and FIG. 7 shows an X-ray diffraction intensity distribution in the azimuth direction at a diffraction peak angle 2θ = about 26 °. Indicates.

The thermal diffusivity α _{Z in} the thickness direction of the film was determined by directly forming electrodes on the surface of each film by sputtering using a thermal diffusivity measuring device (“Eye Phase α” manufactured by Eye Phase Co., Ltd.) Was attached, and a sensor was brought into contact with the lower surface of each film, and a heater was brought into contact with the upper surface, followed by measurement at room temperature. Further, the thermal diffusivity α _{X in} the direction along the surface is determined by the L-shaped length by sputtering on the sample surface using a two-dimensional thermal analyzer (“Eye Phase IR” manufactured by Eye Phase Co., Ltd.) using an infrared camera. An electrode having a width of 4 mm and a width of 1 mm was directly formed, and measurement was performed from observation of heat flow in the X axis direction and the Y axis direction shown in FIG. 1 at room temperature.

The thermal conductivity λ was determined from the thermal diffusivity α of the film according to the following formula (iii).
Thermal conductivity λ = α · ρ · C _P (iii)
(However, alpha is the thermal diffusivity, [rho is the density, C _P represents the specific heat.)
In the polybenzoxazole composite film, the physical property modifier content rate impregnated in the composite was measured by first measuring the basis weight Ds [g / m ² ] of the dried polybenzoxazole composite film. Next, the polybenzoxazole substrate made of only polybenzoxazole prepared under the same conditions as the preparation of the polybenzoxazole composite film is dried without being combined, and the basis weight Dr [g / m ² ] of the polybenzoxazole substrate is obtained. Was measured. From these values, the content of the impregnated material in the polybenzoxazole composite film was determined by the following formula (iv).

Content ratio of physical property adjusting material [% by weight] = (Ds−Dr) / Dr × 100 (iv)
The flex life of each polybenzoxazole composite film was evaluated. The bending life was measured at room temperature under conditions of a bending radius of about 10 mm, a bending speed of 100 times / minute, and a stroke of 20 mm. The number of bending times was 50,000 times or more. did.

表１に示すように、参考例１、実施例２〜９においては、いずれも配向度Ａは０．６以上の値を示しており、ポリベンゾオキサゾール複合フィルム中において、ポリベンゾオキサソール分子鎖（参考例１および８）またはポリベンゾオキサソールおよび物性調整材の混合分子鎖（実施例２〜５および９）は磁場を印加した方向であるＺ軸またはＸ軸方向に高度に配向していた。また、参考例１、実施例２〜９の各ポリベンゾオキサゾール複合フィルム１は前記配向方向において、いずれも高い熱拡散率および熱伝導率を有するといった優れた異方性機能を発現した。加えて、それらポリベンゾオキサゾール複合フィルム１は、可撓性を有するため、十分な屈曲寿命を有していた。ポリベンゾオキサゾール複合フィルムは可撓性を有するとともに熱伝導性に優れているため、例えば種々の電子機器の屈曲部等において発熱を伴う回路を配する場合や、熱が蓄積し易いような狭い場所に複数の配線板を高密度で配する場合等に好適に使用することができる。

As shown in Table 1, in Reference Example 1 and Examples 2 to 9, the orientation degree A shows a value of 0.6 or more. In the polybenzoxazole composite film, the polybenzoxazole molecular chain ( Reference Examples 1 and 8) or mixed molecular chains of polybenzoxazole and physical property modifiers (Examples 2 to 5 and 9) were highly oriented in the Z-axis or X-axis direction, which is the direction in which the magnetic field was applied. . In addition, each of the polybenzoxazole composite films 1 of Reference Example 1 and Examples 2 to 9 exhibited excellent anisotropic functions such as high thermal diffusivity and thermal conductivity in the orientation direction. In addition, since these polybenzoxazole composite films 1 have flexibility, they had a sufficient bending life. The polybenzoxazole composite film has flexibility and excellent thermal conductivity. For example, when a circuit with heat generation is arranged in a bent part of various electronic devices, or in a narrow place where heat is likely to accumulate. It can be suitably used when arranging a plurality of wiring boards at a high density.

On the other hand, in Comparative Examples 1 to 7, as shown in Table 2, the degree of orientation A in the Z-axis direction showed a low value of less than 0.6. Therefore, the thermal diffusivity and thermal conductivity in the X-axis direction were generally an order of magnitude smaller than those of Reference Example 1 and Examples 2 to 7.

In Comparative Example 8, as shown in Table 2, the degree of orientation A in the Z-axis direction was as high as 0.75, but the obtained film was brittle and a sufficient bending life could not be obtained.
The polyimide film of Comparative Example 9 was excellent in the bending life, but both the thermal diffusivity and thermal conductivity in the Z-axis direction showed smaller values than in the Examples.

The technical idea that can be grasped from the above embodiment will be described below.
· In Po Li benzazole complex molded article is formed from polybenzazole having at least one of the repeating units of the general formula (1) and (2), in the general formula (1) and (2) , X is an oxygen atom, and Ar ₁ and Ar ₂ are polybenzazole complexes showing that in formulas (I) to (VIII), Z is an oxygen atom or a direct bond.

According to this polybenzazole complex, a polybenzazole molecular chain or a mixed molecular chain containing polybenzazole is more highly oriented in the molded body, thereby exhibiting an excellent anisotropic function. it can.
Po in Li benzazole complex, polybenzazole composite molded product is in the form of a film. Thereby, the polybenzazole composite which can be used in the use for which the film which has an anisotropic function is requested | required is obtained.
-In the said polybenzazole complex, the polybenzazole complex in which the mixed molecular chain containing a polybenzazole molecular chain or a polybenzazole is orientated in the direction along the surface of a film. Thereby, the polybenzazole composite which can be used in the use for which the film which has an anisotropic function is requested | required along the surface is obtained.
-A polybenzazole complex in which the polybenzazole molecular chain or a mixed molecular chain containing polybenzazole is oriented in the thickness direction of the film. Thereby, the polybenzazole composite which can be used in the use for which the film which has an anisotropic function in the thickness direction is requested | required is obtained.
-The polybenzazole composite body whose thermal conductivity (lambda) of the thickness direction is 1-50 W / (m * K) in the said polybenzazole composite body. Thereby, the film-form polybenzazole composite can exhibit the thermal conductivity excellent in the thickness direction.
In-process for producing a port re benzazole complex, in the alignment step, wherein at least a portion of the polybenzazole solution is in a liquid crystalline state.
- a process for the preparation of Po Li benzazole complex, in the alignment step, wherein at least a portion of the mixed solution is in a liquid crystalline state.

The perspective view which shows one Embodiment of the polybenzazole composite_body | complex of this invention. The graph which shows the example of the X-ray-diffraction pattern of radial direction from the center of the Debye ring of the polybenzazole complex of this invention. The graph which shows the example of the X-ray diffraction intensity distribution of the azimuth direction of the polybenzazole composite of this invention. Schematic which shows the manufacturing method of the polybenzazole complex in which the molecular chain which comprises a polybenzazole complex was orientated in the thickness direction. Schematic which shows the apparatus used for the manufacturing method of the polybenzazole complex in which the molecular chain which comprises a polybenzazole complex was orientated in the direction along a surface. The graph which shows the X-ray-diffraction pattern of radial direction from the center of the Debye ring of the polybenzazole complex of the comparative example 4. The graph which shows the X-ray-diffraction intensity distribution of the azimuth direction of the polybenzazole composite of the comparative example 4.

Explanation of symbols

  DESCRIPTION OF SYMBOLS 1 ... Polybenzazole composite film, 2 ... Film intermediate body, 3 ... Base material, 4 ... Permanent magnet, 5 ... Magnetic field line, (DELTA) B ... Half value width

Claims (5)

A method for producing a polybenzazole complex comprising polybenzazole and at least one physical property modifier, wherein the polybenzazole is a repeating unit represented by the following general formulas (1) to (4) Having at least one of

In the above formula, X represents a sulfur atom, an oxygen atom or an imino group, Ar ₁ and Ar ₂ each represent an aromatic hydrocarbon group, n is an integer of 10 to 500, and is determined by the following formula (i). The molecular chain orientation degree A of the polybenzazole and the physical property modifier is in the range of 0.6 or more and less than 1.0,
Orientation degree A = (180−ΔB) / 180 (i)
(In the formula, ΔB represents the half-value width in the intensity distribution from 0 to 360 ° in the azimuth direction with the peak scattering angle measured by X-ray diffraction measurement of the molded body fixed)
The physical property adjusting material is
Polyolefin compounds, polyester compounds, polyacrylic compounds, polymethacrylic compounds, polyvinyl compounds, polystyrene compounds, polyurethane compounds, polyether amide compounds, polyester amide compounds, aromatic polymers, fluoroalkyl polymers , Liquid crystalline polymer, bisphenol A type epoxy resin, phenol novolac type epoxy resin, cresol novolac type epoxy resin, glycidylamine type epoxy resin, naphthalene type epoxy resin, triphenolalkane type epoxy resin, biphenyl type epoxy resin, and It is chosen from liquid crystalline epoxy resins,
The method is
A step of said polybenzazole and saw including at least one physical property adjusting material to prepare a mixed solution capable of expressing a lyotropic liquid crystal of said polybenzazole,
Applying a magnetic field or an electric field in a certain direction to the mixed solution in which the lyotropic liquid crystallinity is expressed, thereby orienting molecular chains of the polybenzazole and the physical property modifier in the mixed solution in a certain direction;
A step of solidifying the mixed solution while maintaining the orientation state of the molecular chains of the polybenzazole and the physical property adjusting material to form a composite substrate in which the physical property adjusting material is impregnated between the molecular chains of the polybenzazole. When,
Curing the composite substrate. A method for producing a polybenzazole composite comprising polybenzazole and first and second physical property modifiers, wherein the polybenzazole is represented by the following general formulas (1) to (4): Having at least one of the repeating units,

In the above formula, X represents a sulfur atom, an oxygen atom or an imino group, Ar ₁ and Ar ₂ each represent an aromatic hydrocarbon group, n is an integer of 10 to 500, and is determined by the following formula (i). The degree of orientation A of the polybenzazole molecular chain and the first physical property modifier is in the range of 0.6 or more and less than 1.0,
Orientation degree A = (180−ΔB) / 180 (i)
(In the formula, ΔB represents the half-value width in the intensity distribution from 0 to 360 ° in the azimuth direction with the peak scattering angle measured by X-ray diffraction measurement of the molded body fixed)
The first and second property adjusting materials are:
Polyolefin compounds, polyester compounds, polyacrylic compounds, polymethacrylic compounds, polyvinyl compounds, polystyrene compounds, polyurethane compounds, polyetheramide compounds, polyesteramide compounds, aromatic polymers, fluoroalkyl polymers , Liquid crystalline polymer, bisphenol A type epoxy resin, phenol novolac type epoxy resin, cresol novolac type epoxy resin, glycidylamine type epoxy resin, naphthalene type epoxy resin, triphenolalkane type epoxy resin, biphenyl type epoxy resin, and It is chosen from liquid crystalline epoxy resins,
The method is
A step of said polybenzazole and saw including a first physical property adjusting material to prepare a mixed solution capable of expressing a lyotropic liquid crystal of said polybenzazole,
By applying a constant direction of the magnetic field or electric field to the mixed solution prepared by expressing the lyotropic liquid crystalline, a step of orienting the polybenzazole and molecular chains of the first physical property adjusting material of the mixed solution in a given direction,
Maintaining the orientation state of the molecular chains of the polybenzazole and the first physical property modifier, solidifying the mixed solution to form a composite substrate of the polybenzazole and the first physical property modifier,
Impregnating a second physical property adjusting material between the molecular chains of the composite substrate;
Curing the composite substrate impregnated with the second physical property adjusting material. A polybenzazole complex comprising polybenzazole and at least one physical property modifier, wherein the polybenzazole is at least one of repeating units represented by the following general formulas (1) to (4): Have either

In the above formula, X represents a sulfur atom, an oxygen atom or an imino group, Ar ₁ and Ar ₂ represent an aromatic hydrocarbon group, n is an integer of 10 to 500,
The physical property adjusting material is polyimide,
The complex, said polyimide between the molecular chains of the polybenzazole by polybenzazole to be obtained from a mixed solution containing the said polyimide is impregnated, the molecular chains of the polyimide, the Poribenzu It is oriented in a certain direction together with the molecular chain of the azole, and the orientation degree A of the molecular chain of the polybenzazole and the polyimide determined by the following formula (i) is in the range of 0.6 or more and less than 1.0. Polybenzazole complex characterized.
Orientation degree A = (180−ΔB) / 180 (i)
(In the formula, ΔB represents the half-value width in the intensity distribution from 0 to 360 ° in the azimuth direction with the peak scattering angle measured by X-ray diffraction measurement of the molded body fixed) A polybenzazole complex comprising polybenzazole and at least one physical property modifier, wherein the polybenzazole is at least one of repeating units represented by the following general formulas (1) to (4): Have either

In the above formula, X represents a sulfur atom, an oxygen atom or an imino group, Ar ₁ and Ar ₂ represent an aromatic hydrocarbon group, n is an integer of 10 to 500,
The physical property adjusting material is polyimide,
The complex, said polyimide between the molecular chains of the polybenzazole by polybenzazole to be obtained from a mixed solution containing the said polyimide is impregnated, the molecular chains of the polyimide, the Poribenzu The polybenzazole composite substrate oriented in a certain direction together with the azole molecular chain is impregnated with an epoxy resin , and the degree of orientation of the molecular chains of the polybenzazole, the polyimide and the epoxy resin determined by the following formula (i) A polybenzazole complex, wherein A is in the range of 0.6 or more and less than 1.0. The polybenzazole complex according to claim 4 , wherein the polybenzazole complex substrate is in the form of a film.

Images