JP2008101191A - Composite material using polycarbonate resin with reactive groups at the ends - Google Patents

Abstract

[PROBLEMS] To improve compatibility with other thermoplastic resins and inorganic fillers, high fluidity, solvent resistance in molded products, compatibility (no delamination or poor appearance), slidability, impact resistance To provide a composite material with improved heat resistance and toughness for a curable material.
A reduced viscosity [ηsp / c] at 20 ° C. of a 0.5 g / dl solution having a specific structure at the end, containing a repeating unit of a specific structure and containing methylene chloride as a solvent is 0.1-3. A composite material using a polycarbonate resin of 0.0 dl / g.
[Selection figure] None

Description

  The present invention relates to a composite material using a (copolymerized) polycarbonate resin having a specific structure having a reactive group at the terminal. More specifically, a reactive end group is used, and these reactive groups are reacted by an appropriate method to form a linear and / or networked (copolymerized) polycarbonate resin, which is compatible with other materials. The present invention relates to a composite material having various good physical properties such as excellent mechanical strength and heat resistance.

The bisphenol A type polycarbonate resin that is currently in wide use is an engineering plastic having excellent transparency, mechanical strength, impact resistance, and toughness. However, it has drawbacks such as high hygroscopicity, being easily affected by organic solvents and the like, and inferior in slidability. Therefore, inventions relating to blends with polyolefin resins have been proposed. In addition, from the desire to improve mechanical strength, heat resistance, hardness, dimensional stability, stress crack resistance, inventions related to composite materials added with inorganic fillers such as glass fiber, heat resistance, optical properties, solubility An invention relating to a polycarbonate resin having a molecular structure different from that of the bisphenol A type for the purpose of improvement or the like has been proposed.
For example, Patent Document 1 includes a blend of a polycarbonate resin and a polyethylene resin, and Patent Document 2 includes a blend of a polycarbonate resin and a polypropylene resin. However, since polycarbonate and polyolefin are inherently poorly compatible and good physical properties cannot be obtained, the amount of polyolefin added is limited and the improvement effect is small. In order to improve the compatibility of these two components, an attempt has been made to coexist with a compatibilizing agent. For example, a method using a modified polypropylene resin (Patent Document 3) and a method using a modified polypropylene resin and an oxazoline group-containing resin (Patent Document 4) have been proposed. Furthermore, blending polyolefin modified with an epoxy group to improve compatibility has also been proposed (Patent Document 5). Although the compatibility between polycarbonate and polyolefin is improved to some extent by these formulations, impact strength and the like are lowered, and the level of practical use has not been reached. Moreover, although the technique which adds an inorganic filler to polycarbonate resin and polyolefin resin is disclosed by patent document 6, it does not describe compatibilization.
Examples of composite materials to which inorganic fillers such as glass fibers are added for the purpose of improving mechanical strength, heat resistance, hardness, dimensional stability, stress crack resistance, etc. are disclosed in Patent Document 7 and Patent Document 8. Has been. This composite system also has a problem that the impact strength of the molded product is extremely lowered because the mutual adhesion between the polycarbonate and the inorganic filler is not sufficient.

  On the other hand, curable materials such as ultraviolet curable resins and thermosetting resins used in a wide range of fields such as the electrical / electronic industry, civil engineering / architecture, aviation / space industry, and automobile industries can be easily molded. In addition, it has balanced performance in adhesion, electrical insulation, water resistance and chemical resistance. Therefore, it is known as a useful material as a matrix material for various composite materials. However, since curable materials have the drawbacks of poor toughness and lack of tensile properties and impact resistance, development of curable materials having excellent toughness is eagerly desired. For example, a method of modifying with a plastic elastomer is proposed in Patent Document 9 and Patent Document 10, etc., and as a typical modification method, a diene elastomer having a carboxyl group at a terminal is used as a modifying material, A method for modifying the elastomer by reacting with an epoxy resin has been proposed. However, in the method of modifying an epoxy resin with an elastomer, the elongation rate is improved by the modification, but there is a problem that a decrease in tensile strength and heat resistance is inevitable.

Japanese Patent Publication No. 40-13663 Japanese Patent Publication No.40-13664 JP 59-223742 A Japanese Patent Laid-Open No. 3-269034 Japanese Examined Patent Publication No. 61-44897 JP-A-7-102165 JP-A-60-199055 JP 61-9456 A JP 58-49719 A Japanese Patent Publication No. 63-17285

  The present invention uses reactive end groups and uses polycarbonate resins that are linearized and / or reticulated (copolymerized) by reacting these reactive groups by an appropriate method, and are compatible with other materials. Another object is to provide a composite material having various good physical properties such as excellent mechanical strength and heat resistance.

As a result of earnest research to solve the above problems, the present inventors have at least one functional group selected from the group consisting of a specific structure such as a hydroxyl group, an amino group, an epoxy group, a carboxyl group, etc. at the terminal. The present inventors have found that a composite material containing a polycarbonate resin having a specific structure can meet the above object of the present invention, and completed the present invention.
That is, this invention is comprised from the following.

［式中、Ｒは、それぞれ独立に、ハロゲン原子、炭素数１〜１０の置換もしくは無置換のアルキル基、炭素数１〜１０の置換もしくは無置換のアルキルオキシ基、炭素数１〜１０のアルキルチオ基、炭素数５〜７の置換もしくは無置換のシクロアルキル基、炭素数６〜２４の置換もしくは無置換のアリール基、炭素数６〜１２の置換もしくは無置換のアリールオキシ基又は炭素数６〜１２のアリールチオ基を表す。
ｎ１は０〜６の整数を表し、ｎ１’は１〜６の整数を表し、ｎ２は１〜５の整数を表し、ｎ３は０〜４の整数を表し、ｎ２＋ｎ３は１〜５の整数を表し、ｎ４は１又は２である。
Ｒ₃、Ｒ₄、Ｒ₅及びＲ₆は、それぞれ独立に、水素原子、ハロゲン原子、炭素数１〜１０の置換もしくは無置換のアルキル基、炭素数１〜１０の置換もしくは無置換のアルキルオキシ基、炭素数１〜１０のアルキルチオ基、炭素数５〜７の置換もしくは無置換のシクロアルキル基、炭素数６〜２４の置換もしくは無置換のアリール基、炭素数６〜１２の置換もしくは無置換のアリールオキシ基、又は炭素数６〜１２のアリールチオ基を表し、Ｒ₄とＲ₅とは炭素数１〜４のメチレン鎖で互いに連結されていてもよい。
ｎ５及びｎ７は各々独立に０又は１であり、ｎ５＋ｎ７は１又は２であり、ｎ６は０又は１であり、ｎ８は０〜５の整数を表す。
またＺは、下記の置換基のいずれかを表す。

（Ｒ₁及びＲ₂は、それぞれ独立に、水素原子、炭素数１〜１０の置換もしくは無置換のアルキル基、炭素数５〜７の置換もしくは無置換のシクロアルキル基、又は炭素数６〜２４の置換もしくは無置換のアリール基を表し、同一繰り返し単位中に存在する２つの−ＣＯＯＨ基は下記式（ａ）の構造をとっていてもよい。）］

下記一般式（６）で表される繰り返し単位を含み、塩化メチレンを溶媒とする濃度０．５ｇ／ｄｌ溶液の２０℃における還元粘度［ηｓｐ／ｃ］が０．１〜３．０ｄｌ／ｇであるポリカーボネート樹脂。

（式中、Ａ₁は二価のフェノール性水酸基を有する化合物残基を示す。） (1) at least one structure selected from the group consisting of the following general formulas (1) to (5) at the end;

[Wherein, each R is independently a halogen atom, a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, a substituted or unsubstituted alkyloxy group having 1 to 10 carbon atoms, or an alkylthio group having 1 to 10 carbon atoms. Group, a substituted or unsubstituted cycloalkyl group having 5 to 7 carbon atoms, a substituted or unsubstituted aryl group having 6 to 24 carbon atoms, a substituted or unsubstituted aryloxy group having 6 to 12 carbon atoms, or 6 to 6 carbon atoms 12 arylthio groups are represented.
n1 represents an integer of 0 to 6, n1 ′ represents an integer of 1 to 6, n2 represents an integer of 1 to 5, n3 represents an integer of 0 to 4, and n2 + n3 represents an integer of 1 to 5. , N4 is 1 or 2.
R ₃ , R ₄ , R ₅ and R ₆ are each independently a hydrogen atom, a halogen atom, a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, or a substituted or unsubstituted alkyloxy group having 1 to 10 carbon atoms. Group, alkylthio group having 1 to 10 carbon atoms, substituted or unsubstituted cycloalkyl group having 5 to 7 carbon atoms, substituted or unsubstituted aryl group having 6 to 24 carbon atoms, substituted or unsubstituted group having 6 to 12 carbon atoms aryloxy group, or an arylthio group having 6 to 12 carbon atoms, R ₄ and R ₅ may be linked to each other by a methylene chain of 1 to 4 carbon atoms.
n5 and n7 are each independently 0 or 1, n5 + n7 is 1 or 2, n6 is 0 or 1, and n8 represents an integer of 0 to 5.
Z represents any of the following substituents.

(R ₁ and R ₂ are each independently a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, a substituted or unsubstituted cycloalkyl group having 5 to 7 carbon atoms, or 6 to 24 carbon atoms. And the two —COOH groups present in the same repeating unit may have the structure of the following formula (a))]

The reduced viscosity [ηsp / c] at 20 ° C. of a 0.5 g / dl solution containing methylene chloride as a solvent containing a repeating unit represented by the following general formula (6) is 0.1 to 3.0 dl / g. A polycarbonate resin.

(In the formula, A ₁ represents a compound residue having a divalent phenolic hydroxyl group.)

（Ｘ₃は、上記一般式（８）〜（１１）のいずれかの構造である。

（Ｘ₂は炭素原子又は硫黄原子である。またＸ₂が炭素原子の場合、Ｒ₁₁は各々のＸ₂に関して個々に選択され、そして互いに独立して、水素原子又は炭素数１〜６のアルキル基を表す。ｍは４〜７の整数である。Ｒ₁₂、Ｒ₁₃及びＲ₁₄は、それぞれ独立に、炭素数１〜６のアルキル基を表す。ｍ₁は０〜２の整数であり、ｍ₂、ｍ₃及びｍ₄はそれぞれ０〜３の整数である。）
Ｒ₂₂及びＲ₂₃は、それぞれ独立に、ハロゲン原子、置換もしくは無置換の炭素数１〜１２のアルキル基、置換もしくは無置換の炭素数１〜１２のアルコキシ基、置換もしくは無置換の炭素数６〜１２のアリール基、置換もしくは無置換の炭素数７〜１３のアリールアルキルもしくはアリールアルケニル基、置換もしくは無置換の炭素数１〜１２のフルオロアルキル基、又は置換もしくは無置換の炭素数６〜２４の縮合多環式炭化水素を示す。
ｍ５及びｍ６は、それぞれ独立に、０〜４の整数である。）
下記一般式（１６）で表される繰り返し単位を含み、塩化メチレンを溶媒とする濃度０．５ｇ／ｄｌ溶液の２０℃における還元粘度［ηｓｐ／ｃ］が０．１〜３．０ｄｌ／ｇである共重合ポリカーボネート樹脂。

［式中、Ｒ₂₄ 、Ｒ₂₅ は、それぞれ独立に、ハロゲン原子、置換もしくは無置換の炭素数１〜１２のアルキル基、置換もしくは無置換の炭素数１〜１２のアルコキシ基、置換もしくは無置換の炭素数６〜１２のアリール基、置換もしくは無置換の炭素数７〜１３のアリールアルキルもしくはアリールアルケニル基、置換もしくは無置換の炭素数１〜１２のフルオロアルキル基、置換もしくは無置換の炭素数６〜２４の縮合多環式炭化水素を示す。
ｕ及びｖは、それぞれ独立に、０〜４の整数である。
Ｘ₄ は、単結合、−Ｏ−、−ＣＯ−、−Ｓ−、−ＳＯ−、−ＳＯ₂ −、−ＣＲ₂₆Ｒ₂₇ −（ただし、Ｒ₂₆ 及びＲ₂₇ は、それぞれ独立に、水素原子、置換もしくは無置換の炭素数１〜２４のアルキル基、置換もしくは無置換のフェニル基及びトリフルオロメチル基から選ばれる）、置換もしくは無置換の炭素数５〜１２のシクロアルキリデン基、２，２−アダマンチル基、１，３−アダマンチル基、置換もしくは無置換の炭素数２〜１２のα，ω−アルキレン基、置換もしくは無置換の炭素数１３〜２５の９，９−フルオレニリデン基、１，８−メンタンジイル基、２，８−メンタンジイル基、置換もしくは無置換の炭素数４〜１０のピラジリデン基、置換もしくは無置換の炭素数６〜１２のアリーレン基、−Ｃ（ＣＨ₃）₂−Ｐｈ−Ｃ（ＣＨ₃）₂−、及び天然テルペン類から誘導される二価の基、から選ばれる基を示す（Ｐｈは、フェニレン基を示す）］ (2) At least one structure selected from the group consisting of the above general formulas (1) to (5) at the terminal, a repeating unit represented by the following general formula (15),

(X ₃ is the structure of any of the above general formula (8) to (11).

(X ₂ is a carbon atom or a sulfur atom. When X ₂ is a carbon atom, R ₁₁ is individually selected for each X ₂ , and independently of each other, a hydrogen atom or an alkyl having 1 to 6 carbon atoms. M represents an integer of 4 to 7. R ₁₂ , R ₁₃ and R ₁₄ each independently represents an alkyl group having 1 to 6 carbon atoms, m ₁ is an integer of 0 to 2; m ₂ , m ₃ and m ₄ are each an integer of 0 to _3. )
R ₂₂ and R ₂₃ are each independently a halogen atom, a substituted or unsubstituted alkyl group having 1 to 12 carbon atoms, a substituted or unsubstituted alkoxy group having 1 to 12 carbon atoms, a substituted or unsubstituted carbon number 6 -12 aryl group, substituted or unsubstituted arylalkyl or arylalkenyl group having 7 to 13 carbon atoms, substituted or unsubstituted fluoroalkyl group having 1 to 12 carbon atoms, or substituted or unsubstituted 6 to 24 carbon atoms Of the condensed polycyclic hydrocarbon.
m5 and m6 are each independently an integer of 0 to 4. )
The reduced viscosity [ηsp / c] at 20 ° C. of a 0.5 g / dl solution containing methylene chloride as a solvent containing a repeating unit represented by the following general formula (16) is 0.1 to 3.0 dl / g. A copolymer polycarbonate resin.

[Wherein R ₂₄ and R ₂₅ each independently represent a halogen atom, a substituted or unsubstituted alkyl group having 1 to 12 carbon atoms, a substituted or unsubstituted alkoxy group having 1 to 12 carbon atoms, substituted or unsubstituted. An aryl group having 6 to 12 carbon atoms, a substituted or unsubstituted arylalkyl or arylalkenyl group having 7 to 13 carbon atoms, a substituted or unsubstituted fluoroalkyl group having 1 to 12 carbon atoms, a substituted or unsubstituted carbon number 6-24 condensed polycyclic hydrocarbons are shown.
u and v are each independently an integer of 0 to 4.
X ₄ is a single bond, —O—, —CO—, —S—, —SO—, —SO ₂ —, —CR ₂₆ R ₂₇ — (wherein R ₂₆ and R ₂₇ are each independently a hydrogen atom, A substituted or unsubstituted alkyl group having 1 to 24 carbon atoms, a substituted or unsubstituted phenyl group or a trifluoromethyl group), a substituted or unsubstituted cycloalkylidene group having 5 to 12 carbon atoms, 2, 2 -Adamantyl group, 1,3-adamantyl group, substituted or unsubstituted α, ω-alkylene group having 2 to 12 carbon atoms, substituted or unsubstituted 9,9-fluorenylidene group having 13 to 25 carbon atoms, 1,8 - Mentanjiiru group, 2,8 Mentanjiiru group, a substituted or unsubstituted Pirajiriden group having 4 to 10 carbon atoms, a substituted or unsubstituted arylene group having 6 to 12 carbon _{atoms, -C (CH 3) 2 -Ph} -C (CH _{3 2} -, and a divalent radical group selected from, derived from natural terpenes (Ph represents a phenylene group)]

  (3) A combination of 60 to 90% by mass of a polycarbonate resin and 10 to 40% by mass of a polyolefin resin, and 1 to 25 parts by mass of a modified polyolefin resin and 100% by mass of the polycarbonate resin described in (1) above A composite material comprising 1 to 25 parts by mass of a resin and / or the copolymer polycarbonate resin described in the above item (2).

  (4) The polycarbonate resin and / or the combination of 65 to 95% by mass of the polycarbonate resin and 5 to 35% by mass of one or more inorganic fillers and 100 parts by mass of the polycarbonate resin and / or A composite material comprising 5 to 30 parts by mass of the copolymer polycarbonate resin described in the above item (2).

  (5) A composite material comprising a curable material and the polycarbonate resin described in (1) above and / or the copolymerized polycarbonate resin described in (2) above.

  (6) The above (5) in which the polycarbonate resin described in the above (1) and / or the copolymer polycarbonate resin described in the above (2) contains 1 to 100 parts by mass with respect to 100 parts by mass of the curable material. The composite material according to the item).

  (7) The composite material according to (5) or (6) above, which is one of an LED sealing material, a semiconductor package material, and a semiconductor mounting material.

  (8) An electronic component using the composite material according to the above (5) or (6).

  (9) A sheet or film formed using the composite material according to any one of (3) to (6) above.

  (10) A coating material comprising the composite material according to any one of (3) to (6) above and an organic solvent.

  (11) A paint comprising the composite material according to any one of (3) to (6) above and an organic solvent.

  According to the present invention, a reactive end group is used and a polycarbonate resin linearized and / or reticulated (copolymerized) by reacting these reactive groups by an appropriate method is used. A composite material having various good physical properties such as excellent mechanical strength and heat resistance can be provided while improving compatibility and adhesion.

The present invention is described in detail below.
The polycarbonate resin of the present invention has two modes of polycarbonate resin I and polycarbonate resin II.

［式中、Ｒは、それぞれ独立に、ハロゲン原子、炭素数１〜１０の置換もしくは無置換のアルキル基、炭素数１〜１０の置換もしくは無置換のアルキルオキシ基、炭素数１〜１０のアルキルチオ基、炭素数５〜７の置換もしくは無置換のシクロアルキル基、炭素数６〜２４の置換もしくは無置換のアリール基、炭素数６〜１２の置換もしくは無置換のアリールオキシ基又は炭素数６〜１２のアリールチオ基を表す。
ｎ１は０〜６の整数を表し、ｎ１’は１〜６の整数を表し、ｎ２は１〜５の整数を表し、ｎ３は０〜４の整数を表し、ｎ２＋ｎ３は１〜５の整数を表し、ｎ４は１又は２である。
Ｒ₃、Ｒ₄、Ｒ₅及びＲ₆は、それぞれ独立に、水素原子、ハロゲン原子、炭素数１〜１０の置換もしくは無置換のアルキル基、炭素数１〜１０の置換もしくは無置換のアルキルオキシ基、炭素数１〜１０のアルキルチオ基、炭素数５〜７の置換もしくは無置換のシクロアルキル基、炭素数６〜２４の置換もしくは無置換のアリール基、炭素数６〜１２の置換もしくは無置換のアリールオキシ基、又は炭素数６〜１２のアリールチオ基を表し、Ｒ₄とＲ₅とは炭素数１〜４のメチレン鎖で互いに連結されていてもよい。
ｎ５及びｎ７は各々独立に０又は１であり、ｎ５＋ｎ７は１又は２であり、ｎ６は０又は１であり、ｎ８は０〜５の整数を表す。
またＺは、下記の置換基のいずれかを表す。

（Ｒ₁及びＲ₂は、それぞれ独立に、水素原子、炭素数１〜１０の置換もしくは無置換のアルキル基、炭素数５〜７の置換もしくは無置換のシクロアルキル基、又は炭素数６〜２４の置換もしくは無置換のアリール基を表し、同一繰り返し単位中に存在する２つの−ＣＯＯＨ基は下記式（ａ）の構造をとっていてもよい。）］

下記一般式（６）で表される繰り返し単位を含み、塩化メチレンを溶媒とする濃度０．５ｇ／ｄｌ溶液の２０℃における還元粘度［ηｓｐ／ｃ］が０．１〜３．０ｄｌ／ｇであるポリカーボネート樹脂である。

（式中、Ａ₁は二価のフェノール性水酸基を有する化合物残基を示す。） First, the polycarbonate resin I has at least one structure selected from the group consisting of the following general formulas (1) to (5) at the end;

[Wherein, each R is independently a halogen atom, a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, a substituted or unsubstituted alkyloxy group having 1 to 10 carbon atoms, or an alkylthio group having 1 to 10 carbon atoms. Group, a substituted or unsubstituted cycloalkyl group having 5 to 7 carbon atoms, a substituted or unsubstituted aryl group having 6 to 24 carbon atoms, a substituted or unsubstituted aryloxy group having 6 to 12 carbon atoms, or 6 to 6 carbon atoms 12 arylthio groups are represented.
n1 represents an integer of 0 to 6, n1 ′ represents an integer of 1 to 6, n2 represents an integer of 1 to 5, n3 represents an integer of 0 to 4, and n2 + n3 represents an integer of 1 to 5. , N4 is 1 or 2.
R ₃ , R ₄ , R ₅ and R ₆ are each independently a hydrogen atom, a halogen atom, a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, or a substituted or unsubstituted alkyloxy group having 1 to 10 carbon atoms. Group, alkylthio group having 1 to 10 carbon atoms, substituted or unsubstituted cycloalkyl group having 5 to 7 carbon atoms, substituted or unsubstituted aryl group having 6 to 24 carbon atoms, substituted or unsubstituted group having 6 to 12 carbon atoms aryloxy group, or an arylthio group having 6 to 12 carbon atoms, R ₄ and R ₅ may be linked to each other by a methylene chain of 1 to 4 carbon atoms.
n5 and n7 are each independently 0 or 1, n5 + n7 is 1 or 2, n6 is 0 or 1, and n8 represents an integer of 0 to 5.
Z represents any of the following substituents.

(R ₁ and R ₂ are each independently a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, a substituted or unsubstituted cycloalkyl group having 5 to 7 carbon atoms, or 6 to 24 carbon atoms. And the two —COOH groups present in the same repeating unit may have the structure of the following formula (a))]

The reduced viscosity [ηsp / c] at 20 ° C. of a 0.5 g / dl solution containing a repeating unit represented by the following general formula (6) and using methylene chloride as a solvent is 0.1 to 3.0 dl / g. It is a certain polycarbonate resin.

(In the formula, A ₁ represents a compound residue having a divalent phenolic hydroxyl group.)

［式中、Ｒ₇ 及びＲ₈ は、それぞれ独立に、ハロゲン原子、置換もしくは無置換の炭素数１〜１２のアルキル基、置換もしくは無置換の炭素数１〜１２のアルコキシ基、置換もしくは無置換の炭素数６〜１２のアリール基、置換もしくは無置換の炭素数７〜１３のアリールアルキルもしくはアリールアルケニル基、置換もしくは無置換の炭素数１〜１２のフルオロアルキル基、又は置換もしくは無置換の炭素数６〜２４の縮合多環式炭化水素を示す。
ｓ、ｔは各々独立に０〜４の整数である。
Ｘ₁ は、単結合、−Ｏ−、−ＣＯ−、−Ｓ−、−ＳＯ−、−ＳＯ₂ −、−ＣＲ₉Ｒ₁₀ −（ただし、Ｒ₉ 、Ｒ₁₀ は、それぞれ独立に、水素、置換もしくは無置換の炭素数１〜２４のアルキル基、及び置換もしくは無置換のフェニル基及びトリフルオロメチル基から選ばれる）、置換もしくは無置換の炭素数５〜１２のシクロアルキリデン基、２，２−アダマンチル基、１，３−アダマンチル基、置換もしくは無置換の炭素数２〜１２のα，ω−アルキレン基、置換もしくは無置換の炭素数１３〜２５の９，９−フルオレニリデン基、１，８−メンタンジイル基、２，８−メンタンジイル基、置換もしくは無置換の炭素数４〜１０のピラジリデン基、置換もしくは無置換の炭素数６〜１２のアリーレン基、−Ｃ（ＣＨ₃）₂−Ｐｈ−Ｃ（ＣＨ₃）₂− 、及び天然テルペン類から誘導される二価の基、から選ばれる基を示す（Ｐｈは、フェニレン基を示す）。]
で表される二価の基を挙げることができる。 As the compound residue A ₁ having a dihydric phenolic hydroxyl group in the general formula (6), the following general formula (7)

[Wherein R ₇ and R ₈ are each independently a halogen atom, a substituted or unsubstituted alkyl group having 1 to 12 carbon atoms, a substituted or unsubstituted alkoxy group having 1 to 12 carbon atoms, substituted or unsubstituted. An aryl group having 6 to 12 carbon atoms, a substituted or unsubstituted arylalkyl or arylalkenyl group having 7 to 13 carbon atoms, a substituted or unsubstituted fluoroalkyl group having 1 to 12 carbon atoms, or a substituted or unsubstituted carbon The condensed polycyclic hydrocarbon of the number 6 to 24 is shown.
s and t are each independently an integer of 0 to 4.
X ₁ is a single bond, —O—, —CO—, —S—, —SO—, —SO ₂ —, —CR ₉ R ₁₀ — (wherein R ₉ and R ₁₀ are independently hydrogen, A substituted or unsubstituted alkyl group having 1 to 24 carbon atoms, a substituted or unsubstituted phenyl group or a trifluoromethyl group), a substituted or unsubstituted cycloalkylidene group having 5 to 12 carbon atoms, 2, 2 -Adamantyl group, 1,3-adamantyl group, substituted or unsubstituted α, ω-alkylene group having 2 to 12 carbon atoms, substituted or unsubstituted 9,9-fluorenylidene group having 13 to 25 carbon atoms, 1,8 - Mentanjiiru group, 2,8 Mentanjiiru group, a substituted or unsubstituted Pirajiriden group having 4 to 10 carbon atoms, a substituted or unsubstituted arylene group having 6 to 12 carbon _{atoms, -C (CH 3) 2 -Ph} -C (CH ₃ ) ₂ And a group selected from divalent groups derived from natural terpenes (Ph represents a phenylene group). ]
The bivalent group represented by these can be mentioned.

［Ｘ₂は炭素原子又は硫黄原子である。またＸ₂が炭素原子の場合、Ｒ₁₁は各々のＸ₂に関して個々に選択され、そして互いに独立して、水素原子又は炭素数１〜６のアルキル基を表す。
ｍは４〜７の整数である。
Ｒ₁₂、Ｒ₁₃及びＲ₁₄は、それぞれ独立に、炭素数１〜６のアルキル基を表す。
ｍ₁は０〜２の整数であり、ｍ₂、ｍ₃及びｍ₄はそれぞれ０〜３の整数である。
Ｒ₁₅〜Ｒ₂₁は、炭素数１〜１０のアルキル基、炭素数６〜１２のアリール基、及び炭素数３〜１２のシクロアルキル基から選ばれる基を示す］ Moreover, as X < ₁ > in the said General formula (7), group represented by either of the following general formula (8)-(14) can be mentioned.

[X ₂ is a carbon atom or a sulfur atom. Moreover, when X < ₂ > is a carbon atom, R < ₁₁ > is individually selected regarding each X < ₂ > and represents a hydrogen atom or a C1-C6 alkyl group mutually independently.
m is an integer of 4-7.
R ₁₂ , R ₁₃ and R ₁₄ each independently represents an alkyl group having 1 to 6 carbon atoms.
m ₁ is an integer from 0 to 2, and m ₂ , m ₃ and m ₄ are each an integer from 0 to 3.
R _{15 to} R ₂₁ represent a group selected from an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 12 carbon atoms, and a cycloalkyl group having 3 to 12 carbon atoms.

（Ｘ₃は、上記一般式（８）〜（１１）のいずれかの構造である。
Ｒ₂₂及びＲ₂₃は、それぞれ独立に、ハロゲン原子、置換もしくは無置換の炭素数１〜１２のアルキル基、置換もしくは無置換の炭素数１〜１２のアルコキシ基、置換もしくは無置換の炭素数６〜１２のアリール基、置換もしくは無置換の炭素数７〜１３のアリールアルキルもしくはアリールアルケニル基、置換もしくは無置換の炭素数１〜１２のフルオロアルキル基、置換もしくは無置換の炭素数６〜２４の縮合多環式炭化水素を示す。
ｍ５及びｍ６は、それぞれ独立に、０〜４の整数である。）
下記一般式（１６）で表される繰り返し単位を含み、塩化メチレンを溶媒とする濃度０．５ｇ／ｄｌ溶液の２０℃における還元粘度［ηｓｐ／ｃ］が０．１〜３．０ｄｌ／ｇである共重合ポリカーボネート樹脂である。

［式中、Ｒ₂₄ 、Ｒ₂₅ は、それぞれ独立に、ハロゲン原子、置換もしくは無置換の炭素数１〜１２のアルキル基、置換もしくは無置換の炭素数１〜１２のアルコキシ基、置換もしくは無置換の炭素数６〜１２のアリール基、置換もしくは無置換の炭素数７〜１３のアリールアルキルもしくはアリールアルケニル基、置換もしくは無置換の炭素数１〜１２のフルオロアルキル基、置換もしくは無置換の炭素数６〜２４の縮合多環式炭化水素を示す。
ｕ及びｖは、それぞれ独立に、０〜４の整数である。
Ｘ₄ は、単結合、−Ｏ−、−ＣＯ−、−Ｓ−、−ＳＯ−、−ＳＯ₂ −、−ＣＲ₂₆Ｒ₂₇ −（ただし、Ｒ₂₆ 及びＲ₂₇ は、それぞれ独立に、水素原子、置換もしくは無置換の炭素数１〜２４のアルキル基、置換もしくは無置換のフェニル基及びトリフルオロメチル基から選ばれる）、置換もしくは無置換の炭素数５〜１２のシクロアルキリデン基、２，２−アダマンチル基、１，３−アダマンチル基、置換もしくは無置換の炭素数２〜１２のα，ω−アルキレン基、置換もしくは無置換の炭素数１３〜２５の９，９−フルオレニリデン基、１，８−メンタンジイル基、２，８−メンタンジイル基、置換もしくは無置換の炭素数４〜１０のピラジリデン基、置換もしくは無置換の炭素数６〜１２のアリーレン基、−Ｃ（ＣＨ₃）₂−Ｐｈ−Ｃ（ＣＨ₃）₂−、及び天然テルペン類から誘導される二価の基、から選ばれる基を示す（Ｐｈは、フェニレン基を示す）］ On the other hand, the polycarbonate resin II has at least one structure selected from the group consisting of the above general formulas (1) to (5) at a terminal, a repeating unit represented by the following general formula (15),

(X ₃ is the structure of any of the above general formula (8) to (11).
R ₂₂ and R ₂₃ are each independently a halogen atom, a substituted or unsubstituted alkyl group having 1 to 12 carbon atoms, a substituted or unsubstituted alkoxy group having 1 to 12 carbon atoms, a substituted or unsubstituted carbon number 6 -12 aryl group, substituted or unsubstituted arylalkyl or arylalkenyl group having 7 to 13 carbon atoms, substituted or unsubstituted fluoroalkyl group having 1 to 12 carbon atoms, substituted or unsubstituted 6 to 24 carbon atoms A condensed polycyclic hydrocarbon is shown.
m5 and m6 are each independently an integer of 0 to 4. )
The reduced viscosity [ηsp / c] at 20 ° C. of a 0.5 g / dl solution containing methylene chloride as a solvent and containing a repeating unit represented by the following general formula (16) is 0.1 to 3.0 dl / g. A copolymer polycarbonate resin.

[Wherein R ₂₄ and R ₂₅ each independently represent a halogen atom, a substituted or unsubstituted alkyl group having 1 to 12 carbon atoms, a substituted or unsubstituted alkoxy group having 1 to 12 carbon atoms, substituted or unsubstituted. An aryl group having 6 to 12 carbon atoms, a substituted or unsubstituted arylalkyl or arylalkenyl group having 7 to 13 carbon atoms, a substituted or unsubstituted fluoroalkyl group having 1 to 12 carbon atoms, a substituted or unsubstituted carbon number 6-24 condensed polycyclic hydrocarbons are shown.
u and v are each independently an integer of 0 to 4.
X ₄ is a single bond, —O—, —CO—, —S—, —SO—, —SO ₂ —, —CR ₂₆ R ₂₇ — (wherein R ₂₆ and R ₂₇ are each independently a hydrogen atom, A substituted or unsubstituted alkyl group having 1 to 24 carbon atoms, a substituted or unsubstituted phenyl group or a trifluoromethyl group), a substituted or unsubstituted cycloalkylidene group having 5 to 12 carbon atoms, 2, 2 -Adamantyl group, 1,3-adamantyl group, substituted or unsubstituted α, ω-alkylene group having 2 to 12 carbon atoms, substituted or unsubstituted 9,9-fluorenylidene group having 13 to 25 carbon atoms, 1,8 - Mentanjiiru group, 2,8 Mentanjiiru group, a substituted or unsubstituted Pirajiriden group having 4 to 10 carbon atoms, a substituted or unsubstituted arylene group having 6 to 12 carbon _{atoms, -C (CH 3) 2 -Ph} -C (CH _{3 2} -, and a divalent radical group selected from, derived from natural terpenes (Ph represents a phenylene group)]

  Hereinafter, in the present invention, the polycarbonate resin I and the polycarbonate resin II may be collectively referred to as the (copolymerized) polycarbonate resin of the present invention.

In the (copolymerization) polycarbonate resin of the present invention (hereinafter, the polycarbonate resin may be simply abbreviated as PC), the important point is that the temperature of a solution having a concentration of 0.5 g / dl using methylene chloride as a solvent is 20 ° C. The reduced viscosity [ηsp / c] is required to be 0.1 to 3.0 dl / g. When the reduced viscosity [ηsp / c] is less than 0.1 dl / g, the original mechanical strength and heat resistance as a polycarbonate resin cannot be sufficiently obtained when used in a composite material. When the reduced viscosity exceeds 3.0 dl / g, the melt viscosity and solution viscosity of the resin become too high, so that the compatibility of the materials and the handleability when used as a coating material are deteriorated. In addition, the productivity of the resin also deteriorates. The range of preferable reduced viscosity [ηsp / c] is 0.15 to 2.0 dl / g, particularly preferably 0.18 to 1.5 dl / g. As described above, a polycarbonate resin having a specific structure and a specific reduced viscosity [ηsp / c] is a polycarbonate having excellent impact resistance, mechanical strength, heat resistance, and toughness, and can be used for various applications. However, it can be advantageously used as a resin for the composite material of the present invention.
There is no restriction | limiting in particular as a manufacturing method of the (copolymerization) polycarbonate resin of this invention, It can manufacture by various methods according to a well-known method using a suitable monomer.

［式中、Ｒは、それぞれ独立に、ハロゲン原子、炭素数１〜１０の置換もしくは無置換のアルキル基、炭素数１〜１０の置換もしくは無置換のアルキルオキシ基、炭素数１〜１０のアルキルチオ基、炭素数５〜７の置換もしくは無置換のシクロアルキル基、炭素数６〜２４の置換もしくは無置換のアリール基、炭素数６〜１２の置換もしくは無置換のアリールオキシ基又は炭素数６〜１２のアリールチオ基を表す。
ｎ１は０〜６の整数を表し、ｎ１は１〜６の整数を表し、ｎ２は１〜５の整数を表し、ｎ３は０〜４の整数を表し、ｎ２＋ｎ３は１〜５の整数を表し、ｎ４は１又は２である。
Ｒ₃、Ｒ₄、Ｒ₅及びＲ₆は、それぞれ独立に、水素原子、ハロゲン原子、炭素数１〜１０の置換もしくは無置換のアルキル基、炭素数１〜１０の置換もしくは無置換のアルキルオキシ基、炭素数１〜１０のアルキルチオ基、炭素数５〜７の置換もしくは無置換のシクロアルキル基、炭素数６〜２４の置換もしくは無置換のアリール基、炭素数６〜１２の置換もしくは無置換のアリールオキシ基、又は炭素数６〜１２のアリールチオ基を表し、Ｒ₄とＲ₅とは炭素数１〜４のメチレン鎖で互いに連結されていてもよい。
ｎ５及びｎ７は各々独立に０又は１であり、ｎ５＋ｎ７は１又は２であり、ｎ６は０又は１であり、ｎ８は０〜５の整数を表す。
またＺは、下記の置換基のいずれかを表す。

（Ｒ₁及びＲ₂は、それぞれ独立に、水素原子、炭素数１〜１０の置換もしくは無置換のアルキル基、炭素数５〜７の置換もしくは無置換のシクロアルキル基、又は炭素数６〜２４の置換もしくは無置換のアリール基を表し、同一繰り返し単位中に存在する２つの−ＣＯＯＨ基は下記式（ａ）の構造をとっていてもよい。）］

(1) Terminal reactive group Specific examples of the terminal terminator having a reactive group in the (copolymerization) polycarbonate resin of the present invention are as follows.
The terminal has a structure represented by the following general formulas (1) to (5).

[Wherein, each R is independently a halogen atom, a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, a substituted or unsubstituted alkyloxy group having 1 to 10 carbon atoms, or an alkylthio group having 1 to 10 carbon atoms. Group, a substituted or unsubstituted cycloalkyl group having 5 to 7 carbon atoms, a substituted or unsubstituted aryl group having 6 to 24 carbon atoms, a substituted or unsubstituted aryloxy group having 6 to 12 carbon atoms, or 6 to 6 carbon atoms 12 arylthio groups are represented.
n1 represents an integer of 0 to 6, n1 represents an integer of 1 to 6, n2 represents an integer of 1 to 5, n3 represents an integer of 0 to 4, n2 + n3 represents an integer of 1 to 5, n4 is 1 or 2.
R ₃ , R ₄ , R ₅ and R ₆ are each independently a hydrogen atom, a halogen atom, a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, or a substituted or unsubstituted alkyloxy group having 1 to 10 carbon atoms. Group, alkylthio group having 1 to 10 carbon atoms, substituted or unsubstituted cycloalkyl group having 5 to 7 carbon atoms, substituted or unsubstituted aryl group having 6 to 24 carbon atoms, substituted or unsubstituted group having 6 to 12 carbon atoms aryloxy group, or an arylthio group having 6 to 12 carbon atoms, R ₄ and R ₅ may be linked to each other by a methylene chain of 1 to 4 carbon atoms.
n5 and n7 are each independently 0 or 1, n5 + n7 is 1 or 2, n6 is 0 or 1, and n8 represents an integer of 0 to 5.
Z represents any of the following substituents.

(R ₁ and R ₂ are each independently a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, a substituted or unsubstituted cycloalkyl group having 5 to 7 carbon atoms, or 6 to 24 carbon atoms. And the two —COOH groups present in the same repeating unit may have the structure of the following formula (a))]

一般式（１）で表される末端基の導入には、下記一般式（１’）で表される１価フェノールが用いられる。

上記１価フェノール（１’）の具体例としては、例えば下記のものが挙げられる。

(1-1) Terminal reactive group 1
Specific examples of the general formula (1) include the following.

For the introduction of the end group represented by the general formula (1), a monohydric phenol represented by the following general formula (1 ′) is used.

Specific examples of the monohydric phenol (1 ′) include the following.

一般式（２）で表される末端基の導入には、下記一般式（２’）で表される１価アルコールが用いられる。

上記１価アルコール（２’）の具体例としては、例えば下記のものが挙げられる。

(1-2) Terminal reactive group 2
Specific examples of the general formula (2) include the following.

For the introduction of the terminal group represented by the general formula (2), a monohydric alcohol represented by the following general formula (2 ′) is used.

Specific examples of the monohydric alcohol (2 ′) include the following.

一般式（３）で表される末端基の導入には、下記一般式（３’）または（３’’）で表される１価フェノールが用いられる。

上記１価フェノール（３’）及び（３’’）の具体例としては、例えば下記のものが挙げられる。

エチレン性二重結合を有するものを用いてポリカーボネートを合成した場合は、得られたポリカーボネートを前駆体として、例えば、二重結合に対して過剰量のメタクロロ過安息香酸（ＭＣＰＢＡ）を塩化メチレン中で一昼夜ほど反応させることにより、エポキシ基を有するポリカーボネートとすることができる。 (1-3) Terminal reactive group 3
Specific examples of the general formula (3) include the following.

For the introduction of the end group represented by the general formula (3), a monohydric phenol represented by the following general formula (3 ′) or (3 ″) is used.

Specific examples of the monohydric phenols (3 ′) and (3 ″) include the following.

When a polycarbonate is synthesized using one having an ethylenic double bond, for example, an excess amount of metachloroperbenzoic acid (MCPBA) relative to the double bond in methylene chloride is used as a precursor. By reacting for about a day and night, a polycarbonate having an epoxy group can be obtained.

一般式（４）で表される末端基の導入には、下記一般式（４’）または（４’’）で表される１価フェノールが用いられる。

上記１価フェノール（４’）及び（４’’）の具体例としては、例えば下記のものが挙げられる。

エチレン性二重結合を有するものを用いてポリカーボネートを合成した場合は、得られたポリカーボネートを前駆体として、例えば、二重結合に対して過剰量のメタクロロ過安息香酸（ＭＣＰＢＡ）を塩化メチレン中で一昼夜ほど反応させることにより、エポキシ基を有するポリカーボネートとすることができる。 (1-4) Terminal reactive group 4
Specific examples of the general formula (4) include the following.

For the introduction of the end group represented by the general formula (4), a monohydric phenol represented by the following general formula (4 ′) or (4 ″) is used.

Specific examples of the monohydric phenols (4 ′) and (4 ″) include the following.

When a polycarbonate is synthesized using one having an ethylenic double bond, for example, an excess amount of metachloroperbenzoic acid (MCPBA) relative to the double bond in methylene chloride is used as a precursor. By reacting for about a day and night, a polycarbonate having an epoxy group can be obtained.

一般式（５）で表される末端基の導入には、下記一般式（５’）または（５’’）で表される１価アルコールが用いられる。

上記１価アルコール（５’）及び（５’’）の具体例としては、例えば下記のものが挙げられる。

エチレン性二重結合を有するものを用いてポリカーボネートを合成した場合は、得られたポリカーボネートを前駆体として、例えば、二重結合に対して過剰量のメタクロロ過安息香酸（ＭＣＰＢＡ）を塩化メチレン中で一昼夜ほど反応させることにより、エポキシ基を有するポリカーボネートとすることができる。 (1-5) Terminal reactive group 5
Specific examples of the general formula (5) include the following.

For the introduction of the end group represented by the general formula (5), a monohydric alcohol represented by the following general formula (5 ′) or (5 ″) is used.

Specific examples of the monohydric alcohols (5 ′) and (5 ″) include the following.

When a polycarbonate is synthesized using one having an ethylenic double bond, for example, an excess amount of metachloroperbenzoic acid (MCPBA) relative to the double bond in methylene chloride is used as a precursor. By reacting for about a day and night, a polycarbonate having an epoxy group can be obtained.

Next, in the polycarbonate resin I of the present invention, the compounds having a divalent phenolic hydroxyl group as the raw material constituting the general formula (6) and the polycarbonate resin II constitute the general formulas (15) and (16). The raw material compound having a divalent phenolic hydroxyl group will be described.
(2) Divalent phenolic hydroxyl compound (bisphenol)
(Copolymerization) Specific examples of the compound having a divalent phenolic hydroxyl group used as a raw material for the polycarbonate resin are as follows.
For example, bis (4-hydroxyphenyl) methane, 1,1-bis (4-hydroxyphenyl) ethane, 1,2-bis (4-hydroxyphenyl) ethane, 2,2-bis (4-hydroxyphenyl) propane, 2,2-bis (3-methyl-4-hydroxyphenyl) butane, 2,2-bis (4-hydroxyphenyl) butane, 2,2-bis (4-hydroxyphenyl) octane, 4,4-bis (4 -Hydroxyphenyl) heptane, 1,1-bis (4-hydroxyphenyl) -1,1-diphenylmethane, 1,1-bis (4-hydroxyphenyl) -1-phenylethane, 1,1-bis (4-hydroxy) Phenyl) -1-phenylmethane, bis (4-hydroxyphenyl) ether, bis (4-hydroxyphenyl) sulfide, bis (4-hydroxy) Loxyphenyl) sulfone, bis (3-phenyl-4-hydroxyphenyl) sulfone, 2,2-bis (3-methyl-4-hydroxyphenyl) propane, 2,2-bis (3-phenyl-4-hydroxyphenyl) Propane, 2- (3-methyl-4-hydroxyphenyl) -2- (4-hydroxyphenyl) -1-phenylethane, bis (3-methyl-4-hydroxyphenyl) sulfide, bis (3-methyl-4- Hydroxyphenyl) sulfone, bis (3-methyl-4-hydroxyphenyl) methane, 1,1-bis (3-methyl-4-hydroxyphenyl) cyclohexane, 4,4-biphenol, 3,3′-dimethyl-4, 4'-biphenol, 3,3'-diphenyl-4,4'-biphenol, 3,3'-dichloro-4,4'-bipheno 3,3′-difluoro-4,4′-biphenol, 3,3 ′, 5,5′-tetramethyl-4,4′-biphenol, 2,7-naphthalenediol, 2,6-naphthalenediol, , 4-naphthalenediol, 1,5-naphthalenediol, 2,6-resorcin, 2,2-bis (2-methyl-4-hydroxyphenyl) propane, 1,1-bis (2-butyl-4-hydroxy-) 5-methylphenyl) butane, 1,1-bis (2-tert-butyl-4-hydroxy-3-methylphenyl) ethane, 1,1-bis (2-tert-butyl-4-hydroxy-5-methylphenyl) ) Propane, 1,1-bis (2-tert-butyl-4-hydroxy-5-methylphenyl) butane, 1,1-bis (2-tert-butyl-4-hydroxy-5-methyl) Enyl) isobutane, 1,1-bis (2-tert-butyl-4-hydroxy-5-methylphenyl) heptane, 1,1-bis (2-tert-butyl-4-hydroxy-5-methylphenyl) -1 -Phenylmethane, 1,1-bis (2-tert-amyl-4-hydroxy-5-methylphenyl) butane, bis (3-chloro-4-hydroxyphenyl) methane, bis (3,5-dibromo-4- Hydroxyphenyl) methane, 2,2-bis (3-chloro-4-hydroxyphenyl) propane, 2,2-bis (3-fluoro-4-hydroxyphenyl) propane, 2,2-bis (3-bromo-4) -Hydroxyphenyl) propane, 2,2-bis (3,5-difluoro-4-hydroxyphenyl) propane, 2,2-bis (3,5-dichloro- -Hydroxyphenyl) propane, 2,2-bis (3,5-dibromo-4-hydroxyphenyl) propane, 2,2-bis (3-bromo-4-hydroxy-5-chlorophenyl) propane, 2,2-bis (3,5-dichloro-4-hydroxyphenyl) butane, 2,2-bis (3,5-dibromo-4-hydroxyphenyl) butane, 1-phenyl-1,1-bis (3-fluoro-4-hydroxy) Phenyl) ethane, bis (3-fluoro-4-hydroxyphenyl) ether, 3,3′-difluoro-4,4′-dihydroxybiphenyl, 2,2-bis (4-hydroxyphenyl) hexafluoropropane, 2,2 -Bis (3-phenyl-4-hydroxyphenyl) propane,

1,1-bis (4-hydroxyphenyl) cyclopentane, 1,1-bis (4-hydroxyphenyl) cyclohexane, 1,1-bis (3-cyclohexyl-4-hydroxyphenyl) cyclohexane, 1,1-bis ( 3-phenyl-4-hydroxyphenyl) cyclohexane, 4,4 ′-(3,3,5-trimethylcyclohexylidene) diphenol,

  4,4 ′-[1,4-phenylenebis (1-methylethylidene)] bisphenol, 4,4 ′-[1,3-phenylenebis (1-methylethylidene)] bisphenol, 4,4-bis (4- Hydroxyphenyl) thiopyran, 4,4-bis (3-methyl-4-hydroxyphenyl) thiopyran,

  9,9'-bis (4-hydroxyphenyl) fluorene, 9,9'-bis (3-methyl-4-hydroxyphenyl) fluorene, 9,9'-bis (3-ethyl-4-hydroxyphenyl) fluorene,

  2,2-bis (4-hydroxyphenyl) adamantane, 2,2-bis (3-methyl-4-hydroxyphenyl) adamantane, 2,2-bis (3-ethyl-4-hydroxyphenyl) adamantane, 2,2 -Bis (3-n-propyl-4-hydroxyphenyl) adamantane, 2,2-bis (3-i-propyl-4-hydroxyphenyl) adamantane, 2,2-bis (3-n-butyl-4-hydroxy) Phenyl) adamantane, 2,2-bis (3-i-butyl-4-hydroxyphenyl) adamantane, 2,2-bis (3-sec-butyl-4-hydroxyphenyl) adamantane, 2,2-bis (3- t-butyl-4-hydroxyphenyl) adamantane, 2,2-bis (3-cyclohexyl-4-hydroxyphenyl) adamantane 2,2-bis (3-phenyl-4-hydroxyphenyl) adamantane, 2,2-bis (3-chloro-4-hydroxyphenyl) adamantane, 2,2-bis (3-bromo-4-hydroxyphenyl) adamantane 2,2-bis (3,5-dimethyl-4-hydroxyphenyl) adamantane, 2,2-bis (3,5-diethyl-4-hydroxyphenyl) adamantane, 2,2-bis (3,5-dichloro) -4-hydroxyphenyl) adamantane, 2,2-bis (3,5-dibromo-4-hydroxyphenyl) adamantane,

1,3-bis (3-chloro-4-hydroxyphenyl) adamantane, 1,3-bis (3-bromo-4-hydroxyphenyl) adamantane, 1,3-bis (3-fluoro-4-hydroxyphenyl) adamantane 1,3-bis (3-methyl-4-hydroxyphenyl) adamantane, 1,3-bis (3-ethyl-4-hydroxyphenyl) adamantane, 1,3-bis (3-n-propyl-4-hydroxy) Phenyl) adamantane, 1,3-bis (3-i-propyl-4-hydroxyphenyl) adamantane, 1,3-bis (3-n-butyl-4-hydroxyphenyl) adamantane, 1,3-bis (3- i-Butyl-4-hydroxyphenyl) adamantane, 1,3-bis (3-sec-butyl-4-hydroxyphenyl) adamanta 1,3-bis (3-t-butyl-4-hydroxyphenyl) adamantane, 1,3-bis (3-n-pentyl-4-hydroxyphenyl) adamantane, 1,3-bis (3-n-hexyl) -4-hydroxyphenyl) adamantane, 1,3-bis (3-cyclohexyl-4-hydroxyphenyl) adamantane, 1,3-bis (3-methoxy-4-hydroxyphenyl) adamantane, 1,3-bis (3- Ethoxy-4-hydroxyphenyl) adamantane, 1,3-bis (3-phenyl-4-hydroxyphenyl) adamantane, 1,3-bis (3-benzyl-4-hydroxyphenyl) adamantane, 1,3-bis (3 -Naphtyl-4-hydroxyphenyl) adamantane, 1,3-bis (3-tetrafluoromethyl-4-hydroxy) Phenyl) adamantane, 1,3-bis (3,5-dichloro-4-hydroxyphenyl) adamantane, 1,3-bis (3,5-dibromo-4-hydroxyphenyl) adamantane, 1,3-bis (3 5-difluoro-4-hydroxyphenyl) adamantane, 1,3-bis (3,5-dimethyl-4-hydroxyphenyl) adamantane, 1,3-bis (3,5-dimethoxy-4-hydroxyphenyl) adamantane, , 3-bis (3,5-diethoxy-4-hydroxyphenyl) adamantane and the like.

  Examples of the divalent group derived from natural terpenes include 4- [1- [3- (4-hydroxyphenyl) -4-methylcyclohexyl] -1-methylethyl] -phenol, 4,4 ′-[1. -Methyl-4- (1-methylethyl) -1,3-cyclohexanediyl] bisphenol, 4- [1- [4- (4-hydroxyphenyl) -4-methylcyclohexyl] -1-methylethyl] phenol, 4 -[1- [4- (4-hydroxy-3-methylphenyl) -4-methylcyclohexyl] -1-methylethyl] -2-methylphenol and the like.

Among these bisphenol compounds, 1,1-bis (4-hydroxyphenyl) ethane, 2,2-bis (4-hydroxyphenyl) propane, 1,1-bis (4-hydroxyphenyl) -1,1- Diphenylmethane, 1,1-bis (4-hydroxyphenyl) -1-phenylethane, bis (4-hydroxyphenyl) sulfone, 1,1-bis (4-hydroxyphenyl) cyclohexane, 2,2-bis (3-methyl) -4-hydroxyphenyl) propane, 2,2-bis (3-phenyl-4-hydroxyphenyl) propane, 4,4-biphenol, 2,7-naphthalenediol, 2,2-bis (3-phenyl-4-) Hydroxyphenyl) propane, 4,4 ′-(3,3,5-trimethylcyclohexylidene) diphenol, 4,4 ′-[1, -Phenylenebis (1-methylethylidene)] bisphenol, 9,9'-bis (4-hydroxyphenyl) fluorene, 9,9'-bis (3-methyl-4-hydroxyphenyl) fluorene, 9,9'-bis (3-ethyl-4-hydroxyphenyl) fluorene, 2,2-bis (4-hydroxyphenyl) adamantane, 4- [1- [4- (4-hydroxyphenyl) -4-methylcyclohexyl] -1-methylethyl Phenol, 4,4-bis (4-hydroxyphenyl) thiopyran, and the like are mentioned as preferred compounds. This is because it is excellent in terms of cost and mass productivity, and also has excellent heat resistance, and therefore does not adversely affect the heat resistance of the material after compatibilization.
These bisphenol compounds may be used alone or in combination of two or more.

(3) Polymerization method (3-1) Oligomer Carbonic ester forming compounds (hereinafter also referred to as carbonate precursors) include halogenes such as phosgene, phosgene dimer, phosgene trimer, and the like, or haloformates such as chloroformate. It is done.
For example, when a dihalogenated carbonyl such as phosgene or a haloformate such as chloroformate is used as the carbonate precursor, this reaction may be carried out in an appropriate solvent using an acid acceptor (for example, alkali metal hydroxide or alkali metal carbonate). In the presence of a basic alkali metal compound such as a salt or an organic base such as pyridine). Various alkali metal hydroxides and alkali metal carbonates can be used, but from an economical aspect, sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, etc. are usually preferably used. The These are usually suitably used as an aqueous solution. The proportion of the carbonate precursor used may be appropriately adjusted in consideration of the stoichiometric ratio (equivalent) of the reaction. Moreover, when using gaseous carbonate precursors, such as phosgene, the method of blowing this in a reaction system can be employ | adopted suitably. Similarly, the use ratio of the acid acceptor may be appropriately determined in consideration of the stoichiometric ratio (equivalent) of the reaction. Specifically, it is preferable to use 2 equivalents or a slightly excessive amount of acid acceptor relative to the total number of moles of bisphenol used (usually 1 mole corresponds to an equivalent amount).
(3-2) Reaction solvent As said solvent, what is necessary is just to use various solvents, such as what is used in the case of manufacture of a well-known polycarbonate, individually by 1 type or as a mixed solvent. As typical examples, hydrocarbon solvents such as toluene and xylene, and halogenated hydrocarbon solvents such as methylene chloride and chlorobenzene can be preferably used.
(3-3) Catalyst In order to accelerate the polycondensation reaction, a catalyst such as a tertiary amine such as triethylamine or a quaternary ammonium salt is further used, and further phloroglucin, pyrogallol, 4,6-dimethyl-2, 4,6-tris (4-hydroxyphenyl) -2-heptene, 1,3,5-tris (4-hydroxyphenyl) benzene, 1,1,1-tris (4-hydroxyphenyl) ethane, tris (4- Hydroxyphenyl) phenylmethane, 2,2-bis [4,4-bis (4-hydroxyphenyl) cyclohexyl] propane, 2,4-bis [2-bis (4-hydroxyphenyl) -2-propyl] phenol, 2 , 6-Bis (2-hydroxy-5-methylbenzyl) -4-methylphenol, 2- (4-hydroxyphenyl) -2- (2,4- Add branching agents such as dihydroxyphenyl) propane, tetrakis (4-hydroxyphenyl) methane, tetrakis [4- (4-hydroxyphenylisopropyl) phenoxy] methane, 2,4-dihydroxybenzoic acid, trimesic acid, cyanuric acid The reaction can be performed.
(3-4) Antioxidant Moreover, you may add small amounts of antioxidants, such as sodium sulfite and hydrosulfite, if desired.
(3-5) Reaction The reaction is usually carried out at a temperature in the range of 0 to 150 ° C, preferably 5 to 40 ° C. The reaction pressure can be any of reduced pressure, normal pressure, and increased pressure. Usually, it can be suitably carried out at normal pressure or about the pressure of the reaction system. The reaction time is usually about 0.5 minutes to 10 hours, preferably about 1 minute to 2 hours. As the reaction method, any of a continuous method, a semi-continuous method, a batch method and the like can be adopted. The reduced viscosity [ηsp / c] of the obtained polymer can be adjusted to the above range by, for example, various methods such as selection of the reaction conditions and the amount of the terminal terminator used. In some cases, the obtained polymer is appropriately subjected to physical treatment (mixing, fractionation, etc.) and / or chemical treatment (polymer reaction, crosslinking treatment, partial decomposition treatment, etc.) to obtain a predetermined reduced viscosity [ηsp / c ] Can also be obtained as polycarbonate. The obtained reaction product (crude product) can be recovered as polycarbonate having a desired purity (purity) by performing various post-treatments such as known separation and purification methods.

(4) Kneading method <PC + polyolefin, inorganic filler>
The manufacturing method of the composite material using the (copolymerization) polycarbonate resin which has a reactive group at the terminal of this invention is demonstrated. A composite material with a polycarbonate resin other than a polycarbonate resin having a reactive group at the end of the present invention (copolymerization) and a polyolefin resin, a composite material with an inorganic filler such as glass fiber, and an additional component used as necessary It is obtained by blending at a predetermined ratio and kneading. At this time, the blending and kneading are premixed with commonly used equipment such as a ribbon blender, a drum tumbler, etc., and then a Banbury mixer, a single screw extruder, a twin screw extruder, a multi screw extruder and It can be performed by a method using a conida or the like. The heating temperature at the time of kneading is appropriately selected in the range of usually 240 to 350 ° C. As this melt-kneading molding, it is preferable to use an extrusion molding machine, particularly a vent type extrusion molding machine. In addition, components other than the polycarbonate resin having a reactive group at the terminal of the present invention can be added as a master batch.
Furthermore, composite materials can be produced directly using the above-mentioned melt-kneading machine, or the obtained pellets can be used as raw materials for injection molding, injection compression molding, extrusion molding, blow molding, press Various molded products can be manufactured by a molding method, a vacuum molding method, a foam molding method, or the like. However, a pellet-shaped forming raw material can be produced by the melt-kneading method, and then the pellet can be used particularly suitably for production of an injection-molded product by injection molding or injection compression molding. In addition, as an injection molding method, gas injection molding for preventing the appearance of sink marks or for weight reduction can be adopted.

(5) Polycarbonate resin other than polycarbonate resin having a reactive group at the terminal of the present invention (copolymerization) The polycarbonate resin according to claim 5 and claim 6 has a reactive group at the terminal of the present invention (copolymerization). Polycarbonate resins other than polycarbonate resins can be used. Specific examples of the compound having a divalent phenolic hydroxyl group used as a raw material for the polycarbonate resin include the aforementioned compounds. Moreover, the said method is employable as a polymerization method.
When a commercially available polycarbonate resin is used as the polycarbonate resin according to claims 5 and 6, there is an advantage that the quality of the composite material of the present invention is useful for stabilization and cost reduction.
(6) Polyolefin resin Examples of the polyolefin resin include various polyolefin resins such as a polyethylene resin (PE), a polypropylene resin (PP), and a poly-1-butene resin. Here, examples of the polyethylene resin include low density polyethylene, linear low density polyethylene, medium density polyethylene, high density polyethylene, and copolymers of ethylene and other α-olefins. Polypropylene resins include crystalline propylene homopolymers, crystalline propylene-ethylene blocks and random copolymers, crystalline propylene-ethylene-α-olefin copolymers, and crystalline propylene polymers thereof. And mixtures of elastomers and elastomers. These polyolefin resins can be used singly or as a mixture of two or more.
It is preferable that the compounding quantity with respect to polycarbonate resin exists in the range of 10-40 mass% based on the total amount with polycarbonate resin from the balance of impact strength, slidability, chemical resistance, and heat resistance.

(7) Modified polyolefin resin Examples of the modified polyolefin resin include modified polyethylene resins and modified polypropylene resins. Acid-modified polyethylene with maleic anhydride, acid-modified polypropylene, ethylene propylene rubber (EPR), acid-modified EPR, etc. However, it is not limited to these.
As an example of the method for producing the modified polyolefin, 0.8 parts by weight of maleic anhydride and 0.2 parts by weight of Park Mill D (peroxide, manufactured by NOF Corporation) are added to 100 parts by weight of polyethylene and polypropylene, These two types of mixtures can be respectively extruded by a 35φ twin-screw extruder, and after cooling, cutting can be performed to obtain pellets of modified polyethylene and modified polypropylene. Examples of commercially available modified polyolefins include “Modic-AP” ( Made by Mitsubishi Chemical, anhydrous maleated polyethylene), “Adtex” (manufactured by Nippon Polyethylene, modified polyethylene), Adhesive polyolefin “Admer” LB548, LF128 (LDPE base), QB510, QB550, QF500, QF551, etc. (PP Base) And so on.
The addition amount is preferably 1 to 25 parts by mass, more preferably 3 to 20 parts by mass with respect to 100 parts by mass in total of the polycarbonate resin and the polyolefin resin. If it is less than 1 part by mass, there is a problem in the compatibility between the polycarbonate resin and the polyolefin resin, and if it exceeds 20 parts by mass, it is not preferable in terms of a decrease in elastic modulus or chemical resistance and a production cost.
Moreover, the addition amount of the (copolymerization) polycarbonate resin having a reactive group at the terminal is preferably 1 to 25 parts by mass, more preferably 1 to 25 parts by mass with respect to 100 parts by mass of the total amount of the polycarbonate resin and the polyolefin resin. 20 parts by mass.

(8) Inorganic filler As an inorganic filler, various things can be used. Specifically, glass, carbon fiber, and other inorganic fillers are used. First, as the glass material, for example, glass fibers, glass beads, glass flakes, glass powder, and the like can be used. Here, the glass fiber used may be any of alkali-containing glass, low alkali glass, and non-alkali glass. The fiber length is usually 0.1 to 8 mm, preferably 0.3 to 6 mm, and the fiber diameter is usually 0.1 to 30 μm, preferably 0.5 to 25 μm. And the form of this glass fiber does not have a restriction | limiting in particular, For example, various things, such as roving, a milled fiber, a chopped strand, are mentioned. These glass fibers may be used alone or in combination of two or more. These glass materials were surface treated with silane coupling agents such as amino silane, epoxy silane, vinyl silane, methacryl silane, chromium complex compounds, boron compounds, etc. in order to increase the affinity with the resin. It may be a thing. As such a glass material, for example, commercially available MA-409C (average fiber diameter 13 μm) or TA-409C (average fiber diameter 23 μm) manufactured by Asahi Fiber Glass Co., Ltd. can be suitably used.
Next, the carbon fiber used is generally produced by firing from cellulose fiber, acrylic fiber, lignin, petroleum or coal-based pitch, etc., and has flame resistance, carbon or graphite, etc. There are various types. The fiber length of the carbon fiber is usually 0.01 to 10 mm, preferably 0.02 to 8 mm, and the fiber diameter is usually 1 to 15 μm, preferably 5 to 13 μm. The form of the carbon fiber is not particularly limited, and examples thereof include various types such as roving, milled fiber, chopped strand, and strand. These carbon fibers may be used alone or in combination of two or more. The surface of these carbon fibers may be subjected to a surface treatment with an epoxy resin or a urethane resin in order to increase the affinity with the resin. As such a carbon fiber, for example, Besfite (average fiber diameter: 7 μm) manufactured by Toho Rayon Co., Ltd. can be suitably used.
Other inorganic fillers include, for example, aluminum fiber, calcium carbonate, magnesium carbonate, dolomite, silica, diatomaceous earth, alumina, iron oxide, zinc oxide, magnesium oxide, calcium sulfate, magnesium sulfate, calcium sulfite, talc, clay, mica Asbestos, calcium silicate, montmorillonite, bentonite, graphite, iron powder, lead powder, aluminum powder, etc. can also be used.
It is preferable that the compounding quantity of the inorganic filler with respect to polycarbonate resin exists in the range of 5-35 mass% based on the total amount with polycarbonate resin.
Moreover, the addition amount of the (copolymerization) polycarbonate resin having a reactive group at the terminal is preferably 5 to 30 parts by mass with respect to 100 parts by mass of the total amount of the polycarbonate resin and the inorganic filler.

(9) Preparation method <PC + curable material>
There is no particular limitation on the blending ratio of the polycarbonate resin having a reactive group at the terminal (copolymerization) and the curable material, but the balance of physical properties such as compatibility, heat resistance, toughness, impact strength, adhesion to the support substrate, When the viscosity (handling property), cost, etc. of the material are taken into consideration, the polycarbonate resin having a reactive group at the terminal with respect to 100 parts by mass of the curable material (copolymerization) is usually 1 to 100 parts by mass, preferably 3 to 90 parts. Part by mass, particularly preferably 5 to 80 parts by mass.
Moreover, about the mixture ratio of the hardening | curing agent added as needed, in the case of general reaction, it is preferable to prepare based on the equivalent of the reactive group which can react, and the reactive group (oxetane group in a curable material). The total amount of reactive groups of the (copolymerization) polycarbonate resin and the curing agent relative to one equivalent or the total amount of reactive groups of the curing agent relative to the total amount of the reactive groups of the curable material and (copolymerization) polycarbonate resin is 0.1 -3 equivalents, more preferably 0.2-2.5 equivalents, particularly preferably 0.5-2 equivalents. However, in the case of a reaction using a polymerization initiator such as a cationic polymerization initiator or a photoinitiator, the material having a reactive group can undergo a self-crosslinking reaction, and thus is not limited thereto.
Further, by optimizing the blending ratio of the (copolymerization) polycarbonate resin of the present invention, the curable material, and the curing agent, it is possible to suppress a delay in the curing rate.
In addition, the composite material of the present invention, if necessary, has been conventionally used, for example, a compounding solvent, a curing accelerator, a reaction diluent, a deterioration inhibitor, a modifier, a silane coupling agent, a defoaming agent. Various known additives such as additives, inorganic powders, leveling agents, mold release agents, dyes and pigments may be appropriately blended.
The composite material of the present invention is a mold (resin, metal, glass) in which the above-mentioned (terminated) polycarbonate resin having a reactive group (copolymerization), a curable material, and a curing agent and various additives are mixed as necessary. Etc.) or by coating onto a support substrate, etc., after forming into a desired shape such as a molded body or film, reaction by cationic polymerization, reaction using a curing agent such as acid anhydride or amine, thermal curing or ultraviolet light It can be cured by a known method such as by curing.
The curing temperature is 50 to 300 ° C, preferably 100 to 250 ° C. By setting the temperature to 50 ° C. or higher, curing does not become defective, and by setting the temperature to 250 ° C. or lower, decomposition or coloring does not occur. The curing time varies depending on the polycarbonate resin having a reactive group to be used, a curable material, a curing agent, an accelerator and an initiator, but is usually about 0.2 to 12 hours, preferably 0.5 to 6 hours.

(10) Blending method The method for preparing the composite material including the above (copolymerization) polycarbonate resin and the curable material is not particularly limited, and the (copolymerization) polycarbonate resin having a reactive group at the terminal of the present invention and the curability. Materials, and if necessary, curing agents, curing accelerators, various solvents, additives, and the like can be compatibilized using a ball mill, ultrasonic wave, homogenizer, paint shaker, red devil, sand mill, mixer, attritor or the like.

(11) Solvent for PC compound In addition, when using a solvent in order to mix | blend the (copolymerization) polycarbonate resin of this invention with another material, the following solvents can be used. That is, there is no particular limitation as long as it can dissolve the (copolymerization) polycarbonate resin of the present invention, for example, aliphatic hydrocarbon solvents such as n-hexane, cyclohexane, n-heptane, and rubber volatile oil; mineral spirits, high boiling point Aromatic hydrocarbon solvents such as petroleum solvent (ink oil), toluene, xylene, trimethylbenzene, solvent naphtha, tetralin, dipentene; methyl alcohol, ethyl alcohol, n-propyl alcohol, isopropyl alcohol, n-butyl alcohol, sec-butyl Alcohol solvents such as alcohol, isobutyl alcohol, cyclohexyl alcohol, 2-methylcyclohexyl alcohol, and tridecyl alcohol (tridecanol); Estes such as methyl acetate, ethyl acetate, isopropyl acetate, and butyl acetate Solvents: Ketone solvents such as acetone, methyl ethyl ketone (MEK), methyl isobutyl ketone (MIBK), cyclohexanone, methylcyclohexanone, diacetone alcohol (DAA), isophorone; ethylene glycol, propylene glycol, diethylene glycol, triethylene glycol, dipropylene Glycol solvents such as glycol; glycol ether solvents such as ethylene glycol monobutyl ether (butyl cellosolve), propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monobutyl ether, diethylene glycol monobutyl ether (butyl carbitol); ethylene glycol Monobutyl ether acetate (butyl cellosolve acetate ), Propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate (butyl carbitol acetate) and the glycol ether ester solvent such as such.
The concentration of the polycarbonate resin in the blended liquid is not particularly limited, and is usually 1 to 50% by mass, preferably 5 to 40% by mass, and particularly preferably 10 to 30% by mass from the viewpoint of easy handling and work efficiency. It is.

(12) Curable material On the other hand, the curable material used in the present invention is not particularly limited, and is an oxetane compound, an epoxy compound, a vinyl ether compound, a lactone compound, a cyclic ether compound, ketones, styrenes, acrolein, and vinyl arenes. And cycloaliphatic vinyl compounds such as vinylcyclohexene, spiroorthoester compounds, spiroorthocarbonate compounds, bicycloorthoester compounds, diene compounds, and phenol / formaldehyde resins. Among them, photocuring resins such as radical UV curing resins and thermosetting resins using acrylic base resins, cationic UV curing resins, thermosetting resins, and oxetane resins using epoxy base resins, and thermosetting resins. System resins are preferred. In particular, oxetane resins and epoxy base resins are preferable. For example, an epoxy resin is a main component for increasing the strength of a cured product by a cross-linking curing reaction, and any molecular weight or molecular structure may be used as long as it has two or more epoxy groups per molecule. Preferable examples include bisphenol type epoxy resin, novolac type epoxy resin, glycidyl ester type epoxy resin, glycidyl amine type epoxy resin, linear aliphatic epoxy resin, alicyclic epoxy resin, heterocyclic type epoxy resin, halogen And epoxy resin. These can also be used in combination of two or more that can be used alone. Examples of products include oxetane compounds (Aron Oxetane OXT-121, OXT-221, OXT-212, OXT-101, SiOX, etc.) manufactured by Toa Gosei Co., Ltd., and alicyclic epoxy (Celoxide 2021, Celoxide 2021) manufactured by Daicel Industries, Ltd. A, Celoxide 2021 P, Celoxide 2000, Celoxide 3000), Epoxy Compound (Epicoat YX8000, Epicoat 828), Multifunctional Epoxy (Epolide GT301, Epolide GT401, Epolide PB3600), Epoxy Resin with Alicyclic Skeleton (EHPE3150, EHPE3150CE), (meth) acrylate having an epoxy group (Cyclomer A400, Cyclomer M100) and the like can be mentioned, but not limited thereto.
The above curable resins (materials) having reactive groups such as epoxy and oxetane have excellent properties such as adhesion, chemical resistance, and electrical properties (insulating properties). Because of its good handling properties, it is used in a wide range of applications as a base material for structural adhesives, coating agents, and electrical insulating materials. In the present invention, the (copolymerized) polycarbonate of the present invention is used as a modifier for this material. Is proposed to apply.

(13) Curing agent When a curable material is used as a component of the composite material of the present invention, a curing agent can be added. In addition to promoting the curing reaction of curable materials such as epoxy compounds and oxetane compounds, the curing agent is directly involved in the curing reaction and incorporated into the chain, which may contribute to the modification of the composite material. .
As the curing agent, an acid anhydride curing agent, a phenol curing agent, an amine curing agent, a cyanate ester curing agent, or the like may be used in combination depending on the purpose. Examples of the acid anhydride curing agent include phthalic anhydride, maleic anhydride, trimellitic anhydride, pyromellitic anhydride, hexahydrophthalic anhydride, tetrahydrophthalic anhydride, methyl nadic anhydride, nadic anhydride, glutaric anhydride. Examples include acid, het anhydride, methyl hexahydrophthalic anhydride, methyl hymic anhydride, methyl tetrahydrophthalic anhydride, and the like. Examples of the phenolic curing agent include phenol novolak resin, cresol novolak resin, bisphenol A novolak resin, triazine-modified phenol novolak resin, and the like. Examples of amine-based curing agents include dicyandiamide, aromatic diamines such as m-phenylenediamine, 4,4′-diaminodiphenylmethane, 4,4′-diaminodiphenylsulfone, and m-xylylenediamine, diethylenetriamine, triethylenetetramine, Examples include aliphatic amines such as isophoronediamine, N-aminoethylpiperazine, and m-xylenediamine. Examples of the cyanate ester include 2,2-bis (4-cyanatephenyl) propane and 4,4′-ethylidene diphenyl diisocyanate. Two or more of these curing agents may be used in combination.
The curing agent is preferably added in a stoichiometric amount with respect to the number of terminal reactive groups of the polycarbonate resin according to the present invention and the number of functional groups of the curable material, but is not limited thereto. Conditions such as curing time and temperature may be appropriately set according to the type and addition amount of the polycarbonate resin, curable material, and curing agent to be used. Among these curing agents, physical properties such as transparency of the cured resin. From this point, an acid anhydride-based curing agent is preferable, and among them, hexahydrophthalic anhydride, tetrahydrophthalic anhydride, methylhexahydrophthalic anhydride, and the like are applicable. Examples of commercially available curing agents include HN-2200 (3or4-methyl-1,2,3,6-tetrahydrophthalic anhydride), HN-2000, and HN-5500 (available from Hitachi Chemical Co., Ltd.). 3or4-methyl-hexahydrophthalic anhydride), MHAC-P (methyl-3,6 endomethylene-1,2,3,6-tetrahydrophthalic anhydride) and the like.
Further, when a curing accelerator such as a tertiary amine or a phosphorus compound is added and mixed uniformly, a room temperature or heat curable resin composition can be obtained.

(14) Polymerization initiator When a curable material is used as a component of the composite material of the present invention, a polymerization initiator such as a cationic polymerization initiator is added and cured together with the curing agent or in place of the curing agent. Can do.
Any cationic polymerization initiator may be used as long as it reacts with the active group in the composite material by heat or ultraviolet rays. For example, aromatic diazonium salts such as p-methoxybenzenediazonium hexafluorophosphate, triphenylsulfonium hexafluoro, etc. Aromatic sulfonium salts such as phosphate, aromatic iodonium salts such as diphenyliodonium hexafluorophosphate, aromatic iodosyl salts, aromatic sulfoxonium salts, metallocene compounds and the like can be mentioned. Of these, aromatic sulfonium salts such as triphenylsulfonium hexafluorophosphate and aromatic iodonium salts such as diphenyliodonium hexafluorophosphate are optimal. Commercial initiators include, for example, Irgacure 184, 2959, 369, 907, 1300, 819, 2022, 2100, 250, DAROCUR 1173, MBF, TPO, 4265, etc. sold by Ciba Specialty Chemicals. Agents such as Sun-Aid SI-60L, 80L, 100L, 110L, 180L and the like sold by Sanshin Chemical Industry Co., Ltd. are applicable, but not limited thereto. The content of the cationic polymerization initiator is not particularly limited, but is preferably 0.01 to 5.0% by mass, more preferably 0.1 to 3.0% by mass with respect to the composite material. It is.

(15) Curing accelerator When a curable material is used as a component of the composite material of the present invention, the curing reaction can be accelerated by adding a curing accelerator together with or in place of the curing agent. it can.
The curing accelerator is not particularly limited. For example, 1,8-diaza-bicyclo (5.4.0) undecene-7, triethylenediamine, tris (2,4,6-dimethylaminomethyl) phenol. Tertiary amines such as 2-ethyl-4-methylimidazole, imidazoles such as 2-methylimidazole, triphenylphosphine, tetraphenylphosphonium bromide, tetraphenylphosphonium tetraphenylborate, tetra-n-butylphosphonium-o, Examples include phosphorus compounds such as o-diethyl phosphorodithioate, quaternary ammonium salts, organometallic salts, and derivatives thereof. These may be used alone or in combination. Among these curing accelerators, tertiary amines, imidazoles, and phosphorus compounds are preferably used.
It is preferable that the content rate of a hardening accelerator is 0.01-8.0 mass% with respect to the said material, More preferably, it is 0.1-3.0 mass%.
Tertiary amines used as curing accelerators include N, N-dimethylpiperazine, triethylenediamine, 2,4,6-tris (dimethylaminomethyl) phenol (DMP-30), benzyldimethylamine (BDMA), 2- (Dimethylaminomethyl) phenol (DMP-10), triethanolamine and the like, and imidazoles include 2-ethyl-4-methylimidazole, 1-isobutyl-2-methylimidazole and the like. Examples of the phosphorus compound include triphenylphosphine and tri (methylphenyl) phosphine.

(16) Reactive Diluent A reactive diluent is a component that lowers the viscosity of a composite material solution to improve handling workability, and is itself incorporated into a cured product to effectively improve physical properties. 1 or more, more preferably 2 or more epoxy groups, and a relatively low viscosity, preferably 5 Pa · s or less at 25 ° C., more preferably 1 Pa · s or less. As alkyl glycidyl ether, n-butyl glycidyl ether, allyl glycidyl ether, 2-ethylhexyl glycidyl ether, styrene oxide, phenyl glycidyl ether, cresyl glycidyl ether, p-sec-butylphenyl glycidyl ether, glycidyl methacrylate, tertiary carboxylic acid Acid glycidyl ether, diglycidyl ether, (poly) Ethylene glycol diglycidyl ether, (poly) propylene glycol diglycidyl ether, butanediol glycidyl ether, diglycidylaniline, 1,6-hexanediol glycidyl ether, cyclohexanedimethanol diglycidyl ether, neopetyl glycol diglycidyl ether, resorcinol diglycidyl Examples include ether, trimethylolethane triglycidyl ether, trimethylolpropane triglycidyl ether, glycerin triglycidyl ether, polyoxyalkylene glycol diglycidyl ether, castor oil polyglycidyl ether, and the like.
These reactive diluents may be used alone or in combination of two or more.
Moreover, the density | concentration of a mixing | blending solution is not specifically limited, From the point of the ease of handling and work efficiency, it is 1-50 mass% normally, Preferably it is 5-40 mass%, Most preferably, it is 5-30 mass%.

(17) Deterioration preventive agent Examples of the deterioration preventive agent include conventionally known deterioration preventive agents such as phenol compounds, amine compounds, organic sulfur compounds, and phosphorus compounds.
Examples of phenolic compounds include Irganox 1010 (Irganox 1010, Ciba Specialty Chemicals, Inc.), Irganox 1076 (Irganox 1076, Ciba Specialty Chemicals, Inc.), Irganox 1330 (Irganox 1330, Ciba Specialty Chemicals, Inc.) Irganox 3114 (Irganox 3114, Ciba Specialty Chemicals, Trademark), Irganox 3125 (Irganox 3125, Ciba Specialty Chemicals, Trademark), Irganox 3790 (Irganox 3790, Ciba Specialty Chemicals, Trademark) BHT, Cyanos 1790 Cyanox 1790, Cyanamid Co., Ltd.), Sumilizer GA-80 (S milizerGA-80, Sumitomo Chemical Co., Ltd., trademark) can be mentioned a commercially available product, such as.
Examples of amine compounds include Irgas Tab FS042 (Ciba Specialty Chemicals, Trademark), GENOX EP (Crimpton, Trademark, Compound Name; Dialkyl-N-methylamine oxide), and also a hindered amine product manufactured by Asahi Denka Co., Ltd. ADKSTAB LA-52, LA-57, LA-62, LA-63, LA-67, LA-68, LA-77, LA-82, LA-87, LA-94, Tinuvin 123, 144 manufactured by CSC 440, 662, Chimassorb 2020, 119, 944, Hostechn N30 manufactured by Hoechst, Cyasorb UV-3346, UV-3526 manufactured by Cytec, Uval 299 manufactured by GLC, and Sanduvor PR-31 manufactured by Clariant. be able to.
Examples of organic sulfur compounds include DSTP (Yoshitomi, Trademark), DLTP (Yoshitomi, Trademark), DLTOIB (Yoshitomi, Trademark), DMTP (Yoshitomi, Trademark), Seeox 412S. (Cypro Kasei Co., Ltd., Trademark), Cyanox 1212 (Cyanamide Co., Ltd., Trademark) and other commercial products.

(18) Modifier The modifier is used for the purpose of further improving the compatibility between the filler and the resin. Specifically, the filler is surface-treated with a silane coupling agent or the like. For paints, a modifier such as silicone oil that lowers the surface tension is used so that the coated surface is uniform (not uneven). A defoaming agent can also be used.
Examples of the modifying agent include conventionally known modifying agents such as glycols, silicones, and alcohols. Examples of the silane coupling agent include conventionally known silane coupling agents such as silane and titanate. Examples of the defoaming agent include conventionally known defoaming agents such as silicone.

  Examples of the present invention will be described in detail below, but the present invention is not limited to these examples.

  End stopper (A), dihydric phenol (B), polyolefin resin (C), modified polyolefin (C ′), curable material (D), curing agent (E), curing accelerator (F) used in the examples ), Polymerization initiator (G) and others are abbreviated as follows.

A1 (HPEtOH): 2- (4-hydroxyphenyl) ethanol A2: 4-hydroxybenzylamine A3: 3-hydroxyphthalic anhydride A4: 4-vinylphenol A5 (PTBP): p-tert-butylphenol

B1 (BisB): 2,2-bis (4-hydroxyphenyl) butane B2 (BisZ): 1,1-bis (4-hydroxyphenyl) cyclohexane B3 (BisI): 4,4 ′-(3,3,5 -Trimethylcyclohexylidene) diphenol B4 (BisTCD): 9,9-bis (4-hydroxyphenyl) tricyclodecane B5 (terpene): 4- [1- [4- (4-hydroxyphenyl) -4-methyl Cyclohexyl] -1-methylethyl] phenol B6 (Bis2,2ADM): 2,2-bis (4-hydroxyphenyl) adamantane B7 (BisFLC): 9,9′-bis (3-methyl-4-hydroxyphenyl) fluorene B8 (BisTP): 1,1-bis (4-hydroxyphenyl) -1,1-diphenylmethane B9 (BisBP ): 4,4′-biphenol B10 (BisM): 4,4 ′-(1,3-phenylenebis (1-methylethylidene) bisphenol B11 (BisZ4S): 4,4-bis (4-hydroxyphenyl) thiopyran

C1: Homopolypropylene Idemitsu J-700M (formerly Idemitsu Petrochemical)
C2: Low density polyethylene 291A (manufactured by Tosoh)

Add 100 parts by mass of polypropylene (compound C1) and polyethylene (compound C2), respectively, 0.8 parts by mass of maleic anhydride and 0.2 parts by mass of park mill D (peroxide, manufactured by NOF Corporation) The pellets of modified polyethylene (compound C1 ′) and modified polypropylene (compound C2 ′) were obtained with an extruder.

D1: Epicoat YX8000 (manufactured by Japan Epoxy Resin, Epoxy equivalent: 205)
D2: Celoxide 2021P (manufactured by Daicel Chemical Industries, compound name: 3,4-epoxycyclohexenylmethyl-3, '4'-epoxycyclohexene carboxylate, molecular weight: 252)
D3: Aron oxetane OXT-121 (manufactured by Toa Gosei Co., Ltd., molecular weight: 334)

E1: HN-5500 (3,4-methyl-hexahydrophthalic anhydride, molecular weight: 168)

F1: Triphenylphosphine F2: Benzyldimethylamine (BDMA)

G1: Sun-Aid SI-100L (cationic polymerization initiator, manufactured by Sanshin Chemical Industry Co., Ltd.)

MCPBA: Metachloroperbenzoic acid (oxidizing agent that converts vinyl group to epoxy group)

[Synthesis Example 1] (PC-1)
102 g of 2,2-bis (4-hydroxyphenyl) butane <compound B1> 550 ml of a 2 mol / liter sodium hydroxide aqueous solution, 400 ml of methylene chloride, 2- (4-hydroxyphenyl) ethanol as a terminal terminator <compound A1 > 1.9 g and 3 ml of a 10% strength by weight triethylamine aqueous solution as a catalyst were mixed and stirred, and phosgene gas was blown into the liquid at a rate of 340 ml / min for 30 minutes while cooling. After completion of the reaction, the organic phase is diluted with 1 liter of methylene chloride, washed with water, dilute hydrochloric acid and water in this order, then poured into methanol, crystallized, and the precipitate is dried and reacted at the end of the following structure A polycarbonate polymer having groups was obtained. The polycarbonate polymer thus obtained had a reduced viscosity [ηsp / c] at 20 ° C. of 0.48 dl / g in a solution having a concentration of 0.5 g / dl using methylene chloride as a solvent.
The reduced viscosity (ηsp / c), which is an index of the molecular weight of the polycarbonate resin, is 20 ° C. using an automatic viscosity measuring device VMR-042 (Ubbelohde improved viscometer for automatic viscosity (RM type), manufactured by Hosei Co., Ltd.). The viscosity of a solution having a concentration of 0.5 g / dl using methylene chloride as a solvent was measured and calculated. The resin structure was identified by ¹ H-NMR spectrum measurement.

[Synthesis Example 2] (PC-2)
A polycarbonate resin (reduced viscosity [ηsp / c] 0) was prepared in the same manner as in Synthesis Example 1 except that p-hydroxyphenylethanol was changed to 4-hydroxybenzylamine <Compound A2> (1.0 g) in Synthesis Example 1. .64 dl / g).

[Synthesis Example 3] (PC-3)
A polycarbonate resin (reduced viscosity [ηsp / c]) was prepared in the same manner as in Synthesis Example 1 except that p-hydroxyphenylethanol was changed to 3-hydroxyphthalic anhydride <Compound A3> (1.8 g) in Synthesis Example 1. 0.49 dl / g) was obtained.

[Synthesis Example 4] (PC-4)
In Synthesis Example 1, except that p-hydroxyphenylethanol was changed to 4-vinylphenol <compound A4> (1.2 g) and the steps after the reaction were changed, polycarbonate resin ( Reduced viscosity [ηsp / c] 0.47 dl / g) was obtained.
After completion of the reaction, the reaction product was diluted with 1 liter of methylene chloride and then washed twice with 1.5 liter of water. The resulting solution was bathed in ice, and 51.6 g of metachloroperbenzoic acid (MCPBA). Was added in several portions and slowly added. After the whole amount has been added, return to room temperature, stir for 24 hours, and then wash with 0.01 mol / liter aqueous sodium hydroxide, wash once with 1 liter of 0.01 mol / liter hydrochloric acid, and twice with 1 liter of water. The organic layer was poured into methanol, and the precipitated polymer was filtered and dried to obtain a polycarbonate resin.

[Synthesis Example 5] (PC-5)
The same procedure as in Synthesis Example 1 was repeated except that Compound B1 was changed to 1,1-bis (4-hydroxyphenyl) cyclohexane (98 g) and the amount of Compound A1 was changed to 2.1 g in Synthesis Example 1. A resin (reduced viscosity [ηsp / c] 0.44 dl / g) was obtained.

[Synthesis Example 6] (PC-6)
In Synthesis Example 1, except that Compound B1 was changed to 4,4 ′-(3,3,5-trimethylcyclohexylidene) diphenol (95 g) and Compound A1 was changed to Compound A3 (1.7 g), A polycarbonate resin (reduced viscosity [ηsp / c] 0.42 dl / g) was obtained in the same manner as in Synthesis Example 1.

[Synthesis Example 7] (PC-7)
In Synthesis Example 1, compound B1 was changed to 9,9-bis (4-hydroxyphenyl) tricyclodecane (92 g), and the amount of compound A1 was changed to 1.5 g. By operation, a polycarbonate resin (reduced viscosity [ηsp / c] 0.48 dl / g) was obtained.

[Synthesis Example 8] (PC-8)
In Synthesis Example 1, compound B1 was changed to 4- [1- [4- (4-hydroxyphenyl) -4-methylcyclohexyl] -1-methylethyl] phenol (101 g), and the amount of compound A1 was 1.9 g. A polycarbonate resin (reduced viscosity [ηsp / c] 0.42 dl / g) was obtained in the same manner as in Synthesis Example 1 except that

[Synthesis Example 9] (PC-9)
A polycarbonate resin was prepared in the same manner as in Synthesis Example 1, except that Compound B1 was changed to 4,4-bis (4-hydroxyphenyl) thiopyran (98 g) and Compound A1 was changed to 2.6 g in Synthesis Example 1. (Reduced viscosity [ηsp / c] 0.33 dl / g) was obtained.

[Synthesis Example 10] (PC-10)
In Synthesis Example 1, compound B1 was changed to 1,1-bis (4-hydroxyphenyl) -1,1-diphenylmethane (97 g), compound A1 was changed to compound A4 (0.9 g), The polycarbonate resin (reduced viscosity [ηsp / c] 0. 81 dl / g) was obtained.

[Synthesis Example 11] (PC-11)
A solution prepared by dissolving Compound B2 (100 g) in 900 ml of a 2 mol / liter aqueous potassium hydroxide solution and 450 ml of methylene chloride was mixed and stirred, and under cooling, phosgene gas was added to the solution at a rate of 950 ml / min. Blowed for about 30 minutes. Next, this reaction solution was left and separated to obtain an methylene chloride solution of an oligomer having a degree of polymerization of 2 to 5 in the organic phase and having a chloroformate group at the molecular end.
Then, methylene chloride was added to the obtained oligomer solution to make a total amount of 600 ml, and then mixed with a solution obtained by dissolving Compound B9 (19 g) in 200 ml of 2 mol / liter potassium hydroxide aqueous solution, and the end-stopping was performed. Compound A1 (2.2 g) as an agent was added. Next, while vigorously stirring the mixed solution, 2 ml of a 7% by mass triethylamine aqueous solution was added as a catalyst, and the reaction was performed at 25 ° C. with stirring for 1.5 hours.
After completion of the reaction, the reaction product is diluted with 1 liter of methylene chloride and then washed twice with 1.5 liters of water, twice with 1 liter of 0.01 mol / liter hydrochloric acid and twice with 1 liter of water in this order. After crystallization by pouring into methanol, the precipitate was dried to obtain a polycarbonate resin having the following structure (reduced viscosity [ηsp / c] was 0.42 dl / g).

[Synthesis Example 12] (PC-12)
In Synthesis Example 11, the procedure of Synthesis Example 11 was repeated, except that Compound B2 was changed to Compound B1 (101 g), Compound B9 was changed to Compound B3 (27 g), and Compound A1 was changed to Compound A3 (2.2 g). A polycarbonate resin (reduced viscosity [ηsp / c] 0.51 dl / g) having the following structure was obtained.

[Synthesis Example 13] (PC-13)
In Synthesis Example 11, Compound B9 was changed to Compound B5 (21 g), and the amount of Compound A1 as a terminal terminator (2.4 g) was changed, and the same structure as in Synthesis Example 11 was used. A polycarbonate resin (reduced viscosity [ηsp / c] 0.38 dl / g) was obtained.

[Synthesis Example 14] (PC-14)
45 g of 2,2-bis (4-hydroxyphenyl) adamantane <compound B6> and 25 g of 1,1-bis (4-hydroxyphenyl) cyclohexane <compound B2> were dissolved in 1360 ml of a 2 mol / liter aqueous potassium hydroxide solution. While the solution and 700 ml of methylene chloride were mixed and stirred, phosgene gas was blown into the liquid at a rate of 950 ml / min for about 30 minutes under cooling. Next, this reaction solution was left and separated to obtain an methylene chloride solution of an oligomer having a degree of polymerization of 2 to 5 in the organic phase and having a chloroformate group at the molecular end.
Then, methylene chloride was added to the obtained oligomer solution to make the total amount 150 ml, and then 5 g of 1,1-bis (4-hydroxyphenyl) cyclohexane was dissolved in 50 ml of 2 mol / liter potassium hydroxide aqueous solution. And compound A1 (2.4 g) as a terminal terminator was added thereto. Next, while vigorously stirring the mixed solution, 2 ml of a 7% by mass triethylamine aqueous solution was added as a catalyst, and the reaction was performed at 25 ° C. with stirring for 1.5 hours.
After completion of the reaction, the reaction product is diluted with 1 liter of methylene chloride and then washed twice with 1.5 liters of water, twice with 1 liter of 0.01 mol / liter hydrochloric acid and twice with 1 liter of water in this order. After crystallization by pouring into methanol, the precipitate was dried to obtain a polycarbonate resin having the following structure (reduced viscosity [ηsp / c] was 0.22 dl / g).

[Synthesis Example 15] (PC-15)
Compound A1 was changed to Compound A4 (1.1 g) in Synthesis Example 14, and the steps after completion of the reaction were changed to the steps described in Synthesis Example 4 (reaction with MCPBA, washing with aqueous sodium hydroxide, etc.). The polycarbonate resin having the following structure (reduced viscosity [ηsp / c] 0.53 dl / g) was obtained in the same manner as in Synthesis Example 14.

[Synthesis Example 16] (PC-16)
In Synthesis Example 14, except that Compound B6 was changed to Compound B7 (28 g) and 1.0 g was changed to the amount of Compound A1, polycarbonate resin having the following structure (reduced viscosity [ηsp / c]) was obtained in the same manner as in Synthesis Example 1. 0.44 dl / g) was obtained.

[Synthesis Example 17] (PC-17)
In Synthesis Example 14, compound B2 was changed to compound B10 (initial charge: 35 g, post-charge: 21 g), and compound A1 was changed to compound A3 (1.7 g). Polycarbonate resin (reduced viscosity [ηsp / c] 0.49 dl / g) was obtained.

[Comparative Synthesis Example 1] (PC-18)
A polycarbonate resin (reduced viscosity [ηsp / c] 0.48 dl / g) was prepared in the same manner as in Synthesis Example 1 except that the terminal stopper was changed to p-tert-butylphenol (1.5 g) in Synthesis Example 1. Obtained.

[Comparative Synthesis Example 2] (PC-19)
A polycarbonate resin (reduced viscosity [ηsp / c] 0.44 dl / g) was prepared in the same manner as in Synthesis Example 5 except that the terminal stopper was changed to p-tert-butylphenol (1.7 g) in Synthesis Example 5. Obtained.

[Comparative Synthesis Example 3] (PC-20)
A polycarbonate resin (reduced viscosity [ηsp / c] 0.42 dl / g) was prepared in the same manner as in Synthesis Example 11 except that the terminal stopper was changed to p-tert-butylphenol (1.9 g) in Synthesis Example 11. Obtained.

[Example 1] <Reactive PC + polyolefin resin>
Polycarbonate resin (Teflon A2200, manufactured by Idemitsu Petrochemical Co., Ltd.) 90% by mass, homopolypropylene Idemitsu J-700M (C1) 10% by mass, modified polypropylene (C1 ′) with respect to 100 parts by mass of the total amount of polycarbonate resin and compound C1 20 parts by mass and a proportion of 20 parts by mass of a polycarbonate resin (PC-1) having a reactive group at the end are supplied to a bent type twin screw extruder (model name: TEM35, manufactured by Toshiba Machine Co., Ltd.). It was melt-kneaded at 0 ° C and pelletized. The obtained pellets were dried at 120 ° C. for 12 hours and then molded at a molding temperature of 280 ° C. and a mold temperature of 90 ° C. to obtain test pieces.

[Examples 2 to 4] <PC terminal species change>
In Example 1, a test piece was obtained in the same manner as in Example 1, except that (PC-1) was changed to (PC-2), (PC-3) and (PC-4), respectively.

[Example 5] <Modification of polyolefin resin content>
In Example 1, the amount of polycarbonate resin was changed to 60% by mass, the amount of C1 was changed to 40% by mass, the amount of (PC-1) was changed to 5 parts by mass, and the amount of compound C1 ′ was changed to 5 parts by mass. A test piece was obtained in the same manner as in Example 1.

[Example 6] <Modification of polyolefin resin>
In Example 1, the same operation as in Example 1 was performed except that Compound C1 was changed to 10% by mass of low-density polyethylene 291A (C2) and modified polypropylene (C1 ′) was changed to 20 parts by mass of modified polyethylene (C2 ′). A specimen was obtained.

[Example 7] <PC resin change>
In Example 1, a test piece was obtained in the same manner as in Example 1 except that the polycarbonate resin having a reactive group at the terminal was changed to (PC-11) and the molding temperature was changed to 290 ° C.

[Example 8] <Inorganic filler (glass)>
Reacts at the end with respect to 70% by mass of polycarbonate resin (manufactured by Idemitsu Petrochemical Co., Ltd., Toughlon A2200), 30% by mass of glass fiber MA-409C (manufactured by Asahi Fiber Glass Co., Ltd.), and 100 parts by mass of the total amount of polycarbonate resin and glass fiber. 30 parts by mass of a polycarbonate resin (PC-14) having a group, 3-glycidoxypropyltrimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd., KBM-403) 3 as a binder (modifier) between the polycarbonate resin and glass fiber It mix | blended in the ratio of the mass part, it supplied to the vent type twin-screw extruder (model name: TEM35, Toshiba Machine Co., Ltd. make), melt-kneaded at 280 degreeC, and pelletized. The obtained pellets were dried at 120 ° C. for 12 hours and then molded at a molding temperature of 280 ° C. and a mold temperature of 90 ° C. to obtain test pieces.

[Comparative Example 1] <Reactive PC + polyolefin resin>
In Example 1, except that it was blended except for PC-1, it was pelletized by the method described in Example 1 to obtain a test piece.

[Comparative Example 2] <Inorganic filler (glass)>
In Example 8, a test piece was obtained in the same manner as in Example 8, except that PC-14 was blended.

(1) Evaluation method 1
Using the obtained test piece, the performance was evaluated by the following various tests, and the results are shown in Table 3.

(1-1) IZOD (Izod impact strength)
According to ASTM D256, 23 ° C. (wall thickness: 3.2 mm), unit: kJ / m ² .
(1-2) Friction coefficient In accordance with method A of sliding characteristics JIS K7218 (plastic sliding wear test method), a disc-shaped test piece when rotating a plate-shaped test piece under a load of 19.6 N The average value (N) of the maximum frictional force generated on the contact surface of the cylinder for 5 minutes was measured. Coefficient of friction = friction force (N) / load 19.6 N. The smaller the coefficient of friction, the better the slidability, and the less likely the material will wear.
(1-3) Q value (flow value)
According to JIS K7210, the load was 1.57 KN and the temperature was 280 ° C. The Q value represents the outflow amount per unit time, and the higher the numerical value, the better the fluidity.
(1-4) Grease resistance It conformed to the grease resistance and chemical resistance evaluation method (limit strain due to ¼ ellipse). A specimen piece (thickness 3 mm) was fixed to the jig (1/4 ellipse surface) shown in FIG. 1 (perspective view), and Albania grease (manufactured by Showa Shell Sekiyu KK) was applied to the specimen piece and held for 48 hours. . The minimum length (X) at which cracks occurred was read, and the critical strain (%) was determined from the following formula. A large critical strain (%) indicates a high chemical resistance (solvent resistance) and is related to the addition of a polyolefin resin.
Limit strain (%) = (b / 2a ² ) [1- [1 / a ² − (b ² / a ⁴ )] X ² ] ⁻³ / ² · t
(T: test piece thickness)
(1-5) Surface layer peeling / appearance The cut surface of the molded product was visually observed.
◯: Good without surface layer peeling, Δ: Some surface layer peeling, ×: With surface layer peeling

[Examples 9 to 18 and Comparative Examples 3 to 5]
By blending (part by mass) described in Table 1, a curable material, a polycarbonate resin solution having a reactive group at the terminal (cyclohexane, solid content concentration: 20% by mass), a curing agent are blended, and a curing accelerator is added. Then, after pouring into a petri dish made of Teflon (registered trademark), it was dried at 100 ° C. for 4 hours and cured at 160 ° C. for 3 hours to form a sheet made of a composite material to obtain a test piece. In Examples 17 and 18, test pieces were prepared without blending the curing agent.

[Examples 19 to 25 and Comparative Examples 6 and 7]
By blending (parts by mass) described in Table 1, a curable material and a polycarbonate resin solution having a reactive group at the terminal (cyclohexane, solid content concentration: 20% by mass) were blended, a polymerization initiator was added, and Teflon ( After pouring into a petri dish made of (registered trademark), similarly, it was dried at 100 ° C. for 3 hours and cured at 180 ° C. for 3 hours to form a sheet made of a composite material, thereby obtaining a test piece.

[Examples 26 to 31 and Comparative Examples 8 and 9]
By blending (parts by mass) described in Table 2, a curable material, a polycarbonate resin solution having a reactive group at the terminal (cyclohexane, solid content concentration: 20% by mass), and adding a photocationic polymerization initiator, Poured into a Teflon (registered trademark) petri dish, dried at 100 ° C. for 2 hours, and cured by irradiation with ultraviolet rays of 3000 mJ / cm ² with a UV curing machine (ECS-301G1 manufactured by Eye Graphic). The sheet | seat which consists of was formed and the test piece was obtained.

(2) Evaluation method 2
The performance was evaluated by the following various tests using the obtained test pieces, and the results are shown in Table 4.
(2-1) Heat resistance (glass transition temperature)
Immediately after heating at 25 ° C. to 350 ° C. in a nitrogen stream (20 ml / min) at a temperature rising rate of 10 ° C./min using an input compensated differential scanning calorimeter DSM (Perkin Elmer Japan) The glass was quickly cooled to remove the thermal history of the sample, and further measured at the same rate of temperature rise to determine the glass transition temperature.
(2-2) Toughness (tensile elongation)
Using a tensile tester, a test piece (length 40 mm × width 5 mm × thickness about 500 μm) cut into a strip shape was tested at a tensile rate of 10% strain / minute, and toughness (tensile elongation) was measured. evaluated.
(2-3) DuPont impact Using a DuPont impact tester, place a test piece between the striker with a certain roundness at the tip and a cradle that matches the roundness, and add a weight from any height (100g ) Was dropped, and traces (cracks) given to the test surface of the striker were visually judged to evaluate the impact strength. The impact strength was expressed as the height at which the weight was dropped when cracking occurred.

  As is clear from the results in Table 3, the composite material of the present invention has better compatibility and adhesion with other thermoplastic resins and inorganic fillers than the composite material of the comparative example. As a result, high fluidity, solvent resistance in molded products, compatibility (no delamination and appearance failure), excellent slidability and impact resistance, and composite materials containing curable materials are also shown. From the results of 4 and 5, it can be seen that the heat resistance, toughness and impact resistance are excellent.

  The composite material of the present invention can be preferably used in the electric / electronic industry field, civil engineering / building field, aviation / space industry field, automobile industry field, and the like. In particular, it can be widely used as electronic parts such as capacitors, sensors, relays, and electronic circuit boards.

: It is a perspective view of the jig | tool used in order to evaluate the grease resistance of a test piece.

Explanation of symbols

a: Bottom length of the 1/4 elliptical jig b: Height of the 1/4 elliptical jig X: Distance to the crack occurrence location

Claims (13)

At least one structure selected from the group consisting of the following general formulas (1) to (5) at the end;

[Wherein, each R is independently a halogen atom, a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, a substituted or unsubstituted alkyloxy group having 1 to 10 carbon atoms, or an alkylthio group having 1 to 10 carbon atoms. Group, a substituted or unsubstituted cycloalkyl group having 5 to 7 carbon atoms, a substituted or unsubstituted aryl group having 6 to 24 carbon atoms, a substituted or unsubstituted aryloxy group having 6 to 12 carbon atoms, or 6 to 6 carbon atoms 12 arylthio groups are represented.
n1 represents an integer of 0 to 6, n1 ′ represents an integer of 1 to 6, n2 represents an integer of 1 to 5, n3 represents an integer of 0 to 4, and n2 + n3 represents an integer of 1 to 5. , N4 is 1 or 2.
R ₃ , R ₄ , R ₅ and R ₆ are each independently a hydrogen atom, a halogen atom, a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, or a substituted or unsubstituted alkyloxy group having 1 to 10 carbon atoms. Group, alkylthio group having 1 to 10 carbon atoms, substituted or unsubstituted cycloalkyl group having 5 to 7 carbon atoms, substituted or unsubstituted aryl group having 6 to 24 carbon atoms, substituted or unsubstituted group having 6 to 12 carbon atoms aryloxy group, or an arylthio group having 6 to 12 carbon atoms, R ₄ and R ₅ may be linked to each other by a methylene chain of 1 to 4 carbon atoms.
n5 and n7 are each independently 0 or 1, n5 + n7 is 1 or 2, n6 is 0 or 1, and n8 represents an integer of 0 to 5.
Z represents any of the following substituents.

(R ₁ and R ₂ are each independently a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, a substituted or unsubstituted cycloalkyl group having 5 to 7 carbon atoms, or 6 to 24 carbon atoms. And the two —COOH groups present in the same repeating unit may have the structure of the following formula (a))]

The reduced viscosity [ηsp / c] at 20 ° C. of a 0.5 g / dl solution containing a repeating unit represented by the following general formula (6) and using methylene chloride as a solvent is 0.1 to 3.0 dl / g. A composite material comprising a polycarbonate resin.

(In the formula, A ₁ represents a compound residue having a divalent phenolic hydroxyl group.) 2. The composite material comprising the polycarbonate resin according to claim 1, wherein the compound residue A ₁ having a divalent phenolic hydroxyl group in the general formula (6) is represented by the following general formula (7).

[Wherein R ₇ and R ₈ are each independently a halogen atom, a substituted or unsubstituted alkyl group having 1 to 12 carbon atoms, a substituted or unsubstituted alkoxy group having 1 to 12 carbon atoms, substituted or unsubstituted. An aryl group having 6 to 12 carbon atoms, a substituted or unsubstituted arylalkyl or arylalkenyl group having 7 to 13 carbon atoms, a substituted or unsubstituted fluoroalkyl group having 1 to 12 carbon atoms, or a substituted or unsubstituted carbon The condensed polycyclic hydrocarbon of the number 6 to 24 is shown.
s and t are each independently an integer of 0 to 4.
X ₁ is a single bond, —O—, —CO—, —S—, —SO—, —SO ₂ —, —CR ₉ R ₁₀ — (wherein R ₉ and R ₁₀ are independently hydrogen, A substituted or unsubstituted alkyl group having 1 to 24 carbon atoms, a substituted or unsubstituted phenyl group or a trifluoromethyl group), a substituted or unsubstituted cycloalkylidene group having 5 to 12 carbon atoms, 2, 2 -Adamantyl group, 1,3-adamantyl group, substituted or unsubstituted α, ω-alkylene group having 2 to 12 carbon atoms, substituted or unsubstituted 9,9-fluorenylidene group having 13 to 25 carbon atoms, 1,8 - Mentanjiiru group, 2,8 Mentanjiiru group, a substituted or unsubstituted Pirajiriden group having 4 to 10 carbon atoms, a substituted or unsubstituted arylene group having 6 to 12 carbon _{atoms, -C (CH 3) 2 -Ph} -C (CH ₃ ) ₂ And a group selected from divalent groups derived from natural terpenes (Ph represents a phenylene group). ] Composite material X ₁ in the general formula (7), characterized in that it contains a polycarbonate resin according to claim 2 represented by any of the following general formula (8) to (14).

[X ₂ is a carbon atom or a sulfur atom. Moreover, when X < ₂ > is a carbon atom, R < ₁₁ > is individually selected regarding each X < ₂ > and represents a hydrogen atom or a C1-C6 alkyl group mutually independently.
m is an integer of 4-7.
R ₁₂ , R ₁₃ and R ₁₄ each independently represents an alkyl group having 1 to 6 carbon atoms.
m ₁ is an integer from 0 to 2, and m ₂ , m ₃ and m ₄ are each an integer from 0 to 3.
R _{15 to} R ₂₁ represent a group selected from an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 12 carbon atoms, and a cycloalkyl group having 3 to 12 carbon atoms. At least one structure selected from the group consisting of the above general formulas (1) to (5) at the end, and a repeating unit represented by the following general formula (15);

(X ₃ is the structure of any of the above general formula (8) to (11).
R ₂₂ and R ₂₃ are each independently a halogen atom, a substituted or unsubstituted alkyl group having 1 to 12 carbon atoms, a substituted or unsubstituted alkoxy group having 1 to 12 carbon atoms, a substituted or unsubstituted carbon number 6 -12 aryl group, substituted or unsubstituted arylalkyl or arylalkenyl group having 7 to 13 carbon atoms, substituted or unsubstituted fluoroalkyl group having 1 to 12 carbon atoms, substituted or unsubstituted 6 to 24 carbon atoms A condensed polycyclic hydrocarbon is shown.
m5 and m6 are each independently an integer of 0 to 4. )
The reduced viscosity [ηsp / c] at 20 ° C. of a 0.5 g / dl solution containing methylene chloride as a solvent and containing a repeating unit represented by the following general formula (16) is 0.1 to 3.0 dl / g. A composite material comprising a copolymer polycarbonate resin.

[Wherein R ₂₄ and R ₂₅ each independently represent a halogen atom, a substituted or unsubstituted alkyl group having 1 to 12 carbon atoms, a substituted or unsubstituted alkoxy group having 1 to 12 carbon atoms, substituted or unsubstituted. An aryl group having 6 to 12 carbon atoms, a substituted or unsubstituted arylalkyl or arylalkenyl group having 7 to 13 carbon atoms, a substituted or unsubstituted fluoroalkyl group having 1 to 12 carbon atoms, a substituted or unsubstituted carbon number 6-24 condensed polycyclic hydrocarbons are shown.
u and v are each independently an integer of 0 to 4.
X ₄ is a single bond, —O—, —CO—, —S—, —SO—, —SO ₂ —, —CR ₂₆ R ₂₇ — (wherein R ₂₆ and R ₂₇ are each independently a hydrogen atom, A substituted or unsubstituted alkyl group having 1 to 24 carbon atoms, a substituted or unsubstituted phenyl group or a trifluoromethyl group), a substituted or unsubstituted cycloalkylidene group having 5 to 12 carbon atoms, 2, 2 -Adamantyl group, 1,3-adamantyl group, substituted or unsubstituted α, ω-alkylene group having 2 to 12 carbon atoms, substituted or unsubstituted 9,9-fluorenylidene group having 13 to 25 carbon atoms, 1,8 - Mentanjiiru group, 2,8 Mentanjiiru group, a substituted or unsubstituted Pirajiriden group having 4 to 10 carbon atoms, a substituted or unsubstituted arylene group having 6 to 12 carbon _{atoms, -C (CH 3) 2 -Ph} -C (CH _{3 2} -, and a divalent radical group selected from, derived from natural terpenes (Ph represents a phenylene group)]   The combination which consists of 60-90 mass% of polycarbonate resin and 10-40 mass% of polyolefin resin, and 1-25 mass parts of modified polyolefin resin with respect to 100 mass parts, and the polycarbonate in any one of Claims 1 thru | or 3 A composite material comprising 1 to 25 parts by mass of a resin and / or the copolymer polycarbonate resin according to claim 4.   The polycarbonate resin according to any one of claims 1 to 3 and / or a combination of 65 to 95% by mass of a polycarbonate resin and 5 to 35% by mass of one or more inorganic fillers, and 100 parts by mass thereof. A composite material comprising 5 to 30 parts by mass of the copolymer polycarbonate resin according to claim 4.   A composite material comprising a curable material and the polycarbonate resin according to claim 1 and / or the copolymer polycarbonate resin according to claim 4.   The polycarbonate resin according to any one of claims 1 to 3 and / or the copolymer polycarbonate resin according to claim 4 containing 1 to 100 parts by mass with respect to 100 parts by mass of the curable material. Composite material.   The composite material according to claim 7, wherein the composite material is any one of an LED sealing material, a semiconductor packaging material, and a semiconductor mounting material.   An electronic component comprising the composite material according to claim 7 or 8.   A sheet or film formed using the composite material according to claim 5.   A coating material comprising the composite material according to claim 5 and an organic solvent.   A paint comprising the composite material according to claim 5 and an organic solvent.

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