JPH1077338A - Polycarbonate resin and its production - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain the subject new resin suitable for the production of a crosslinked polycarbonate resin having improved surface hardness, heat- resistance, mechanical properties, etc., in balanced state by homogeneously dispersing a recurring unit having unsaturated bond in a recurring unit free from unsaturated bond. SOLUTION: This resin has a structure containing a recurring unit of the formulas I and II (R<1> is a bivalent group having a reactive unsaturated bond on the side chain; R<2> is a bivalent group free from reactive unsaturated bond on the side chain) and free from the units of the formula I adjacent to each other in the polymer chain. The objective resin can be produced by forming an oligomer of the unit II having halomate on both terminals and copolymerizing a monomer having hydroxyl groups on both terminals and expressed by the formula HO-R<1> -OH. The oligomer of the unit II having halomate on both terminals is preferably produced by reacting a monomer of the formula HO-R<2> - OH with a carbonyl halide. The molar ratio of the unit I to the sum of the units I and II is preferably 0.01-0.4.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a novel polycarbonate resin suitably used for producing a crosslinked polycarbonate resin and a method for producing the same. Also, the present invention
The present invention relates to a novel crosslinked polycarbonate resin in which various properties such as surface hardness, heat resistance, and mechanical properties are improved in a well-balanced manner.

[0002]

2. Description of the Related Art Polycarbonate resins having excellent transparency, dimensional stability, heat resistance and impact resistance are widely used as substitutes for inorganic glass and the like. However, as the use has spread to industrial materials such as electric / electronic parts, mechanical parts, and automobile parts, a technique for increasing the surface hardness and mechanical strength while utilizing the above-mentioned properties has been required.

[0003] Such a technique is disclosed in Japanese Patent Laid-Open No. 4-291.
No. 348 discloses a polycarbonate resin containing a repeating unit having an unsaturated bond in a side chain, and a crosslinking agent is added to the resin to perform crosslinking.
A crosslinked polycarbonate resin having improved surface hardness has been obtained. However, since the crosslinkable polycarbonate resin described in this publication is crosslinked by a crosslinking agent having a relatively long aliphatic chain, it lacks rigidity and the surface hardness is insufficiently improved. In addition, the publication does not distinguish between intramolecular crosslinks and intermolecular crosslinks,
There is no disclosure about intermolecular crosslinking which is considered to be deeply related to surface hardness and mechanical strength.

[0004]

SUMMARY OF THE INVENTION The present invention has been made based on the above circumstances, and provides a novel polycarbonate resin suitably used for producing a crosslinked polycarbonate resin having an intermolecular crosslink, and a method for producing the same. The purpose is to do. Another object of the present invention is to provide a novel crosslinked polycarbonate resin having transparency and improved properties such as surface hardness, heat resistance, and mechanical properties in a well-balanced manner.

[0005]

Means for Solving the Problems The inventors of the present invention have conducted intensive studies to solve the above problems, and as a result, in a polycarbonate resin, a repeating unit having an unsaturated bond in a repeating unit having no unsaturated bond. By uniformly dispersing and containing units, when crosslinking is performed using this unsaturated bond, intermolecular crosslinking takes precedence, and various properties such as surface hardness, heat resistance, and mechanical properties are improved in a well-balanced manner. It has been found that a crosslinked polycarbonate resin can be obtained, and as a method for producing the polycarbonate resin, an oligomer obtained by reacting a monomer having no unsaturated bond having reactivity even after polymerization with a carbonate-forming compound. To find a way to react with a monomer having an unsaturated bond that is reactive after polymerization via an intermediate It has led to the completion of the more the present invention.

That is, the gist of the present invention is as follows. [1]. It contains a repeating unit (I) represented by the following general formula (1) and a repeating unit (II) represented by the following general formula (2), and the repeating unit (I) is continuously contained in a polymer chain. A polycarbonate resin characterized by not being present.

[0007]

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[R ¹ in the general formula (1) represents a divalent group having a reactive unsaturated bond in the side chain, and R ¹ in the general formula (2)
² represents a divalent group having no reactive unsaturated bond in the side chain. ]

[2]. The above-mentioned [1], wherein the repeating unit (I) is a repeating unit (III) represented by the following general formula (3):
The polycarbonate resin as described.

[0010]

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[X in the general formula (3) is a single bond, -O-,-
S-, -SO-, -SO_Two-, -CO-, -CR^FiveR⁶
-(However, R^FiveAnd R⁶Are independently hydrogen and tri
Fluoromethyl group, alkyl group having 1 to 10 carbon atoms or charcoal
An aryl group having a prime number of 6 to 24), and having 3 to 12 carbon atoms.
Cycloalkylidene group, α, ω-alkyl having 2 to 12 carbon atoms
Alkylene group, fluorenylidene group, mentandiyl group,
Radilidene group, arylene group having 6 to 12 carbon atoms or
α, ω-siloxanediyl group,^ThreeAnd R ^FourHaso
Each independently hydrogen, trifluoromethyl, halogen
, An alkyl group having 1 to 10 carbon atoms, an alkyl group having 6 to 24 carbon atoms.
Reel group, cycloalkyl group having 3 to 12 carbon atoms, carbon number
1 to 10 alkyloxy groups or 6 to 24 carbon atoms
An aryloxy group, m and n each independently represent 0
A to d are integers, and c + d is 1 to
8, a + c is 4, and b + d is 4. ]

[3]. The above-mentioned [1], wherein the repeating unit (II) is a repeating unit (IV) represented by the following general formula (4):
Or the polycarbonate resin according to [2].

[0013]

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[In the general formula (4), Y is a single bond, -O-,-
S -, - SO -, - SO 2 -, - CO -, - CR 7 R 8
-(However, R ⁷ and R ⁸ are each independently hydrogen, a trifluoromethyl group, an alkyl group having 1 to 10 carbon atoms or an aryl group having 6 to 24 carbon atoms), a cycloalkylidene group having 3 to 12 carbon atoms A α, ω-alkylene group having 2 to 12 carbon atoms, a fluorenylidene group, a menthanediyl group, a pyradylidene group, an arylene group having 6 to 12 carbon atoms or an α, ω-siloxanediyl group, and R ^{9 to} R ¹⁶ are each independently A hydrogen, a trifluoromethyl group, a halogen atom, an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 24 carbon atoms, a cycloalkyl group having 3 to 12 carbon atoms, an alkyloxy group having 1 to 10 carbon atoms or carbon It is an aryloxy group of the number 6 to 24. ]

[4]. A crosslinked polycarbonate resin obtained by crosslinking the polycarbonate resin according to any one of [1] to [3].

[5]. Repeating unit (II) or (I
After forming an oligomer of a haloformate having both ends having V), a monomer (V) having a hydroxyl group at both ends represented by the following general formula (5) or a monomer having a hydroxyl group at both ends represented by the following general formula (7) ( The method for producing a polycarbonate resin according to any one of the above [1] to [3], which is copolymerized with VII).

[0017]

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[R ¹ in the general formula (5) represents a divalent group having a reactive unsaturated bond in a side chain. General formula (7)
X in a single bond, -O -, - S -, - SO -, - SO 2
-, --CO--, --CR ⁵ R ^6- (provided that R ⁵ and R ⁶
Is independently hydrogen, a trifluoromethyl group, an alkyl group having 1 to 10 carbon atoms or an aryl group having 6 to 24 carbon atoms), a cycloalkylidene group having 3 to 12 carbon atoms, α, having 2 to 12 carbon atoms, ω-alkylene group, fluorenylidene group, menthanediyl group, pyradylidene group, having 6 to 6 carbon atoms
12 is an arylene group or α, ω-siloxanediyl group, and R ³ and R ⁴ are each independently hydrogen, a trifluoromethyl group, a halogen atom, an alkyl group having 1 to 10 carbon atoms, or an aryl having 6 to 24 carbon atoms. Group, 3-12 carbon atoms
A cycloalkyl group, an alkyloxy group having 1 to 10 carbon atoms or an aryloxy group having 6 to 24 carbon atoms,
m and n are each independently an integer of 0 to 6;
Is an integer, c + d is 1 to 8, a + c is 4, and b + d is 4. ]

[6]. Repeating unit (II) or (I
After forming an oligomer of hydroxyl groups at both ends having V), a monomer (VI) of both ends haloformate represented by the following general formula (6) or a monomer of haloformate both ends represented by the following general formula (8) The method for producing a polycarbonate resin according to any one of the above [1] to [3], wherein the method is copolymerized with (VIII).

[0020]

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[R ¹ in the general formula (6) represents a divalent group having a reactive unsaturated bond in a side chain, and A represents a halogen atom. X in the general formula (8) is a single bond, -O-, -S
-, - SO -, - SO 2 -, - CO -, - CR 5 R 6 -
(Where R ⁵ and R ⁶ are each independently hydrogen, a trifluoromethyl group, an alkyl group having 1 to 10 carbon atoms or an aryl group having 6 to 24 carbon atoms), a cycloalkylidene group having 3 to 12 carbon atoms, An α, ω-alkylene group having 2 to 12 carbon atoms, a fluorenylidene group, a menthanediyl group, a pyradylidene group, an arylene group having 6 to 12 carbon atoms, or an α, ω-siloxanediyl group, wherein R ³ and R ⁴ are each independently A hydrogen, a trifluoromethyl group, a halogen atom, an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 24 carbon atoms, a cycloalkyl group having 3 to 12 carbon atoms, an alkyloxy group having 1 to 10 carbon atoms or carbon An aryloxy group of the formulas 6 to 24, wherein m and n are each independently 0
A to d are integers, and c + d is 1 to
8, a + c is 4, and b + d is 4. A in the general formula (8) represents a halogen atom. ]

[7]. Repeating unit (II) or (I
After forming an oligomer of a carbonate having both terminals having V), the monomer is mixed with a monomer (V) having a hydroxyl group at both terminals represented by the general formula (5) or a monomer (VII) represented by the general formula (7). The above [1] to characterized in that it is polymerized
The method for producing a polycarbonate resin according to any one of [3].

[8]. Repeating unit (II) or (I
After forming an oligomer having hydroxyl groups at both ends having V), a monomer (IX) of a carbonate at both ends represented by the following general formula (9) or a monomer (X) of a carbonate at both ends represented by the following general formula (10) The method for producing a polycarbonate resin according to any one of the above [1] to [3], which is copolymerized with (1).

[0024]

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[R ¹ in the general formula (9) represents a divalent group having a reactive unsaturated bond in a side chain, and R ¹⁷ and R ¹⁸ represent a monomer (IX) and an oligomer of the above-mentioned hydroxyl groups at both terminals. Represents a group that does not inhibit the polycondensation reaction of X in the general formula (10) is a single bond, -O -, - S -, - SO -, - SO 2 -, - C
O—, —CR ⁵ R ⁶ — (where R ⁵ and R ⁶ each independently represent hydrogen, a trifluoromethyl group,
An alkyl group or an aryl group having 6 to 24 carbon atoms), a cycloalkylidene group having 3 to 12 carbon atoms, an α, ω-alkylene group having 2 to 12 carbon atoms, a fluorenylidene group, a menthanediyl group, a pyrazilidene group, and a carbon number. 6-1
R ³ and R ⁴ are each independently hydrogen, a trifluoromethyl group, a halogen atom, an alkyl group having 1 to 10 carbon atoms, or an aryl having 6 to 24 carbon atoms. A cycloalkyl group having 3 to 12 carbon atoms, an alkyloxy group having 1 to 10 carbon atoms or an aryloxy group having 6 to 24 carbon atoms;
¹⁷ , R ¹⁸ are groups that do not inhibit the polycondensation reaction between the monomer (X) and the oligomer having the hydroxyl groups at both terminals, m and n each independently represent an integer of 0 to 6, and a to d represent integers. , C + d is 1 to 8, a + c is 4, and b + d is 4. ]

[0026]

BEST MODE FOR CARRYING OUT THE INVENTION

[Polycarbonate Resin] The polycarbonate resin of the present invention may be either linear or cyclic. Further, by using a terminal stopper or a branching agent during the synthesis, a special terminal structure or a special terminal in the polymer chain can be obtained. A branching structure may be introduced.

The polycarbonate resin of the present invention contains a repeating unit (I) and a repeating unit (II), and has a structure in which the repeating unit (I) is not continuous. For this reason, when performing a crosslinking reaction using an unsaturated bond present in the side chain of the repeating unit (I), intermolecular crosslinking takes precedence.

Repeating unit (I) and repeating unit (II)
A ratio (molar ratio) of the repeating unit (I) to the total of
(I) / [(I) + (II)], preferably 0.001
To 0.5, more preferably 0.01 to 0.4. The ratio of the repeating unit (I) is 0.001
If it is less than 100%, the proportion of unsaturated bonds in the polycarbonate resin is too small to obtain sufficient cross-linking, and mechanical properties such as surface hardness and tensile strength may not be improved.

Further, the polycarbonate resin of the present invention comprises
It may have a repeating unit other than the repeating units (I) and (II) as long as the object of the present invention is not hindered. Specific examples include repeating units derived from polyester, polyurethane, and polyether.

The polycarbonate resin of the present invention includes:
Those having a reduced viscosity of 0.1 to 2.0 measured at 20 ° C. at a concentration of 0.5 g / deciliter in a methylene chloride solvent,
It is preferable from the viewpoint of polymer properties after crosslinking. If the reduced viscosity is less than 0.1, desired mechanical properties may not be obtained even after crosslinking, and if it exceeds 2.0, the moldability of the polymer after crosslinking is reduced. there is a possibility.

The polycarbonate resin of the present invention improves surface hardness, heat resistance and mechanical properties by promoting an intermolecular crosslinking reaction utilizing unsaturated bonds present in the side chains. However, even if it is not applied, it can be used as an engineering plastic having excellent transparency, dimensional stability, heat resistance and impact resistance for use in industrial materials and the like.

It is also possible to introduce various functional groups by utilizing reactive unsaturated bonds present in the repeating unit to impart functionality, and it is also possible to use such a functional resin as a raw material. Available. Furthermore, graft copolymerization utilizing the unsaturated bond is also possible, and various characteristics can be imparted by this method.

In the repeating unit (I) represented by the general formula (1), R ¹ may be any divalent group having a reactive unsaturated bond in a side chain. The unsaturated bond is given reactivity by, for example, a radical initiator or the like, and can react with an unsaturated bond in another polymer chain to form an intermolecular crosslink. As such a group, specifically, for example, a vinyl group, an allyl group, a propenyl group, an isopropenyl group, a 1,4-butadienyl group,
And a 3-pentadienyl group.

The repeating unit (I) preferably has an arylene group in the main chain in order to improve surface hardness and mechanical properties. As such, the general formula (3)
And a repeating unit (III) having the following structure:

Also in the general formula (2), it is preferable to use a repeating unit having an arylene group in the main chain in order to improve surface hardness and mechanical properties. Such a compound includes a repeating unit (IV) having a structure represented by the general formula (4).

X in the general formula (3) represents -CR ⁵ R ^6-
In the above, examples of the alkyl group having 1 to 10 carbon atoms represented by R ⁵ and R ⁶ include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, a 2-butyl group and a ter
Examples include a t-butyl group, an isobutyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a nonyl group, and a decyl group. Examples of the aryl group having 6 to 24 carbon atoms include a phenyl group, a tolyl group, a naphthyl group, a styryl group,
Examples include a biphenyl group, a terphenyl group, a quarterphenyl group, an anthracenyl group, and a phenanthrenyl group.

Examples of the cycloalkylidene group having 3 to 12 carbon atoms represented by X include a cyclopentylidene group, a cyclohexylidene group, a cycloheptylidene group, a cyclooctylidene group, a cyclononylidene group, a cyclodecylidene group, a cyclodecylidene group, And an undecylidene group.

Examples of the α, ω-alkylene group having 2 to 12 carbon atoms represented by X include ethylene, trimethylene, tetramethylene, pentamethylene, hexamethylene, heptamethylene, octamethylene and nonamethylene. Group, decamethylene group, undecamethylene group and dodecamethylene group.

The fluorenylidene group represented by X includes, for example, a 9,9-fluorenylidene group.

Examples of the menthanediyl group represented by X include a 1,8-menthanediyl group and a 2,8-menthanediyl group.

Examples of the pyradylidene group represented by X include a 2,3-pyrazylidene group, a 2,5-pyrazylidene group, and a 2,6-pyrazylidene group.

The arylene group having 6 to 12 carbon atoms represented by X includes, for example, an o-phenylene group, an m-phenylene group, a p-phenylene group, a naphthylene group and a biphenylene group.

The α, ω-siloxanediyl group represented by X is, for example, a group represented by the following general formula (11).

[0044]

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[R ^{19 to} R ²⁶ in the general formula (11) each independently represent hydrogen, an alkyl group having 1 to 6 carbon atoms or an aryl group having 6 to 12 carbon atoms. Further, p and q each independently represent an integer of 2 to 5, and r represents an integer of 10 to 100. In the general formula (11), the number of carbon atoms represented by R ^{19 to} R ²⁶ is 1 to
Examples of the alkyl group of 6 include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, a 2-butyl group, a tert-butyl group, an isobutyl group, a pentyl group, and a hexyl group. Examples of the 12 aryl groups include a phenyl group, a naphthyl group, and a biphenyl group.

In the present invention, in view of transparency, surface hardness and mechanical properties of the obtained crosslinked polycarbonate resin, X represents a single bond, —CR ⁵ R ⁶ —, —SO ₂ —, and C 5 -C 5. It is preferable to have a repeating unit which is a cycloalkylidene group of 11, a 9,9-fluorenylidene group or an arylene group having 6 to 12 carbon atoms.

The halogen atom represented by R ³ and R ⁴ is particularly preferably a fluoro group or a chloro group.

The alkyl group having 1 to 10 carbon atoms represented by R ³ and R ⁴ includes, for example, methyl group, ethyl group, propyl group, isopropyl group, butyl group, 2-butyl group, te
Examples include an rt-butyl group, an isobutyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a nonyl group, and a decyl group.

The aryl group having 6 to 24 carbon atoms represented by R ³ and R ⁴ includes, for example, phenyl, tolyl, naphthyl, styryl, biphenyl, terphenyl,
Examples include a quarter phenyl group, an anthracenyl group, and a phenanthrenyl group.

Examples of the cycloalkyl group having 3 to 12 carbon atoms represented by R ³ and R ⁴ include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group,
Examples include a cycloheptyl group, a cyclooctyl group, and a cyclodecyl group.

The alkyloxy group having 1 to 10 carbon atoms represented by R ³ and R ⁴ includes, for example, methyloxy group, ethyloxy group, propyloxy group, isopropyloxy group, butyloxy group, 2-butyloxy group, tert-
Examples thereof include a butyloxy group, an isobutyloxy group, a pentyloxy group, a hexyloxy group, a heptyloxy group, an octyloxy group, a nonyloxy group, and a decyloxy group.

The aryloxy group having 6 to 24 carbon atoms represented by R ³ and R ⁴ includes, for example, a phenyloxy group, a naphthyloxy group and a biphenyloxy group.

As for X, R ^{3 to} R ⁶ and R ^{19 to} R ²⁶ , the functional groups as described above can be mentioned. However, as long as the object of the present invention is not impaired, these functional groups may be further substituted with a substituent. Added functional groups can be used. Examples of the substituent that can be added include a halogen atom, a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, and a se.
C-butyl group, tert-butyl group, C1-C4 alkyl group such as isobutyl group, phenyl group, naphthyl group, C6-C12 aromatic hydrocarbon group such as biphenyl group, methoxy group, Ethoxy, propoxy, isopropoxy, butoxy, sec-butoxy, te
1 to 1 carbon atoms such as rt-butoxy group and isobutoxy group
And a sulfide group such as an alkyloxy group, a methylthio group, and a phenylthio group.
One or more substituents can be independently bonded at the bondable positions.

In the general formula (3), the number of substituents c and d
Can be an integer of 1 to 4, each having 3 substituents.
In the case of 4 or 4, the efficiency of intermolecular crosslinking may be reduced, so that 1 or 2 is preferable. When the number of substituents is 2, it is preferable to add them so as to be in a meta-position or a para-position with each other for the above-mentioned reason.

In the general formula (3), m and n indicating the number of methylene groups in the substituents c and d each independently represent 0 to 0.
Although an integer of 8 can be employed, an integer of 0 to 2 is preferable because the mechanical properties of the polymer after crosslinking may be reduced.

Specific examples of the substituent that can be employed as Y in the general formula (4) include the same substituents as those described above for X.

Specific examples of the substituent that can be employed as R ^{9 to} R ¹⁶ in formula (4) include the same substituents as those described above for R ³ .

Specific examples of the polycarbonate resin of the present invention include those containing at least one of the following repeating units as the repeating unit (I), wherein the repeating unit is not continuous:

[0059]

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Further, those containing at least one kind of the above-mentioned repeating units and the following repeating units as the repeating unit (II) may be mentioned.

[0061]

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[Production Method of Polycarbonate Resin] The polycarbonate resin of the present invention can be produced, for example, by the following general formula (1)
The monomer (XII) represented by 2), preferably the general formula (1)
It can be synthesized by reacting the monomer (XIII) represented by 3) with a carbonate-forming compound and then reacting the monomer represented by the general formula (5), preferably the general formula (7). it can.

[0063]

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[In the general formula (12), R ² has the same meaning as described above; in the general formula (13), Y and R ^{9 to} R ¹⁶ have the same meanings as described above; , R ¹ have the same meaning as described above, and in the general formula (7), X, R ³ , R ⁴ , a, b, c,
d, m, and n have the same meaning as described above. As a production method, for example, a method in which a carbonyl halide such as phosgene is used as a carbonate-forming compound and polycondensation with a dihydric phenol in the presence of a suitable acid binder can be applied. In addition, a method in which a bisaryl carbonate is used as a carbonate-forming compound and a transesterification reaction is performed is also applicable.

As a production method using a carbonyl halide, for example, first, a monomer represented by the general formula (12) or (13) is reacted with a carbonyl halide,
A method of forming an oligomer of haloformate at both terminals having a repeating unit represented by the general formula (2) or (4) and then reacting the monomer represented by the general formula (5) or (7) can be applied. Further, a method of reacting an oligomer of a hydroxyl group at both ends having a repeating unit represented by the general formula (2) or (4) with a monomer of a haloformate at both terminals represented by the general formula (6) or (8) can also be applied. .

As a method using a transesterification reaction,
For example, first, a monomer represented by the general formula (12) or (13) is reacted with a bisaryl carbonate,
A method of forming an oligomer of a carbonate having both ends having a repeating unit represented by the general formula (2) or (4) and then reacting the monomer represented by the general formula (5) or (7) can be applied. Further, a method of reacting an oligomer of a hydroxyl group at both ends having a repeating unit represented by the general formula (2) or (4) with a monomer of a carbonate at both ends represented by the general formula (9) or (10) can also be applied. .

The method for producing a polycarbonate according to the present invention comprises starting from a monomer represented by the general formula (12) or (13) as a starting material and having both terminals having a repeating unit represented by the general formula (2) or (4). It is preferable to use a method of forming an oligomer of a haloformate or a carbonate at both ends and then reacting the monomer represented by the general formula (5) or (7) from the viewpoint of ease of resin production.

The degree of polymerization of the oligomer depends on the structure of the repeating unit, but is preferably from 1 to 5. If the number is 6 or more, the ratio of the repeating unit having a reactive unsaturated bond may decrease, and the polymer properties may not be sufficiently modified by crosslinking. Also,
In the method for producing a polycarbonate of the present invention, a terminal terminator and / or a branching agent can be co-present as needed, as long as the object of the present invention is not impaired.

In the monomer (V) represented by the general formula (5), R ¹ may be any divalent group having a reactive unsaturated bond in the side chain. It is preferable to have an arylene group in the main chain for improving the mechanical properties. Such a monomer includes the monomer (VII) represented by the general formula (7).

Specific examples of the monomer (VII) represented by the general formula (7) include the following. X
Are, for example, 3,3′-divinyl-4,4′-dihydroxybiphenyl, 3,3′-difluoro-4,4′-dihydroxy-5, 5'-divinylbiphenyl, 4,4 '
-Dihydroxy-3,3'-dimethyl-5,5'-divinylbiphenyl, 4,4'-dihydroxy-2,2'-
Dimethyl-5,5'-divinylbiphenyl, 4,4'-
Dihydroxy-2,2 ', 3,3'-tetramethyl-
5,5'-divinylbiphenyl, 4,4'-dihydroxy-3,3'-diphenyl-5,5'-divinylbiphenyl, 3,3'-dicyclohexyl-4,4'-dihydroxy-5,5'-divinyl Biphenyl, hexafluoro-4,4'-dihydroxy-5,5'-divinylbiphenyl, 3,3'-diallyl-4,4'-dihydroxybiphenyl, 3,3'-difluoro-4,4'-dihydroxy-5 , 5'-Diallylbiphenyl, 4,4'-dihydroxy-3,3'-dimethyl-5,5'-diallylbiphenyl, 4,4'-dihydroxy-2,2'-dimethyl-5,5'-diallylbiphenyl , 4,4'-dihydroxy-2,2 ', 3,3'-tetramethyl-5
5'-diallylbiphenyl, 4,4'-dihydroxy-
3,3′-diphenyl-5,5′-diallylbiphenyl, 3,3′-dicyclohexyl-4,4′-dihydroxy-5,5′-diallylbiphenyl, 3,3′-difluoro-4,4′-dihydroxy -5,5'-diallylbiphenyl and hexafluoro-4,4'-dihydroxy-5,5'-diallylbiphenyl.

Monomer (VII) wherein X is a compound of —O—
Are, for example, bis (3-vinyl-4-hydroxyphenyl) ether, bis (5-vinyl-3-
Fluoro-4-hydroxyphenyl) ether, bis (3-allyl-4-hydroxyphenyl) ether and bis (5-allyl-3-fluoro-4-hydroxyphenyl) ether.

A monomer (VII) wherein X is a compound of —S—
Are, for example, bis (3-vinyl-4-hydroxyphenyl) sulfide, bis (5-vinyl-3)
-Methyl-4-hydroxyphenyl) sulfide, bis (3-allyl-4-hydroxyphenyl) sulfide,
Bis (5-allyl-3-methyl-4-hydroxyphenyl) sulfide is exemplified.

Specific examples of the monomer (VII) in which X is a compound of —SO ₂ — include, for example, bis (3-vinyl-
4-hydroxyphenyl) sulfone, bis (5-vinyl-3-methyl-4-hydroxyphenyl) sulfone, bis (5-vinyl-3-phenyl-4-hydroxyphenyl) sulfone, bis (3-allyl-4-hydroxy) Phenyl) sulfone, bis (5-allyl-3-methyl-4-)
Hydroxyphenyl) sulfone, bis (5-allyl-3)
-Phenyl-4-hydroxyphenyl) sulfone.

A monomer in which X is a compound of —CO— (VI
Specific examples of I) include, for example, 4,4′-dihydroxy-3,3′-divinylbenzophenone.

Specific examples of the monomer (VII) wherein X is a compound of —CR ⁵ R ⁶ — and having a vinyl group as a group having a reactive unsaturated bond include, for example, bis (3- Vinyl-4-hydroxyphenyl) methane, 1,1-bis (3-vinyl-4-hydroxyphenyl) ethane, 2,2-bis (3-vinyl-4-hydroxyphenyl) propane, 2,2-bis (5 -Vinyl-3
-Methyl-4-hydroxyphenyl) butane, 2,2-
Bis (3-vinyl-4-hydroxyphenyl) butane,
2,2-bis (3-vinyl-4-hydroxyphenyl)
Octane, 4,4-bis (3-vinyl-4-hydroxyphenyl) heptane, 1,1-bis (3-vinyl-4-
Hydroxyphenyl) -1,1-diphenylmethane,
1,1-bis (3-vinyl-4-hydroxyphenyl)
-1-phenylethane, 1,1-bis (3-vinyl-4
-Hydroxyphenyl) -1-phenylmethane, 2,2
-Bis (5-vinyl-3-methyl-4-hydroxyphenyl) propane, 2- (5-vinyl-3-methyl-4-
(Hydroxyphenyl) -2- (3-vinyl-4-hydroxyphenyl) -1-phenylethane, bis (5-vinyl-3-methyl-4-hydroxyphenyl) methane,
2,2-bis (3-vinyl-2-methyl-4-hydroxyphenyl) propane, 1,1-bis (3-vinyl-2
-Butyl-4-hydroxy-5-methylphenyl) butane, 1,1-bis (3-vinyl-2-tert-butyl-4-hydroxy-3-methylphenyl) ethane, 1,
1-bis (3-vinyl-2-tert-butyl-4-hydroxy-5-methylphenyl) propane, 1,1-bis (3-vinyl-2-tert-butyl-4-hydroxy-5-methylphenyl) Butane, 1,1-bis (3-
Vinyl-2-tert-butyl-4-hydroxy-5-
Methylphenyl) isobutane, 1,1-bis (3-vinyl-2-tert-butyl-4-hydroxy-5-methylphenyl) heptane, 1,1-bis (3-vinyl-2
-Tert-butyl-4-hydroxy-5-methylphenyl) -1-phenylmethane, 1,1-bis (3-vinyl-4-hydroxy-5-methyl-2-tert-pentylphenyl) butane, bis (5 -Vinyl-3-chloro-4-hydroxyphenyl) methane, bis (3-vinyl-5-dibromo-4-hydroxyphenyl) methane,
2,2-bis (5-vinyl-3-chloro-4-hydroxyphenyl) propane, 2,2-bis (5-vinyl-3)
-Fluoro-4-hydroxyphenyl) propane, 2,
2-bis (5-vinyl-3-bromo-4-hydroxyphenyl) propane, 2,2-bis (3-vinyl-5-difluoro-4-hydroxyphenyl) propane, 2,2
-Bis (3-vinyl-5-dichloro-4-hydroxyphenyl) propane, 2,2-bis (3-vinyl-5-dibromo-4-hydroxyphenyl) propane, 2,2-
Bis (3-vinyl-4-hydroxy-5-chlorophenyl) propane, 2,2-bis (3-vinyl-5-dichloro-4-hydroxyphenyl) butane, 2,2-bis (3-vinyl-5-dibromo -4-hydroxyphenyl) butane, 1-phenyl-1,1-bis (5-vinyl-3-fluoro-4-hydroxyphenyl) ethane,
2,2-bis (3-vinyl-4-hydroxyphenyl)
-1,1,1,3,3,3-hexafluoropropane,
2,2-bis (4-vinyl-3-hydroxyphenyl)
-1,1,1,3,3,3-hexafluoropropane,
2,2-bis (5-vinyl-3-phenyl-4-hydroxyphenyl) propane, bis (3-vinyl-2-hydroxyphenyl) methane, 3-vinyl-2-hydroxyphenyl-3-vinyl-4-hydroxy Phenylmethane, bis (3-vinyl-2-hydroxy-4-methylphenyl) methane, bis (3-vinyl-6-tert-butyl-2-hydroxy-4-methylphenyl) methane,
Bis (3-vinyl-2-hydroxy-4,6-dimethylphenyl) methane, 1,1-bis (3-vinyl-2-hydroxy-4-methylphenyl) ethane, 2,2-bis (3-vinyl- 2-hydroxy-4,6-dimethylphenyl) propane, 2,2-bis (3-vinyl-2-hydroxy-4-sec-butylphenyl) propane, bis (5-vinyl-4-hydroxy-3-methylphenyl) )
Methane, bis (4-hydroxy-3-vinyl-5-methylphenyl) methane, bis (5-vinyl-3-fluoro-4-hydroxyphenyl) methane, bis (3-vinyl-4-hydroxyphenyl) methane, bis (5-vinyl-4-hydroxy-3-nonylphenyl) methane, 2,
2-bis (4-hydroxy-3-vinyl-5-methylphenyl) propane, 2,2-bis (5-vinyl-4-hydroxy-3-isopropylphenyl) propane, 2,
2-bis (5-vinyl-3-vinyl-4-hydroxyphenyl) propane, 2,2-bis (5-vinyl-3-s
ec-butyl-4-hydroxyphenyl) propane,
1,1-bis (3-vinyl-4-hydroxyphenyl)
Propane, 2,2-bis (3-vinyl-4-hydroxyphenyl) pentane, 2,2-bis (3-vinyl-4-
Hydroxyphenyl) hexane, 2,2-bis (3-vinyl-4-hydroxyphenyl) nonane, 2,2-bis (3-vinyl-4-hydroxyphenyl) decane, 2-
Ethyl-1,1-bis (3-vinyl-4-hydroxyphenyl) hexane, 2,2-bis (3-vinyl-4-hydroxyphenyl) -3-methylbutane, 1,1-bis (3-vinyl-4) -Hydroxyphenyl) -3-methylbutane, 1,1-bis (3-vinyl-4-hydroxyphenyl) -2-methylpropane, 1,1-bis (5-vinyl-4-hydroxy-3-methylphenyl)- 1-phenylethane and 1,1-bis (5-vinyl-4-hydroxy-3-phenylphenyl) -1-phenylethane are exemplified.

Specific examples of the monomer (VII) in which X is a compound of —CR ⁵ R ⁶ — and having an allyl group as a group having a reactive unsaturated bond include, for example, bis (3- Allyl-4-hydroxyphenyl) methane, 1,1-bis (3-allyl-4-hydroxyphenyl) ethane, 2,2-bis (3-allyl-4-hydroxyphenyl) propane, 2,2-bis (5 -Allyl-3
-Methyl-4-hydroxyphenyl) butane, 2,2-
Bis (3-allyl-4-hydroxyphenyl) butane,
2,2-bis (3-allyl-4-hydroxyphenyl)
Octane, 4,4-bis (3-allyl-4-hydroxyphenyl) heptane, 1,1-bis (3-allyl-4-
Hydroxyphenyl) -1,1-diphenylmethane,
1,1-bis (3-allyl-4-hydroxyphenyl)
-1-phenylethane, 1,1-bis (3-allyl-4
-Hydroxyphenyl) -1-phenylmethane, 2,2
-Bis (5-allyl-3-methyl-4-hydroxyphenyl) propane, 2- (5-allyl-3-methyl-4-
(Hydroxyphenyl) -2- (3-allyl-4-hydroxyphenyl) -1-phenylethane, bis (5-allyl-3-methyl-4-hydroxyphenyl) methane,
2,2-bis (3-allyl-2-methyl-4-hydroxyphenyl) propane, 1,1-bis (3-allyl-2
-Butyl-4-hydroxyphenyl-5-methylphenyl) butane, 1,1-bis (3-allyl-2-tert)
-Butyl-4-hydroxy-3-methylphenyl) ethane, 1,1-bis (3-allyl-2-tert-butyl-4-hydroxy-5-methylphenyl) propane,
1,1-bis (3-allyl-2-tert-butyl-4
-Hydroxy-5-methylphenyl) butane, 1,1-
Bis (3-allyl-2-tert-butyl-4-hydroxy-5-methylphenyl) isobutane, 1,1-bis (3-allyl-2-tert-butyl-4-hydroxy-5-methylphenyl) heptane, 1,1-bis (3-
Allyl-2-tert-butyl-4-hydroxy-5-
Methylphenyl) -1-phenylmethane, 1,1-bis (3-allyl-4-hydroxy-5-methyl-2-te
rt-pentylphenyl) butane, bis (5-allyl-
3-chloro-4-hydroxyphenyl) methane, bis (3-allyl-5-dibromo-4-hydroxyphenyl) methane, 2,2-bis (5-allyl-3-chloro-)
4-hydroxyphenyl) propane, 2,2-bis (5
-Allyl-3-fluoro-4-hydroxyphenyl) propane, 2,2-bis (5-allyl-3-bromo-4-)
Hydroxyphenyl) propane, 2,2-bis (3-allyl-5-difluoro-4-hydroxyphenyl) propane, 2,2-bis (3-allyl-5-dichloro-4-
Hydroxyphenyl) propane, 2,2-bis (3-allyl-5-dibromo-4-hydroxyphenyl) propane, 2,2-bis (3-allyl-4-hydroxy-5-
Chlorophenyl) propane, 2,2-bis (3-allyl-5-dichloro-4-hydroxyphenyl) butane,
2,2-bis (3-allyl-5-dibromo-4-hydroxyphenyl) butane, 1-phenyl-1,1-bis (5-allyl-3-fluoro-4-hydroxyphenyl) ethane, 2,2- Bis (3-allyl-4-hydroxyphenyl) -1,1,1,3,3,3-hexafluoropropane, 2,2-bis (4-allyl-3-hydroxyphenyl) -1,1,1,1 3,3,3-hexafluoropropane, 2,2-bis (5-allyl-3-phenyl-4-hydroxyphenyl) propane, bis (3-allyl-2-hydroxyphenyl) methane, 3-allyl-2
-Hydroxyphenyl-3-allyl-4-hydroxyphenylmethane, bis (3-allyl-2-hydroxy-4
-Methylphenyl) methane, bis (3-allyl-6-t
tert-butyl-2-hydroxy-4-methylphenyl) methane, bis (3-allyl-2-hydroxy-4,
6-dimethylphenyl) methane, 1,1-bis (3-allyl-2-hydroxy-4-methylphenyl) ethane,
2,2-bis (3-allyl-2-hydroxy-4,6-
Dimethylphenyl) propane, 2,2-bis (3-allyl-2-hydroxy-4-sec-butylphenyl) propane, bis (5-allyl-4-hydroxy-3-methylphenyl) methane, bis (4-hydroxy -3-allyl-5-methylphenyl) methane, bis (5-allyl-
3-fluoro-4-hydroxyphenyl) methane, bis (3-allyl-4-hydroxyphenyl) methane, bis (5-allyl-4-hydroxy-3-nonylphenyl)
Methane, 2,2-bis (4-hydroxy-3-allyl-
5-methylphenyl) propane, 2,2-bis (5-allyl-4-hydroxy-3-isopropylphenyl) propane, 2,2-bis (5-allyl-3-allyl-4-
(Hydroxyphenyl) propane, 2,2-bis (5-allyl-3-sec-butyl-4-hydroxyphenyl)
Propane, 1,1-bis (3-allyl-4-hydroxyphenyl) propane, 2,2-bis (3-allyl-4-
Hydroxyphenyl) pentane, 2,2-bis (3-allyl-4-hydroxyphenyl) hexane, 2,2-bis (3-allyl-4-hydroxyphenyl) nonane,
2,2-bis (3-allyl-4-hydroxyphenyl)
Decane, 2-ethyl-1,1-bis (3-allyl-4-
Hydroxyphenyl) hexane, 2,2-bis (3-allyl-4-hydroxyphenyl) -3-methylbutane,
1,1-bis (3-allyl-4-hydroxyphenyl)
-3-Methylbutane, 1,1-bis (3-allyl-4-
(Hydroxyphenyl) -2-methylpropane, 1,1-
Bis (5-allyl-4-hydroxy-3-methylphenyl) -1-phenylethane and 1,1-bis (5-allyl-4-hydroxy-3-phenylphenyl) -1-phenylethane are exemplified.

Specific examples of the monomer (VII) in which X is a cycloalkylidene group having 3 to 12 carbon atoms include, for example,
1,1-bis (3-vinyl-4-hydroxyphenyl)
Cyclopentane, 1,1-bis (3-vinyl-4-hydroxyphenyl) cyclohexane, 1,1-bis (5-
Vinyl-3-methyl-4-hydroxyphenyl) cyclohexane, 1,1-bis (5-vinyl-3-cyclohexyl-4-hydroxyphenyl) cyclohexane,
1-bis (5-vinyl-3-phenyl-4-hydroxyphenyl) cyclohexane, 1,1-bis (3-vinyl-4-hydroxyphenyl) -3,3,5-trimethylcyclohexane, 1,1-bis ( 4-hydroxy-3-
Vinyl-5-methylphenyl) cyclohexane, 1,1
-Bis (3-allyl-4-hydroxyphenyl) cyclopentane, 1,1-bis (3-allyl-4-hydroxyphenyl) cyclohexane, 1,1-bis (5-allyl-3-methyl-4-hydroxyphenyl) ) Cyclohexane, 1,1-bis (5-allyl-3-cyclohexyl-)
4-hydroxyphenyl) cyclohexane, 1,1-bis (5-allyl-3-phenyl-4-hydroxyphenyl) cyclohexane, 1,1-bis (3-allyl-4-
(Hydroxyphenyl) -3,3,5-trimethylcyclohexane and 1,1-bis (4-hydroxy-3-allyl-5-methylphenyl) cyclohexane.

Specific examples of the monomer (VII) in which X is an α, ω-alkylene group having 2 to 12 carbon atoms include, for example,
1,2-bis (3-vinyl-4-hydroxyphenyl)
Ethane and 1,2-bis (3-allyl-4-hydroxyphenyl) ethane are exemplified.

Specific examples of the monomer (VII) in which X is a fluorenylidene group include, for example, 9,9-bis (3-
(Allyl-4-hydroxyphenyl) fluorene, 9,9
-Bis (3-allyl-4-hydroxy-5-methylphenyl) fluorene.

A monomer (VI) wherein X is a menthanediyl group
Specific examples of I) include, for example, 1,8-bis (3-allyl-4-hydroxyphenyl) menthane and 2,8-bis (3-allyl-4-hydroxyphenyl) menthane.

A monomer (VII) wherein X is a pyradylidene group
Specific examples of 2,3-bis (3-allyl-4-hydroxyphenyl) pyrazine, 2,3-bis (3-allyl-4-hydroxyphenyl) pyrazine,
2,6-bis (3-allyl-4-hydroxyphenyl)
Pyrazine.

Specific examples of the monomer (VII) in which X is an arylene group having 6 to 12 carbon atoms include, for example, 1,2-bis (3-allyl-4-hydroxyphenyl) benzene,
1,3-bis (3-allyl-4-hydroxyphenyl)
Benzene, 1,4-bis (3-allyl-4-hydroxyphenyl) benzene, 2,6-bis (3-allyl-4-
(Hydroxyphenyl) naphthalene.

Specific examples of the monomer (VII) in which X is an α, ω-cyclohexanediyl group include, for example, α, ω-cyclohexanediyl
Bis {3- (3-allyl-4-hydroxyphenyl) propyl} polydimethylsiloxane.

Among them, 2,2-bis (3-vinyl-4)
-Hydroxyphenyl) propane, 1,1-bis (3-
Vinyl-4-hydroxyphenyl) -1,1-diphenylmethane, 1,1-bis (3-vinyl-4-hydroxyphenyl) -1-phenylethane, 1,1-bis (3-
Vinyl-4-hydroxyphenyl) cyclohexane,
2,2-bis (5-vinyl-3-methyl-4-hydroxyphenyl) propane, 3,3′-divinyl-4,4 ′
-Dihydroxybiphenyl, 2,2-bis (5-vinyl-3-phenyl-4-hydroxyphenyl) propane,
2,2-bis (3-allyl-4-hydroxyphenyl)
Propane, 1,1-bis (3-allyl-4-hydroxyphenyl) -1,1-diphenylmethane, 1,1-bis (3-allyl-4-hydroxyphenyl) -1-phenylethane, 1,1-bis (3-allyl-4-hydroxyphenyl) cyclohexane, 2,2-bis (5-allyl-3-methyl-4-hydroxyphenyl) propane,
3,3'-diallyl-4,4'-dihydroxybiphenyl, 2,2-bis (5-allyl-3-phenyl-4-hydroxyphenyl) propane, 9,9-bis (3-allyl-4-hydroxyphenyl ) Fluorene and the like are preferred.

The monomer (XII) represented by the general formula (12)
In the formula, R ² may be a divalent group having no reactive unsaturated bond in the side chain, but preferably has an arylene group in the main chain for the purpose of improving surface hardness and mechanical properties. . Examples of such a compound include a monomer (XIII) having a structure of the general formula (13).

The monomer represented by the general formula (13) (XII
Specific examples of I) include, 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-hydroxyphenyl) -1-phenylmethane, bis (4-hydroxyphenyl) ether, bis (4-hydroxyphenyl) sulfide, bis (4-hydroxyphenyl) sulfone, 1,1-bis (4-hydroxyphenyl) ) Cyclopentane, 1,1-bis (4-
Hydroxyphenyl) cyclohexane, 2,2-bis (3-methyl-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′-dihydroxybiphenyl , 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-ter
t-butyl-4-hydroxy-5-methylphenyl) 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 (4-hydroxy-5-methyl-2-tert-pentylphenyl) 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-4-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-hydroxyphenyl) ethane, bis (3-fluoro-4-hydroxyphenyl) ether , 3,3'-
Difluoro-4,4'-dihydroxybiphenyl, 1,
1-bis (3-cyclohexyl-4-hydroxyphenyl) cyclohexane, 4,4′-dihydroxy-3,
3'-dimethylbiphenyl, 4,4'-dihydroxy-
2,2′-dimethylbiphenyl, 4,4′-dihydroxy-2,2 ′, 3,3′-tetramethylbiphenyl,
4,4'-dihydroxy-3,3 ', 5,5'-hexamethylbiphenyl, 4,4'-dihydroxy-3,3'
-Diphenylbiphenyl, 3,3'-dicyclohexyl-4,4'-dihydroxybiphenyl, 3,3'-difluoro-4,4'-dihydroxybiphenyl, 3,
3 ', 5,5'-tetrafluoro-4,4'-dihydroxybiphenyl, octafluoro-4,4'-dihydroxybiphenyl, 2,2-bis (4-hydroxyphenyl) -1,1,1,3,3 3,3-hexafluoropropane, 2,2-bis (3-hydroxyphenyl) -1,
1,1,3,3,3-hexafluoropropane, 2,2
-Bis (3-phenyl-4-hydroxyphenyl) propane, 1,1-bis (3-phenyl-4-hydroxyphenyl) cyclohexane, 4,4'-dihydroxybenzophenone, bis (3-phenyl-4-hydroxyphenyl) Sulfone, 1,1-bis (4-hydroxyphenyl) -3,3,5-trimethylcyclohexane, bis (2-hydroxyphenyl) methane, 2-hydroxyphenyl-4-hydroxyphenylmethane, bis (2-hydroxy-4 -Methylphenyl) methane, bis (6-t
tert-butyl-2-hydroxy-4-methylphenyl) methane, bis (2-hydroxy-4,6-dimethylphenyl) methane, 1,1-bis (2-hydroxy-4)
-Methylphenyl) ethane, 2,2-bis (2-hydroxy-4,6-dimethylphenyl) propane, 2,2-
Bis (2-hydroxy-4-sec-butylphenyl)
Propane, bis (4-hydroxy-3-methylphenyl) methane, bis (4-hydroxy-3,5-dimethylphenyl) methane, bis (3-fluoro-4-hydroxyphenyl) methane, bis (4-hydroxy-3) -Nonylphenyl) methane, 2,2-bis (4-hydroxy-
3,5-dimethylphenyl) propane, 2,2-bis (4-hydroxy-3-isopropylphenyl) propane, 2,2-bis (3-sec-butyl-4-hydroxyphenyl) propane, 1,1-bis (4-hydroxyphenyl) propane, 2,2-bis (4-hydroxyphenyl) pentane, 2,2-bis (4-hydroxyphenyl) hexane, 2,2-bis (4-hydroxyphenyl) nonane, 2,2 -Bis (4-hydroxyphenyl)
Decane, 2-ethyl-1,1-bis (4-hydroxyphenyl) hexane, 2,2-bis (4-hydroxyphenyl) -3-methylbutane, 1,1-bis (4-hydroxyphenyl) -3-methylbutane , 1,1-bis (4
-Hydroxyphenyl) -2-methylpropane, 1,1
-Bis (4-hydroxy-3-methylphenyl) -1-
Phenylethane, 1,1-bis (4-hydroxy-3-
Phenylphenyl) -1-phenylethane, 1,1-bis (4-hydroxy-3,5-dimethylphenyl) cyclohexane, 9,9-bis (4-hydroxyphenyl)
Fluorene, 9,9-bis (4-hydroxy-3-methylphenyl) fluorene, 9,9-bis (3-ethyl-
4-hydroxyphenyl) fluorene, 9,9-bis (4-hydroxy-3-phenylphenyl) fluorene, 4,4 ″ -dihydroxy-p-terphenyl,
4,4 ″ ′-dihydroxy-p-quarterphenyl, 2,5-bis (4-hydroxyphenyl) pyrazine, 2,5-bis (4-hydroxyphenyl) -3,6
-Dimethylpyrazine, 2,5-bis (4-hydroxyphenyl) -2,6-diethylpyrazine, 1,8-bis (4-hydroxyphenyl) menthane, 1,8-bis (4-hydroxy-3-methylphenyl ) Mentan,
1,8-bis (4-hydroxy-3,5-dimethylphenyl) menthane, 1,4-bis [2- (4-hydroxyphenyl) -2-propyl] benzene, 1,3-bis [2- (4 -Hydroxyphenyl) -2-propyl] benzene, 1,4-naphthalene diol, 1,5-naphthalene diol, 1,6-naphthalene diol, 2,6-
Examples include naphthalene diol and 2,7-naphthalene diol.

In particular, 2,2-bis (4-hydroxyphenyl) propane, 1,1-bis (4-hydroxyphenyl) -1,1-diphenylmethane, 1,1-bis (4
-Hydroxyphenyl) -1-phenylethane, 1,1
-Bis (4-hydroxyphenyl) cyclohexane,
2,2-bis (3-methyl-4-hydroxyphenyl)
Propane, 4,4'-dihydroxybiphenyl, 2,2-
Bis (3-phenyl-4-hydroxyphenyl) propane, bis (4-hydroxyphenyl) sulfone, 9,9
-Bis (4-hydroxyphenyl) fluorene, 9,9
-Bis (3-methyl-4-hydroxyphenyl) fluorene, 2,7-naphthalenediol and the like are preferred.

As the terminal terminator which can be used for producing the polycarbonate resin of the present invention, monovalent carboxylic acids and derivatives thereof, and monovalent phenols can be used. For example, p- (tert-butyl) phenol,
p-phenylphenol, p- (perfluorononylphenyl) phenol, p- (perfluoroxylphenyl) phenol, p-tert-perfluorobutylphenol, 1- (p-hydroxybenzyl) perfluorodecane, p- (2- (1H, 1H-perfluorotridecyloxy) -1,1,1,3,3,3-hexafluoropropyl) phenol, 3,5-bis (perfluorohexyloxycarbonyl) phenol, p-hydroxybenzoic acid par Fluorododecyl, p- (1H, 1H
-Perfluorooctyloxy) phenol, 2H, 2
H, 9H-perfluorononanoic acid, p-cumylphenol and the like are preferably used.

The preferable range of the total amount of the terminal terminating agent is 1 to 30 mol%, more preferably 1 to 1 as a copolymer composition ratio.
0 mol%. If it exceeds 30 mol%, the mechanical strength of the crosslinked polycarbonate resin may be reduced.
On the other hand, if it is less than 1 mol%, the melt viscosity and the solution viscosity both increase, and there is a possibility that resin production and molding processing become difficult.

As the branching agent, trivalent or higher phenol or carboxylic acid can be used. Examples of branching agents include phloroglysin, pyrogallol, 4,6-dimethyl-2,4,6-tris (4-hydroxyphenyl) -2.
-Heptene, 2,4-dimethyl-2,4,6-tris (4-hydroxyphenyl) heptane, 2,6-dimethyl-2,4,6-tris (4-hydroxyphenyl)-
3-heptene, 1,3,5-tris (2-hydroxyphenyl) benzene, 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- (4-hydroxyphenyl)-
2-propyldiphenol, 2,6-bis (2-hydroxy-5-methylbenzyl) -4-methylphenol,
2- (4-hydroxyphenyl) -2- (2,4-dihydroxyphenyl) propane, tetrakis (4-hydroxyphenyl) methane, tetrakis (4- (4-hydroxyphenylisopropyl) phenoxy) methane,
4-bis (4 ', 4 "-dihydroxytriphenylmethyl) benzene, 2,4-dihydroxybenzoic acid, trimesic acid, cyanuric acid, 3,3-bis (3-methyl-4-
(Hydroxyphenyl) -2-oxo-2,3-dihydroindole, 3,3-bis (4-hydroxyaryl)
Oxindole, 5-chloroisatin, 5,7-dichloroisatin, 5-bromoisatin and the like can be mentioned.

Of these, phloroglysin, 1,3,5-tris (4-hydroxyphenyl) benzene, 1,1,1-tris (4-hydroxyphenyl) ethane and the like are preferably used. A preferred range of the amount of the branching agent is 30 mol% or less, more preferably 5 mol% or less as a copolymer composition ratio. If it exceeds 30 mol%, both the melt viscosity and the solution viscosity increase, and there is a possibility that resin production and molding processing become difficult.

The reaction of performing polycondensation in the presence of an acid binder by using various carbonyl halides such as phosgene, chloroformate and other haloformates as a carbonate-forming compound, and a carbonate compound, etc. Usually, it is carried out in a solvent. When a gaseous carbonate-forming compound such as phosgene is used, a method of blowing it into the reaction system can be suitably employed. The proportion of the carbonate-forming compound used may be appropriately adjusted in consideration of the stoichiometric ratio (equivalent) of the reaction.

Examples of the acid binder include alkali metal hydroxides such as sodium hydroxide and potassium hydroxide; alkali metal carbonates such as sodium carbonate and potassium carbonate;
An organic base such as pyridine or a mixture thereof is used.

The proportion of the acid binder used may be appropriately determined in consideration of the stoichiometric ratio (equivalent) of the reaction. Specifically, 2 equivalents or an excess amount, preferably 2 to 10 equivalents, of the molar number of the hydroxyl group monomer at both ends of the dihydric phenol or the like (1 mol usually corresponds to 2 equivalents) is used. It is preferable to use

As the solvent, various solvents such as those used in the production of known polycarbonate resins may be used alone or as a mixed solvent. Representative examples include, for example, hydrocarbon solvents such as toluene and xylene, and halogenated hydrocarbon solvents such as methylene chloride, chloroform, and chlorobenzene.
The interfacial polycondensation reaction may be performed using two types of solvents that do not mix with each other.

In order to accelerate the polycondensation reaction, it is desirable to carry out the reaction by adding a catalyst such as a tertiary amine such as triethylamine or a quaternary ammonium salt. If desired, a small amount of an antioxidant such as sodium sulfite or hydrosulfide may be added. The reaction is
Usually, it is carried out at a temperature in the range of 0 to 150C, preferably 5 to 40C. The reaction pressure can be any of reduced pressure, normal pressure and pressurized pressure, but usually, it can be suitably performed at normal pressure or about the self-pressure of the reaction system. The reaction time depends on the reaction temperature and the like, but is usually about 0.5 minute to 10 hours, preferably about 1 minute to 2 hours.

The reduced viscosity of the obtained polycarbonate resin can be adjusted to the above range by various methods such as selection of the reaction conditions and adjustment of the amount of the terminal terminating agent or the branching agent. Also, in some cases,
Appropriate physical treatment (mixing, fractionation, etc.) and / or chemical treatment (polymer reaction,
(Partial decomposition treatment, etc.) to obtain a polycarbonate resin having a predetermined reduced viscosity.

[Crosslinked Polycarbonate Resin] The crosslinked polycarbonate resin of the present invention is obtained by crosslinking using the unsaturated bond present in the side chain of the above polycarbonate resin of the present invention. The crosslinked polycarbonate resin of the present invention is excellent in surface hardness, heat resistance, and mechanical properties because it is rich in intermolecular crosslinking. In addition, it has transparency.

The crosslinking reaction of the polycarbonate resin is as follows:
It can be carried out by ordinary radical polymerization, for example, by heating or irradiation of ultraviolet rays, infrared rays, electron beams, microwaves, or the like. Examples of the thermal polymerization initiator used for the crosslinking reaction (thermal polymerization) by heating include 2,2'-azobisisobutyronitrile and 2,2'-azo-di- (2,4-dimethylvaleronitrile). Azoyl peroxide, di-t-butyl peroxide, acetyl peroxide, t-butyl perbenzoate, peroxides such as methyl ethyl ketone peroxide, and persulfates such as ammonium persulfate and potassium persulfate.
Redox initiators such as the above peroxides and cobalt naphthenate or aromatic amines can also be used.

Examples of the photoinitiator used in the crosslinking reaction by ultraviolet irradiation include benzoin such as benzoin and benzoin methyl ether and derivatives thereof,
4'-bis (dimethylamino) benzophenone, 2-chloroanthracene, 2-methylanthraquinone, thioxanthone, diphenyldisulfide, dimethyldithiocarbamate and the like.
A value of 00 mJ / cm ² is used.

The crosslinking reaction by ionizing radiation such as an electron beam is usually performed in the absence of a catalyst, and is usually irradiated at an intensity of 2 to 10 MeV.

These cross-linking reactions may be performed in the presence of a monomer having an ethylenic double bond. When such a monomer is used, its amount is usually 1 to 50% by weight based on the total of the polycarbonate resin of the present invention and the monomer.
Is preferred. As the monomer having an ethylenic double bond suitably used in the present invention, for example, diallyl isophthalate, diallyl carbonate, diallyl ether,
Examples thereof include divinylbenzene, styrene, acrylonitrile, methacrylonitrile, methyl acrylate, methyl methacrylate, and acrylamide.

The amount of the various initiators to be used is generally 0.01 to 20 with respect to the amount of the polycarbonate resin of the present invention or the total amount of the polycarbonate resin and the monomer having an ethylenic double bond. % By weight, preferably 0.
1 to 10% by weight. If the amount is less than 0.01% by weight, the crosslinking reaction proceeds, but a long time is required, which is not preferable.

The crosslinking reaction by the above-mentioned thermal polymerization is usually carried out by 5
The reaction is performed at 0 to 160 ° C, preferably 60 to 140 ° C, and the crosslinking reaction by irradiation with ultraviolet light or the like is generally performed at 0 to 50 ° C, preferably 20 to 40 ° C.

The reaction time of the crosslinking reaction of the polycarbonate resin varies depending on the crosslinking method, the type of the monomer having an ethylenic double bond used, the monomer concentration, the type of the initiator, and the like, and cannot be specified unconditionally. But usually 0.1 to 5
0 hours, preferably 0.1 to 25 hours. Choosing a reaction time in excess of 50 hours is not economical.

The crosslinking reaction can be carried out under any pressure from reduced pressure to increased pressure, but is preferably carried out under reduced pressure or normal pressure.

The confirmation of intermolecular cross-linking can be carried out by insolubilizing the polycarbonate resin in a solvent such as methylene chloride or dimethyl sulfoxide.

The crosslinked polycarbonate resin thus obtained is excellent in mechanical properties such as transparency, surface hardness, heat resistance and impact resistance as an engineering plastic, so that it can be used for industrial materials such as electric / electronic parts, machine parts, and automobile parts. Can be used in a wide range of fields.

[0109]

The present invention will be described in more detail with reference to examples and comparative examples, but the present invention is not limited to these examples.

Example 1 52 g of 2,2-bis (4-hydroxyphenyl) propane (bisphenol A) was added to 6
A phosgene gas was blown into the solution at a rate of 950 ml / min for 15 minutes under cooling while stirring and mixing a solution dissolved in 550 ml of an aqueous solution of sodium hydroxide having a concentration of weight% and 250 ml of methylene chloride. Then, the reaction solution was allowed to stand to separate an organic layer,
A methylene chloride solution of bisphenol A polycarbonate (oligomer) was obtained. A part of the oligomer was recovered from the methylene chloride solution, and its structure was analyzed by ¹ H-NMR and GPC. As a result, it was confirmed that the oligomer was a chloroformate oligomer having a polymerization degree of 1 to 5 at both ends.

Methylene chloride was further added to the methylene chloride solution of the above oligomer to make the total amount 450 ml, and then mixed with 150 ml of an 8% by weight aqueous sodium hydroxide solution. 61 g of (allyl-4-hydroxyphenyl) propane and p-tert-butylphenol which is a molecular weight regulator was 3.
0 g was added. Then, while vigorously stirring this mixture, 2 ml of a 7% by weight aqueous solution of triethylamine was added as a catalyst, and the mixture was stirred at 28 ° C. for 1.5 ml.
A time reaction was performed. At the end of the reaction, the reaction product is diluted with 1 liter of methylene chloride and then diluted with 1.5 liter of water.
Wash once with 1 liter of 0.01N hydrochloric acid and twice with 1 liter of water, and the organic layer is poured into methanol.
The precipitated polymer was filtered and dried to obtain 110 g of a polycarbonate resin.

The reduced viscosity [η _{SP / C} ] of the polycarbonate resin thus obtained (methylene chloride solvent;
5 g / deciliter, measured at 20 ° C.) was 0.83 deciliter / g. The reduced viscosity was measured using an automatic viscosity measuring machine VMR-042 (manufactured by Rigo Co., Ltd.) using an automatic viscosity Ubbelohde improved viscometer (RM type).

The obtained polycarbonate resin was ¹ H--N
From the result of MR analysis, 3.3 ppm (2H; d), 5.0
A signal specific to an allyl group was observed at ppm (2H; d) and 5.8 ppm (1H; br). The results of IR spectral analysis, 3030cm ^-1, 1590cm ^-1, 830
Absorption of a benzene ring was observed at cm ⁻¹ and absorption by a carbonate group was observed at 1730 cm. From these analysis results,
This polycarbonate resin was found to contain 40 mol% of the repeating units derived from 2,2-bis (3-allyl-4-hydroxyphenyl) propane and 60 mol% of the repeating units derived from bisphenol A. The proportion of each repeating unit is determined by the signal derived from the allyl group in the ¹ H-NMR measurement results (3.3 ppm, 5.0 ppm).
(0 ppm, 5.8 ppm) and the integral ratio of signals derived from all aromatics.

1 part by weight of the obtained polycarbonate resin,
0.05 parts by weight of azobisisobutyronitrile (AIBN) was dissolved in 6 parts by weight of methylene chloride, and a molded product (200 mm × 50 mm × 4 mm (thickness)) was obtained by a casting method. This was heated at 140 ° C. for 10 minutes to prepare a test piece (crosslinked polycarbonate resin) containing a methylene chloride-insoluble content, and the physical properties were measured. The results are shown in Table 1.
The heat distortion temperature in Table 1 is based on JIS-K6871.
(Method A: stress 1.813 MPa), Vickers hardness is JIS-Z2244, and tensile strength is JIS-K-711.
3 (speed C: 5 mm / min). Regarding the transparency, the test piece was visually inspected, and when there was a clear defect (clouding, white spot, etc.), it was evaluated as x, and otherwise, it was evaluated as o.

The solubility of the test piece (crosslinked polycarbonate resin) was measured by adding 0.5 g of the test piece (crosslinked polycarbonate resin) to 50 ml of methylene chloride. As a result, the insoluble content was 40% by weight.

Example 2 52 g of bisphenol A in Example 1 was changed to 75 g of 1,1-bis (4-hydroxyphenyl) cyclohexane (bisphenol Z), and 2,2-bis (3-allyl-4-hydroxyphenyl) was used. ) 61 g of propane was added to 1,1-bis (3-allyl-4-
(Hydroxyphenyl) polycarbonate resin 13 having a repeating unit derived from the monomer in the same manner as in Example 1 except that the amount was changed to 52 g.
1 g was obtained.

The 1,1-bis (3-allyl-4-hydroxyphenyl) cyclohexane was prepared by the following method. 53.6 g of 1,1-bis (4-hydroxyphenyl) cyclohexane was dissolved in a methanol solution (500 ml) of NaOH (30 g), and 51.8 g of allyl bromide was slowly added, followed by refluxing for 5 hours. The obtained solution was dried under reduced pressure, dissolved in methylene chloride, washed with 0.1N hydrochloric acid, and then washed twice with water. The organic layer was separated, dried over magnesium sulfate, and then the solvent was distilled off.
By heating at 0 ° C. for 5 hours, 1,1-bis (3-
(Allyl-4-hydroxyphenyl) cyclohexane 56
g was obtained.

The reduced viscosity of the polycarbonate resin thus obtained was measured in the same manner as in Example 1, and was found to be 0.75 deciliter / g. When the obtained polycarbonate resin was analyzed by ¹ H-NMR, 3.3 ppm (2H; d) and 5.0 ppm (2
H; d), a signal specific to an allyl group was observed at 5.8 ppm (1H; br), and a signal derived from 1,1-bis (3-allyl-4-hydroxyphenyl) cyclohexane was observed at 2.1 ppm. Results of IR spectra analysis also, 3030cm ^-1, 1590cm ^-1, absorption of the benzene ring to 830 cm ^-1, absorption by carbonate groups to 1730 cm ^-1 were observed. Based on these analysis results, the structure and composition of the polycarbonate resin were analyzed by employing the calculation method of Example 1. As a result, a repeating unit derived from 1,1-bis (3-allyl-4-hydroxyphenyl) cyclohexane was obtained. And 30 mol% of a repeating unit derived from bisphenol Z.

Using the obtained polycarbonate resin,
A test piece (crosslinked polycarbonate resin) was prepared in the same manner as in Example 1, and the physical properties were measured in the same manner as in Example 1. The results are shown in Table 1. When the solubility of the crosslinked polycarbonate resin was measured in the same manner as in Example 1,
The insoluble content was 32% by weight.

Example 3 52 g of bisphenol A in Example 1 was changed to 103 g of 1-phenyl, 1-bis (3-methyl-4-hydroxyphenyl) ethane,
2,2-bis (3-allyl-4-hydroxyphenyl)
Using the same method as in Example 1 except that 61 g of propane was changed to 45 g of 9,9-bis (3-allyl-4-hydroxyphenyl) fluorene, 142 g of a polycarbonate resin having a repeating unit derived from the monomer was obtained. Was.

Incidentally, 9,9-bis (3-allyl-4-hydroxyphenyl) fluorene was prepared by the following method. A solution of 70 g of 9,9-bis (4-hydroxyphenyl) fluorene in a methanol solution of NaOH (30 g) (5 g)
00 ml) and allyl bromide.
After slowly adding 8 g, the mixture was refluxed for 5 hours. The resulting solution was evaporated to dryness under reduced pressure and dissolved in methylene chloride.
After washing with 1N hydrochloric acid, it was washed twice with water. After the organic layer was separated and dried over magnesium sulfate, the solvent was distilled off, and the mixture was directly heated at 200 ° C. for 5 hours in a nitrogen stream to give 9,9-bis (3-allyl-4-hydroxyphenyl). ) 68 g of fluorene were obtained.

The reduced viscosity of the polycarbonate resin thus obtained was measured in the same manner as in Example 1, and it was 0.83 deciliter / g. When the obtained polycarbonate resin was analyzed by ¹ H-NMR, 3.3 ppm (2H; d) and 5.0 ppm (2
H; d), a signal unique to an allyl group was observed at 5.8 ppm (1H; br). Results of IR spectra analysis also, 3030cm ^-1, 1590cm ^-1, 830cm
^-1 to the absorption of the benzene ring, the absorption due to carbonate group was observed at 1730 cm ^-1. Based on these analysis results, the structure and composition of the polycarbonate resin were analyzed using the calculation method of Example 1 to find that the 9,9-bis (3
-Allyl-4-hydroxyphenyl) fluorene was found to contain 20 mol% of the repeating units, and 1-phenyl, 1-bis (3-methyl-4-hydroxyphenyl) ethane to contain 80 mol% of the repeating units. .

Using the obtained polycarbonate resin,
A test piece (crosslinked polycarbonate resin) was prepared in the same manner as in Example 1, and the physical properties were measured in the same manner as in Example 1. The results are shown in Table 1. When the solubility of the crosslinked polycarbonate resin was measured in the same manner as in Example 1,
The insoluble content was 25% by weight.

(Example 4) In Example 1, 52 g of bisphenol A was changed to 66 g of di (4-hydroxyphenyl) ether, and 61 g of 2,2-bis (3-allyl-4-hydroxyphenyl) propane was changed to 3,3. 10 g of 'diallyl-4,4'-dihydroxybiphenyl and di (4
(Hydroxyphenyl) ether 92 g of a polycarbonate resin having a repeating unit derived from the monomer, in the same manner as in Example 1 except that the amount was changed to 14 g.
I got

Incidentally, 3,3 ′ diallyl-4,4′-dihydroxybiphenyl was prepared by the following method. 4,
37.2 g of 4'-dihydroxybiphenyl was added to NaOH
(30 g) was dissolved in a methanol solution (500 ml), 51.8 g of allyl bromide was slowly added, and the mixture was refluxed for 5 hours. The obtained solution was dried under reduced pressure, dissolved in methylene chloride, washed with 0.1N hydrochloric acid, and then washed twice with water. After separating the organic layer and drying over magnesium sulfate, the solvent was distilled off, and the mixture was directly heated at 200 ° C. for 5 hours in a nitrogen stream,
42.5 g of 3,3 ′ diallyl-4,4′-dihydroxybiphenyl was obtained.

The reduced viscosity of the polycarbonate resin thus obtained was measured in the same manner as in Example 1, and was found to be 0.95 deciliter / g. When the obtained polycarbonate resin was analyzed by ¹ H-NMR, 3.3 ppm (2H; d) and 5.0 ppm (2
H; d), a signal unique to an allyl group was observed at 5.8 ppm (1H; br). Results of IR spectra analysis also, 3030cm ^-1, 1590cm ^-1, 830cm
^-1 to the absorption of the benzene ring, the absorption due to carbonate group was observed at 1730 cm ^-1. Based on these analysis results, the structure and composition of the polycarbonate resin were analyzed using the calculation method of Example 1. As a result, the repeating unit derived from 3,3′-diallyl-4,4′-dihydroxybiphenyl contained 10 moles. %, 90 mol% of repeating units derived from di (4-hydroxyphenyl) ether.

Using the obtained polycarbonate resin,
A test piece (crosslinked polycarbonate resin) was prepared in the same manner as in Example 1, and the physical properties were measured in the same manner as in Example 1. The results are shown in Table 1. When the solubility of the crosslinked polycarbonate resin was measured in the same manner as in Example 1,
The insoluble content was 14% by weight.

Example 5 In Example 1, 52 g of bisphenol A was changed to 92 g of 3,3′-dichloro-4,4′-dihydroxybenzophenone, and 2,2-bis (3
-(Allyl-4-hydroxyphenyl) propane (61 g) was treated with di (3-allyl-4-hydroxyphenyl) sulfone 1
117 g of a polycarbonate resin having a repeating unit derived from the monomer was obtained in the same manner as in Example 1 except that 0 g and 21 g of 3,3′dichloro-4,4 dihydroxybenzophenone were used.

Incidentally, di (3-allyl-4-hydroxyphenyl) sulfone was prepared by the following method. Di (4
-Hydroxyphenyl) sulfone in 50 g of NaOH (3
0 g) in a methanol solution (500 ml), and after slowly adding 51.8 g of allyl bromide,
Reflux for 5 hours. After drying the obtained solution under reduced pressure,
It was dissolved in methylene chloride, washed with 0.1N hydrochloric acid, and then washed twice with water. After the organic layer was separated and dried over magnesium sulfate, the solvent was distilled off, and the mixture was directly heated at 200 ° C. for 5 hours in a nitrogen stream to obtain di (3-allyl-4-hydroxyphenyl) sulfone 4.
8.7 g were obtained.

The reduced viscosity of the thus obtained polycarbonate resin was measured in the same manner as in Example 1, and it was 0.86 deciliter / g. When the obtained polycarbonate resin was analyzed by ¹ H-NMR, 3.3 ppm (2H; d) and 5.0 ppm (2
H; d), a signal unique to an allyl group was observed at 5.8 ppm (1H; br). Results of IR spectra analysis also, 3030cm ^-1, 1590cm ^-1, 830cm
^-1 to the absorption of the benzene ring, the absorption due to carbonate group was observed at 1730 cm ^-1. Based on these analysis results, the structure and composition of the polycarbonate resin were analyzed using the calculation method of Example 1 and found to be di (3-allyl-
It was found to contain 5 mol% of repeating units derived from (4-hydroxyphenyl) sulfone and 95 mol% of repeating units derived from 3,3 dichloro-4,4 dihydroxybenzophenone.

Using the obtained polycarbonate resin,
A test piece (crosslinked polycarbonate resin) was prepared in the same manner as in Example 1, and the physical properties were measured in the same manner as in Example 1. The results are shown in Table 1. When the solubility of the crosslinked polycarbonate resin was measured in the same manner as in Example 1,
The insoluble content was 8% by weight.

(Comparative Example 1) Polycarbonate resin [trade name "Idemitsu Polycarbonate A-250" manufactured by Idemitsu Petrochemical Co., Ltd.]
0 "], various physical properties were measured in the same manner as in Example 1. The results are shown in Table 1.

Comparative Example 2 In Example 1, 52 g of bisphenol A was replaced with 50 g of 2,2-bis (3-allyl-4-hydroxyphenyl) propane and bisphenol A
The amount was changed to 36 g, and 61 g of 2,2-bis (3-allyl-4-hydroxyphenyl) propane was replaced with bisphenol A2.
Using the same method as in Example 1 except that it was changed to 4 g,
92 g of a polycarbonate resin having a repeating unit derived from the monomer was obtained.

The reduced viscosity of the polycarbonate resin thus obtained was measured in the same manner as in Example 1, and was found to be 0.72 deciliter / g. When the obtained polycarbonate resin was analyzed by ¹ H-NMR, 3.3 ppm (2H; d) and 5.0 ppm (2
H; d), a signal unique to an allyl group was observed at 5.8 ppm (1H; br). Results of IR spectra analysis also, 3030cm ^-1, 1590cm ^-1, 830cm
^-1 to the absorption of the benzene ring, the absorption due to carbonate group was observed at 1730 cm ^-1. Based on these analysis results, the structure and composition of the polycarbonate resin were analyzed using the calculation method of Example 1 and found to be 2,2-bis (3
It was found that the repeating unit derived from (allyl-4-hydroxyphenyl) propane contained 40 mol%, and the repeating unit derived from bisphenol A contained 60 mol%.

Using the obtained polycarbonate resin,
A test piece (crosslinked polycarbonate resin) was prepared in the same manner as in Example 1, and the physical properties were measured in the same manner as in Example 1. The results are shown in Table 1. When the solubility of the crosslinked polycarbonate resin was measured in the same manner as in Example 1,
The insoluble content was 2% by weight.

[0136]

[Table 1]

Table 1 shows that the commercially available polycarbonate resin (Comparative Example 1) has low Vickers hardness, heat deformation temperature and tensile strength. It was confirmed that the polycarbonate resin of Comparative Example 2 having an insufficient intermolecular cross-linked structure improved the above-mentioned physical properties but was inferior to the cross-linked polycarbonate resin of the present invention. In addition, it was confirmed that the crosslinked polycarbonate resin of the present invention maintained transparency and improved Vickers hardness (surface hardness), heat deformation temperature (heat resistance), and tensile strength (mechanical properties) in a well-balanced manner.

Further, from the ratio of the methylene chloride-insoluble component in the crosslinked polycarbonate resin, it was confirmed that the crosslinked polycarbonate resin of the present invention had more intermolecular crosslinks than the crosslinked polycarbonate resin of Comparative Example 2.

[0139]

The polycarbonate resin of the present invention suppresses intramolecular crosslinking in the crosslinking reaction and gives priority to intermolecular crosslinking. Therefore, the resulting crosslinked polycarbonate resin has transparency, surface hardness, heat resistance, tensile strength and the like. Has excellent mechanical properties.

Claims (8)

[Claims] 1. A composition comprising a repeating unit (I) represented by the following general formula (1) and a repeating unit (II) represented by the following general formula (2), wherein the repeating unit (I) is a polymer chain. A polycarbonate resin characterized by not being continuously present in the inside. Embedded image [R ¹ in the general formula (1) has a divalent group having a reactive unsaturated bond in a side chain, and R ² in the general formula (2) has no reactive unsaturated bond in a side chain. Represents a divalent group. ] 2. The repeating unit (I) has the following general formula (3)
2. The polyamine according to claim 1, which is a repeating unit (III) represented by the formula:
Recarbonate resin. Embedded image[X in the general formula (3) is a single bond, -O-, -S-, -SO
−, −SO_Two-, -CO-, -CR^FiveR⁶− (However,
R^FiveAnd R⁶Are each independently hydrogen or trifluoromethyl
Group, an alkyl group having 1 to 10 carbon atoms or 6 to 24 carbon atoms
An aryl group having 3 to 12 carbon atoms)
A redene group, an α, ω-alkylene group having 2 to 12 carbon atoms,
Fluorenylidene group, menthanediyl group, pyrazilidene
Group, an arylene group having 6 to 12 carbon atoms or α, ω-
A roxandiyl group,^ThreeAnd R ^FourAre independent
Hydrogen, trifluoromethyl group, halogen atom, carbon number
An alkyl group of 1 to 10, an aryl group having 6 to 24 carbon atoms,
C3-C12 cycloalkyl group, C1-C10
Alkyloxy group or arylo group having 6 to 24 carbon atoms
M and n are each independently an integer of 0 to 6
Where a to d are integers, c + d is 1 to 8, a + c
Is 4 and b + d is 4. ] 3. A compound represented by the following general formula (4):
The polycarbonate resin according to claim 1, which is a repeating unit (IV) represented by the following formula: Embedded image [In the general formula (4), Y is a single bond, -O-, -S-, -SO
_{-, - SO 2 -, -} CO -, - CR 7 R 8 - ( where
R ⁷ and R ⁸ each independently represent hydrogen, a trifluoromethyl group, an alkyl group having 1 to 10 carbon atoms, or 6 to 24 carbon atoms.
An aryl group having 3 to 12 carbon atoms, an α, ω-alkylene group having 2 to 12 carbon atoms, a fluorenylidene group, a menthanediyl group, a pyradylidene group, an arylene group having 6 to 12 carbon atoms or α, ω. R ^{9 to} R ¹⁶ are each independently hydrogen, a trifluoromethyl group, a halogen atom,
An alkyl group having 10 to 10 carbon atoms, an aryl group having 6 to 24 carbon atoms, a cycloalkyl group having 3 to 12 carbon atoms, an alkyloxy group having 1 to 10 carbon atoms, or an aryloxy group having 6 to 24 carbon atoms. ] 4. A crosslinked polycarbonate resin obtained by crosslinking the polycarbonate resin according to claim 1. 5. After forming an oligomer of haloformate at both terminals having a repeating unit (II) or (IV), a monomer (V) having a hydroxyl group at both terminals represented by the following general formula (5) or the following general formula (5): The method for producing a polycarbonate resin according to any one of claims 1 to 3, wherein the method is copolymerized with the monomer (VII) having hydroxyl groups at both ends represented by 7). Embedded image [R ¹ in the general formula (5) represents a divalent group having a reactive unsaturated bond in a side chain. X in the general formula (7) is a single bond, -O -, - S -, - SO -, - SO 2 -, - CO
—, —CR ⁵ R ⁶ — (where R ⁵ and R ⁶ are each independently hydrogen, a trifluoromethyl group, an alkyl group having 1 to 10 carbon atoms or an aryl group having 6 to 24 carbon atoms),
C3-C12 cycloalkylidene group, C2-C1
2, an α, ω-alkylene group, a fluorenylidene group, a menthanediyl group, a pyradylidene group, an arylene group having 6 to 12 carbon atoms or an α, ω-siloxanediyl group;
R ³ and R ⁴ are each independently hydrogen, a trifluoromethyl group, a halogen atom, an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 24 carbon atoms, a cycloalkyl group having 3 to 12 carbon atoms, An alkyloxy group of 10 to 10 or an aryloxy group of 6 to 24 carbon atoms, m and n are each independently an integer of 0 to 6, ad is an integer, c + d is 1 to 8, and a + c is 4, b + d is 4. ] 6. After forming an oligomer of hydroxyl groups at both ends having a repeating unit (II) or (IV), a monomer (VI) of haloformate at both ends represented by the following general formula (6) or the following general formula: The method for producing a polycarbonate resin according to any one of claims 1 to 3, wherein the copolymer is copolymerized with a monomer (VIII) of a haloformate at both ends represented by (8). Embedded image [R ¹ in the general formula (6) represents a divalent group having a reactive unsaturated bond in a side chain, and A represents a halogen atom. X in the general formula (8) is a single bond, -O-, -S-, -SO
-, -SO _2- , -CO-, -CR ⁵ R ^6- (however,
R ⁵ and R ⁶ are each independently hydrogen, a trifluoromethyl group, an alkyl group having 1 to 10 carbon atoms or a carbon atom having 6 to 24 carbon atoms.
An aryl group having 3 to 12 carbon atoms, an α, ω-alkylene group having 2 to 12 carbon atoms, a fluorenylidene group, a menthanediyl group, a pyradylidene group, an arylene group having 6 to 12 carbon atoms, or α , Ω-
R ³ and R ⁴ are each independently hydrogen, a trifluoromethyl group, a halogen atom, an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 24 carbon atoms, or a cyclo group having 3 to 12 carbon atoms. Alkyl group, having 1 to 1 carbon atoms
0 is an alkyloxy group or an aryloxy group having 6 to 24 carbon atoms, m and n are each independently an integer of 0 to 6, a to d are integers, c + d is 1 to 8, a
+ C is 4 and b + d is 4. A in the general formula (8) represents a halogen atom. ] 7. After forming an oligomer of a carbonate at both ends having a repeating unit (II) or (IV),
A hydroxyl-terminated monomer (V) represented by the general formula (5) or a monomer (VI) represented by the general formula (7)
The method for producing a polycarbonate resin according to any one of claims 1 to 3, wherein the method is copolymerized with (I). 8. After forming an oligomer having hydroxyl groups at both ends having a repeating unit (II) or (IV), a monomer (IX) of a carbonate at both ends represented by the following general formula (9) or the following general formula (10) The method for producing a polycarbonate resin according to any one of claims 1 to 3, wherein the copolymer is copolymerized with the monomer (X) of a carbonate having both terminals represented by the formula (1). Embedded image [R ¹ in the general formula (9) represents a divalent group having a reactive unsaturated bond in a side chain, and R ¹⁷ and R ¹⁸ represent a monomer (IX)
And a group which does not inhibit the polycondensation reaction between the above-mentioned hydroxyl groups at both ends and the oligomer. X in the general formula (10) is a single bond, -O
-, - S -, - SO -, - SO 2 -, - CO -, - CR
⁵ R ⁶ — (where R ⁵ and R ⁶ are each independently hydrogen, a trifluoromethyl group, an alkyl group having 1 to 10 carbon atoms or an aryl group having 6 to 24 carbon atoms), 3 carbon atoms
~ 12 cycloalkylidene group, C2 ~ 12 α,
an ω-alkylene group, a fluorenylidene group, a menthanediyl group, a pyradylidene group, an arylene group having 6 to 12 carbon atoms or an α, ω-siloxanediyl group, wherein R ³ and R ⁴ are each independently hydrogen, trifluoromethyl, halogen, Atom, alkyl group having 1 to 10 carbon atoms, 6 to carbon atoms
24 aryl group, a cycloalkyl group having 3 to 12 carbon atoms, an aryloxy group of alkyloxy group or having 6 to 24 carbon atoms having 1 to 10 carbon atoms, wherein R ^17, R ¹⁸ and monomer (X) both A group that does not inhibit the polycondensation reaction of the terminal hydroxyl group with the oligomer, m and n are each independently an integer of 0 to 6, a to d are integers, and c + d is 1
-8, a + c is 4, and b + d is 4. ]