JP2000044785A - Polycarbonate resin composition and laminate - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a polycarbonate resin compsn. and a laminate thereof, not only having mechanical strength, heat resistance, impact strength, or the like which are inherent to a polycarbonate resin, but also providing rigidity, and a satisfiable recyclability without giving an adverse effect on the surface smoothness of a molded article. SOLUTION: This polycarbonate resin compsn. comprises 99.9-0.1 wt.% of a crystalline polycarbonate with a crystallinity of >=25%, and 0.1-99.9 wt.% of a polycarbonate with a crystallinity of <25%. The laminate consists of a layer of the same crystalline polycarbonate resin and a layer of the same polycarbonate resin.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a polycarbonate resin composition comprising a crystalline polycarbonate and a polycarbonate, and to a laminate obtained by laminating a crystalline polycarbonate resin layer and a polycarbonate resin layer.

[0002]

2. Description of the Related Art Polycarbonate (hereinafter sometimes abbreviated as "PC") resins are used in large quantities as engineering plastics because of their excellent mechanical strength, heat resistance and impact resistance. Have been.
By the way, since polycarbonate resin has low rigidity compared to glass or metal, in applications where high rigidity is required, such requirements are satisfied by appropriately selecting and blending fillers such as glass fiber and carbon fiber. I have.

However, when a filler such as glass fiber or carbon fiber is added to a polycarbonate resin, its rigidity is improved, but the filler is exposed on the surface of the molded product, and the smoothness of the surface of the molded product is significantly impaired. There was a problem. To solve this problem, for example,
As disclosed in JP-A-09-157509, it is known to mix an inorganic filler having a specific particle size, but a composite material containing these fillers contains components other than polycarbonate. Therefore, it is difficult to recycle, and some inorganic fillers have a function of decomposing the polycarbonate resin, so that there is a problem that thermal stability is poor.

[0004]

DISCLOSURE OF THE INVENTION The present invention provides a polycarbonate resin that has inherent mechanical strength, heat resistance, impact resistance, and the like, and further provides rigidity without impairing the smoothness of the surface of a molded product. Further, it is an object of the present invention to provide a polycarbonate resin composition and a laminate that also satisfy recyclability.

[0005]

Means for Solving the Problems The present inventors have found that the above problems can be solved by adding a polycarbonate having a high crystallinity in place of the inorganic filler, and have completed the present invention. That is, the present invention provides the following polycarbonate resin composition and laminate. (1) A polycarbonate resin composition comprising 99.9 to 0.1% by weight of a crystalline polycarbonate having a crystallinity of 25% or more and 0.1 to 99.9% by weight of a polycarbonate having a crystallinity of less than 25%. object. (2) A laminate obtained by laminating a layer made of a crystalline polycarbonate resin having a crystallinity of 25% or more and a layer made of a polycarbonate resin having a crystallinity of less than 25%.

[0006]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention will be described below in detail. 1. Crystalline Polycarbonate (1) In the present invention, “crystalline polycarbonate” refers to one having a crystallinity of 25% or more.

Here, the crystallinity is a value obtained by the following method. That is, a differential scanning calorimeter (SEIKO)
-Instrument SSC5200) was used to raise the temperature of 5 mg of the sample from room temperature to 320 ° C at a rate of 20 ° C / min. Based on the endothermic enthalpy value at that time, the crystallinity is calculated from the following equation. Crystallinity (%) = (Endothermic enthalpy value (mJ / mg)
(109.7 is an endothermic enthalpy value of a sample having a crystallinity of 100%.) (2) Production method of crystalline polycarbonate There is no particular limitation. The method can be used.

Raw Material (A) Dihydroxy Compound For example, an aromatic dihydroxy compound and an aliphatic dihydroxy compound are mentioned, and at least one compound selected from these is used. As the aromatic dihydroxy compound, general formula (1)

[0009]

Embedded image

Compounds represented by the following formulas can be mentioned.
In the general formula (1), R ¹ and R ² are each a halogen atom of fluorine, chlorine, bromine, or iodine or an alkyl group having 1 to 8 carbon atoms, for example, a methyl group, an ethyl group, an n-
Propyl, isopropyl, n-butyl, isobutyl, sec-butyl, t-butyl, pentyl,
It represents a hexyl group, a cyclohexyl group, a hebutyl group, an octyl group, or the like. R ¹ and R ² may be the same or different. The plurality of R ¹ is when R ¹ are a plurality may be the same or different, a plurality of R ² if R ² there are a plurality may be the same or different. m and n are each an integer of 0-4. Z is a single bond, an alkylene group having 1 to 8 carbon atoms, an alkylidene group having 2 to 8 carbon atoms, a cycloalkylene group having 5 to 15 carbon atoms, a cycloalkylidene group having 5 to 15 carbon atoms, or -S-, −
SO—, —SO ₂ —, —O—, —CO— bond or formulas (2) and (3)

[0011]

Embedded image

[0012] The bond represented by Examples of the alkylene group having 1 to 8 carbon atoms and the alkylidene group having 2 to 8 carbon atoms include:
Examples thereof include a methylene group, an ethylene group, a propylene group, a butylene group, a pentylene group, a hexylene group, an ethylidene group, an isopropylidene group and the like. As a cycloalkylene group having 5 to 15 carbon atoms and a cycloalkylidene group having 5 to 15 carbon atoms, Examples thereof include a cyclopentylene group, a cyclohexylene group, a cyclopentylidene group, and a cyclohexylidene group.

Specifically, hydroquinone, 4,4'-
Dihydroxydiphenyl, bis (4-hydroxyphenyl) alkane, bis (4-hydroxyphenyl) cycloalkane, bis (4-hydroxyphenyl) oxide,
Bis (4-hydroxyphenyl) sulfide, bis (4
-Hydroxyphenyl sulfone, bis (4-hydroxyphenyl) ketone, 9,9-bis (4-hydroxyphenyl)
Examples thereof include fluorene and the like and halogen derivatives thereof. Among them, 2,2-bis (4-hydroxyphenyl) propane (bisphenol A) is preferable. As the dihydroxy compound of the component (A), one or more of the above compounds are appropriately selected and used. (B) Carbonic diester Various types are used. For example, it is at least one compound selected from diaryl carbonate compounds, dialkyl carbonate compounds and alkylaryl carbonate compounds.

The diaryl carbonate compound used as one of the components (B) is represented by the following general formula (4)

[0015]

Embedded image

Wherein Ar ¹ and Ar ² each represent an aryl group, which may be the same or different, or a compound represented by the following general formula (5):

[0017]

Embedded image

(In the formula, Ar ³ and Ar ⁴ each represent an aryl group, which may be the same or different, and D ¹ represents a residue obtained by removing two hydroxyl groups from the above aromatic dihydroxy compound. ). The dialkyl carbonate compound is represented by the following general formula (6)

[0019]

Embedded image

Wherein R ³ and R ⁴ each have 1 carbon atom
And represents an alkyl group having from 6 to 6 or a cycloalkyl group having from 4 to 7 carbon atoms, which may be the same or different. Or a compound represented by the following general formula (7)

[0021]

Embedded image

(Wherein R ⁵ and R ⁶ each have 1 carbon atom)
And a cycloalkyl group having 4 to 7 carbon atoms, which may be the same or different, and D ² represents a hydroxyl group 2 from the aromatic dihydroxy compound.
The residue excluding the number is shown. ). The alkylaryl carbonate compound is represented by the following general formula (8)

[0023]

Embedded image

(Wherein, Ar ⁵ represents an aryl group, R ⁷ represents an alkyl group having 1 to 6 carbon atoms or a cycloalkyl group having 47 carbon atoms), or the following general formula (9)

[0025]

Embedded image

(Wherein, Ar ⁶ is an aryl group, R ⁸ is an alkyl group having 1 to 6 carbon atoms or a cycloalkyl group having 4 to 7 carbon atoms, and D ³ is a group obtained by removing two hydroxyl groups from the aromatic dihydroxy compound. The compound is a compound represented by the following formula:
As the carbonic acid diester of the component (B), one or more of the above compounds are appropriately selected and used, and among these, diphenyl carbonate is preferably used. (C) Terminal terminator In the present invention, as the terminal terminator, the following general formula (1)
It is necessary to use the compound represented by 0).

[0027]

Embedded image

(Wherein X is -OH, -COOH, -CO
Cl or —NH ₂ , R is an alkyl group having a branched structure having 5 to 20 carbon atoms, and n is an integer of 1 to 5. Specifically, 4- (1,1,3,3-tetramethylbutyl) phenol, 4- (3,5-dimethylheptyl) phenol, 2- (3,5-dimethylheptyl) phenol, p-tert -Amylphenol, 3,5,5-trimethylhexanoic acid, 3,5,5-trimethylhexanoic acid chloride, 2-hexyldecanoic acid and the like, among which 4- (1,1,3,3-tetramethylbutyl) Phenol, that is, p-tert-octylphenol is preferably used. These terminal stoppers may be used alone or in combination of two or more. Furthermore, other terminal stoppers, namely, p-tert-butylphenol, p
-It may be used in combination with cumylphenol or the like. (D) Branching agent As a branching agent, if it is a compound having three or more functional groups,
There is no particular limitation. For example, 1,1,1-tris (4-hydroxyphenyl) ethane, α, α ′, α ″ -tris (4
-Hydroxyphenyl) -1,3,5-triisopropylbenzene, 1- [α-methyl-α- (4′hydroxyphenyl) ethyl] -4- [α ′, α′-bis4 ″ -hydroxyphenyl) [Ethyl] benzene, phloroglucin, trimellitic acid, isatin bis (o-cresol), β-resorcinic acid and the like.

Furthermore, 1,1,2,2-tetra (4-
Hydroxyphenyl) ethane, 1,1,3,3-tetra (4-hydroxyphenyl) propane, α, α, α ′,
α′-tetra (4-hydroxyphenyl) -p-xylene, 1,1,2,2-tetra (3-methyl-4-hydroxyphenyl) ethane, α, α, α ′, α′-tetra (3- Tetravalent phenols such as methyl-4-hydroxyphenyl) -p-xylene and α, α′-dimethyl-α, α, α ′, α′-tetra (4-hydroxyphenyl) -p-xylene may be used. .

These branching agents may be used alone or in combination of two or more. Catalyst The reaction between the dihydroxy compound and the carbonic acid diester is preferably carried out using a catalyst. The catalyst is not particularly limited, but a nitrogen-containing basic compound or a phosphorus-containing basic compound is preferably used. These may be used alone or in combination of two or more.

The nitrogen-containing organic basic compound is not particularly limited, and includes various compounds. For example, trimethylamine, triethylamine, tripropylamine, tributylamine, tripentylamine, trihexylamine,
Aliphatic tertiary amine compounds such as dimethylbenzylamine, aromatic tertiary amine compounds such as triphenylamine, N, N-dimethyl-4-aminopyridine, 4-diethylaminopyridine, 4-pyrrolidinopyridine, Aminopyridine, 2-aminopyridine, 2-hydroxypyridine, 4-hydroxypyridine, 2-methoxypyridine, 4-methoxypyridine, imidazole, 2-methylimidazole, 4-methylimidazole, 2-dimethylaminoimidazole, 2-methoxyimidazole , 2-
Examples include nitrogen-containing heterocyclic compounds such as mercaptoimidazole, aminoquinoline, and diazabicyclooctane (DABCO).

Furthermore, the following general formula _{^{(11) (NR 9 4)}} + (X 1) - quaternary ammonium salt represented by (11) can be exemplified.
In the general formula (IX), R ⁹ is an organic group such as a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group,
Examples thereof include an alkyl group such as a hexyl group, an octyl group and a cyclohexyl group, a cycloalkyl group, an aryl group such as a phenyl group, a tolyl group, a naphthyl group and a biphenyl group, and an arylalkyl group such as a benzyl group. The four R ^{9 's} may be the same or different, and two R ^{9' s} may combine to form a ring structure. X ¹ represents a halogen atom, a hydroxyl group or BR ₄ . Here, R represents a hydrogen atom or a hydrocarbon group such as an alkyl group or an aryl group,
The four Rs may be the same or different.

As such a quaternary ammonium salt,
For example, ammonium hydroxides having an alkyl group, an aryl group, an araryl group and the like, such as tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrabutylammonium hydroxide, trimethylbenzylammonium hydroxide, tetramethylammonium borohydride, tetrabutylammonium Examples include basic salts such as borohydride, tetrabutylammonium tetraphenylborate, and tetramethylammonium tetraphenylborate.

Among these nitrogen-containing organic basic compounds,
Quaternary ammonium salts represented by the above general formula (I), such as tetramethylammonium hydroxide and tetrabutylammonium, have high catalytic activity, are easily thermally decomposed, and do not easily remain in the polymer. Hydroxide, tetramethylammonium borohydride and tetrabutylammonium borohydride are preferred, and tetramethylammonium hydroxide is particularly preferred.

Such nitrogen-containing organic basic compounds may be used alone or in combination of two or more.
Examples of the phosphorus-containing basic compound include a trivalent phosphorus compound, a pentavalent phosphorus compound, and a quaternary phosphonium salt. Among them, a quaternary phosphonium salt is preferably used. The quaternary phosphonium salt is not particularly limited and includes various salts. For example, the following general formula (12) or general formula (13) (PR ¹⁰ ₄ ) ⁺ (X ² ) ^- (12) ( The compound represented by PR ¹⁰ ₄ ) ₂ ⁺ (Y ¹ ) ^2- (13) is preferably used.

In the above formulas (12) and (13), R ¹⁰ represents an organic group such as a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group and an octyl group. And alkyl groups such as cyclohexyl group and cycloalkyl group, aryl groups such as phenyl group, tolyl group, naphthyl group and biphenyl group, and arylalkyl groups such as benzyl group. Four R ¹⁰ may be the same with or different from each other, or may form a ring structure by bonding two R ^10. X ² is a halogen atom, a hydroxyl group, an alkyloxy group, an aryloxy group, R′COO, HCO ₃ , (R ′
O) shows the ₂ P (= O) O or BR '' ₄ 1 monovalent anion forming group capable of such. Here, R 'represents a hydrocarbon group such as an alkyl group or an aryl group, and two R'Os may be the same or different. R ″ represents a hydrogen atom or a hydrocarbon group such as an alkyl group or an aryl group, and the four R ″ s may be the same or different. Y ¹
Represents a group capable of forming a divalent anion such as CO ₃ .

Such quaternary phosphonium salts include:
For example, tetraphenylphosphonium hydroxide, tetranaphthylphosphonium hydroxide, tetra (chlorophenyl) phosphonium hydroxide, tetra (biphenyl) phosphonium hydroxide, tetratolylphosphonium hydroxide, tetramethylphosphonium hydroxide, tetraethylphosphonium hydroxide, tetrabutylphosphonium hydroxy (Aryl or alkyl) phosphonium hydroxides such as tetramethylphosphonium tetraphenylborate, tetraphenylphosphonium bromide, tetraphenylphosphonium phenolate, tetraphenylphosphonium tetraphenylborate, methyltriphenylphosphonium tetraphenylborate, benzyl Triphenylphosphonium La tetraphenylborate, biphenyl triphenylphosphonium tetraphenylborate, tetra-tolyl phosphonium tetraphenylborate, tetraphenylphosphonium phenolate, tetra (p-t
-Butylphenyl) phosphonium diphenyl phosphate, triphenylbutylphosphonium phenolate, triphenylbutylphosphonium tetraphenylborate and the like.

In addition to the compounds represented by the above general formulas (12) and (13), for example, bis-tetraphenylphosphonium salt of 2,2-bis (4-hydroxyphenyl) propane, ethylenebis (triphenylphosphonium) ) Dibromide, trimethylenebis (triphenylphosphonium) -bis (tetraphenylborate) and the like.

Among these quaternary phosphonium salts, phosphonium salts having an alkyl group, specifically tetrabutylphosphonium, are preferred because of their high catalytic activity, easy thermal decomposition, and low persistence in the polymer. Tetraphenyl borate, tetraethyl phosphonium tetraphenyl borate and the like are preferred. Furthermore, a quaternary phosphonium salt having an aryl group and / or a branched alkyl group can also be used. For example, the general formula _{^{(14) (R 11 n PR}} 12 4-n) + (X 3) - ···· (14) or the general formula _{^{(15) (R 11 n PR}} 12 4-n) + 2 ( Y ² ) ² -... The compound represented by (15) is used.

In the above general formula (14) or (15), n is an integer of 1 to 4. R ¹¹ represents at least one selected from an aryl group and a branched alkyl group. The term “branched alkyl group” means “R ₃ C
Wherein R is at least one selected from hydrogen, an alkyl group, an alkyl group having a substituent, an aryl group, and an aryl group having a substituent. At least two of them may combine to form a ring structure. However, this excludes the case where two are hydrogen at the same time. For example, cycloalkyl group, isopropyl group,
Examples include a branched alkyl group such as a tert-butyl group and an arylalkyl group such as a benzyl group.

When n is 2 or more, R may be the same or different. R ¹² is an alkyl group, an alkyl group having a substituent, an aryl group or an aryl group having a substituent. X ³ : halogen atom, hydroxyl group, alkyloxy group, aryloxy group, R′COO, HCO ₃ , (R′O) ₂ P
(= O) O or a group capable of forming a monovalent anion such as BR " ₄ . Here, R 'represents a hydrocarbon group such as an alkyl group or an aryl group, and two R'Os may be the same or different. R ″ represents a hydrogen atom or a hydrocarbon group such as an alkyl group or an aryl group, and the four R ″ s may be the same or different.

Y ² : a group capable of forming a divalent anion such as CO ₃ . Such quaternary phosphonium salts include, for example, tetraphenylphosphonium hydroxide,
Tetra (aryl or alkyl) phosphonium hydroxides such as tetranaphthylphosphonium hydroxide, tetra (chlorophenyl) phosphonium hydroxide, tetra (biphenyl) phosphonium hydroxide, tetratolylphosphonium hydroxide, tetrahexylphosphonium hydroxide, and methyltriphenylphosphonium Hydroxide, ethyltriphenylphosphonium hydroxide, propyltriphenylphosphonium hydroxide, butyltriphenylphosphonium hydroxide, octyltriphenylphosphonium hydroxide,
Tetradecyltriphenylphosphonium hydroxide,
Benzyltriphenylphosphonium hydroxide, ethoxybenzyltriphenylphosphonium hydroxide,
Methoxymethyltriphenylphosphonium hydroxide, acetoxymethyltriphenylphosphonium hydroxide, phenacyltriphenylphosphonium hydroxide, chloromethyltriphenylphosphonium hydroxide, bromomethyltriphenylphosphonium hydroxide, biphenyltriphenylphosphonium hydroxide, naphthyltriphenyl Phosphonium hydroxide,
Mono (aryl or alkyl) triphenylphosphonium hydroxy such as chlorophenyltriphenylphosphonium hydroxide, phenoxyphenyltriphenylphosphonium hydroxide, methoxyphenyltriphenylphosphonium hydroxide, acetoxyphenyltriphenylphosphonium hydroxide, naphthylphenyltriphenylphosphonium hydroxide (Aryl) such as phenyltrimethylphosphonium hydroxide, biphenyltrimethylphosphonium hydroxide, phenyltrihexylphosphonium hydroxide, biphenyltrihexylphosphonium hydroxide
Diaryldialkylphosphonium hydroxides such as trialkylphosphonium hydroxides, dimethyldiphenylphosphonium hydroxide, diethyldiphenylphosphonium hydroxide, di (biphenyl) diphenylphosphonium hydroxide, and further, tetraphenylphosphonium tetraphenylborate and tetranaphthylphosphonium tetraphenyl Borate, tetra (chlorophenyl) phosphonium tetraphenylborate,
Tetraaryl phosphonium tetraphenyl borates such as tetra (biphenyl) phosphonium tetraphenyl borate, tetratolyl phosphonium tetraphenyl borate, methyl triphenyl phosphonium tetraphenyl borate, ethyl triphenyl phosphonium tetraphenyl borate, propyl triphenyl phosphonium tetraphenyl borate, butyl Triphenyl phosphonium tetraphenyl borate, octyl triphenyl phosphonium tetraphenyl borate, tetradecyl triphenyl phosphonium tetraphenyl borate, benzyl triphenyl phosphonium tetraphenyl borate,
Ethoxybenzyltriphenylphosphonium tetraphenylborate, methoxymethyltriphenylphosphonium tetraphenylborate, acetoxymethyltriphenylphosphonium tetraphenylborate, phenacyltriphenylphosphonium tetraphenylborate, chloromethyltriphenylphosphonium tetraphenylborate, bromomethyltriphenylphosphonium Tetraphenyl borate, biphenyl triphenyl phosphonium tetraphenyl borate, naphthyl triphenyl phosphonium tetraphenyl borate, chlorophenyl triphenyl phosphonium tetraphenyl borate, phenoxyphenyl triphenyl phosphonium tetraphenyl borate, acetoxyphenyl triphenyl phosphonium tetraphenyl (Aryl or alkyl) triphenylphosphonium tetraphenylborate, such as naphthylphenyltriphenylphosphonium tetraphenylborate, phenyltrimethylphosphonium tetraphenylborate, biphenyltrimethylphosphonium tetraphenylborate, phenyltrihexylphosphonium tetraphenylborate, biphenyltriate Monoaryltrialkylphosphonium tetraphenylborate such as hexylphosphonium tetraphenylborate, diaryldialkylphosphonium tetraphenyl such as dimethyldiphenylphosphonium tetraphenylborate, diethyldiphenylphosphonium tetraphenylborate, di (biphenyl) diphenylphosphonium tetraphenylborate Rate class, and the like.

As the counter anion, an aryloxy group such as phenoxide, an alkyloxy group such as methoxide or ethoxide, an alkylcarbonyloxy group such as acetate or the like, or an aryloxy group such as benzoate, in place of the above hydroxides and tetraphenylborates. The above quaternary phosphonium salts using a halogen atom such as a carbonyloxy group, chloride and bromide are mentioned.

Further, in addition to the compound represented by the general formula (14), those having a divalent counter anion represented by the general formula (15), for example, bis (tetraphenylphosphonium) carbonate, bis ( Quaternary phosphonium salts such as biphenyltriphenylphosphonium) carbonate, and further, for example, bis-tetraphenylphosphonium salt of 2,2-bis (4-hydroxyphenyl) propane, ethylenebis (triphenylphosphonium) dibromide, trimethylenebis ( Triphenylphosphonium)
And bis (tetraphenyl borate).

Further, a compound represented by formula (16) or (17) is also used. _{^{((R 13 -Ph) n -PPh}} (4-n)) + (X 4) - ··· (16) ((R 13 -Ph) n -PPh (4-n)) 2 + (Y 3) ^2- (17) wherein R ¹³ represents an organic group, which may be the same or different, and X ⁴ represents a halogen atom, a hydroxyl group, an alkyloxy group, an aryloxy group, an alkylcarbonyloxy group , Arylcarbonyloxy group, HCO ₃ or BR
₄ (R represents a hydrogen atom or a hydrocarbon group, and four Rs may be the same or different), Ph represents a phenyl group, Y ³ represents CO ₃ , and n represents 1 to 4 Indicates an integer. As specific examples of such a quaternary phosphonium compound,
For example, tetraphenylphosphonium hydroxide, biphenyltriphenylphosphonium hydroxide, methoxyphenyltriphenylphosphonium hydroxide, phenoxyphenyltriphenylphosphonium hydroxide, naphthylphenyltriphenylphosphonium hydroxide, tetraphenylphosphonium tetraphenylborate, biphenyltriphenylphosphonium tetra Phenyl borate, methoxyphenyl triphenyl phosphonium tetraphenyl borate, phenoxyphenyl triphenyl phosphonium tetraphenyl borate, naphthyl phenyl triphenyl phosphonium tetraphenyl borate, tetraphenyl phosphonium phenoxide,
Biphenyltriphenylphosphonium phenoxide, methoxyphenyltriphenylphosphonium phenoxide, phenoxyphenyltriphenylphosphonium phenoxide, naphthylphenyltriphenylphosphonium phenoxide, tetraphenylphosphonium chloride, biphenyltriphenylphosphonium chloride,
Examples thereof include methoxyphenyltriphenylphosphonium chloride, phenoxyphenyltriphenylphosphonium chloride, and naphthylphenyltriphenylphosphonium chloride. Of these quaternary phosphonium salts, tetraphenylphosphonium tetraphenylborate is preferably used in view of the balance between the catalytic effect and the quality of the obtained polycarbonate.

Specific examples of the quaternary phosphonium salt containing a branched alkyl group include isopropyltrimethylphosphonium; isopropyltriethylphosphonium; isopropyltributylphosphonium; isopropyltriphenylphosphonium; tetraisopropylphosphonium; cyclohexyltriethylphosphonium; cyclohexyltrimethylphosphonium; cyclohexyltributyl Phosphonium; cyclohexyltriphenylphosphonium; tetracyclohexylphosphonium; 1,1,1-
Triphenylmethyltrimethylphosphonium; 1,1,
1-triphenylmethyltriethylphosphonium; 1,
1,1-triphenylmethyltributylphosphonium;
1,1,1-triphenylmethyltriphenylphosphonium and the like can be mentioned.

Specific examples of X ⁴ relating to the counter anion include:
Hydroxide; borohydride; tetraphenylborate; acetate; propionate;
Chloride; hydrocarbonate and the like. Specific examples of Y ² include carbonate and the like. Specific examples of the salt composed of a quaternary phosphonium (cation) containing a branched alkyl group and X or Y (anion) include various combinations of the above specific examples, and isopropyltrimethylphosphonium hydroxide Cyclohexyltriphenylphosphonium chloride; 1,1,1-triphenylmethyltriethylphosphonium acetate; bis (isopropyltriethylphosphonium) carbonate;

Among these quaternary phosphonium salts containing a branched alkyl group, cyclohexyltriphenylphosphonium tetraphenylborate and cyclopentyltriphenylphosphonium tetraphenylborate are particularly preferred because of their excellent balance between the catalytic effect and the quality of the polycarbonate obtained. used. Further, tetramethylphosphonium acetate, tetraethylphosphonium acetate, tetrapropylphosphonium acetate,
Tetrabutylphosphonium acetate, tetrapentylphosphonium acetate, tetrahexylphosphonium acetate, tetraheptylphosphonium acetate,
Tetraoctylphosphonium acetate, tetradecylphosphonium acetate, tetradodecylphosphonium acetate, tetratolylphosphonium acetate, tetraphenylphosphonium acetate, tetramethylphosphonium benzoate, tetraethylphosphonium benzoate, tetrapropylphosphonium benzoate, tetraphenylphosphonium benzoate, tetramethylphosphonium formate, Tetraethylphosphonium formate, tetrapropylphosphonium formate, tetraphenylphosphonium formate, tetramethylphosphonium propionate, tetraethylphosphonium propionate, tetrapropylphosphonium propionate, tetramethylphosphonium butyrate,
Carboxylates such as tetraethylphosphonium butyrate and tetrapropylphosphonium butyrate can also be mentioned.

It is preferable that these quaternary phosphonium salts contain as little metal impurities as possible.
In particular, those having a content of an alkali metal or alkaline earth metal compound of 50 ppm or less are preferable. Production Method of Crystalline Polycarbonate Specific procedures and conditions of a preferred production method will be specifically described.

(I) Method of Polymerizing in Solid State or Swelled Solid State Using the above raw materials (A) dihydroxy compound and (B) carbonic acid diester or phosgene, and if necessary, the above-mentioned terminal terminator or branching agent, etc. Then, a prepolymer is prepared by performing prepolymerization in the presence of the catalyst, and then the prepolymer is subjected to main polymerization in a solid state or a swollen solid state in the presence of the terminal terminating agent to obtain a crystalline form. This is a method for producing polycarbonate. In this case, the above-mentioned catalyst may be added at the time of preliminary polymerization, or may be added again at the time of main polymerization. Preferred procedures and conditions for the production method are specifically shown below.

(A) Preparation of Prepolymer by Prepolymerization By treating the dihydroxydiaryl compound and the diaryl carbonate compound with heating, the prepolymer can be prepared while the aromatic monohydroxy compound is eliminated. In this case, for example, a solvent inert to the reaction, such as methylene chloride or chloroform, may be used. However, the reaction is usually carried out without a solvent and in a molten state.

The use ratio (preparation ratio) of the dihydroxydiaryl compound and the diaryl carbonate compound varies depending on the kind used, the reaction temperature, and the reaction conditions, but the diaryl carbonate compound is used per 1 mol of the dihydroxydiaryl compound. Thus, it is usually used at a ratio of 0.9 to 2.5 mol. The catalyst is usually used in an amount of 10 ^-1 to 10 based on 1 mol of the dihydroxy compound as the raw material (A).
^-8 mol, preferably 10 ^-2 to 10 ^-7 mol, more preferably 10 ^-3 to 10 ^-6 mol. If the amount of the catalyst is less than 10 ^-8 mol, the catalytic effect may not be exhibited. On the other hand, if it exceeds 10 ^-1 mol, the physical properties of the final polycarbonate product, particularly heat resistance and hydrolysis resistance, may be reduced.

The reaction temperature and the reaction time vary depending on the kind and amount of the raw materials and the catalyst used, the required polymerization amount of the obtained prepolymer, other reaction conditions, and the like.
It is selected at a temperature of 50 ° C., preferably in the range of 1 minute to 100 hours. In order not to color the prepolymer, it is desirable to carry out the prepolymerization reaction at a temperature as low as possible and in a short time. In this prepolymerization, a prepolymer having a relatively low molecular weight may be produced, so that a colorless and transparent prepolymer having a required degree of polymerization can be easily obtained under the above conditions. The pressure during the reaction is preferably 1 Torr or more.
It is 5 kg / cm ² G.

Further, in order to obtain a spherical prepolymer, an organic solvent solution of the polycarbonate prepolymer is supplied to a granulation container in which the prepolymer powder obtained in the prepolymerization step is present, and the organic solvent solution is obtained. The organic solvent may be evaporated while contacting the powder with the polycarbonate prepolymer powder to form a spherical prepolymer. further,
Preferably, the prepolymer may be crystallized by performing a solvent treatment or heating.

(B) Main polymerization After preparing the polycarbonate prepolymer, the prepolymer is subjected to main polymerization in a solid state or a swollen solid state. In the main polymerization, the above-mentioned catalysts can be used as the catalyst. The above-mentioned terminal stoppers can also be used. a. Polymerization in Solid State The solid prepolymer in the crystallized state is further polymerized. In this case, the reaction is promoted by extracting the aromatic monohydroxy compound, the diaryl carbonate compound, or both, which are by-produced by the reaction, out of the system. For this purpose, it is preferable to introduce an inert gas such as nitrogen or a lower hydrocarbon gas, etc., to remove the gas accompanying the gas, to carry out the reaction under reduced pressure, or to use a combination of these. Used.

There is no particular limitation on the shape of the crystallized prepolymer when this solid-phase polymerization reaction is carried out, but a shape such as a pellet or a bead is preferred. As a reaction catalyst in this solid-phase polymerization, even if it is added in the prepolymer production step and the remaining one is used as it is,
Alternatively, the catalyst may be added again in a powder, liquid or gas state. At this time, the amount of the catalyst is adjusted so as to be usually 10 ^-1 to 10 ^-6 mol, preferably 10 ^-2 to 10 ^-5 mol, per 1 mol of the unit derived from the dihydroxy compound as the component (A). . If the amount of the catalyst is less than 10 ^-6 mol, the crystallinity of the obtained polycarbonate may not be 25% or more. On the other hand, if it exceeds 10 ^-1 mol, the physical properties of the final polycarbonate product, particularly heat resistance and hydrolysis resistance, may be reduced.

Regarding the reaction temperature and the reaction time of the polymerization,
Although it depends on various conditions, preferably at a temperature not lower than the glass transition temperature of the target aromatic polycarbonate, and at a temperature in a range in which the crystallized prepolymer during the solid-state polymerization keeps the solid state without melting, for 1 minute to 100 hours. It is performed by heating. b. Polymerization in Swelled Solid State This is a method in which the prepolymer obtained in the prepolymerization step is crystallized and then further polymerized by solid state polymerization in a state swollen by a swelling gas described later.

This method can be divided into a flake forming step of the prepolymer obtained as described above, and a high-molecular weight forming step (solid swelling solid-state polymerization step) in which solid-phase polymerization is performed under the flow of a swelling solvent. In the flake forming step, a conventionally known method, for example, a rolling granulation method, an extrusion granulation method, or the like is used as the case may be.

Next, in the swelling solid phase polymerization step, the molecular weight of the prepolymer is further increased while maintaining the flakes in the solid state. This step is characterized in that solid-phase polymerization is performed in an atmosphere of a swelling solvent to remove phenol produced as a by-product.
Through this step, it is possible to lower the temperature as compared with a normal melt transesterification reaction, and further, it is possible to greatly shorten the reaction time as compared with a normal solid-state polymerization or melt transesterification. The swelling solvent used here is a solvent capable of swelling the polycarbonate under the following reaction conditions, a mixture of two or more of them, or one or more poor solvents for the polycarbonate in the solvent or a mixture thereof. It is a mixture of several kinds. The swelling state in this step means, under the reaction conditions described below,
This refers to a state in which the prepolymer flakes, which are the reaction raw materials, are increased in volume or weight above the thermal swelling value. The swelling solvent is a single compound having a boiling point of completely vaporizing under the following reaction conditions, or a single compound having a vapor pressure of usually 50 mmHg or more, or a mixture thereof, and can simultaneously form the above-mentioned swelling state. A thing.

Such a swelling solvent is not particularly limited as long as it satisfies the above swelling conditions. For example, aromatic compounds and oxygen-containing compounds having a solubility parameter in the range of usually 4 to 20 (cal / cm ³ ) ^1/2 , preferably 7 to 14 (cal / cm ³ ) ^1/2 are applicable. Specific swelling solvents include, for example, benzene, toluene, xylene, ethylbenzene,
Aromatic hydrocarbons such as diethylbenzene, propylbenzene and dipropylbenzene; ethers such as tetrahydrofuran and dioxane; ketones such as methyl ethyl ketone and methyl isobutyl ketone. Among these, a single compound of an aromatic hydrocarbon having 6 to 20 carbon atoms or a mixture thereof is preferable.

The conditions of the poor solvent mixed with the swelling solvent are as follows. Under the reaction conditions described below, the solubility of the polycarbonate in the solvent is 0.1% by weight or less, and there is little possibility of being involved in the reaction. A saturated hydrocarbon compound having 4 to 18 carbon atoms having a chain, or an unsaturated hydrocarbon compound having 4 to 18 carbon atoms and a low degree is preferred. If the boiling point of both the swelling solvent and the poor solvent exceeds 250 ° C., it becomes difficult to remove the residual solvent, and the quality may deteriorate, which is not preferable.

When a mixture of such a poor solvent and a swelling solvent is used, 1% by weight of the swelling solvent is contained in the mixed solvent.
The swelling solvent is preferably contained in the mixed solvent in an amount of at least 5% by weight. Alternatively, the poor solvent may be used alone. In this swelling solid phase polymerization step, the reaction temperature is preferably 100 to 240 ° C., and the pressure during the reaction is preferably 10 Torr to 5 kg / cm ² G, particularly preferably at atmospheric pressure. If the reaction temperature is lower than the above range, the transesterification reaction does not proceed, and under the high temperature condition where the reaction temperature exceeds the melting point of the prepolymer, the solid state cannot be maintained, and phenomena such as fusion between particles occur. Properties are significantly reduced. Therefore, the reaction temperature must be lower than the melting point.

As the reaction catalyst in the swelling solid-state polymerization step, the catalyst added in the prepolymer production step and the remaining catalyst may be used as it is, or the catalyst may be powdered again.
It may be added in a liquid or gaseous state. The swelling solvent gas may be supplied to the reactor in a liquid state and vaporized in the reactor, or may be supplied to the reactor after being vaporized by a heat exchanger or the like in advance. The flow rate of the swelling solvent gas is 1 × 10 ^-3
cm / s or more, preferably 1 × 10 ⁻³ cm
/ S or more is good. Further, it is preferable that a gas supply amount of 0.5 liter (standard state) / hr or more per gram of the prepolymer is supplied to the reactor.

The step of drying and pelletizing the polycarbonate having a high molecular weight may be performed by a known method. When mixing the additives, it is preferable to apply the additive powder directly to the flakes before or after drying, or to spray the liquid and absorb the gas, but it is also possible to mix them with an extruder at the time of pelletizing. The mixing ratio between the inert gas and the swelling solvent may be such that the mixing solvent gas contains at least 1% by volume of the swelling solvent, and preferably 5% by volume or more of the swelling solvent is mixed with the mixed solvent. It is better to let it. (Ii) Further, known methods such as a method of subjecting a polycarbonate resin having a low crystallinity obtained by a known method to a heat treatment at a temperature equal to or higher than the glass transition point, a method by a solvent treatment, a method by a plasticizer treatment, and the like. The crystallinity may be improved by performing it alone or in combination. 2. Polycarbonate having a degree of crystallinity of less than 25% (1) Method for producing polycarbonate having a degree of crystallinity of less than 25% There is no particular limitation, and any known method, for example, JP-A-09-2
It can be produced by the method described in JP-A-35368 and JP-A-10-45896.

Specifically, the following melting method can be mentioned. Melting Method The transesterification reaction between the dihydroxy compound of the component (A) and the carbonic acid diester of the component (B) is performed in a molten state at a ratio such that the molar ratio of the carbonic acid diester to the dihydroxy compound is 0.9 to 1.5 times. . In addition, depending on the situation, 0.98 ~
1.20 moles are preferred. In the above transesterification reaction, when the amount of the terminal terminating agent is in the range of 0.05 to 10 mol% with respect to the dihydroxy compound as the component (A), the balance between impact resistance and fluidity is obtained. This is preferable because a polycarbonate excellent in water content can be obtained. Such a terminal terminator may be previously added to the reaction system in its entirety. Alternatively, a part may be added to the reaction system in advance, and the remainder may be added as the reaction proceeds. Further, in some cases, the whole amount may be added to the reaction system after the transesterification reaction between the dihydroxy compound of component (A) and the diester carbonate of component (B) partially proceeds.

The catalyst is usually used in an amount of 10 ^-1 to 10 ^{-8 based on} 1 mol of the dihydroxy compound as the component (A).
Mol, preferably 10 ^-2 to 10 ^-7 mol, more preferably 10 ^-3 to 10 ^-6 mol.
If it exceeds 10 ^-1 mol, the physical properties of the final polycarbonate product, particularly heat resistance and hydrolysis resistance, may be reduced.

In carrying out the transesterification, the reaction temperature is not particularly limited and is usually selected in the range of 100 to 330 ° C., preferably in the range of 180 to 300 ° C.
More preferably, 180 to 180
A good method is to raise the temperature to 300 ° C. If the temperature of this transesterification reaction is lower than 100 ° C., the reaction rate becomes slow. On the other hand, if the temperature exceeds 330 ° C., side reactions occur or the produced polycarbonate is colored, which is not preferable. The reaction pressure is set according to the vapor pressure of the monomer used and the reaction temperature. This may be set so that the reaction is performed efficiently, and is not limited. Usually, in the early stage of the reaction, 1 to 5
Atmospheric pressure (normal pressure) up to 0 atm (760-38,000 torr) or pressurized state.
In many cases, the pressure is reduced, preferably 0.01 to 100 torr.

The reaction may be carried out until the target molecular weight is reached, and is usually about 0.2 to 10 hours. The above transesterification reaction is usually carried out in a molten state in the absence of an inert solvent, but may be carried out in the presence of an inert solvent in an amount of 1 to 150% by weight of the obtained polycarbonate, if necessary. . Here, as the inert solvent,
For example, aromatic compounds such as diphenyl ether, halogenated diphenyl ether, benzophenone, polyphenyl ether, dichlorobenzene, and methylnaphthalene;
Tricyclo (5,2,10) decane, cyclooctane,
And cycloalkanes such as cyclodecane.
If necessary, the reaction may be performed in an inert gas atmosphere. Examples of the inert gas include gases such as argon, carbon dioxide, nitrous oxide, and nitrogen, chlorofluorohydrocarbon, ethane, and propane. And alkenes such as ethylene and propylene. If necessary, an antioxidant may be added to the reaction system.

As the reaction proceeds, phenols and alcohols corresponding to the used carbonic acid diester, or their esters and an inert solvent are eliminated from the reactor. Purification and recycling are also possible, and it is preferable to have equipment for removing these. In addition, the reaction can be performed in a batch system or a continuous system, and any device can be used. In the case of continuous production, it is preferable to use at least two or more reactors and set the above reaction conditions. The material and structure of the reactor used are not particularly limited, but may be any one having a normal stirring function. However,
Since the viscosity increases in the latter stage of the reaction, those having a high-viscosity type stirring function are preferable. Further, the shape of the reactor is not limited to a tank type, and may be an extruder type reactor or the like.

After completion of the transesterification reaction, in order to improve the quality (coloring) of the obtained polycarbonate,
It is preferable to heat-treat the reaction product at a temperature equal to or higher than the decomposition temperature of the catalyst, preferably around 300 ° C., and to thermally decompose the catalyst. 3. Polycarbonate resin composition (1) Polycarbonate 9 having a crystallinity of 25% or more
9.9-0.1% by weight, preferably 99.0-1.0% by weight, more preferably 95.0-5.0% by weight, and polycarbonates 0.1-99 having a crystallinity of less than 25%. It is composed of 0.9% by weight, preferably 1.0 to 99.0% by weight, and more preferably 5.0 to 95.0% by weight.

If the content of the crystalline polycarbonate is less than 0.1% by weight, the rigidity may not be improved. If it exceeds 99.9% by weight, it may become brittle. (2) The difference in crystallinity between a polycarbonate having a crystallinity of 25% or more and a polycarbonate having a crystallinity of less than 25% is not particularly limited, but is usually 10% or more, preferably 20% or more, and furthermore It is preferably at least 30%. (3) The polycarbonate resin composition according to the present invention may contain various additives as long as the object of the present invention is not impaired. For example, hindered phenol-based, ester-based, phosphate-based, amine-based antioxidants,
UV absorbers, internal lubricants, common flame retardants, flame retardant aids, release agents, antistatic agents, coloring agents and the like. (4) Method for Producing Polycarbonate Resin Composition The polycarbonate resin composition according to the present invention has a crystallinity of 2% or more and a polycarbonate having a crystallinity of 2% or more.
It can be produced by mixing both components of the polycarbonate at less than 5% by dry blending or the like. (5) Molding Using Polycarbonate Resin Composition The polycarbonate resin composition according to the present invention can be molded by various known molding methods such as press molding and injection molding, but press molding is particularly preferably used. In molding, the temperature is usually preferably 280 to 320 ° C.
3. A laminate formed by laminating a layer made of a polycarbonate resin having a crystallinity of 25% or more and a layer made of a polycarbonate resin having a crystallinity of less than 25% (1) The crystallinity in the present invention is 25% or more And the polycarbonate having a crystallinity of less than 25% are the same as those described for the polycarbonate resin composition. (2) There are no particular restrictions on the mode of lamination in the laminate, and it may be appropriately selected according to the purpose. In particular,
Not only those consisting of a crystalline PC layer and a PC layer,
Examples thereof include those having a three-layer structure of PC layer / crystalline PC layer / PC layer, crystalline PC layer / PC layer / crystalline PC layer. (3) The ratio of the thickness of the crystalline PC layer to the thickness of the PC layer is also not particularly limited, and the thickness of the crystalline PC layer may be appropriately selected according to the value of the required elastic modulus of the target laminate. .

[0072]

Next, the present invention will be described in more detail with reference to examples, but the present invention is not limited to these examples. [Synthesis Example] Production of crystalline polycarbonate In a nickel steel autoclave with an internal volume of 1 liter and equipped with a stirrer, 228 g (1.0 mol) of bisphenol A (BPA), 224.7 g (1.05 mol) of diphenyl carbonate, tetramethylammonium Hydroxide (TM
AH) 0.5 mmol was added, and the atmosphere was replaced with argon five times. Thereafter, the mixture was heated to 180 ° C. and reacted under an argon atmosphere for 30 minutes. Then gradually increase the temperature to 210
At the same time as increasing the temperature to 60 mmHg.
The reaction was carried out for 0 minute, and the temperature was raised to 240 ° C., and at the same time, the degree of vacuum was raised to 40 mmHg and the reaction was carried out for 30 minutes. After raising the degree of vacuum to 10 mmHg and reacting for 20 minutes,
The reaction was carried out at 70 ° C for 20 minutes, and the degree of vacuum was raised to 1 mmHg.
The reaction was allowed to complete for a minute.

After the completion of the reaction, the inside of the reactor was returned to the atmospheric pressure with argon, and the content of the prepolymer was taken out and pulverized. The viscosity average molecular weight of this prepolymer was 7,000, and the terminal was 44.6% of phenyl carbonate. The prepolymer thus obtained was dissolved in methylene chloride, and then cyclohexyltriphenylphosphonium tetraphenylborate (10 ^-4 mol / BPA mol) was added. Then, n-heptane was added to precipitate a powder, After concentration to dryness, vacuum drying was performed to obtain a prepolymer powder. 40 g of this powder is SUS with a diameter of 10 cm and a length of 200 cm.
The mixture was placed in a tube, and argon was flowed at a rate of 50 ml / min, the temperature was raised from room temperature to 240 ° C., and solid-state polymerization was performed for 4 hours and 20 minutes to obtain a polycarbonate. Crystallinity is 50
%, Melting point: 283 ° C. The molecular weight is 24,20
It was 0. [Evaluation method] The evaluation method of the items in the examples and comparative examples is as follows. -Viscosity average molecular weight (Mv) The intrinsic viscosity [η] of the methylene chloride solution at 20 ° C was measured using an Ubbelohde type viscosity tube, and calculated by the following relational expression.

[Η] = 1.23 × 10 ⁻⁵ · Mv ^0.83 · Crystallinity Using a differential scanning calorimeter (SSC5200, manufactured by SEIKO-Instrument), 5 mg of a sample was sampled from room temperature to 320 ° C at 20 ° C / min. The temperature was raised at a rate of temperature increase. The crystallinity was calculated from the following equation based on the endothermic enthalpy value at that time.

Crystallinity (%) = (Endothermic enthalpy value (mJ / mg) /109.7) × 100 (where, 109.7 is an endothermic enthalpy value of a sample having a crystallinity of 100%). Flexural modulus Measured according to JIS K-7203. Example 1 A polycarbonate ("Teflon FN2500" manufactured by Idemitsu Petrochemical Co., Ltd., crystallinity: 20%) and the crystalline polycarbonate obtained in the above Synthesis Example were dry-blended at a weight ratio of 90:10, and heated at 110 ° C. After vacuum drying overnight, 5cm x 5cm x (thickness) 0.5cm at 280 ° C
Was press-formed. This is 1cm x 5cm x
(Thickness) The sheet was cut to 0.5 cm, and a bending test was performed at a bending speed of 0.5 mm / min. Flexural modulus is 3090 (MP
a). [Example 2] In Example 1, the weight ratio of the polycarbonate ("Taflon FN2500" manufactured by Idemitsu Petrochemical Co., Ltd.) to the crystalline polycarbonate obtained in the above synthesis example was 80:20.
The procedure was performed in the same manner as in Example 1 except that the above was changed. The flexural modulus was 3100 (MPa). [Example 3] In Example 1, the weight ratio of polycarbonate ("Taflon FN2500" manufactured by Idemitsu Petrochemical Co., Ltd.) to the crystalline polycarbonate obtained in the above synthesis example was 50:50.
The procedure was performed in the same manner as in Example 1 except that the above was changed. The flexural modulus was 3100 (MPa). [Comparative Example 1] In Example 1, the weight ratio of the polycarbonate ("Taflon FN2500" manufactured by Idemitsu Petrochemical Co., Ltd.) to the crystalline polycarbonate obtained in the above synthesis example was 100:
0, that is, in the same manner as in Example 1 except that only the polycarbonate was changed. The flexural modulus is 2930 (M
Pa). [Comparative Example 2] In Example 1, the weight ratio of the polycarbonate ("Taflon FN2500" manufactured by Idemitsu Petrochemical Co., Ltd.) to the crystalline polycarbonate obtained in the above Synthesis Example was 0:10.
0, that is, in the same manner as in Example 1 except that only the crystalline polycarbonate was changed. A sufficient test piece could not be prepared, and measurement of flexural modulus was impossible. [Example 4] A sheet (0.2 m thick) made of polycarbonate ("Taflon FN2500" manufactured by Idemitsu Petrochemical Co., Ltd.)
m) and a sheet (0.2 mm thick) made of the crystalline polycarbonate obtained in the above synthesis example were laminated in three layers so as to have a crystalline PC / PC / crystalline PC, and pressed at 280 ° C. This was subjected to a bending test under the same conditions as in Example 1.
The flexural modulus was 3220 (MPa). Example 5 Using the same sheet as used in Example 4,
The same operation as in Example 4 was performed except that PC / crystalline PC / PC was used. The flexural modulus was 3070 (MPa). Comparative Example 3 A sheet (0.2 m thick) made of polycarbonate ("Teflon FN2500" manufactured by Idemitsu Petrochemical Co., Ltd.)
m) was performed in the same manner as in Example 4 except that only m) was laminated in three layers and pressed at 280 ° C. Flexural modulus is 2800 (MP
a).

[0076]

According to the present invention, the rigidity is further given to the mechanical strength, heat resistance, impact resistance, etc. inherently possessed by the polycarbonate resin, and the recyclability is improved without impairing the smoothness of the molded product surface. A polycarbonate resin composition and a laminate satisfying the above conditions were also obtained.

 ──────────────────────────────────────────────────続 き Continued on the front page F term (reference) 4F100 AK45A AK45B AL05A BA01 BA02 BA26 GB51 JA11A JA11B JJ03 JK01 JK10 JK15 JL16 YY00A YY00B 4J002 CG001 CG002 CG011 CG012 GF00

Claims (2)

[Claims] 1. A crystalline polycarbonate having a crystallinity of 25% or more, from 99.9 to 0.1% by weight, and a crystallinity of 25%.
% Polycarbonate resin composition of less than 0.1% to 99.9% by weight. 2. A laminate comprising a layer made of a crystalline polycarbonate resin having a crystallinity of 25% or more and a layer made of a polycarbonate resin having a crystallinity of less than 25%.