JP2613338B2 - Polycarbonate resin composition and method for producing the same - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a polycarbonate resin composition and a method for producing the same, and more particularly to a polycarbonate resin composition having excellent transparency and a method for producing the same effectively.

[0002]

2. Description of the Related Art Polycarbonate resins have excellent mechanical strength, electrical properties, transparency, etc.
It is widely used in various fields such as electronic devices and automobiles. As a polycarbonate resin having such characteristics, a glass fiber reinforced polycarbonate resin to which glass fibers are added in order to improve rigidity and dimensional stability is well known. However, polycarbonate resins have the drawback that the addition of glass fibers significantly reduces the transparency and gives an unpleasant translucent or hazy appearance. This is due to the difference in the refractive index (n _D ) between the polycarbonate resin and the glass fiber. The refractive index of polycarbonate resin is about 1.585
The "E" glass widely used for glass fiber reinforced resin has a difference of about 1.545, which is a considerable difference. As a method for improving this disadvantage, Japanese Patent Publication No. Sho 62
As disclosed in JP-A-1338, a special glass fiber obtained by adding ZrO ₂ or TiO ₂ having a refractive index improving effect to SiO ₂ , which is a main component of glass, is blended with a polycarbonate resin. However, the addition of TiO ₂ has a problem that the polycarbonate resin is colored brown. Further, there is a disadvantage that adding ZrO ₂ or TiO ₂ to glass increases the cost.

[0003] The inventors of the present invention have intensively studied to solve the drawbacks of the conventional method and to develop a polycarbonate resin composition having excellent transparency. As a result, the type and ratio of the comonomer units to be copolymerized with the polycarbonate are selected, and resins having different refractive indices composed of the comonomer units are copolymerized (block or grafted) or the comonomer units are copolymerized (randomly). As a result, it has been found that a polycarbonate resin composition having desired properties can be obtained by mixing a polycarbonate copolymer having a changed refractive index with E glass and a polycarbonate resin. In addition, they have found that a desired polycarbonate resin composition can be obtained by using a linear aliphatic dicarboxylic acid or bisphenol C as a copolymer component. The present invention has been completed based on such findings.

[0004]

That is, the present invention provides:
(A) The type of comonomer unit is organosiloxane unit
Position, acrylic monomer unit, spiro ring-containing bispheno
Dihydric phenol units excluding alcohols or linear aliphatic 2
Polycarbonate copolymer which is a polycarboxylic acid unit 1
0 to 95% by weight, (B) 5 to 70% by weight of E glass and (C) 0 to 85% by weight of a polycarbonate resin, and the type and ratio of comonomer units in the polycarbonate copolymer (A) are determined. By selecting
A polycarbonate resin characterized in that the difference (absolute value) between the refractive index of the mixed resin of (A) and (C) and the refractive index of (B) E glass is adjusted to 0.01 or less. The present invention provides a method for producing a composition. The present invention also relates to (A) a polycarbonate copolymer 1 containing a linear aliphatic divalent carboxylic acid or bisphenol C as a copolymerization component.
0-95% by weight, (B) 5-70% by weight of E glass and (C) 0-85% by weight of polycarbonate resin,
A polycarbonate resin composition, wherein the difference (absolute value) between the refractive index of the mixed resin of (A) and (C) and the refractive index of (B) E glass is 0.01 or less. It also provides things.

First, in the method for producing a polycarbonate resin composition of the present invention, the comonomer unit of the component (A)
Is an organosiloxane unit or an acrylic monomer
-Unit, divalent pheno, excluding spiro ring-containing bisphenol
Or a straight-chain aliphatic dicarboxylic acid unit.
That polycarbonate-based copolymer, by selecting the type and proportion of the comonomer units of the polycarbonate-based copolymer, to be close to the refractive index to the refractive index of the E glass. That is, as a polycarbonate-based copolymer having a different refractive index that can be made smaller than the refractive index of the polycarbonate resin, the comonomer unit has an comonomer unit of O.
Luganosiloxane unit, acrylic monomer unit, spin
Dihydric phenol units excluding b-ring-containing bisphenol or
Those which are linear aliphatic bivalent carboxylic acid units are most preferred.
However, ether glycol units can also be used. Also,
The different copolymer resin having a refractive index can be made larger than the refractive index of the polycarbonate resin, a polycarbonate - there is a polystyrene copolymer, generally, E moth
Refractive index of the lath is smaller than the refractive index of the polycarbonate resin. Therefore, a polycarbonate copolymer having a refractive index smaller than that of the polycarbonate resin is required.
Become. It is also the main monomer of polycarbonate resin
Reducing the refractive index by copolymerization with bisphenol A
Of the comonomer of the dihydric phenol unit
The following may be mentioned as examples . A) 3,3-bis (3-cyclohexyl-4-hydroxyphenyl) pentane b) 2,2-bis (3-cyclohexyl-4-hydroxyphenyl) propane c) 1,1-bis (3-cyclohexyl- 4-hydroxyphenyl) cyclohexane d) bis (3-cyclohexyl-4-hydroxyphenyl)
Diphenylmethane e) 1,1-bis (3-methyl-4-hydroxyphenyl) propane [bisphenol C] f) 1,1- (3-cyclohexyl-4-hydroxyphenyl)-
1-phenylethane g) 3,3-bis (4-hydroxyphenyl) pentane h) 2,2-bis (4-hydroxyphenyl) -1,1,1,3,3,3-hexafluoropropane (bisphenol AF : BPAF]. Among them, BPAF is effective. As examples of the divalent carboxylic acid, straight-chain aliphatic as comonomer which can change the refractive index by copolymerization, for example, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, decane dicarboxylic acid Is mentioned. In particular, it is effective for those having a long aliphatic chain. These effective polycarbonate-based copolymers
They may be mixed and used to obtain a desired refractive index. When the refractive index of these polycarbonate copolymers is smaller than the desired value, the desired refractive index can be obtained by mixing an appropriate amount of a general polycarbonate resin.

Here, typical examples of the polycarbonate-based copolymer will be specifically described. First,
A resin having a different refractive index is copolymerized with a polycarbonate resin, and the refractive index is smaller than that of the polycarbonate resin.
A polycarbonate-polyorganosiloxane copolymer in which the comonomer unit is an organosiloxane unit (PC
-PDMS copolymer) will be described. The polycarbonate-polyorganosiloxane copolymer may be of various types, but is preferably of the general formula (I)

[0007]

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[In the formula, X is a hydrogen atom, a halogen atom (eg, chlorine, bromine, fluorine, iodine) or an alkyl group having 1 to 8 carbon atoms. When a plurality of Xs are present, they are the same. A and b may each be an integer of 1 to 4. Y 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 general formula (II)

[0009]

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[0010] The bond represented by Having a repeating unit having a structure represented by the following formula, and a polycarbonate part having a degree of polymerization of 3 to 50;

[0011]

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Wherein R ¹ , R ² and R ³ are each a hydrogen atom, an alkyl group having 1 to 5 carbon atoms or a phenyl group, which may be the same or different. Further, c and d are each an integer of 0 or 1 or more. And a polyorganosiloxane part having a repeating unit represented by the formula: The degree of polymerization of the polyorganosiloxane moiety is preferably 100 or less, more preferably 50 or less. If the degree of polymerization exceeds 100, the transparency of the copolymer decreases, which is not preferable. The above-mentioned polycarbonate-polyorganosiloxane copolymer is a block comprising a polycarbonate part having a repeating unit represented by the general formula (I) and a polyorganosiloxane part having a repeating unit represented by the general formula (III). A copolymer having a viscosity average molecular weight of 10.0
00 to 40,000, preferably 15,000 to 35,000
belongs to.

The ratio of the polycarbonate part and the polyorganosiloxane part in the polycarbonate-polyorganosiloxane copolymer depends on the required refractive index and cannot be determined uniquely, but is usually 50 to 99.9. % By weight, preferably 60-9
The content is selected in the range of 9.5% by weight, 50 to 0.1% by weight, preferably 40 to 0.5% by weight of the polyorganosiloxane part.
Such a polycarbonate-polyorganosiloxane copolymer includes, for example, a polycarbonate oligomer (PC oligomer) constituting a polycarbonate portion prepared in advance and a polyorganosiloxane having a reactive group at a terminal constituting a polyorganosiloxane portion. (For example,
Polydialkylsiloxanes such as polydimethylsiloxane and polydiethylsiloxane or polymethylphenylsiloxane) with methylene chloride, chlorobenzene,
It can be produced by dissolving in a solvent such as chloroform, adding an aqueous sodium hydroxide solution of bisphenol, and performing an interfacial reaction using triethylamine or trimethylbenzylammonium chloride as a catalyst.
Japanese Patent Publication No. 44-30105 and Japanese Patent Publication No. 45-2
It is also possible to use a polycarbonate-polyorganosiloxane copolymer produced by the method described in JP-A-0510. Here, the polycarbonate oligomer having a repeating unit represented by the general formula (I) is represented by the general formula (IV)

[0014]

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Wherein X, Y, a and b are the same as above, and Hal is a halogen atom (eg, chlorine, bromine,
Fluorine, iodine), and t = 2 to 80. ]. This polycarbonate oligomer is prepared by a solvent method,
That is, a known acid acceptor in a solvent such as methylene chloride,
Formula (V) in the presence of a molecular weight regulator

[0016]

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(Wherein X, Y, a and b are the same as described above), and are easily produced by reacting a dihydric phenol represented by the following formula with a carbonate precursor such as phosgene or a carbonate compound. be able to. That is, for example, by reacting a dihydric phenol with a carbonate precursor such as phosgene in a solvent such as methylene chloride in the presence of a known acid acceptor or molecular weight regulator, or as in the case of dihydric phenol and diphenyl carbonate. It is produced by a transesterification reaction with a suitable carbonate precursor. Here, there are various dihydric phenols represented by the general formula (V).
2-bis (4-hydroxyphenyl) propane [bisphenol A] is preferred. Further, bisphenol A may be obtained by partially or entirely substituting another dihydric phenol. Examples of the dihydric phenol other than bisphenol A include 1,1- (4-hydroxyphenyl) methane as bis (4-hydroxyphenyl) alkane other than bisphenol A; 1,1- (4-hydroxyphenyl) ethane; hydroquinone; Bis (4-hydroxyphenyl) cycloalkane; bis (4-hydroxyphenyl) sulfide; bis (4-hydroxyphenyl) sulfone; bis (4-hydroxyphenyl) sulfoxide; bis (4-hydroxyphenyl) ) Ether; bis (4-hydroxyphenyl)
Compounds such as ketones or bis (3,5-dibromo-4
-Hydroxyphenyl) propane; halogenated bisphenols such as bis (3,5-dichloro-4-hydroxyphenyl) propane; These dihydric phenols may be used alone or in combination of two or more. In addition, carbonate precursors other than phosgene include bromophosgene, diphenyl carbonate, di-p-tolyl carbonate, phenyl-p-tolyl carbonate, di-p-chlorophenyl carbonate, dinaphthyl carbonate,
Dimethyl carbonate, diethyl carbonate and the like can be mentioned. In the present invention, polycarbonate-
Polycarbonate oligomers used in the production of polyorganosiloxane copolymers include these dihydric phenols 1
It may be a homopolymer using species or a copolymer using two or more species. Further, it may be a thermoplastic random branched polycarbonate obtained by using a polyfunctional aromatic compound in combination with the dihydric phenol. The refractive index (n _D ) of the polycarbonate-polyorganosiloxane copolymer thus obtained can be changed by appropriately selecting the content of the polyorganosiloxane in the copolymer. For example, when using polydimethylsiloxane as the polyorganosiloxane,
n _D can be changed from 1.585 to about 1.50 of the polycarbonate alone.

Next, a polycarbonate resin having a different refractive index is similarly copolymerized with the polycarbonate resin, and the refractive index is smaller than that of the polycarbonate resin, and the comonomer unit is a polycarbonate-acryl copolymer (PC-PMMA) which is an acrylic monomer. (Copolymer) will be described. This polycarbonate-acrylic copolymer is a copolymer comprising a polycarbonate portion and an acrylic portion (correctly, a polyacrylate portion), and there are various types. Among them, the general formula (VI)

[0019]

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(Wherein, X, Y, a and b are the same as described above. Z represents a single bond, —O—, —COO— or —NH—. R ⁴ is a hydrogen atom Or a methyl group, and R ⁵ is an alkyl group having 1 to 18 carbon atoms or 3 to
Indicate 18 cycloalkyl groups. And m = 2-4
0, n = 3 to 41, h = 10 to 500, and i = 1 to 10. Or a polycarbonate-based graft copolymer represented by the general formula (VII):

[0021]

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(Where X, Y, Z, a, b, R ⁴ and R
⁵ is the same as above. Also, p = 10 to 500, q
= 10 to 500, r = 3 to 80. ) Is a polycarbonate-based block copolymer. These polycarbonate-based graft copolymers and block copolymers can be synthesized by various methods. For example, it can be synthesized by reacting a prepolymer obtained by reacting a polycarbonate oligomer and an acrylic resin macromonomer with bisphenol A. Here, the polycarbonate oligomer may be manufactured in the same manner as described above.

On the other hand, various acrylic resin macromonomers can be used. For example, to produce the polycarbonate-based graft copolymer described above, the general formula
(VIII)

[0024]

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Wherein R ⁴ , R ⁵ , h and Z are the same as above. ] Is used. Further, to produce the polycarbonate block copolymer described above, the general formula (IX)

[0026]

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Wherein R ⁴ , R ⁵ , p and Z are the same as above. ] May be used. When the acrylic resin macromonomer represented by the general formula (VIII) is, for example, an acrylate and / or a methacrylate, the polymerization degree is 1
0-500, preferably 20-300,
Those having any one of —OH, —COOH, and —NH _{2 at} the terminal are preferable. Examples of the acrylate include methyl acrylate, ethyl acrylate, propyl acrylate, and butyl acrylate. Examples of the methacrylate include methyl methacrylate, ethyl methacrylate, butyl methacrylate, and cyclohexyl methacrylate. In addition, such an acrylic resin macromonomer is manufactured as follows, for example. That is, an acrylic acid ester and / or a methacrylic acid ester of a comonomer unit are dissolved in a solvent, a chain transfer agent and a polymerization initiator are added, and the mixture is reacted in a temperature range of 40 to 70 ° C. for 30 minutes to 5 hours. Next, the reaction product can be obtained by pouring into a precipitant to precipitate, and then filtering, drying and purifying. Here, as the solvent, polar solvents such as tetrahydrofuran and dimethylformamide, benzene, toluene,
Aromatic hydrocarbon solvents such as xylene and aliphatic hydrocarbons such as hexane, heptane and octane can be used. Among these, tetrahydrofuran is particularly preferably used. Further, as the chain transfer agent, thiomalic acid, 2-methicapto-1,4-butanedicarboxylic acid and the like can be used. And as a polymerization initiator, azobisisobutyronitrile, benzoyl peroxide,
A radical initiator such as lauroyl peroxide can be used. Further, the acrylic resin macromonomer represented by the general formula (IX) is used as a chain transfer agent as -OH, -C
OOH, it can be prepared similarly to acrylic resin macromonomers of the general formula (VIII) with a mercaptan having one -NH ₂ (e.g. thioglycolic acid).

The viscosity average molecular weight of the polycarbonate-acrylic copolymer thus obtained is not particularly limited.
What is necessary is just to select suitably according to a use etc. Normally 100,00
0 to 200,000, preferably 15,000 to 100,000
0. The refractive index (n _D ) of the polycarbonate-acrylic copolymer can be freely changed by changing the content of the acrylic portion in the copolymer. That is, it can be changed from n _D = 1.585 of the homopolymer having only the polycarbonate portion (PC portion) to n _D = 1.489 of the homopolymer having only the acryl portion.
Therefore, the ratio of the polycarbonate part and the acrylic part in this polycarbonate-acrylic copolymer differs depending on the required refractive index, and cannot be uniquely determined.

In order to change the refractive index of the polycarbonate resin, a spiro ring-containing bisphenol is used as a comonomer.
A polycarbonate-fluoropolycarbonate copolymer (PC-FPC copolymer) obtained by copolymerization using dihydric phenols excluding phenol, particularly BPAF effective therein will be described. There are various polycarbonate-fluoropolycarbonate copolymers,
Preferably, the general formula (X)

[0030]

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(Wherein R ⁶ and R ⁷ each represent hydrogen or an alkyl group having 1 to 4 carbon atoms), and a general formula (XI)

[0032]

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And a repeating unit represented by the formula: Here, the number of each repeating unit is 1 or more. The PC-FPC copolymer may be a block copolymer, a random copolymer, an alternating copolymer, or a graft copolymer in which one or more of the respective repeating units are polymerized. Further, it may be a homopolymer of only FPC containing no PC. Its viscosity average molecular weight is from 10,000 to 50,000, preferably 1
5,000 to 40,000. The refractive index (n _D ) of this PC-FPC copolymer can be freely changed by changing the content of FPC in the copolymer. That is, from n _D = 1.585 of the homopolymer of PC alone, F
It can be changed up to n _D = 1.50 for a homopolymer of PC only. Therefore, the ratio between the polycarbonate part (PC) and the fluoropolycarbonate part (FPC) in the PC-FPC copolymer differs depending on the required refractive index, and cannot be uniquely determined.

Such a PC-FPC copolymer has the general formula (XII)

[0035]

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(Wherein R ⁶ and R ⁷ are the same as those described above), and a bis (4-hydroxyphenyl) alkane (BPAL) represented by the following general formula (XIII):

[0037]

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2,2-bis (4-hydroxyphenyl) 1,1,1,3,3,3-hexafluoropropane (BPAF) represented by the following formula and a carbonate such as phosgene or diphenyl carbonate. It can be produced by a method usually employed for producing a polycarbonate in which a forming compound is reacted. For example, B
PC-FPC oligomer is synthesized from PAL and BPAF and phosgene, and a copolymer obtained by reacting BPAL and / or BPAF with the oligomer, BPAL or BPAF
Copolymers obtained by reacting BPAL and / or BPAF with PC oligomers or FPC oligomers of F and phosgene, and copolymers of BPAL and BPAF with phosgene, and the like. The bis (4-hydroxyphenyl) alkane used in the synthesis of the PC-FPC copolymer may be any one as long as it is represented by the above general formula (XII), and there are various types. For example, 1,1-bis (4-hydroxyphenyl) ethane; 2,2-bis (4-hydroxyphenyl) propane [bisphenol A: BP
A]; 2,2-bis (4-hydroxyphenyl) butane and the like. Among them, bisphenol A (BP
A) is particularly preferred.

Further, as a comonomer for changing the refractive index of the polycarbonate resin, a spiro ring-containing bisphenol
A polycarbonate-bisphenol C polycarbonate copolymer (PC-BPC copolymer) obtained by copolymerizing with bisphenol C (BPC) will be described as another effective example of dihydric phenols excluding phenol. . There are various PC-BPC copolymers,
Preferably, the general formula (X)

[0040]

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(Wherein R ⁶ and R ⁷ each represent hydrogen or an alkyl group having 1 to 4 carbon atoms); and a general formula (XIV)

[0042]

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And a repeating unit represented by the formula: Here, the number of each repeating unit is 1 or more. The PC-BPC copolymer may be a block copolymer, a random copolymer, an alternating copolymer or a graft copolymer in which one or more of the respective repeating units are polymerized. Further, it may be a homopolymer of only BPC containing no PC. Its viscosity average molecular weight is from 10,000 to 50,000, preferably 1
5,000 to 40,000. The PC-BPC copolymer can freely change the refractive index (n _D) by changing the content of BPC in the copolymer. That is, from n _D = 1.585 of the homopolymer of PC only,
It can be changed up to n _D = 1.57 for a homopolymer of PC only. Therefore, the ratio of the polycarbonate portion (PC) and the bisphenol C polycarbonate portion (BPC) in the PC-BPC copolymer differs depending on the required refractive index, and cannot be uniquely determined.

Such a PC-BPC copolymer has the general formula (XII)

[0045]

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(Wherein R ⁶ and R ⁷ are the same as described above) and a bis (4-hydroxyphenyl) alkane (BPAL) represented by the general formula (XV)

[0047]

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1,1-bis (3-methyl-
4-hydroxyphenyl) propane [bisphenol C: BPC] can be produced by a method usually employed in the production of polycarbonate by reacting these with a carbonate-forming compound such as phosgene or diphenyl carbonate. For example, a BPAL-BPC oligomer is synthesized from BPAL and BPC and phosgene, and a copolymer obtained by reacting BPAL and / or BPC with the BPAL and / or BPC is reacted with BPAL or a PC oligomer or a BPC oligomer from BPC and phosgene. Or a copolymer obtained by reacting BPC, BPAL and a copolymer of BPC and phosgene. The bis (4-hydroxyphenyl) alkane used for the synthesis of the PC-BPC copolymer may be any one as long as it is represented by the above general formula (XII), and various types are available. For example, 1,1-bis (4-hydroxyphenyl) ethane; 2,2-bis (4-hydroxyphenyl)
Propane [bisphenol A: BPA]; and 2,2-bis (4-hydroxyphenyl) butane. Among them, bisphenol A (BPA) is particularly preferred.

Further, as a comonomer, a linear aliphatic 2
The polycarbonate-decanedicarboxylic acid copolymer (PC-DDCA copolymer) obtained by copolymerization using an effective decanedicarboxylic acid among the polyvalent carboxylic acids will be described. The PC-DDCA copolymer may be of various types, but is preferably of the general formula (X)

[0050]

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(Wherein R ⁶ and R ⁷ are the same as described above), and a compound represented by the general formula (XVI) Is a copolymer using decanedicarboxylic acid represented by the formula (1) as a comonomer. Here, the number of repeating units of the general formula (X) is 1 or more. The repeating unit of decanedicarboxylic acid is 1. The PC-DDCA copolymer is a random copolymer or an alternating copolymer in which at least one of the repeating unit of the general formula (X) and decanedicarboxylic acid is polymerized. Its viscosity average molecular weight is 10,000-5
0,000, preferably 15,000 to 40,000.
The refractive index (n _D ) of the PC-DDCA copolymer can be freely changed by changing the content of DDCA in the copolymer. That is, it can be changed from n _D = 1.585 to about 1.56 for the homopolymer of PC alone. Accordingly, in the PC-DDCA copolymer, a copolymer portion of polycarbonate (PC) and DDCA (DDCA) was used.
The ratio of A) differs depending on the required refractive index and cannot be uniquely determined.

Such a PC-DDCA copolymer has the general formula (XII)

[0053]

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(Wherein R ⁶ and R ⁷ are the same as those described above), and a compound represented by the general formula (XVI): Can be produced by a method usually employed in the production of polycarbonate by reacting decanedicarboxylic acid (DDCA) represented by the formula (II) with a carbonate-forming compound such as phosgene or diphenyl carbonate. For example, a PC-DDCA oligomer is synthesized from BPAL and DDCA and phosgene,
A copolymer obtained by reacting AL and / or DDCA, a PC oligomer from BPAL and phosgene
DCA alone or a copolymer obtained by reacting BPAL and DDCA, a copolymer of BPAL, DDCA and phosgene, and the like. The bis (4-hydroxyphenyl) alkane to be used in the synthesis of the PC-DDCA copolymer may be any one represented by the above general formula (XII), and various types are available. 1-bis (4
-Hydroxyphenyl) ethane; 2,2-bis (4-hydroxyphenyl) propane [bisphenol A: BP
A]; 2,2-bis (4-hydroxyphenyl) butane and the like. Among them, bisphenol A (BP
A) is particularly preferred.

Next, the polycarbonate resin (PC) which is the component (C) of the present invention has the general formula (V)

[0056]

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Wherein X, Y, a and b are the same as above. Can be easily produced by reacting the dihydric phenol represented by the formula (1) with phosgene or a carbonate compound. That is, for example, by reacting a dihydric phenol with a carbonate precursor such as phosgene in a solvent such as methylene chloride in the presence of a known acid acceptor or a molecular weight regulator, or as in the case of dihydric phenol and diphenyl carbonate. It is produced by a transesterification reaction with a suitable carbonate precursor. Here, there are various dihydric phenols, and 2,2-bis (4-hydroxyphenyl) propane [bisphenol A] is particularly preferable. Examples of the dihydric phenol other than bisphenol A include bis (4-hydroxyphenyl) alkane other than bisphenol A, hydroquinone; 4,4′-dihydroxydiphenyl;
(Hydroxyphenyl) cycloalkane; bis (4-hydroxyphenyl) sulfide; bis (4-hydroxyphenyl) sulfone; bis (4-hydroxyphenyl) sulfoxide; bis (4-hydroxyphenyl) ether; bis (4-hydroxyphenyl) ketone And bis (3,5-dibromo-4-hydroxyphenyl) propane; and halogenated bisphenols such as bis (3,5-dichloro-4-hydroxyphenyl) propane. These dihydric phenols may be used alone or in combination of two or more. Examples of the carbonate compound include diaryl carbonates such as diphenyl carbonate and dialkyl carbonates such as dimethyl carbonate and diethyl carbonate.

On the other hand, (A) a specific type of comonomer unit
As the (B) E glass used together with the polycarbonate copolymer having (C) the polycarbonate resin,
Various types or forms can be applied. For example, glass fibers, glass beads, glass flakes, glass powder, etc. made of E glass can be used, and these may be used alone or in combination of two or more. Among these, the glass fibers widely used for resin reinforcement may be any of alkali-containing glass, low-alkali glass, and non-alkali glass. The fiber length is 1 to 8 mm, preferably 3 to 6 mm, and the fiber diameter is 3 to 30 μm, preferably 5 to 25 μm. The form of the glass fiber is not particularly limited,
For example, various types such as roving, milled fiber, chopped strand and the like can be mentioned. These glass fibers may be used in combination of two or more in combination. Further, these glass materials are surface-treated with a silane coupling agent such as aminosilane, epoxysilane, vinylsilane, methacrylsilane, chromium complex compound, boron compound, etc. in order to enhance the affinity with the resin. May be used.

The resin composition of the present invention comprises the above (A)
The component (C) is used, and the mixing ratio thereof is as follows: (A) 10 to 95% by weight, preferably 10% by weight of a polycarbonate copolymer having a specific type of comonomer unit.
90% by weight, (B) 5 to 70% by weight, preferably 10 to 60% by weight of E glass and (C) 0 to 85% by weight, preferably 0 to 80% by weight of a polycarbonate resin. Here, (A) a polycarbonate copolymer having a specific type of comonomer unit is a spiro ring-containing bisphenol.
When using a copolymer having a high copolymerization ratio of the polycarbonate portion of the dihydric phenol except for (C), the blending amount of the polycarbonate resin (C) can be reduced, and the polycarbonate resin as the component (C) can be omitted. In some cases, it may be acceptable. In the resin composition of the present invention, (B) E
If the mixing ratio of the lath is less than 5% by weight, the dimensional stability decreases, which is not preferable. On the other hand, if it exceeds 70% by weight, kneading of the resin becomes difficult or impossible, and the appearance is further deteriorated. And as a glass, the refractive index n _D
Uses about 1.545 E glass, so for example, P
When a C-PDMS copolymer is used, (A) a specific species
Be made close to 1.555 to 1.535 and a refractive index of n _D of the polycarbonate copolymer by a proportion of the copolymer part in the copolymer having a small mer units of the kind in 13 to 30 wt% Yes, it is very effective in improving transparency. In the present invention, (A) a specific kind of como
The difference (absolute value) between the refractive index of the mixed resin obtained by blending the polycarbonate copolymer having a monomer unit and (C) the polycarbonate resin (PC) with the refractive index of the (B) E glass.
0.01 or less, preferably 0.005 or less. If the difference (absolute value) between the refractive index of the mixed resin and the E glass exceeds 0.01, the transparency of a molded product obtained from the resin composition decreases, which is not preferable.

In the process for producing the resin composition of the present invention, as described above, the type and ratio of the comonomer units to be copolymerized with the polycarbonate are selected, and the copolymer is obtained by polymerizing the comonomer or polymerizing the comonomer. The polycarbonate copolymer is referred to as (A), and the component (A)
The components (B) and (C) and various optional components used as needed are blended and kneaded, and a desired resin composition can be obtained by doing so. For the compounding and kneading, a method usually used, for example, a ribbon blender, a Henschel mixer, a Banbury mixer, a drum tumbler, a single screw extruder, a twin screw extruder, a co-kneader, a multi-screw extruder, etc. It can be performed by the method used. The heating temperature during kneading is usually selected in the range of 250 to 300 ° C. The polycarbonate resin composition thus obtained is subjected to various known molding methods, for example, injection molding, hollow molding, extrusion molding, compression molding, calendar molding, rotational molding and the like, and is used in the automotive field such as automotive glass and sunroof. Molded products and molded products in the field of home appliances can be manufactured. In the resin composition of the present invention, various additives, other synthetic resins, elastomers and the like can be blended, if necessary, as long as the object of the present invention is not hindered. For example, various additives include antioxidants such as hindered phenols, phosphites, phosphates, and amines; ultraviolet absorbers such as benzotriazoles and benzophenones; and light absorbers such as hindered amines. Examples include stabilizers, external lubricants such as aliphatic carboxylic acid esters and paraffins, common flame retardants, release agents, antistatic agents, coloring agents, and the like.

[0061]

[Production of polycarbonate (PC) oligomer]

60 liters in 400 liters of 5% aqueous sodium hydroxide solution
kg bisphenol A was dissolved to prepare an aqueous sodium hydroxide solution of bisphenol A. Next, this aqueous solution of sodium hydroxide of bisphenol A kept at room temperature was supplied at a flow rate of 138 l / hr, and methylene chloride was added at a flow rate of 69
At a flow rate of 1 liter / hr, an orifice plate was introduced into a tubular reactor having an inner diameter of 10 mm and a pipe length of 10 m, and phosgene was co-currently blown into the reactor at a flow rate of 10.7 kg / hr to continuously react for 3 hours. The tubular reactor used here was a double tube, and the outlet temperature of the reaction solution was kept at 25 ° C. by passing cooling water through the jacket. The pH of the discharged liquid is 10
１１11. The reaction solution thus obtained was allowed to stand, and the aqueous phase was separated and removed. A methylene chloride phase (220 liters) was collected, and 170 liters of methylene chloride was further added thereto, followed by stirring sufficiently. Was used as a PC oligomer (concentration: 317 g / liter). The degree of polymerization of the PC oligomer obtained here was 3-4.

Example 1-2 [Production of reactive polydimethylsiloxane (PDMS)] 1483 g of octamethylcyclotetrasiloxane, 9
6 g of 1,1,3,3-tetramethyldisiloxane and 35 g
Of 86% sulfuric acid and stirred at room temperature for 17 hours. Thereafter, the oil phase was separated, 25 g of sodium hydrogen carbonate was added, and the mixture was stirred for 1 hour. After filtration, vacuum distillation was performed at 150 ° C. and 3 torr to remove low-boiling substances. To a mixture of 60 g of 2-allylphenol and 0.0014 g of platinum as a platinum chloride-alcolate complex, 294 g of the oil obtained above were added at a temperature of 90 ° C. This mixture is 90-1
The mixture was stirred for 3 hours while maintaining the temperature at 15 ° C. The product was extracted with methylene chloride and washed three times with 80% aqueous methanol to remove excess 2-allylphenol. The product was dried over anhydrous sodium sulphate and evaporated in vacuo to a temperature of 115 ° C. The obtained terminal phenol PD
In MS, the number of repeating dimethylsilanooxy units was 30 as measured by NMR.

Example 1-3-1 (Preparation of PC-PDMS copolymer A) 858 g of the reactive PDMS obtained in Example 1-2 was dissolved in 2 liter of methylene chloride to obtain Example 1-1. PC
Mix with 10 liters of oligomer. A solution of 46 g of sodium hydroxide in 1 liter of water and 5.7 cc of triethylamine were added thereto, followed by stirring at 500 rpm for 1 hour at room temperature. Thereafter, a solution prepared by dissolving 600 g of bisphenol A in 5 l of a 5.2% by weight aqueous sodium hydroxide solution, 8 l of methylene chloride and 60 g of p-tert-butylphenol were added, and the mixture was stirred at 500 rpm for 2 hours at room temperature. Thereafter, 5 liters of methylene chloride was added, followed by water washing with 5 liters of water, alkali washing with 5 liters of a 0.01N aqueous sodium hydroxide solution, acid washing with 5 liters of 0.1N hydrochloric acid, and water washing with 5 liters of water. Methylene chloride was removed to obtain a chip-shaped PC-PDMS copolymer. The obtained copolymer was dried at 100 ° C. for 6 hours,
Press molding was performed at 290 ° C., and the PDMS content and the refractive index (n _D ) were measured. Example 1-3-2 (Production of PC-PDMS copolymer B) In Example 1-3-1, the reactive PDMS was changed to 1,653.
g and sodium hydroxide were changed to 90 g, and the same procedure as in Example 1-3-1 was carried out. In Examples 1-3-1-2
PDMS content of the obtained PC-PDMS copolymer ( weight
%) And n _D are shown in Table 1.

[0064]

[Table 1]

The measurement of the PDMS content, PDMS chain length (dimethylsilanooxy unit) and n _D is as follows. 1) Measurement of PDMS content and PDMS chain length PDMS content was determined by the peak of the isopropyl methyl group of bisphenol A at 1.7 ppm in ¹ H-NMR.
It was determined by the intensity ratio of the peak of the methyl group of dimethylsiloxane found at 0.2 ppm. The PDMS chain length is ¹ H-
It was determined by the intensity ratio of the peak of the methyl group of dimethylsiloxane found at 0.2 ppm in NMR and the peak of the methylene group of the PC-PDMS bond at 2.6 ppm. 2) was measured using a refractometer measurement Abbe n _D. And PC-PDM
As the S copolymer B and polycarbonate resin, Teflon FN-2200 (manufactured by Idemitsu Petrochemical Co., Ltd.) was mixed in an extruder at 300 ° C. at a ratio (weight) of 61.4: 38.6. N _D of the resulting mixed resin was 1.547. This mixed resin was used in Example 1-4-4.

Examples 1-4-1 to 5 and Comparative Examples 1 to 4 (mixing of composite members) The PC-PDMS copolymer obtained in Example 1-3 was used, and the polycarbonate resin was Tufflon FN.
-2200 [Idemitsu Petrochemical Co., Ltd.] a and E glass,
The above-mentioned glass A and B were used as pellets, and pellets were prepared at a ratio shown in Table 2 at 300 ° C. by a 30 mm vented extruder. In addition, the said glass was supplied from the downstream of the hopper supply position of the raw material resin of an extruder. The obtained pellet was press-molded at 300 ° C. For the molded products obtained in Examples and Comparative Examples, haze was measured as performance evaluation. Table 2 shows the results of the performance evaluation. The measurement of haze was performed by pressing the obtained pellets at 300 ° C. according to the following test method. 1) Measurement of haze A test piece having a thickness of 3 mm was measured according to JIS K 7105.

[0067]

[Table 2]

[0068]

[Table 3]

Example 2-1-1 (Production of Reactive PMMA-A) Methyl methacrylate 1 was added to 2 liters of tetrahydrofuran.
kg, azobisisobutyronitrile (polymerization initiator) 11.5
g, thiomalic acid (chain transfer agent) 31.7 g
The mixture was heated to 0 ° C. and reacted for 3 hours. The reaction product was poured into 20 liters of petroleum ether with stirring, and the polymer was precipitated, separated by filtration and dried. Next, the obtained polymer was dissolved in methylene chloride, washed with water, and the methylene chloride was evaporated to dryness to obtain a flake-like reactive PMMA-A. KOH
Number average molecular weight is 1
It was 000. Example 2-1-2 (Production of reactive PMMA-B) Example 2-1 was conducted in the same manner as in Example 2-1-1 except that 19.5 g of thioglycolic acid was used instead of thiomalic acid.
-1 was performed. As a result of titration of the carboxyl group with KOH, the number average molecular weight was 9,900.

Example 2-2-1 (Production of PC-PMMA Copolymer A: Graft Copolymer) The PC obtained in Example 1-1 was added to 2 liters of methylene chloride.
450 g of the oligomer and 410 g of the reactive PMMA-A obtained in Example 2-1-1 were dissolved, and triethylamine 1
After adding 1.4 cc and reacting for 1 hour with stirring, 0.1
After washing with N hydrochloric acid, the organic phase was separated to obtain a prepolymer solution. Methylene chloride was added to the obtained prepolymer solution to make 4 liters, and 4 g of p-tert-butylphenol was added to obtain an organic solvent solution. On the other hand, bisphenol A8
1 g, 50 g of sodium hydroxide and 0.1 g of triethylamine.
54 cc was dissolved in water to make 1.1 liter and interfacial polycondensation with an organic solvent solution at 500 rpm for 1 hour at room temperature. Thereafter, 4 liters of methylene chloride was added, followed by washing with 4 liters of water, alkali washing with 5 liters of 0.01N sodium hydroxide aqueous solution, acid washing with 5 liters of 0.1N hydrochloric acid, and water washing with 5 liters of water. Methylene chloride was removed to obtain a chip-shaped PC-PMMA copolymer. The obtained copolymer was dried at 100 ° C. for 6 hours, press-molded at 290 ° C., and the refractive index was measured. Example 2-2-2 (Production of PC-PMMA copolymer B: block copolymer) In Example 2-2-1, 410 g of reactive PMMA-B was used instead of reactive PMMA-A, and triethylamine was used. Was changed to 5.7 cc, bisphenol A to 85 g and sodium hydroxide to 52 g, except that p-tert-butylphenol was not added. PC obtained in Example 2-2-1-2
-PMMA content and refractive index of PMMA copolymer
(N _D ) is shown in Table 3. In addition, PC-PMMA copolymerization
The PMMA content of the body is determined by measuring the PDMS content described above.
It measured similarly. The measurement of the refractive index (n _D )
Followed above.

[0071]

[Table 4]

Examples 2-3-1 to 5 (mixing of composite materials) PC-PMMA copolymers were used in Examples 2-2-1 to 2-2-1 .
The PC-PMMA copolymers A and B obtained in 2 were used.
No polycarbonate resin (PC) was used
Was. And, as the E glass , the above-mentioned glasses A and B
And pellets were prepared at a rate shown in Table 4 at 300 ° C. by an extruder with a 30 mm vent. The E glass was supplied from the downstream side of the hopper supply position of the raw material resin of the extruder. 300 ° C.
Was press molded. For the molded product obtained in the example, measurement of haze and measurement of the refractive index were performed in the same manner as in Example 1-4-1 as performance evaluation. Table 4 shows the results of the performance evaluation. The performance evaluation was in accordance with the above.

[0073]

[Table 5]

[0074]

[Table 6]

Example 3-1-1 (Production of FPC Oligomer A) In 400 liters of a 5% aqueous sodium hydroxide solution, 34.
8 kg of BPA and 25.2 kg of BPAF were dissolved. Then, the BPA-BPAF aqueous sodium hydroxide solution kept at room temperature was passed through an orifice plate at a flow rate of 138 l / hr and methylene chloride at a flow rate of 69 l / hr through a tubular reactor having an inner diameter of 10 mm and a length of 10 m. Phosgene was introduced thereinto and blown at a flow rate of 10.7 kg / hr in parallel, and reacted continuously for 3 hours. The reaction tube used here was a double tube, and the discharge temperature of the reaction solution was kept at 25 ° C. by passing cooling water through the jacket portion. Further, the pH of the discharged liquid was adjusted to be 10 to 11. The reaction solution thus obtained was allowed to stand, whereby the aqueous phase was separated and removed, and the methylene chloride phase (220 liters) was collected.
Further, 170 l of methylene chloride was added thereto, and the mixture was sufficiently stirred to obtain FPC oligomer A (concentration: 317 g / l). Example 3-1-2 (Production of FPC oligomer B) In Example 3-1-1, 34.8 kg of BPA and 25.
14.4 kg BPA and 45.6 instead of 2 kg BPAF
The procedure was performed in the same manner as in Example 3-1-1, except that kg of BPAF was used. Example 3-1-3 (Production of FPC oligomer C) In Example 3-1-1, 34.8 kg of BPA and 25.
The procedure was performed in the same manner as in Example 3-1-1, except that 60 kg of BPAF was used instead of 2 kg of BPAF.

Example 3-2-1 (Production of PC-FPC Copolymer A) A solution I was prepared by adding 2 liters of methylene chloride to 1.26 liters of the FPC oligomer A. Separately, 76.4 g of sodium hydroxide and 193 g of BPAF were dissolved in 0.9 liter of water to obtain a solution II. Solution I and solution II were mixed, 0.34 ml of triethylamine and 8 g of p-tert-butylphenol were added as catalysts, and the mixture was stirred for 2 hours to carry out a reaction. After the reaction, 5 l of water and 5 l of methylene chloride were added, and the mixture was separated into an organic phase and an aqueous phase. Then the organic phase
After alkali washing using a 0.01 N sodium hydroxide solution, washing was further performed using 0.1 N hydrochloric acid. Thereafter, the resultant was washed with water to remove methylene chloride, and a flake-like PC-FPC copolymer A was obtained. BP by NMR analysis
The mole% of AF was determined. The obtained flake was dried at 100 ° C. for 6 hours, press-molded at 290 ° C., and the refractive index was measured. Example 3-2-2 (Production of PC-FPC copolymer B) Example 3-2-1 was carried out in the same manner as in Example 3-2-1, except that FPC oligomer B was used. Example 3-2-3 (Production of PC-FPC copolymer C) The same operation as in Example 3-2-1 was performed except that PC oligomer C was used in Example 3-2-1. Example 3
-PC-FPC copolymers A, B, obtained in 2-1-3
Table 5 shows the mole% of BPAF and the refractive index (n _D ) of C.

[0077]

[Table 7]

Then, the PC obtained in Example 3-2-2
-FPC copolymer B and Teflon FN-2200 (manufactured by Idemitsu Petrochemical Co., Ltd.) as a polycarbonate resin were mixed at 300 ° C in a 6: 4 ratio (weight) using an extruder. N _D of the resulting mixed resin was 1.545. This mixed resin was used in Examples 3-3-2 to 4. Further, the PC-FPC copolymer C obtained in Example 3-2-3 and Tufflon FN-2200 as a polycarbonate resin were extruded at 300 ° C. in a ratio (weight) of 44.3: 55.7. And mixed. N _D of the resulting mixed resin was 1.544. This mixed resin was used in Example 3-3-5.

Examples 3-3-1 to 6 (Mixing of Composite Materials) As PC-FPC copolymers, Examples 3-2-1 to 3-3 were used.
The PC-FPC copolymers A, B and C obtained in the above were used.
On the other hand, as the polycarbonate resin, Toughlon FN-
2200 [made by Idemitsu Petrochemical Co., Ltd.] was used. And
As E glass , the E glasses A and B were used and pellets were prepared at a rate shown in Table 6 at 300 ° C. by a 30 mm vented extruder. The glass was supplied from the downstream side of the hopper supply position of the raw material resin of the extruder. The obtained pellet was press-molded at 300 ° C. For the molded product obtained in the example, measurement of haze and measurement of the refractive index were performed in the same manner as in Example 1-4-1 as performance evaluation. Table 6 shows the results of the performance evaluation. The performance evaluation was in accordance with the above.

[0080]

[Table 8]

[0081]

[Table 9]

[0082]

As described above, according to the present invention, it is possible to obtain a polycarbonate resin composition having excellent transparency while having the original mechanical properties of polycarbonate. Therefore, the polycarbonate resin composition obtained by the method of the present invention can be effectively used as a material for various molded articles widely used in the fields of electric / electronic devices, automobiles, and the like.

Claims (4)

(57) [Claims] (1) The type of comonomer unit (A) is organosi
Loxane unit, acrylic monomer unit, spiro ring contained
Dihydric phenol units other than bisphenol or linear
10 to 95% by weight of a polycarbonate copolymer which is an aliphatic divalent carboxylic acid unit , (B) 5 to 70% by weight of E glass and (C) 0 to 85% by weight of a polycarbonate resin are kneaded, and (A) By selecting the type and proportion of the comonomer units in the polycarbonate copolymer of (A), the refractive index of the mixed resin of (A) and (C) and (B) E
A method for producing a polycarbonate resin composition, wherein the difference (absolute value) from the refractive index of glass is adjusted to 0.01 or less. 2. The method according to claim 1, wherein the E glass is glass fiber. 3. A composition comprising: (A) 10 to 95% by weight of a polycarbonate copolymer containing bisphenol C as a copolymer component; (B) 5 to 70% by weight of E glass; and (C) 0 to 85% by weight of a polycarbonate resin. Wherein a difference (absolute value) between the refractive index of the mixed resin of (A) and (C) and the refractive index of (B) E glass is 0.01 or less. 4. A polycarbonate copolymer 10 containing (A) a linear aliphatic dicarboxylic acid as a copolymerization component.
95% by weight, (B) 5 to 70% by weight of E glass and (C) 0 to 85% by weight of a polycarbonate resin,
A polycarbonate resin composition, wherein the difference (absolute value) between the refractive index of the mixed resin of (A) and (C) and the refractive index of (B) E glass is 0.01 or less. Stuff.