JPH05310956A - Glass-reinforced polycarbonate resin molded product and its production - Google Patents

Abstract

PURPOSE:To provide the subject molded product excellent in transparency. CONSTITUTION:The molded product can be obtained by molding a polycarbonate resin composition comprising (A) a polycarbonate copolymer and (B) glass fibers with the refractive index difference between the components A and B being >=0.01 (absolute value) using a mold in which a resin film or sheet is fitted in advance. Thus, this molded product is such that the surface of a molded product of said polycarbonate resin composition is laminated with the above- mentioned resin film or sheet.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a glass-reinforced polycarbonate resin molded product and a method for producing the same, and more specifically, a polycarbonate resin molded product having a smooth surface and excellent transparency (visibility) and its effect. The present invention relates to a method for manufacturing the same.

[0002]

2. Description of the Related Art Polycarbonate resins are excellent in mechanical strength, and also in heat resistance and transparency, so that they are used as engineering plastics in the fields of electric and electronic devices, automobiles, etc. Although it is widely used in various fields, it is also widely used in various fields as it has many uses as plastic glass. However, as a plastic glass, it has a drawback of being inferior in rigidity as compared with the conventional inorganic glass.
In order to improve this drawback, for example, JP-A-58-60 is used.
Japanese Patent Laid-Open No. 641 and Japanese Patent Laid-Open No. 62-251227 disclose a glass fiber reinforced polycarbonate resin composition in which glass fibers having a refractive index similar to that of the polycarbonate resin are blended with the polycarbonate resin. There is. However, in a molded product obtained by injection molding a glass fiber reinforced polycarbonate resin composition containing these glass fibers, a phenomenon in which the glass fiber floats on the surface of the molded product is observed. Embossment on the surface of this glass fiber causes a lack of surface smoothness of the molded product, and parallel rays passing through the molded product are scattered on the surface of the molded product,
It has the drawback of poor visibility (the object is clearly visible through the molded product).

Therefore, the inventors of the present invention have conducted intensive studies to solve the drawbacks of the conventional method and develop a polycarbonate resin molded product having a smooth surface and excellent transparency (visibility). .. As a result, in molding using a polycarbonate resin composition composed of a polycarbonate resin and glass, the absolute value of the difference between the refractive index of the polycarbonate resin and the refractive index of the glass is 0.01 or less It has been found that the desired polycarbonate resin molded article can be obtained by mounting a resin film or resin sheet on and molding. The present invention has been completed based on such findings.

[0004]

That is, the present invention is
(A) Polycarbonate resin 30 to 99% by weight and (B) Glass 70 to 1% by weight, and the difference between the refractive index of the polycarbonate resin (A) and the refractive index of the glass (B) (absolute value). ) Is a glass-based polycarbonate resin composition characterized in that when a polycarbonate-based resin composition of 0.01 or less is molded in a mold, a resin film or a resin sheet is previously mounted in the mold. A method for manufacturing a molded product is provided. Also,
The present invention comprises (A) a polycarbonate-based resin of 30 to 99% by weight and (B) a glass of 70 to 1% by weight, and includes the refractive index of the (A) polycarbonate-based resin and the refractive index of the (B) glass. Also provided is a glass-reinforced polycarbonate resin molded product, which is characterized in that a resin film or a resin sheet is laminated on the surface of a molded product of a polycarbonate resin composition having a difference (absolute value) of 0.01 or less. To do.

First, as the polycarbonate resin of component (A) which constitutes the polycarbonate resin composition (hereinafter abbreviated as resin composition) used for the production of the glass-reinforced polycarbonate resin molded article of the present invention, Various ones can be used. For example, a polycarbonate-based copolymer in which the refractive index is variously changed by using an ordinary polycarbonate resin or by selecting the type and ratio of the comonomer unit, etc., is appropriately selected and used. Here, the polycarbonate resin (PC) is usually of the general formula (I)

[0006]

[Chemical 1]

[In the formula, X is a hydrogen atom, a halogen atom (for example, chlorine, bromine, fluorine, iodine) or an alkyl group having 1 to 8 carbon atoms, and when there are a plurality of X, they are the same. May be present or different, and a and b are each 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)

[0008]

[Chemical 2]

The bond represented by ] It can be easily produced by reacting a dihydric phenol represented by the above 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 by reacting dihydric phenol with diphenyl carbonate. It is produced by a transesterification reaction with another carbonate precursor. Here, there are various dihydric phenols represented by the above general formula (I), and 2,2-bis (4-hydroxyphenyl) propane [bisphenol A] is particularly preferable. As dihydric phenols other than bisphenol A, bis (4-hydroxyphenyl) alkanes other than bisphenol A are 1,1- (4-hydroxyphenyl) methane; 1,1- (4-hydroxyphenyl) ethane; hydroquinone; 4 , 4'-dihydroxydiphenyl; bis (4-hydroxyphenyl) cycloalkane; bis (4
-Hydroxyphenyl) sulfide; bis (4-hydroxyphenyl) sulfone; bis (4-hydroxyphenyl) sulfoxide; bis (4-hydroxyphenyl) ether; compounds such as bis (4-hydroxyphenyl) ketone or bis (3,3) 5-dibromo-4-hydroxyphenyl) propane; halogenated bisphenols such as bis (3,5-dichloro-4-hydroxyphenyl) propane. And these dihydric phenols may be used alone, or 2
You may mix and use 1 or more types. Examples of the carbonic acid ester compound include diaryl carbonate such as diphenyl carbonate and dialkyl carbonate such as dimethyl carbonate and diethyl carbonate.

Next, there are various polycarbonate-based copolymers whose refractive index is variously changed by selecting the kind and ratio of the comonomer unit. For example, as a polycarbonate-based copolymer having a refractive index different from that of a normal polycarbonate resin, a polyorganosiloxane, an acrylic resin, or a polyether whose comonomer units are an organosiloxane unit, an acrylic monomer unit, and an ether glycol unit, respectively. Examples thereof include glycol. Polystyrene or the like is used as a polycarbonate-based copolymer having a refractive index different from that of the polycarbonate resin. Further, as a comonomer that changes the refractive index by copolymerization, a comonomer that can reduce the refractive index when copolymerized with bisphenol A which is the main monomer of the polycarbonate resin, Can be mentioned. That is, 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 [BPAF] And so on. Among these, BPAF is effective. Further, as another comonomer whose refractive index can be changed by copolymerization, a linear aliphatic divalent carboxylic acid also has an effect of reducing the refractive index. Examples thereof include adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, dodecanedicarboxylic acid and the like. In particular, it is effective for long aliphatic chains. These effective polycarbonate-based copolymers may be mixed and used to obtain a desired refractive index. In addition, when the refractive index of these polycarbonate-based copolymers is smaller than the target value, the target refractive index can be obtained by mixing an appropriate amount of a general polycarbonate resin.

Here, a typical example of the polycarbonate copolymer will be specifically described. First,
Copolymerized with a resin having a different refractive index to the polycarbonate resin, the refractive index is smaller than the polycarbonate resin,
Polycarbonate-polyorganosiloxane copolymer (PC in which the comonomer unit is an organosiloxane unit)
-PDMS copolymer) will be described. This PC-P
There are various DMS copolymers, but the one represented by the general formula (III) is preferable.

[0012]

[Chemical 3]

[In the formula, X, Y, a and b are the same as described above. ] A polycarbonate unit having a repeating unit having a structure represented by the following formula and having a degree of polymerization of 3 to 50;
V)

[0014]

[Chemical 4]

[In the formula, 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, and may be the same or different. Further, c and d are each an integer of 0 or 1 or more. ] A polyorganosiloxane part having a repeating unit represented by The degree of polymerization of the polyorganosiloxane part is preferably 100 or less, more preferably 50 or less. When the degree of polymerization exceeds 100, the transparency of the copolymer decreases, which is not preferable. The PC-PDMS copolymer is a block copolymer composed of a polycarbonate part having a repeating unit represented by the general formula (III) and a polyorganosiloxane part having a repeating unit represented by the general formula (IV). It is a coalesced product and has a viscosity average molecular weight of 10,000 to 40,000, preferably 15,000 to 35,000.

The ratio of the polycarbonate part to the polyorganosiloxane part in this PC-PDMS copolymer is
It depends on the desired refractive index and cannot be uniquely determined, but is usually 50 to 99.9% by weight of the polycarbonate part, preferably 60 to 99.5% by weight, and 50 to 0.1% by weight of the polyorganosiloxane part, preferably It is selected in the range of 40 to 0.5% by weight. Such a PC-PDMS copolymer includes, for example, a polycarbonate oligomer (PC oligomer) that constitutes a pre-manufactured polycarbonate part and a polyorganosiloxane having a reactive group at the terminal that constitutes a polyorganosiloxane part (for example, , Polydimethylsiloxane, polydiethylsiloxane, etc., or polymethylphenylsiloxane, etc.) in a solvent such as methylene chloride, chlorobenzene, pyridine, etc., and an aqueous sodium hydroxide solution of bisphenol is added, and triethylamine or trimethyl is used as a catalyst. It can be produced by the interfacial reaction with benzyl ammonium chloride or the like. Further, Japanese Patent Publication No. 44-30105 and Japanese Patent Publication No. 45
It is also possible to use a polycarbonate-polyorganosiloxane copolymer produced by the method described in JP-20510A. Here, the PC oligomer having the repeating unit represented by the general formula (III) has the general formula (V)

[0017]

[Chemical 5]

[In the formula, X, Y, a and b are the same as defined above, and Hal represents a halogen atom (eg chlorine, bromine, fluorine, iodine), and t = 2 to 80. ] Is represented. This PC oligomer is represented by the general formula (I) in the solvent method, that is, in the presence of a known acid acceptor and molecular weight modifier in a solvent such as methylene chloride.

[0019]

[Chemical 6]

[In the formula, X, Y, a and b are the same as described above. ] It can be easily produced by reacting a dihydric phenol represented by the above with a phosgene or a carbonate precursor such as 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 by reacting dihydric phenol with diphenyl carbonate. It is produced by a transesterification reaction with another carbonate precursor. Here, as the dihydric phenol represented by the general formula (I), the same ones as described above can be used. In the present invention, the PC oligomer used for producing the PC-PDMS copolymer may be a homopolymer using one of these dihydric phenols.
It may be a copolymer of 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 PC-PDMS copolymer thus obtained can be changed by appropriately selecting the content of polyorganosiloxane in the copolymer. For example, when polydimethylsiloxane is used as the polyorganosiloxane, n _D can be changed from 1.585 of a single polycarbonate product to about 1.50.

Similarly, a polycarbonate resin is copolymerized with a resin having a different refractive index to obtain a polycarbonate-acrylic copolymer (PC-PMMA) whose comonomer unit is an acrylic monomer whose refractive index is smaller than that of the polycarbonate resin. The copolymer) will be described. This P
The C-PMMA copolymer is a copolymer composed of a polycarbonate part and an acrylic part (correctly, a polyacrylate part), and there are various kinds. Typical of them is the general formula (VI)

[0022]

[Chemical 7]

[In the formula, 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
18 represents a cycloalkyl group. And m = 2-4
0, n = 3 to 41, h = 10 to 500, and i = 1 to 10. ] A polycarbonate-based graft copolymer represented by the general formula (VII)

[0024]

[Chemical 8]

[Wherein 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. ] It is a polycarbonate type block copolymer represented by these. 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 PC oligomer with an acrylic resin macromonomer and bisphenol A. Here, the PC oligomer may be produced in the same manner as described above.

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

[0027]

[Chemical 9]

[In the formula, R ⁴ , R ⁵ , h and Z are the same as defined above. ] An acrylic resin macromonomer represented by the following is used. Further, in order to produce the polycarbonate block copolymer, the general formula (IX)

[0029]

[Chemical 10]

[Wherein R^Four, R^Five, P and Z are as described above.
Is the same. ] Acrylic resin macromonomer represented by
-Can be used. Represented by the above general formula (VIII)
Acrylic resin macromonomer is, for example, acrylic acid ester.
In the case of tellurium and / or methacrylic acid ester, the degree of polymerization is 1
0 to 500, preferably 20 to 300,
-OH, -COOH, -NH at the end ₂Have any of
One is preferable. And with the acrylic ester
For example, methyl acrylate, ethyl acrylate
And propyl acrylate, butyl acrylate, etc.
Be done. Further, as the methacrylic acid ester,
Methyl tacrylate, ethyl methacrylate, methacrylic acid
Butyl, cyclohexyl methacrylate, etc.
It In addition, such an acrylic resin macromonomer,
For example, it is manufactured as follows. That is, Komono
Acrylic ester and / or methacrylic acid in mer units
Dissolve the ester in a solvent and use a chain transfer agent and a polymerization initiator.
30 minutes to 5 hours within the temperature range of 40 to 70 ° C.
React. Then, the reaction product is poured into a precipitating agent to precipitate.
It can be obtained by precipitation, filtration, drying and purification.
Wear. Here, as the solvent, tetrahydrofuran, diene
Polar solvents such as methylformamide, benzene, and toluene
Aromatic hydrocarbon solvent such as benzene, xylene, hexane,
Use aliphatic hydrocarbons such as heptane and octane.
You can Among these, especially tetrahydrofuran
Are preferably used. Further, as the chain transfer agent,
Thiomalic acid, 2-mercapto-1,4-butanedicar
Boric acid or the like can be used. And a polymerization initiator
As, azobisisobutyronitrile, benzoic peroxide
Radical initiators such as vinyl and lauroyl peroxide are used
be able to. In addition, the formula represented by the general formula (IX)
The Kuryl resin macromonomer is used as a chain transfer agent, -O.
H, -COOH, -NH₂With a single mercaptan
(Eg thioglycolic acid) of formula (VIII)
It can be manufactured in the same way as acrylic resin macromonomer.
Wear.

The viscosity average molecular weight of the PC-PMMA copolymer thus obtained is not particularly limited and may be appropriately selected according to the application. Usually from 10,000 to 200,0
00, preferably 15,000 to 100,000. Then, the PC-PMMA copolymer has a refractive index (n _D ) by changing the content of the acrylic part in the copolymer.
Can be changed freely. That is, n _D = 1.585 of a homopolymer containing only the polycarbonate part (PC part).
From the homopolymer of acrylic part only n _D = 1.489
Can be changed. Therefore, this PC-PMMA
The ratio of the polycarbonate part to the acrylic part in the copolymer depends on the required refractive index and cannot be uniquely determined.

A polycarbonate-fluoropolycarbonate copolymer (PC-) obtained by copolymerizing a dihydric phenol, particularly BPAF effective therein, as a comonomer for changing the refractive index of the polycarbonate resin. The FPC copolymer) will be described. The PC-FPC copolymer may be of various types, but is preferably of the general formula (X)

[0033]

[Chemical 11]

[In the formula, R ⁶ and R ⁷ each represent hydrogen or an alkyl group having 1 to 4 carbon atoms. ] The repeating unit represented by the general formula (XI)

[0035]

[Chemical formula 12]

It is a copolymer composed of a repeating unit represented by: 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 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
It is 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 the homopolymer of PC only n _D = 1.585, F
PC alone homopolymers can vary up to n _D = 1.50. Therefore, the ratio of the polycarbonate part (PC) to the fluoropolycarbonate part (FPC) in this PC-FPC copolymer varies depending on the required refractive index and cannot be uniquely determined.

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

[0038]

[Chemical 13]

[In the formula, R ⁶ and R ⁷ are the same as defined above. ] And a bis (4-hydroxyphenyl) alkane (BPAL) represented by the general formula (XIII)

[0040]

[Chemical 14]

2,2-bis (4-hydroxyphenyl) 1,1,1,3,3,3-hexafluoropropane (BPAF) represented by the formula (1) and carbonic acid ester such as phosgene or diphenyl carbonate are used. It can be produced by a method usually used for producing a polycarbonate in which a forming compound is reacted. For example, B
A copolymer, BPAL or BPA obtained by synthesizing a PC-FPC oligomer from PAL and BPAF and phosgene and reacting this with BPAL and / or BPAF.
A PC oligomer obtained from F and phosgene, or a copolymer obtained by reacting BPAF with an FPC oligomer,
For example, BPAL and a copolymer of BPAF and phosgene. The bis (4-hydroxyphenyl) alkane used for the synthesis of this PC-FPC copolymer may be any one represented by the above general formula (XII), and there are various kinds. For example, 1,1-bis (4-hydroxyphenyl) ethane; 2,2-bis (4-hydroxyphenyl)
Propane [bisphenol A: BPA]; 2,2-bis (4-hydroxyphenyl) butane and the like.
Of these, bisphenol A (BPA) is particularly preferable.

Further, as another example effective among the dihydric phenols as a comonomer for changing the refractive index of the polycarbonate resin, polycarbonate-bisphenol C obtained by copolymerizing bisphenol C (BPC). The copolymer (PC-BPC copolymer) will be described. The PC-BPC copolymer may be of various types, but is preferably of the general formula (X)

[0043]

[Chemical 15]

[In the formula, R ⁶ and R ⁷ each represent hydrogen or an alkyl group having 1 to 4 carbon atoms. ] A repeating unit represented by the general formula (XIV)

[0045]

[Chemical 16]

It is a copolymer composed of a repeating unit represented by: 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 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
It is 5,000 to 40,000. In this PC-BPC copolymer, the refractive index (n _D ) can be freely changed by changing the content of BPC in the copolymer. That is, from the homopolymer of PC only n _D = 1.585, B
PC only homopolymers can vary up to n _D = 1.57. Therefore, the ratio of the polycarbonate part (PC) to the bisphenol C polycarbonate part (BPC) in this PC-BPC copolymer varies depending on the required refractive index and cannot be uniquely determined.

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

[0048]

[Chemical 17]

[In the formula, R ⁶ and R ⁷ are the same as defined above. ] And a bis (4-hydroxyphenyl) alkane (BPAL) represented by the general formula (XV)

[0050]

[Chemical 18]

1,1-bis (3-methyl-) represented by
4-hydroxyphenyl) propane [bisphenol C: BPC] can be used to produce a polycarbonate by reacting these with a carbonate-forming compound such as phosgene or diphenylcarbonate. For example, a BPAL-BPC oligomer is synthesized from BPAL and BPC and phosgene, and a copolymer obtained by reacting this with BPAL and / or BPC, BPAL or a PC oligomer from BPC and phosgene or BPC is reacted with BPC. The copolymer obtained by the above, BPAL, and the copolymer of BPC and phosgene. This P
The bis (4-hydroxyphenyl) alkane used for the synthesis of the C-BPC copolymer may be any one represented by the above general formula (XII), and there are various kinds. For example, 1,1-bis (4-hydroxyphenyl) ethane; 2,
2-bis (4-hydroxyphenyl) propane [bisphenol A: BPA]; 2,2-bis (4-hydroxyphenyl) butane and the like. Of these, bisphenol A (BPA) is particularly preferable.

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

[0053]

[Chemical 19]

[In the formula, R ⁶ and R ⁷ are the same as defined above. A repeating unit represented by] a general formula _{(XVI) HOOC (CH 2)} 10 COOH ··· dodecane dicarboxylic acid represented by (XVI) (DDCA) was a comonomer copolymer. Here, the number of each repeating unit is 1 or more. The repeating unit of dodecanedicarboxylic acid is 1. And this PC-DDC
The copolymer A is a random copolymer or alternating copolymer in which one or more repeating units of the general formula (X) and dodecanedicarboxylic acid are polymerized. Its viscosity average molecular weight is 1
0,000 to 50,000, preferably 15,000 to 40,0
00. The PC-DDCA copolymer has a different refractive index (n _D ) by changing the content of DDCA in the copolymer.
Can be changed freely. That is, the homopolymer of PC alone can be changed from n _D = 1.585 to about 1.56. Therefore, the ratio of the polycarbonate part (PC) and the DDCA copolymer part (DDCA) in this PC-DDCA copolymer differs depending on the required refractive index and cannot be uniquely determined.

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

[0056]

[Chemical 20]

[In the formula, R ⁶ and R ⁷ are the same as defined above. ] And bis (4-hydroxyphenyl) alkane (BPAL) represented by the general formula (XVI) HOOC (CH ₂ ) ₁₀ COOH ... (XVI) represented by the use of phosgene and diphenyl carbonate It can be produced by a method usually employed for producing a polycarbonate in which such a carbonic acid ester-forming compound is reacted. For example, B
Copolymer, BPAL or DD obtained by synthesizing a PC-DDCA oligomer from PAL and DDCA and phosgene and reacting this with BPAL and / or DDCA
PC oligomer or DDC from CA and phosgene
Examples thereof include copolymers obtained by reacting A oligomer with DDCA, BPAL and copolymers of DDCA and phosgene. The bis (4-hydroxyphenyl) alkane used for the synthesis of this PC-DDCA copolymer may be any one represented by the above general formula (XII), and there are various ones. 1-bis (4-hydroxyphenyl) ethane; 2,2-bis (4-hydroxyphenyl) propane [bisphenol A: BPA]; 2,
2-bis (4-hydroxyphenyl) butane and the like can be mentioned. Of these, bisphenol A (BPA) is particularly preferable.

On the other hand, in the present invention, as the glass of the component (B) constituting the resin composition, if the difference (absolute value) in refractive index (n _D ) from the polycarbonate resin is 0.01 or less, Various types or forms can be applied. For example, glass fibers, glass beads, glass flakes, glass powder and the like can be used, and these may be used alone or in combination of two or more kinds.
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 1 to 30 μm, preferably 5 to 25 μm. The form of the glass fiber is not particularly limited, and various forms such as roving, milled fiber and chopped strand can be used. These glass fibers may be used alone or in combination of two or more. Further, these glass materials are surface-treated with a silane coupling agent such as aminosilane, epoxysilane, vinylsilane, or methacrylsilane, a chromium complex compound, or a boron compound in order to enhance the affinity with the polycarbonate resin. It may be processed.

The resin composition in the present invention has the above (A)
And (B) component, and their compounding ratio is (A) polycarbonate resin 30 to 99% by weight, preferably 50 to 95% by weight, and (B) glass 70 to
It is 1% by weight, preferably 50 to 5% by weight. In this resin composition, if the compounding ratio of the component (B) glass is less than 1% by weight, dimensional stability is lowered and desired rigidity cannot be obtained, which is not preferable. On the other hand, if it exceeds 70% by weight, it is not preferable because it is difficult or impossible to knead the resin and the appearance is further deteriorated. The polycarbonate resin as the component (A) in this resin composition is appropriately selected from the above-mentioned polycarbonate resin or polycarbonate copolymer. On the other hand, the glass of the component (B) may be appropriately selected from the above glasses so that the difference (absolute value) with the refractive index of the polycarbonate resin of the component (A) is 0.01. For example, since a normal polycarbonate resin having a repeating unit derived from bisphenol A has a refractive index of about 1.585, a glass material suitable for this polycarbonate resin is Asahi Fiber having a refractive index of 1.579. ECR glass manufactured by Glass Co., Ltd. may be selected and used. Moreover, since the refractive index (n _D ) of “E” glass, which is widely used for glass fiber reinforced resin, is about 1.545, when this E glass is used, the above-mentioned ordinary polycarbonate resin is used instead. A polycarbonate-based copolymer whose refractive index is close to 1.545 may be used. In the present invention, the difference (absolute value) in refractive index between the (A) polycarbonate resin and (B) glass is set to 0.01 or less, preferably 0.005 or less. The difference (absolute value) between the refractive index of this polycarbonate resin and glass is 0.0
When it exceeds 1, the transparency of the molded product obtained from the resin composition is lowered, which is not preferable.

In the present invention, the resin composition is composed of the component (A) and the component (B), and if necessary, various additive components are blended, kneaded, and poured into a mold. Here, various additive components that can be blended into the resin composition as needed include various additives, other synthetic resins,
Elastomers and the like can be blended within the range not impairing the object of the present invention. For example, various additives include hindered phenol-based, phosphite-based, phosphate-based, amine-based antioxidants, benzotriazole-based and benzophenone-based ultraviolet absorbers,
Examples thereof include light stabilizers such as hindered amine type, external lubricants such as aliphatic carboxylic acid ester type and paraffin type, commonly used flame retardants, mold release agents, antistatic agents, colorants and the like.
And, a method usually used for blending and kneading the above resin composition, 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,
It can be carried out by a method using a multi-screw extruder or the like. The heating temperature during kneading is usually 250 to 3
It is selected in the range of 00 ° C. The resin composition obtained by kneading in this manner is subjected to various known molding methods, for example, injection molding, extrusion molding, compression molding, and the like, to obtain windshields for ships and vehicles in the field of replacing inorganic glass, sunroofs. It is possible to manufacture molded products such as molded products and building materials.

In the present invention, when molding the kneaded resin composition in a mold, a resin film or resin sheet is mounted in the mold. That is, under normal injection molding conditions, a resin film or a resin sheet is attached to both surfaces of the cavity side and the core side in the mold or one surface of the mold, and then the kneaded resin composition is injected into the mold. , Mold. Here, as the resin film or resin sheet mounted in the mold, for example, a resin film of the same or different polycarbonate resin, polyethylene, polypropylene, polyethylene terephthalate (PET), polybutylene terephthalate, polymethyl methacrylate, or the like, or It is a resin sheet. The resin film or resin sheet installed in these molds is
After molding, it may be laminated integrally with the molded product, or may be peeled off from the molded product after molding. By thus acting as a heat insulating material, the resin film or resin sheet mounted in the mold can prevent rapid cooling and solidification of the surface of the molded product and reduce the float of the glass. Further, when peeled off from the molded product, the smooth surface of the resin film or the resin sheet surface is transferred, and remarkably excellent transparency can be obtained as compared with the conventional case where no mounting is performed.
In the case of integrally laminating after molding without peeling from the molded product, it is desirable to use a polycarbonate resin film or sheet from the viewpoints of heat fusion property and optical uniformity. The thickness of these resin films or resin sheets is usually 50 to 1000 μm, preferably 5
It is 0 to 500 μm. The surface roughness is 0.1μ.
It is preferably m or less because the transparency is improved.

The glass-reinforced polycarbonate resin molded article of the present invention can be obtained by various methods. For example, 30 to 99% by weight of (A) polycarbonate resin and (B) glass 70 to 1 obtained by the above-described method.
And the difference (absolute value) between the refractive index of the polycarbonate resin (A) and the refractive index of the glass (B) is
It is a glass-reinforced polycarbonate resin molded article obtained by laminating a resin film or a resin sheet on the surface of a molded article of a polycarbonate resin composition of 0.01 or less. As described above, the resin film or resin sheet acts as a heat insulating material during molding, thereby preventing rapid cooling and solidification of the surface of the molded product and reducing glass float. Also, when peeled off from the molded product, the smooth surface of the resin film or resin sheet can be transferred to make the surface smoother, so it is far superior to the case without conventional mounting. It is possible to obtain an excellent transparency.

[0063]

EXAMPLES Next, the present invention will be described in more detail with reference to Examples and Comparative Examples. The polycarbonate resin, glass and film used are as follows. Polycarbonate-based resin A: Tafflon A2200 (trade name, manufactured by Idemitsu Petrochemical Co., Ltd.) (n _D = 1.585) B: Lexan SP1100 (trade name, manufactured by General Electric Co.) (n _D = 1.581) C: PC-PDMS copolymer produced in Production Example 3 (n _D
= 1.544) Types of glass ECR glass: glass fiber [Asahi Fiber Glass Co., Ltd.] (n _D = 1.579, diameter = 23 μm) E glass: TA-409C [Asahi Fiber Glass Co., Ltd., glass Fiber] (n _D = 1.545, diameter = 23 μm) Film type PC film: Panlite sheet [Teijin Kasei Co., Ltd.
Made, product name] (Thickness 200 μm, surface roughness 0.06 μm) PET film: Lumirror sheet [made by Toray Industries, Inc., product name] (Thickness 70 μm, surface roughness 0.06 μm)

Examples 1 and 2 Tufflon A2200 as a polycarbonate resin and ECR glass as a glass were pre-weighed in a mixing ratio shown in Table 1 and dried, and a 40 mmφ single screw extruder (manufactured by Toshiba Machine Co., Ltd.). And kneaded at 280 ° C. to prepare a resin composition. Then, the resin composition was heated at 120 ° C. for 5 minutes.
After hot air drying for an hour, injection molding machine IS-25EP (manufactured by Toshiba Machine Co., Ltd.) was used to mount PC films on both sides of the mold, and the molding temperature was 280 ° C and the mold temperature was 80 ° C. Injection molding was performed in the mold cavity to produce a flat plate molded product having a thickness of 2 mm.

Example 3 Example 1 was carried out in the same manner as in Example 1 except that the mixing ratio of the resin composition and the film in the mold were changed as shown in Table 1. The film laminated on the obtained molded product was mechanically peeled off. Example 4 The procedure of Example 1 was repeated, except that as the polycarbonate resin, Lexane SP1100 was used, and the mixing ratio of the resin composition was changed as shown in Table 1.

Production Example 1 [Production of PC Oligomer] 60 kg of bisphenol A was dissolved in 400 liters of a 5% sodium hydroxide aqueous solution to prepare an aqueous solution of bisphenol A sodium hydroxide. Then, this bisphenol A kept at room temperature
Of sodium hydroxide solution at a flow rate of 138 liters / hr and methylene chloride at a flow rate of 69 liters / hr were introduced into a tubular reactor having an inner diameter of 10 mm and a tube length of 10 m through an orifice plate, and phosgene was co-flowed thereto. 10.7
It was blown in at a flow rate of kg / hr and continuously reacted for 3 hours. The tubular reactor used here is a double tube, and cooling water is passed through the jacket to keep the reaction solution discharge temperature at 2
It was kept at 5 ° C. Further, the pH of the discharged liquid was adjusted to be 10-11. The reaction liquid thus obtained was allowed to stand still to separate and remove the aqueous phase, a methylene chloride phase (220 liters) was collected, and 170 liters of methylene chloride was further added to this and stirred thoroughly. PC
It was an oligomer (concentration: 317 g / liter). The degree of polymerization of the PC oligomer obtained here was 3 to 4.

Production Example 2 [Production of Reactive Polydimethylsiloxane (PDMS)]
1,483 g of octamethylcyclotetrasiloxane, 3
86 g of 1,1,3,3-tetramethyldisiloxane and 35 g of 86% sulfuric acid were mixed and stirred at room temperature for 17 hours. Then, the oil phase was separated, 25 g of sodium hydrogen carbonate was added, and the mixture was stirred for 1 hour. After filtration, 150 ℃,
Vacuum distillation was performed at 3 torr to remove low-boiling substances. To a mixture of 60 g of 2-allylphenol and 0.0014 g of platinum as platinum chloride-alcoholate complex was added 294 g of the oil obtained above at a temperature of 90 ° C. The mixture was stirred for 3 hours while maintaining the temperature of 90 to 115 ° C. The product was extracted with methylene chloride and washed 3 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. In the obtained terminal phenol PDMS, the number of repeating dimethylsilanooxy units was 30 as measured by NMR.

Production Example 3 [Production of PC-PDMS Copolymer] 858 g of the reactive PDMS produced in Production Example 2 was dissolved in 2 liters of methylene chloride and mixed with 10 liters of the PC oligomer obtained in Production Example 1. 70 g of sodium hydroxide dissolved in 1 liter of water and 5.7 cc of triethylamine were added thereto.
The mixture was stirred at 00 rpm at room temperature for 1 hour. Then, a solution prepared by dissolving 600 g of bisphenol A in 5 liter of a 5.2 wt% sodium hydroxide aqueous solution, 8 liter 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. After that, 5 liters of methylene chloride was added, and further washed with 5 liters of water, washed with 5 liters of 0.01N aqueous sodium hydroxide solution with alkali, washed with 5 liters of 0.1N hydrochloric acid and washed with water.
It was washed successively with liters of water, and finally methylene chloride was removed to obtain a chip-shaped PC-PDMS copolymer. The obtained copolymer was dried at 100 ° C. for 6 hours, press-molded at 290 ° C., and the PDMS content and refractive index (n _D ) were measured. The PDMS content was 19.3% by weight. Also,
Its refractive index was 1.544. The PDMS content, PDMS chain length (dimethylsilanooxy unit) and n
The measurement of _D is as follows. Measurement of PDMS content rate and PDMS chain length (dimethylsilanooxy unit) The PDMS content rate was determined by ¹ H-NMR to show the peak of the isopropyl methyl group of bisphenol A observed at 1.7 ppm and the peak of dimethylsiloxane observed at 0.2 ppm. It was determined by the intensity ratio of the peak of the methyl group. The PDMS chain length is ¹
H-NMR peak of the methyl group of dimethylsiloxane at 0.2 ppm and PC-PD at 2.6 ppm.
It was determined by the intensity ratio of the peak of the methylene group at the MS bond. Measurement of n _{D It} was measured using an Abbe refractometer.

Example 5 In place of the Tufflon A2200 used as the polycarbonate resin in Example 1, the P produced in Production Example 3 was used.
TA-409C as C-PDMS copolymer and glass
Was carried out in the same manner as in Example 1 except that the compounding ratio of the resin composition was changed as shown in Table 1.

Comparative Example 1 The procedure of Example 2 was repeated, except that the PC film was not mounted on both sides of the mold. Comparative Example 2 The procedure of Example 1 was repeated, except that TA-409C was used as the glass.

The haze of the molded products obtained in the examples and comparative examples was measured as a performance evaluation. The results of performance evaluation are shown in Table 1. The haze is measured according to JIS K
It measured based on -7105.

[0072]

[Table 1]

[0073]

As described above, according to the present invention, it is possible to obtain a glass-reinforced polycarbonate resin molded article having excellent transparency while having the original mechanical properties of polycarbonate. Therefore, the glass-reinforced polycarbonate-based resin molded product of the present invention can be effectively used in a wide range of fields, such as a field for substituting inorganic glass for windows for ships and vehicles, and construction materials.

─────────────────────────────────────────────────── ───

[Procedure amendment]

[Submission date] April 15, 1993

[Procedure Amendment 1]

[Document name to be amended] Statement

[Correction target item name] 0018

[Correction method] Change

[Correction content]

[In the formula, X, Y, a and b are the same as defined above, and Hal represents a halogen atom (for example, chlorine, bromine, fluorine, iodine), and t = 2 to 20. ] Is represented. This PC oligomer is represented by the general formula (I) in the solvent method, that is, in the presence of a known acid acceptor and molecular weight modifier in a solvent such as methylene chloride.

[Procedure Amendment 2]

[Document name to be amended] Statement

[Correction target item name] 0064

[Correction method] Change

[Correction content]

Examples 1 and 2 Tufflon A2200 as a polycarbonate resin and ECR glass as a glass were pre-weighed in a mixing ratio shown in Table 1 and dried, and a 40 mmφ single screw extruder (manufactured by Toshiba Machine Co., Ltd.). And kneaded at 280 ° C. to prepare a resin composition. Then, the resin composition was heated at 120 ° C. for 5 minutes.
After drying with hot air for an hour, using an injection molding machine IS-25EP (manufactured by Tanabe Plastic Machinery Co., Ltd.), PC films were attached to both surfaces in the mold, and a molding temperature of 280 ° C., 80 ° C.
Injection molding was performed in the mold cavity at the mold temperature of 3 to prepare a flat plate molded product having a thickness of 2 mm.

[Procedure 3]

[Document name to be amended] Statement

[Correction target item name] 0067

[Correction method] Change

[Correction content]

Production Example 2 [Production of Reactive Polydimethylsiloxane (PDMS)]
1,483 g of octamethylcyclotetrasiloxane, 9
6 g of 1,1,3,3-tetramethyldisiloxane and 35 g of 86% sulfuric acid were mixed and stirred at room temperature for 17 hours.
Then, the oil phase was separated, 25 g of sodium hydrogen carbonate was added, and the mixture was stirred for 1 hour. After filtration, 150 ℃, 3t
Vacuum distillation was performed at orr to remove low-boiling substances. 60 g of 2-
To a mixture of allylphenol and 0.0014 g of platinum as platinum chloride-alcoholate complex was added 294 g of the oil obtained above at a temperature of 90 ° C. The mixture was stirred for 3 hours while maintaining the temperature of 90 to 115 ° C. The product was extracted with methylene chloride and washed 3 times with 80% aqueous methanol to remove excess 2-allylphenol.
The product was dried over anhydrous sodium sulfate and 1 in vacuo
The solvent was distilled off to a temperature of 15 ° C. In the obtained terminal phenol PDMS, the number of repeating dimethylsilanooxy units was 30 as measured by NMR.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁵ Identification number Reference number within the agency FI Technical display location C08L 69:00 8416-4J (72) Inventor Masaya Okamoto 1 Iezaki Kaigan, Ichihara, Chiba Idemitsu Petroleum Chemical Co., Ltd.

Claims (2)

[Claims] 1. A polycarbonate resin (A) 30 to 9
9% by weight and (B) 70 to 1% by weight of glass, and the difference (absolute value) between the refractive index of the polycarbonate resin of (A) and the refractive index of the glass of (B) is 0.01 or less. A method for producing a glass-reinforced polycarbonate resin molded article, which comprises molding a certain polycarbonate resin composition in a mold by previously mounting a resin film or a resin sheet in the mold. 2. A polycarbonate resin (A) 30 to 9
9% by weight and (B) 70 to 1% by weight of glass, and the difference (absolute value) between the refractive index of the polycarbonate resin of (A) and the refractive index of the glass of (B) is 0.01 or less. A glass-reinforced polycarbonate resin molded article, comprising a resin film or a resin sheet laminated on the surface of a molded article of a certain polycarbonate resin composition.