JPH05140461A - Polycarbonate resin composition - Google Patents

Abstract

PURPOSE:To obtain the subject composition excellent in transparency and also in flame retardancy and mold release. CONSTITUTION:The objective composition comprises a polycarbonate polyorganosiloxane copolymer (A), glass (B) and a polycarbonate resin (C), and the difference (in terms of an absolute value) in the refractive index between the mixture of components A and C and that of component B is 0.01 or smaller.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a polycarbonate resin composition, and more particularly to a polycarbonate resin composition having excellent transparency, flame retardancy and releasability.

[0002]

2. Description of the Related Art Polycarbonate resins are excellent in mechanical strength, electrical characteristics and transparency and are widely used as engineering plastics in various fields such as electric and electronic equipment fields and automobile fields. There is. As the polycarbonate resin having such characteristics, a glass fiber reinforced polycarbonate resin to which glass fiber is added in order to improve rigidity and dimensional stability is well known. However, the polycarbonate resin has a drawback that the transparency is significantly lowered by the addition of the glass fiber, and an unpleasant semi-transparent or hazy appearance is exhibited. 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, and that of "E" glass widely used for glass fiber reinforced resin is about 1.545, which is a considerable difference.
As a method for improving this drawback, Japanese Patent Publication No. 62-133.
As disclosed in Japanese Patent Publication No. 8, ZrO ₂ and TiO ₂ which have a refractive index improving effect on SiO ₂ which is a main component of glass.
It is blended with a polycarbonate resin using a special glass fiber added with. However, the compounding of TiO ₂ causes a problem that the glass is colored brown. Further, adding ZrO ₂ or TiO ₂ to glass has a drawback that it becomes expensive.

Therefore, the present inventor has conducted earnest studies to solve the drawbacks of the conventional methods and to develop a polycarbonate resin composition having excellent transparency, flame retardancy and releasability. As a result, they have found that a resin composition comprising a polycarbonate-polyorganosiloxane copolymer, glass and a polycarbonate resin can provide a polycarbonate resin composition having desired properties. The present invention has been completed based on such findings.

[0004]

That is, the present invention is
(A) Polycarbonate-polyorganosiloxane copolymer 10 to 95% by weight, (B) glass 5 to 60% by weight and (C) polycarbonate resin 0 to 85% by weight, and a mixed resin of (A) and (C). The present invention provides a polycarbonate resin composition, characterized in that the difference (absolute value) between the refractive index of 1 and the refractive index of glass is 0.01 or less.

Polycarbonate-polyorganosiloxane copolymer (PC-PDM) which is the component (A) of the present invention.
There are various S), but the general formula (I) is preferable.

[0006]

[Chemical 1]

[Wherein R ¹ and R ² are a hydrogen atom and a halogen atom (for example, chlorine, bromine, fluorine, iodine), respectively.
Or an alkyl group having 1 to 8 carbon atoms, which may be the same or different, m and n are each an integer of 1 to 4, and m is 2 to 4; Is R ¹
May be the same or different from each other,
When n is 2 to 4, they may be the same or different. Z is an alkylene group having 1 to 8 carbon atoms, an alkylidene group having 2 to 8 carbon atoms, and 5 to 15 carbon atoms.
Cycloalkylene group, a cycloalkylidene group or -SO ₂ of 5 to 15 carbon atoms -, - SO -, - S -, - O-,
-CO- bond or general formula (II)

[0008]

[Chemical 2]

The bond represented by ] A polycarbonate unit having a degree of polymerization of 3 to 50, which has a repeating unit having a structure represented by the following general formula (III)

[0010]

[Chemical 3]

[In the formula, R ³ , R ⁴ and R ⁵ 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, p and q are each an integer of 0 or 1 or more. ] It consists of the polyorganosiloxane part which has a repeating unit represented by this. 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 above polycarbonate-polyorganosiloxane copolymer is a block composed of 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 100,000
It is from 0 to 40,000, preferably from 15,000 to 35,000.

The ratio of the polycarbonate part to the polyorganosiloxane part in the (A) polycarbonate-polyorganosiloxane copolymer varies depending on the required refractive index and cannot be uniquely determined, but usually the polycarbonate part 50 to 50 parts. 99.9% by weight, preferably 6
0-99.5% by weight, polyorganosiloxane part 50-0.
It is selected in the range of 1% by weight, preferably 40 to 0.5% by weight. Such a polycarbonate-polyorganosiloxane copolymer constitutes, for example, a polycarbonate oligomer (PC oligomer) which constitutes the polycarbonate part produced in advance and a polyorganosiloxane part,
A polyorganosiloxane having a reactive group at the end (eg, polydialkylsiloxane such as polydimethylsiloxane or polydiethylsiloxane or polymethylphenylsiloxane) is dissolved in a solvent such as methylene chloride, chlorobenzene or pyridine, and bisphenol water is added. It can be produced by adding an aqueous solution of sodium oxide and using an interface catalyst such as triethylamine or trimethylbenzylammonium chloride as a catalyst.
In addition, Japanese Patent Publication No. 44-30105 and Japanese Patent Publication No. 45-2
It is also possible to use the polycarbonate-polyorganosiloxane copolymer produced by the method described in Japanese Patent No. 0510. Here, the polycarbonate oligomer having a repeating unit represented by the general formula (I) can be prepared by the solvent method, that is, in the presence of a known acid acceptor and a molecular weight modifier in a solvent such as methylene chloride.

[0013]

[Chemical 4]

(Wherein R ¹ , R ² , Z, m and n are the same as described above) or the reaction of the dihydric phenol with a carbonate precursor such as phosgene or the dihydric phenol and diphenyl. It can be produced by a transesterification reaction with a carbonate precursor such as carbonate. There are various dihydric phenols represented by the above general formula (IV), and particularly 2,2-bis (4-
Hydroxyphenyl) propane [bisphenol A] is preferred. Further, a part or all of bisphenol A may be replaced with another dihydric phenol. Examples of dihydric phenols other than bisphenol A include bis (4-hydroxyphenyl) alkanes other than bisphenol A, 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 (3,5-dibromo-4-hydroxyphenyl) Bropan; halogenated bisphenols such as bis (3,5-dichloro-4-hydroxyphenyl) bropan and the like can be mentioned. In the present invention, the polycarbonate oligomer used for producing the polycarbonate-polyorganosiloxane copolymer may be a homopolymer using one of these dihydric phenols, or a copolymer using two or more thereof. May be. 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 thus obtained polycarbonate-polyorganosiloxane copolymer 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.

Next, the polycarbonate resin (PC) which is the component (C) of the present invention can be easily produced by reacting a dihydric phenol 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, the dihydric phenol may be the same as or different from the compound represented by the general formula (IV). Examples of the carbonic acid ester compound include diaryl carbonate such as diphenyl carbonate and dialkyl carbonate such as dimethyl carbonate and diethyl carbonate.

On the other hand, as the glass (B) used together with the polycarbonate-polyorganosiloxane copolymer and the polycarbonate resin, various kinds 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 3 to 20 μm, preferably 5 to 15 μm.
Is. The form of the glass fiber is not particularly limited, and examples thereof include various types such as roving, milled fiber, chopped strand and the like. These glass fibers may be used alone or in combination of two or more kinds.
Further, these glass materials are surface-treated with silane coupling agents such as aminosilane-based, epoxysilane-based, vinylsilane-based, methacrylsilane-based, chromium complex compounds, boron compounds, etc. in order to enhance the affinity with resins. It may be

The resin composition of the present invention comprises the above (A) to
Although it is composed of the component (C), the blending ratio thereof is 10 to 95% by weight, preferably 10 to 90% by weight of the polycarbonate-polyorganosiloxane copolymer (A), and 5 to 60% by weight of the glass (B). %, Preferably 10-5
0% by weight and 0 to 85% by weight of the (C) polycarbonate resin, preferably 0 to 80% by weight. Where (A)
The polycarbonate-polyorganosiloxane copolymer can reduce the compounding amount of the (C) polycarbonate resin when using a copolymer having a high copolymerization ratio of the polycarbonate part, and the polycarbonate resin as the (C) component. In some cases, it may not be necessary to blend. In the resin composition of the present invention, if the compounding ratio of the glass (B) is less than 5% by weight, the dimensional stability is lowered, which is not preferable. On the other hand, if it exceeds 60% by weight, it is difficult or impossible to knead the resin, which is not preferable. And as glass,
When “E” glass is used, it is preferable that the polyorganosiloxane part in the copolymer as the component (A) is made of polydimethylsiloxane. That is, since the refractive index n _{D of} E glass is about 1.545, the n _D of the entire resin composition is 1.30 by adjusting the proportion of polydimethylsiloxane in the copolymer (A) to 13 to 30% by weight. 555 to 1.535
It is possible to make the refractive index close to, and it is very effective in improving transparency. In the present invention, the difference (absolute value) between the refractive index of the mixed resin containing the (A) polycarbonate-polyorganosiloxane copolymer and the (C) polycarbonate and the refractive index of the glass is 0.01 or less, preferably 0.1. 005 or less. If the difference (absolute value) in the refractive index between this resin and glass exceeds 0.01, the transparency of the molded product obtained from the resin composition is reduced, which is not preferable.

The resin composition of the present invention can be obtained by blending the above-mentioned components (A), (B) and (C) and various additive components used as necessary and kneading. The compounding and kneading are carried out by a commonly used method, for example, a method using a ribbon blender, a Henschel mixer, a Banbury mixer, a drum tumbler, a single-screw extruder, a twin-screw extruder, a co-kneader or a multi-screw extruder. It can be carried out. The heating temperature during kneading is usually 250 to 300 ° C.
It is selected in the range of. The polycarbonate resin composition thus obtained is subjected to various known molding methods such as injection molding, blow molding, extrusion molding, compression molding, calender molding,
By applying rotational molding and the like, it is possible to manufacture molded articles in the automotive field such as automotive glass and sunroofs, and molded articles in the home appliance field. If necessary, various additives, other synthetic resins, elastomers and the like can be added to the resin composition of the present invention within a range that does not impair the object of the present invention. For example, various additives include hindered phenol-based additives,
Antioxidants such as phosphite ester, phosphate ester and amine, UV absorbers such as benzotriazole and benzophenone, light stabilizers such as hindered amine, and aliphatic carboxylic acid ester and paraffin Examples include external lubricants, commonly used flame retardants, mold release agents, antistatic agents, coloring agents and the like.

[0019]

EXAMPLES Next, the present invention will be described in more detail with reference to production examples, examples and comparative examples. Production Example 1 [Production of Polycarbonate (PC) Oligomer] 400
60 kg of bisphenol A was dissolved in liter of 5% sodium hydroxide aqueous solution to prepare a sodium hydroxide aqueous solution of bisphenol A. Then, a sodium hydroxide aqueous solution of bisphenol A kept at room temperature was flown at a flow rate of 138 l / hr, and methylene chloride was added at 69 l / hr.
At a flow rate of hr, it was introduced into a tubular reactor with an inner diameter of 10 mm and a tube length of 10 m through an orifice plate, and phosgene was co-flowed to
It was blown in at a flow rate of 0.7 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.

[Reactive polydimethylsiloxane A (PD
Synthesis of MS-A) Preparation Example 2-1 1483 g of octamethylcyclotetrasiloxane, 3
36 g of 1,1,3,3-tetramethyldisiloxane and 35
86 g sulfuric acid (g) was 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, 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 platinum chloride-alcoholate complex was added 294 g of the oil obtained above at a temperature of 90 ° C. 90 to 1 of this mixture
The mixture was stirred for 3 hours while maintaining the temperature of 15 ° C. Excess 2-allylphenol was removed by washing 3 times with 80% aqueous methanol. The product was dried over anhydrous sodium sulphate and evaporated in vacuo to a temperature of 115 ° C. In the obtained terminal phenol PDMS-A, the number of repeating dimethylsilanooxy units was 10 as measured by NMR. Production Example 2-2 (Synthesis of Reactive PDMS-B) In Production Example 2-1, 1,
Example 1 was repeated except that the amount of 1,3,3-tetramethyldisiloxane was changed to 96 g. The number of repeating dimethylsilanooxy units of the obtained terminal phenol PDMS-B was 30 as measured by NMR. Production Example 2-3 (Synthesis of Reactive PDMS-C) In Production Example 2-1,
Example 1 was repeated except that the amount of 1,3,3-tetramethyldisiloxane was changed to 56 g. The obtained terminal phenol PDMS-C had a repeating number of dimethylsilanooxy units of 50 as measured by NMR. Production Example 2-4 (Synthesis of Reactive PDMS-D) In Production Example 2-1,
The procedure of Preparation Example 2-1 was repeated, except that the amount of 1,3,3-tetramethyldisiloxane was changed to 18.1 g. The obtained terminal phenol PDMS-D was measured by NMR,
The number of repeating dimethylsilanooxy units was 150.

Production Examples 3-1 to 8 Ag of reactive PDMS-X was dissolved in 2 liters of methylene chloride and mixed with 10 liters of the PC oligomer obtained in Production Example 1. 50 g of sodium hydroxide bg dissolved in 1 liter of water and 5.7 cc of triethylamine were added thereto.
The mixture was stirred at 0 rpm at room temperature for 1 hour. After that, 5.2% by weight
Of bisphenol A 600 g dissolved in 5 liter of sodium hydroxide aqueous solution, methylene chloride 8 liter and p-tert-butylphenol 60 g were added to 500 rp.
Stirred at room temperature for 2 hours at m 2. Then, add 5 liters of methylene chloride, wash with 5 liters of water, and add 0.01 liter.
Alkaline cleaning with 5 liters of N sodium hydroxide solution,
Acid washing with 5 liters of 0.1N hydrochloric acid and water washing with 5 liters of water were sequentially performed, and finally methylene chloride was removed to obtain a chip-shaped PC-PDMS copolymer. The obtained copolymer is 1
It was dried at 00 ° C. for 6 hours, press-molded at 290 ° C., and the refractive index (n _D ) was measured. X, a in Production Examples 3-1 to 8
Table 1 shows the value of b, the PDMS content of the obtained PC-PDMS copolymer, and the value of n _D.

[0022]

[Table 1]

The PDMS content, PDMS chain length (dimethylsilanooxy unit) and n _D are measured as follows. 1) Measurement of PDMS content rate and PDMS chain length The PDMS content rate is the peak of the isopropyl methyl group of bisphenol A observed 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-
The intensity was determined by the intensity ratio of the peak of the methyl group of dimethylsiloxane seen at 0.2 ppm by NMR and the peak of the methylene group of the PC-PDMS bond seen at 2.6 ppm. 2) Measurement of n _D An Abbe refractometer was used.

Examples 1 to 7 and Comparative Examples 1 to 5 The PC-PDMS copolymers obtained in Production Examples 3-1 to 7 were used, and the polycarbonate resin was FN-2.
200 [manufactured by Idemitsu Petrochemical Co., Ltd.], and MA-409C [manufactured by Asahi Fiber Glass Co., Ltd., n _D = 1.545] as the glass fiber, and extruded with a 30 mm vent at a ratio shown in Table 2. Pellets were made on a machine at 300 ° C. The glass fiber was supplied from the downstream side of the hopper supply position of the extruder. The obtained pellets were press-molded at 300 ° C. Example 8 The copolymer obtained in Production Example 3-7 and FN-2000 (manufactured by Idemitsu Petrochemical Co., Ltd.) as a polycarbonate resin were used in an extruder at a ratio of 61.4: 38.6 at 300 ° C. (By weight). It carried out like Example 1 except having used the obtained mixed resin. The n _{D of} this mixed resin is 1.
It was 547. Example 9 and Comparative Example 6 Example 9 and Comparative Example 6 were carried out in the same manner as in Example 1 except that glass beads [EGB-731A: manufactured by Toshiba Parodyni Co., Ltd., n _D = 1.545] were used. Example 10 As a glass with the copolymer obtained in Production Example 3-8, glass fiber [ECR (electric corrosion resista
nt) Glass: Asahi Fiber Glass Co., Ltd., n _D = 1.5
79] was used, and the same procedure as in Example 9 was performed. Example 11 The copolymer obtained in Production Example 3-2 and FN-2200 (manufactured by Idemitsu Petrochemical Co., Ltd.) as a polycarbonate resin were used in an extruder at a ratio of 11.2: 88.8 at 300 ° C. (By weight). It carried out like Example 1 except having used the obtained mixed resin. The n _{D of} this mixed resin is 1.
It was 579. It carried out like Example 9 except having used glass fiber (ECR glass) as the obtained mixed resin and glass. The molded articles obtained in Examples and Comparative Examples were subjected to haze measurement and flame retardancy test as performance evaluations. The results of performance evaluation are shown in Table 3. The performance evaluation was performed according to the following test method. 1) Measurement of haze A test piece having a thickness of 3 mm was measured according to JIS K7105. 2) Flame-retardant test Flame-retardant test UL-94 1/16 inch (thickness) A vertical combustion test was conducted according to Underriders Laboratory Subject 94.

[0025]

[Table 2]

[0026]

[Table 3]

[0027]

As described above, according to the present invention, a polycarbonate resin composition having excellent transparency and flame retardancy and releasability while having the original mechanical properties of polycarbonate is obtained. be able to. Therefore, the polycarbonate resin composition of the present invention,
It is effectively used as a material for various molded products that are widely used in the automobile field and the like.

Claims (4)

[Claims] 1. A polycarbonate-polyorganosiloxane copolymer (A) 10 to 95% by weight, (B) glass 5 to
60% by weight and 0 to 85% by weight of (C) polycarbonate resin, and the difference (absolute value) between the refractive index of the mixed resin of (A) and (C) and the refractive index of glass is 0.01 or less. A polycarbonate resin composition comprising: 2. The polycarbonate resin composition according to claim 1, wherein the polyorganosiloxane is polydimethylsiloxane. 3. The polycarbonate resin composition according to claim 1, wherein the glass is E glass. 4. The polycarbonate resin composition according to claim 1, wherein the glass is glass fiber.