JP3026612B2 - Polycarbonate resin composition - Google Patents

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 containing a novel polycarbonate-polydimethylsiloxane (PC-PDMS) copolymer and a rubber-like elastic material and having excellent impact resistance. About things.

[0002]

2. Description of the Related Art In general, polycarbonate resins are resins having excellent impact resistance, and improvement by blending with other resins has been widely performed. For example, the impact resistance of a polycarbonate resin has been improved by adding a rubber-like elastic body. However, improvement in impact resistance could not be expected in a range where strength and elastic modulus were not greatly reduced only by adding a rubber-like elastic body. As a solution to this problem, a polycarbonate resin comprising a graft copolymer of polycarbonate-polysiloxane and acrylic rubber or polydimethylsiloxane (PDMS) and a rubber (see JP-A-61-200161) and a polycarbonate-polysiloxane Polycarbonate resin consisting of styrene and isobutylene
No. 51452). However, such polycarbonate resin compositions use polycarbonate-polysiloxane for both, so that the impact resistance is improved, but there is a problem that the improvement effect is low. By the way, recently, the group of the present inventors has succeeded in developing a polycarbonate copolymer having a new structure with improved impact resistance while maintaining the mechanical and optical properties of a conventional polycarbonate. Japanese Patent Application No. 1-174046 and PCT / JP90 / 00864). The present inventors have intensively studied to further improve the properties while maintaining the advantages of the above-mentioned novel polycarbonate copolymer.

[0003]

As a result, it has been found that the impact resistance can be further improved by adding a rubber-like elastic material to this novel polycarbonate-based copolymer. The present invention has been completed based on such findings. That is, the present invention relates to (A) the general formula (a)

[0004]

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[Wherein R ¹ and R ² each independently represent hydrogen and an alkyl group having 1 to 4 carbon atoms, and R ³ and R ⁴ each independently represent hydrogen, a halogen, an alkyl group having 1 to 20 carbon atoms. Or an aryl group, x represents an integer of 1 to 5, y represents an integer of 1 to 4, and n represents an integer of 1 to 100. And a general formula (b)

[0006]

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[Wherein, R ⁵ and R ⁶ each independently represent an organic residue containing an aromatic nucleus, and m represents an integer of 100 or more. A copolymer comprising a polydimethylsiloxane block represented by the formula: wherein the proportion of the polydimethylsiloxane block portion in the copolymer is 0.5 to 10% by weight and n-hexane Solute content is 1.0% by weight
Polycarbonate-polydimethylsiloxane having a viscosity average molecular weight of 10,000 to 50,000 (PC-PD
(MS) A polycarbonate resin composition comprising 40 to 99% by weight of a copolymer and (B) 60 to 1% of a rubber-like elastic body.

[0008] The composition of the present invention comprises (A) PC
PC-PD which is mainly composed of a PDMS copolymer and (B) a rubber-like elastic material, wherein the component (A) is
As described above, the MS copolymer includes a polycarbonate (hereinafter, sometimes referred to as PC) block represented by the general formula (a) and a polydimethylsiloxane (hereinafter, sometimes referred to as PDMS) represented by the general formula (b). It is a block copolymer composed of blocks. R ¹ in the general formula (a)
And R ² are each independently hydrogen or an alkyl group having 1 to 4 carbon atoms, for example, a methyl group, an ethyl group, an n-propyl group, an i-propyl group, an n-butyl group, an i-butyl group, and s.
-Butyl group and t-butyl group. In addition, the general formula (a)
R ³ and R ^{4 in the above} are each independently hydrogen, halogen (eg, chlorine, fluorine, bromine, etc.), carbon number 1-20.
(E.g., methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, s-butyl, t-butyl, n-octyl, t-butyl)
-Octyl group, n-decyl group, n-octadecyl group, etc.) or aryl group (for example, phenyl group, benzyl group, α, α-dimethylbenzyl group). Also,
R ⁵ and R ⁶ in the general formula (b) are organic residues having an aromatic nucleus. Here, there are various organic residues having an aromatic nucleus, for example, a 3- (o-hydroxyphenyl) propylene group, a 2- (p-hydroxyphenyl) ethylene group or

[0009]

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And the like. Also,
The PC-PDMS copolymer as the component (A) has, for example, the general formula (c):

[0011]

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Wherein R ¹ , R ² , R ⁴ and y are the same as above. An organic dihydroxy compound represented by the general formula (d):

[0013]

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Wherein R ⁵ , R ⁶ and m are the same as above. And a carbonate-forming derivative in a liquid medium in the presence of a molecular weight regulator. Here, there are various organic dihydroxy compounds represented by the general formula (c). For example, bis (4-hydroxyphenyl) alkane may be mentioned, and more specifically, 2,2-bis (4 -Hydroxyphenyl) propane [commonly known as bisphenol A]; bis (4-hydroxyphenyl) methane; 1,1-bis (4-hydroxyphenyl) ethane; 1,1-bis (4-hydroxyphenyl)
Propane; 2,2-bis (4-hydroxyphenyl) butane; 2,2-bis (4-hydroxyphenyl) pentane; 2,2-bis (4-hydroxyphenyl) isopentane; 2,2-bis (4-hydroxy Phenyl) hexane; 2,2-bis (4-hydroxyphenyl) isohexane; 4,4-dihydroxytriphenylmethane;
4-dihydroxytetraphenylmethane; 1,1-bis (4-hydroxyphenyl) cyclohexane; 2,2-
Bisphenols such as bis (4,4-hydroxy-3-methylphenyl) propane; 2,2-bis (4,4-hydroxy-3,5-dimethylphenyl) propane. The polydimethylsiloxane represented by the general formula (d) is obtained by, for example, reacting octamethylcyclotetrasiloxane with disiloxane to produce a polydimethylsiloxane having a hydrogen terminal, and reacting the resulting product with allylphenol. , Terminal phenol polydimethylsiloxane can be synthesized. At this time, the number of repeating dimethylsilanoxy units can be controlled by the ratio of octamethylcyclotetrasiloxane to disiloxane. This production process can be represented by the following reaction formula.

[0015]

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Here, the repeating number m of the dimethylsilanooxy unit needs to be 100 or more. When m is less than 100, the Izod impact resistance is reduced when mixed with, for example, glass fiber used as a filler. If m exceeds 400, the production becomes difficult and is not practical.

After completion of the reaction, low boiling components (mainly 2
It is desirable to perform vacuum distillation in order to remove 〜trimer). The conditions for vacuum distillation are not particularly limited.
Distillation may be performed at 00 ° C. and at 10 Torr or less until low-boiling components are not distilled off (for example, 1 to 200 minutes). As the carbonate-forming derivative, phosgene is usually used. In addition to phosgene, various compounds such as bromophosgene, diphenyl carbonate, di-p-tolyl carbonate, phenyl-p-tolyl carbonate,
It is also possible to use di-p-chlorophenyl carbonate, dinaphthyl carbonate, or the like, or a polycarbonate oligomer comprising these compounds and the organic dihydroxy compound.

In the present invention, when producing a PC-PDMS copolymer from the above-mentioned organic dihydroxy compound and polydimethylsiloxane and a carbonate-forming derivative, a molecular weight modifier is present in the reaction system. As the molecular weight regulator, various substances can be used, and specifically, pentahalogenophenol (for example, pentabromophenol, pentachlorophenol, pentafluorophenol), trihalogenphenol (for example, tribromophenol, trichlorophenol) ,
Trifluorophenol), phenol, p-crezo-
, P-tert-butylphenol, p-tert-octylphenol, p-cumylphenol and the like.

The amount of the organic dihydroxy compound to be charged may be appropriately determined depending on the degree of polymerization of the PC block to be produced. On the other hand, the amounts of the molecular weight regulator and the carbonate-forming derivative to be introduced define the degree of polymerization of the PC block. Therefore, the introduction amount may be an amount according to the purpose.
The specific amount of the molecular weight regulator to be introduced may be an amount sufficient to bond to the terminal positions (particularly, both terminal positions) of the produced polycarbonate or an amount slightly larger than the amount.

The polydimethylsiloxane is contained in the copolymer
It is preferred that the compounding agent be present in an amount of 0.5 to 10% by weight, particularly 1 to 10% by weight. When the amount is less than 0.5% by weight, the Izod impact resistance is reduced when mixed with, for example, glass fiber used as a filler. However, if it exceeds 10% by weight, the heat distortion temperature decreases. The PC-PDMS copolymer used in the present invention can be produced by allowing the reaction to proceed in a liquid medium. Specifically, the reaction can be carried out according to a known interfacial polymerization method or pyridine method. I just need.

The PC block represented by the general formula (a) obtained as described above and the P block represented by the general formula (b)
The copolymer composed of DMS blocks is 10,000 to 50,000,
Preferably it has a viscosity average molecular weight of 12,000 to 30,000. If the viscosity average molecular weight is less than 10,000, the Izod impact resistance is low, which is not suitable for the purpose of the present invention. However, those having a viscosity average molecular weight of more than 50,000 are difficult to produce.

The PC-PDMS copolymer of the present invention has an n-hexane soluble content of 1.0% by weight or less. Here, when the n-hexane soluble content exceeds 1.0% by weight,
When mixed with an inorganic filler such as glass fiber, the effect of improving impact resistance is small. In particular, in order to enhance the effect of improving the impact resistance when mixed with glass fiber or the like, the above-mentioned PC-P
It is preferable that the DMS copolymer has a crystallinity of 30% or more. In order to produce a PC-PDMS copolymer having an n-hexane soluble content of 1.0% by weight or less, for example, the content of PDMS in the copolymer is reduced to 10% by weight or less, and the content of PDMS in PDMS is reduced. The above-mentioned copolymerization reaction may be carried out by using one having a repeating number of dimethylsilanooxy units of 100 or more and using a catalyst such as a tertiary amine or the like in an amount of 5.3 × 10 ⁻³ mol / kg oligomer or more.

On the other hand, examples of the rubbery elastic body which is the component (B) used in the present invention include natural rubber, synthetic rubber, and graft copolymer. The rubber-like elastic body used here is not particularly limited, and for example, natural rubber (N
R), styrene-butadiene rubber (SBR), butyl rubber (BR), isoprene rubber (IR), nitrile-butadiene rubber (NBR), nitrile-isoprene rubber (N
IR), diene rubbers such as chloroprene rubber (CR), isobutylene-isopropylene rubber (IIR), ethylene-propylene rubber (EPM), ethylene-propylene-diene rubber (EPDM), chlorosulfonated polyethylene rubber (CSM), halogen Butyl rubber, styrene-butadiene block copolymer rubber, styrene
Isoprene block copolymer rubber, rubbery chlorosulfonated polyethylene (CSM), rubbery chlorinated polyethylene (CPE), acrylic rubber, copolymer of alkyl acrylate and 2-chloroethyl vinyl ether (A
CM), copolymer of alkyl acrylate and acrylonitrile (ANM), urethane rubber (thermoplastic type), silicone rubber, fluoro rubber, polyester
Polyether-polyester block copolymer rubber, epichlorohydrin rubber, ethylene-vinyl acetate rubber (E
Olefin rubbers such as VM), various acrylic rubbers, other organic silicon compounds, organic fluorine compounds, urethanes, ethers, and the like. Furthermore, M
AS resin (graft copolymer of 60 to 80% by weight of n-butyl acrylate with styrene and methyl methacrylate) and MABS resin (copolymerized octyl acrylate and butadiene at a weight ratio of 7: 3). Styrene and methyl methacrylate are added to the obtained rubber latex and copolymerized by graft polymerization, MBS resin (styrene is added to the rubber latex obtained by copolymerizing methyl methacrylate and butadiene, and grafting is performed. (A copolymer obtained by polymerization).

In the composition of the present invention described above, the mixing ratio of the component (A) and the component (B) is usually 40 to 99% by weight of the component (A) and 60 to 1% by weight of the component (B). It is. Preferably, 50 to 95% by weight of the component (A) and 50 to 5% by weight of the component (B) are good. When the content of the component (A) is less than 40% by weight, the inherent impact resistance of the PC-PDMS copolymer is not sufficiently exhibited, and when it exceeds 99% by weight, the fluidity becomes poor. When the amount of the component (B) is less than 1% by weight, no improvement in fluidity is observed, and when it exceeds 60% by weight, the strength and the elastic modulus decrease.

The polycarbonate resin composition of the present invention contains various inorganic fillers, as long as the object of the present invention is not impaired.
Glass fibers, additives or other synthetic resins can be blended as required. First, examples of the inorganic filler compounded for the purpose of increasing the mechanical strength, durability, or weight of the polycarbonate resin composition include, for example, glass fiber (GF), carbon fiber (CF), glass beads, glass flake, carbon black, Examples include calcium sulfate, calcium carbonate, calcium silicate, titanium oxide, alumina, silica, asbestos, talc, clay, mica, and quartz powder. Examples of the additive include phosphorus-based (phosphite-based, phosphate-based, etc.) and amine-based antioxidants, such as benzotriazole-based and benzophenone-based ultraviolet absorbers, such as aliphatic carboxylic acids. Examples thereof include ester-based and paraffin-based external lubricants, commonly used flame retardants, release agents, antistatic agents, and colorants. Examples of other synthetic resins include resins such as polyethylene, polypropylene, polystyrene, AS resin, ABS resin, and polymethyl methacrylate.

The polycarbonate resin composition of the present invention comprises
It can be obtained by blending and kneading the above components. For the compounding and kneading, a usual method can be adopted. For example, it can be carried out by 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, or the like. A suitable heating temperature for kneading is usually from 250 to 300 ° C. The polycarbonate resin composition thus obtained is subjected to various known molding methods, for example, injection molding, extrusion molding, compression molding, calender molding, rotational molding and the like, and is applied to molded articles in the automobile field such as bumpers for automobiles and in the field of home appliances. Molded articles can be manufactured. The polycarbonate resin composition of the present invention,
Especially in the field of automobiles, it is suitable for interior materials.

[0027]

Next, the present invention will be described in more detail with reference to examples. Production Example 1 (Synthesis of PDMS with terminal phenol) 1483 g of octamethylcyclotetrasiloxane, 1,1,3
18.1 g of 3-tetramethyldisiloxane and 35 g of 86% sulfuric acid were mixed 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 chloride-alcoholate complex, 294
g of the oil obtained above were added at a temperature of 90 ° C.
The mixture was stirred for 3 hours while maintaining the temperature at 90-115 ° 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. According to the measurement of nuclear magnetic resonance (NMR), the number of repeating dimethylsilanooxy units of the obtained terminal phenol PDMS was 150.

Production Example 2 (Synthesis of polycarbonate oligomer of bisphenol A) 60 kg of bisphenol A was dissolved in 400 liter of 5% aqueous sodium hydroxide solution.
An aqueous sodium hydroxide solution of bisphenol A was prepared. Then, the sodium hydroxide aqueous solution of bisphenol A kept at room temperature was introduced at a flow rate of 138 liters / hour and methylene chloride at a flow rate of 69 liters / hour through an orifice plate into a tubular reactor having an inner diameter of 10 mm and a length of 10 m. Then, phosgene was co-currently added to the mixture and 10.7
The reaction was continuously performed for 3 hours by blowing at a flow rate of kg / hour. The tubular reactor used here was a double tube, and the outlet temperature of the reaction solution was set to 2 by passing cooling water through the jacket.
It was kept at 5 ° C. Further, the pH of the discharged liquid was adjusted so as to indicate 10 to 11. 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 and sufficiently stirred. Was used as a polycarbonate oligomer (concentration: 317 g / liter). The degree of polymerization of the obtained polycarbonate oligomer was 3 to 4.

Preparation Examples 3 to 5 91 g of the reactive PDMS obtained in Preparation Example 1 was dissolved in 2 L of methylene chloride and mixed with 10 L of the PC oligomer obtained in Preparation Example 2. A solution prepared by dissolving 26 g of sodium hydroxide in 1 liter of water and triethylamine (TEA) b (cc) were added thereto, followed by stirring at 500 rpm for 1 hour at room temperature. Thereafter, bisphenol A600 was dissolved in 5 liters of a 5.2% by weight aqueous sodium hydroxide solution, 8 liters of methylene chloride and p-tert.
-Butylphenol (PTBP) a (g)
Stirred at room temperature for 2 hours at rpm. Thereafter, 5 liters of methylene chloride was added, and the mixture was 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 with acid, and washed with 5 liters of water.
Water washing was sequentially performed with 1 liter, and finally methylene chloride was removed to obtain a chip-shaped PC-PDMS copolymer.
A property test of the obtained PC-PDMS copolymer was performed under the following conditions. (Measurement of PDMS content and PDMS chain length (dimethylsilanooxy unit)) PDMS content was ¹ H
The intensity ratio was determined from the intensity ratio between the peak of the methyl group of isopropyl bisphenol A at 1.7 ppm and the peak of the methyl group of dimethylsiloxane at 0.2 ppm in NMR. P
The DMS chain length was determined by the intensity ratio of the peak of the methyl group of dimethylcycloxane at 0.2 ppm and the peak of the methylene group of the PC-PDMS bond at 2.6 ppm in ¹ HNMR. (Measurement of n-hexane soluble component) This is a component obtained by Soxhlet extraction using n-hexane as a solvent. That is, 15 g of a chip-shaped copolymer was used as a sample and the filter paper No. 84 (28 × 1
(00 mm) and extracted with 300 ml of n-hexane by refluxing once every 3 to 4 minutes (20 ml / time) for 8 hours. Thereafter, the residue after evaporating 300 ml of n-hexane was weighed, and this was regarded as n-hexane soluble matter. Table 1 shows the obtained results.

Examples 1 to 11 and Comparative Examples 1 to 7 A predetermined amount of the PC-PDMS copolymer and the rubber-like elastic material shown in Tables 2 and 3 were premixed by a drum tumbler and then supplied to an extruder. Then, the mixture was kneaded at a temperature of 280 ° C. to obtain a polycarbonate resin composition, which was pelletized.
Further, the obtained pellet was injection molded at a molding temperature of 280 ° C. and a mold temperature of 80 ° C. to obtain a test piece. The Izod impact strength of the obtained test piece and the tensile breaking strength of the pellet were measured. The results are shown in Tables 2 and 3. The test was performed under the following conditions. The Izod impact test (kg · cm / cm) is based on JIS K-7110.
23 ° C, -30 ° C using 1/8 inch thick pellets
I went in. The tensile strength test (kg / cm ² ) is based on JIS
Performed according to K-7113.

[0031]

[Table 1] * 1 PC-PDMS copolymer of Production Example 3 * 2 PC-PDMS copolymer of Production Example 4 * 3 Paraloid KM330 (acrylic rubber) manufactured by Rohm and Haas Co., Ltd. * 4 Hybrene B611 (acrylic rubber) Japan * 5 Butyl 268 (butyl rubber) manufactured by Zeon Corporation * 6 03MA409C (length 3 mm, diameter 13 μm) manufactured by Asahi Fiberglass Co., Ltd. * a PC-PDMS copolymer and rubber-like elastic material Percentage based on the total amount * b The total amount of the PC-PDMS copolymer and the rubber-like elastic material is 10
Ratio when 0 parts by weight

[0032]

[Table 2]

[0033]

[Table 3]

[0034]

[Table 4]

[0035]

As described above, the polycarbonate resin composition of the present invention can be obtained by mixing a PC-PDMS copolymer and a rubber-like elastic material. According to this polycarbonate resin composition, a molded article having excellent impact resistance can be manufactured. Therefore, the polycarbonate resin composition of the present invention is expected to be effectively used as a material for molded articles having excellent impact resistance.

──────────────────────────────────────────────────続 き Continuation of front page (56) References JP-A-2-36258 (JP, A) JP-A-2-250887 (JP, A) JP-A-4-31457 (JP, A) JP-A-55- 160052 (JP, A) International Publication 91/885 (WO, A1) (58) Fields investigated (Int. Cl. ⁷ , DB name) C08L 69/00 C08G 64/00-64/42

Claims (1)

(57) [Claims] (A) General formula (a) [Wherein, R ¹ and R ² each independently represent hydrogen, carbon number 1
And R ³ and R ⁴ each independently represent hydrogen, halogen, an alkyl group or an aryl group having 1 to 20 carbon atoms, x represents an integer of 1 to 5, and y represents 1 to 4
And n represents an integer of 1 to 100. And a polycarbonate block represented by the general formula (b): [Wherein, R ⁵ and R ⁶ each independently represent an organic residue containing an aromatic nucleus, and m represents an integer of 100 or more. A copolymer comprising a polydimethylsiloxane block represented by the formula: wherein the proportion of the polydimethylsiloxane block portion in the copolymer is 0.5 to 10% by weight and n-hexane 40 to 99% by weight of a polycarbonate-polydimethylsiloxane copolymer having a soluble content of 1.0% by weight or less and a viscosity average molecular weight of 10,000 to 50,000 and (B) 60 to 1% by weight of a rubber-like elastic material. The polycarbonate resin composition characterized by the above-mentioned.