JP3287414B2 - 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 having excellent impact resistance and excellent rigidity, flame retardancy and mold release properties.

[0002]

2. Description of the Related Art Polycarbonate resins are excellent in mechanical strength, electrical characteristics, transparency, etc., and are widely used as engineering plastics in various fields such as electric / electronic devices and automobiles. ing. As a polycarbonate resin having such characteristics, a glass fiber reinforced polycarbonate resin to which glass fibers are added in order to improve impact resistance and dimensional stability is known. However, the impact resistance is significantly reduced by the addition of glass fibers. Various methods have been studied for improving the impact resistance, which is reduced by adding glass fibers to a polycarbonate resin. For example, JP-A-55-160052 and JP-A-2-173306 disclose a method of introducing a polycarbonate-polyorganosiloxane copolymer into a polycarbonate resin. By introducing the polycarbonate-polyorganosiloxane copolymer, an improvement in impact resistance is observed. However, the effect is not yet sufficient and improvement is demanded.

[0003]

Means for Solving the Problems Accordingly, the present inventors have:
Eliminates the disadvantages of the conventional method and has excellent impact resistance.
Intensive research was conducted to develop a polycarbonate resin composition having excellent flame retardancy and release properties. As a result,
As a glass generally used for resin modification, instead of E glass whose flux is B ₂ O ₃ , Ti flux is used as a flux.
It has been found that a polycarbonate resin composition having desired properties can be obtained by blending a glass using O ₂ with a polycarbonate-polyorganosiloxane copolymer. This is thought to be due to the interaction between TiO _{2 in the} glass and the polyorganosiloxane portion of the polycarbonate-polyorganosiloxane copolymer, which improves the adhesion between the resin and the glass. The present invention has been completed based on such findings. That is, the present invention, (A) polycarbonate - polyorganosiloxane copolymer 5-95%, (B) a polycarbonate resin 0 to 90 wt% and (C) TiO ₂ 0.5 to 10 wt%
(A) comprising 5 to 60% by weight of glass containing
The polycarbonate resin composition, wherein the proportion of the polyorganosiloxane part in the polycarbonate-polyorganosiloxane copolymer is 0.5 to 40% by weight based on the total amount of the components (A) and (B). Is provided.

The polycarbonate-polyorganosiloxane copolymer (PC-PDM) which is the component (A) of the present invention is used.
S) includes various ones, but preferably has the general formula (I)

[0005]

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Wherein R ¹ and R ² are each a hydrogen atom, a halogen atom (eg, chlorine, bromine, fluorine, iodine) or an alkyl group having 1 to 8 carbon atoms, which may be the same. And may be different, m and n
Are each an integer of 1 to 4, and when m is 2 to 4, R ¹ may be the same or different, and when n is 2 to 4, R ¹ may be the same. Or different ones. Z is an alkylene group having 1 to 8 carbon atoms, an alkylidene group having 2 to 8 carbon atoms, and 5 carbon atoms.
15 cycloalkylene groups, cycloalkylidene group or -SO ₂ of 5 to 15 carbon atoms -, - SO -, - S -, -
O-, -CO- bond, single bond or general formula (II)

[0007]

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[0008] The bond represented by A polycarbonate unit having a repeating unit having a structure represented by the general formula (III)

[0009]

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Wherein R ³ , R ⁴ and R ⁵ are each a hydrogen atom, an alkyl group having 1 to 6 carbon atoms or a phenyl group, which may be the same or different. P and q are each an integer of 0 or 1 or more. And a polyorganosiloxane unit having a repeating unit represented by the formula: The degree of polymerization of the polyorganosiloxane moiety is preferably 5 or more, more preferably 100 or more. The polycarbonate-polyorganosiloxane copolymer has a block composed of a polycarbonate portion having a repeating unit represented by the above general formula (I) and a polyorganosiloxane portion having a repeating unit represented by the above general formula (III). A copolymer having a viscosity average molecular weight of 10,000 to 50,000
0, preferably 15,000 to 35,000.
The polycarbonate-polyorganosiloxane copolymer preferably has an n-hexane soluble content of 1.0% by weight or less.

The polycarbonate-polyorganosiloxane copolymer is, for example, a polycarbonate oligomer (PC
Oligomer) and a polyorganosiloxane having a reactive group at a terminal (for example, polydialkylsiloxane such as polydimethylsiloxane (PDMS) or polydiethylsiloxane, or polymethylphenylsiloxane) constituting a polyorganosiloxane portion. Dissolve in a solvent such as methylene, chlorobenzene, chloroform, etc., add sodium hydroxide aqueous solution of bisphenol,
It can be produced by interfacial reaction using triethylamine, trimethylbenzylammonium chloride or the like as a catalyst. Also, Japanese Patent Publication No. 44-30105
Or a polycarbonate-polyorganosiloxane copolymer produced by the method described in Japanese Patent Application Publication No. JP-B-45-20510 or JP-B-45-20510 can also be used. Here, the polycarbonate oligomer having a repeating unit represented by the general formula (I) is prepared by a solvent method, that is, in a solvent such as methylene chloride in the presence of a known acid acceptor and a molecular weight regulator.
General formula (IV)

[0012]

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(Wherein R ¹ , R ² , Z, m and n are
Same as above. ) And a transesterification reaction between a dihydric phenol and a carbonate precursor such as diphenyl carbonate. There are various dihydric phenols represented by the above general formula (IV), and in particular, 2,2-bis (4
-Hydroxyphenyl) propane (so-called bisphenol A) is preferred. Further, bisphenol A may be obtained by partially or entirely substituting another dihydric phenol. As dihydric phenols other than bisphenol A,
Bis (4-hydroxyphenyl) alkane 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-
Compounds such as bis (4-hydroxyphenyl) ketone or bis (3,5-dibromo-4-hydroxyphenyl) propane; such as bis (3,5-dichloro-4-hydroxyphenyl) propane Examples thereof include halogenated bisphenols.

In the present invention, the polycarbonate oligomer used in the production of the polycarbonate-polyorganosiloxane copolymer may be a homopolymer using one kind of these dihydric phenols, or a mixture using two or more kinds of these dihydric phenols. It may be a copolymer. Further, it may be a thermoplastic random branched polycarbonate obtained by using a polyfunctional aromatic compound in combination with the dihydric phenol. In order to produce a polycarbonate-polyorganosiloxane copolymer having an n-hexane soluble content of 1.0% by weight or less, for example, the content of the polyorganosiloxane in the copolymer is reduced to 10% by weight or less. The copolymerization is carried out by using a compound having the number of repeating units represented by the general formula (III) 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. It is preferred to do so.
The ratio of the polyorganosiloxane part to the total amount of the above components (A) and (B) is 0.5 to 40% by weight, preferably 1.0 to 35% by weight. Here, when the content is less than 0.5% by weight, no improvement in impact resistance is observed, while the content is 40% by weight.
If it exceeds 3, a copolymer having a sufficient molecular weight cannot be obtained.

Next, the polycarbonate resin (PC) as the component (B) 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 as in the case of dihydric phenol and diphenyl carbonate. It is produced by a transesterification reaction with a suitable carbonate precursor. Here, the dihydric phenol may be the same as or different from the compound represented by the general formula (IV) described above. Examples of the carbonate compound include diaryl carbonates such as diphenyl carbonate and dialkyl carbonates such as dimethyl carbonate and diethyl carbonate.

On the other hand, the glass (C) used together with the (A) polycarbonate-polyorganosiloxane copolymer and (B) the polycarbonate resin is one using TiO ₂ as a flux. That is, TiO _{2 is set} to 0.
It is a glass containing 5 to 10% by weight, preferably 1 to 5% by weight. If the content of TiO ₂ is less than 0.5% by weight, the improvement in impact resistance is so small that it is not effective. If it exceeds 10% by weight, the molecular weight of the copolymer decreases, which is not preferable. As the form of the glass, for example, glass fiber, glass beads, glass flake, glass powder, and the like can be used, and these may be used alone or in combination of two or more. Among these, the glass fiber widely used for resin reinforcement may be any of alkali-containing glass, low-alkali glass, and alkali-free glass. The fiber length is 1 to 8 mm, preferably 3 to 6 mm, and the fiber diameter is 3 to 30 μm, preferably 5 to 25 μm. The form of the glass fiber is not particularly limited, and examples thereof include various types such as roving, milled fiber, and chopped strand. These glass fibers can 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, methacrylsilane, chromium complex compound, boron compound, etc. in order to enhance the affinity with the resin. May be used. As a preferred example of such a glass, a commercially available glass manufactured by Asahi Fiberglass Co., Ltd.
CR glass (TiO ₂ : 2.2% by weight).

The resin composition of the present invention comprises the above-mentioned components (A), (B) and (C).
5 to 95% by weight, preferably 10 to 90% by weight of the polyorganosiloxane copolymer, 0 to 90% by weight, preferably 0 to 80% by weight of the polycarbonate resin as the component (B)
And (C) of TiO ₂ is a component 0.5 to 10 wt%,
The glass content is preferably 5 to 60% by weight, preferably 10 to 50% by weight. If the blending amount of the glass as the component (C) is less than 5% by weight, dimensional stability is reduced, and at the same time, rigidity is little improved, and a desired mechanical strength cannot be obtained. If it exceeds 60% by weight, kneading of the resin is difficult or impossible, which is not preferable.

The resin composition of the present invention may optionally contain various additives as component (D) as long as the object of the present invention is not impaired. For example,
Various additives include antioxidants such as hindered phenols, phosphites, phosphates, and amines; ultraviolet absorbers such as benzotriazoles and benzophenones; and light stabilizers such as hindered amines. And external lubricants such as aliphatic carboxylic acid esters and paraffins, common flame retardants, release agents, antistatic agents, coloring agents and the like.

The resin composition of the present invention is obtained by mixing and kneading the above components (A), (B) and (C) with (D) if necessary. A resin composition can be obtained. For the compounding and kneading, a method usually used, for example, a ribbon blender, a Henschel mixer, a Banbury mixer, a drum tumbler, a single screw extruder, a twin screw extruder, a co-kneader, a multi-screw extruder, etc. It can be performed by the method used. The heating temperature during kneading is
Usually, it is selected in the range of 250 to 300 ° C. The polycarbonate resin composition thus obtained can be applied to various known molding methods, for example, injection molding, hollow molding, extrusion molding, compression molding, calendar molding, rotational molding, and the like.
A molded article such as a chassis of OA equipment, a molded article in an automobile field or an electric / electronic field, and the like can be manufactured.

[0020]

Next, the present invention will be described in more detail with reference to Production Examples, Examples and Comparative Examples. Note that the following two types of glass fibers were used as glass in the examples and comparative examples. Glass A: manufactured by Asahi Fiber Glass Co., Ltd., ECR glass (TiO ₂ : containing 2.2% by weight) Glass B: manufactured by Asahi Fiber Glass Co., Ltd., MA-409
C (E glass, TiO ₂ : 0.2% by weight) Production Example 1 Production of Polycarbonate (PC) Oligomer 400
60 kg of bisphenol A was dissolved in 1 liter of a 5% aqueous sodium hydroxide solution to prepare an aqueous sodium hydroxide solution of bisphenol A. Then, an aqueous sodium hydroxide 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 into a tubular reactor having an inner diameter of 10 mm and a length of 10 m through an orifice plate. Phosgene was blown into the mixture at a flow rate of 10.7 kg / hour, and the reaction was continuously performed for 3 hours. The tubular reactor used here was a double tube, and the outlet temperature of the reaction solution was kept at 25 ° C. by passing cooling water through the jacket. The pH of the discharged liquid is 10
~ 11 was prepared. The reaction solution thus obtained was allowed to stand, whereby the aqueous phase was separated and removed, and a methylene chloride phase (220 liters) was collected. The methylene chloride was removed by evaporation to obtain a flake-like polycarbonate oligomer. The degree of polymerization of the obtained polycarbonate oligomer was 3 to 4.

Production Example 2-1 (Synthesis of Reactive PDMS) 1483 g of octamethylcyclotetrasiloxane, 18.1 g of 1,1,3,3-tetramethyldisiloxane and 35 g of 86% sulfuric acid were mixed and stirred at room temperature for 17 hours. did. Thereafter, the oil phase was separated, 25 g of sodium hydrogen carbonate was added, and the mixture was stirred for 1 hour. After filtration, vacuum distillation was performed at 150 ° C. and 3 torr to remove low-boiling substances. To a mixture of 60 g of 2-allylphenol and 0.0014 g of platinum as platinum chloride-alcoholate complex, 294 g of the oil obtained above were added at a temperature of 90C. The mixture was stirred for 3 hours while maintaining the temperature at 90-115 ° C. The product is extracted with methylene chloride,
Washed three times with 80% aqueous methanol to remove excess 2-allylphenol. The product was dried over anhydrous sodium sulfate and the solvent was distilled off in vacuo to a temperature of 115 ° C. The obtained terminal phenol PDMS was analyzed by NMR to find that the number of repeating dimethylsilanooxy units was 150.
Met.

Production Example 2-2 (Synthesis of Reactive PDMS)
7.72 g of 1,3,3-tetramethyldisiloxane
Except having changed to, it carried out similarly to manufacture example 2-1. NMR measurement of the obtained terminal phenol PDMS showed that the number of repeating dimethylsilanooxy units was 350. Production Example 2-3 (Synthesis of Reactive PDMS)
137 g of 1,3,3-tetramethyldisiloxane
Except having changed to, it carried out similarly to manufacture example 2-1. NMR measurement of the obtained terminal phenol PDMS revealed that the number of repeating dimethylsilanooxy units was 20. Production Example 2-4 (Synthesis of Reactive PDMS)
33.5 g of 1,3,3-tetramethyldisiloxane
Except having changed to, it carried out similarly to manufacture example 2-1. The obtained terminal phenol PDMS was measured by NMR to find that the number of repeating dimethylsilanooxy units was 80.

Preparation Examples 3-1 to 12 The reactive PDMSag obtained in Preparation Examples 2-1 to 4 was dissolved in 2 L of methylene chloride and mixed with 10 L of the PC oligomer obtained in Preparation Example 1. Thereto was added 26 g of sodium hydroxide dissolved in 1 liter of water and triethylamine dcc, and the mixture was stirred at 500 rpm for 1 hour at room temperature. Thereafter, a 5.2% by weight aqueous sodium hydroxide solution 5
A solution of 600 g of bisphenol A in 1 liter, 8 liter of methylene chloride and bg of p-tert-butylphenol were added, and the mixture was stirred at 500 rpm for 2 hours at room temperature. Then, add 5 liters of methylene chloride,
Further washing with 5 liters of water, alkali washing with 5 liters of 0.01N sodium hydroxide aqueous solution, acid washing with 5 liters of 0.1N hydrochloric acid, and washing with 5 liters of water sequentially,
Finally, the methylene chloride is removed, and a chip-shaped PC-PDM
An S copolymer was obtained. Table 1 shows the amounts of a, b, and d used in Production Examples 3-1 to 12-12.

[0024]

[Table 1]

Table 2 shows the Mv (viscosity average molecular weight), PDMS chain length (n: dimethylsilanooxy unit), PDMS content and n-hexane soluble matter of the obtained PC-PDMS copolymer. .

[0026]

[Table 2]

The PDMS chain length (n: dimethylsilanooxy unit), PDMS content and n-hexane soluble content were measured by the following methods. [PDMS chain length (n: dimethylsilanooxy unit), P
Measurement of DMS content] PDMS chain length is measured by ¹ H-NMR.
It was determined by the intensity ratio of the peak of the methyl group of dimethylsiloxane found at 0.2 ppm to the peak of the methylene group of the PC-PDMS bond at 2.6 ppm. Also, PDMS
The content was determined by ¹ H-NMR at 1.7 ppm of the peak of the isopropyl methyl group of bisphenol A and 0.2 pp.
It was determined from the intensity ratio of the peak of the methyl group of dimethylsiloxane found in m.

(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 the chip-shaped copolymer, which is a sample, was added to a cylindrical filter paper N.
o.84 (28.times.100 mm), and extracted with 300 ml of n-hexane by refluxing once every 3 to 4 minutes (20 ml / time) for 8 hours. After evaporating 300 ml of n-hexane, the residue was weighed and used as n-hexane soluble matter.

Examples 1 to 18 and Comparative Examples 1 to 27 The Ps obtained in Production Examples 3-1 to 12 as base polymers
As a C-PDMS copolymer, polycarbonate resin,
Toughlon A-2200 (trade name: Mv = 21,000; manufactured by Idemitsu Petrochemical Co., Ltd.) and Iupilon H4000 (trade name: Mv = 15,000; manufactured by Mitsubishi Gas Chemical Co., Ltd.)
Then, using the glass fiber, blended in the proportions shown in Table 3, pellets were formed by a 30 mm vented extruder,
A molded product was obtained by injection molding at a molding temperature of 300 ° C. In addition,
The glass fiber was supplied from a downstream side of the hopper supply position of the raw resin of the extruder.

[0030]

[Table 3]

[0031]

[Table 4]

[0032]

[Table 5]

With respect to the molded products obtained in Examples and Comparative Examples, Izod impact strength and flexural modulus were measured as performance evaluations. In addition, a combustion test was performed. Table 4 shows the results.

[0034]

[Table 6]

[0035]

[Table 7]

[0036]

[Table 8]

The measuring methods and test methods were as follows. Izod impact strength: based on JIS K-7110. Flexural modulus: based on JIS K-7103. Flame retardancy test: UL-94 1/16 inch (thickness) A vertical burn test was performed according to Underwriters Laboratory Subject 94.

[0038]

As described above, according to the present invention, a polycarbonate resin composition which is excellent in impact resistance and excellent in rigidity, flame retardancy and mold release while having the original mechanical properties of polycarbonate. You can get things. Therefore, the polycarbonate resin composition of the present invention can be effectively used as a material for various molded articles widely used in the fields of electric / electronic devices, automobiles, and the like.

──────────────────────────────────────────────────続 き Continued on the front page (58) Field surveyed (Int. Cl. ⁷ , DB name) C08L 83/10 C08L 69/00 C08K 3/40

Claims (1)

(57) [Claims] 1. A (A) polycarbonate - polyorganosiloxane copolymer 5-95%, 0.5 (B) a polycarbonate resin 0 to 90 wt% and (C) TiO ₂
5 to 60% by weight of glass containing 10% by weight, and (A) the proportion of the polyorganosiloxane part in the polycarbonate-polyorganosiloxane copolymer is (A)
And (B) a polycarbonate resin composition characterized in that 0.5 to 40% by weight relative to the total amount of components (only
And the refractive index of the mixed resin of (A) and (B) and (C)
Excluding the resin composition whose difference from the refractive index of the resin is 0.01 or less.
H) .