JPH03273052A - Glass fiber-reinforced polycarbonate resin composition - Google Patents

Abstract

PURPOSE:To improve impact characteristics and moldability without degrading strengths and rigidity by compounding a polycarbonate resin, a glass fiber, and a specific heat-resistant styrenic elastomer. CONSTITUTION:A polycarbonate resin having a viscosity-average mol.wt. of 10000-100000 is prepd. by reacting a dihydric phenol with a carbonate precursor in the presence of an acid acceptor and a mol.wt. controller in a solvent. The title compsn. is prepd. by compounding 100 pts.wt. said resin, 5-150 pts.wt. glass fiber having a length of 0.02-2mm and, if necessary, having been surface-treated and bundled, and 1-15 pts.wt. heat-resistant styrenic elastomer comprising a block copolymer which has a number-average mol.wt. of 10000-400000, is shown by formula I or II [wherein A is a styrene polymer block; and B is a (hydrogenated) isoprene polymer block or a hydrogenated butadiene polymer block], and contains 20-80wt.% component A, and in which both A and B blocks have a number-average mol.wt. per block of 5000-200000.

Description

DETAILED DESCRIPTION OF THE INVENTION Field of Industrial Application The present invention relates to a novel glass fiber reinforced polycarbonate resin composition, and more particularly, to a novel glass fiber reinforced polycarbonate resin composition, which improves impact properties and moldability without impairing the inherent strength and rigidity of the polycarbonate resin. The present invention relates to a glass fiber reinforced polycarbonate resin composition.

Conventional technology Traditionally, aromatic polycarbonate resins have been used as amorphous engineering plastics because they exhibit well-balanced physical properties such as rigidity and impact resistance, heat resistance, electrical properties, and dimensional stability. , are widely used in many fields, and recently, because they have low birefringence and are transparent, demand for them in optical fields such as optical discs has increased.

On the other hand, in fields that require particularly excellent heat resistance, mechanical properties, and dimensional stability, such as chassis for electrical and electronic equipment, glass fiber-reinforced polycarbonate resin is used in bulk molding compounds and aluminum die. Attempts are being made to use it as an alternative to casting.

However, although this glass fiber-reinforced polycarbonate resin generally has improved rigidity, strength, and heat resistance compared to a polycarbonate resin alone, it has the disadvantage of poor impact properties (U.S. Pat. No. 3,577,378). Specification). In order to improve this impact property, it is conceivable to increase the blending amount of glass fiber, but since there is a limit to the blending amount, a significant improvement in the impact property cannot be expected.

In addition, attempts have been made to incorporate elastomers to improve impact properties, but elastomers made of polyimbutylene or styrene-butadiene copolymers do not sufficiently improve impact resistance. 1
No. 2946, Japanese Patent Publication No. 58-32176).

Problems to be Solved by the Invention The present invention overcomes the drawbacks of conventional glass fiber-reinforced polycarbonate resins, and provides a glass with improved impact properties and moldability without sacrificing the inherent strength and rigidity of polycarbonate resins. This was made for the purpose of providing a fiber-reinforced polycarbonate resin composition.

Means for Solving the Problems The present inventors have conducted extensive research to develop a glass fiber-reinforced polycarbonate resin composition having the above-mentioned preferable properties. It was discovered that the object could be achieved by a composition containing elastomer in a predetermined ratio, and the present invention was completed based on this knowledge.

That is, the present invention provides (A) polycarbonate resin 10
0 parts by weight, (B) 5 to 150 parts by weight of glass fiber and (C) general formula % formula % () ([) A-(B-A is a styrene polymer block, B is an isoprene polymer block, hydrogenated at least one block selected from the butadiene polymerized block and the hydrogenated isoprene polymerized block, n is an integer of 1 or more), and the A component content is 20 to 80% by weight, Number average molecular weight per single block of component A: 5.0 (10 to 2
00,000, a heat-resistant styrenic elastomer 1 to 1 consisting of a block copolymer having a number average molecular weight per block of component B of 5,000 to 200.000 and a number average molecular weight of the entire copolymer of 10,000 to 400.000. The present invention provides a glass fiber-reinforced polycarbonate resin composition characterized in that it contains 15 parts by weight.

The present invention will be explained in detail below.

In the composition of the present invention, A-(
B-Z is 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, a single bond, -
so, --5o--5--O--CO- or R1 and R2 are each a hydrogen atom, a chlorine atom, a bromine atom, or an alkyl copolymer having 1 to 8 carbon atoms, and they are the same and p and q are each an integer of 1 to 4, and when p is 2 to 4, R1 may be different from each other, and q
is 2 to 4, R2 may be different from each other).

The polycarbonate resin can be prepared by reacting a dihydric phenol with a carbonate precursor such as phosgene or by reacting a dihydric phenol with a carbonate precursor such as phosgene in a solvent such as methylene chloride in the presence of a known acid acceptor or molecular weight modifier. It can be produced by a transesterification reaction with a carbonate precursor such as.

As the dihydric phenol, for example, 2,2-bis(4
-Hydroxyphenyl)propane (bisphenol A)
, 2.2-bis(3-methyl-4-hydroxyphenyl)propane, 2.2-bis(3,5-dimethyl-4-
hydroxyphenyl)propane, 1,2-bis(4-hydroxyphenyl)ethane, 3,3-bis(4-hydroxyphenyl)pentane, l,1-(4-hydroxyphenyl)cyclohexane, 4,4'-dihydroxydiphenyl , bis(4-hydroxyphenyl) sulfite,
Bis(4-hydroxyphenyl)sulfone, bis(4-
2,2-bis(3,5-dibromo-4-hydroxyphenyl)propane, 2,2-bis(3,5-dibromo-4-hydroxyphenyl)propane, etc.
Bis(3,5-dichloro-4-hydroxyphenyl)propane, 2.2-bis(3-chloro-4-hydroxyphenyl)propane, 2.2-bis(3-bromo-4-hydroxyphenyl)propane Examples include halogenated bisphenols, and among these dihydric phenols, bisphenol A is particularly preferred. Further, these dihydric phenols may be used alone or in combination of two or more types. Further, the polycarbonate resin used in the present invention may be a thermoplastic random branched polycarbonate made by reacting a polyfunctional aromatic compound with a dihydric phenol and a carbonate precursor, or a blend of two or more types of polycarbonate resins. It may be.

The polycarbonate resin has a viscosity average molecular weight of 10,000 to 100.0 in terms of mechanical strength and moldability.
00 is preferable, especially 20,000 to 40,00
A value of 0 is preferred.

In the composition of the present invention, any of alkali-containing glass, low-alkali glass, and alkali-free glass can be used as the glass fiber used as component (B), but the length in the composition is preferably 0.02~
2 vllm, more preferably in the range of 0.05 to 1 vol. This glass fiber may break when kneaded with the polycarbonate resin, so the size of the glass fiber when kneading is as follows:
General number: The length is preferably in the range of 0.1 to 5 m11+, and the diameter is usually 1 to 20 μm. There are no particular restrictions on the form of the glass fiber,
For example, any form such as roving, milled fiber, chopped strand, etc. can be used.

Furthermore, it is desirable to use glass fibers that have been surface treated with a surface treatment agent and then bundled with a suitable binding agent in order to improve adhesion to the polycarbonate resin.

Examples of the surface treatment agent include silane-based, titanate-based, aluminum-based, chromium-based, zirconium-based, and poran-based coupling agents, among which silane-based coupling agents, titanate-based coupling agents, Particularly suitable are silane coupling agents.

There are no particular limitations on the method of treating the glass fibers with the surface treatment agent, and any conventionally used method, such as an aqueous solution method, an organic solvent method, a spray method, etc., can be used.

Further, as the sizing agent, there are, for example, urethane type, acrylic type, acrylonitrile-styrene type copolymer type, epoxy type, etc., and any of them can be used.

There are no particular restrictions on the method of convergence treatment of glass fibers using this convergence agent, and any conventionally used method such as dipping, roller coating, spray coating, flow coating, or spray coating may be used. be able to.

In the composition of the present invention, the glass fiber (B) is blended in an amount of 5 to 1.50 parts by weight, preferably 10 to 120 parts by weight, based on 100 parts by weight of the polycarbonate resin (A). It is necessary.

If the amount is less than 5 parts by weight, mechanical properties such as strength and rigidity will be insufficient, and if it exceeds 150 parts by weight, no improvement in mechanical properties such as strength or rigidity can be expected for the amount. Rather, the take-up during kneading becomes unstable.

In the composition of the present invention, a block copolymer represented by the general formula %() () is used as component (C). A in the general formulas (I) and (n) is a styrene polymer block, and in formula (I), the degree of polymerization may be the same or different at both ends of the molecular chain. B is at least one block selected from an isoprene polymer block, a hydrogenated butadiene polymer block, and a hydrogenated isoprene polymer block. Further, n is an integer of 1 or more.

The content of AIE in the block copolymer is 20
It is necessary that the content be in the range of 80% by weight. If this amount is less than 20% by weight, strength and rigidity will be poor, and if it exceeds 80% by weight, moldability and impact strength will be reduced.

In addition, the number average molecular weight per single block of the A component is:
5,000 to 200,000, and the number average molecular weight per block of component B is 5,000 to 200.
．． It must be in the range of 000. If the number average molecular weight per single block of component A is less than 5,000, or if the number average molecular weight per block of component B is less than 5,000, the mechanical properties are insufficient, and the When the number average molecular weight per single block exceeds 200.000 or when the number average molecular weight per block of component B is 200.000.
,000, moldability deteriorates. Furthermore, the number average molecular weight of the entire block copolymer is 10,00
It is necessary that there be a range of 0 to 400.000,
If the number average molecular weight is less than 10,000, mechanical properties will be poor, and if it exceeds 400,000, moldability will be reduced.

As the heat-resistant styrene elastomer, diblock, triblock, and tetrablock types are mainly used.

Examples of the styrenic polymer block of A in the general formulas (I) and (n) include blocks such as styrene, α-methylstyrene, vinyltoluene, vinylxylene, and vinylnaphthalene.

Examples of the heat-resistant styrene elastomer of component (C) include styrene-hydrogenated butadiene-styrene triblock polymer (SEBS), styrene-isoprene-styrene triblock polymer, and styrene-hydrogenated isoprene-styrene triblock polymer (SEBS). SEPS)
, styrene-hydrogenated isoprene diblock polymer (SE
P), styrene-imprene diblock polymer, styrene-hydrogenated butadiene diblock polymer, and the like.

In the composition of the present invention, the component (C) may be used alone or in combination of two or more, and the amount thereof is 1 per 100 parts by weight of the polycarbonate resin of the component (A). -15 parts by weight, preferably 2 to 10 parts by weight. If this amount is less than 1 part by weight, the effect of improving impact properties and moldability (flowability, mold releasability) will not be sufficiently exhibited, and if it exceeds 15 parts by weight, moldability will improve, but impact properties will be affected by the amount. Although an improvement effect is recognized in comparison, there is a tendency for strength and rigidity to decrease significantly.

If desired, the composition of the present invention may include calcium carbonate, calcium sulfate, barium sulfate, aluminum hydroxide, talc, clay, mica, silica, glass peas, diatomaceous earth, etc. Inorganic fillers such as montmorillonite, bentonite, zinc borate, barium metaborate, antioxidants, light stabilizers, lubricants,
Additives such as antistatic agents, flame retardants, and colorants can be added.

There are no particular limitations on the method for preparing the glass fiber-reinforced polycarbonate resin composition of the present invention, and methods conventionally used for preparing glass fiber-reinforced polycarbonate resin compositions can be used. For example, the component (A),
Component (E), component CC'), and various additive components used as necessary are mixed in required amounts using, for example, a V-blender, ribbon blender, Henschel mixer, or tumbler blender, or after mixing, further e.g. A method of melt-kneading using a Banbury mixer, a kneader, an oven roll, a single-screw extruder, a twin-screw extruder, a single-screw reciprocating screw kneader, etc. can be used. At this time, the supply of glass fiber is
Either top or side feeding method may be used.

The composition of the present invention thus obtained can be molded into a desired molded article by a molding method such as injection molding, extrusion molding, or compression molding.

Effects of the Invention The glass fiber-reinforced polycarbonate resin composition of the present invention is a polycarbonate resin blended with glass fibers and a heat-resistant styrene elastomer, and maintains the strength and rigidity inherent to the polycarbonate resin, as well as exhibits excellent impact properties. and moldability (flowability, mold releasability, etc.), and is suitably used as a material for various parts in, for example, the electrical/electronic equipment field, the OA office equipment field, and the industrial material field.

Examples Next, the present invention will be explained in more detail with reference to examples.
The present invention is not limited in any way by these examples.

In addition, each physical property was calculated|required by the following method.

(1) Mechanical properties (b) Izotsu impact strength Determined in accordance with JIS K-7110 (notched).

(b) Bending strength and bending modulus It was determined in accordance with JISK-7203.

(2) Fluidity (spiral flow length) Cylinder temperature 320℃, wall thickness 311111, injection pressure 80kg/cra
”・Evaluated under the conditions of G.

(3) Mold releasability Evaluation was made using a rib mold and a boombox chassis mold.

(a) When the pressure was increased from the rib minimum filling pressure and the mold was released protrudingly, the pressure at which mold release failure occurred was determined, and the evaluation was made from the pressure difference between this pressure and the minimum filling pressure. The greater the pressure difference, the better the mold releasability.

(b) Radio-cassette chassis Using a radio-cassette chassis mold, the mold release resistance (unit: kg/cm) during protrusion mold release was measured.

The lower the resistance value, the better the mold releasability.

(4) Exterior appearance Ratings were made by visual observation according to the following symbols.

◎: Good (there is almost no floating of GF) O: Generally good (the floating of GF is small) △: Slightly poor (the floating of GF is moderate) ×: Poor (the floating of GF is large) , the following was used.

(1) Polycarbonate resin (PC) Idemitsu Petrochemical (
Co., Ltd., A2200 (Mv22.000) (2) Glass fiber (GF) Nippon Denki Glass Co., Ltd., chopped strand EC50
3T-509 (length 311I11 diameter 13μm, treated with urethane sizing agent and aminosilane coupling agent) (3)
Elastomers are shown in Table 1.

Examples 1 to 8, Comparative Examples 1 to 14 57 total - Using a vented twin-screw extruder, 100 parts by weight of polycarbonate resin and elastomer of the type and amount shown in Table 2 were top-fed, and as shown in Table 2. Amount of glass fiber was side-fed and melt-kneaded at a cylinder temperature of 280° C. and a screw rotation speed of 150 rpm to form pellets.

After pre-drying the obtained pellet at 120°C overnight, the cylinder temperature was adjusted to 320°C using a vented injection molding machine.
A test piece was prepared at a mold temperature of 80°C, and each physical property was determined. The results are shown in Table 2.

Further, gas generation was visually evaluated, and no difference was observed between the 5EES-added system and the non-additive system.

432-

Claims (1)

[Claims] 1 (A) For 100 parts by weight of polycarbonate resin,
(B) 5 to 150 parts by weight of glass fiber and (C) General formula A
-(B-A)n or (A-B)n (where A is a styrene polymer block, B is selected from an isoprene polymer block, a hydrogenated butadiene polymer block, and a hydrogenated isoprene polymer block) (n is an integer of 1 or more), and the content of component A is 20 to 80% by weight, and the number average molecular weight per single block of component A is 5,000 to 20.
0,000, number average molecular weight per block of component B 5,
000 to 200,000 and a heat-resistant styrenic elastomer comprising a block copolymer having a total number average molecular weight of 10,000 to 400,000. Resin composition.