JP3380072B2 - Reinforced aromatic polycarbonate resin composition excellent in fluidity and molded article - Google Patents

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a reinforced aromatic polycarbonate resin composition and molded articles made therefrom. More specifically, the present invention relates to a reinforced aromatic polycarbonate resin composition having excellent fluidity and high rigidity, which is useful in a wide range of industrial fields such as cameras, audios, car audios, VTRs, and OA equipments, and molded articles made from the same.

[0002]

2. Description of the Related Art Conventionally, aromatic polycarbonate resins have been excellent in transparency, heat resistance and impact resistance. Therefore, many of them have been melt-molded by injection molding, compression molding, extrusion molding, blow molding or the like. It is used for purposes. Further, the aromatic polycarbonate resin has low rigidity as compared with glass, metal, etc., therefore, in applications requiring high rigidity, the improvement thereof can be achieved by blending an appropriate filler such as glass fiber or carbon fiber. I am trying.
However, when glass fibers, carbon fibers, etc. are blended, their mechanical properties are improved, but on the other hand, the fluidity is lowered and they cannot be used for thin-walled molded articles requiring particularly high fluidity. was there.

[0003]

SUMMARY OF THE INVENTION It is an object of the present invention to provide a reinforced aromatic polycarbonate resin composition having excellent fluidity and high rigidity. The inventor
As a result of earnest researches aimed at achieving the above object, as a result, an aromatic polycarbonate resin having a viscosity average molecular weight of 10,000 to 40,000, a fibrous filler with L / D ≧ 3, and optionally other fillers and fats were added. The present invention has been completed by finding that a composition containing a specific amount of a group polycarbonate is surprisingly excellent in fluidity and has high rigidity.

[0004]

The present invention relates to (A) an aromatic polycarbonate resin having a viscosity average molecular weight of 10,000 to 40,000, and (B-
1) 5 to 240 parts by weight of a fibrous filler having L / D ≧ 3, (B
-2) A reinforced aromatic polycarbonate resin composition consisting essentially of 0 to 240 parts by weight of a filler other than (B-1) and (C) 1 to 60 parts by weight of an aliphatic polycarbonate having a number average molecular weight of 500 to 10,000. And a molded article formed therefrom.

The aromatic polycarbonate resin used as the component (A) in the present invention is a resin usually used as an engineering resin, and is an aromatic polycarbonate resin obtained by reacting a dihydric phenol with a carbonate precursor. . Typical examples of the dihydric phenol used here include 2,2-bis (4-hydroxyphenyl) propane (commonly called bisphenol A), bis (4-hydroxyphenyl) methane, and 1,1-bis (4
-Hydroxyphenyl) ethane, 1,1-bis (4-hydroxyphenyl) cyclohexane, 2,2-bis (4
-Hydroxy-3,5-dimethylphenyl) propane,
2,2-bis (4-hydroxy-3,5-dibromophenyl) propane, 2,2-bis (4-hydroxy-3-methylphenyl) propane, bis (4-hydroxyphenyl) ether, 4,4'- Dihydroxydiphenyl, bis (4-hydroxyphenyl) sulfide, bis (4-
Examples thereof include hydroxyphenyl) sulfone. A preferred dihydric phenol is bis (4-hydroxyphenyl) alkane, and bisphenol A is particularly preferred.

As the carbonate precursor, carbonyl halide, carbonate ester, haloformate or the like is used, and specific examples thereof include phosgene, diphenyl carbonate and dihaloformate of dihydric phenol.

In producing the aromatic polycarbonate resin by reacting the above dihydric phenol with the carbonate precursor, the dihydric phenol may be used alone or in combination of two or more kinds, and the aromatic polycarbonate resin may be trifunctional or more than trifunctional. It may be a branched polycarbonate resin obtained by copolymerizing a polyfunctional aromatic compound or a mixture of two or more aromatic polycarbonate resins.

The degree of polymerization of the aromatic polycarbonate resin used as the component (A) is in the range of 10,000 to 40,000 in terms of viscosity average molecular weight,
The range of 00 to 30,000 is preferable. If the viscosity average molecular weight is less than 10,000, the mechanical strength of the molded product is not sufficient, and if it exceeds 40,000, extrusion and molding become difficult and a good molded product cannot be obtained. The viscosity average molecular weight (M) referred to in the present invention is 0.7 g of aromatic polycarbonate resin.
It was obtained from the intrinsic viscosity [η] calculated from the specific viscosity measured at a temperature of 20 ° C. by dissolving it in 00 ml of methylene chloride using the following formula. [Η] = 1.23 × 10 ⁻⁴ M ^{0.83 In} producing the aromatic polycarbonate resin having such a molecular weight, a suitable terminal stopper can be used.
Examples of the terminal terminator include phenol and p-tert-
Monofunctional phenols such as butylphenol, p-cumylphenol, isooctylphenol, p-te
rt-Butylphenol is preferred. Further, if necessary, an antioxidant, a catalyst for accelerating the reaction and the like may be used. The filler used as the component (B-1) in the present invention is a fibrous filler having L / D ≧ 3, and examples of the fibrous filler include glass fiber, carbon fiber, silicon carbide and yellow steel fiber. , Stainless steel fibers, fibers made of potassium titanate or aluminum borate or whiskers, aromatic polyamide fibers and the like are preferable, and surface-treated with an amino silane coupling agent and / or an epoxy silane coupling agent, and an epoxy resin. And / or glass fibers bundled with urethane resin are more preferred. The fibrous filler has L / D = fiber length / fiber diameter of 3 or more, which is a measure of the reinforcing effect of the fibers. If a fibrous filler having an L / D of less than 3 is used, a sufficient reinforcing effect cannot be obtained. The filler is 5 to 240 parts by weight, preferably 7 to 200 parts by weight, and more preferably 1 to 100 parts by weight of the aromatic polycarbonate resin.
It is used in the range of 0 to 150 parts by weight. If it is less than 5 parts by weight, it is insufficient to increase the rigidity of the product.
If it exceeds the weight part, extrusion and molding itself become difficult, and it is difficult to obtain a good molded product.

As the component (B-2), a filler other than the component (B-1) can be used. Examples of the filler include silica, talc, mica, glass beads, glass flakes, glass powder, metal powder, plate-like flakes such as molybdenum disulfide, powdered fillers, which are surface-treated. Is preferred. The filler is 0 to 240 parts by weight with respect to 100 parts by weight of the aromatic polycarbonate resin,
Preferably 5 to 200 parts by weight, more preferably 10 to
Used in the range of 150 parts by weight.

The aliphatic polycarbonate used as the component (C) in the present invention is an aliphatic polycarbonate obtained by the following production method using an aliphatic diol as a raw material. The aliphatic diol used here is represented by the following general formula HO-R ¹ -OH [wherein R ¹ is a divalent aliphatic hydrocarbon group having 2 to 15 carbon atoms, or the aliphatic hydrocarbon groups are ethers with each other. It represents a divalent group composed of a bond or an ester bond, and the hydrocarbon group may be substituted with a halogen atom. ] One or more aliphatic diols selected from the aliphatic diols represented by
4-butanediol, 1,5-pentanediol, 1,6
-Hexanediol, 1,7-heptanediol, 2,2
-Dimethyl-1,3-propanediol and the like, and particularly 1,6-hexanediol is preferably used. As a raw material, this aliphatic diol is used in at least 70 mol% or more, preferably 80 mol% or more of all diols,
An aromatic dihydroxy compound may be contained as the remaining component. As the aromatic dihydroxy compound, the dihydric phenol mentioned in the description of the component (A) is preferably used. The aliphatic polycarbonate may also be a mixture of two or more aliphatic polycarbonates.

Various methods have been proposed as a method for producing an aliphatic polycarbonate. For example, a method of reacting an aliphatic diol with phosgene in the presence of a strong alkali (JP-A-51-63894), a method of reacting an aliphatic diol with ethylene carbonate, and azeotropically removing the produced ethylene glycol ( JP-A-51-1444
No. 92), an alkylene carbonate having a 5- to 7-membered ring and an aliphatic diol having a carbon number of 4 to 40 are reacted in two steps to obtain an aliphatic polycarbonate (Japanese Patent Laid-Open No. Sho 5)
5-56124), and a method for producing a transesterification reaction of ethylene carbonate and an aliphatic diol while controlling ethylene carbonate in the reaction solution during the reaction period (JP-A-63-284222). However, it may be manufactured by any method.

Although the terminal end of the aliphatic polycarbonate is used even as a hydroxyl group, the molecular weight of the aromatic polycarbonate resin may be lowered during extrusion and molding, and terminal treatment such as esterification, etherification and carboxylation is carried out. It is preferable.

The aliphatic polycarbonate used in the present invention has a number average molecular weight of 500 to 10,000, preferably 1,000 to 6,000. If the number average molecular weight is less than 500, the fluidity is not sufficiently improved, and 1
If it exceeds 2,000, the desired effect cannot be obtained because the compatibility with the aromatic polycarbonate resin is insufficient. The number average molecular weight is measured by a method of calculating the number of hydroxyl groups at the terminals by titration using an aliphatic polycarbonate having hydroxyl groups at all terminals before the terminal treatment. In addition, the aliphatic polycarbonate of the present invention is 1 to 6 with respect to 100 parts by weight of the aromatic polycarbonate resin.
It is used in an amount of 0 part by weight, preferably 5 to 50 parts by weight. If the amount of the aliphatic polycarbonate is less than 1 part by weight, the fluidity is not sufficiently improved, and if it exceeds 60 parts by weight, the strength and thermal characteristics (deflection temperature under load) of the molded article are deteriorated and it cannot be put to practical use. These aliphatic polycarbonates are easily available on the market, for example, carbodiol of Toagosei Co., Ltd., and PLACCE of Daicel Chemical Industries Ltd.
LCD etc. are mentioned.

The resin composition of the present invention contains a flame retardant (for example, brominated bisphenol, brominated polystyrene, brominated polycarbonate, etc.) within a range that does not impair the purpose and effect.
Triphenyl phosphate, phosphonic acid amide, red phosphorus, etc.), flame retardant aids (eg, antimony trioxide, sodium antimonate, etc.), nucleating agents (eg, sodium stearate, ethylene-sodium acrylate copolymer, etc.), You may mix | blend a stabilizer (for example, phosphoric acid ester, phosphorous acid ester, etc.) and antioxidant (for example, hindered phenol type compound, etc.). Further, an effective expression amount of, for example, a stabilizer, a release agent, an ultraviolet absorber or the like may be added within a range that does not impair the purpose and effect.

Any method may be employed to produce the reinforced aromatic polycarbonate resin composition of the present invention. For example, a method in which an aromatic polycarbonate resin, a filler, an aliphatic polycarbonate, and other additives as appropriate are sufficiently mixed using a mixing means such as a V-type blender, and then pelletized by a vent-type uniaxial ruder, an aromatic polycarbonate resin Prepare a mixture of aliphatic polycarbonate and other additives in advance with a powerful means such as a super mixer, and supply this from the first chute of a vent-type twin-screw ruder. A method generally used industrially, such as a method of supplying from a second chute on the way, kneading, and pelletizing, is appropriately used. The composition thus obtained, injection molding, extrusion molding,
It can be easily molded by any method such as compression molding or rotational molding.

[0016]

EXAMPLES The present invention will be described below with reference to examples. In addition, the part in an Example is a weight part and the evaluation method implemented with the content of the following (1)-(6). (1) Viscosity average molecular weight (M) 0.7 g of an aromatic polycarbonate resin was dissolved in 100 ml of methylene chloride, and the intrinsic viscosity [η] calculated from the specific viscosity measured at a temperature of 20 ° C. . [Η] = 1.23 × 10 ⁻⁴ M ^0.83 (2) Number average molecular weight Before the end treatment, the number of hydroxyl groups at the terminals was determined by titration using an aliphatic polycarbonate having hydroxyl groups at all the terminals. It was calculated. (3) Izod impact strength Measured according to ASTM D256 with an Izod notch and a thickness of 3.2 mm (kgf · cm / cm) (4) Flexural modulus (kgf / cm ² ) Measured according to ASTM D-790. (5) Heat distortion temperature (° C) Measured according to ASTM D-648. (6) Molding fluidity Archimedes type spiral flow value (flow channel width: 8 mm,
The channel thickness was 1 mm and the injection pressure was 1200 kgf / cm ² ) for evaluation.

[Examples 1 to 5 and Comparative Examples 1 to 6] Aromatic polycarbonate resins, aliphatic polycarbonates and fillers in the amounts (parts by weight) shown in Table 1 were placed in a tumbler in the amounts (shown in parts by weight) shown in Table 1. And blended, and pelletized at 290 ° C. by an extruder with a 40 mmφ vent. A test piece was prepared from the obtained pellets at a cylinder temperature of 300 ° C and a mold temperature of 100 ° C by an injection molding machine (Nestal Cycap 480/150 manufactured by Sumitomo Heavy Industries, Ltd.), and the evaluation results are shown in Table 1. It was Regarding the Archimedes-type spiral flow value, the obtained pellets were subjected to the same injection molding machine at a cylinder temperature of 300 ° C., a mold temperature of 100 ° C. and an injection pressure of 1.
Measure the spiral flow length under the condition of 200 kgf / cm ² ,
The results are shown in Table 1.

The contents of the aromatic polycarbonate resin, the aliphatic polycarbonate and the filler used are as follows. PC: Aromatic polycarbonate resin (viscosity average molecular weight 2
2,200) [Panlite L-1 manufactured by Teijin Kasei Co., Ltd.
225] GF: Glass chopped strand fiber (fiber diameter 13 μm, fiber length 6 mm, L / D = 462) [Nippon Electric Glass Co., Ltd. T-511] MF: Glass milled fiber (fiber diameter 10 μm, fiber length 40 μm, L / D = 4) [PFB-made by Nitto Boseki Co., Ltd.
301] CF: carbon fiber (fiber diameter 9 μm, fiber length 3 m
m, L / D = 333) [Vesphite HTA-C6-U manufactured by Toho Rayon Co., Ltd.] PCD: Aliphatic polycarbonate (number average molecular weight of 2.0)
00) Non-fibrous filler: Mica (scaly, average particle size 20 μm)
[Mica A-41 manufactured by Yamaguchi Mica Industry Co., Ltd.]

[0019]

[Chemical 1]

[0020]

[Table 1]

[0021]

As is clear from Table 1, the resin composition of the present invention exhibits excellent fluidity not found in conventional reinforced aromatic polycarbonate resins and has excellent mechanical properties, and thus has high rigidity. It is extremely useful because it can be widely used in applications requiring water resistance and fluidity, such as the outer shell of OA equipment, automobiles, and home appliances.

Continuation of front page (58) Fields surveyed (Int.Cl. ⁷ , DB name) C08L 69/00

Claims (2)

(57) [Claims] 1. (A) viscosity average molecular weight 10,000 to 4
0,000 aromatic polycarbonate resin, its resin 1
(B-1) length / diameter ratio (L / D) to 00 parts by weight
5 to 240 parts by weight of fibrous filler of ≧ 3, (B-2) (B
-1) A reinforced aromatic polycarbonate resin composition consisting essentially of 0 to 240 parts by weight of a filler and (C) 1 to 60 parts by weight of an aliphatic polycarbonate having a number average molecular weight of 500 to 10,000. 2. A molded product formed from the resin composition according to claim 1.