JPH05311079A - Aromatic polycarbonate resin composition - Google Patents

Abstract

PURPOSE:To obtain an aromatic polycarbonate resin composition excellent in hue and impact resistance by mixing a resin component comprising two specified aromatic polycarbonate resins with a phosphorus-base stabilizer and glass fibers in a specified mixing ratio. CONSTITUTION:100 pts.wt. resin component prepared by mixing 99.7-0 pt.wt. aromatic polycarbonate resin with 0.3-100 pts.wt. copolysiloxane carbonate resin comprising 20-70mol% structural units of formula I (wherein R<1> is -CH2CH2 or a group of formula II; and n is 1-300) and structural units of formula III (wherein W is a single bond, alkylene, alkylidene, cycloalkylene, cycloalkylidene or the like; R<2> to R<5> are each H, halogen, 1-6C alkyl or the like) and having a specific viscosity of 0.275-0.952 when measured in a solution prepared by dissolving 0.7g of the polymer in 100ml of methylene chloride is mixed with 0.001-0.1 pt.wt. stabilizer selected from among trialkyl phosphates and phenylphosphonates (phosphonite) and 5-120 pts.wt. glass fibers.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to an aromatic polycarbonate resin composition. More specifically, it relates to a glass fiber reinforced aromatic polycarbonate resin composition having excellent hue and impact resistance.

[0002]

Aromatic polycarbonate resins are used in a wide variety of fields because they have many excellent properties.
Further, in order to improve its heat resistance and rigidity, and to reduce the molding shrinkage rate and the thermal expansion coefficient, it is reinforced with glass fiber. However, when reinforced with glass fiber, the aromatic polycarbonate resin has its characteristic impact resistance lowered.

Conventionally, it has been known that a polycarbonate-polyorganosiloxane copolymer (copolysiloxane carbonate resin) is added to a glass fiber reinforced aromatic polycarbonate resin to improve impact resistance (JP-A-55-55). 160052, Japanese Patent Laid-Open No. 2-173061). However, although the impact resistance is improved by this method, the hue is deteriorated and it is not practical as a colorless or light-colored colored molded article.

[0004]

SUMMARY OF THE INVENTION An object of the present invention is to provide a glass fiber reinforced aromatic polycarbonate resin composition which is useful as a colorless or light-colored molded article and is excellent in both hue and impact resistance.

The present inventor has conducted extensive studies to achieve this object, and as a result, made a specific polysiloxane diphenol, a dihydric phenol and a polycarbonate precursor react with a glass fiber reinforced aromatic polycarbonate resin composition. It has been found that the above object can be achieved by adding a specific amount of the resulting copolysiloxane carbonate resin and a specific phosphorus stabilizer. The present invention has been completed as a result of further studies based on this finding.

[0006]

The present invention provides the following formula [1]:

[0007]

[Chemical 4]

[In the formula, R ¹ is --CH ₂ CH ₂ --or

[0009]

[Chemical 5]

Where n is an integer from 1 to 300. ]
The structural unit represented by and the following formula [2]

[0011]

[Chemical 6]

[Wherein W represents a single bond, an alkylene group, an alkylidene group, a cycloalkylene group, a cycloalkylidene group or a benzene-substituted alkylidene group, and R ^{2 to} R ^2
5 is hydrogen, halogen, an alkyl group having 1 to 6 carbon atoms,
It is a cycloalkyl group or a phenyl group, and R ^{2 to} R ⁵ may be the same or different. ] The constitutional unit represented by the formula [1] is 20 to 7
0.3 to 100% by weight of a copolysiloxane carbonate resin and 0 to 99.7% of a polypolycarbonate carbonate resin having a specific viscosity of 0.275 to 0.952 in a solution of 0 mol% and 0.7 g dissolved in 100 ml of methylene chloride. 0.001 to 0.1 part by weight of at least one stabilizer selected from trialkyl phosphate, phenylphosphonic acid ester and phenylphosphonous acid ester and 100 parts by weight of glass fiber The present invention relates to an aromatic polycarbonate resin composition containing 120 parts by weight.

The siloxane-containing dihydric phenol used for the production of the unit [1] constituting the copolysiloxane carbonate resin used in the present invention is, for example, a Si-H group-containing siloxane and a p-tert. It is obtained by addition-reacting with butoxystyrene and then hydrolyzing the tert-butoxy group with hydrochloric acid. The number n of repeating dimethylsiloxane units is preferably 1 to 100, more preferably 1 to
60 is more preferred.

The copolysiloxane carbonate resin can be easily obtained by reacting the siloxane-containing dihydric phenol with another dihydric phenol in the presence of a solvent with phosgene. Examples of the dihydric phenol other than the siloxane-containing dihydric phenol include hydroquinone, resorcin, biphenol, bis (4-hydroxyphenyl) methane, 1,1-bis (4-hydroxyphenyl) ethane, 1,1-bis (4- Hydroxyphenyl) -1-phenylethane, 2,2-bis (4-hydroxyphenyl) propane [commonly called bisphenol A],
1,1-bis (4-hydroxyphenyl) cyclohexane, 2,2-bis (3-methyl-4-hydroxyphenyl) propane, 2,2-bis (3,5-dimethyl-4-)
Hydroxyphenyl) propane, 2,2-bis (3-phenyl-4-hydroxyphenyl) propane, bis (4
-Hydroxyphenyl) ketone, bis (4-hydroxyphenyl) sulfone, bis (4-hydroxyphenyl)
Oxides, bis (4-hydroxyphenyl) sulfides or their halides are used. Of these, bisphenol A is most preferable. A small amount of trivalent or higher phenolic compound may be used as a branching agent.

The copolysiloxane carbonate resin has a constitutional unit represented by the above formula [1] of 20 to 70 mol%, and a solution of 0.7 g dissolved in 100 ml of methylene chloride has a specific viscosity of 0.275 to 0. 952. If the constitutional unit represented by the formula [1] does not reach 20 mol%, the impact resistance of the glass fiber reinforced polycarbonate resin is not sufficiently improved, and if it exceeds 70 mol%, the aromatic polycarbonate resin is originally excellent. It is not suitable because the transparency and high glass transition temperature, which are the characteristics, are impaired. Further, if the specific viscosity does not reach 0.275, the strength is weak and it is difficult to obtain the effect of improving the impact resistance.
If it is higher than 52, the fluidity at the time of melting is deteriorated, so that it is not suitable.

The stabilizer to be added to the copolysiloxane carbonate resin is selected from phosphoric acid trialkyl ester, phenylphosphonic acid ester and phenylphosphonous acid ester. Examples of the phosphoric acid trialkyl ester include trimethyl phosphate, triethyl phosphate, tripropyl phosphate and tributyl phosphate, and examples of the phenylphosphonic acid ester include phenylphosphonic acid dimethyl ester, phenylphosphonic acid diethyl ester and phenyl. Phosphonic acid diphenyl ester,
3,5-di-tert-butyl-4-hydroxybenzylphosphonic acid diethyl ester may be mentioned, and examples of the phenylphosphonous acid ester include tetrakis (2,4-
Di-tert-butylphenyl) -4,4'-biphenylene diphosphonite. These stabilizers may be used alone or in combination of two or more.

The amount of the stabilizer used is 100 parts by weight of the resin component.
It is 0.001 to 0.1 parts by weight with respect to parts by weight. 0.
If the amount is less than 001 parts by weight, it is difficult to obtain a sufficient hue improving effect, and even if 0.1 part by weight or more is added, the hue improving effect is saturated at the earliest and adversely affects the physical properties.

Further, the glass fiber to be blended with the above stabilizer may be any glass fiber used in the aromatic polycarbonate resin. The preferable diameter of the glass fiber is 3 to 20 μm, and the length of the glass fiber in the molded product is about 0.02 to 0.5 mm. In addition, glass fiber,
A surface treatment of a silane coupling agent or the like may be performed for the purpose of improving the affinity with the resin, or a focusing treatment may be performed with an acrylic resin or a urethane resin for the purpose of improving the handleability.

The amount of glass fiber used is 5 to 120 parts by weight per 100 parts by weight of the resin component. When the amount is less than 5 parts by weight, it is difficult to obtain a sufficient glass fiber reinforcing effect,
If it is more than 120 parts by weight, the moldability is deteriorated, which is not suitable.

The system in which the stabilizer and the glass fiber are blended with the copolysiloxane carbonate resin has been described above. In the glass fiber reinforced resin composition of the present invention, the copolysiloxane carbonate resin and the aromatic polycarbonate resin are used as resin components. Resins mixed with are also included. That is, it is a glass fiber reinforced resin composition in which an aromatic polycarbonate resin is blended with the copolysiloxane carbonate, glass fibers and the stabilizer.

The aromatic polycarbonate resin of interest here is a usual aromatic polycarbonate resin obtained by reacting a dihydric phenol with a polycarbonate precursor. Examples of the dihydric phenol used here include the dihydric phenol described above in the description of the copolysiloxane carbonate resin, and bisphenol A is particularly preferably used.

The mixing ratio of the aromatic polycarbonate resin and the copolysiloxane carbonate resin is 99.7 wt% or less for the aromatic polycarbonate resin and 0.3 wt% or more for the copolysiloxane carbonate resin. When the amount of the copolysiloxane carbonate resin does not reach 0.3% by weight, the glass fiber-reinforced resin composition obtained has poor impact resistance. Particularly for the purpose of improving the impact resistance of the glass fiber reinforced aromatic polycarbonate resin composition, the amount of the copolysiloxane carbonate resin is preferably in the range of 0.5 to 80% by weight.

Any method may be used to produce the glass fiber reinforced resin composition of the present invention. For example, a method of dry blending each component using a tumbler, a super mixer, a Nauta mixer, etc., and pelletizing with an extruder, an aromatic polycarbonate resin, a copolysiloxane carbonate resin, and a stabilizer are mixed in advance, and then extruded with glass fiber. Any method such as pelletizing may be used.

At the time of pelletizing or molding, the glass fiber reinforced resin composition of the present invention may be pelletized or molded as it is, but if necessary, a light stabilizer, a coloring agent,
You may add additives, such as an antistatic agent, a lubricant, and a mold release agent.

[0025]

EXAMPLES The present invention will be further described with reference to the following examples. In addition, the part in an Example is a weight part and% is weight%. The hue (b value) was measured according to JIS K 7105, and the impact strength was measured according to ASTM D 256.

[0026]

[Synthesis Example 1] <Synthesis of copolysiloxane carbonate resin> 530 parts of ion-exchanged water, 48% in a reactor equipped with a thermometer and a stirrer
Add 96.8 parts of aqueous caustic soda solution and add bisphenol A.
After dissolving 94.2 parts and 0.2 parts of hydrosulfite, polysiloxane bisphenol (n = 20, R ¹ is a mixture of ethylene group and ethylidene group) giving 749 parts of methylene chloride to the constitutional unit of the formula [1]. Yes The ratio is 85:
(15, APHA: 20) 114.8 parts was dissolved and added, and 55.5 parts of phosgene was blown thereinto under stirring at 15 to 25 ° C. over 60 minutes. Then, p-tert-butylphenol (0.05 parts) and a 48% aqueous sodium hydroxide solution (19.3 parts) were added, and the mixture was emulsified, followed by addition of triethylamine (0.32 part) to give 28-3.
The reaction was completed by stirring at 3 ° C. for 2 hours. After completion of the reaction, the product was diluted with methylene chloride, washed with water, acidified with hydrochloric acid and washed with water. When the conductivity of the aqueous phase became almost the same as that of ion-exchanged water, methylene chloride was removed by evaporation to remove copolysiloxane carbonate. 210 parts of resin was obtained (yield 95
%). 0.7 of this polymer using methylene chloride as a solvent
The specific viscosity of the solution with a concentration of g / 100 ml was 0.671.

[0027]

[Synthesis Example 2] <Synthesis of copolysiloxane carbonate resin> Using the same apparatus as in Synthesis Example 1, polysiloxane bisphenol (n = 40, R ¹ is a mixture of ethylene group and ethylidene group and the ratio is 85:15). , APHA: 15) 119.
221 parts of copolysiloxane carbonate resin was obtained in the same manner as in Synthesis Example 1 except that 8 parts, 98.2 parts of bisphenol A, and 0.68 part of p-tert-butylphenol were used (yield 96%). The specific viscosity of this polymer is 0.692.
Met.

[0028]

Example 1 79.5 parts of polycarbonate powder [Panlite L-1250 WP manufactured by Teijin Chemicals Ltd.], 0.5 part of the copolysiloxane carbonate resin synthesized in Synthesis Example 1, and glass fiber chopped strand 20
Parts and tetrakis (2,4-di-t-butylphenyl)
0.03 parts of -4,4'-biphenylene diphosphonite was dry blended in a tumbler and pelletized by an extruder at a temperature of 280 ° C. This product was dried at 120 ° C. for 6 hours, and then 50 × 90 × 2 mm by an injection molding machine [Sumitomo Heavy Industries Ltd. Nestal Sai Cap 480/150].
63 × 12.7 × 3.2 mm and 6.4 mm test pieces were injection-molded, the hue and impact strength were evaluated, and the results are shown in Table 1.

[0029]

Example 2 The polycarbonate powder of Example 1 was added to 7
9 parts, 1.0 part of the polymer synthesized in Synthesis Example 2 as a copolysiloxane carbonate resin, and tetrakis (2,
4-di-t-butylphenyl) -4,4'-biphenylenediphosphonite was replaced by 0.03 part of phosphoric acid trimethyl ester, and the same operation as in Example 1 was carried out, and the evaluation results are shown in Table 1. It was

[0030]

Example 3 The polycarbonate powder of Example 2 was added
Example 1 was repeated except that 5 parts and 5.0 parts of the copolysiloxane carbonate resin were used, and the evaluation results are shown in Table 1.

[0031]

[Comparative Example 1] The polycarbonate powder of Example 1 was 8
Example 1 was repeated except that 0 part of the copolysiloxane carbonate resin was not used and no stabilizer was used, and the evaluation results are shown in Table 1.

[0032]

Comparative Example 2 Tetrakis (2,4-di-t-) of Example 1
(Butylphenyl) -4,4-biphenylene diphosphonite was used in the same manner as in Example 1 except that the evaluation results were shown in Table 1.

[0033]

Comparative Example 3 The procedure of Example 3 was repeated except that the copolysiloxane carbonate resin of Example 3 was not used, and the evaluation results are shown in Table 1.

[0034]

[Table 1]

[0035]

As is apparent from Table 1, the resin composition of the present invention is excellent in both hue and impact resistance, and is particularly useful for parts or housings in the fields of electrical and electronic and mechanical fields.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁵ Identification code Internal reference number FI Technical display location C08K 7/14 C08L 69/00 LPS 8416-4J

Claims (1)

[Claims] 1. The following formula [1]: [In the formula, R ¹ is —CH ₂ CH ₂ — or And n is an integer of 1 to 300. ] And a structural unit represented by the following formula [2] [In the formula, W is a single bond, an alkylene group, an alkylidene group,
A cycloalkylene group, a cycloalkylidene group or a benzene-substituted alkylidene group, R ^{2 to} R ⁵ are hydrogen, halogen, an alkyl group having 1 to 6 carbon atoms, a cycloalkyl group, a phenyl group, and R ^{2 to} R ⁵ are It may be the same or different. ] The constitutional unit represented by the formula [1] is 20 to 70 mol% and the specific viscosity of a solution of 0.7 g dissolved in 100 ml of methylene chloride is 0.275 to 0.952. 100 parts by weight of a resin component consisting of 0.3 to 100% by weight of a copolysiloxane carbonate resin and 0 to 99.7% by weight of an aromatic polycarbonate resin, and a trialkyl phosphate, a phenylphosphonic acid ester, and a phenylphosphonous acid ester. 0.001 to at least one stabilizer selected from
An aromatic polycarbonate resin composition comprising 0.1 part by weight and 5 to 120 parts by weight of glass fiber.