JPH0987504A - Polycarbonate resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To prepare a polycarbonate resin compsn. which has excellent transparency and sliding property by incorporating a predetermined amt. of a polycaprolactone into a resin compsn. comprising a polycarbonate resin and a particular silicone oil. SOLUTION: A polycaprolactone, pref. a polymer of ε-caprolactone, is incorporated in an amt. of 1 to 10 pts.wt. into 100 pts.wt. resin compsn. comprising 95.0 to 99.9wt.% polycarbonate resin and 0.1 to 5.0wt.% phenyl-contg. silicone oil, having a refractive index (nd) of 1.42 to 1.58, which is pref. at least one member selected from the group consisting of compds. represented by formulae I and II (wherein Ph represents phenyl; 0<=x<=100; 1<=y<=100; (m) represents (x); and (n) represents (y)). Pref., the polycarbonate resin has a viscosity average mol.wt. of 10,000 to 40,000.

Description

Detailed Description of the Invention

[0001]

[0001] The present invention relates to a polycarbonate resin composition. More specifically, the present invention relates to a polycarbonate resin composition which is transparent and has excellent slidability.

[0002]

2. Description of the Related Art Hitherto, polycarbonate resins have been supplied to many uses by injection molding, compression molding, extrusion molding, blow molding and the like because of their excellent properties of transparency, heat resistance and impact resistance. In recent years, attempts have been made to use polycarbonate resins for product parts that require slidability. However, in such product parts,
The slidability is insufficient with ordinary polycarbonate resins. Therefore, a composition containing a lubricating oil has been proposed for the purpose of improving the slidability of a polycarbonate resin (Japanese Patent Application Laid-Open No. 50-101441). However, molded articles obtained using this composition are opaque, although exhibiting sliding properties. For the purpose of improving the slidability while maintaining the transparency, a composition containing a specific polyorganosiloxane having a phenyl group has been proposed (Japanese Patent Publication No. 59-39449, Japanese Patent Publication No. 1-40856). Gazette). However, molded articles obtained using this composition are also white and turbid and do not have sufficient transparency.

[0003]

SUMMARY OF THE INVENTION An object of the present invention is to provide a polycarbonate resin composition having excellent slidability without impairing the inherent transparency of the polycarbonate resin.

As a result of earnest studies aimed at achieving the above object, the present inventor has found that by blending a specific phenyl group-containing silicone oil with a polycarbonate resin, and by further using a specific amount of polycaprolactone in combination, the original polycarbonate resin The inventors have found that the slidability can be improved without impairing the transparency, and have completed the present invention.

[0005]

The present invention provides a phenyl group-containing silicone oil having (A) a polycarbonate resin of 95.0 to 99.9% by weight and (B) a refractive index (nd) of 1.42 to 1.58. 1 to 10 parts by weight of (C) polycaprolactone in 100 parts by weight of a resin composition consisting of 0.1 to 5.0% by weight.
The present invention relates to a polycarbonate resin composition containing parts by weight.

The polycarbonate resin as the component (A) used in the present invention is an aromatic polycarbonate resin obtained by reacting a dihydric phenol with a carbonate precursor. Representative examples of the dihydric phenol used here include 2,2-bis (4-hydroxyphenyl) propane (commonly known as bisphenol A), 1,1-bis (4-hydroxyphenyl) ethane, and 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) sulfide, bis (4-hydroxyphenyl) sulfone And the like. Preferred dihydric phenols are 2,2-bis (4-hydroxyphenyl) alkanes, especially bisphenol A. As the carbonate precursor, carbonyl halide, carbonate ester or haloformate is used, and specific examples include phosgene, diphenyl carbonate, dihaloformate of dihydric phenol and the like. In producing the polycarbonate resin by reacting the dihydric phenol and the carbonate precursor, a catalyst, a molecular weight modifier, an antioxidant, and the like may be used as necessary, and the dihydric phenol alone or Two or more kinds may be used in combination. Further, it may be a branched polycarbonate resin obtained by copolymerizing a trifunctional or higher polyfunctional aromatic compound, or a mixture of two or more polycarbonate resins.

The molecular weight of the polycarbonate resin does not need to be particularly limited, but if it is too low, the strength will be insufficient,
If it is too high, the melt viscosity becomes high and molding becomes difficult, so it is usually expressed as a viscosity average molecular weight of 10,000 to 40,40.
000, preferably 15,000 to 30,000. The viscosity average molecular weight (M) as used herein is determined by inserting the specific viscosity (η _sp ) obtained from a solution of 0.7 g of polycarbonate resin dissolved in 100 ml of methylene chloride at 20 ° C. into the following equation. η _sp /C=[η]+0.45×[η] ² C [η] = 1.23 × 10 ^-4 M ^0.83 (where [η] is the intrinsic viscosity and C is the polymer concentration of 0.7)

The basic means for producing a polycarbonate resin will be briefly described. In the solution method using phosgene as a carbonate precursor, the reaction is usually performed in the presence of an acid binder and an organic solvent. As the acid binder, for example, an alkali metal hydroxide such as sodium hydroxide or potassium hydroxide or an amine compound such as pyridine is used. As the organic solvent, for example, halogenated hydrocarbons such as methylene chloride and chlorobenzene are used. Further, a catalyst such as a tertiary amine or a quaternary ammonium salt can be used to promote the reaction, and a terminal stopper such as an alkyl-substituted phenol such as phenol or p-tert-butylphenol can be used as a molecular weight regulator. It is desirable to use. The reaction temperature is usually 0 to 40 ° C., the reaction time is several minutes to 5 hours, and the pH during the reaction is preferably 10 or more.

In the transesterification reaction (melting method) using a carbonic acid diester as a carbonate precursor, a predetermined proportion of a dihydric phenol is heated and stirred with a carbonic acid diester in the presence of an inert gas to generate an alcohol or phenols. The method of distilling is used. The reaction temperature varies depending on the boiling point of the alcohol or phenol to be formed, but is usually in the range of 120 to 300 ° C. The reaction is completed while distilling off alcohol or phenols produced by reducing the pressure from the beginning. Further, a catalyst usually used in a transesterification reaction to promote the reaction can be used. Examples of the carbonic acid diester used in this transesterification reaction include diphenyl carbonate, dinaphthyl carbonate, dimethyl carbonate,
Examples thereof include diethyl carbonate and dibutyl carbonate. Of these, diphenyl carbonate is particularly preferred.

The silicone oil used as the component (B) is a phenyl group-containing silicone oil. A typical silicone oil is dimethyl silicone oil. Dimethyl silicone oil is widely used as a surface lubricant and mold release agent because it has a small change in viscosity with temperature, is chemically stable, and has properties such as high heat resistance and high weather resistance. . However, since the difference in the refractive index (nd) between the polycarbonate resin and the dimethyl silicone oil is large, when the dimethyl silicone oil is blended with the polycarbonate resin, the resulting composition becomes opaque. The silicone oil used in the present invention is obtained by substituting a part of the methyl group of dimethyl silicone oil with a phenyl group, and such a phenyl group-containing silicone oil has improved heat resistance and disappears the melting point as compared with dimethyl silicone oil. Therefore, the low temperature characteristics are improved and the fluidity is maintained up to -70 ° C. In addition, as the substitution amount of the phenyl group increases, the refractive index increases, and the compatibility with the organic resin improves, so that the transparency of the resin is maintained and the dispersibility in the resin also improves.

The phenyl group-containing silicone oil used in the present invention has a large amount of phenyl group substitution and has a refractive index (nd).
Are 1.42 to 1.58. When the phenyl group-containing silicone oil is added to the polycarbonate resin, the composition obtained when the refractive index (nd) is less than 1.42 becomes opaque, and also when the refractive index (nd) exceeds 1.58. The composition becomes opaque, and the addition of the polycaprolactone, which is a feature of the present invention, does not improve the opacity. Particularly, phenyl group-containing silicone oils represented by the following formulas [1] to [4] are preferable, and the repeating units of the following formulas [1], [2] and [4] may be random or block.

[0012]

Embedded image

[Wherein Ph is a phenyl group and x and y are 0≤
x ≤ 100, 1 ≤ y ≤ 100]

[0014]

[Chemical 6]

[Wherein Ph is a phenyl group, m and n are 0≤
m≤100, integer in the range of 1≤n≤100]

[0016]

[Chemical 7]

[Wherein Ph is a phenyl group]

[0018]

Embedded image

[Wherein Ph is a phenyl group, p and q are 7 to
Value that gives a phenyl group content of 80% by weight] Further, two or more kinds of these phenyl group-containing silicone oils may be used. Further, as a typical commercially available phenyl group-containing silicone oil of the above formula [1], there is methylphenyl silicone oil SH-710 (refractive index 1.533) manufactured by Toray Dow Corning Silicone Co., Ltd. Available.

The polycaprolactone used as the component (C) is a polymer of caprolactone, particularly ε-caprolactone, that is, the repeating unit is represented by the following formula.

[0021]

Embedded image

A part of the hydrogen atoms of the methylene chain of polycaprolactone or the repeating unit may be substituted with a halogen atom or a hydrocarbon group. The terminal of polycaprolactone may be subjected to terminal treatment such as esterification or etherification. The molecular weight of the polycaprolactone is not particularly limited, but it is usually 5,000 to 4 in terms of number average molecular weight.
It is 0000. Such polycaprolactone can be produced by ring-opening polymerization of caprolactone in the presence of a catalyst such as an acid, a base, and an organometallic compound. Examples of commercially available products of such polycaprolactone include polycaprolactone Placcel H-1 manufactured by Daicel Chemical Industries, Ltd. (number average molecular weight 10,
000).

The proportion of the phenyl group-containing silicone oil (B) is 0.1 to 5.0% by weight, preferably 100% by weight of the total amount of the polycarbonate resin (A) and the silicone oil (B). Is 0.5 to 1.0% by weight. 0.1% by weight of silicone oil (B)
If less than 5, the slidability of the obtained molded product is insufficient, and
If it exceeds 0% by weight, the transparency becomes insufficient. The blending ratio of the polycaprolactone (C) is 1 to 10 parts by weight, preferably 2 parts by weight, relative to 100 parts by weight of the resin composition comprising the polycarbonate resin (A) and the silicone oil (B).
˜10.0 parts by weight. When the polycaprolactone (C) does not reach 1 part by weight, the transparency of the obtained molded product is not sufficient, and when it exceeds 10 parts by weight, the strength and thermal properties (load deflection temperature) of the obtained molded product are deteriorated. Come to do.

The polycarbonate resin composition of the present invention comprises
Additives having an effective expression level within the range that does not impair the object of the present invention, such as stabilizers (eg, phosphoric acid ester, phosphorous acid ester), release agents, ultraviolet absorbers (eg, hindered phenolic compounds), flame retardants (eg Brominated bisphenol, brominated polycarbonate) or the like may be added.

Any method may be used to produce the polycarbonate resin composition of the present invention. For example, the polycarbonate resin of (A), the phenyl group-containing silicone oil of (B), the polycaprolactone of (C), and other additives as appropriate may be used simultaneously or in any order, for example, using a mixing means such as a V-type blender. A method generally used in industry, such as a method of pelletizing with a vented twin-screw rudder, etc., is appropriately used.

[0026]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention will be further described below with reference to examples. In the examples, parts and% are parts by weight and% by weight, respectively. (1) Dynamic friction force; measured using a surface property measuring device HEIDON-14 type. The conditions are a test piece of 45 mm x 50 mm x 2 mm, a test piece moving speed of 100 mm / min, and a ball indenter diameter of 1
The ball indenter was made of steel and the load was 200 g. (2) Total light transmittance; ASTM using a reflectance / transmittance meter (HR-100) manufactured by Murakami Color Research Laboratory
It measured based on D-1003. The test piece used had the same shape as that of the dynamic friction force measurement.

[Examples 1 to 3 and Comparative Examples 1 to 6] (A) Polycarbonate resin, (B) silicone oil and (C) polycaprolactone were blended in the proportions shown in Table 1, and a screw diameter of 30 mmφ with a vent was used. It was melt-kneaded at a cylinder temperature of 270 ° C. by a shaft extruder [TEX-30XSST manufactured by Japan Steel Works Ltd.] and pelletized by strand cutting. The obtained pellets were dried at 120 ° C for 5 hours with a hot air circulation dryer, and then injection molded at a cylinder temperature of 280 ° C and a mold temperature of 80 ° C by an injection molding machine [SG-150U manufactured by Sumitomo Heavy Industries, Ltd.]. 45mm ×
A 50 mm × 2 mm plate-shaped test piece was molded. Using this test piece, the dynamic friction force and the total light transmittance were evaluated, and the results are shown in Table 1.
It was shown to. The components used in the examples and comparative examples shown in Table 1 are as follows. (A) PC; polycarbonate resin having a viscosity average molecular weight of 22,400 [manufactured by Teijin Chemicals Ltd.] (B) Oil A; methylphenyl silicone oil having a refractive index (nd) of 1.533 [Toray Dow Corning Silicone Co., Ltd. ) SH710] (B) oil B; dimethyl silicone oil having a refractive index (nd) of 1.404 [SH200 manufactured by Toray Dow Corning Silicone Co., Ltd.] (C) PCL; number average molecular weight of 10,000 Polycaprolactone [Placcel H-1 manufactured by Daicel Chemical Industries, Ltd.]

[0028]

[Table 1]

[0029]

As is apparent from Table 1, the polycarbonate resin composition of the present invention has excellent slidability while maintaining the original transparency of the polycarbonate resin, and no conventional polycarbonate resin has been applied. It is possible to expand into other fields, and the industrial effect that it produces is exceptional.

Claims (4)

[Claims] (A) a polycarbonate resin of 95.0 to
99.9% by weight and (B) a refractive index (nd) of 1.42 or more
Phenyl group-containing silicone oil 0.15 which is 1.58
A polycarbonate resin composition obtained by mixing 1 to 10 parts by weight of (C) polycaprolactone with 100 parts by weight of a resin composition of 5.0 to 5.0% by weight. 2. The molecular weight of the polycarbonate resin (A) is from 10,000 to 40,000, expressed as a viscosity average molecular weight.
The polycarbonate resin composition according to claim 1, which is 0. 3. The phenyl group-containing silicone oil (B) is at least one phenyl group-containing silicone oil selected from the group of compounds represented by the following formulas [1] to [4]: 2. The polycarbonate resin composition according to 2. Embedded image [Wherein Ph is a phenyl group, x and y are 0 ≦ x ≦ 100,
An integer in the range of 1 ≦ y ≦ 100] [Wherein Ph is a phenyl group, m and n are 0 ≦ m ≦ 100,
An integer in the range of 1 ≦ n ≦ 100] [Wherein Ph is a phenyl group] [Where Ph is a phenyl group, and p and q are values that give a phenyl group content of 7 to 80% by weight] 4. The polycarbonate resin composition according to claim 1, wherein the polycaprolactone (C) is a polymer of ε-caprolactone.