JP3097930B2 - 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 resin composition reinforced with an inorganic filler, which comprises a copolyester carbonate as a basic resin.

[0002]

2. Description of the Related Art Polycarbonate resins are widely used as engineering plastics because of their excellent physical properties. A technique for improving impact resistance by blending polyethylene with such a polycarbonate has been known for a long time (Japanese Patent Publication No. 40-13663).

[0003] Further, in order to improve the rigidity of polycarbonate, it is widely used to add an inorganic filler such as glass fiber or carbon fiber.

However, when polyethylene is added to polycarbonate reinforced with an inorganic filler such as glass fiber, the effect of improving the impact resistance is recognized, but glass fiber or the like appears on the surface of the molded product. This causes a problem that the appearance is poor because the surface of the toner is raised and the surface becomes conspicuous white.

Accordingly, the present invention provides an improved surface appearance.
An object of the present invention is to provide a polycarbonate resin composition containing an inorganic filler and a polyolefin resin.

[0006]

The inventors of the present invention used a specific copolyestercarbonate as a polycarbonate resin and blended it with an inorganic filler and a polyolefin resin to significantly improve the surface appearance. Further, they have found that they have excellent impact resistance, and have reached the present invention.

That is, the present invention provides: (A) the following formula (Formula 3):

[0008]

Embedded image And the following formula (Formula 4):

[0009]

Embedded image In the above formula, R and R 'are each independently a halogen atom, a monovalent hydrocarbon group or a hydrocarbonoxy group, and W is a divalent hydrocarbon group, -S-, -SS-, -O
-, -S (= O)-,-(O =) S (= O)-, or -C (= O)-, and n and n 'are each independently an integer of 0 to 4, X is a divalent aliphatic group having 6 to 18 carbon atoms, b is 0 or 1, and has a structural unit represented by the formula: ) And 2 mol% of the total amount of the structural units of
It contains 97 to 40 parts by weight of copolyester carbonate occupying at least 25 mol% and (B) 3 to 60 parts by weight of an inorganic filler, and further comprises (C) a polyolefin-based resin in the total of (A) and (B). A resin composition containing 0.05 to 20 parts by weight per 100 parts by weight is provided.

The copolyester carbonate used in the present invention must have the structural units represented by the above formulas (Chemical Formula 3) and (Chemical Formula 4). First, the structural unit represented by Chemical Formula 3 is composed of a diphenol component and a carbonate component. The following formula (Formula 5) shows a diphenol that can be used to introduce a diphenol component.

[0011]

Embedded image In the above formula, R, R ', W, n, n' and b have the same meanings as described above. Regarding R and R ', examples of the halogen atom include a chlorine atom and a bromine atom. As a monovalent hydrocarbon group, a carbon number of 1 to 1
Alkyl group having 2 such as methyl group, ethyl group, propyl group, decyl group; cycloalkyl group having 4 to 8 carbon atoms such as cyclopentyl group and cyclohexyl group; aryl group having 6 to 12 carbon atoms such as Phenyl group, naphthyl group, biphenyl group and the like; aralkyl group having 7 to 14 carbon atoms such as benzyl group and cinnamyl group; or alkaryl group having 7 to 14 carbon atoms such as tolyl group and cumenyl group. And preferably an alkyl group. Examples of the hydrocarbon group of the hydrocarbon oxy group include the aforementioned hydrocarbon groups. Such a hydrocarbon oxy group is an alkoxy group, a cycloalkyloxy group, an aryloxy group, an aralkyloxy group or an alkaryloxy group, and an alkoxy group and an aryloxy group are preferred.

When W is a divalent hydrocarbon group,
Alkylene groups having 2 to 30 carbon atoms, such as alkylene groups having 1 to 30 carbon atoms, for example, methylene group, ethylene group, trimethylene group, octamethylene group, etc., or ethylidene group, propylidene group, etc .;
And a cycloalkylene group having 6 such as a cyclohexylene group, a cyclododecylene group or the like, or a cycloalkylidene group such as a cyclohexylidene group.

The diphenols useful in the present invention include, for example, 2,2-bis (4-hydroxyphenyl) propane (so-called bisphenol A); 2,2-bis (3,5-dibromo-4-hydroxyphenyl) propane ; 2,2-bis (3,5-
Dimethyl-4-hydroxyphenyl) propane; 1,1-bis (4-hydroxyphenyl) cyclohexane; 1,1-bis (3,5-dimethyl-4-hydroxyphenyl) cyclohexane; 1,1-bis (4-hydroxy 1,4-bis (4-hydroxyphenyl) propane; 1,1-bis (4-hydroxyphenyl) cyclododecane; 1,1-bis (3,5-dimethyl-4-hydroxyphenyl) cyclododecane 4,4-
Dihydroxydiphenyl ether; 4,4-thiodiphenol; 4,4-dihydroxy-3,3-dichlorodiphenyl ether; and 4,4-dihydroxy-2,5-dihydroxydiphenyl ether, and the like.
The diphenols described in 2,999,835, 3,028,365, 3,334,154 and 4,131,575 can be used.

[0014] Examples of the precursor for introducing the carbonate component include phosgene and diphenyl carbonate.

Next, the structural unit represented by the chemical formula (4) comprises a diphenol component and a diacid component. For the introduction of the diphenol component, the same diphenol as described above can be used. The monomer used to introduce the diacid component is a diacid or an equivalent thereof. The divalent acid is, for example, an aliphatic diacid having 8 to 20 carbon atoms, preferably 10 to 12 carbon atoms. The divalent acid or its equivalent may be linear, branched, or cyclic. The aliphatic diacid is preferably α, ω-dicarboxylic acid. As such a divalent acid, for example, straight-chain saturated aliphatic dicarboxylic acids such as sebacic acid (decandioic acid), dodecandioic acid, tetradecandioic acid, icodecandioic acid, and the like are preferable, and sebacic acid and dodecane acid are preferable. Diacids are particularly preferred. Examples of the equivalent substance include the above-mentioned divalent acids, for example, acid halides such as acid chloride, and diaromatic esters such as diphenyl ester. However, the carbon number of the ester portion of the ester is not included in the carbon number of the acid described above. The above divalent acid or its equivalent may be used alone or in combination of two or more.

The copolyester carbonate of the component (A) has the above-mentioned two types of structural units represented by the following chemical formulas (3) and (4) in the following proportions. That is, the amount of the structural unit represented by (Chem. 4) is 2 to 30 mol%, preferably 5 to 25 mol%, more preferably 7 to 20 mol% of the total amount of (Chem. 3) and (Chem. 4). It is. If the amount of the compound (Chem. 4) is less than 2 mol%, the transition temperature (Tg) is insufficiently reduced, so that the effect of improving the fluidity is not seen. On the other hand, if it is more than 30 mol%, excellent physical properties equivalent to those of conventional polycarbonate, for example, mechanical strength, heat resistance and the like cannot be obtained.

The weight average molecular weight of the copolyester carbonate of component (A) is usually from 10,000 to 100,000, preferably from 18,000 to 40,000. Here, the weight average molecular weight is a value measured by GPC (gel permeation chromatography) using polystyrene corrected for polycarbonate. (Also, in methylene chloride, 25 ℃
It is preferable that the intrinsic viscosity measured in the step is 0.35 to 0.65 dl / g. The component (A) copolyester carbonate can be produced by a known polycarbonate production method, for example, an interfacial polymerization method using phosgene, a melt polymerization method, or the like. See, for example, Quinn U.S. Pat. No. 4,238,596 and Quinn and Markezich.
In U.S. Pat. No. 4,238,597. Specifically, first, an acid halide is formed prior to the reaction between the ester-forming group and the diphenol, and then reacted with phosgene. In the Goldberg basic solution method (US Pat. No. 3,169,121), a pyridine solvent can be used and a dicarboxylic acid is used. Diesters of α, ω-dicarboxylic acids (eg, sebacic acid) (eg, diphenyl esters)
Can also be used. A preferred method of manufacture is the improvement of Kochanowski in U.S. Pat. No. 4,286,083. In this method, a lower diacid such as adipic acid is converted into a salt form (preferably an alkali metal salt such as a sodium salt) in advance, and is added to a reaction vessel in which diphenol is present. During the reaction with phosgene, the aqueous phase is maintained at an alkaline pH, preferably about pH 8-9, and then raised to pH 10-11, with a minimum of about 5% remaining in the reaction with phosgene.

In the case of the interfacial polymerization method, for example, the bischloroformate method, it is preferable to use a general catalyst system well-known in the synthesis of polycarbonate and copolyestercarbonate. Primary catalyst systems include amines such as tertiary amines, amidines or guanidines. Tertiary amines are commonly used, of which trialkylamines such as triethylamine are particularly preferred.

The copolyester carbonate of the component (A) has a sufficient impact strength even if the terminal is phenol, but pt-butylphenol, isononylphenol, isooctylphenol, m- or p-cumylphenol. By introducing a bulkier terminal group such as (preferably p-cumylphenol), a chromanyl compound, for example, chroman, a copolyester carbonate having better low-temperature impact properties can be obtained.

The inorganic filler (B) that can be used in the present invention is not particularly limited, and includes all commonly used inorganic fillers. Specific examples include glass fiber, glass flake, glass beads, milled glass, talc, clay, mica, carbon fiber, wollastonite, potassium titanate whisker, titanium oxide whisker, and zinc oxide whisker.

The component (B) inorganic filler is composed of the component (A) 97
3 to 60 parts by weight, preferably 5 to 50 parts by weight, per 95 to 50 parts by weight of (A). If the amount of the component (B) is less than 3 parts by weight, the rigidity is not improved, and if it exceeds 60 parts by weight, the fluidity is impaired.

In the present invention, the above component (A)
And 0.05 to 2 with respect to a total of 100 parts by weight of
0 parts by weight, preferably 0.1 to 5 parts by weight of a polyolefin resin is added. The amount of polyolefin resin is 0.0
If the amount is less than 5 parts by weight, the effect of improving the impact resistance is small, and
If the amount is more than the weight part, the rigidity is impaired. Polyolefin-based resins are known per se and include, for example, polyethylene, polypropylene, polyisobutylene, ethylene-propylene-diene copolymers, ethylene-ethyl acrylate copolymers, and copolymers and terpolymers thereof. Other suitable polyolefins for use in the present invention will be apparent to those skilled in the art. Preferred polyolefins are polyethylene, ethylene-ethyl acrylate copolymer. Such polyolefins and their copolymers and terpolymers are available via commercial routes.

The resin composition of the present invention may further contain other resins in addition to the above components. Examples of such other resins include polyester such as PBT, ABS resin,
AES resin, SAN resin, polystyrene and the like can be mentioned. Such resins can be used in amounts up to 200 parts by weight per 100 parts by weight of component (A).

The resin composition of the present invention may also contain other conventional additives, such as pigments, dyes, etc., at the time of mixing and molding the resin according to the purpose, as long as the physical properties are not impaired.
Heat-resistant agents, antioxidant deterioration inhibitors, weathering agents, lubricants, release agents, plasticizers, flame retardants, flow improvers, antistatic agents and the like can be added.

The method for producing the resin composition of the present invention is not particularly limited, and ordinary methods can be used satisfactorily. However, the melt mixing method is generally preferred. The use of small amounts of solvents is possible but generally not necessary. Examples of the apparatus include an extruder, a Banbury mixer, a roller, a kneader, etc., which are operated batchwise or continuously. The order of mixing the components is not particularly limited.

[0026]

The present invention will be described in more detail with reference to the following examples.
I will tell. In the examples, the following components were used as the components.
Was used.Component (A)  CPEC: Copolyester moss produced as follows
-Carbonate: 7.2 g of dodecane diacid (DDDA) (31
Mmol) and 2.7 g of NaOH tablets (68 mmol)
Is dissolved in 180 ml of water, and disodium
A salt was produced. Next, a sample outlet is provided at the bottom, and
Into a 2000ml Molton flask with 5 ports
Stirrer blade, pH measuring end, injection tube and dry ice condenser
A claisen adapter with a denser was attached. this
In a polymerization flask, add 71 g (311 mm) of bisphenol A.
Mol), 0.9 ml of triethylamine, p-cumylfe
2.0 g (9 mmol) of phenol, methylene chloride 22
0 ml and the previously prepared disodium salt of DDDA
I charged. Subsequently, the flask was charged with 2 phosgene.
Injected at a rate of g / min. At this time, 50% NaOH aqueous solution
The solution was brought to pH 8 for 10 minutes while adding the solution through the injection tube.
Maintained. After that, continue to inject more phosgene
Add a 50% NaOH aqueous solution from the injection tube to
H was adjusted to 10.5 and maintained at this pH for 10 minutes. use
The total amount of phosgene that was added was 40 g (400 mmol)
there were. After the reaction, adjust the pH of the solution to 11 to 11.5.
And the organic solvent phase was separated from the aqueous phase. Organic solvent phase
Three times with 300 ml of 2% hydrochloric acid, and then with 30 parts of ion-exchanged water.
After washing 5 times with 0 ml, dry with anhydrous magnesium sulfate
And filtered. Put this in 1500 ml of methanol
To precipitate the polymer. Filter the resulting polymer by filtration
Separate, once with 500 ml of methanol and then ion exchange.
After washing four times with 500 ml of water replacement, at 110 ° C for 15 hours
Dried. Thus, the structures of the following formulas (Formula 6) and (Formula 7)
Copolyester having units in a 90:10 molar ratio
-Carbonate was obtained. This intrinsic viscosity (25 in methylene chloride)
° C) was 0.46 dl / g. In the following this
Abbreviated as CPEC.

[0027]

Embedded image

[0028]

Embedded imagePC: Poly of bisphenol A used for comparison
Carbonate, trademark LEXAN (Nippon GE Plastics
Co., Ltd.), measured in methylene chloride at 25 ° C.
Viscosity 0.46 dl / gComponent (B)  Glass fiber: trademark; T505, manufactured by Nippon Electric Glass Co., Ltd. Carbon fiber: trademark: A9000, manufactured by Asahi Kasei CorporationComponent (C)  Polyethylene resin: Trademark; GML 2420, Nihon Uni
Ethylene-ethyl acrylate resin manufactured by Ka Corporation: Trademark; NUC 6
570, manufactured by Nippon Yunika CorporationExamples 1-3 and Comparative Examples 1-6  Each component was mixed at the ratio (weight ratio) shown in Table 1,
Extrude with a single screw extruder (65 mm) set to 100 rpm,
Created The pellets are set at a temperature of 280 ° C.
Injection molding at 100 ° C mold temperature for impact strength measurement and
A test piece for appearance evaluation was prepared. About this, off-surface
The appearance was evaluated and the Izod impact strength was measured. result
Are shown in Table 1.

The surface appearance was evaluated by visual evaluation and by measuring glossiness. The evaluation criteria by visual inspection are as follows: floating of the inorganic filler is clearly seen, and the surface looks whitish. ×: floating of the inorganic filler is clearly observed. Δ: floating of the inorganic filler is slightly recognized. The appearance of the surface is similar to that without inorganic filler, and the gloss of the surface of the molded product (50 × 50 × 3 mm square plate) is measured at an angle of 60 ° using a digital gonio-gloss meter (UGV). -4
0, manufactured by Suga Test Instruments Co., Ltd.).

Further, the Izod impact strength is ASTM D256
The Izod impact strength with a 1 / 8-inch bar notch was measured according to the above.

[0031]

[Table 1]

[0032]

The carbonate resin composition of the present invention comprises:
The surface appearance is improved very well, and the impact resistance is also excellent. Therefore, it can be used in a wide range of applications and is industrially useful.

──────────────────────────────────────────────────続 き Continued on front page (58) Field surveyed (Int. Cl. ⁷ , DB name) C08L 67/00 C08L 69/00

Claims (1)

(57) [Claims] (A) The following formula (Formula 1): And the following formula (Formula 2): In the above formula, R and R 'are each independently a halogen atom, a monovalent hydrocarbon group or a hydrocarbonoxy group, and W is a divalent hydrocarbon group, -S-, -SS-, -O
-, -S (= O)-,-(O =) S (= O)-, or -C (= O)-, and n and n 'are each independently an integer of 0 to 4, X is a divalent aliphatic group having 6 to 18 carbon atoms, b is 0 or 1, and has a structural unit represented by the formula: ) And 2 mol% of the total amount of structural units of
It contains 97 to 40 parts by weight of a copolyester carbonate occupying less than 25 mol% and (B) 3 to 60 parts by weight of an inorganic filler, and further comprises (C) a polyolefin-based resin in the total of (A) and (B). A resin composition containing 0.05 to 20 parts by weight per 100 parts by weight.