JPH05125260A - Polycarbonate resin composition - Google Patents

Abstract

PURPOSE:To obtain the title compsn. excellent in impact resistance by compounding a specific carbonate resin compsn., a specific graft copolymer, and a specific polyolefin resin. CONSTITUTION:A resin compsn. contg. a polycarbonate resin and/or a copolyester carbonate having structural units of formulas I and II [wherein R and R' are each halogen or a monovalent hydrocarbon(oxy) group; W is a divalent hydrocarbon groups,-S-,-S-S-,-O-,-S(=O)-,-(O=)S(=O)-, or-C(=O)-; n and n' are each 0-4; X is a 6-18C divalent aliph. group; and b is 0-1] in a molar ratio of units of formula I to those of formula II of 98:2-70:30 is compounded with an inorg. filler (e.g. glass fiber), a graft copolymer at least comprising a diene elastomer or diene-vinyl monomer copolymer and at least one monomer selected from the group consisting of a 1-6C alkyl (meth)acrylate and (meth)acrylic acid, and a polyolefin resin each in a specified amt.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a polycarbonate resin composition reinforced with an inorganic filler.

[0002]

2. Description of the Related Art It is well known that polycarbonate resins have high impact strength. Attempts have also been made to improve the rigidity and dimensional accuracy of the polycarbonate resin by blending the polycarbonate resin with an inorganic filler such as glass fiber or glass flakes.

[0003]

However, when an inorganic filler is added to the polycarbonate resin, the notched Izod impact strength is significantly reduced, and the high impact strength originally characteristic of the polycarbonate resin is impaired. The problem arises.

Therefore, the present invention aims to improve the impact resistance of a polycarbonate resin reinforced with an inorganic filler.

[0005]

The present invention includes (A) a polycarbonate resin and / or the following formula (Formula 3):

[0006]

[Chemical 3] And the following formula (Formula 4):

[0007]

[Chemical 4] In the above formula, R and R'are each independently a halogen atom, a monovalent hydrocarbon group or a hydrocarbon oxy 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 the amount of the structural unit represented by (Chemical Formula 4) is (Chemical Formula 3) 2 to 30 of the total amount of the structural units of
Copolyester carbonate, which accounts for mol%,
And (B) a resin composition containing an inorganic filler,
(C) for 100 parts by weight of the total of (A) and (B)
Diene elastomer or diene-vinyl monomer copolymer, C ₁ -C ₆ alkyl acrylate, C ₁ -C ₆
A resin containing 0.05 to 20 parts by weight of a graft copolymer selected from the group consisting of alkyl methacrylate, acrylic acid and methacrylic acid and at least the above monomer, and (D) a polyolefin resin 0.05 to 10 parts by weight. A composition is provided.

In the present invention, component (A) is a polycarbonate and / or a copolyestercarbonate. The polycarbonate used in the present invention is an aromatic polycarbonate produced by a known phosgene method or a melting method (see, for example, JP-A-63-215763 and JP-A-2-124934).

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

[0010]

[Chemical 5] In the above formula, R, R ', W, n, n'and b have the same meanings as described above. Regarding R and R ', first, examples of the halogen atom include a chlorine atom or a bromine atom. The monovalent hydrocarbon group has 1 to 1 carbon atoms.
An alkyl group having 2 such as a methyl group, an ethyl group, a propyl group, a decyl group and the like; a cycloalkyl group having a carbon number of 4 to 8, such as a cyclopentyl group and a cyclohexyl group; an aryl group having a carbon number of 6 to 12, such as Phenyl group, naphthyl group, biphenyl group and the like; aralkyl group having 7 to 14 carbon atoms, such as benzyl group, cinnamyl group and the like; or alkaryl group having 7 to 14 carbon atoms, such as tolyl group and cumenyl group, etc. And is preferably an alkyl group. Further, the hydrocarbon group of the hydrocarbon oxy group may be the above-mentioned hydrocarbon group. Such a hydrocarbonoxy 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 preferable.

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

Examples of the diphenol effective in the present invention include 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) Phenyl) decane; 1,4-bis (4-hydroxyphenyl) propane; 1,1-bis (4-hydroxyphenyl) cyclododecane; 1,1-bis (3,5-dimethyl-4-hydroxyphenyl) cyclododecane ; 4,4-
Examples include dihydroxydiphenyl ether; 4,4-thiodiphenol; 4,4-dihydroxy-3,3-dichlorodiphenyl ether; and 4,4-dihydroxy-2,5-dihydroxydiphenyl ether.
The diphenols described in 2,999,835, 3,028,365, 3,334,154 and 4,131,575 can be used.

Further, examples of the precursor for introducing the carbonate component include phosgene and diphenyl carbonate.

Next, the constitutional unit represented by the chemical formula 4 is composed of a diphenol component and a diacid component. Regarding the introduction of the diphenol component, the same diphenol as described above can be used. The monomer used for introducing the divalent acid component is a divalent acid or its equivalent. 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. Examples of such a divalent acid include linear saturated aliphatic dicarboxylic acids such as sebacic acid (decanedioic acid), dodecanedioic acid, tetradecanedioic acid, octadecanedioic acid, and eicosanedioic acid, and sebacic acid and dodecane are preferred. Diacids are especially preferred. Examples of equivalent substances include acid halides such as the above-mentioned divalent acids, such as acid chlorides, and diaromatic esters such as diphenyl esters. However, the carbon number of the ester portion of the ester is not included in the carbon number of the above-mentioned acid. The above divalent acids or their equivalents may be used alone or in combination of two or more.

The copolyestercarbonate used as the component (A) has the above-mentioned two kinds of structural units represented by (Chemical Formula 3) and (Chemical Formula 4) in the following proportions. That is, the amount of the structural unit represented by (Chemical formula 4) is 2 to 30 mol%, preferably 5 to 25 mol%, more preferably 7 to 20 mol% of the total amount of (Chemical formula 3) and (Chemical formula 4). Is. If the amount of (Chemical Formula 4) is less than 2 mol%, the transition temperature (Tg) is not sufficiently lowered, so that the fluidity is lowered. If it is more than 30 mol%, excellent physical properties equivalent to those of polycarbonate, such as mechanical strength and heat resistance, cannot be obtained.

The weight average molecular weight of the copolyestercarbonate is usually 10,000 to 100,000, preferably 18,000 to 4
It is 0,000. The term "weight average molecular weight" as used herein means that polystyrene corrected for polycarbonate is used,
It is measured by C (gel permeation chromatography). Further, it is preferable that the intrinsic viscosity measured at 25 ° C in methylene chloride is 0.35 to 0.65 dl / g.

The above copolyestercarbonate can be produced by a known method for producing polycarbonate, for example, an interfacial polymerization method using phosgene or a melt polymerization method. For example, it can be produced by the method described in Quinn U.S. Pat. No. 4,238,596 and Quinn and Markezich U.S. Pat. No. 4,238,597. Specifically, first, an acid halide is formed prior to the reaction between the ester-forming group and diphenol, and then reacted with phosgene. Goldberg (Goldb
erg) basic solution method (US Pat. No. 3,169,121)
In, a pyridine solvent can be used and a dicarboxylic acid is used. α, ω-dicarboxylic acid (eg sebacic acid)
Melt polymerization processes using diesters of, for example, diphenylesters can also be used. A preferred manufacturing method is
U.S. Pat.No. 4,286,083, Kochanowski
Nowski) improved method. In this method, a lower diacid such as adipic acid is made into a salt form (preferably an alkali metal salt such as sodium salt) in advance and then added to a reaction vessel containing diphenol. During the reaction with phosgene, the aqueous phase is brought to an alkaline pH, preferably between about pH 8 and
9 and then the minimum remaining reaction with phosgene of about 5
%, Raise to pH 10-11.

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

Further, the copolyestercarbonate of the component (A) has sufficient impact resistance even if its terminal is phenol, but pt-butylphenol, isononylphenol, isooctylphenol, m- or p-cumylphenol. By introducing a bulkier end group (preferably p-cumylphenol), a chromanyl compound, for example, chroman, a copolyestercarbonate having excellent low temperature impact resistance can be obtained.

When the component (A) contains both polycarbonate and copolyestercarbonate, the compounding ratio of both is arbitrary.

Next, the inorganic filler is not particularly limited, and all conventional inorganic fillers can be mentioned. Specifically, glass fiber, glass flakes, glass beads, milled glass, talc, clay, mica, carbon fiber, wollastonite, potassium titanate whiskers,
Examples thereof include titanium oxide whiskers and zinc oxide whiskers. The above-mentioned inorganic filler is preferably component (A) 9
The amount is 3 to 60 parts by weight with respect to 7 to 40 parts by weight, and more preferably 5 to 50 parts by weight with respect to 95 to 50 parts by weight of (A).

As the component (C) graft copolymer itself, known ones can be used.
-81455 and Japanese Patent Laid-Open No. 1-141944. Typically, it is composed of a shell (coating phase) formed by grafting (meth) acrylate or (meth) acrylic acid on a core composed of a diene elastomer. Preferably, 50% or more by weight of an elastomeric core composed of polymerized dienes and optionally a second phase composed of polymerized vinyl monomers grafted to the core, C ₁
To C ₆ alkyl acrylate, C _{1 to} C ₆ alkyl methacrylate, acrylic acid, methacrylic acid, and a monomer selected from the group consisting of a mixture of one or more of these monomers (which may be mixed with a crosslinking agent in some cases). It comprises a graft copolymer composed of the above polymerization products and having a core and an envelope phase (shell) grafted to a second phase which may optionally be present. More preferably, the core comprises polymerized conjugated diene units or copolymers of polymerized diene units and polymerized units of vinyl compounds (preferably aromatic). Suitable conjugated dienes are butadiene, isoprene, 1,3-pentadiene, etc. Examples of suitable vinyl compounds are styrene, α-methylstyrene, vinyltoluene, p-methylstyrene, and esters of acrylic (methacrylic) acid. There is. The core of the graft copolymer is preferably composed of a styrene-butadiene copolymer consisting of about 10 to 50% by weight of styrene and about 90 to 50% by weight of butadiene and has a molecular weight of 250.
It is 00 to 1500000, preferably 150000 to 500000. The core may contain a crosslinking agent as described in detail later.

The graft copolymer preferably comprises a second intermediate phase of polymerized vinyl monomer grafted to the first phase or core. However, the existence of such a second phase is not strictly necessary. Suitable vinyl monomers for this second intermediate phase include, for example, vinyltoluene, α-methylstyrene, halogenated styrene,
There are naphthalene and non-aromatic compounds (acrylonitrile, methacrylonitrile, α-halogenated acrylonitrile, etc.). It is possible to use one or more of these vinyl monomers. Preference is given to using styrene.

The third phase of the graft copolymer is C _1-
A monomer selected from the group consisting of C ₆ alkyl acrylates, C ₁ -C ₆ alkyl methacrylates, acrylic acid, methacrylic acid, and mixtures of one or more of these compounds, optionally with a crosslinking monomer. It consists of polymerized units. Monomer compounds are especially C ₁ -C
₆ alkyl acrylates (eg methyl acrylate, ethyl acrylate, hexyl acrylate, etc.),
C ₁ -C ₆ alkyl methacrylate (for example, methyl methacrylate, ethyl methacrylate, hexyl methacrylate, etc.), acrylic acid, or methacrylic acid. Preference is given to using methyl methacrylate.

The shell phase of the graft copolymer may contain, in addition to the monomer compound, a crosslinking monomer in an amount of from about 0.1 to about 2.5 parts by weight, based on the weight of the graft copolymer. The crosslinking monomer is a polyethylenically unsaturated monomer that is addition polymerization reactive and has some groups that all polymerize at about the same reaction rate. Suitable cross-linking monomers are polyacrylic and polymethacrylic acid esters of polyols such as butylene diacrylate and methacrylate, trimethylolpropane trimethacrylate and the like, divinyl and trivinylbenzene, vinyl acrylate and methacrylate, and the like. The preferably used crosslinking monomer is butylene diacrylate.

Usually, the graft copolymer has a core of about 60-
80 parts by weight, the second intermediate phase is about 10 to 20 parts by weight, and the third shell phase is about 10 to 20 parts by weight. In particular, 71 parts of butadiene,
A core consisting of 3 parts of styrene, 4 parts of methyl methacrylate and 1 part of divinylbenzene, a second phase of 11 parts by weight of styrene and 11 parts by weight of methyl methacrylate, methyl methacrylate and 1,3-butylene glycol dimethacrylate.
Good results have been obtained with graft copolymers having 0.1 part by weight of shell phase. Such a graft copolymer (MBS resin) is commercially available from Rohm and Haas Chemical Company as ACRYLOID KM653 ™.

The above-mentioned graft copolymers and their method of preparation are described in US Pat. No. 4,180,494. In addition, Metabrene-C-100, Metabrene-C-202, and Metabrene-C-223 (all are trademarks, Mitsubishi Rayon Co., Ltd.), Kane Ace B-12, Kane Ace B-22, and Kane Ace B-56 (all are trademarks , Kanebuchi Chemical Co., Ltd.), BTA, IIIS and IIIN (all are trademarks, Kureha Chemical Industry Co., Ltd.) and the like.

The above-mentioned (C) graft copolymer is
0.0 for 100 parts by weight of the total of (A) and (B)
The amount is 5 to 20 parts by weight, preferably 0.5 to 10 parts by weight. If the amount of (C) is less than 0.05 parts by weight, the effect of the present invention will not be achieved, and if it is more than 20 parts by weight, the fluidity and rigidity of the resin composition will be impaired.

The (D) polyolefin resins used in the present invention are known per se and include, for example, polyethylene, polypropylene, polyisobutylene, ethylene-propylene-diene copolymer, ethylene-ethyl acrylate copolymer, and copolymers and terpolymers thereof. To do. Other polyolefins suitable for use in the present invention will be apparent to those skilled in the art. Suitable polyolefins are polyethylene, ethylene-ethyl acrylate copolymer and polypropylene. These polyolefins and their copolymers and terpolymers are available via commercial routes. These polyolefin-based resins may be modified polyolefin-based resins having functional groups such as carboxylic acid groups, acid anhydride groups and epoxy groups.

The polyolefin resin (D) is used in an amount of 0.05 to 10 relative to 100 parts by weight of the total of (A) and (B).
Parts by weight, preferably 0.2 to 5 parts by weight are blended.
If the amount of (D) is less than 0.05 parts by weight, the effect of the present invention will not be achieved, and if it is more than 10 parts by weight, the rigidity of the resin composition will be impaired.

The resin composition of the present invention comprises, in addition to the above components,
Any conventional additives such as pigments, dyes, reinforcing agents, heat-resistant agents, antioxidants, weathering agents, lubricants, release agents, crystal nucleating agents, plasticizers, flame retardants, fluidity improvers, antistatic agents. And other resins and the like.

The resin composition of the present invention is obtained by mixing the above components in any order, and generally a melt mixing method is desirable. There is no particular limitation on the temperature and time required for melt mixing, and they can be appropriately determined by the composition of the materials.
As the mixing device, an extruder, a Banbury mixer, a roller, a kneader and the like can be mentioned as an example.

[0033]

The present invention will be described in more detail with reference to the following examples, but the present invention is not limited thereto.

The following compounds were used in the examples. Component (A) Polycarbonate resin: Bisphenol A polycarbonate (trademark; Lexan, manufactured by Nippon GE Plastics Co., Ltd.), intrinsic viscosity measured at 25 ° C. in methylene chloride.
0.45 dl / g copolyester carbonate (CPEC): copolyester carbonate prepared as follows; dodecanedioic acid (DDDA) 7.2 g (31 mmol) and Na
2.7 g (68 mmol) of OH tablets was dissolved in 180 ml of water to produce a disodium salt of DDDA. Next, a sample outlet is provided at the bottom and five ports are provided at the top.
In a 0 ml Molton flask, stirring blade, pH measuring end,
A Claisen adapter with injection tube and dry ice condenser was fitted. To this polymerization flask, 71 g (311 mmol) of bisphenol A, 0.9 ml of triethylamine, 2.0 g (9 mmol) of p-cumylphenol, 220 ml of methylene chloride and the disodium salt of DDDA prepared above were charged. Then,
Phosgene was injected into the flask at a rate of 2 g / min. At this time, the solution was maintained at pH 8 for 10 minutes while adding a 50% NaOH aqueous solution through the injection tube. After that, while continuing to inject phosgene, a 50% NaOH aqueous solution was added from the injection tube to adjust the pH of the solution to 10.5 and 10
Maintained at this pH for minutes. The total amount of phosgene used was 40 g (400 mmol). After the reaction was completed, the pH of the solution was adjusted to 11 to 11.5, and the organic solvent phase was separated from the aqueous phase. The organic solvent phase was washed 3 times with 300 ml of 2% hydrochloric acid and then 5 times with 300 ml of deionized water, dried over anhydrous magnesium sulfate, and filtered. This was put into 1500 ml of methanol to precipitate a polymer. The obtained polymer was separated by filtration, and methanol 5
After washing once with 00 ml and then four times with 500 ml of ion-exchanged water, it was dried at 110 ° C. for 15 hours. Thus, a copolyestercarbonate having structural units of the following formulas (Formula 6) and (Formula 7) in a molar ratio of 90:10 was obtained. Its intrinsic viscosity (measured in methylene chloride at 25 ° C) is 0.46.
It was dl / g. Hereinafter, this is abbreviated as CPEC.

[0035]

[Chemical 6]

[0036]

[Chemical 7] Component (B) Glass fiber: trademark; T505, manufactured by Nippon Electric Glass Co., Ltd. Carbon fiber: trademark; A9000, manufactured by Asahi Kasei Corporation Component (C) Graft copolymer: trademark Acryloid KM 653, manufactured by Rohm and Haas, MBS resin component ( D) Polyethylene resin: trademark; GML 2420, manufactured by Nippon Unica Co., Ltd. Ethylene-ethyl acrylate resin: trademark; NUC 6570,
Nihon Unica Co., Ltd. Examples 1 to 4 and Comparative Examples 1 to 12 The respective components were mixed in the proportions (parts by weight) shown in Table 1, and 250 ° C,
Extruded into pellets with a 65 mm single screw extruder set at 100 rpm. The pellet is then set to a set temperature of 260
C., mold temperature was 80.degree. C., and injection molding was performed to prepare a test piece for measuring impact strength. Using this, the Izod impact strength with 1/8 inch notch at 23 ° C was measured by ASTM D256.
Was measured according to. The results are shown in Table 1.

[0037]

[Table 1] For example, the impact strength of Example 2 is +13.
2 (21.4-8.2). On the other hand, Comparative Example 3
The improvement predicted from (+4.2) and Comparative Example 5 (+5) is +9.2. That is, in Example 2, an effect which is not predicted from the component (C) alone and the component (D) alone is exhibited. The same applies to the other examples. The components of Examples 5 to 6 and Comparative Examples 13 to 17 were mixed in the proportions (parts by weight) shown in Table 2, and 280 ° C.
Extruded into pellets with a 65 mm single screw extruder set at 100 rpm. The pellet is then placed at the set temperature of 280
C., mold temperature was 80.degree. C., and injection molding was performed to prepare a test piece for measuring impact strength. Using this, the Izod impact strength with 1/8 inch notch at 23 ° C was measured by ASTM D256.
Was measured according to. The results are shown in Table 2.

[0038]

[Table 2]

Since the resin composition of the present invention has excellent impact resistance, it has a wide range of applications and is industrially useful.

Claims (3)

[Claims] 1. A polycarbonate resin and / A
Or 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 hydrocarbon oxy 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 the amount of the structural unit of (Chemical Formula 2) is (Chemical Formula 1) 2 to 30 of the total amount of the structural units of
Copolyester carbonate, which accounts for mol%,
And (B) a resin composition containing an inorganic filler,
(C) for 100 parts by weight of the total of (A) and (B)
Diene elastomer or diene-vinyl monomer copolymer, C ₁ -C ₆ alkyl acrylate, C ₁ -C ₆
A resin containing 0.05 to 20 parts by weight of a graft copolymer selected from the group consisting of alkyl methacrylate, acrylic acid and methacrylic acid and at least the above monomer, and (D) a polyolefin resin 0.05 to 10 parts by weight. Composition. 2. The polyolefin resin is polyethylene,
The resin composition according to claim 1, which is selected from the group consisting of ethylene-ethyl acrylate copolymer and polypropylene. 3. The resin composition according to claim 1, wherein the graft copolymer is obtained by grafting a vinyl monomer onto an elastomer or a copolymer, and further grafting the monomer.