JPH05345850A - Thermoplastic resin composition - Google Patents

Abstract

PURPOSE:To provide a thermoplastic resin composition excellent in impact resistance, heat resistance, mechanical properties and chemical resistance, suitable for automotive trim and facing materials etc., comprising a polycarbonate, polyester and specific olefin elastomer at specified proportion. CONSTITUTION:The composition comprising a total of 100 pts.wt. of (A) 95-5 pts.wt. of a polycarbonate and (B) 5-95 pts.wt. of a polyester such as polyethylene terephthalate and (C) 2-10 pts.wt. of an olefin elastomer modified with an unsaturated glycidyl compound of the formula (R is H or 1-6C alkyl; Ar is 6-20C aromatic hydrocarbon bearing at least one glycidyloxy group; n is 1-4).

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a thermoplastic resin composition containing a polycarbonate, a polyester and an olefin elastomer modified with a specific unsaturated glycidyl compound. More specifically, the present invention relates to a thermoplastic resin composition suitable for interior / exterior parts of automobiles, industrial material parts such as belts and pipes, electric / communication parts, sporting goods, molded articles such as home electric appliances, and the like.

[0002]

2. Description of the Related Art Polycarbonate is a resin having excellent heat resistance and mechanical properties, and since it is particularly excellent in impact resistance, it is used as a film or a molded article in various applications. Insufficient chemical resistance.
To improve the properties of such polycarbonates,
Blending of polyester with excellent chemical resistance is performed. However, a composition composed of polycarbonate and polyester has a low impact resistance, which is a characteristic of polycarbonate, and a thermoplastic resin composition having excellent chemical resistance and impact resistance can be obtained by simply blending polycarbonate and polyester. I can't get anything. Therefore,
As a third component, a composition of a polycarbonate and a polyester may be blended with an ethylene copolymer modified with an unsaturated carboxylic acid or a derivative thereof (JP-A-51-144452).
JP-A-58-25352 and JP-A-59-174646 by blending an acrylic core-shell rubber or an ethylene-glycidyl methacrylate copolymer.
However, the improvement of impact resistance is still insufficient. Therefore, it is an object of the present invention to provide a thermoplastic resin composition having a good balance of properties of polycarbonate and polyester, and particularly good impact resistance.

[0003]

Means for Solving the Problems As a result of intensive studies in view of the above objects, the present inventors have identified an olefin elastomer modified with a specific glycidyl compound having an acrylamide group and an epoxy group in a polycarbonate and a polyester. The present invention has been accomplished by finding that a thermoplastic resin composition having the properties of polycarbonate and polyester in a well-balanced manner and having improved impact resistance can be obtained by blending and kneading in a sufficient amount to achieve the present invention. ..

That is, the present invention provides (a) 95 to 5 parts by weight of polycarbonate, (b) 5 to 95 parts by weight of polyester, and the sum of the above polycarbonate and polyester.
With respect to 00 parts by weight, (c) the following general formula (1)

[0005]

[Chemical 2]

[In the formula, R is a hydrogen atom or 1 to 6 carbon atoms.
Of Ar, Ar is an aromatic hydrocarbon group having 6 to 20 carbon atoms and having at least one glycidyloxy group, and n represents an integer of 1 to 4. ] 2-100 weight part of olefinic elastomers modified with the unsaturated glycidyl compound represented by these are contained, The thermoplastic resin composition characterized by the above-mentioned.

Hereinafter, the thermoplastic resin composition of the present invention will be described in detail. The (a) polycarbonate used in the present invention is generally (1) a reaction of a dihydric phenol with a carbonate precursor such as phosgene in the presence of an acid acceptor and a molecular weight modifier, or (2) a dihydric phenol. And a thermoplastic resin produced by a transesterification reaction with a carbonate precursor such as diphenyl carbonate. As the dihydric phenol used in the reaction with the carbonate precursor, bisphenols are preferable, and 2,2-bis (4-hydroxyphenyl) propane (bisphenol A) is particularly preferable. Moreover, what substituted a part or all of bisphenol A with another dihydric phenol can also be used.

Examples of dihydric phenols other than bisphenol A include hydroquinone, 4,4'-dihydroxydiphenyl, bis (4-hydroxyphenyl) alkane, bis (4-hydroxyphenyl) cycloalkane,
Bis (4-hydroxyphenyl) sulfide, bis (4
-Hydroxyphenyl) sulfone, bis (4-hydroxyphenyl) sulfoxide, bis (4-hydroxyphenyl) ketone, bis (4-hydroxyphenyl) ether, etc., and bis (3,5-dibromo-4-hydroxyphenyl) propane Mention may be made of such halogenated bisphenols. Furthermore, it is also possible to use two or more copolymers of these dihydric phenols, homopolymers thereof, or a mixture of these homopolymers and copolymers. Although such a polycarbonate can be easily obtained as a commercial product, it preferably has a weight average molecular weight of 10,000 to 100,000, more preferably 20,000 to 50,000. When the weight average molecular weight is less than 10,000, mechanical properties are insufficient, and when it exceeds 100,000, molding becomes difficult.

The (b) polyester used in the present invention is
Generally, a thermoplastic resin obtained by polycondensation of a saturated dicarboxylic acid and a saturated dihydric alcohol, such as polyethylene terephthalate, polypropylene terephthalate, polytetramethylene terephthalate (polybutylene terephthalate), polyhexamethylene terephthalate, polycyclohexane-1,4. Examples include dimethylol terephthalate and polyneopentyl terephthalate.
Of these, polyethylene terephthalate and polybutylene terephthalate are preferred.

As the polyester, the intrinsic viscosity [η] (dl / g) determined from the solution viscosity measured at 25 ° C. in an o-chlorophenol solvent is 0.30 to 1.8, and the concentration of the terminal carboxyl group is 10 to 200 meq. / Kg is preferable. In the case of polyethylene terephthalate, the intrinsic viscosity [η] is 0.30 to 1.2 and the terminal carboxyl group concentration is 10
It is preferably about 200 meq / kg. The terephthalic acid component in polyethylene terephthalate may be substituted with an alkyl group, a halogen group or the like, and the glycol component may be ethylene glycol up to about 50% by weight of another glycol such as 1,4-butylene. It may contain glycol, propylene glycol, hexamethylene glycol or the like. In the case of polybutylene terephthalate, it is preferable that the intrinsic viscosity [η] is 0.30 to 1.8 and the terminal carboxyl group concentration is 10 to 200 meq / kg. Also in this case, the terephthalic acid component is an alkyl group,
It may be substituted with a halogen group or the like, and the glycol component is 50% by weight in addition to 1,4-butylene glycol.
To the extent other glycols, such as ethylene glycol,
It may contain propylene glycol, hexamethylene glycol or the like.

In the modified olefin elastomer modified with the unsaturated glycidyl compound (c) used in the present invention, the olefin elastomer used as the modifying raw material is ethylene, propylene, butene-1, hexene-1, 4 -Means a copolymer rubber with one or more α-olefins other than ethylene, such as methyl-pentene-1. Specific examples of the copolymer rubber with one or more α-olefins include ethylene-propylene copolymer rubber (EPR), ethylene-butene copolymer rubber (EBR), and ethylene-propylene-diene copolymer. Polymer rubber (EPDM) and the like can be mentioned. Examples of the diene component in the ethylene-propylene-diene copolymer rubber (EPDM) include non-conjugated dienes such as dicyclopentadiene, 1,4-hexadiene, cyclooctadiene and methylenenorbornene, or conjugated dienes such as butadiene and isoprene. Can be mentioned. The ethylene content in the olefin elastomer is preferably 5 to 95% by weight, more preferably 10 to 90% by weight. If the ethylene content is less than 5% by weight or more than 95% by weight, it becomes difficult to exhibit properties as an elastomer. The crystallinity of the olefin elastomer is preferably 40% by weight or less.

The ethylene-propylene copolymer rubber (EPR) used in the present invention has a repeating unit content of ethylene of 50 to 80 mol% and a repeating unit content of propylene of 20 to 20% by mole. It is preferably 50 mol%. More preferably, the content of ethylene-based repeating units is 60 to 70 mol%, and the content of propyne-based repeating units is 30 to 40 mol%.
Also, EPR melt flow rate (MFR, 230
C., 2.16 kg load) is preferably in the range of 0.01 to 50 g / 10 minutes, more preferably 0.5 to 30 g / 10 minutes.

The ethylene-butene copolymer rubber (EBR) used in the present invention has a content of repeating units derived from ethylene of 50 to 90 mol% and a content of repeating units derived from butene of 10 to 10. It is preferably 50 mol%. More preferably, the content of ethylene-based repeating units is 60 to 80 mol% and the content of butene-based repeating units is 20 to 40 mol%. Also, EB
The melt flow rate of R (MFR, 230 ° C., 2.16 kg load) is preferably in the range of 0.01 to 50 g / 10 minutes, more preferably 0.5 to 30 g / 10 minutes.

The ethylene used in the present invention
The propylene-diene copolymer (EPDM) has a repeating unit content of 40 to 70 mol% derived from ethylene, a repeating unit content of 30 to 60 mol% derived from propylene, and a diene-derived copolymer. The content of the repeating unit is preferably 1 to 10 mol%. More preferably, the content of ethylene-based repeating units is 50 to 60 mol%, the content of propylene-based repeating units is 40 to 50 mol%, and the content of diene-based repeating units is 3 to 6 mol%. .. In addition, EPDM melt flow rate (MFR, 230 ℃, 2.16kg load)
Is preferably in the range of 0.01 to 50 g / 10 minutes,
It is more preferably 0.1 to 30 g / 10 minutes.

The ethylene-propylene copolymer (EPR), ethylene-butene copolymer rubber (EBR), and ethylene-propylene-diene copolymer (EPDM) used in the present invention are within the range that does not impair the characteristics. Thus, other repeating units such as repeating units derived from other α-olefins such as 4-methylpentene-1 may be contained up to a proportion of 10 mol% or less.

In the present invention, an olefin elastomer composition containing a polyolefin, preferably a crystalline polyolefin, may be used as the above-mentioned olefin elastomer. Examples of the crystalline polyolefin include homopolymers of α-olefins such as ethylene, propylene, butene-1, hexene-1, 4-methyl-pentene-1, and non-elastomeric copolymers of ethylene and propylene or other α-olefins. A polymer, a non-elastomeric copolymer of two or more kinds of these α-olefins, homopolymers of these, or a mixture of a homopolymer and a copolymer can be used. When the polyolefin is mixed, the mixing amount is based on the total amount of the olefin elastomer and the polyolefin (10
0% by weight) is 80% by weight or less, preferably 50% by weight or less. 80% by weight of polyolefin
If it exceeds, the properties as an elastomer are lost.

The unsaturated glycidyl compound used for modifying the olefinic elastomer in the present invention means the following general formula (1) having an acrylamide group and an epoxy group in the molecule.

[0018]

[Chemical 3]

[Each symbol in the formula has the same meaning as described above. ] It is a glycidyl compound represented by these. Among the glycidyl compounds represented by the above general formula, the glycidyl compound represented by the following general formula (2) is particularly preferable.

[0020]

[Chemical 4]

[In the formula, R represents the same meaning as described above. ]
Such a glycidyl compound is disclosed in, for example, JP-A-60-13058.
It can be produced by the method shown in No. 0. These glycidyl compounds are usually used alone, but two or more kinds can be used in combination.

Preferred modified olefin elastomers in the present invention are the above-mentioned raw material olefin elastomers, especially EPR, EBR or EPDM, which are glycidyl compounds represented by the general formula (1), particularly glycidyl compounds represented by the general formula (2). It has been modified with a compound. The content of the unsaturated glycidyl compound as a modifier of the modified olefin elastomer varies depending on the kind of the raw material olefin elastomer and cannot be said unconditionally, but is generally about 0.01 to 30% by weight, preferably
It is 0.1 to 10% by weight. When the content of the unsaturated glycidyl compound is less than 0.01% by weight, the modification of the olefin elastomer is insufficient, and when it exceeds 30% by weight, gelation occurs when the polycarbonate and the polyester are blended, resulting in poor moldability.

Such a preferable modified olefin elastomer can be obtained by utilizing a known modification method such as a solution method or a melt-kneading method. In addition, a desired product may be appropriately selected from commercially available products and used. As a specific example of the modification method, a modification example (graft polymerization) of the olefinic elastomer with the glycidyl compound is shown below. That is, in the melt-kneading method, an olefin elastomer, the glycidyl compound described above, and a catalyst as required are used, and these components are charged into an extruder, a twin-screw kneader, or the like and heated to a temperature of about 180 to 300 ° C. While being melted, the mixture is kneaded for about 0.1 to 20 minutes to obtain a modified olefin elastomer. In the case of the solution method, the above-mentioned starting materials are dissolved in an organic solvent such as xylene, and modification is carried out while stirring at a temperature of about 90 to 200 ° C for 0.1 to 100 hours.
In any of the modification methods, it is possible to use a normal radical polymerization catalyst as a catalyst, for example, benzoyl peroxide, lauroyl peroxide, ditertiary butyl peroxide,
Acetyl peroxide, tertiary butyl peroxybenzoic acid, dicumyl peroxide, peroxybenzoic acid, peroxyacetic acid, tertiary butyl peroxypivalate, 2,
Peroxides such as 5-dimethyl-2,5-ditert-butylperoxyhexyne, azo compounds such as azobisisobutyronitrile, etc. are used. The amount of the catalyst added is 0.1 to 100 parts by weight of the modifying glycidyl compound.
It is about 10 parts by weight. It is also possible to add a phenolic antioxidant during the above graft reaction.
As the modified olefin-based elastomer, the above-mentioned modified olefin-based elastomer in which an unmodified olefin-based elastomer is blended in an amount of 80% by weight or less can also be used.

The blending ratio of each component in the thermoplastic resin composition of the present invention is such that (a) polycarbonate and (b) polyester are in a weight ratio of (a) / (b) = 95 / 5-5.
/ 95, preferably 90/10 to 10/90. When the weight ratio is less than 95/5 or exceeds 5/95, the ratio of one of polycarbonate and polyester is small, and a thermoplastic resin composition having both properties cannot be obtained. The (c) olefin-based elastomer modified with an unsaturated glycidyl compound is 2 parts with respect to 100 parts by weight of the total of polycarbonate and polyester.
-100 parts by weight, preferably 5-80 parts by weight. Two
If the amount is less than parts by weight, the effect of improving the physical properties of the composition by using the modified olefin elastomer modified with an unsaturated glycidyl compound is insufficient. On the other hand, if it exceeds 100 parts by weight, the proportion of the polycarbonate and the polyester becomes small, and a thermoplastic resin composition having both properties cannot be obtained.

In the present invention, in addition to the above-mentioned substances, other substances for the purpose of strengthening and modifying the thermoplastic resin composition, for example, fillers and reinforcing materials such as glass fibers, heat stabilizers, and light stabilizers. , Flame retardant, plasticizer, antistatic agent, foaming agent,
A nucleating agent or the like can be added and compounded. The thermoplastic resin composition of the present invention is a kneading machine such as a single-screw extruder, a twin-screw extruder, a Banbury mixer, a kneading roll, a Brabender, etc., each of the above components and various additives added as necessary. It can be obtained by melt kneading. The kneading temperature varies depending on the type of polycarbonate, polyester and modified olefin elastomer and cannot be generally stated, but it is suitable to be about 180 to 300 ° C, preferably 220 to 260 ° C. Kneading temperature is 18
If the temperature is below 0 ° C, the components will not be sufficiently kneaded, and
If the temperature exceeds 00 ° C, the thermoplastic resin composition may deteriorate. In the present invention, the kneading order of each component is not particularly limited, and the components (a), (b) and (c) may be kneaded together, or after kneading the components (a) and (b), The component (c) may be kneaded. Furthermore, other kneading orders can be adopted.

[0026]

The thermoplastic resin composition of the present invention is obtained by blending polycarbonate and polyester with a specific amount of an olefinic elastomer modified with a specific unsaturated glycidyl compound having an acrylamide group and an epoxy group and melt-kneading the mixture. It is a resin composition excellent in moldability, chemical resistance, mechanical properties, and the like, which has the properties of polycarbonate and polyester in a well-balanced manner. Although the detailed reason why the thermoplastic resin composition of the present invention exerts such an effect is not always clear, the polycarbonate and the polyester are compatibilized through the action of the unsaturated glycidyl compound component in the modified olefin elastomer. At the same time, it is considered that the mechanical strength, especially impact resistance, is improved by the elastic force of the elastomer component.

[0027]

EXAMPLES The present invention will be described in more detail with reference to Examples and Comparative Examples. In each of the examples and comparative examples, the following materials were used as raw materials and additives. Polycarbonate PC: [L1225 manufactured by Teijin Chemicals Co., Ltd.] Polyester (1) Polyethylene terephthalate PET: [TR4550 manufactured by Teijin Limited, intrinsic viscosity [η]
0.70 (in o-chlorophenol)] (2) Polybutylene terephthalate PBT: [C7000N manufactured by Teijin Limited, intrinsic viscosity [η]
1.05 (in o-chlorophenol)] Olefin-based elastomer (1) Ethylene-propylene copolymer rubber EPR: [PO180 manufactured by Mitsui Petrochemical Co., Ltd., melt flow rate (MFR, 230 ° C, 2.16 kg load) 6.3 g / 1
0 minutes, propylene content 70%] (2) Ethylene-butene copolymer rubber EBR: [Japan Synthetic Rubber Co., Ltd. EBM2041P, melt flow rate (MFR, 230 ° C, 2.16 kg load) 5.5 g
/ 10 min] Modification monomer AXE: glycidyl compound represented by the following chemical formula [Kanefuchi Chemical Industry Co., Ltd.]

[0028]

[Chemical 5]

Radical generator POX: Perhexin 25B [made by NOF Corporation]

AXE-modified olefin elastomer (1) AXE-modified ethylene-propylene copolymer rubber (Production Example 1) 100 parts by weight of EPR, 3 parts by weight of AXE and POX.
After dry blending 1 part by weight, this was melt-kneaded using a uniaxial extruder with a diameter of 30 mm at 200 ° C and 80 rpm to obtain a melt flow rate (MFR, 230 ° C, 2.16).
(kg load) 3.1 g / 10 min of AXE-modified olefin elastomer (M-EPR) was obtained. The AXE graft ratio of this modified olefin elastomer was 2.6% by weight. The graft ratio was calculated by the following method. AX
The E-modified olefin elastomer is dissolved in boiling xylene, the insoluble matter is removed, and then the dissolved components are precipitated with methanol and pressed to a thickness of about 50 μm.
The spectrum was measured and calculated from the ratio of the stretching peak (1648 cm ⁻¹ ) of the C═O bond of AXE to the film thickness.

(2) AXE-modified ethylene-butene copolymer rubber (Production Example 2) 100 parts by weight of EBR, 3 parts by weight of AXE and POX.
After dry blending 1 part by weight, this was melt-kneaded using a uniaxial extruder having a diameter of 30 mm at 200 ° C and 80 rpm to obtain a melt flow rate (MFR, 230 ° C, 2.16).
(kg load) 3.9 g / 10 minutes to obtain an AXE-modified olefin elastomer (M-EBR). The AXE graft ratio of this modified olefin elastomer was 2.7% by weight.

Other than AXE-modified olefin elastomer
Elastomer (1) MAH-modified ethylene - propylene copolymer of maleic anhydride in place of AXE in the rubber Production Example 1 (MA
H) is used as a modifier, 100 parts by weight of EPR and M
After dry blending 1 part by weight of AH and 0.1 part by weight of POX, this was blended with a single screw extruder having a diameter of 30 mm for 20
Melt kneading at 0 ° C. and 80 rpm, melt flow rate (MFR, 230 ° C., 2.16 kg load) 1.2 g / 10 min MAH-modified olefin elastomer (MAH-EP
R) was obtained. MA of this modified olefin elastomer
The graft ratio of H was 0.82% by weight. The graft ratio is the peak of stretching of C = O bond of MAH (1780 cm ^-1 ).
It was determined in the same manner as in the case of M-EPR except that the above was used as a reference. (2) Ethylene-glycidyl methacrylate copolymer rubber EGMR: [Sumitomo Chemical Co., Ltd., Bond First E] (3) Acrylic core shell rubber ACR: [Takeda Pharmaceutical Co., Ltd. Staphyroid 1
M-120]

Examples 1 to 9 and Comparative Examples 1 to 5 Polycarbonate (PC), polyester (PET or PBT), AXE-modified olefin elastomer (M-EPR or M-EBR), and other than AXE-modified olefin elastomer Elastomer (EPR, MA
H-EPR, EGMR or ACR) was dry-blended with a Henschel mixer in the proportions shown in Table 1, and then with a twin-screw extruder (L / D = 30) having a diameter of 45 mm.
The pellets of the thermoplastic resin composition were obtained by melt-kneading at 250 ° C. and 200 rpm. The thermoplastic resin composition thus obtained was injection molded to obtain a molded product at 23 ° C. and −30 ° C.
The Izod impact strength at 0 ° C, the tensile elongation at break, the tensile yield strength and the flexural modulus were measured. The results are shown in Table 1.

[0034]

[Table 1]

[0035]

[Table 2]

The methods for measuring the physical properties shown in Table 1 above are as follows. (1) Izod impact strength: Measured according to JIS K7110. (2) Tensile elongation at break: Measured according to JIS K6767. (3) Tensile yield strength: Measured according to JIS K6767. (4) Flexural modulus: Measured according to JIS K7203.

As is apparent from Table 1, the thermoplastic resin composition of the present invention comprising polycarbonate, polyester and AXE-modified olefin elastomer is a composition comprising only polycarbonate and polyester (Comparative Example 1), and polycarbonate. And polyester and AX
Compared to the compositions (Comparative Examples 2 to 5) containing an elastomer other than the E-modified olefin elastomer, all physical properties of Izod impact strength, tensile elongation at break, tensile yield strength, and flexural modulus are well balanced, and particularly impact resistance It has excellent properties.

[0038]

As described above, the thermoplastic resin composition of the present invention comprises polycarbonate and polyester,
It is made by blending a specific amount of an olefinic elastomer modified with a specific unsaturated glycidyl compound having an acrylamide group and an epoxy group, and melt-kneading it. It also combines the properties of polycarbonate and polyester in a well-balanced manner, and also has impact resistance. It is a composition having excellent properties. Such a thermoplastic resin composition of the present invention is a resin composition for various engineering plastics, especially for interior and exterior parts of automobiles, industrial material parts such as belts and pipes, electric / communication parts, sports equipment, home appliances, etc. It is suitable as a product.

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Yuji Fujita 1-3-1 Nishitsurugaoka, Oi-cho, Iruma-gun, Saitama Tonen Research Institute

Claims (1)

[Claims] 1. For (a) 95 to 5 parts by weight of polycarbonate, (b) 5 to 95 parts by weight of polyester, and 100 parts by weight of the sum of the polycarbonate and polyester, (c) the following general formula (1): [Chemical 1] [In the formula, R is a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, Ar is an aromatic hydrocarbon group having 6 to 20 carbon atoms having at least one glycidyloxy group, and n is 1
Represents an integer of ~ 4. ] Olefinic elastomers 2-10 modified with unsaturated glycidyl compound represented by
A thermoplastic resin composition containing 0 parts by weight.