JPH0543765A - Thermoplastic resin composition - Google Patents

Abstract

PURPOSE:To obtain the subject composition having excellent mechanical strength and mold-releasability of the molded article and suitable for interior and exterior trims of automobile, etc., by compounding a polyolefin containing a modified polyolefin with a polyester and an ethylene copolymer at specific ratios. CONSTITUTION:The objective composition can be produced by compounding (A) 100 pts.wt. of a mixture produced by mixing (i) a polyester such as poyethylene terephthalate and (ii) a polyolefin containing >=2wt.% of a modified polyolefin produced by modifying PP with preferably an unsaturated glycidyl compound of formula (R is H or 1-6C alkyl; Ar is 6-20C aromatic hydrocarbon group having glycidyloxy group; n is integer of 1-4) at a weight ratio (i/ii) of 3/97 to 97/3 and (B) 2-50 pts.wt. of a copolymer of an ethylene and an unsaturated carboxylic acid such as acrylic acid.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a thermoplastic resin composition containing a polyester and a polyolefin. More specifically, polyester and polyolefin are well compatibilized, impact resistance, mechanical strength, mechanical properties such as surface peelability, water resistance, chemical resistance, heat resistance, excellent surface properties such as appearance, The present invention relates to a thermoplastic resin composition suitable for molded articles such as automobile interior and exterior parts, electrical components, home appliances, sports equipment, furniture, office supplies and the like.

[0002]

2. Description of the Related Art Polyester has heat resistance,
It is a resin with excellent mechanical strength and insulation. On the other hand, polyolefin has the features of being lightweight and excellent in impact resistance, and having good environmental characteristics such as moldability, water resistance, and chemical resistance. Therefore, attempts have been made to prepare a resin composition having the advantages of both by blending polyester and polyolefin, each of which has excellent characteristics. However, since the compatibility of polyester and polyolefin is poor, there is a problem that impact resistance and mechanical strength of the thermoplastic resin composition containing both are lowered. Therefore, in order to improve the compatibility between the polyester and the polyolefin, the polyester is blended with a polyolefin modified with an unsaturated carboxylic acid or a derivative thereof, particularly an anhydride of an unsaturated dicarboxylic acid such as maleic anhydride (MAH). It is known that the melt-kneading is performed to improve the compatibility dispersibility of the polyester and the polyolefin, improve impact resistance, and prevent deterioration due to water absorption. However, in this method, when the unsaturated dicarboxylic acid is added to the polyolefin, alteration or deterioration occurs due to crosslinking of the polyolefin, the physical properties are not sufficiently improved by compatibilization, and the unreacted acid and polyester to be added to the polyolefin are It may react to cause coloration and impair the appearance. Therefore, the object of the present invention is to compatibilize polyester and polyolefin well, mechanical properties,
It is intended to provide a thermoplastic resin composition having excellent surface characteristics and environmental characteristics such as water resistance.

[0003]

Means for Solving the Problems As a result of intensive studies made by the present inventors, polyester and polyolefin were modified with a specific amount of an unsaturated glycidyl compound-modified polyolefin, and ethylene and an unsaturated carboxylic acid or a derivative thereof. Incorporating the copolymer of the above, the polyester and the polyolefin are well compatibilized, it has been found that a thermoplastic resin composition having excellent mechanical properties, surface properties and environmental properties can be obtained, and arrived at the present invention Is. That is, the present invention provides (a) a polyester, (b) a polyolefin containing 2% by weight or more of a modified polyolefin modified with an unsaturated glycidyl compound, and (c) a copolymerization of ethylene with an unsaturated carboxylic acid or a derivative thereof. It contains a combination, and the ratio of the component (a) and the component (b) is (a) / (b) =
3/97 to 97/3, and the content of the component (c) is 2 to 50 parts by weight with respect to 100 parts by weight of the total of (a) + (b). It is about.

Hereinafter, the thermoplastic resin composition of the present invention will be described in detail. The (a) polyester of the thermoplastic resin composition component used in the present invention is a thermoplastic resin generally obtained by polycondensation of a saturated dicarboxylic acid and a saturated dihydric alcohol, for example, polyethylene terephthalate, polypropylene terephthalate, polytetramethylene. Examples thereof include terephthalate (polybutylene terephthalate), polyhexamethylene terephthalate, polycyclohexane-1,4-dimethylol terephthalate and polyneopentyl terephthalate. Of these, polyethylene terephthalate and polybutylene terephthalate are preferred.

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

The unmodified polyolefin, which is one of the components (b) of the thermoplastic resin composition in the present invention, means ethylene, propylene, butene-1, and hexene-.
1,3-methylbutene-1,4-methyl-pentene-
1, homopolymers of α-olefins having 3 or more carbon atoms, such as 1, heptene-1, octene-1, and decene-1, copolymers of two or more kinds of these monomers such as random, block, and graft, mixtures thereof, A random, block, or graft copolymer of ethylene or a main part of an α-olefin having 3 or more carbon atoms and another unsaturated monomer. Among these polyolefins, ethylene or propylene homopolymers, ethylene and propylene copolymers, and ethylene or propylene and other α-olefin copolymers are preferable. Particularly preferred is an ethylene content of 20.
It is an ethylene-propylene copolymer of not more than wt%, and such polypropylene usually has a melt flow rate (MFR, JIS K7210, load of about 0.1 to 200 g / 10 minutes).
16 kg, 230 ° C). As the ethylene polymer, high-pressure low-density polyethylene (LDPE) or low-pressure high-density polyethylene (HDPE) is preferable, and linear low-density polyethylene (LLDPE) known as medium-low-pressure ethylene copolymer may also be used. it can.

Further, in the present invention, the polyolefin may contain up to about 40% by weight of an olefin elastomer. Here, the olefin elastomer means ethylene, propylene, butene-1, hexene-
2 of α-olefins such as 1,4-methyl-pentene-1
It means a copolymer rubber of one kind or three or more kinds, or a copolymer of α-olefin and another kind of monomer. Specific examples of the copolymer rubber of two or more kinds of α-olefins include ethylene-propylene rubber (EPR), ethylene-butene rubber (EBR) and ethylene-propylene-diene rubber (EPDM).

The modified polyolefin contained in the component (b) of the thermoplastic resin composition of the present invention in an amount of 2% by weight or more is a product obtained by modifying the above-mentioned various polyolefins with an unsaturated glycidyl compound. Here, the unsaturated glycidyl used as the modifier is a compound having an acrylamide or methacrylamide group and an epoxy group, and the unsaturated glycidyl compound represented by the following general formula (1) is preferably used.

[0011]

[Chemical 2]

[In the formula, R represents a hydrogen atom or a carbon number of 1 to 6]
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. Among the unsaturated glycidyl compounds represented by the above general formula, a glycidyl compound represented by the following general formula (2) is particularly preferable.

[0013]

[Chemical 3]

[Wherein R represents a hydrogen atom or a carbon number of 1 to 6]
Is an alkyl group. Such a glycidyl compound can be produced, for example, by the method described in JP-A-60-130580, and these polymerizable compounds can be used alone or in combination of two or more kinds.

The content of the modifier of the modified polyolefin varies depending on the kind of the raw material polyolefin and cannot be generally stated, but it is generally about 0.01 to 30% by weight, preferably 0.05 to 10% by weight, and more preferably 0.3 to 7% by weight. % By weight. The modified polyolefin preferably has a number average molecular weight of about 3,000 to 100,000.

Examples of the raw material polyolefin modified with such a modifier include ethylene, propylene, butene-1, hexene-1,3-methylbutene-1,4-methyl-pentene-1, and heptene-1. ,
In addition to homopolymers of α-olefins having 3 or more carbon atoms such as octene-1, decene-1 and the like, copolymers of two or more kinds of these monomers such as random, block and graft, mixtures thereof, ethylene or carbon number. A random, block, or graft copolymer of 3 or more main parts of α-olefin and another unsaturated monomer. Further, as described above, an olefin elastomer, that is, a copolymer rubber of two or more kinds of α-olefins such as ethylene, propylene, butene-1, hexene-1, and 4-methyl-pentene-1, or α. -It may contain a copolymer of an olefin and another type of monomer. As these raw material polyolefins, polypropylene is particularly preferably used.

Such a modified polyolefin can be obtained by utilizing a known modification method such as a solution method or a melt-kneading method. In addition, a commercially available product may be appropriately selected and used. As a specific example of the modification method, a modification example of the polyolefin with the glycidyl compound (graft polymerization)
Is shown below. That is, in the melt-kneading method, a polyolefin, the above-mentioned glycidyl compound, and, if necessary, a catalyst are used, and these components are put into an extruder, a biaxial 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 polyolefin. 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, a conventional radical polymerization catalyst can be used as a catalyst, for example, benzoyl peroxide, lauroyl peroxide, di-t-butyl peroxide, acetyl peroxide, perbenzoic acid. Peroxides such as t-butyl, dicumyl peroxide, perbenzoic acid, peracetic acid, t-butyl perpivalate, and 2,5-dimethyl-2,5-di-t-butylperoxyhexyne, and azo. Diazo compounds such as bisisobutyronitrile are used. The amount of the catalyst added was 0. 0 based on 100 parts by weight of the glycidyl compound for modification.
It is about 1 to 10 parts by weight. It is also possible to add a phenolic antioxidant during the above graft reaction.

The graft ratio of the modified polyolefin thus obtained is about 0.3 to 7% by weight, and the graft ratio is 1 to 1000 g.
/ 10 minutes melt flow rate (MFR, JISK721
0, load 2.16kg, 230 ℃).

The component (c) of the thermoplastic resin composition of the present invention is a copolymer of ethylene and an unsaturated carboxylic acid or its derivative. Here, as the unsaturated carboxylic acid or a derivative thereof, for example, unsaturated carboxylic acid such as acrylic acid, methacrylic acid, crotonic acid, isocrotonic acid, or a derivative thereof, for example, an acid, a halide, an amide, an imide, an ester and the like can be mentioned. Be done. Specific examples of the derivative include methyl acrylate and methyl methacrylate. Of these, acrylic acid is particularly preferable. Ethylene and unsaturated carboxylic acid or its derivative can be copolymerized by a well-known suitable method, for example, anionic polymerization or radical polymerization. The catalyst used here is not particularly limited, and for example, a radical polymerization catalyst can be selected and used from those mentioned above in the modification of the polyolefin. As the copolymer of ethylene and unsaturated carboxylic acid or its derivative, random, block or graft can be used. The ratio of ethylene to unsaturated carboxylic acid or its derivative in the copolymer is 50 to 95% by weight in the former and 5 to 50 in the latter.
It is 50% by weight. If the ethylene content is less than 50% by weight, gelation occurs at the time of kneading, resulting in deterioration of mechanical properties.
If it exceeds 5% by weight, the compatibility will decrease. Among the copolymers of ethylene and unsaturated carboxylic acid or its derivative,
In particular, ethylene-acrylic acid copolymer is preferably used. The ethylene-acrylic acid copolymer having an acrylic acid content of 5 to 50% by weight, which is particularly preferably used as the component (c) in the present invention, is usually 1 to 1000 g / 10 min (MFR,
JISK7210, load 2.16kg, 190 ℃) melt flow rate. As such an ethylene-acrylic acid copolymer, a commercially available product can be appropriately selected and used.

In the present invention, the mixing ratio of the above-mentioned components (a) and (b) is (a) / (b) = 3 / in terms of weight ratio.
It is 97-97 / 3. If the weight ratio is less than 3/97, the strength and flexural modulus are insufficient, and if it exceeds 97/3, the impact strength is lowered, and a thermoplastic resin composition having both properties cannot be obtained. In the component (b), the weight ratio of the unmodified polyolefin to the modified polyolefin is 98/2 to 0/100, preferably 95/5 to 0/10.
It is 0. The present invention also includes compositions in which the total amount of component (b) is a modified polyolefin. That is, a composition comprising a polyester as the component (a), a modified polyolefin as the component (b), and a copolymer of a styrenic monomer as the component (c) and an unsaturated carboxylic acid or a derivative thereof is excellent in compatibility and It has the features of polyester and polyester and is included in the present invention. However, if the weight ratio of the unmodified polyolefin to the modified polyolefin in the component (b) is less than 98/2, the amount of the modified polyolefin is too small, and the effect of improving the compatibility between the polyolefin and the polyester due to the blending is not recognized. The content of the component (c) is 2 to 50 based on 100 parts by weight of the total of (a) + (b).
Parts by weight. When the weight ratio of (c) is less than 2% by weight, the compatibility is lowered and the molded product is exfoliated on the surface. If it exceeds 50% by weight, mechanical properties are deteriorated.

In the present invention, in addition to the above-mentioned components, other substances for the purpose of strengthening or modifying the thermoplastic resin composition,
For example, a filler such as glass fiber or a reinforcing material, a heat stabilizer, a light stabilizer, a flame retardant, a plasticizer, an antistatic agent, a foaming agent, a nucleating agent and the like can be added and blended.

Each of the above components, namely polyester,
2 polyolefins modified with unsaturated glycidyl compounds
By blending and kneading a polyolefin containing wt% and a copolymer of ethylene and an unsaturated carboxylic acid or a derivative thereof in the above proportions, the polyester and the polyolefin are well compatibilized, and the characteristics of the polyester and the polyolefin are improved. A combined thermoplastic resin composition can be obtained. As the melt-kneading method, various conventionally known methods can be adopted. That is, a batch kneading method using a batch type kneading machine, a kneading method using a kneading machine such as a Banbury mixer, a Brabender, a kneading roll, a single-screw extruder, or a twin-screw extruder can be exemplified. The temperature of kneading is 200 to 300 ° C, preferably 210 to 280 ° C
The range is. If the kneading temperature is less than 200 ° C, the compatibility of the polyester and the polyolefin is insufficient, and 30
At temperatures above 0 ° C, the original properties of the resin may be impaired.

The kneading order of each component is not particularly limited, and various orders can be adopted. For example, (i) the component (a), the component (b), and the component (c) are simultaneously charged into a batch-type kneader, a Brabender, or a kneader such as a single-screw or twin-screw extruder at the same time, and they are packaged together Method of kneading, (ii) Component (a) and component (b) are simultaneously charged into an extruder, and then component (c) is charged from the middle of the barrel to be kneaded, (iii) Component (b) And the component (c) are simultaneously charged into the extruder, and then the component (a) is charged halfway. (Iv) The component (a) and the component (c) are simultaneously charged into the extruder, and then the component ( For example, a method of inserting b) halfway.

[0025]

[Function] Containing polyester, polyolefin containing polyolefin modified with unsaturated glycidyl compound (compound having acrylamide or methacrylamide group and epoxy group), and copolymer of ethylene and unsaturated carboxylic acid or its derivative In the thermoplastic resin composition of the present invention, the reason why the polyester and the polyolefin are well compatibilized is not always clear, but especially the (meth) acrylic acid group and the epoxy group of the modified polyolefin, the ethylene and the unsaturated carboxylic acid or It is considered that the polyester and the polyolefin are compatibilized through the interaction with the copolymer with the derivative.

[0026]

The present invention will be described in more detail with reference to Examples and Comparative Examples, but the present invention is not limited to the following examples. In the examples and comparative examples, the following raw material components and additives were used. Polyester (1) Polybutylene terephthalate (PBT): C7000N manufactured by Teijin Limited, intrinsic viscosity [η] 1.05 (in o-chlorophenol, 25 ° C). (2) Polyethylene terephthalate (PET): TR 4550BH manufactured by Teijin Limited, intrinsic viscosity [η] 0.7 (o-
25 ° C in chlorophenol).

Unmodified polyolefin (1) Polypropylene homopolymer (PP (1)): J209 manufactured by Tonen Chemical Co., Ltd., melt flow rate (MF)
R, 230 ° C, 2.16kg load) 8.5g / 10 minutes. (2) Polypropylene homopolymer (PP (2)): BJ309 manufactured by Tonen Chemical Co., Ltd., melt flow rate (MF
R, 230 ° C, 2.16kg load) 8.5g / 10 minutes.

Modified Polyolefin (1) Modified Polypropylene (Modified PP (1)): Polypropylene [Melt Flow Rate (MFR, 230
℃, 2.16kg load) 1g / 10min] to 100 parts by weight,
0.1 parts by weight of organic peroxide (Perhexin 25B: manufactured by NOF CORPORATION) and 1 part by weight of maleic anhydride were added, and a single screw type extruder having a diameter of 30 mm and an L / D ratio of 25 was used, and the screw rotation speed was 250 rpm, Melt kneaded at a temperature of 200 ° C. Graft ratio of maleic anhydride: 0.4% by weight, melt flow rate (MFR, 230 ° C, 2.16 kg load) 20
0 g / 10 minutes. (2) Modified polypropylene (modified PP (2)): Polypropylene [melt flow rate (MFR, 230
℃, 2.16kg load) 1g / 10min] to 100 parts by weight,
0.03 parts by weight of organic peroxide (Perhexin 25B), unsaturated glycidyl compound represented by the following chemical formula (AXE)
[Made by Kanegafuchi Chemical Industry Co., Ltd.]

[0029]

[Chemical 4]

3 parts by weight of is added, the diameter is 30 mm, L /
Using a single-screw extruder with a D ratio of 25, the screw rotation speed is 2
Melt-kneaded at 50 rpm and temperature of 200 ° C. AX graft ratio: 2.5% by weight, melt flow rate (MFR,
230 ° C, 2.16 kg load) 111 g / 10 minutes. Copolymerization of ethylene with unsaturated carboxylic acids or their derivatives
Combined (1) Ethylene-acrylic acid copolymer (EAA (1)): Primacol 3440 manufactured by Dow Chemical Co., acrylic acid 9% by weight, melt flow rate (MFR, 190 ° C., 2.16 kg)
Load) 10 g / 10 minutes. (2) Ethylene-acrylic acid copolymer (EAA (2)): Dow Chemical Co. Primacol 5980, acrylic acid 20
% By weight, melt flow rate (MFR, 190 ° C, 2.16
kg load) 300 g / 10 minutes.

Examples 1 to 15, Comparative Examples 1 to 6 Polyester (PET or PBT), polyolefin (PP (1) or PP (2)), modified polyolefin (modified PP (1) or modified PP (2)) ) And a copolymer of ethylene and an unsaturated carboxylic acid or its derivative (EAA)
(1) or EAA (2)) in the proportions shown in Table 1,
Using a twin-screw extruder having a diameter of 45 mm, this was melt-kneaded at a screw rotation speed of 200 rpm and a temperature of 250 ° C. to be pelletized. The melt flow rate (MFR, 250 ° C., 2.16 kg load), surface peeling property, tensile strength, flexural modulus, Izod impact strength and heat distortion temperature of the thermoplastic resin composition thus obtained were measured. First result
Shown according to the table.

[0032]

[Table 1]

[0033]

[Table 2]

[0034]

[Table 3]

The methods for measuring the physical properties shown in Table 1 above are as follows. (1) Melt flow rate: measured at 250 ° C. and a load of 2.16 kg. (2) Surface peeling property: 100 squares of 1 mm x 1 mm were attached to the surface of the test piece using a razor, cellophane tape (manufactured by Nichiban Co., Ltd.) was attached to the squares, and then peeled off. Among 100 squares, the number of squares remaining on the surface of the test piece without adhering to the cellophane tape was counted. (3) Tensile strength: Measured according to ASTM D638 (23 ° C). (4) Flexural modulus: measured by ASTM D790 (23 ° C). (5) Izod impact strength: measured by ASTM D256 (23 ° C). (6) Heat distortion temperature: Measured according to ASTM D648.

As is apparent from Table 1, the thermoplastic resin compositions obtained by the method of the present invention are the same as those of Comparative Examples 1 to 4 which are composed only of AXE and a polyester lacking an ethylene-acrylic acid copolymer and a polyolefin. Composition and AX
Compared to the compositions of Comparative Examples 5 to 6 in which MAH was used instead of E and the ethylene-acrylic acid copolymer was lacking, the surface peeling property, tensile strength, flexural modulus, Izod impact strength and heat distortion temperature were better. In particular, the surface peeling property and impact strength are remarkably improved.

[0037]

INDUSTRIAL APPLICABILITY As described in detail above, the present invention provides a polyolefin modified with an unsaturated glycidyl compound and a copolymer of ethylene and an unsaturated carboxylic acid or a derivative thereof in order to improve the compatibility between the polyester and the polyolefin. The present invention provides a thermoplastic resin composition in which is blended with polyester. The resin composition of the present invention is excellent in impact resistance, heat resistance, chemical resistance, mechanical strength, and insulation, and at the same time, the peelability of a molded product is improved and the appearance is good. Such a thermoplastic resin composition of the present invention is used as various engineering plastics, especially as a resin composition for interior and exterior parts of automobiles, home electric appliance parts, industrial material parts, sports equipment, furniture, office supplies, packaging materials and the like. It is suitable.

Front page continuation (72) Inventor Tatsuo Teraya 1-3-3 Nishitsurugaoka, Oi-cho, Iruma-gun, Saitama Prefecture Tonen Corporation Research Institute (72) Yuji Fujita 1-3-3 Nishitsurugaoka, Oi-cho, Iruma-gun, Saitama Prefecture No. 1 Tonen Co., Ltd. Research Institute

Claims (3)

[Claims] 1. A copolymer of (a) a polyester, (b) a polyolefin containing 2% by weight or more of a modified polyolefin modified with an unsaturated glycidyl compound, and (c) an ethylene and an unsaturated carboxylic acid or a derivative thereof. Containing
The weight ratio of the component (a) and the component (b) is (a) /
(B) = 3/97 to 97/3, and the content of the component (c) is 2 to 5 relative to 100 parts by weight of the total of (a) + (b).
The thermoplastic resin composition is 0 parts by weight. 2. The modified polyolefin as the component (b) has the following general formula: [In the formula, R represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, Ar represents an aromatic hydrocarbon group having 6 to 20 carbon atoms having at least one glycidyloxy group, and n
Represents an integer of 1 to 4. ] It is polypropylene modified with the unsaturated glycidyl compound represented by these.
The thermoplastic resin composition according to. 3. The thermoplastic resin composition according to claim 1, wherein the copolymer of ethylene as the component (c) and the unsaturated carboxylic acid or its derivative is an ethylene-acrylic acid copolymer. ..