JPH07103281B2 - Thermoplastic resin composition - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial field of application] The present invention is a thermoplastic resin containing aromatic polycarbonate and polyolefin as main components and having good rigidity, impact resistance, heat distortion resistance, moldability and chemical resistance. It relates to a composition.

[Conventional technology and problems]

Aromatic polycarbonates have excellent impact resistance, heat resistance, rigidity and dimensional stability, but have the drawback of poor solvent resistance and moldability. In order to obtain a composition having well-balanced mechanical properties while covering these drawbacks,
Various studies have been made on blends with polyolefins. However, since the compatibility between polyolefin and polycarbonate is not so good, it has been proposed to add various third components in order to improve the compatibility.

JP-A-57-108151 discloses a polycarbonate resin composition prepared by mixing 100 parts by weight of a polycarbonate resin with 0.3 to 20 parts by weight of polyethylene and 0.3 to 20 parts by weight of butyl rubber. Further, JP-A-57-108152 discloses a polycarbonate resin composition containing 0.3 to 20 parts by weight of an ethylene / propylene copolymer and / or an ethylene / propylene / diene copolymer as a third component. Further, JP-A-57-111351 discloses a polycarbonate resin composition containing 0.3 to 20 parts by weight of isoprene rubber and / or methylpentene polymer as a third component. However, in all of these polycarbonate resin compositions, when the amount of polyethylene exceeds 10%, the impact strength sharply decreases and the surface peeling of the molded product is also observed.

Further, JP-A-61-215649 discloses at least one high molecular weight aromatic polycarbonate and at least one olefin.
Disclosed are compositions of vinyl ester copolymers and olefin-vinyl alcohol copolymers or polyolefins. Although this composition has relatively good solvent resistance, it has a problem of insufficient compatibility. In addition, various compositions obtained by adding polyester and / or modified polyolefin to aromatic polycarbonate have been disclosed (JP-A Nos. 61-225245, 61-235456, 61-23).
No. 8847. However, since neither of these compositions contains polyolefin, there is a problem that the solvent resistance is poor. Thus, a composition having a sufficient compatibility between the aromatic polycarbonate and the polyolefin and excellent mechanical strength, moldability and solvent resistance is desired for automobile parts, etc., but still The reality is that we have not been able to obtain satisfactory results.

Therefore, an object of the present invention is to provide a thermoplastic resin composition in which the compatibility between an aromatic polycarbonate and a polyolefin is improved and which has a good balance of mechanical strength, moldability, solvent resistance and the like.

[Means for solving problems]

As a result of earnest research in view of the above object, the present inventor significantly improved the compatibility between the aromatic polycarbonate and the polyolefin by adding an appropriate amount of the modified polyolefin and polybutylene terephthalate to the composition of the aromatic polycarbonate and the polyolefin. Mechanical properties, moldability,
The present invention was discovered by discovering that a composition having excellent solvent resistance and the like can be obtained.

That is, the thermoplastic resin composition of the present invention comprises (a) 95 to 5% by weight of an aromatic polycarbonate, (b) 5 to 95% by weight of polypropylene, and (c) a total of 100 parts by weight of the aromatic polycarbonate and the polypropylene. Against 2-100
Parts by weight of 0.1 to 10% by weight of an unsaturated carboxylic acid or an anhydride thereof grafted modified polyolefin, (d)
It is characterized by containing 2 to 100 parts by weight of polybutylene terephthalate based on 100 parts by weight of the aromatic polycarbonate and the polypropylene.

The aromatic polycarbonate used in the present invention is (a)
Producing by 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 (b) transesterification reaction of a dihydric phenol with a carbonate precursor such as diphenyl carbonate. You can The dihydric phenol that can be used here is preferably bisphenol, and particularly 2,2-bis (4-
Hydroxyphenyl) propane (bisphenol A) is preferred. Further, a part or all of bisphenol A may be replaced with another dihydric phenol. Examples of dihydric phenols other than bisphenol A include hydroquinone and
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-) Mention may be made of halogenated bisphenols such as hydroxyphenyl) propane. It may be a homopolymer of these dihydric phenols, a comopolymer using two or more thereof, or a mixture thereof. Such a polycarbonate resin can be easily obtained as a commercial product.

The weight average molecular weight of the aromatic polycarbonate is 10,000 to
It is preferably 100,000, and if it is less than 10,000, the mechanical properties are insufficient, and if it exceeds 100,000, molding is difficult. A more preferable weight average molecular weight is 20,000 to 50,000.

Examples of the polyolefin include polyethylene, polypropylene, polybutene-1, poly-4-methylpentene-1 and other α-olefin polymers, and polypropylene is preferable. The polyolefin need not be a homopolymer and may be a copolymer with another α-olefin. For example, in the case of polypropylene, it may contain up to 20% by weight of other α-olefin. Other preferred comonomers for the propylene copolymer include ethylene and the like. The copolymer may be a random copolymer, a block copolymer or a graft copolymer. The weight average molecular weight of the polyolefin is 10,000 to 1,000,000, preferably 30,000 to 300,000.

The modified polyolefin used in the present invention is a polyolefin modified with an unsaturated carboxylic acid or an anhydride thereof.

As the unsaturated carboxylic acid or its anhydride, acrylic acid, monocarboxylic acid such as methacrylic acid, maleic acid, fumaric acid, dicarboxylic acid such as itaconic acid, maleic anhydride, dicarboxylic acid anhydride such as itaconic anhydride and the like. Among them, dicarboxylic acid is particularly preferable.

Examples of the polyolefin modified with an unsaturated carboxylic acid or the like include homopolymers of olefins such as polyethylene, polypropylene, polybutene 1 and polypentene-1, ethylene-propylene copolymers, ethylene-butene-1 copolymers, propylene- Butene-1 copolymer, ethylene-vinyl acetate copolymer, propylene-vinyl acetate copolymer, ethylene-butadiene copolymer, ethylene-
Examples thereof include copolymers with different olefins or diolefins such as an isoprene copolymer, an ethylene-chloroprene copolymer, a propylene-butediene copolymer, and an ethylene-propylene-diene copolymer. The form of the copolymer may be any of a random copolymer, a block copolymer, a graft copolymer and an alternating copolymer.

The modified polyolefin does not contain unreacted monomer,
It preferably has a weight average molecular weight of 10,000 or more. More preferably, the weight average molecular weight is about 30,000 to 300,000.

The content of unsaturated carboxylic acid, its anhydride or its ester in the modified polyolefin is preferably 0.1 to 10% by weight. If the amount of modification is less than 0.1% by weight, the effect of improving the compatibility between the aromatic polycarbonate and the polyolefin by adding the modified polyolefin is not sufficient, and if it exceeds 10% by weight, the compatibility with the polyolefin decreases.
A preferable modification amount is 0.5 to 5% by weight.

The modified polyolefin can be produced by either a solution method or a melt-kneading method. In the case of the melt kneading method, the polyolefin, the unsaturated carboxylic acid for modification (or acid anhydride) and the catalyst are put into an extruder or a twin-screw kneader, and the mixture is heated to a temperature of 150 to 250 ° C and kneaded while melting. . In the case of the solution method, the starting material is dissolved in an organic solvent such as xylene,
Perform at a temperature of ~ 140 ° C with stirring. In any case, a usual radical polymerization catalyst can be used as a catalyst, for example, benzoyl peroxide, lauroyl peroxide,
Peroxides such as ditertiary butyl peroxide, acetyl peroxide, tertiary butyl peroxybenzoic acid, dicumyl peroxide, peroxybenzoic acid, peroxyacetic acid, tertiary butyl peroxypivalate, and azobisisobutyronitrile Diazo compounds and the like are preferable. The amount of catalyst added is 10% by weight of unsaturated carboxylic acid for modification or its anhydride.
It is about 1 to 100 parts by weight with respect to 0 parts by weight.

Polybutylene terephthalate is a polyester composed of terephthalic acid and 1,4-butylene glycol, and has an intrinsic viscosity [η] (phenol / tetrachloroethane = 50/50 (weight ratio), which was obtained from a solution viscosity measured at 30 ° C. in a solvent. ) Is 0.
It is preferably about 5 to 2.0. The terephthalic acid component may be substituted with an alkyl group, a halogen group, etc.,
In addition to 1,4-butylene glycol, the glycol component is 2
Other glycols such as ethylene glycol, propylene glycol and hexamethylene glycol may be contained up to about 0% by weight.

In the present invention, the ratio of polyolefin to aromatic polycarbonate is 95-5% by weight to 5-95% by weight. If the aromatic polycarbonate is less than 5% by weight, sufficient impact resistance and strength cannot be obtained, and if it exceeds 95% by weight, moldability and solvent resistance are deteriorated. Aromatic polycarbonate is preferably 10 to 90 relative to 90 to 10% by weight of polyolefin.
% By weight, more preferably polyolefin 80 to 20
20-80% by weight of aromatic polycarbonate with respect to% by weight.

The content of the modified polyolefin is 2 to 100 parts by weight based on 100 parts by weight of the total amount of the aromatic polycarbonate and the polyolefin. If it is less than 2 parts by weight, the effect of improving the compatibility between the aromatic polycarbonate and the polyolefin by adding the modified polyolefin cannot be obtained, and if it exceeds 100 parts by weight, mechanical properties such as impact resistance are deteriorated. The content of the modified polyolefin is preferably 5 to 50 parts by weight.

The content of polybutylene terephthalate is 2 to 100 parts by weight based on 100 parts by weight of the total amount of the aromatic polycarbonate and the polyolefin. If it is less than 2 parts by weight, the effect of improving the compatibility with the aromatic polycarbonate by the addition of polybutylene terephthalate cannot be obtained, and if it exceeds 100 parts by weight, mechanical properties such as impact resistance are deteriorated. The preferable content of polybutylene terephthalate is 5 to 50 parts by weight.

The thermoplastic resin composition of the present invention further comprises a low crystalline ethylene-α-olefin copolymer, an acrylic elastomer,
A rubber component such as butyl rubber may be contained in an amount of 100 parts by weight or less based on 100 parts by weight of the crystalline polyolefin + polycarbonate.

In addition, for the purpose of modifying the thermoplastic resin composition of the present invention, other additives, for example, reinforcing materials such as glass fibers and carbon fibers, inorganic fillers, heat stabilizers, antioxidants, light Stabilizer, flame retardant, plasticizer, antistatic agent, release agent,
A foaming agent, a nucleating agent, etc. can be added.

The thermoplastic resin composition of the present invention is a single screw extruder, a twin screw extruder, a Banbury mixer, a kneading roll, a Brabender,
A kneader such as a kneader or a mixer such as a Henschel mixer is used to obtain the mixture by kneading in a heated and molten state.

[Action]

Although the compatibility between the aromatic polycarbonate and the polyolefin is poor, the compatibility between the polyolefin and the modified polyolefin is good, and the aromatic polycarbonate and the polybutylene terephthalate are compatibilized by transesterification during kneading. Furthermore, a reaction occurs between the carboxylic acid group of the modified polyolefin and the less than -OH group of polybutylene terephthalate to form a graft copolymer. These reactions contribute to the compatibilization of the aromatic polycarbonate / polyolefin. By the above mechanism, by kneading the aromatic polycarbonate and the polyolefin, and the modified polyolefin and the polybutylene terephthalate, good compatibilization of the aromatic polycarbonate and the polyolefin is brought about, resulting in mechanical properties, moldability and resistance. It is considered that a thermoplastic resin composition having a good balance of solvent properties and the like can be obtained.

〔Example〕

 The invention will be explained in more detail by the following examples.

In addition, in each Example and Comparative Example, the measurement of the physical property value was performed as follows.

(1) Heat deformation temperature = When the temperature is raised at a constant rate (2 ° C / min), the test piece (simple flash) bends by a predetermined amount (0.25mm) under a constant load (4.6kg / cm ² ). When temperature is JIS K720
Measured according to 7.

(2) Dynamic melt viscosity (η @ 100rad / sec) = 250 ° C, 1 with a dynamic spectrometer manufactured by Rheometrics
Measured at 00 rad / sec.

(3) Weight change due to immersion in methanol = The molded product was immersed in methanol at 25 ° C for 30 days and the change in weight was measured.

(4) Surface peeling resistance = 100 squares of 1 mm x 1 mm were attached to the surface of the test piece using a razor, and cellophane tape (Nichiban) was attached to the squares and then stripped off. Among 100 squares, the number of squares remaining on the surface of the test piece without adhering to the cellophane tape was counted.

Examples 1 to 5 polypropylene pellets (J209, M manufactured by Tonen Petrochemical Co., Ltd.)
FR = 9g / 10 minutes), aromatic polycarbonate (Panlite L1225, Teijin Kasei Co., Ltd., weight average molecular weight 22,500),
Maleic anhydride modified polypropylene (Graft amount = 0.6
% By weight, unreacted maleic anhydride content = 0) and polybutylene terephthalate (C7000 manufactured by Teijin Ltd., intrinsic viscosity [η] 1.2) were dry-blended in the proportions shown in Table 1 below, and the twin-screw kneader was used. Was kneaded at 280 ° C. to produce thermoplastic resin composition pellets. A test piece was prepared from each of the obtained thermoplastic resin composition pellets by injection molding (280 ° C.), and the heat distortion temperature, the dynamic melt viscosity, the weight change due to methanol immersion and the surface peeling resistance were measured. The results are also shown in Table 1.

Example 6 Block polypropylene (BJ309 manufactured by Tonen Petrochemical Co., Ltd.)
MFR = 9g / 10min), aromatic polycarbonate (Tanjin Kasei Co., Ltd. Panlite L1225, weight average molecular weight 22,500),
Maleic anhydride modified polypropylene (Graft amount = 0.6
% By weight, unreacted maleic anhydride content = 0) and polybutylene terephthalate (C7000 manufactured by Teijin Ltd., intrinsic viscosity [η] 1.2) were dry-blended in the proportions shown in Table 1 below, respectively, to give Example 1. Similarly, a thermoplastic resin composition pellet was produced. A test piece was prepared from the obtained thermoplastic resin composition pellet by injection molding (280 ° C.), and the same measurement as in Example 1 was performed. The results are also shown in Table 1.

Example 7 Polypropylene pellets (J209, M manufactured by Tonen Petrochemical Co., Ltd.)
FR = 9g / 10 minutes), aromatic polycarbonate (Panlite L1225, Teijin Kasei Co., Ltd., weight average molecular weight 22,500),
Acrylic acid-modified polypropylene (graft amount = 0.8% by weight, unreacted acrylic acid content = 0) and polybutylene terephthalate (C7000 manufactured by Teijin Ltd., intrinsic viscosity [η] 1.
2) were dry blended in the proportions shown in Table 1 below, and thermoplastic resin composition pellets were produced in the same manner as in Example 1. A test piece was prepared from the obtained thermoplastic resin composition pellet by injection molding (280 ° C.), and the same measurement as in Example 1 was performed. The results are also shown in Table 1.

Comparative Example 1 In the case of 100% by weight of polypropylene, a thermoplastic resin composition was prepared in the same manner as in Example 1, and the physical properties were measured.
The results are shown in Table 2.

Comparative Example 2 In the case of 100% by weight of aromatic polycarbonate, a thermoplastic resin composition was prepared in the same manner as in Example 1, and the physical properties were measured. The results are shown in Table 2.

Comparative Examples 3 and 4 A thermoplastic resin composition was prepared in the same manner as in Example 1 except that the two-component system of polypropylene and aromatic polycarbonate was used, and the physical properties were measured. The results are shown in Table 2.

Comparative Examples 5 and 6 Polypropylene pellets, aromatic polycarbonate and modified polyolefin alone were mixed in a composition shown in Table 2 with a Henschel mixer at room temperature, and then mixed with a biaxial kneader.
Kneading was carried out at 0 ° C. to obtain thermoplastic resin composition pellets. The same physical property values as in Example 1 were measured for the obtained thermoplastic resin composition. The results are shown together in Table 2.

Comparative Examples 7 and 8 Only polypropylene pellets, aromatic polycarbonate and polybutylene terephthalate were used in the composition shown in Table 2.
Kneading was carried out at 280 ° C. to obtain thermoplastic resin composition pellets. Example 1 was applied to the obtained thermoplastic resin composition.
The same physical property values as were measured. The results are shown together in Table 2.

As is clear from the results of Tables 1 and 2, the thermoplastic resin composition of the present invention has a heat distortion resistance (represented by a heat deformation temperature) as compared with a thermoplastic resin composition outside the scope of the present invention. ), Moldability (represented by dynamic melt viscosity), surface peel resistance and solvent resistance are well balanced.

〔The invention's effect〕

As described above, since the thermoplastic resin composition of the present invention is composed of the aromatic polycarbonate and the polyolefin, and the modified polyolefin and the polybutylene terephthalate are added together, the compatibility between the aromatic polycarbonate and the polyolefin is remarkably improved. , Heat resistance, moldability,
Good balance between surface peel resistance and solvent resistance. Further, it has excellent impact resistance and mechanical strength. The thermoplastic resin composition of the present invention can be suitably used as an engineering plastic material, particularly for automobile parts.

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Shigeru Sato 1-4-6, Nishitsurugaoka, Oi-cho, Iruma-gun, Saitama (72) Inventor Tetsuya Kawamura 3-2-1-20, Hikarigaoka, Nerima-ku, Tokyo (72) ) Inventor Takashi Mikami 3-2348 Izumihonmachi, Komae City, Tokyo (72) Inventor Takao Nomura Toyota City, Aichi Prefecture Toyota City 1 Toyota Motor Corporation (72) Inventor Toshio Yokoi Toyota City, Aichi Prefecture Toyota Town 1 Toyota Motor Co., Ltd. (72) Inventor Takesumi Nishio 1 Toyota Town, Toyota City, Aichi Prefecture Toyota Motor Co., Ltd. (56) Reference JP-A-59-66448 (JP, A) JP 58-167644 (JP, A) JP-A-57-92045 (JP, A)

Claims (3)

[Claims] (A) 95 to 5% by weight of aromatic polycarbonate, (b) 5 to 95% by weight of polypropylene, (c) 2 to 100 relative to 100 parts by weight of the total of the aromatic polycarbonate and the polypropylene. 0.1 to 10 parts by weight
A modified polyolefin which is grafted with an unsaturated carboxylic acid or an anhydride thereof in a weight percentage of: (d) 2 to 100 parts by weight of polybutylene terephthalate per 100 parts by weight of the total amount of the aromatic polycarbonate and the polypropylene. A thermoplastic resin composition comprising: 2. The thermoplastic resin composition according to claim 1, wherein the polypropylene is 90 to 10% by weight.
And the aromatic polycarbonate is 10 to 90% by weight. 3. The thermoplastic resin composition according to claim 1 or 2, wherein the modified polyolefin is 5 to 50 parts by weight based on 100 parts by weight of the total amount of the aromatic polycarbonate and the polypropylene. And the polybutylene terephthalate is 5 to 50 relative to 100 parts by weight of the total amount of the aromatic polycarbonate and the polypropylene.
A thermoplastic resin composition, characterized in that it is parts by weight.