JPH05230298A - Thermoplastic resin composition - Google Patents

Abstract

PURPOSE:To provide a novel thermoplastic resin compsn. which is capable of homogeneously micro-dispersing therein particles to a degree of at most 1mum in dispersed particle size, has a very good balance among various properties such as processability, rigidity, flawing resistance, heat resistance, impact resistance, oil resistance, chemical resistance and water resistance, and is excellent in appearance and transparency when formed into a film, a sheet, etc. CONSTITUTION:100 pts.wt. resin compsn. comprising 5-95wt.% polypropylene and 95-5wt.% methacrylic resin is blended with 1-20 pts.wt. polyolefin modified by grafting or copolymn. with a methacrylic resin to prepare a thermoplastic resin compsn.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a novel thermoplastic resin composition which can be used as a molded product, sheet or film by injection molding, extrusion molding or the like. More specifically, the present invention relates to a novel thermoplastic resin composition in which the compatibility between polypropylene and a methacrylic resin is remarkably improved and the balance of physical properties, appearance and transparency are excellent.

[0002]

2. Description of the Related Art Polypropylene has a good moldability, toughness,
Since it is excellent in water resistance, gasoline resistance, chemical resistance, etc., and has low specific gravity and is inexpensive, it has been widely used for various molded products, films, sheets and the like. However, polypropylene has drawbacks or improvements in heat resistance, rigidity, scratch resistance, paintability, adhesiveness, printability, etc., and in order to develop new applications, it is necessary to further improve these. Is desired. On the other hand, methacrylic resin has excellent properties such as optical properties such as transparency and surface gloss, mechanical properties, high scratch resistance, and weather resistance among polymer materials, and is also excellent in molding processability. It has characteristics. Utilizing these characteristics, it is used in many fields such as lighting equipment, signboards, window materials, optical lenses, vehicle parts and various displays. However, since the methacrylic resin lacks impact resistance, there is a strong demand for improvement in many fields of application, and the method of imparting impact resistance without impairing the original characteristics of the methacrylic resin is old. Is being considered by. For example, when MBS resin or ABSM resin (acrylonitrile-butadiene-styrene-methylmethacrylate) is mixed, the impact resistance can be remarkably improved without lowering the transparency, but an unmelted material called fish eye is generated. In particular, in the case of an extruded product, unevenness is likely to occur on the surface, which hinders its appearance properties, resulting in a case where its use is significantly limited, and in water resistance and chemical resistance,
Satisfaction has not been obtained.

[0003]

DISCLOSURE OF THE INVENTION According to the present invention, polypropylene and methacrylic resin are blended with a modified polyolefin so that the dispersed particle diameter is 1 μm or less, preferably 0.3 μm or less.
Uniformly dispersed microscopically to less than μm, forming processability, rigidity,
A new thermoplastic that has a very good balance of physical properties such as scratch resistance, heat resistance, impact resistance, oil resistance, chemical resistance, and water resistance, and has excellent appearance and transparency during molding of films and sheets. It is intended to provide a resin composition.

[0004]

The present invention relates to polypropylene (A) 5 to 95% by weight and methyl methacrylate alone,
Alternatively, a resin composition 1 comprising 95 to 5% by weight of a methacrylic resin (B) obtained by polymerizing a mixture of methyl methacrylate and another copolymerizable vinyl or vinylidene monomer.
It relates to a thermoplastic resin composition comprising 1 to 20 parts by weight of a modified polyolefin (C) modified by grafting or copolymerizing at least one methacrylic resin with respect to 00 parts by weight. is there.

In general, in order to obtain a resin having good transparency when two or more kinds of resins are combined, it is necessary to select resins having almost the same refractive index and to disperse dispersed particles in a microscopic size. Can be considered. In the case of the present invention,
By selecting resins having almost the same refractive index and making the dispersed particle diameter finer, it was possible to obtain a thermoplastic resin having a good balance of physical properties and excellent transparency, which has never existed before.

The polypropylene (A) used in the present invention is crystalline polypropylene, and in addition to polypropylene homopolymer, polypropylene is used in the first step, and α and α, such as ethylene and polypropylene, butene-1 in the second step. -Including random copolymers copolymerized with olefins. The homopolymer, block or random copolymer of polypropylene can be obtained by reacting in the presence of a combination catalyst of titanium trichloride and an alkylaluminum compound, which is usually called Ziegler-Natta type catalyst.

The methacrylic resin (B) used in the present invention is obtained by polymerizing methyl methacrylate alone or a mixture of methyl methacrylate and another copolymerizable vinyl or vinylidene monomer. , Preferably containing 80% by weight or more of methyl methacrylate. Other copolymerizable vinyl or vinylidene-based monomers are preferably methyl acrylate, ethyl acrylate, butyl acrylate, alkyl acrylates having 1 to 8 carbon atoms such as 2-ethylhexyl acrylate, styrene, And acrylonitrile.

The modified polyolefin (C) used in the present invention is a polyolefin modified by grafting or copolymerizing at least one methacrylic resin. Here, polyolefin means ethylene, propylene, butene-1, pentene-1, hexene-1, 3-methylbutene-1, 4-methylpentene-
1, homopolymers of α-olefins such as heptene-1, octene-1, mutual copolymers in the form of random or block, randomization of a majority weight of these α-olefins and other unsaturated monomers It is a compound obtained by oxidative halogenation or sulfonation of a block, graft, or other copolymer, and is at least partially crystalline. Here, as the other unsaturated monomer, acrylic acid, methacrylic acid, maleic acid, itaconic acid, methyl acrylate, ethyl acrylate, methyl methacrylate, maleic anhydride,
Unsaturated organic acids such as aryl maleic imides and alkyl maleic imides or derivatives thereof; vinyl esters such as vinyl acetate and vinyl butyrate; aromatic vinyl compounds such as styrene and methyl styrene; vinyl trimethylmethoxysilane, γ-methacryloyloxypropyl Vinylsilane such as trimethoxysilane; dicyclopentadiene, 4-
A non-conjugated diene such as ethylidene-2-norbornene can be used. In the case of copolymerization, the α-olefin and other monomers are not limited to two types, and may be a plurality of types.

The methacrylic resin introduced by grafting or copolymerization is obtained by polymerizing methyl methacrylate alone or a mixture of methyl methacrylate and another copolymerizable vinyl or vinylidene monomer. It preferably contains 80% by weight or more of methyl methacrylate. Other copolymerizable vinyl or vinylidene-based monomers are preferably methyl acrylate, ethyl acrylate, butyl acrylate, alkyl acrylates having 1 to 8 carbon atoms such as 2-ethylhexyl acrylate, styrene, And acrylonitrile. The methacrylic resin to be introduced is not limited to one kind, and may be plural kinds.

Specific examples of the modified polyolefins which are particularly useful in the present invention include polyethylene-g-polymethylmethacrylate (PE-g-PMMA) ("g" represents a graft, the same applies hereinafter), polypropylene-g. -Polymethylmethacrylate (PP-g-PMMA), Poly (ethylene / propylene) -g-
Polymethylmethacrylate (EPM-g-PMMA), poly (ethylene / ethyl acrylate) -g-polymethylmethacrylate (E
EA-g-PMMA), poly (ethylene / vinyl acetate) -g-polymethylmethacrylate (EVA-g-PMMA), poly (ethylene / ethyl acrylate / maleic anhydride) -g-polymethylmethacrylate (E / VA / MAH-g-PMMA) etc.

In the thermoplastic resin composition according to the present invention, 5 to 95% by weight of polypropylene (A) and methyl methacrylate alone or a mixture of methyl methacrylate and another copolymerizable vinyl or vinylidene monomer are used. 1 to 20 parts by weight of the modified polyolefin (C) must be added to 100 parts by weight of the resin composition consisting of 95 to 5% by weight of the methacrylic resin (B) obtained by polymerization.
When the content of the component (A) is less than 5% by weight, moldability, water resistance, and chemical resistance are insufficient, and 95% by weight.
If the amount is larger than the above range, favorable properties in rigidity cannot be obtained. When the content of the component (B) is less than 5% by weight, the rigidity and surface gloss are insufficient, and when it is more than 95% by weight, the impact resistance is insufficient. Further, regarding the component (C), when the content is less than 1 part by weight, there is a problem in the compatibility dispersibility of the resin composition, and the dispersed particle diameter is several tens to several hundreds μm.
And the appearance and transparency are insufficient. When the content is more than 20 parts by weight, heat resistance, rigidity and the like are remarkably deteriorated and a desirable result cannot be obtained.

Further, if necessary, additives such as dyes and pigments, stabilizers, plasticizers, antistatic agents, ultraviolet absorbers, antioxidants, lubricants, fillers, etc. are added to the extent that basic properties are not impaired.
Also, an elastomer or the like which imparts flexibility can be added. The thermoplastic resin composition according to the present invention is easily processed into a molded product, a film, by a processing method used for a usual thermoplastic resin composition, such as injection molding or extrusion molding.
Although it is processed into a sheet or the like, if the molded product is thick by injection molding or the like, transparency may be impaired by crystallization of polypropylene in the cooling process.
It is desirable to set the temperature to cool rapidly in the range of ° C.

[0013]

EXAMPLES The present invention will be described with reference to the following examples, but these are merely examples and the present invention is not limited thereto. A T-die sheet of 0.25 mm was used, and light transmittance and Haze were ASTM-D1003.
Also, the tensile test is ASTM-D638, the bending test is ASTM-D790, and the Izod impact test is ASTM.
It is a result measured by -D256. The appearance was visually determined. The results of the blended composition and each characteristic value are shown in Table 1.

Examples 1 to 3 Noblene S131 (PP; manufactured by Sumitomo Chemical Co., Ltd.) was used as the component (A), and Sumipex-B LO-6 was used as the component (B).
(PMMA; manufactured by Sumitomo Chemical Co., Ltd.) and MODIPER A1200 (PE-g-PMMA; manufactured by NOF CORPORATION) was used as the component (C). (Examples 4 and 5) Noblene S1 was used as the component (A).
31 (PP; manufactured by Sumitomo Chemical Co., Ltd.), Sumipex-B LO-6 (PMMA; manufactured by Sumitomo Chemical Co., Ltd.) used as the component (B), and Modiper A5200 (EEA-) as the component (C). g-PMMA; manufactured by NOF CORPORATION) was used. (Example 6) As the component (A), Noblene S131
(PP; manufactured by Sumitomo Chemical Co., Ltd.) is used, as the component (B), Sumipex-B LO-6 (PMMA; manufactured by Sumitomo Chemical Co., Ltd.) is used, and as the (C) component, Modiper A8200 (E / EA) / MAH-g-PMMA; manufactured by NOF CORPORATION) was used. (Comparative Example 1) As the component (A), Noblene S131
(PP; Sumitomo Chemical Co., Ltd.) was used, and as the component (B), Sumipex-B LO-6 (PMMA; Sumitomo Chemical Co., Ltd.) was used.

[0015]

[Table 1]

[0016]

EFFECT OF THE INVENTION The thermoplastic resin composition according to the present invention can be easily processed into molded articles, films, sheets, etc. by the processing methods used for ordinary thermoplastic resin compositions such as injection molding and extrusion molding. It has an excellent balance of physical properties such as moldability, rigidity, scratch resistance, heat resistance, impact resistance, oil resistance, chemical resistance, water resistance, etc., and the appearance and transparency of the film and sheet during molding. Gives excellent product.

Claims (1)

[Claims] 1. A methacrylic resin obtained by polymerizing 5 to 95% by weight of polypropylene (A) and methyl methacrylate alone or a mixture of methyl methacrylate and another copolymerizable vinyl or vinylidene monomer. B) 95-5
Modified polyolefin (C) 1 to 20 in which at least one or more methacrylic resin is modified by grafting or copolymerization with respect to 100 parts by weight of a resin composition consisting of 10% by weight.
A thermoplastic resin composition, characterized by being mixed with parts by weight.