JPH0649292A - Thermoplastic resin composition - Google Patents

Abstract

PURPOSE:To provide the composition comprising polypropylene, a methacrylic resin, and a glycidyl acrylate compound-modified hydrogenated block copolymer, and giving films excellent in moldability, scratch resistance, heat resistance, chemical resistance, etc., and good in transparency. CONSTITUTION:The objective thermoplastic resin composition comprises 100 pts. wt. of a resin composition comprising (A) 5-95wt.% of polypropylene and (B) 95-5wt.% of a methacrylic resin obtained by polymerizing methyl methacrylate alone or its mixture with another copolymerizable vinyl or vinylidene monomer (e.g. methyl acrylate), and (C) 1-20 pts.wt. of a hydrogenated block copolymer modified with glycidyl methacrylate or glycidyl acrylate. The thermoplastic resin composition contains fine particles having dispersed particle diameters of <=1mum and homogeneously dispersed therein, is good in the balance between the physical properties such as moldability, rigidity, scratch resistance, heat resistance, impact resistance, oil resistance, chemical resistance, water resistance, etc., and gives molded products such as films excellent in appearances and transparency.

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 has excellent 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 it is necessary to further improve these in order to develop new applications. 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 methacrylic resin lacks impact resistance, there is a strong demand for improvement in many fields of application, and the method for imparting impact resistance without impairing the original properties of the methacrylic resin described above 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 unmelted matter called fish eye is generated. In particular, in the case of extruded products, unevenness is likely to occur on the surface for this reason, which hinders the appearance properties of the product, and the use of the product may be significantly limited, and in terms of 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 hydrogenated block copolymer modified with glycidyl methacrylate or glycidyl acrylate to obtain a dispersed particle diameter of 1 μm or less, preferably 0.3 μm. Disperse microscopically in the following,
It has a very good balance of physical properties such as moldability, rigidity, scratch resistance, heat resistance, impact resistance, oil resistance, chemical resistance, water resistance, and the appearance and transparency of film and sheet during molding. It is an object of the present invention to provide an excellent novel thermoplastic resin composition.

[0004]

The present invention comprises 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. 1 to 20 parts by weight of a hydrogenated block copolymer (C) modified with glycidyl methacrylate or glycidyl acrylate based on 100 parts by weight of a resin composition consisting of 95 to 5% by weight of a methacrylic resin (B) obtained by polymerization. And a thermoplastic resin composition. Generally, in order to obtain good transparency when combining two or more kinds of resins, it is conceivable to select ones having almost the same refractive index of each resin and to disperse the dispersed particle diameter in a microscopic manner. . In the case of the present invention, a resin having a refractive index of almost the same is selected as the resin, and a thermoplastic resin having a good balance of physical properties and excellent transparency, which has never existed by making the dispersed particle size fine. I was able to get it.

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, for example, ethylene and propylene, butene-1 and other α are used in the second step. -Including random and / or block 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. 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.
Further, those containing at least one kind of acid and / or acid anhydride are preferable. Examples thereof include carboxylic acid and maleic anhydride. Above all, a copolymer containing a vinyl monomer unit containing a methacrylic acid and / or an acrylic acid unit is heat-treated to contain a 6-membered acid anhydride unit. Also, aromatic vinyl compounds such as styrene,
Those containing α-methylstyrene, dimethylstyrene and the like are also preferable.

Next, the hydrogenated block copolymer (C) modified with glycidyl methacrylate or glycidyl acrylate used in the present invention means at least one polymer block mainly containing a vinyl aromatic compound and at least one polymer block. It is obtained by hydrogenating a block copolymer composed of individual polymer blocks mainly composed of conjugated diene compounds, and is obtained by hydrogenating a vinyl aromatic compound-conjugated diene compound block copolymer. As the vinyl aromatic compound constituting the hydrogenated block copolymer, for example, one kind or two or more kinds selected from styrene, α-methylstyrene, vinyltoluene, p-tertiary butylstyrene, and 1,1-diphenylethylene. Can be selected, and styrene is particularly preferable. Examples of the conjugated diene compound before hydrogenation constituting the hydrogenated olefin compound polymer block include butadiene, isoprene, 1,3-pentadiene, and 2,3-dimethyl-1,3.
One or more selected from butadiene and the like, and among them, butadiene, isoprene, and combinations thereof are preferable. At least 80% of the aliphatic double bonds based on the conjugated diene compound of the vinyl aromatic compound-conjugated diene compound block copolymer are hydrogenated, and the polymer block mainly composed of the conjugated diene compound is morphologically modified. It needs to be converted to a coalesced block. The charged glycidyl methacrylate or glycidyl acrylate for obtaining the modified hydrogenated block copolymer of the present invention can be suitably used usually in the range of 0.02 to 30 parts by weight per 100 parts by weight of the hydrogenated block copolymer. The modified hydrogenated block copolymer obtained by this modification reaction is 0.0 per 100 parts by weight of the hydrogenated block copolymer.
1 to 20 parts by weight, preferably 0.05 to 15 parts by weight of glycidyl methacrylate and / or glycidyl acrylate are grafted. If the graft amount exceeds 20 parts by weight, the processability of the modified hydrogenated block polymer is deteriorated and gel is generated, which is not preferable. Further, if the graft amount is less than 0.01 part by weight, the improvement effect is not so great.

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 a hydrogenated block copolymer (C) modified with glycidyl methacrylate or glycidyl acrylate based on 100 parts by weight of a resin composition consisting of 95 to 5% by weight of a methacrylic resin (B) obtained by polymerization. Must be mixed in parts. When the content of the component (A) is less than 5% by weight, moldability, water resistance and chemical resistance are insufficient, and when it is more than 95% by weight, preferable 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. Also,
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, the dispersed particle diameter is as large as several tens to several hundreds of μm, and the appearance and the transparency are poor. It is enough. 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.
Furthermore, if necessary, additives such as dyes and pigments, stabilizers, plasticizers, antistatic agents, ultraviolet absorbers, antioxidants, lubricants, fillers, etc., and flexibility are added within a range that does not impair the basic properties. It is also possible to add an elastomer or the like. The thermoplastic resin composition according to the present invention is 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. When the molded product is thick by molding or the like, transparency may be impaired by crystallization of polypropylene during the cooling process, so it is desirable to set the cooling condition to be rapidly cooled in the range of 30 to 60 ° C.

[0009]

EXAMPLES The present invention will be described below with reference to examples, but these are merely examples and the present invention is not limited thereto. A T-die sheet of 0.25 mm is used, and the light transmittance and Haze are ASTM-D1003.
In addition, 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) As the component (A), Noblene JS-2871 (PP
Mitsui Toatsu Chemical Co., Ltd.), and as the component (B), Sumipex-B TR (PMMA; Sumitomo Chemical Co., Ltd.)
(Manufactured by Co., Ltd.) is used as the component (C).
-513 (SEBS-GMA; Asahi Chemical Industry Co., Ltd.) was used. (Examples 4 and 5) As the component (A), Noblene JS-2871 (PP
Mitsui Toatsu Chemical Co., Ltd.), and as the component (B), Sumipex-B TR (PMMA; Sumitomo Chemical Co., Ltd.)
(Manufactured by Co., Ltd.) is used as the component (C).
-514 (SEBS-GMA; manufactured by Asahi Kasei Kogyo Co., Ltd.) was used. (Example 6) As the component (A), Hipol CJ-700 (PP
Mitsui Petrochemical Industry Co., Ltd.) is used, as the component (B), Sumipex-B TR (PMMA; manufactured by Sumitomo Chemical Co., Ltd.) is used, and as the component (C), Tuftec Z- is used. 514 (SEBS-GMA; manufactured by Asahi Chemical Industry Co., Ltd.) was used. (Comparative Example 1) As the component (A), Noblene JS-2871 (PP
Mitsui Toatsu Chemical Co., Ltd.), and as the component (B), Sumipex-B TR (PMMA; Sumitomo Chemical Co., Ltd.)
(Manufactured by Co., Ltd.) was used.

[0010]

[0011]

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 a very good balance of physical properties such as moldability, rigidity, scratch resistance, heat resistance, impact resistance, oil resistance, chemical resistance, and water resistance, and the appearance and transparency of the film and sheet during molding. Gives excellent product.

Claims (2)

[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-
1 to 20 parts by weight of a hydrogenated block copolymer (C) modified with glycidyl methacrylate or glycidyl acrylate is mixed with 100 parts by weight of a resin composition consisting of 5% by weight. Resin composition. 2. The thermoplastic resin composition according to claim 1, wherein the methacrylic resin (B) contains at least one kind of acid and / or acid anhydride.