JPH0665380A - Compatibilizer and thermoplastic resin composition - Google Patents

Abstract

PURPOSE:To obtain a compatibilizer which can give a thermoplastic resin composition well balanced among the properties and capable of giving a molding good in appearance and transparency by melt reacting a hydroxy compound highly compatible with polypropylene with an acid-containing methacrylic resin. CONSTITUTION:The compatibilizer is obtained by melt reacting a composition comprising 5-95wt.% hydroxy compound highly compatible with polypropylene and 95-5wt.% methacrylic resin containing at least one acid and/or acid anhydride. The objective composition well balanced among the properties and excellent in appearance and transparency is obtained by mixing 100 pts.wt. resin component comprising 5-95wt.% polypropylene and 95-5wt.% methacrylic resin obtained by polymerizing methyl methacrylate or a mixture thereof with 0.1-20 pts.wt. this compatibilizer.

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 dispersed by blending a novel compatibilizer obtained by melt-reacting a methacrylic resin containing a hydroxyl group-containing compound and an acid and / or an acid anhydride. Particle size is 1
It has a microscopically uniform dispersion of less than μm, preferably less than 0.3 μm, and 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. Moreover, it is an object of the present invention to provide a novel thermoplastic resin composition which has excellent appearance and transparency during molding such as film and sheet.

[0004]

The present invention relates to polypropylene (C) 5 to 95% by weight and methyl methacrylate alone,
Alternatively, a resin composition 1 comprising 95 to 5% by weight of a methacrylic resin (D) obtained by polymerizing a mixture of methyl methacrylate and another copolymerizable vinyl or vinylidene monomer.
A hydroxyl group-containing compound (A) having an excellent compatibility with polypropylene (5 to 95% by weight) and a methacrylic resin (B) containing at least one acid and / or an acid anhydride (95 to 5% by weight) per 100 parts by weight. The present invention relates to a thermoplastic resin composition comprising 0.1 to 20 parts by weight of a compatibilizer characterized by being melt-reacted with a 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.

As the hydroxyl group-containing compound (A) used in the present invention, for example, rosin, rosin ester, terpene resin, coumarone indene resin, petroleum resin having a hydroxyl group in the molecule, or terpene phenol resin, rosin modified Those with very good affinity and compatibility with polypropylene, such as those with phenolic hydroxyl groups such as phenolic resins, or those with polyolefinic saturated hydrocarbon skeletons that have hydroxyl groups at one or both ends of the molecule. Can be mentioned. In addition, these can also be used as a mixture of 2 or more types.

The polypropylene (C) 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 propylene, butene-1 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 resins (B) and (D) used in the present invention are obtained by polymerizing methyl methacrylate alone or a mixture of methyl methacrylate and another copolymerizable vinyl or vinylidene monomer. That is
Preferably, it 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 (B) must contain at least one type of acid and / or acid anhydride. 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. Further, those containing an aromatic vinyl compound such as styrene, α-methylstyrene, dimethylstyrene and the like are also preferable.

In the thermoplastic resin composition according to the present invention, 5 to 95% by weight of polypropylene (C) and methyl methacrylate alone or a mixture of methyl methacrylate and another copolymerizable vinyl or vinylidene monomer are polymerized. 5 to 95% by weight of a hydroxyl group-containing compound (A) having excellent compatibility with polypropylene based on 100 parts by weight of a resin composition composed of 95 to 5% by weight of the obtained methacrylic resin (D), and at least one or more acids. And / or a methacrylic resin (B) containing an acid anhydride, which is prepared by melting and reacting a composition of 95 to 5% by weight.
1 to 20 parts by weight must be blended. When the content of the component (C) 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. (D)
If the content of the component is less than 5% by weight, the rigidity and surface gloss are insufficient, and if it exceeds 95% by weight, the impact resistance is insufficient.

In the compatibilizing agent of the present invention, the methacrylic resin (B) containing a hydroxyl group-containing compound (A) having excellent compatibility with polypropylene and at least one acid and / or acid anhydride is 5:95 to 95: It is compounded in the range of 5% by weight. If the compounding ratio of the hydroxyl group-containing compound (A) and the methacrylic resin (B) is less than 5% by weight, the effect of improving the compatibility decreases. The content of the compatibilizer is 0.1
When the amount is less than the weight part, 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 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 during the cooling process.
It is desirable to set the temperature to cool rapidly in the range of ° C.

[0011]

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), 90 parts by weight of a polyolefin saturated hydrocarbon skeleton having a reactive hydroxyl group at the molecular end (Polytail HE; manufactured by Mitsubishi Kasei), and as the component (B) , Acid anhydride modified poly (methyl methacrylate) (SUMIPEX-B TR; Sumitomo Chemical Co., Ltd.)
(Manufactured by Mfg. Co., Ltd.)
A compatibilizing agent A was obtained by melting and kneading at 50 ° C. for 10 to 30 minutes to allow sufficient reaction, forming a sheet with a roll and pelletizing with a sheet pelletizer. And, as the component (C),
Noblen JS-2871 (PP; Mitsui Toatsu Chemicals, Inc.)
(Manufactured by) and as the component (D), Sumipex-B
LO (PMMA; manufactured by Sumitomo Chemical Co., Ltd.) was used, and the compatibilizing agent A was used as the compatibilizing agent. (Examples 4 and 5) As the component (A), 10 parts by weight of a polyester diol having a rosin skeleton at both ends (KE-601; manufactured by Arakawa Chemical Industry Co., Ltd.), and as the component (B), an acid anhydride was used. 90 parts by weight of substance-modified polymethylmethacrylate (Sumipex-B TR; manufactured by Sumitomo Chemical Co., Ltd.) was put into a pressure kneader, melt-kneaded at 230 to 250 ° C. for 10 to 30 minutes, sufficiently reacted, and then rolled. After making a sheet,
Compatibilizer B was obtained by pelletizing with a sheet pelletizer. And, as the component (C), Noblene JS-2
871 (PP; manufactured by Mitsui Toatsu Chemicals, Inc.)
As the component (D), Sumipex-B LO (PMM
A; manufactured by Sumitomo Chemical Co., Ltd.) was used, and the compatibilizing agent B was used as the compatibilizing agent. (Example 6) As the component (C), Hipol CJ-7
00 (PP; manufactured by Mitsui Petrochemical Industry Co., Ltd.)
As the component (D), Sumipex-B LO (PMM
A; manufactured by Sumitomo Chemical Co., Ltd.) was used as the compatibilizing agent. (Comparative Example 1) As the component (C), Noblene JS-2
871 (PP; manufactured by Mitsui Toatsu Chemicals, Inc.)
As the component (D), Sumipex-B LO (PMM
A: Sumitomo Chemical Co., Ltd.) was used.

[0012]

[0013]

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 composition comprising 5 to 95% by weight of a hydroxyl group-containing compound (A) having excellent compatibility with polypropylene and 95 to 5% by weight of a methacrylic resin (B) containing at least one acid and / or an acid anhydride. A compatibilizing agent, which is obtained by melting and reacting with. 2. A methacrylic resin obtained by polymerizing 5 to 95% by weight of polypropylene (C) and methyl methacrylate alone, or a mixture of methyl methacrylate and another copolymerizable vinyl or vinylidene monomer. D) 95-5
A thermoplastic resin composition, characterized in that 0.1 to 20 parts by weight of the compatibilizing agent according to claim 1 is blended with 100 parts by weight of the resin composition comprising 100% by weight.