JPH0328255A - Thermoplastic resin composition - Google Patents

Abstract

PURPOSE:To obtain the subject composition having both of the chemical resistance and gas barrier properties inherent in high nitrile resin and the impact resistance and moldability inherent in rubber-modified resin by blending a high nitrile resin with a rubber-modified resin. CONSTITUTION:The subject composition is obtained by blending 10-90wt.% high nitrile resin (containing at least 50wt.% nitrile monomer unit) with 90-10wt.% rubber-modified resin (prepared by graft copolymerization of an aromatic vinyl compound, an unsaturated nitrile compound, and in some cases other copolymerizable vinyl compound onto a rubber polymer).

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention particularly relates to a thermoplastic resin composition that has excellent gas barrier properties, chemical resistance, formability, and impact resistance. [Prior art] High nitrile resins have excellent chemical resistance, gas barrier properties, and impact resistance, and are used for containers for liquids and solids, food packaging materials, etc. However, they have poor melt viscosity and rigidity. Its use is extremely limited due to its high value. In addition, rubber-modified resins obtained by polymerizing a monomer mixture consisting of an aromatic vinyl compound, an unsaturated nitrile compound, and, if necessary, other vinyl monomers copolymerizable with these in the presence of a rubber polymer, are resistant to Although it has excellent impact resistance and moldability, it has poor chemical resistance, which also limits its use. [Problems to be Solved by the Invention] The object of the present invention is to provide a new thermoplastic resin that has both the chemical resistance and gas barrier properties of high nitrile resins and the impact resistance and shapeability of the above-mentioned rubber-modified resins. The objective is to provide a composition. [Means for Solving the Problems] The present inventors have arrived at the present invention as a result of intensive studies to solve the above problems. That is, the present invention provides (a)
a polymer having a nitrile functional group, 10 to 90% by weight of a high nitrile resin in which monomer units having the nitrile group account for 50% by weight or more; (b) in the presence of a rubber polymer;
A thermoplastic resin composition consisting of 90 to 10% by weight of a rubber-modified resin obtained by polymerizing a monomer mixture consisting of an aromatic vinyl compound, an unsaturated nitrile compound, and, if necessary, another vinyl monomer copolymerizable with these. It is a thing. The high nitrile resin (a) that constitutes the thermoplastic resin composite of the present invention is a polymer having a nitrile functional group, in which monomer units having the nitrile group account for 50% by weight or more. Specifically, as a monomer unit component having a nitrile group, unsaturated nitrile compounds such as acrylonitrile and methacrylonitrile are used, and if necessary, other monomers that can be copolymerized with these, such as styrene, putadiene, isoprene, methyl acrylate, ethyl acrylate, and methyl. Copolymers of one or more of methacrylate, ethyl methacrylate, etc., and rubbers such as butadiene-acrylonitrile copolymer, butadiene-styrene copolymer, isoprene-styrene copolymer, polyptadiene, polyisobrene, etc. A mixture of the above unsaturated nitrile compound and other copolymerizable monomers may be graft copolymerized in the presence of a copolymer. This high nitrile resin can be produced by, for example, bulk polymerization, solution polymerization, emulsion polymerization or suspension polymerization, as a batch method, or by adding monomers and other components continuously, or It can be manufactured by adding it intermittently. Constituting the thermoplastic resin composition of the present invention (
Examples of the rubber-modified resin of component b) include ABS resin and high-impact polystyrene, which are generally commercially available, and methods for producing these include emulsion polymerization, bulk polymerization, and solution polymerization well known to those skilled in the art. or suspension polymerization may be used. That is, the rubber polymers used include polyalpha-olefins such as polyethylene and polypropylene, random copolymers and block copolymers of ethylene-propylene, random copolymers and block copolymers of ethylene-butene, etc. Olefin copolymers, copolymers of ethylene and unsaturated carboxylic acid esters such as ethylene-methyl methacrylate and ethylene-butyl acrylate, copolymers of ethylene and fatty acid vinyl such as ethylene-vinyl acetate, ethyl and butyl acrylates. , polymers of acrylic acid alkyl esters such as hexyl, 2-ethylhexyl, and lauryl esters, ethylene-propylene nonconjugated terpolymers such as ethylene-propylene-ethritenorbornene copolymers, ethylene-propylene-hexadiene copolymers, and polyptadiene. , styrene-butadiene random copolymers and block copolymers, acrylonitrile-butadiene copolymers, butadiene-isoprene copolymers, and other gene-based rubbers, styrene-isoprene copolymers, and aromatic hydrocarbons such as styrene. There are hydrogenated block copolymers of carbon dioxide and aliphatic diene hydrocarbons such as butadiene and isoprene, and these may be used singly or in combination of two or more. Further, aromatic vinyl compounds to be subjected to polymerization include styrene, α-methylstyrene, methylstyrene, vinylxylene, monochlorostyrene, dichlorostyrene, monobromustyrene, dibromostyrene, p-tertiarybutylstyrene, ethylstyrene, Examples include butylnaphthalene, and unsaturated nitrile compounds such as acrylonitrile, methacrylonitrile, ethacrylonitrile, or their analogs are used. Furthermore, the above
Aromatic vinyl compounds, other heptanomers copolymerizable with unsaturated nitrile compounds, such as methyl acrylate, ethyl acrylate, propylene acrylate, butyl acrylate, aryl acrylate, hexyl acrylate,
Alkyl esters of acrylic acid such as octyl acrylate, 2-ethylhexyl acrylate, cyclohexyl acrylate, dodecyl acrylate, octadecyl acrylate, phenyl acrylate, pendyl acrylate, methyl methacrylate, ethyl methacrylate,
Alkyl esters of methacrylic acid such as propylene methacrylate, butyl methacrylate, amyl methacrylate, hexyl methacrylate, octyl methacrylate, 2-ethylhexyl methacrylate, cyclohexyl methacrylate, dodecyl methacrylate, octadecyl methacrylate, phenyl methacrylate, pendyl methacrylate, maleic anhydride , unsaturated acid anhydrides such as itaconic anhydride and citraconic anhydride, unsaturated acids such as acrylic acid and methacrylic acid, etc. may be used in combination. In the thermoplastic resin composition of the present invention, the ratio of the high nitrile resin (a) and the rubber modified resin (b) used is as follows:
(a) is 10-90% by weight, (b) is 90-10% by weight
If (a) is less than 10% by weight, water vapor permeability becomes high and gas barrier properties also deteriorate. Moreover, if it exceeds 90% by weight, the formability deteriorates, which is not preferable. There are no particular restrictions on the method of manufacturing the thermoplastic resin composite sole of the present invention, and generally known methods can be employed.
That is, the high nitrile resin (a) and the rubber-modified resin (h) used in the above proportions are uniformly mixed using a high-speed stirrer, etc., and then mixed using a single-screw or multi-screw extruder with sufficient kneading capacity. It can be manufactured by melting and kneading. Furthermore, pigments, dyes, reinforcing materials such as glass fibers, metal fibers, and carbon fibers, fillers such as talc and calcium carbonate, antioxidants, ultraviolet absorbers, and the like may be added to the thermoplastic resin composition of the present invention, if necessary. May be added. For example, mechanical strength such as impact strength can be improved by adding various elastomers, such as methacrylate or acrylate grafted with methacrylic acid, or a graft cobolimer (acrylic core-shell type elastomer) consisting of a polyacrylate core. can.

〔Example〕

The present invention will be explained in more detail with reference to Examples below. The characteristics of the polymers and shaped products described in the Examples and Comparative Examples were evaluated using the following method. (1) Impact resistance Evaluated by Izod impact strength. Compliant with JIS-K7110. (2) Heat resistance Evaluated by heating deformation temperature. JrS-K? Compliant with 207. Bending stress 18
．． 56kg/cd (3) Evaluated by stiffness and flexural modulus. JIS-K7203 to I! Based on. (4) Formability evaluated by melt flow index. JIS-K
4 to 7210! Based on. 200°C, 2.16kg load (5) Chemical resistance Compliant with JIS-K7114.

23°C, 24 hours (6) Gas barrier properties Compliant with JIS-21707. (Plastic film for food packaging). 23°C, 24 hours Examples 1 to 3 High nitrile resin [manufactured by Mitsui Toatsu Chemicals, trade name: Ba]
rexJ, ABS resin [manufactured by Nippon Gokai Rubber Co., Ltd., product name JSR, ABSIO] was used as the rubber modified resin. Table 1
Blend in the proportions shown in and screw diameter 30III1
Using a shaft extruder, the resin was extruded and pelletized at a resin salinity of 200'C. Using this pellet, the injection pressure was 20
Each test molded product was produced using a 200° C. injection molding machine at a temperature of 200° C. during injection.

Table 1 shows the results of each physical property. Also, screw diameter 3
The above pellet was extruded into a single-screw extruder with a temperature of 0°C, and the thickness was reduced to 0°C under the condition of a resin temperature of 200°C. Im+w film was produced. The measurement results of the gas barrier properties of the film are also shown in Table 1. Examples 1 to 3 are all excellent in impact resistance, formability, chemical resistance, and gas barrier properties, and have sufficient practical physical properties. Comparative Example 1 The high nitrile resin used in the example was pelletized alone,
Examples 1-3 except that injection molded specimens and films were obtained.
I did the same thing. Compared to the example, the shape processability is inferior,
It has high rigidity.

Comparative Example 2 The same procedure as Examples 1 to 3 was carried out, except that the ABS resin used in the example was pelletized alone to obtain injection molded test pieces and films. Gas barrier properties are poor compared to Examples. [Effects of the Invention] The thermoplastic resin composition of the present invention has excellent moldability, chemical resistance, impact resistance, and gas barrier properties, and is suitable for use in packaging materials for foods, industrial parts, and the like.

Claims (1)

Scope of Claims: (a) a polymer having a nitrile functional group, 10 to 90% by weight of a high nitrile resin in which monomer units having the nitrile group account for 50% by weight or more; (b) in the presence of a rubber polymer; A thermoplastic resin consisting of 90 to 10% by weight of a rubber-modified resin obtained by polymerizing a monomer mixture consisting of an aromatic vinyl compound, an unsaturated nitrile compound, and, if necessary, another vinyl monomer copolymerizable with these. Composition.