JPS6134059A - Thermoplastic resin composition - Google Patents

Abstract

PURPOSE:To provide a resin compsn. which has excellent compatibility, is highly flexible and inexpensive and gives moldings having good appearance, by blending a polyamide resin, a vinyl chloride resin and a carboxyl or epoxy group- contg. olefin copolymer in a specified ratio. CONSTITUTION:A polyamide resin (A), a vinyl chloride resin (B) and an olefin copolymer (C) contg. carboxyl and/or epoxy groups are blended in a weight ratio of A/B of 95/5-40/60 and C/(A+B) of 1/100-100/100. Preferred examples of the polyamide resins are nylon 11 and nylon 12. Examples of the vinyl chloride resins are vinyl chloride homopolymer, vinyl chloride copolymers obtd. by copolymerizing 85-99.9wt% vinyl chloride and 0.1-15wt% copolymerizable monomer and (co)polymers contg. a plasticizer.

Description

Detailed Description of the Invention (Industrial Field of Application) The present invention provides a thermoplastic resin composition mainly composed of polyamide resin, which has excellent compatibility, good appearance of molded products, is highly flexible, and is inexpensive. relating to things.

(Prior art and problems) A soft polyamide resin composition in which flexibility is imparted by adding a plasticizer or a flexible polymer to a polyamide resin is as follows:
As a thermoplastic nidistomer that has both the excellent mechanical properties of polyamide resin as an engineering plastic and the flexibility of a nidistomer, it is attracting attention for applications such as various tubes, hoses, and the soles of sports shoes.

However, many of these soft polyamide resins have lost a large amount of the original properties of polyamide resins, have poor compatibility with the blended polymer, significantly impair the appearance of molded products, or have poor moldability. However, there are many problems, and improvements are desired.

(Means for Solving the Problems) As a result of intensive studies in view of the above circumstances, the present inventors have formulated a polyamide resin with a vinyl chloride resin and an olefin copolymer containing a carboxyl group and/or an epoxy group. The present inventors have discovered that, in some cases, it is possible to obtain a thermoplastic resin composition free of the above-mentioned drawbacks and at low cost, and have completed the present invention.

That is, the present invention combines a polyamide resin (A) and a vinyl chloride resin CB) with a first/fin copolymer (O) containing a carboxyl group and/or an epoxy group.
4015~60, (C)/{prisoner + (8)) = 1/100
The present invention provides thermoplastic resin compositions characterized in that they are blended in a weight ratio of ~100/100.

The polyamide resin (A) used in the present invention refers to known polyamide resins such as nylon 6°, nylon 11, nylon 12, nylon 610, or copolymers containing these as main components. Including those containing.

These polyamide resins can be obtained by conventionally known manufacturing methods. For example, mixtures of ε-caglolactam, ω-aminoundecanoic acid, lauric acid, hexamethylenediamine and sepacic acid, each of which is a corresponding monomer, and, as some say, mixtures of these, etc., can be easily obtained by polycondensation. It will be done.

Nylon 11 and nylon 12 are particularly preferred polyamides used in the present invention.

Due to their chemical processing, nylon 11 and nylon 12 have features that are intermediate between ordinary polyamide resins such as nylon 6 and nylon 66 and elastic bodies such as polyamide elastomers, and have a wide range of performance properties. plasticizers commonly used in plastics materials,
Particularly preferred are aromatic hydroxy derivatives, such as 2-
Ethylhexyl-P-hydroxybenzoate; sulfonic acid amide, ? jJ, tJf By mixing a plasticizer for polyamide such as benzenesulfonic acid butylamide, excellent properties as an elastic body can be easily imparted. In the present invention, polyamide resin gold containing 0 to 40X amount of these plasticizers can be suitably used. If the amount of plasticizer added is more than 40% by weight, the mechanical properties will deteriorate and the migration of the plasticizer will be large, which is undesirable.

On the other hand, the vinyl chloride resin (Bl) used in the present invention refers to a homopolymer of vinyl chloride and a polymer completely copolymerized with 85 to 999% by weight of vinyl chloride and 0.1 to 15% by weight of a monomer that can be copolymerized therewith. It refers to a vinyl chloride copolymer, and includes those containing a plasticizer for vinyl chloride resin.As the monomer that can be copolymerized with vinyl chloride, any known monomer can be used,
Examples include vinyl acetate, vinylidene chloride, acrylonitrile, vinyl stearate, diethyl maleate, dibutyl maleate, diethyl hepta-maleate, methyl acrylate, ethyl acrylate, methyl methacrylate, and butyl methacrylate.

Vinyl chloride resin CB> contains 0 to 0 plasticizer for vinyl chloride resin.
It can be contained in an amount of 50% by weight. Examples of plasticizers include phthalic acid esters, trimellitic acid esters, phosphoric acid esters, dibasic acid esters, chlorinated paraffins, chlorinated fatty acid esters, epoxidized fats and oils, and epoxidized fatty acid esters.

General plasticizers for vinyl chloride, such as dibasic acids, oligoester plasticizers (molecular weight 500-8000) whose main components are glycol, and mixtures thereof, as well as polyester-based nidistomers, polyamide-based nidistomers, polyurethane elastomers, and styrene-based elastomers. , various elastomers such as olefin-based nydistomers, and ethylene-
Olefin copolymers such as vinyl acetate copolymer, ethylene-vinyl acetate-vinyl chloride copolymer, ethylene-propylene copolymer, ethylene-buteno 1 copolymer, AB
Examples include polymers such as S resin, MBSI (resin), chlorinated polyethylene, acrylic resin, and epoxy resin.

In the present invention, the mixing ratio of polyamide resin (A) and vinyl chloride resin (B) is 1 child's ratio (Al/(B)=
9515 to 40/6 [1] If the content of polyamide resin (A) exceeds 95% by weight, the effect of improving the polyamide resin (v) cannot be obtained; Each of these is undesirable because the original properties of the resin are largely lost.

The carboxyl group-containing olefin copolymer used in the present invention contains at least 50 mol%, preferably 70 mol% of 1-
Olefins, such as ethylene, propylene, butene-1
, inbutene, pentene-1, hexene-1, decene-
1,4-methylbutene-1,4-methylpentene-1,
It should contain 4,4-dimethylpentene-1, vinylcyclohexane, styrene, α-methylstyrene, styrene substituted with lower alkyl substituents or the like;
It is also possible to use mixtures of the abovementioned olefins.

Among these, copolymers obtained from ethylene and butene-1 or propylene are preferred, and commercially available products include, for example, Tafmer A4085, Tafmer A4090. Tafmer A series such as Tafmer A20090 [ethylene-butene-1 copolymer, Mitsui Petrochemical Products] and Tafmer PO280, Tafmer PO480, Tafmer P06
80. Examples include Tafmer P series (ethylene-propylene copolymer, Mitsui Petrochemical Industries, Ltd. product) such as Tafmer PO380.

The carboxyl group-containing olefin copolymer is produced by a known method such as direct copolymerization of an α,β-unsaturated carboxylic acid comonomer with the above olefin or graft copolymerization with a polyolefin and a polyolefin copolymer.

Examples of the acid component used here include acrylic acid, methacrylic acid, methacrylic acid, itaconic acid, (anhydrous) maleic acid, fumaric acid, and monoesters of the above-mentioned carboxylic acids. Preferably, acrylic acid and methacrylic acid are used. as well as(
anhydrous) maleic acid. Among these, lamelaic anhydride is particularly preferable because it can provide a sufficient acid modification effect with a small amount of addition compared to other acids.A suitable carboxyl group-containing olefin copolymer is ethylene-butene-1-(anhydrous)maleic. Examples include acid copolymers, ethylene-propylene-(anhydride)maleic acid copolymers, and the like.

The epoxy group-containing olefin copolymer is produced by a known method such as direct copolymerization of the glycidyl ester of α,β-Fukiwa carboxylic acid and the above olefin, or graft copolymerization with a polyolefin and a polyolefin copolymer. Ru.

Glycidyle of the α,β-unsaturated carboxylic acid used here (wherein R is a hydrogen atom or a lower alkyl group)
Examples of the mixture include one or more of the following: glycidyl acrylate, glycidyl methacrylate, glycidyl methacrylate, etc. Among them, glycidyl methacrylate is preferably used.

Such carboxyl group- and/or epoxy group-containing olefin copolymers contain monomers having these functional groups as constituent components, and are usually α01 to 20x% by amount, preferably rio
, os to 5% by weight.

The amount of the olefin copolymer (O added) is the total amount of the polyamide resin and the vinyl chloride resin (B) (factor +) i
1 to 100 parts by weight, preferably 5 to 5 parts by weight
It is in the range of 0i parts. If the amount added is more than 100 parts by weight, the mechanical strength, thermal properties, molding processability, etc. of the resulting molded product will deteriorate, which is undesirable. Also 1
If the weight part is small, the effect of the present invention will be small and it will be difficult to achieve the full scope of the present invention.

Furthermore, the thermoplastic resin composition of the present invention can be added with an inorganic and/or organic filler as necessary to improve rigidity and the like. Suitable fillers include glass fiber,
Carbon fiber, metal fiber, aramid fiber, potassium titanium, asbestos, silicon carbide, ceramic, silicon nitride,
Barium sulfate, calcium sulfate, kaolin, clay, pyrophyllite, bentonite, sericite, zeolite, mica, mica, nephelinsinite, Merck, atalpulgite, wollastonite, PMF, ferrite, calcium silicate, calcium carbonate , magnesium carbonate, dolomite, zinc oxide, titanium oxide, magnesium oxide, ferric iron, molybdenum disulfide, graphite, gypsum, glass beads, glass powder, glass balloons, quartz, quartz glass, and other reinforcing fillers. .

The thermoplastic resin composition of the present invention also contains heat stabilizers, weather stabilizers, lubricants, colorants, coupling agents, blowing agents, rust preventives, flame retardants, flame retardant aids such as antimony trioxide, etc. can also be added.

In addition, when carrying out the present invention, other thermoplastic resins or polymers such as polyvinyl chloride, polyester, polyether polyester, urethanized polyester, ethylene-vinyl acetate copolymer, polyurethane may be used without departing from the purpose of the present invention. , styrene elastomer, polybutadiene, vinyl chloride elastomer, acrylic polymer, polyimide, polyamideimide, polyphenylene sulfide, etc. can also be used in combination.

The thermoplastic resin composition of the present invention can be prepared by various known methods. For example, after uniformly mixing all the raw materials in a tumbler or a mixer such as a Henschel mixer, -
There is a method of supplying it to a screw or twin screw extruder, melting and kneading it, and then preparing it as pellets.

(Effects of the Invention) The thermoplastic resin composition of the present invention obtained as described above has the components (4), Q3), and (C) blended with good compatibility, and has excellent wear resistance. , cold resistance, rebound resilience,
It does not lose the original properties of polyamide resin, such as excellent impact resistance and chemical resistance, and has the advantage of having a good molded product appearance, being highly flexible, and being inexpensive because it contains a large amount of vinyl chloride resin.

The thermoplastic resin composition of the present invention can be used for various purposes due to its excellent properties, such as tubes, hoses, pipes, rods, films, sheets, wire coatings,
Wire coating, optical fiber coating, various plans, fishing nets, nets, hot melt adhesives, conveyor belts, belts, soles of sports shoes for golf, baseball, soccer, track and field, ski boots, gears, cams, bearings, bearings, etc. , backing, gasket, O-ring, fastener, pulp, joint, grip, caster, roller,
Switch cases, clips, watch bands, emblems,
badminton shuttlecocks, tennis racket parts,
Ganlin tanks, bellows, floats, ball game poles,
It can be used for fishing buoys, tank inner coatings, various other automobile parts, electronic/electrical equipment parts, precision machine parts, etc. It can also be used as powder coating, solution-type adhesive, paint, etc.

(Examples) The present invention will be specifically explained below with reference to Examples, but the present invention is not limited only to these Examples.

still.

Ethylene-butene-1 copolymer (Tafmer A4090)
100 parts of 1,6-binu(1ert-butylperoxyprobyl)benzene, 0.5 part, and 1 part of maleic anhydride were uniformly mixed. Next, the mixture was mixed in an extruder whose cylinder temperature was set to 220° C., and the entire mixture was pelletized to obtain a carboxyl group-containing olefin copolymer. When the amount of grafted maleic anhydride was measured using an infrared spectrum, this olefin copolymer was found to be 100% ethylene-butene-1 copolymer.
It was confirmed that 0.75 parts of maleic anhydride was grafted to each part. This is called total copolymer (I).

Reference Example 2 (Production of epoxy group-containing olefin copolymer)
Ethylene-butene-1 copolymer (Tough 7-A4090)
100 parts of dicumyl peroxide, 0.5 parts of dicumyl peroxide, and 2 parts of glycidyl methacrylate were uniformly mixed. Next, the mixture was mixed with a twin-screw extruder set at a cylinder temperature of 200° C., and pelletization was carried out to obtain an epoxy group-containing olefin copolymer. When the grafting amount of methacrylic acid glycidyl ether was measured using a hydrochloric acid-methyl ethyl ketone solution, it was found that this olefin copolymer had 1.25 parts of methacrylic acid glycidyl ether grafted to 100 parts of the ethylene-butene-1 copolymer. It has been found. This is called copolymer (n).

Examples 1 to 14 and Comparative Examples 1 to 5 GRILAMID L-20G (Nylon 12 manufactured by MSU Chemie) Benzene sulfo/acid phthylamide, G
eon'ID5EP C Nippon Zeon ■ vinyl chloride resin), plasticized vinyl chloride resin pre-mixed with Ceon 103EP and dioctyl phthalate at '11Do150 (, ii ratio), copolymer (I), copolymer (...),
Table 1 shows Tough f-A4090 and Ba-Zn stabilizers.
They were mixed in the proportions shown in Table 2 and kneaded using a 40% extruder at a cylinder temperature of 180°C to obtain a thermoplastic resin composition 1-.

Using the pellets, 18
A test piece was molded at 0°C and various tests described below were conducted.

The results are shown in Table-1 and Table-2.

(1) Compatibility test: A 3-thickness test piece is repeatedly placed on the diffraction target 24 times to observe and evaluate the condition of the crease.

○: No layer peeling X: Layer peeling (21 Shore D hardness: according to ASTM D-2240.

(3) Tensile breaking strength: According to JIS K-6301.

(4) Notched Izo impact strength: ASTM D-2
56.

However, the measurement temperatures are 23°C and -20°C.

Claims (1)

[Claims] The polyamide resin (A), the vinyl chloride resin (B), and the carboxyl group- and/or epoxy group-containing olefin copolymer (C) are mixed in a ratio of (A)/(B) = 95/5 to 40/60.
, (C)/{(A)+(B)}=1/100~100/
A thermoplastic resin composition characterized in that it is blended in a weight ratio of 100.