JPS6134060A - Polyamide elastomer 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 elastomer, a vinyl chloride resin and a carboxyl or epoxy group- contg. olefin copolymer in a specified ratio. CONSTITUTION:A polyamide elastomer (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 or 95/5-40/60 and C/(A+B) of 1/100-100/100. Example of the polyamide elastomers are block copolymers composed of a hard segment consisting of a polyamide component such as nylon 6, 66 or 11 and a soft segment consisting of a polyester component and/or a polyether component. Examples of the vinyl chloride resin are vinyl chloride homopolymer and vinyl chloride copolymers obtd. by copolymerizing 85-99.9wt% vinyl chloride and 0.1- 15wt% copolymerizable monomer.

Description

Detailed Description of the Invention (Industrial Application Field) The present invention has good compatibility, good appearance of molded products, and excellent mechanical strength, impact resistance, cold resistance, heat aging resistance, bending resistance, etc. , and relates to an inexpensive polyamide elastomer composition.

(Prior Art and Problems) Previous attempts have been made to use polyamide elastomer compositions, which are a blend of polyamide elastomer and vinyl chloride resin, for purposes such as the soles of sports shoes, various tubes, and hoses. has the disadvantage of poor compatibility, and as a result, the original properties of the polyamide elastomer are completely lost. It had many problems, such as the appearance of the molded product being significantly impaired and poor impact resistance, cold resistance, heat aging resistance, etc. Attempts were made to improve the compatibility by further blending olefin copolymers, etc., but this was not sufficient and further improvements were desired.

(Means for solving the problem) As a result of intensive study in view of the above situation, the inventors of the present invention have found that
When a carboxyl group- and/or epoxy group-containing olefin copolymer is further blended into a mixture of a polyamide elastomer and a vinyl chloride resin, the compatibility is sufficiently improved and a polyamide elastomer composition free from the above-mentioned problems can be obtained. The present inventors have discovered that the following can be obtained, and have completed the present invention.

That is, the present invention combines polyamide elastomer (A), vinyl chloride m fat (tB), and carboxyl group- and/or epoxy group-containing olefin copolymer (C1) into tAl/
(B1=9515~40/60, (C'l/((Al+
tB)) = 1/100 to 100/100 in a weight ratio.

The polyamide elastomer used in the present invention is a block copolymer having a hard segment made of a polyamide component such as nylon-6, -66, -11, and -12, and a soft segment made of a polyester component and/or a polyether component. It is.

The hard segment polyamide component includes, for example, dicarboxylic acids such as terephthalic acid, inphthalic acid, oxalic acid, adipic acid, sebacic acid, and 1,4-cyclohexyldicarboxylic acid, and ethylenediamine and pentamethylenediamine.

hexamethylene diamine, decamethylene diamine, 1,
Polycondensation of diamines such as 4-cyclohexyldiamine and m-xylylene diamine; Polymerization of cyclic lactams such as caprolactam and laurolactam; Polycondensation of aminocarboxylic acids such as aminoenanthic acid, aminononanoic acid, and aminoundecanoic acid, or the above-mentioned cyclic lactams. It is obtained by copolymerization of lactam, dicarboxylic acid, and diamine, and these starting materials can be used individually or in a mixture.

The polyester component, which is a soft segment, combines the dicarboxylic acid or its ester-forming derivative, which is also used as a polyamide-forming component, with the general formula HO+CH$OH (in the formula,
p represents an integer from 2 to 12) aliphatic diol, 1,
It is obtained by polycondensation with an alicyclic diol such as 4-bis-(hydroxymethyl)-7chlorohexane.

Additionally, lactone compounds such as poly-epsilon-caprolactone can also be used.

Here too, the starting materials can be used individually or in mixtures.

The polyether component, which is a soft segment, is prepared as a starting material using the general formula % (wherein * ns th '' and b are integers of at least 2, preferably integers of 2 to 4, C is integers of 2 to 30, m is 0 or an integer from 2 to 30) is used.

For example, the general formula HtN(-Cud"ro('-(CH total O increase CH&?
'% (wherein C is an integer from 2 to 60, preferably from 6 to
bis-(3-aminopropyl)- which is an integer of 30
Mixture of polytetrahydrofuran, HtN+CHf)-
There are bis-(3-aminopropyl)-polypropylene oxides of rO(-(CHdrO-CH-promoted NH7 (in the formula, C is the same as above).Furthermore, poly(ethylene oxide) glycol, poly(propylene oxide) glycol , polyether glycols such as poly(tetramethylene oxide) glycol, and mixtures or copolymers of these polyether glycols may also be used.

The dicarboxylic acids used here include the dicarboxylic acids exemplified as raw materials for the polyamide component, trimerized fatty acids having 36 carbon atoms, mixtures of polymerized fatty acids containing the trimerized fatty acids as a main component, and the compounds shown. Can be mentioned.

Such a polyamide elastomer is usually produced by a conventionally known conventional condensation reaction between the polyamide component-forming compound and the polyester component-forming compound and/or the polyether component-forming compound. As a preferable method, for example, polyester polyamide elastomer is obtained by melt-mixing polyamide as a hard segment and polyester as soft segment in advance, and polyether polyamide elastomer is obtained by excluding the polyamide component forming compound and polyether glycols. The polyether ester polyamide elastomer is obtained by simultaneously polycondensing the polyether component-forming compound, polyether glycols, and other polyether component-forming compounds. Examples include methods of obtaining it.

Such a polyamide elastomer is preferably one in which the proportion of polyester blocks and/or polyether blocks, which are soft segments, is 8 to 60 weight percent.

An example of polyamide elastomer is GRILAM.
IDELY-1256 (Polyether polyamide elastomer manufactured by M's Hemy, Switzerland), Diamid E4
1TL.

E48TL, E63TL [polyether ester polyamide elastomer manufactured by Daicel], etc. are preferably used.

On the other hand, the vinyl chloride resin (B) used in the present invention is a homopolymer of vinyl chloride and a copolymer of 85 to 999% by weight of vinyl chloride and 0.1 to 15% by weight of a monomer that can be copolymerized therewith. This refers to vinyl chloride copolymers containing vinyl chloride resin plasticizers. Any known monomer can be used as a monomer that can be copolymerized with vinyl chloride,
Examples include vinyl acetate, vinylidene chloride, acrylonitrile, vinyl stearate, diethyl maleate, dibutyl maleate, diethyl fumarate, methyl acrylate, ethyl acrylate, methyl methacrylate, and butyl memethacrylate.

Vinyl chloride resin (B) 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 vinyl chloride plasticizers such as dibasic acids, oligoester plasticizers (molecular weight 500 to 5ooo) whose main components are glycol, and mixtures thereof, as well as polyester elastomers, polyurethane elastomers, styrene elastomers, and olefin elastomers. Various elastomers such as ethylene-vinyl acetate copolymer, ethylene-vinyl acetate-vinyl chloride copolymer, ethylene-propylene copolymer, ethylene-butene-1 copolymer and other olefin copolymers, ABS resin , MBSJvA resin, chlorinated polyethylene, acrylic resin, epoxy resin and the like. In the present invention, the mixing ratio of polyamide elastomer (A) and vinyl chloride resin (Bl) is (Al/(Bl) usually in the range of 9515 to 40/60, preferably 90/10 to 60/40 in weight ratio.

The carboxyl group-containing olefin copolymer used in the present invention contains at least 50 mol%, preferably 70 mol% of 1-
Olefins, e.g. evaethylene, furopylene, butene-1
, inbutene, pentene-1, hexene-1, decene-
1,4-methylbutene ~1,4-methylpentene-1,
should contain 4,4-dimethylpentene-1, vinylcyclohexane, styrene, alpha-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 P0
680, Tafmar PO380 such as Tafmar PO380 [
Ethylene-propylene copolymer, Mitsui Petrochemical Industries, Ltd. product).

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 carboxylic acids, and preferably acrylic acid and methacrylic acid. as well as(
anhydrous) maleic acid. Among these, maleic acid (anhydride) is particularly preferred since a sufficient acid modification effect can be obtained with addition of a small amount compared to other acids. Preferred carboxyl group-containing olefin copolymers include ethylene-butene-1-Ak water) maleic acid copolymer, ethylene-propylene-(anhydride) maleic acid copolymer, and the like.

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

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

Such olefin copolymers containing carboxyl groups and/or epoxy groups usually contain 0.01 to 20% by weight of monomers that completely blind these functional groups, and the weight is 0.
．． It is contained in the range of 0.05 to 5 weight-Jl-%.

The amount of the olefin copolymer (C) added is 1 to 100 parts by weight based on the total amount of the polyamide elastomer (A) and vinyl chloride resin (B) ((4) + (Bl) 100 parts by weight, It is preferably in the range of 5 to 50 parts by weight.If the amount added is as much as 100 parts by weight, the mechanical strength, thermal properties, molding processability, etc. of the obtained molded product will deteriorate, so it is preferable. If the amount is less than 1 part by weight, the effect of the present invention will be small and it will be difficult to achieve the present invention.

Furthermore, the polyamide elastomer composition of the present invention can have an inorganic and/or organic filler added thereto, if necessary, to improve rigidity and the like. Suitable fillers include glass fiber, carbon fiber, metal fiber, aramid fiber, potassium titanate, asbestos, silicon carbide, ceramic, silicon nitride, barium sulfate, calcium sulfate, kaolin,
Clay, pyrophyllite, bentonite, sericite, zeolite, mica, mica, nephelinsinite, merk, atalpulgite, qualastonite, PMF
, ferrite, calcium silicate, calcium carbonate, magnesium carbonate, dolomite, zinc oxide, titanium oxide, magnesium oxide, iron oxide, molybdenum disulfide, graphite, gypsum, glass beads, glass powder, glass balloon, quartz, quartz glass, etc. Mention may be made of reinforcing fillers.

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

Furthermore, in carrying out the present invention, other thermoplastic resins or elastomers such as polyvinyl chloride, polyester, polyether polyester, urethanized polyester, ethylene-vinyl acetate copolymer, polyurethane, styrene elastomer,
It is also possible to use polybutadiene, vinyl chloride elastomer, acrylic polymer, polyimide, polyamideimide, polyphenylene sulfide, etc. in combination.

The polyamide elastomer composition of the present invention can be prepared by various known methods. For example, there is a method in which the raw materials are uniformly mixed in advance using a mixer such as a tumbler or a Hahenschel mixer, then fed to a screw or twin screw extruder, melted and kneaded, and then prepared as pellets. .

(Effects of the Invention) The polyamide elastomer composition of the present invention obtained as described above has the IAI, IB+, and IC11 components blended with good compatibility, has a good molded product appearance, and has good mechanical strength and It has the advantage of being excellent in secondary impact resistance, cold resistance, heat aging resistance, bending resistance, etc., and is inexpensive.

The polyamide elastomer composition of the present invention can be used for various purposes due to its excellent properties, such as tubes, hoses, pipes, ronds, films, sheets,
Electric wire coating, 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 shoes, gears, cams, etc. bearing,
Bearings, backings, gaskets, O-rings, fasteners, valves, joints, grips, casters,
Rollers, switch cases, clips, watch bands, emblems, badminton shuttlecocks, tennis racket parts, gasoline tanks, bellows, floats, ball games, fishing buoys, tank inner coatings, other motor vehicle parts, electronics and It can be used for electrical equipment parts, precision machine parts, etc., and can also be used as powder coatings, solution-type adhesives, paints, etc.

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

In addition, parts in the examples mean parts by weight.

Reference Example 1 (Production of carboxyl group-containing olefin copolymer) Ethylene-butene-1 copolymer (Tafmer A409
0) 100 parts, 0.5 parts of 1,6-bis(tert-butylperoxyglobil)benzene and 1 part of maleic anhydride
parts were mixed uniformly. Next, the mixture was kneaded in an extruder set at a cylinder temperature of 220°C and 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 ethylene-butene-1 copolymer 1.
It was confirmed that 0.75 parts by weight of maleic anhydride was grafted to 00 parts by weight. This is copolymer (I)
It is called.

Reference Example 2 (Production of epoxy group-containing olefin copolymer)
Ethylene-butene-1 copolymer (Tough 7-A 4090
), 0.5 part of dicumyl peroxide, and 2 parts of glycidyl methacrylate were uniformly mixed.

Next, the mixture was kneaded in a twin-screw extruder set at a cylinder temperature of 200° C., and pelletized 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 was ethylene-butene-
It was found that 1.25 parts of methacrylic acid glycidyl ether was grafted to 10 parts of the copolymer. This is called copolymer (II).

Examples 1 to 9 and Comparative Examples 1 to 4 GRILAMID ELY-60 (Nim, <-polyamide elastomer manufactured by Hemi Co., Ltd.), Diamid E41
TL (Daicel (membrane polyamide elastomer), Ge
onl 03EP (vinyl chloride resin manufactured by Nippon Zeon ■),
Geonl 03EP and 100 dioctyl phthalate
Plasticized vinyl chloride resin, copolymer (■), copolymer (■), Tafmer A4090, and Ba-Zn stabilizer mixed in advance at a ratio of 150i were mixed in proportions shown in Table 1.
7: Combine Q and press cylinder i degree ia using 40z extruder
.

The mixture was kneaded at ℃ to obtain a polyamide elastomer composition pellet. Using the pellets, test pieces were molded at 180° C. using a 6-ounce injection molding machine, and the following various tests were conducted. The results are shown in Table-1.

(11 Compatibility test: A test piece with a thickness of 3 mm was repeatedly held at the diffraction target 24 times to observe and evaluate the state of the crease.

O: No layer peeling ×: Layer peeling (21 Shore D hardness: according to ASTM D-2240).

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

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

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

(5) Heat aging resistance test: The tensile strength retention rate of a test piece left at 120° C. for 60 days is measured.

Claims (1)

[Claims] Polyamide elastomer (A) and vinyl chloride resin (B)
and the carboxyl group- and/or epoxy group-containing olefin copolymer (C), (A)/(B) = 95/5-4
0/60, (C)/{(A)+(B)}=1/100~
A polyamide elastomer composition characterized by being blended in a weight ratio of 100/100.