JPS60181159A - Polyamide resin composition - Google Patents

Abstract

PURPOSE:The titled composition having excellent impact resistance in a structure with a notch shape and high rigidity, obtained by blending a polyamide resin with an acid-modified olefin polymer, a polyolefin resin, and a compound containing two or more epoxy groups in a specific ratio in a molten state. CONSTITUTION:(A) 35-85wt% polyamide resin (e.g., nylon 6, etc.) is blended with (B) 10-60wt% acid-modified olefin copolymer obtained by grating 0.1-2pts.wt. monomer containing one or more acid anhydride groups selected from citraconic anhydride, 3-methyl-4-cycloxane-1,2-dicarboxylic acid anhydride, maleic anhydride, etc. onto 100pts.wt. olefin copolymer (e.g., ethylene-butene-1 copolymer, etc.), (C) 5-35wt% olefin resin (e.g., polyethylene, etc.) in such a way that total amounts of the components A, B, and C are 100wt%, to give 100pts.wt. resin composition. 100pts.wt. resin composition is blended with 0.1- 20pts.wt. compound (e.g., bisphenol A) containing two or more epoxy groups.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a polyamide resin composition comprising a polyamide resin, an acid-modified olefin copolymer, a polyolefin resin, and a compound containing two or more epoxy groups.

More specifically, it is characterized by having a structure having a notch shape tW, which has remarkable impact resistance and high rigidity.

Polyamide resin has excellent toughness, abrasion resistance, chemical resistance, self-lubricating properties, and mechanical properties, so it is used in fields such as electrical parts, mechanical parts, automobile parts, general goods, textiles, films, sheets, and tubes. It is used in large quantities.

However, even these excellent properties are not necessarily satisfactory depending on the application, and further performance improvement is required in order to expand the application and improve the performance.

For example, although the impact resistance of polyamide resin is at a high level compared to other resins, it is well known that impact strength is significantly reduced especially in structures with notches. There is a strong market need for polyamide resins that provide excellent impact resistance even in shape-acoustic structures.

As a method of imparting excellent impact resistance even to a structure having a notch shape, there is a method of kneading a specific rubber-like substance such as a maleic anhydride-ethylene-propylene copolymer with a polyamide resin. Although the impact resistance is significantly improved, the use of a soft rubber-like material causes a significant decrease in rigidity, which limits its use as an engineering plastic material.

As a result of intensive research to improve the above drawbacks, the inventors of the present invention found that
By melt-mixing a polyamide resin, an acid-modified olefin copolymer, a polyolefin resin, and a compound having two or more epoxy groups, it has a notched structure with remarkable impact resistance and high rigidity. It was discovered that a certain polyamide resin composition could be obtained, and the present invention was completed.

That is, the present invention includes (a> 65 to 85% by weight of polyamide resin, and (b)
To 100 parts by weight of the olefin copolymer, one selected from citraconic anhydride, 6-methyl-4-cyclohexene-1,2-dicarboxylic anhydride, maleic anhydride, (methyl)nadic anhydride, and itaconic anhydride. 1 to 20 parts by weight of an acid-modified olefin copolymer obtained by combining 0.1 to 2.0 parts by weight of the above acid anhydride group-containing monomer with 1 graft;
(e) polyolefin resin 5 to 35% by weight, (a
), (b), (for 100 parts by weight of a resin composition compounded so that the total amount of el exceeds 100 parts by weight, 2 parts by weight)
The present invention provides a polyamide resin composition characterized by adding 0.1 to 20 parts by weight of a compound having at least 3 epoxy groups.

In the present invention, the polyamide resin used as one of the raw materials includes various well-known polyamide resins.

For example, dicarboxylic acids such as terephthalic acid, isophthalic acid, oxalic acid, adipic acid, sebacic acid, 1,4-cyclohexyldicarboxylic acid and ethylene? Polymerization and condensation of diamines such as amines, pentamethylene diamine, hexamethylene diamine, decamethylene diamine, 1,4-cyclohexyl diamine, m-xylylene diamine; Polymerization of cyclic lactams such as caprolactam and laurolactam; aminocarunic acid, aminononanoic acid, Those obtained by polycondensation of aminocarboxylic acids such as aminoundecanoic acid, or copolymerization of the above-mentioned cyclic lactams, dicarboxylic acids, and diamines, etc., nylon 6, nylon 66, nylon 610, nylon 612, 11+ , 12 nylon, 66/610 copolymerized nylon, and 6/66 copolymerized nylon, among which nylon 6, nylon 66, and nylon 12 are particularly preferred.

In the present invention, the acid-modified olefin copolymer added to improve the impact resistance of the polyamide resin includes at least 50 mol%, preferably 80 mol% of 1-olefins, such as evaporated ethylene, propylene, butene-1, Isobutyne, pentene-1, hexene-1, decene-1,4-methylpentene-L4-1 thylpentene-1,4,4-dimethylpentene-1, vinylcyclohexane, styrene,
It should contain all alpha-methylstyrene, styrene substituted with lower alkyl substituents, or the like. It is also possible to use mixtures of the abovementioned olefins. Preferably, copolymers obtained from ethylene and butene-1 or propylene are used.

As acid components, citraconic anhydride, 3-methyl-4-
Cyclohexene-1,2-dicarboxylic anhydride (hereinafter referred to as
(referred to as PMMA), maleic anhydride, (methyl) nadic anhydride, and itaconic anhydride, usually 0.1 to 2.0 parts by weight per 100 parts by weight of the polyolefin copolymer.
, i part, preferably rio, 2 to 1.5 parts by weight for graft polymerization.

Typical acid-modified olefin copolymers are illustrated below, but the invention is not limited thereto.

Ethylene-butene-1-maleic anhydride copolymer, ethylene-butene-1-(methyl)nadic anhydride copolymer, ethylene-butene-1-itaconic anhydride copolymer,
Ethishi-norbutene-1-citraconic anhydride copolymer,
Ethylene-'7''+7-17-1-P copolymer, ethylene-propylene-maleic anhydride copolymer, ethylene-
Propylene-(methyl)nadic anhydride, ethylene-
Propylene-itaconic anhydride copolymer, ethylene-propylene-citraconic anhydride copolymer, ethylene-propylene-PMMA copolymer, EPDM (ethylene-propylene-ethylidene norbornene)-maleic anhydride copolymer, EPDM-(methyl ) nadic acid anhydride, EPD
M-Itaconic anhydride-based polymerization EPDM-Citraconic anhydride copolymer, EPDM-PMMA copolymer, ethylene-butene-1-maleic anhydride relative-PMMA copolymer, ethylene-butene-1-(methyl)nasic Acid anhydride-P
MMA copolymer, ethylene-butene-1-itaconic anhydride-citraconic anhydride copolymer, ethylene-propylene-maleic anhydride 9-PMMA copolymer, ethylene-propylene-maleic anhydride-citraconic anhydride copolymer,
Ethylene nolobylene-itaconic anhydride-citraconic anhydride copolymer, ethylene-propylene-(methyl)nadic anhydride-itaconic anhydride copolymer, EPDM-maleic anhydride-PMMA copolymer, EPDM-citraconic anhydride Examples include acid-PMMA copolymer.

These acid-modified olefin copolymers can be obtained by known methods.

The polyolefin resin used in the present invention is generally a hydrocarbon resin, such as polyethylene, polybutadiene, polyisoprene, polyisobutylene, polybutylene, polystyrene, polymethylpentene, polypropylene, holiterbene resin, polybutene, EPDM, dicyclopentane resin, etc. Gene-based petroleum resin, ethylene-butadiene copolymer, ethylene-butene-1 copolymer, ethylene-
Examples include propylene copolymers. In particular, IC and polyethylene are preferred in the present invention.

The compound having two or more epoxy groups (hereinafter referred to as an epoxy compound) used in the present invention includes two or more epoxy groups in the molecule.
Any known epoxy group can be used as long as it contains 1 or more epoxy groups, but particularly preferred ones include bisphenol A rsorcinol, hydroquinone, pyrocatechol, bisphenol F, butadiene, 1,6.
5-trihydroxybenzene, bisphenol S,
From bisphenols such as 4-hydroxyphenyl)hexane, diglycidyl ethers of these halogenated bisphenols, butanediol, diglycidyl ethers of diethylene glycol, diglycidyl esters such as phthalic acid glycidyl esters, and novolac type phenolic resins. Examples include novolak-type epoxy resins. These epoxy compounds may be used alone or as a mixture of two or more.

Generally, epoxy compounds are molded by blending curing agents such as amines, acid anhydrides, polysulfides, and phenolic resins, but in the present invention, no curing agent is usually used. However, it may be used as long as the active hydrogen cap has a molar ratio of i to the epoxy group component or less.

(,) used to obtain the resin composition (A) in the present invention
polyamide resin, (b) acid-modified olefin copolymer and (C) poly. The proportion of olefin resin used is (a) polyamide resin 35, assuming that the total amount is 100% by weight.
-85% by weight, preferably 40-80if%, (b) 10-60% by weight of acid-modified olefin copolymer,
The content is preferably 15 to 40% by weight, (c) polyolefin resin 5 to 35% by weight, preferably 10 to 30% by weight.

The proportion of the acid-modified olefin copolymer used is 60% by weight.
If the ratio exceeds 55% by weight, compatibility will be insufficient and layer peeling will occur, which are both undesirable.

In addition, the amount of the epoxy compound added is 100% of the above resin composition.
It is usually in the range of 0.1 to 20 parts by weight, preferably 1 to 15 parts by weight, and if the amount added exceeds 20 parts by weight, the resulting polyamide resin composition will be extremely stiff. Since it has a melt viscosity and gels, moldability and processability are significantly reduced, and if it is less than 0.1 part by weight, the effects of the present invention cannot be obtained, so these are not preferred.

In addition, when carrying out the present invention, other thermoplastic resins or nitrogen gases 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.

In the present invention, inorganic and/or organic fillers are not essential, but rigidity etc. can be improved by using the following fillers as needed. Suitable fillers include glass fibers, carbon fibers, metal fibers, aramid fibers, potassium titanate, asbestos, silicon carbide, ceramic fibers, fibrous reinforcements such as silicon nitride, barium sulfate, calcium sulfate, kaolin, clay, Pyrophyllite, bentonite, sericite, zeolite, mica, mica, 7-erincinite, talc, atalpulgite, wollastonite, PMF, 7-erinite, calcium silicate, calcium carbonate, magnesium carbonate, dolomite, ammonium trioxide, Mention may be made of reinforcing fillers such as zinc oxide, titanium oxide, magnesium oxide, iron oxide, molybdenum disulfide, graphite, gypsum, glass beads, glass powder, glass balloon, quartz, and quartz glass. In addition, plasticizers, mold release agents, camping agents, coloring agents,
A lubricant, a heat stabilizer, a weather stabilizer, a foaming agent, a flame retardant, a flame retardant aid such as antimony trioxide, etc. may be added.

Due to its excellent properties, the composition of the present invention can be used in a variety of applications, including tubes, hoses, pipes, ronds, films, sheets, electrical coatings, wire coatings, optical fiber coatings, and various brushes. , fishing nets, nets, real melt contact agents, conveyor belts, belts, soles of sports shoes for golf, baseball, soccer, track and field, ski boots, gears, cams, bearings, bearings, backings, gaskets, rings, fasteners , pulp, joint, grip, caster, roller, switch case,
Clips, watch bands, emblems, badminton shuttlecocks, tennis racket parts, gas tanks,
Bellows, floats, ball games, fishing buoys, tank inner coats, helmets, agricultural protection equipment, fasteners, power tools, various other automobile parts, electronic/electrical equipment parts, precision machinery parts, and more. It can also be used as powder coating, solution type adhesive, paint, etc.

Next, the present invention will be explained in more detail with reference to Examples and Comparative Examples, but the present invention is not limited to these Examples. In addition, all the parts in the examples are heavy violet parts, and the test method evaluated was as follows.

(1) Izot impact strength In accordance with ASTM D-638, a notch was added to the test piece and the Izot impact strength was measured.

(2) Bending strength, bending modulus Measurement according to ASTM D-790.

(3) Tensile strength Measurement according to ASTM D-638.

Reference Example 1 (Manufacture of acid-modified olefin copolymer) Ethylene-butene-1 copolymer (Tough FF-A4090, manufactured by Mitsui Petrochemical Industries, Ltd. → 100 parts, 1,3-bis (TSRT)
0.5 part of benzene and 1 part of maleic anhydride were mixed uniformly. Next, the mixture was kneaded in an extruder set at a cylinder temperature of 280° C., and pelletized to obtain an acid-modified olefin copolymer (b-1).

When the amount of grafted maleic anhydride was measured using infrared spectroscopy, it was confirmed that 0.75 parts of maleic anhydride was grafted onto this product.

Reference Example 2 (same as above) The same procedure as in Reference Example 1 was used except that ethylene-propylene copolymer (Tafmer PO48, manufactured by Mitsui Petrochemical Industries #) was used instead of ethylene-butene-1 copolymer. Reference Example 3 (same as above) in which an acid-modified olefin copolymer (b-2) having 0.83 parts of maleic acid grafted was obtained. Reference Example 1 except that 0.3 part of acid anhydride was used.
In the same manner as above, an acid-modified olefin copolymer (b-3) having a total of 0.4 parts of maleic anhydride and nadic acid anhydride grafted thereon was obtained.

Reference Example 4 (same as above) The same procedure as Reference Example 2 was carried out except that nadic acid anhydride was used instead of maleic anhydride, and the concentration of nadic acid anhydride was 0.6.
Acid-modified olefin copolymer (b-,
i) was obtained.

Reference example 5 (same above).

An acid-modified olefin copolymer (b- 5) was obtained.

Reference Example 6 (same as above) Same as Reference Example 1 except that 0.2 parts of maleic anhydride and 4 parts of PMMAo were used in place of 1 part of maleic anhydride, but the total amount of maleic anhydride and PMMA was An acid-modified olefin copolymer (b-6'') grafted with 0.6 parts was obtained.

Reference example 7 (same as above) Citraconic anhydride 0 instead of maleic anhydride Dtf part
．． An acid-modified olefin copolymer (b-7) to which 0.4 parts of citraconic anhydride was grafted was obtained in the same manner as in Reference Example 2 except that 5 parts of the copolymer was used.

Examples 1 to 8 and Comparative Examples 1 to 8 66 nylon (Amilan CM-3001N manufactured by Toshi ■),
Acid-modified olefin copolymers (b) obtained in Reference Examples 1 to 5
-1.
type epoxy resin, epoxy equivalent weight 1750-2100, melting point 122-131°C], Ebicuron N-588 (phenol novolac type epoxy resin manufactured by the company, epoxy equivalent 12
00-280, melting point 80-95℃), Epicron 305
0 (bisphenol A type epoxy resin manufactured by the same company, epoxy equivalent 730-830, melting point 94-102°C) and Evicron 760 [polyol ether type epoxy resin manufactured by the same company, epoxy equivalent 150-180, viscosity (25°C) 10
0~500. A polyamide resin (composition) pellet was prepared by tri-blending the raw materials selected from (cps) with the blending composition shown in Table 1 and extruding it at 280°C using a single screw extruder.

These pellets were injection molded, and the resulting test pieces were used to measure Izod impact strength, tensile strength, bending strength, and bending modulus in an absolutely dry state. The results are shown in Table-1.

The test pieces obtained in Examples 1 to 8 all had high impact resistance and rigidity.

Examples 9 to 11 and Comparative Examples 9 to 14
-28), acid-modified olefin copolymer (BS)s high-density polyethylene obtained in Reference Example 6 (Chubu Polyethylene 2000 manufactured by Shindaikyowa Petrochemical Co., Ltd.), Evicron 1400
(Polyhydric carboxylic acid ester type epoxy resin manufactured by Inu Nippon Ink Chemical Industry ■, epoxy equivalent 580-700) Table 2
Tri-blend the composition shown in , and extrude using a uniaxial extruder at 280°C to obtain a polyamide resin (composition).
Peretz) f was created.

These pellets were injection molded, and the resulting test pieces were used to measure Izot impact strength, tensile strength, bending strength, and bending modulus in an absolutely dry state. The results are shown in Table-2.

The test pieces obtained in Examples 9 to 11 all had high impact resistance and rigidity.

Examples 12 to 16 and Comparative Examples 14 to 1712 Nylon (Ms s cgxLAMr, Switzerland).

L-20G), acid-modified olefin copolymers (b-6) and (b 7)% high-density polyethylene obtained in Reference Examples 6 and 7 (Chubu Polyethylene 2 manufactured by Shinkyowa Petrochemical ■)
000), 2 and ethylene glycol diglycidyl ether were triblended with the composition shown in Table 6, and 2
Extrusion was performed using a single screw extruder at 40°C to create a polyamide resin composition pellet.

Using a test piece obtained by injection molding,
Izot impact strength, tensile strength, bending strength and elastic modulus in an absolutely dry state were measured. The results are shown in Table-6.

In addition, all the test pieces obtained in Examples 12 to 16 had high impact resistance and rigidity.

Claims (1)

[Claims] (a) 35-85% by weight of polyamide resin; (b)
To 100 parts by weight of the olefin copolymer, one selected from citraconic anhydride, 6-methyl-4-cyclohexene-1,2-dicarboxylic anhydride, maleic anhydride, (methyl)nadic anhydride, and itaconic anhydride. 1 to 20 parts by weight of an acid-modified olefin copolymer obtained by graft polymerizing 0.1 to 2.0 parts by weight of the above acid anhydride group-containing monomer;
c) 5 to 35 weight polyolefin resin (ag
, (b), and (C) in a total amount of 100% by weight, 0.1 to 0.1 to 100 parts by weight of a compound (6) having two or more epoxy groups to 100 parts by weight of the resin composition. A polyamide resin composition, characterized in that it is made by adding 20 parts by weight and melt-mixing.