JPS60181161A - Preparation of polyamide resin composition - Google Patents

Abstract

PURPOSE:The titled composition having improved impact resilience, compression strength and impact strength, obtained by blending a polyamide resin with an acid-modified polyolefin and an epoxy compound in a specific ratio in a molten state, reacting them. CONSTITUTION:(A) A polyamide resin (e.g., nylon 11, etc.) and/or polyether polyamide elastomer is blended with (B) an acid-modified polyolefin (e.g., ethylene- butene-1-maleic acid (anhydride) copolymer, etc.) containing >=50mol% 1-olefin, (C) an epoxy compound (e.g., bisphenol, etc.) in a reactor or an extruder at 100- 350 deg.C in a molten state, and reacted. A blending ratio of the component A/B by weight is 20/80-95/5, preferably 50/50-90/10, and a blending ratio of the component C/(A+B) is 0.1/100-20/100, preferably 1/100-15/100.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for producing a polyamide resin composition having excellent impact resilience, compressive strength and impact strength.

Polyamide resin (composition) has excellent mechanical properties, electrical properties, chemical resistance, processability, etc., so it is used in many fields such as fibers, films, and molded products. While taking advantage of the excellent properties of polyamide resins, they have the disadvantage of low compressive strength or impact strength, which is not necessarily satisfactory in order to use them in a wider range of applications.

For example, polyamide resins such as nylon 6, nylon 66, and nylon 12 have excellent impact resilience, but have the disadvantage of low impact strength, and if this is improved by blending a rubber component or the like, the compressive strength will decrease. Furthermore, although polyether polyamide elastomer has excellent rebound resilience and impact strength, it has the drawback of extremely low compressive strength. Furthermore, there are polyamide resin compositions that have improved compressive strength by blending polymeric compounds with high compressive strength, such as polybutylene terephthalate, polyphenylene sulfide, polystyrene, etc., and inorganic fillers, such as glass fiber, talc, calcium carbonate, etc. However, impact strength has not been improved, and in some cases, there is a drawback that rebound resilience or impact strength is impaired.

As a result of intensive research in view of the above situation, the present inventors have found that by reacting a polyamide resin, an acid-modified polyolefin, and an epoxy compound, a polyamide resin composition having excellent rebound resilience, compressive strength, and impact strength can be obtained. They discovered this and completed the present invention.

That is, the present invention provides a polyamide resin composition characterized in that (A) a polyamide resin and/or a polyether polyamide elastomer, (B) an acid-modified polyolefin, and (C) an epoxy compound are melt-mixed and reacted. It provides a manufacturing method.

The present invention will be explained in detail below.

Various well-known polyamide resins and polyether polyamide elastomers can be used as one of the raw materials in the present invention.

The polyamide resin is made of a dicarboxylic acid such as terephthalic acid, isophthalic acid, oxalic acid, adipic acid, sebacic acid, 1,4-cyclohexyldicarboxylic acid, and ethylenediamine, pentamethylenediamine, hexamethylenediamine, decamethylenediamine, 1,4-cyclohexyldicarboxylic acid, etc. - Polymerization and condensation of diamines such as cyclohexyldiamine and m-xylylene diamine; Polymerization of cyclic lactams such as caprolactam and laurolactam; Polycondensation of aminocarboxylic acids such as aminocarunic acid, aminononanoic acid and aminoundecanoic acid, or the above cyclic lactams. It is obtained by copolymerization of dicarboxylic acid and diamine, etc.
Examples include nylon, 610 nylon, 6I2 nylon, 11 nylon, 12-7-yen, 66/610 copolymer nylon, 6/66 copolymer nylon, and the like.

Moreover, the polyether polyamide elastomer is a block copolymer having a hard segment made of the above-mentioned polyamide and a soft segment made of a polyether component.

The polyether component, which is a soft segment, has the general formula % as a starting material, where nSβ, a and b are integers of at least 2, preferably integers of 2 to 4, C is an integer of 2 to 30, and m is an integer of 2 to 30. 0 or an integer from 2 to 30, and R represents an amino group or a hydroxyl group) is used.

For example, the general formula u, N-ec++2rof'' (CI+25703pCI
I2h-Nll? (wherein C is an integer of 2 to 30, preferably 6 to 30) bis-(3-aminopropyl)-polytetrahydrofuran, 11, N-cCII
2h- is (C112+r's j C112k N"2"
In the formula, C is an integer of 2 to 30, preferably 6 to 30). Furthermore, polyether glycols such as polyoxypropylene glycol and polyoxytetramethylene glycol can also be used as the polyether component.

Such a polyether polyamide elastomer is usually produced by a condensation reaction between the polyamide component-forming compound, the polyether component-forming compound, and the dicarboxylic acid described below, and preferably has a polyether block weight ratio of 8 to 60% by weight.

The dicarboxylic acids used in the polyether polyamide elastomer include the dicarboxylic acids exemplified as the raw materials for the polyamide, trimerized fatty acids having 36 carbon atoms, mixtures of polymerized fatty acids containing the trimerized fatty acids as the main component, -C112C112C112Cl12 Cl12 C
Examples include a compound represented by t12CI+2!0011.

Particularly suitable polyamide resins include 11 nylon, 1
Particularly suitable polyether polyamide elastomers include Glylux ■-300
(manufactured by Dainippon Ink & Chemicals 0@).

The f''lZ-modified polyolefin (B) used in the present invention contains at least 50 mol%, preferably 80 mol% of 1-olefins, such as ethylene, propylene, butene-11
Isobutyne, pentene-1, hexene-1, decene-1
,4-methylbutene-14-methylpentene-1,4,
It should contain 4-dimethylpenlane-1, vinylcyclohexane, styrene, alpha-methylstyrene, styrene substituted with lower alkyl substituents or the like. A mixture of the above olefins can also be used. Among these, copolymers obtained from ethylene and butene-1 or propylene are preferred.

The acid component is introduced by a known method such as direct copolymerization of an α,β-unsaturated carboxylic acid comonomer with the above-mentioned olefin or graft copolymerization with a polyolefin or polyolefin copolymer. Examples of the acid component include acrylic acid, methacrylic acid, methacrylic acid, itaconic acid, (anhydrous) maleic acid, fumaric acid, and monoesters of carboxylic acids listed in 1. Suitable examples include acrylic acid, methacrylic acid and (anhydrous) maleic acid. Maleic acid (anhydride) is particularly preferred.

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

Ethylene-acrylic acid copolymer, ethylene-methacrylic acid copolymer, ethylene-itaconic acid copolymer, ethylene-methyl hydrogen maleate copolymer, ethylene-acrylic acid-methyl methacrylate copolymer, ethylene-methacrylic acid -Ethyl acrylate copolymer, ethylene-methacrylic acid-vinyl acetate copolymer, ethylene-acrylic acid-vinyl acetate copolymer, ethylene-acrylic acid, vinyl alcohol copolymer, ethylene-methyl vinyl ether acrylic acid copolymer , ethylene-propylene-acrylic acid copolymer, ethylene-styrene-acrylic acid copolymer, ethylene-methacrylic acid-acrylonitrile copolymer, ethylene-fumaric acid-methylhinyl ether copolymer, ethylene-vinyl chloride-acrylic acid Copolymer, ethylene-vinylidene chloride-acrylic acid copolymer, ethylene-vinyl fluoride-methacrylic acid copolymer, ethylene-chlorotrifluoroethylene-methacrylic acid copolymer, chlorinated ethylene-methacrylic acid copolymer, ethylene -Butene-1
-Methacrylic acid copolymer, ethylene-butene-1-(anhydride)maleic acid copolymer, ethylene-propylene-(anhydride)maleic acid copolymer, propylene-acrylic acid copolymer, butene-1-acrylic acid copolymer Polymer, ethylene-isobutylene-acrylic acid copolymer, 3-methylbutene-
1-acrylic acid copolymer, 4-methy, lupentene-1-
Methacrylic acid copolymer, 4,4'-dimethylpentene-
1-acrylic acid copolymer, propylene-undecacrylic Fit copolymer, propylene-α-methyl-styrene-(anhydride)maleic acid copolymer, propylene-butene-
Co-fumaric acid, ethylene-vinylcyclohexane-
Acrylic acid copolymers, chlorinated ethylene-acrylic acid copolymers and the like.

Suitable examples include ethylene-butene-1-(anhydride)maleic acid copolymer, ethylene-propylene-(anhydride)maleic acid copolymer, and ethylene-vinyl acetate-(meth)acrylic acid copolymer. .

It is important that such acid-modified polyolefin contains monomers having acidic groups in an amount of 0.01 to 20% by weight, preferably 0.05 to 10% by weight.
It is.

The epoxy compound used in the present invention has 1 in the molecule.
All compounds containing one or more epoxy groups can be used, but particularly preferred are bisphenol A
Lusorcinol, hydroquinone, pyrocatechol, bisphenol F1 saligenin, 1,3.5-)lihydroxyben-t;, hisphenol S,)rihydroxydiphenyldimethylmethane, 4.4'-dihydroxybiphenyl, 1゜5- Bisphenols such as dihydroxynaphthalene, cashew phenol, 2゜2.5.5-tetrakis(4-hydroxyphenyl)hexane, diglycidyl ether of these halogenated bisphenols, butanediol, diglycidyl ether of diethylene glycol, phthalic acid Examples include diglycidyl esters such as glycidyl esters, and novolak-type epoxy resins derived from novolak-type phenol 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 normally used. However, if the amount of active hydrogen is equal to or less than the epoxy group component, it may be used.

The ratio of (A) polyamide resin and/or polyether polyamide CB) used in the present invention to acid-modified polyolefin is usually (A) / (B) = 2 in weight ratio.
0/80-9515, preferably 50150-90/
If the ratio of the acid-modified polyolefin (B) used is less than 5% by weight, no impact strength improvement effect can be obtained, and if it exceeds 80% by weight, the properties as a polyamide will be lost, so these are not preferred.

In addition, the ratio of the (C,) epoxy compound used is usually (C) / + (A) + (B) ) - 0,1/1 by weight.
00-20/100, preferably 1/100-15/
100, and the usage rate is 0.1/100
If it is less than 20/10, the effect of improving compressive strength or impact strength cannot be obtained, and in some cases, impact resilience may decrease.
When it exceeds 0, the resulting polyamide resin composition has an extremely high melt viscosity and gels, resulting in a significant drop in moldability and processability, which is not preferable.

The method for producing a polyamide resin composition in the present invention involves heating each raw material at 100 to 350°C in a reaction pot or extruder.
Preferably, a method of melt-mixing and reacting at a temperature of 150 to 300° C. is employed. At this time, solvents such as toluene and xylene may be used if necessary.

On the other hand, in the present invention, the method for charging the three types of raw materials into the reaction vessel is as follows: (1) A method in which the three types of raw materials are charged into the reaction vessel, heated and melted, and reacted.

(2) A method in which two of the three types of raw materials are charged into a reaction vessel, heated and melted, and then the remaining one type of raw material is added at any stage of the manufacturing process and reacted.

(2) A method in which arbitrary L types of raw materials among the three types of raw materials are charged into a reaction vessel, heated and melted, and then the remaining two types of raw materials are sequentially added in random order at any stage of the manufacturing process and reacted.

(2) A method may be mentioned in which a composition consisting of any two of the above three types of raw materials is charged into a reaction vessel, heated and melted, and the remaining one type is added at an arbitrary step during the manufacturing process.

Also, the method using an extruder is as follows: (1) The above three types of raw materials are dry blended, and this mixture is melt-mixed and reacted using an extruder, and then extruded.

(2) A method of tri-blending a composition consisting of any two of the three types of raw materials and the remaining 1 ff (type of raw materials), and extruding this mixture by melt-mixing and reacting using an extruder.

etc. Among these, a method using an extruder is preferred in terms of productivity.

In addition, when carrying out the present invention, other thermoplastic resins or elastomers, 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 original I! Although inorganic and/or organic fillers are not essential for Il', rigidity etc. can be improved by using the following fillers as necessary. Suitable fillers include glass fiber, carbon fiber, metal fiber,
Aramid fibers, potassium titanate, asbestos, silicon carbide, ceramic U-fibers, fibrous reinforcing agents such as silicon nitride, barium sulfate, calcium sulfate, kaolin, clay, pyrophyllite, bentonite, sericite, zeolite, mica, mica , neferincinite, talc,
Aklepulgite, wollastonite, PMF, ferrite, calcium silicate, calcium carbonate, magnesium carbonate, dolomite, ammonium trioxide, zinc oxide, titanium oxide, magnesium oxide, iron oxide, molybdenum disulfide, graphite, gypsum, glass beads, Mention may be made of reinforcing fillers such as glass powder, glass balloons, quartz, and quartz glass. In addition, plasticizers, mold release agents, cambling agents, colorants, lubricants, heat stabilizers, weather stabilizers, foaming agents,
Flame retardants, flame retardant aids such as antimony dioxide, etc. may be added.

The composition of the present invention can be used for various purposes due to its excellent properties, such as tubes, bosses, pipes, rondos, films, sheets, electric wire coatings, wire coatings, optical fiber coatings, various brushes, fishing nets, Nets, hot melt adhesives, conveyor belts, belts, soles of sports shoes for golf, baseball, soccer, track and field, etc., ski boots, gears, cams, bearings, bearings, backings, gaskets, 01J 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, coats on the inside of tanks, helmets, protective gear. products, fasteners, power tools, various other automobile parts, electronic/electrical equipment parts, precision machinery parts, etc., as well as powder coatings,
It can also be used as a solution type adhesive, paint, etc.

Next, the present invention will be explained in more detail with reference to reference examples, working examples, and comparative examples, but the present invention is not limited to these examples. All parts in the examples are parts by weight, and the test method used for evaluation is as follows.

(11 rebound modulus Measured in accordance with JIS K-6301.

(2) 1% deformation compressive strength Measured in accordance with 8 STM D-695.

(3) Notched Izotsu impact strength Measured in accordance with ASTM D-256.

Reference Example 1 (Production of acid-modified polyolefin) Ethylene-
100 parts of butene-1 copolymer [Tafmer A4090, manufactured by Mitsui Petrochemical Industries @Cabi), 0.5 part of 1,3-bis(tert-butylperoxypropyl)benzene, and 1 part of maleic anhydride were uniformly mixed. Next, cylinder temperature 2
The mixture was kneaded in an extruder set at 80°C and pelletized to obtain acid-modified polyolefin (B-1). When the amount of maleic anhydride grafted onto this product was measured using an infrared spectrum, it was confirmed that 0.75 parts of maleic anhydride was grafted.

Reference Example 2 (same as above) Maleic anhydride An acid-modified polyolefin (B-2) having 0.83 parts of grafted was obtained.

Examples 1 to 5 and Comparative Examples 1 to 4 Glilux A-300 (manufactured by Dainippon Ink & Chemicals Co., Ltd.,
polyether polyamide elastomer), acid-modified polyolefin (B-2), Ebifront 588 [manufactured by Dainippon Ink & Chemicals @, glycidyl ether of novolac type phenolic resin], glass fiber (length 3 to 6 yen - 1 diameter 1
A pellet of a polyamide resin composition was obtained by tri-blending raw materials selected from 2 to 13 μm) with the blending composition shown in Table 1, and melt-mixing (reacting) using an extruder at 210°C.

These pellets were injection molded, and the resulting test pieces were used to measure impact resilience, 1% deformation compressive strength, and notched isocution impact strength. The results are shown in Table-1. still,
The test pieces obtained in Examples 1 to 5 were all excellent in impact resilience, compressive strength, and impact strength.

Examples 6 to 9 and Comparative Examples 5 to 8 GRILAMID L-20G (manufactured by EMS, Switzerland, 12 nylon), acid-modified polyolefin (B-1),
A tri-blend of raw materials selected from Epiclon 7050 (manufactured by Dainippon Ink & Chemicals, bisphenol glycidyl ether) and glass fiber (length 3 to 6 fi, diameter 12 to 13.pm) is shown in Table 2, 240℃
A pellet of a polyamide resin composition was obtained by melt-mixing and reaction using an extruder, and then each physical property was measured in the same manner as in Example 1. The results are shown in Table-2. The test pieces obtained in Examples 6 to 9 were all excellent in impact resilience, compressive strength, and single-part impact strength.

Example 1O 80 parts of GR L-20G and 20 parts of acid-modified polyolefin (B-1) were extruded using an extruder at 240°C and pelletized. 100 parts of this pellet and 505 parts of Epiclon 70 were triblended, melt-mixed, reacted and extruded using an extruder at 240°C to obtain a pellet of polyamide resin composition, and then each physical property was measured in the same manner as in Example 1. . The results are shown in Table-2. Note that the obtained test piece had excellent impact resilience, compressive strength, and impact strength.

Example 11 Dilsun BMNO (manufactured by Toshi C41, 11 nylon) 6
5 parts, Dexon XEA-4 (Esso Corporation, ethylene-vinyl acetate-acrylic acid copolymer) 35 parts, Evicron 7
30 (Dainippon Ink Chemical Co., Ltd. OIOg, glycidyl ether) was charged into a flask, and the mixture was melted and stirred for 1 hour at 220° C. in a nitrogen gas atmosphere to obtain a highly viscous melt. This was taken out in strands in water, cooled and solidified, and then pelletized and heated to 100°C for 1
After drying for a period of time, pellets of the polyamide resin composition were obtained.

Next, each physical property was measured in the same manner as in Example 1 using this pellet. The results are shown in Table-3. In addition, the obtained test pieces had impact resilience, compressive strength, and town! It was excellent in f1 strength.

Comparative Example 9 Each physical property was measured in the same manner as in Example 1 using a test piece obtained by injection molding Dilsan [ll'lNO. The results are shown in Table 3. 1'1~), the resulting test piece had poor impact strength.

Comparative Example IO 65 parts of Dirsan IIMNO and Dexon XIE^-43
5 parts were mixed and extruded using an extruder at 240°C to obtain pellets, and each physical property was measured in the same manner as in Example 1 using the pellets. The results are shown in Table-3. Note that the obtained test piece had poor compressive strength.

Comparative Example 11 Dilsan! jMN070 parts and glass fiber (length 3-6
12 to 13 μm in diameter) were mixed and extruded using an extruder at 240° C. to obtain pellets, and each physical property was measured in the same manner as in Example 1 using the pellets. The results are shown in Table-3. The obtained test piece had excellent compressive strength, but was inferior in impact resilience and impact strength.

Claims (1)

[Claims] A polyamide resin composition characterized by melt-mixing and reacting (A) a polyamide resin and/or a polyether polyamide elastomer, (B) an acid-modified polyolefin, and (C) an epoxy compound. manufacturing method.