JPS60181160A - 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 anhydride group-containing compound, and a compound containing a hydroxyl group and/or amino group in a molten state. CONSTITUTION:(A) 100pts.wt. polyamide resin (e.g., nylon 11, etc.) and/or polyether amide elastomer is blended with (B) 0.1-150pts.wt., preferably 1-70pts.wt. compound (e.g., ethylene-propylene-maleic anhydride copolymer, etc.) containing an acid anhydride group or a reactive group derived from it in one molecule, and (C) 0.1-80pts.wt., preferably 1-50pts.wt. compound (e.g., partially or totally saponified polyvinyl acetate, hexamethylenediamine, etc.) containing two or more hydroxyl groups and/or amino groups in one molecule at 100-350 deg.C in a molten state.

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, but it has excellent impact resilience. While taking advantage of the characteristics of polyamide resins, they are not necessarily satisfactory in order to be used in a wider range of applications, as they have the disadvantage of low compressive strength or impact strength.

For example, polyamide resins such as nylon 6, nylon 66, and nylon 12 have excellent impact resilience, but have low impact strength, and if this is improved by blending rubber components, 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, the impact strength is not improved, and in some cases, there is a drawback that the impact resilience or impact strength is impaired.

As a result of intensive research in view of the above situation, the present inventors have found that when a polyamide resin, an acid anhydride group-containing compound, and a hydroxyl group- and/or amino group-containing compound are reacted, impact resilience, compressive strength, and impact strength are improved. It was discovered that an excellent polyamide resin composition can be obtained, and the present invention was completed.

That is, the present invention comprises (A) a polyamide resin and/or a polyether polyamide elastomer [hereinafter referred to as compound (A)];
B) A compound having one or more acid anhydride groups or instrumental groups composed of the acid anhydride group in one molecule [hereinafter referred to as compound (B)]; (C) A compound having one or more acid anhydride groups or instrumental groups composed of the same in one molecule; 211
The present invention provides a method for producing a polyamide resin composition, which comprises melt-mixing and reacting a compound having ^I or more [hereinafter referred to as compound (C)].

The present invention will be explained in detail below.

Compound (A) used as one of the raw materials in the present invention
Examples include various well-known polyamide resins and polyether polyamide elastomers.

The polyamide resin is composed 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 .Polymerization and condensation of diamines such as 4-cyclohexyldiamine and m-xylylenediamine; Polymerization of cyclic lactams such as caprolactam and laurolactam; Polycondensation of aminocarboxylic acids such as aminocarunic acid, aminononanoic acid and aminoundecanoic acid, or It is obtained by copolymerization of the above-mentioned cyclic lactam, dicarboxylic acid, and diamine.
Nylon, 610 nylon, 612 nylon, 11 nylon, 12 nylon, 66/610 copolymer nylon, 6
/66 copolymerized 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 n, β, a and b are integers of at least 2, preferably integers of 2 to 4, C is an integer of 2 to 30, m is O or an integer from 2 to 30, and R represents an amino group or a hydroxyl group.

For example, the general formula lhNiCI+2廿0((CI12hOsolutionC11z)r
N112 (wherein C is an integer of 2 to 30, preferably 6 to 30) bis-(3-aminopropyl)-polytetrahydrofuran, MeCl12h−Nl+2 (in the formula,
C is an integer of 2 to 30, preferably 6 to 30) bis-(3-aminopropyl)-polypropylene oxide, and the like. 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 following dicarboxylic acid, and it is desirable that the weight proportion of the polyether polyamide is 8 to 60% by weight. .

The dicarboxylic acids used in the polyether polyamide elastomer include dicarboxylic acids exemplified as raw materials for the polyamide, trimerized fatty acids having 36 carbon atoms, mixtures of polymerized fatty acids containing the trimerized fatty acids as a main component, -C112C112C112CF12C112C11
Examples include compounds represented by 2C112C00I+.

Particularly suitable polyamide resins include 11 nylon, 1
A particularly suitable polyether polyamide elastomer is Glylux ■^-300.
[Dainippon Ink & Chemicals Oi H4) is mentioned.

The compound (B) used in the present invention includes anhydrous pyromellit! L 3,3. ．． Examples include low molecular compounds such as 4.4-benzophenone tetracarboxylic anhydride and the following high molecular compounds.

Examples of polymer compounds include 1-olefins such as ethylene, propylene, butene-1, isobutyne, pentene-1,
1, hexene-1, decene-1,4-methylbutene-1
, 4-methylpentene-1,4,4-dimethylpentene-1, vinylcyclohexane, styrene, α-methylstyrene, etc., and 100 parts by weight of one or more of them, maleic anhydride, cis-4-cyclohexene-1 , 2-dicarboxylic anhydride, nadic anhydride, methyl nadic anhydride, 1-methyl-5-cyclohexene-2,3-dicarboxylic anhydride, dodecenylsuccinic anhydride, itaconic anhydride, etc. One or more monomers 0.01
~250 parts by weight, preferably.

is 0.1 to 200 parts by weight, random copolymerization, block copolymerization, graft-IN: polymerized copolymer, and dicarboxylic acids and monoesters derived from the acid anhydride group of the copolymer. , acid amides, and metal salts of dicarboxylic acids.

Specifically, ethylene-maleic anhydride copolymer, propylene-maleic anhydride copolymer, butene-1-maleic anhydride copolymer, isobutyne-maleic anhydride copolymer, styrene 7-fi water? L/infit-1'41
α-methylstyrene-maleic anhydride copolymer, ethylene-propylene-maleic anhydride copolymer, ethylene-propylene-nadic anhydride copolymer, ethylene-propylene-dodecenyl succinic anhydride copolymer, ethylene -Butene-1-maleic anhydride copolymer, ethylene-butene-1-nasic anhydride copolymer, ethylene-
Butene-1-dodecenyl succinic anhydride 1, ethylene-propylene-1-methyl-5-cyclohexene-2,
3-dicarboxylic anhydride copolymer, ethylene-butene-
1-Methyl-5-cyclohexene-2,3-dicarboxylic anhydride copolymer, ethylene-propylene-divinylnorbornene-maleic anhydride copolymer, ethylene-vinyl acetate-maleic anhydride copolymer, ethylene-acrylic Acid ester-maleic anhydride copolymer, vinyl acetate-maleic anhydride copolymer, acrylic ester-maleic anhydride copolymer, etc., and dicarboxylic acids and monomers derived from the acid anhydride groups of these copolymers. Examples include esters, acid amides, and metal salts of dicarboxylic acids. Two or more of these compounds may be used in combination.

Particularly preferred are ethylene-propylene-maleic anhydride copolymer, ethylene-butene-1-maleic anhydride copolymer, styrene-maleic anhydride copolymer, isobutyne-maleic anhydride copolymer, and ethylene-propylene Nadisocic anhydride copolymer, ethylene-butene-1
- nadic acid anhydride, pyromellitic anhydride.

Examples of the compound (C) used in the present invention include compounds having two or more hydroxyl groups or amino groups, compounds having one or more hydroxyl groups and one or more amino groups, and mixtures thereof. Compounds having two or more groups and mixtures thereof are preferred.

Examples of compounds having two or more hydroxyl groups include alkylene glycols such as ethylene glycol, butylene glycol, and hexanediol; polyoxyalkylene glycols such as polyethylene glycol and polybutylene glycol; partially or completely saponified polyvinyl acetate; Partially or completely saponified vinyl acetate copolymer; bisphenol A, bisphenol S1 hydroquinone, 4.
Adducts of bisphenols such as 4'-dihydroxybiphenyl and ethylene oxide; polymers containing 2-hydroxyethyl (meth)acrylate; methylolated triazines such as methylolated melamine; polyols such as trimethylolpropane and pentaerythritol. Can be mentioned. Two or more of these compounds may be used in combination.

Particularly preferred are partially or completely saponified polyvinyl acetate, partially or completely saponified ethylene-vinyl acetate copolymer, adduct of bisphenol A and ethylene oxide, and pentaerythritol. Compounds having two or more include ethylenediamine,
Alkylene diamines such as hexamethylene diamine, 1
．． 3-diaminocyclohexane, p,p'-diamino-
Alicyclic diamines such as dicyclohexylmethane, triazines containing amino groups such as melamine, o, m, p-phenylene diamine, 2,4-toluidine diamine, 4.4'
- Aromatic amines such as diaminodiphenyl ether, 3.3'-diaminophenyl sulfone, 3.3', 4.4'-tetraamino diphenyl sulfone, 3.3', 4.4'-tetraaminobenzophenone, etc. can be mentioned.

Two or more of these compounds may be used in combination.

Particularly preferred are hexamethylene diamine,
Melamine, phenylenediamine, 3.3', 4.4'-
It is tetraaminobenzophenone.

The ratio of compound (A), compound (B), and compound (C) used in the present invention is usually 0.1 to 150 parts by weight of compound (B) to 100 parts by weight of compound (A). Preferably 1 to 70 parts by weight, compound (C) usually 0.1 to 8 parts by weight
0 parts by weight, preferably 1 to 50 parts by weight. Compound(
If the proportion of B) or compound (C) used is less than 0.1 part by weight, no improvement in compressive strength or impact strength can be obtained;
In some cases, the impact resilience decreases, and compound (B)
If the amount exceeds 0 part by weight or if the amount of compound (C) exceeds 0 part by weight of IC), fluidity will be lost due to excessive crosslinking and gelation will occur, so these are not preferred.

In addition, in the production method of the present invention, the degree of crosslinking is adjusted by changing the ratio of compound (13) and compound (C) to compound <A), and the melt viscosity of the resulting polyamide resin composition is used. Another advantage is that it can be controlled arbitrarily depending on the purpose.

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.
5 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 any one of the three types of raw materials is 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) A method in which the above three types of raw materials are tri-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 one type of raw material, 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 carrying out the present invention, other thermoplastic resins or elastomers such as polyvinyl chloride, polyester, polyether polyester, urethanized polyester, ethylene/vinyl acetate copolymer, etc. may be used without departing from the purpose of the present invention. polyurethane, styrene elastomer,
It is also possible to use polybutadiene, vinyl chloride elastomer, acrylic polymer, polyimide, polyamideimide, polyphenylene sulfide, etc. 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, wA fibrous reinforcements such as silicon nitride, barium sulfate, calcium sulfate, kaolin, clay. , pyrophyllite, bentonite, sericite, zeolite,
Mica, mica, nephelinsinite, talc, aklepulgite, wollastonite, PMF, ferrite,
Calcium silicate, calcium carbonate, magnesium carbonate,
Dolomite, ammonium dioxide, zinc oxide, titanium oxide,
Magnesium oxide, iron oxide, molybdenum disulfide, graphite,
Mention may be made of reinforcing fillers such as gypsum, glass beads, glass powder, glass balloons, quartz, and quartz glass. In addition, plasticizers, mold release agents, coupling agents, colorants, lubricants, heat stabilizers, weather stabilizers, foaming agents, flame retardants,
Flame retardant aids such as antimony dioxide may also be added.

The composition of the present invention can be used for a variety of purposes due to its excellent properties, such as tubes, hoses, pipes, irons, films, sheets, electric wire coatings, wire coatings, optical fiber coatings, various brushes, fishing nets, Nets, true melt adhesives, conveyor belts, belts, soles of sports shoes for golf, baseball, soccer, track and field, ski boots, gears, cams, bearings, bearings, backings, gaskets, OIJ tank fasteners, valves, joints, etc. Grips, casters, rollers, switch cases, clips, watch bands, emblems, badminton shuttlecocks, tennis racket parts, gasoline tanks, bellows, floats, baseballs, fishing buoys, coats on the inside of tanks, helmets, protective equipment. , fasteners, power tools, various other automobile parts, electronic/electrical equipment parts, precision machinery parts, etc.In addition, 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) “Nosochii” Ishiso I-Impact strength ^STM D
Measured in January at -256.

Reference Example 1 (Production of acid-modified olefin copolymer) 100 parts of ethylene-butene-1 copolymer [Tafmer^4090, manufactured by Sangen Petrochemical Industry @1], 1,3-bis(tert)
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 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) Same as Reference Example 1 except that ethylene-propylene copolymer (Tafmer P04B, Mitsui Petrochemicals A111) was used instead of ethylene-butene-1 copolymer.
An acid-modified olefin copolymer (B-2) to which 0.83 parts of maleic anhydride was grafted was obtained.

Reference Example 3 (same as above) An acid modified product in which 1.5 parts of nadic acid anhydride was grafted in the same manner as in Reference Example 1 except that 2 parts of nadic acid anhydride was used instead of 1 part of maleic anhydride. An olefin copolymer (B-3) was obtained.

Reference Example 4 (same as above) Acid-modified olefin grafted with 3.6 parts of nadic acid anhydride in the same manner as in Reference Example 2 except that 5 parts of nadic acid anhydride was used instead of 1 part of maleic anhydride. Copolymer (
B-4) was obtained.

Examples 1 to 6 Grirax 8-300 [manufactured by Dainippon Ink & Chemicals ■,
polyether polyamide elastomer], acid-modified olefin copolymer (B-4), isopane-10 (manufactured by Gml Kuraray, isobutyne-maleic anhydride copolymer), GOHSENOL K11-20 (manufactured by Nippon Gosei Kagaku Kogyo Co., Ltd., polyamide), Partly saponified vinyl acetate, degree of saponification 78.5-81.5
[mol%] and pentaerythritol were charged into a flask with the composition shown in Table 1, heated to 250°C in a nitrogen gas atmosphere for 3 hours, and reacted with continuous stirring to create a high viscosity. A melt was obtained. This was taken out in the form of a strand in water, cooled and solidified, and then pelletized and dried at 100° C. for 1 hour to obtain pellets of polyamide resin and composition.

These pellets were injection molded, and the resulting test pieces were used to measure impact resilience, 1% deformation compressive strength, and notched isot impact strength. The results are shown in Table-1.

The test pieces obtained in Examples 1 to 6 were all excellent in impact resilience, compressive strength, and impact strength.

Comparative Example 1 Each physical property was measured in the same manner as in Example 1 using a test piece obtained by injection molding Glilux^-300. The results are shown in Table-1. Note that the obtained test piece had poor compressive strength.

Comparative Example 2 100 parts of Glylux^-300 and glass fiber (length 3
~5mm, diameter 12~13. um) mixed with 30 parts, 21 parts
Extrusion was performed using an extruder at 0° 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-1. Note that the obtained test piece has excellent compressive strength, but is inferior in impact resilience and impact strength.

Comparative Examples 3 to 4 Physical properties were measured in the same manner as in Example 1, except that raw materials selected from Glylux^-300, Isopan-10, and Gohsenol -20 were used in the formulations shown in Table-1. The results are shown in Table-1. The test piece obtained in Comparative Example 3 was inferior in repulsion (1ii) property and impact strength, and the test piece obtained in Comparative Example 4 was inferior in impact strength.

Examples 7 to 13 and Comparative Examples 5 to 8 GRILAMID L-20G (manufactured by EMS, Switzerland, 12 nylon), acid-modified olefin copolymer (B-1
), acid-modified olefin copolymer (B-3), SMA
-3000 (manufactured by ATOChimie, styrene-maleic anhydride copolymer), Isopan-10, GLM resin [
Completely saponified product of ethylene-vinyl acetate copolymer, manufactured by Nippon Gosei Kagaku Kogyo 01], di(2-hydroxyethyl) bisphenol A, glass fiber (length 3 to 6 mfi, diameter 12
~13 μm), Tubadol-5010 (manufactured by 7 Ryo Kasei QI, polybutylene terephthalate) were tri-blended with the composition shown in Table 2, and then heated in an extruder at 240°C (250°C in Comparative Example 5). The pellets of the polyamide resin composition were obtained by melt-mixing and reacting with the polyamide resin composition, and then each mixture was prepared in the same manner as in Example 1.

Physical properties were measured. The results are shown in Table-2. The test pieces obtained in Examples 7 to 13 were all excellent in impact resilience, compressive strength, and impact strength.

Example 14 Gl? 100 parts of ILAMID L-20G and 30 parts of acid-modified olefin copolymer (B-2) were triblended and extruded using an extruder at 240°C to pelletize.

Next, 100 parts of this pellet, 5 parts of phenylenediamine
Tri-blend 1 part, 10 parts of pyromellitic anhydride, 2 parts
After melt-mixing and reaction using an extruder at 40° C. to obtain a pellet of a polyamide resin composition, each physical property was measured in the same manner as in Example 1. The results are shown below. The obtained test piece had excellent impact resilience, compressive strength, and impact strength.

Impact modulus: 72% 1% deformation Compressive strength: 142 kg/ffl Notched Izotsu impact strength: 85 kg-cm/cI11 Agent Patent attorney Katsutoshi Takahashi Continued from page 1

Claims (1)

[Scope of Claims] (A) a polyamide resin and/or a polyether polyamide elastomer; (B) a compound having one or more acid anhydride groups or reactive groups derived therefrom in one molecule; C) A method for producing a polyamide resin composition, which comprises melt-mixing and reacting a compound having two or more hydroxyl groups and/or amino groups in one molecule.