JPH0618995B2 - Resin composition - Google Patents

Description

TECHNICAL FIELD The present invention relates to a resin composition useful as a constituent material for various automobile parts, mechanical parts, electric or electronic parts and general sundries.

[Prior Art] Thermoplastic polyesters represented by polyethylene terephthalate and polybutylene terephthalate have excellent mechanical properties, particularly high rigidity and strength, and are widely used as excellent engineering plastics. On the other hand, polyamides such as polycaproamide and polyhexamethylene adipamide have been utilized as important materials in the field of molded articles having different polyester applications by taking advantage of their excellent toughness, abrasion resistance and chemical resistance.

Conventionally, it has been attempted to combine the above polyester and polyamide to utilize the excellent properties of each and to alleviate the problems of each. For example, JP-B-47-19101, JP-B-47-24465, and JP-A-48-56.
No. 742, JP-A-49-114661, JP-A-56-34754, JP-A-57-49657 and the like, the composition of the polyester and polyamide is changed according to the purpose, and additives are added. As a related art, there is disclosed a technique in which a problem when a polyester and a polyamide are combined is improved by using a fibrous reinforcing material and an inorganic filler together.

[Problems to be Solved by the Invention] When a polyester and a polyamide are mixed, usually,
Although the melt-kneading method is applied, since the polyester and the polyamide have poor compatibility, a uniform kneaded product cannot be obtained, and as a result, the mechanical properties of the molded product obtained from the kneaded product are satisfactory. Not a thing. In particular, there is a problem that impact strength and tensile strength are low. Further, since the polyester, which is a constituent of the kneaded product, causes a decrease in the molecular weight due to hydrolysis, there is a problem that the mechanical properties deteriorate when the molded product is immersed in hot water for a long time. Therefore, such problems prevent application of the constituent material in which polyester and polyamide are combined to various fields.

The present invention eliminates such problems, the constituent components including polyester and polyamide can be kneaded so as to be uniform, the molded product obtained from the kneaded product does not vary,
An object of the present invention is to provide a resin composition having excellent mechanical properties and having excellent hydrolysis resistance that does not change in mechanical properties even after being immersed in hot water for a long time.

[Means and Actions for Solving Problems] As a result of studies to achieve the above object, the present inventors have found that a mixture of polyamide and polyester in which the concentration ratio of the terminal amino group to the terminal carboxyl group is a specific ratio. In addition, the molded product obtained from a composition further containing a specific grafted polyolefin has not only a dense and homogeneous structure, but also excellent hydrolysis resistance in hot water. The present invention has been completed and the present invention has been completed.

That is, in the present invention, (a) 5 to 95% by weight of polyamide having a concentration ratio of terminal amino groups to terminal carboxyl groups of 1.5 or more, (b) thermoplastic polyesters 95 to 5
100 parts by weight of a mixture of 100% by weight and (c) a modified polyolefin having a functional group in the molecular chain, which is graft-polymerized with an addition polymer having a peroxide bond in the molecular chain. It relates to a resin composition comprising 5 to 35 parts by weight.

The component (a) polyamide used in the present invention has It contains a bond as a repeating unit and has a concentration ratio of terminal amino groups to terminal carboxyl groups of 1.5 or more, preferably 2.0 or more.

Among the monomers used as the raw material for producing the polyamide of the component (a), examples of amino acids include 6-aminocaproic acid, 11-aminoundecanoic acid, 12-aminododecanoic acid, and paraaminomethylbenzoic acid; lactams. Examples of the diamino include ε-caprolactam and ω-laurolactam; examples of the diamino include tetramethylenediamine, hexamethylenediamine, undecamethylenediamine, dodecamethylenediamine, 2,2,4- /. 2, -Methylnonamethylenediamine, metaxylylenediamine, paraxylylenediamine, 1,3-su (aminomethyl) cyclohexane, 1,4-bis (aminomethyl) cyclohexane, 1-amino-3-aminomethyl-3 , 5,5-trimethylcyclohexane, bi (4-aminocyclohexyl) methane, bis (3-methyl-4-aminocyclohexyl) methane, 2,2-bis (4-aminocyclohexyl) propane, bis (aminopropyl) piperazine, aminoethylpiperazine and the like can be mentioned. . Examples of the dicarboxylic acid include adipic acid, suberic acid, azelaic acid, sebacic acid, dodecanenic acid, terephthalic acid, isophthalic acid, 2-chloroterephthalic acid,
2-methylterephthalic acid, 5-methylisophthalic acid, 5
-Sodium sulfoisophthalic acid, hexahydroterephthalic acid, hexahydroisophthalic acid, diglycolic acid, etc. may be mentioned.

Preferred polyamides as the component (a) of the present invention include, for example, polycaproamide (nylon 6), polyhexamethylene adipamide (nylon 6,6), polyhexamethylene sepacamide (nylon 6,10), polyundeca. Examples include methylene adipamide (nylon 11,6), polyhexamethylene dodecamide (nylon 6,12), polyundecane amide (nylon 11), polydodecane amide (nylon 12), and copolyamides and mixed polyamides thereof. be able to.

The polyamide as the component (a) is preferably one in which the relative viscosity at 25 ° C. of a solution prepared by dissolving the polyamide in concentrated sulfuric acid to a concentration of 1% is in the range of 2.0 to 5.0.

The polyamide (a) used in the present invention, which has a molar concentration ratio of terminal amino groups to terminal carboxy groups of 1.5 or more, is known, and a lactam or a nylon salt that is a monomer for forming polyamide has 6 to 6 carbon atoms. By adding and polymerizing 22 monoamines or diamines having 2 to 22 carbon atoms, the above molar concentration ratio can be arbitrarily controlled for production. On the other hand, the above-mentioned polyamide having a molar concentration ratio of less than 1 is obtained by adding a monocarboxylic acid or a dicarboxylic acid and polymerizing.

Examples of the monoamine having 6 to 22 carbon atoms include hexylamine, heptylamine, octylamine, 2-ethylhexylamine, nonylamine, decylamine, undecylamine, dodecylamine, tridecylamine, tetradecylamine, and ocdecylamine. Alicyclic monoamines such as cyclohexylamine and methylcyclohexylamine; aromatic monoamines such as benzylamine. Examples of the diamine having 2 to 22 carbon atoms include ethylenediamine, trimethylenediamine, tetramethylenediamine, pentamethylenediamine, hexamethylenediamine, heptamethylenediamine, octamethylenediamine, nonamethylenediamine, decamethylenediamine, undecamethylenediamine. And aliphatic diamines such as dodecamethylenediamine; alicyclic diamines such as cyclohexanediamine and methylcyclohexanediamine; aromatic diamines such as xylylenediamine. The polymerization method is not particularly limited, and either normal pressure polymerization method or reduced pressure polymerization method can be applied.

The thermoplastic polyester as the component (b) used in the present invention is a polymer obtained by a condensation reaction in which a dicarboxylic acid or an ester-forming derivative thereof and a diol or an ester-forming derivative thereof are main components.

Examples of the dicarboxylic acid used here include terephthalic acid, isophthalic acid, orthophthalic acid, 2,6-naphthalenedicarboxylic acid, 1,5-naphthalenedicarboxylic acid, bisbenzoic acid, bis (p-carboxyphenyl) metal,
Anthracene dicarboxylic acid, 4,4'-diphenyl ether dicarboxylic acid, 4,4'-diphenoxyethane dicarboxylic acid, adipic acid, sebacic acid, azelaic acid, dodecanedioic acid, 1,3-cyclohexanedicarboxylic acid,
Mention may be made of 1,4-cyclohexanedicarboxylic acid or an ester-forming derivative thereof alone or in a mixture. As the diol component, ethylene glycol,
Propylene glycol, 1,4-butanediol, neopentyl glycol, 1,5-pentanediol, 1,
Examples thereof include 6-hexanediol, decamethylene glycol, cyclohexanedimethanol, cyclohexanediol, long-chain glycol having a molecular weight of 400 to 6,000, that is, polyethylene glycol, polypropylene glycol, polytetramethylene glycol, and mixtures thereof.

Examples of the thermoplastic polyester as the component (b) include, for example,
Polyethylene terephthalate, polyethylene naphthalate, polypropylene terephthalate, polybutylene terephthalate, polyhexamethylene terephthalate, polycyclohexane dimethylene terephthalate, poly (ethylene terephthalate / ethylene isophthalate) copolymer, poly (butylene terephthalate / butylene decadedioate) copolymer Examples thereof include coalescing, and particularly useful in the present invention are polyethylene terephthalate and polybutylene terephthalate.

The thermoplastic polyester as the component (b) is preferably one having a relative viscosity at 25 ° C. of 1.15 to 2.5 at 25 ° C., which is obtained by dissolving 0.5% of it in orthochlorophenol. Those of 0.3 to 2.1 are more preferable.

The grafted polyolefin modified product of the component (c) used in the present invention can be obtained by graft polymerizing an addition polymer having a peroxide bond in the molecular chain with a modified polyolefin having a functional group in the molecular chain. The component (c) is a component that contributes to compatibilizing the polyamide of the component (a) and the thermoplastic polyester of the component (b).

The modified polyolefin having a functional group in the molecular chain (hereinafter, simply referred to as “modified polyolefin”), which is one of the raw materials for producing the component (c), is ethylene and an α-olefin having 3 to 20 carbon atoms or a diene such as propylene. , Butene-1, pentene-1, 4-methylpentene-1, isobutylene, 1,4-hexadiene, dicyclopentadiene, 2,5-norbornadiene, 5-ethyl-2,5-
Norbornadiene, 5-ethylidene norbornene, 5-
In a polyolefin obtained by using (1'-propenyl) -2-norbornene, butadiene, isoprene and the like as a main monomer component, a carboxylic acid group represented by the following formulas (I) to (VI), a carboxylic acid metal base, a carboxylic acid ester group , A polymer having a monomer having at least one functional group selected from an acid anhydride group, an epoxy group, an acid amide group and an imide group (hereinafter referred to as “functional group-containing monomer”).

(In the above formula, R _{1 to} R ₄ represent a hydrogen atom or an aliphatic, alicyclic or aromatic residue having 1 to 30 carbon atoms, M is a monovalent metal such as sodium, potassium, magnesium, Examples of functional group-containing monomers include acrylic acid, methacrylic acid, maleic acid, fumaric acid, itaconic acid, crotonic acid, methylmaleic acid, methylfumaric acid, mesaconic acid, citraconic acid, glutaconic acid, and Methyl hydrogen maleate, methyl hydrogen itacone, methyl acrylate, ethyl acrylate, butyl acrylate, 2-ethylhexyl acrylate, hydroxyethyl acrylate, methyl methacrylate, 2-ethylhexyl methacrylate, hydroxyethyl methacrylate, methacrylic acid Aminoethyl, dimethyl maleate, dimethyl itaconate, metac Sodium acetate, potassium methacrylate, magnesium methacrylate, zinc methacrylate, sodium acrylate, magnesium acrylate, zinc acrylate, maleic anhydride, itaconic anhydride, citraconic anhydride, endobicyclo- [2,2,1] -5-heptene-2,3-dicarboxylic acid, endobicyclo- [2,2,1] -5-heptene-2,3-dicarboxylic anhydride, glycidyl acrylate,
Glycidyl methacrylate, allyl glycidyl ether,
Α, β-Unsaturated carboxylic acid derivatives such as vinyl glycidyl ether, vinyl acetate and acrylamide, as well as α, β-unsaturated carboxylic acid or anhydride thereof described above, with ammonia, methylamine, ethylamine, butylamine, hexylamine and dodecyl. Amine, oleylamine, stearylamine, cyclohexylamine, benzylamine, aniline, naphthylamine, dimethylamine, diethylamine, methylethylamine, dibutylamine, distearylamine, dicyclohexylamine,
Ethylcyclohexylamine, methylaniline, phenylnaphthylamine, melamine, ethanolamine, 3-
Amino-1-bropanol, diethanolamine, morpholine, α-amino-1-pyrrolidone, α-amino-ε
-Caprolactam, α-monomethylamino-ε-caprolactam, α-monoethylamino-ε-caprolactam, α-monobenzylamino-ε-caprolactam, N-substituted amides obtained by adding nylon 6 oligomers having terminal amino groups Compounds, N-substituted imide compounds and the like.

As a method for producing a modified polyolefin by introducing a functional group-containing monomer into polyolefin, for example, α-
A method of copolymerizing a monomer such as an olefin and the functional group-containing monomer or a method of graft-polymerizing the monomer with a polyolefin can be applied. Here, the amount of the functional group-containing monomer to be introduced into the polyolefin is preferably 0.001 to 1 in the content of the structural unit based on the monomer in the modified polyolefin.
It is 70% by weight, more preferably 0.01 to 60% by weight.

The modified polyolefins preferable as the raw materials for producing the component (c) are listed below. In the following, "g" means, for example, "X-g-Y" means "a graft copolymer of X and Y". Shall be represented. That is, preferable modified polyolefins include, for example, ethylene / acrylic acid copolymers, ethylene / methacrylic acid / sodium methacrylate copolymers, ethylene / methacrylic acid / zinc methacrylate copolymers, ethylene / methyl methacrylate / methacrylic acid. / Magnesium methacrylate copolymer,
Ethylene / isobutyl acrylate / methacrylic acid / zinc methacrylate copolymer, ethylene / methyl acrylate copolymer, ethylene / methyl acrylate / acrylic acid copolymer, ethylene / ethyl acrylate copolymer, ethylene / methacrylic acid Glycidyl copolymer, ethylene / vinyl acetate / glycidyl methacrylate copolymer, polyethylene-g-maleic anhydride copolymer, polypropylene-g-
Maleic anhydride, poly (ethylene / propylene) -g-
Maleic anhydride, poly (ethylene / propylene / 1,4
-Hexadiene) -g-maleic anhydride, poly (ethylene / propylene / dicyclopentadiene) -g-maleic anhydride, poly (ethylene / propylene / 5-ethylidene norbornene) -g-maleic anhydride, poly (ethylene / propylene) ) -G-Endobicyclo- [2,2,
1] -5-heptene-2,3-dicarboxylic anhydride, poly (ethylene / methacrylic acid / zinc methacrylate) -g-
Nylon 6 oligomer having an average degree of polymerization of 10, a copolymer obtained by adding cyclohexylamine to poly (ethylene / propylene) -g-maleic anhydride, and α-amino-ε to poly (ethylene / propylene) -g-maleic anhydride. Examples thereof include copolymers to which caprolactam is added.

The modified polyolefin has a melt index of preferably 0.05 to 50 g / 10 minutes, more preferably 0.1 to 30 g / 10 minutes. If the melt index is out of these ranges, it is not preferable because the kneading processability is poor at the time of grafting the modified polyolefin with the following addition polymer.

The addition polymer having a peroxide bond in the molecular chain, which is the other raw material for producing the component (c) (hereinafter, simply referred to as "addition polymer").
Is an addition polymer having a peroxide bond in either or both of the main chain and the side chain in the molecular chain.

Such an addition polymer is an allyl compound and / or an acryloyloxy group- or methacryloyloxy group-containing compound having a non-conjugated and / or conjugated vinyl monomer and a peroxide bond (hereinafter, these are referred to as “compound having a peroxide bond”). Is obtained by addition-polymerizing by a conventional method, and, for example, an addition polymer obtained by addition-polymerizing the vinyl monomer and a compound having a peroxide bond or the addition polymer It may be any addition polymer obtained by addition-polymerizing a vinyl monomer which is the same as or different from the vinyl monomer.

Here, examples of the conjugated vinyl monomer include methyl methacrylate, butyl methacrylate, methyl acrylate, butyl acrylate, 3 vinyl methyl acrylate, styrene, vinyl anisole, and the like, and examples of the non-conjugated vinyl monomer include: Examples thereof include vinyl acetate, vinyl chloride, vinyl fluoride, vinyl ketone and vinyl ether. Representative examples of the allyl compound having a peroxide bond include allyl t-butyl peroxycarbonate, but in addition to this, any compound or derivative having an allyl group and having a peroxide bond is not limited thereto. Not something. Examples of the acryloyloxy or methacryloyloxy group-containing compound having a peroxide bond include acryloyloxy t-butyl peroxycarbonate and methacryloyloxy t-butylperoxycarbonate.

Preferred examples of the addition polymer are listed below, but in the following, "b" means "X-Y-block copolymer" in the case of "X-B-Y", for example. .
That is, as the addition polymer, for example, poly (vinyl acetate / allyl t-butylperoxycarbonate-b-styrene) addition polymer, poly (n-butylmethacrylate / methacryloyloxymethyl t-butylperoxycarbonate-b-styrene) attached Addition polymer, poly (acetic acid n
-Butyl / methacryloyloxymethyl t-butyl peroxycarbonate-b-styrene) addition polymer, poly (butyl methacrylate / methacryloyloxymethyl t)
-Butyl peroxycarbonate-b-methyl methacrylate) addition polymer, poly (vinyl acetate / allyl t-butyl peroxycarbonate-b-methyl methacrylate)
An addition polymer etc. can be mentioned.

Such an addition polymer preferably has an average molecular weight of 100
0 to 200,000, more preferably 5,000
It is 0 to 100,000. If the average molecular weight is out of these ranges, the kneading processability in the grafting with the modified polyolefin is deteriorated, which is not preferable. The content of the peroxide bond in the addition polymer is preferably 0.5 to 30% by weight as a constitutional unit based on the compound containing the peroxide bond.
And more preferably 1 to 25% by weight. When the content of the peroxide bond in the addition polymer is too small, the grafting effect in the grafting with the modified polyolefin is significantly reduced, which is not preferable. On the other hand, when the amount is too large, gelation occurs in the grafting with the modified polyolefin, and a preferable grafted polyolefin-modified product cannot be obtained.

The grafted polyolefin modified product of the component (c) can be obtained by graft-polymerizing an addition polymer to the above-mentioned modified polyolefin by a conventional method.

Here, the use ratio of the modified polyolefin and the addition polymer is not particularly limited, but preferably 50 to 99% by weight of the modified polyolefin and 1 to 5 of the addition polymer.
0% by weight, and more preferably modified polyolefin 5
3 to 45% by weight of the addition polymer is used with respect to 5 to 97% by weight. When the amount of the addition polymer used is too small, when the resulting grafted polyolefin-modified product is added to the mixture of the polyamide and the thermoplastic polyester, problems such as the inability to obtain a composition giving preferable physical properties may occur. Occurs. On the other hand, if the amount is too large, it is not possible to form a dense structure of the thermoplastic polyester or polyamide particles, and it is not possible to obtain a composition that gives preferable physical properties. Examples of the grafted polyolefin modified product of the component (C) include poly (ethylene / acrylic acid) -g-poly (butyl acrylate-b-styrene), poly (ethylene / methacrylic acid / sodium methacrylate) -g-. Poly (butyl acrylate-b-styrene), poly (ethylene / methacrylic acid / zinc methacrylate) -g-poly (butyl acrylate-b-styrene), poly (ethylene / methyl methacrylate / magnesium methacrylate) -g -Poly (butyl acrylate-b-styrene), poly (ethylene / isobutyl acrylate / methacrylic acid / methacrylic acid / zinc methacrylate) -g-poly (butyl acrylate-b-styrene), poly (ethylene / acrylic acid Methyl) -g-poly (butyl acrylate-b-styrene),
Poly (ethylene / methyl acrylate / acrylic acid) -g
-Poly (butyl acrylate-b-styrene), poly (ethylene / ethyl acrylate) -g-poly (butyl acrylate-b-styrene), poly (ethylene / glycidyl methacrylate) -g-poly (butyl acrylate) -B-styrene), poly (ethylene / vinyl acetate / glycidyl methacrylate) -g-poly (butyl acrylate-b-styrene), (polyethylene-g-maleic anhydride) -g-poly (butyl acrylate-b) -Styrene), (polypropylene-g-maleic anhydride) -g-poly (butyl acrylate-b-styrene), poly [(ethylene / propylene) -g-maleic anhydride] -g-poly (butyl acrylate-) b-styrene), poly [(ethylene / propylene / 1,4-hexadiene) -g-maleic anhydride] -g
-Poly (butyl acrylate-b-styrene), Poly [(ethylene / propylene / dicyclopentadiene)-
g-maleic anhydride] -g-poly (butyl acrylate-
b-styrene), poly [(ethylene / propylene) -g
Α-Amino-ε-caprolactam adduct to maleic anhydride] -g-poly (butyl acrylate-b-styrene), poly (ethylene / acrylic acid) -g-poly (butyl acrylate-b-acrylic acid) Methyl), poly (ethylene / methacrylic acid / sodium methacrylate) -g-poly (butyl acrylate-b-methyl acrylate), poly (ethylene / methacrylic acid / methacrylic acid) -g-poly (butyl acrylate-b) -Methyl acrylate), poly (ethylene / methacrylic acid / zinc methacrylate) -g-
Poly (butyl acrylate-b-methyl acrylate), poly (ethylene / methyl methacrylate / methacrylic acid / magnesium methacrylate) -g-poly (butyl acrylate-b-methyl acrylate), poly (ethylene / acrylic acid Isobutyl / methacrylic acid / zinc methacrylate)-
g-poly (butyl acrylate-b-methyl acrylate), poly (ethylene / methyl acrylate) -g-poly (butyl acrylate-b-methyl acrylate), poly (ethylene / methyl acrylate / acrylic acid) -G-poly (butyl acrylate-b-methyl acrylate), poly (ethylene / ethyl acrylate) -g-poly (butyl acrylate-b-methyl acrylate), poly (ethylene /
Glycidyl methacrylate) -g-poly (butyl acrylate-b-methyl acrylate), poly (ethylene / vinyl acetate / glycidyl methacrylate) -g-poly (butyl acrylate-b-methyl acrylate), (polyethylene-
g-maleic anhydride) -g-poly (butyl acrylate-)
b-methyl acrylate), (polypropylene-g-maleic anhydride) -g-poly (butyl acrylate-b-methyl acrylate), poly [(ethylene / propylene) -g
-Maleic anhydride] -g-poly (butyl acrylate-b
-Methyl acrylate) and the like.

The following formula of the addition polymer in the grafted polyolefin modified product of the component (c); The graft efficiency calculated from the above is preferably 1% or more, more preferably 5% or more. If the grafting efficiency is too low, the compatibilizing effect between the polyamide and the thermoplastic polyester is not recognized, which is not preferable.

Further, the grafted polyolefin modified product of the component (c) preferably has a melt index of 0.01 to 40 g.
/ 10 minutes, more preferably 0.1 to 30 g / 1
0 minutes. Usually, when the modified polyolefin and the addition polymer are grafted, the melt index is significantly lowered, but the effect of the present invention is not affected at all. When the melt index is more than 40 g / 10 minutes, a composition that gives preferable physical properties cannot be stably obtained when added to polyamide and thermoplastic polyester.

The resin composition of the present invention has a predetermined amount of the component (c) with respect to a mixture obtained by mixing the predetermined amounts of the component (a) and the component (b).
Can be obtained by blending.

The blending amount of the component (a) and the component (b) is such that the component (a) is 5
95% by weight, and the component (b) is 95 to 5% by weight. When the content of the component (a) is less than 5% by weight, the excellent advantages such as chemical resistance and abrasion resistance of polyamide are not exhibited and the disadvantages such as hydrolyzability of thermoplastic polyester are exhibited. Not preferable. On the other hand, if the content of the component (a) exceeds 95% by weight, the water absorption is high and the dimensional change is large, which is not preferable. Furthermore, the preferable mixing ratio of the component (a) and the component (b) is 35 to 9 for the component (a).
0% by weight, and component (b) is 65 to 10% by weight. In the present invention, it is preferable that the polyamide and the thermoplastic polyester constituting the composition form a so-called sea / island structure (where sea represents polyamide and island represents thermoplastic polyester, and The island structure refers to a state in which thermoplastic polyester particles having a small particle size are dispersed in a polyamide matrix), and in the above preferable mixing ratio, when the mixing ratio of the component (a) is less than 35% by weight. However, it is not so preferable because the above-mentioned sea / island structure cannot be formed.

The blending amount of the component (c) is 0.5 to 4 with respect to 100 parts by weight of the mixture of the component (a) and the component (b) having the above blending ratio.
It is 0 part by weight, preferably 1 to 35 parts by weight, and more preferably 2 to 30 parts by weight. Here, when the amount of the component (c) is less than 0.5 part by weight, the effect of compatibilizing the components (a) and (b) decreases, so that the composition is melt-kneaded. In addition, since it is not possible to uniformly disperse both components and the particle size of both dispersed components becomes large, it is not possible to obtain a compact having a dense and homogeneous structure, It causes deterioration and variation. Further, when the blending amount of the component (c) exceeds 40 parts by weight, it becomes difficult to exhibit the characteristics possessed by the component (a) and the component (b).

Moldability of the resin composition of the present invention, other components unless impairing the physical properties, such as pigments, dyes, reinforcing materials, fillers, heat-resistant agents, antioxidants, weathering agents, lubricants, crystal nucleating agents,
An antiblocking agent, a release agent, a plasticizer, a flame retardant, an antistatic agent, a coupling agent, and other polymers can be added and blended. In particular, the addition of reinforcing materials and fillers is important, and glass fibers, asbestos fibers, carbon fibers, graphite fibers, wollastonite, talc, calcium carbonate, mica, clay, potassium whisker titanate, glass beads, or other fibrous or powdery materials. A reinforcing agent can be added and compounded.

The method for producing the resin composition of the present invention is not particularly limited, and for example, a method of melt kneading the components (a) to (c) using a uniaxial or multiaxial extruder can be applied.

The resin composition of the present invention is melt-kneaded as described above, and then molded by a method such as injection molding, extrusion molding, blow molding or compression molding to obtain a molded product having excellent mechanical properties. it can.

Such a molded product is useful as a constituent material for various automobile parts, mechanical parts, electric or electronic parts, and general sundries.

[Examples] Hereinafter, the present invention will be described in more detail with reference to Examples.
In addition, the evaluation of each characteristic of the molded article below was performed by the following methods.

(1) Tensile strength: ASTM D638 (2) Tensile elongation at break: ASTM D638 (3) Flexural modulus: ASTM D790 (4) Izod impact strength: ASTM D256 (5) Heat distortion temperature: ASTM D648 (6) Water resistance Degradability: A dumbbell piece molded according to ASTM D638 was immersed in hot water at 100 ° C for 400 hours, and then the dumbbell piece was dried under reduced pressure at 80 ° C for 7 days. Then, the tensile strength was measured based on ASTM D638, and the hydrolysis resistance was evaluated from the strength retention.

Examples 1 to 5 and Comparative Examples The following components were used as the components (a) to (c) of the resin composition of the present invention, and the resin compositions were combined and blended in the amounts shown in Table 1. Then, a test piece for evaluating each characteristic was manufactured as a molded body.

Component (a) Nylon 6 (PA-) having a concentration ratio ([NH ₂ ] / [COOH]) of terminal amino groups to terminal carboxy groups shown in Table 1
6) and nylon 66 (PA-66) were used.

That is, Nylon 6 synthesized according to Production Example 1 was used in Examples 1 to 4, and Nylon 66 synthesized according to Production Example 2 was used in Example 5.

Production Example 1 In an autoclave of 35, ε-caprolactam 10k
g, 0.2 kg of water, and meta-xylylenediamine as an end group adjusting agent were charged at 1/250 mol with respect to the charged amount of ε-caprolactam, sealed in a nitrogen atmosphere, and sealed.
The temperature was raised to 50 ° C., and the reaction was carried out for 2 hours under pressure with stirring. The stirring was stopped, the reaction product was extracted as a strand, made into chips, and then unreacted monomer was extracted and removed using boiling water and dried. The relative viscosity of the obtained polymer was 2.5, and the molar concentration ratio of the terminal amino group to the terminal carboxyl group was 3.3.

Production Example 2 In an autoclave of 35, hexamethylenediamine.
20 kg of a 50% aqueous solution of adipate and 1/250 mol of metaxylylenediamine were charged to the above amount of hexamethylenediamine adipate, and the mixture was sealed in a nitrogen atmosphere at an internal pressure of 17.5 kg / cm ^2. The temperature was raised to 260 ° C. while maintaining the temperature at G, and the temperature was maintained for 1.5 hours while stirring.
Then, the pressure was gradually released, and the reaction was carried out under normal pressure for 3 hours while maintaining the same temperature. The stirring was stopped, and the reaction product was extracted as a strand, made into chips, and then dried.
The polymer obtained had a relative viscosity of 3.1 and a molar concentration ratio of terminal amino groups to terminal carboxyl groups of 2.5.
Met.

Ingredient (b) Polyethylene terephthalate (PET) (Mitsui PET
Polyethylene terephthalate, grade name J12
5) Component (c) (c) -1 Poly (ethylene / glycidyl methacrylate) copolymer (ethylene / glycidyl methacrylate = 8
5/15) 70 parts by weight and 30 parts by weight of poly (butyl acrylate-b-methyl acrylate) (butyl acrylate / methyl acrylate = 10/90) having a peroxide bond in the side chain are melt extruders. , A poly (ethylene / glycidyl methacrylate) -g-poly (butyl acrylate-b-methyl acrylate) obtained by melt-kneading at a melting temperature of 200 ± 20 ° C. Co., Ltd., grade name MODIPER A4200) (c) -2 Poly (ethylene / glycidyl methacrylate) copolymer (ethylene / glycidyl methacrylate = 8)
5/15) 70 parts by weight and 30 parts by weight of poly (butyl acrylate-b-styrene) (butyl acrylate / styrene = 10/90) having a peroxide bond in the side chain are melted using a melt extruder. Poly (ethylene / glycidyl methacrylate) obtained by melt-kneading at a temperature of 200 ± 20 ° C.-g-
A grafted modified polyolefin (poly (butyl acrylate-b-styrene)) (manufactured by NOF CORPORATION, grade name, MODIPER A4100) A molded body was manufactured by the following method. First, the respective components in the amounts shown in the table were premixed, and then melt-kneaded at 270 to 280 ° C. into pellets by using an extruder having a screw diameter of 30 mm. Then, the pellets are vacuum-dried, and then the temperature of the cylinder is 270 to 280 ° C. and the mold temperature is 8 by an injection molding machine.
Injection molding was performed under the condition of 0 ° C. to obtain a molded body. An evaluation test was conducted using the obtained molded product as a test piece for each characteristic evaluation. The results are shown in Table 2.

As is clear from Table 2 shown above, each of the molded articles of the examples shows excellent values in terms of tensile strength, elongation, flexural modulus and notched impact strength. Furthermore, the molded products of the examples do not show a decrease in the tensile strength after the hydrolysis resistance test, and it can be seen that they have excellent hydrolysis resistance.

On the other hand, each molded product of Comparative Example showed excellent values for tensile strength and flexural modulus, but the elongation and notched impact strength were low, and the decrease in tensile strength after the hydrolysis resistance test was particularly remarkable. .

[Effect of the Invention] As described above, the molded article obtained from the composition of the present invention has excellent mechanical properties and excellent hydrolysis resistance.

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Claims (1)

[Claims] 1. A polyamide having a molar concentration ratio of terminal amino groups to terminal carboxyl groups of 1.5 or more.
100 parts by weight of a mixture of 95% by weight, (b) 95 to 5% by weight of a thermoplastic polyester, and (c) an addition polymer having a peroxide bond in the molecular chain, to a modified polyolefin having a functional group in the molecular chain. A resin composition comprising 0.5 to 35 parts by weight of a grafted polyolefin modified product obtained by graft-polymerizing.