JPH09310014A - Thermoplastic polymer composition, shock resistance modifying agent for thermoplastic resin and thermoplastic polyamide resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a thermoplastic polymer composition which contains a polyether rubber and a carboxylic acid group or epoxy group-containing polyolefin and is suitable as a shock resistance modifier for a thermoplastic polyamide resin. SOLUTION: This modifier is prepared by melt-kneading 3-70wt.% of a mixture of an epichlorohydrin rubber and a maleic acid-modified polyethylene (comprising 5-95wt.% of epichlorohydrin rubber and 95-5wt.% of a maleic acid- modified polyethylene) and 97-30wt.% of nylon and gives a nylon composition whose shock resistance is improved at room and lower temperatures.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a thermoplastic polymer composition comprising a polyether rubber suitable as an impact modifier for a thermoplastic polyamide resin and a polyolefin containing a carboxylic acid group or an epoxy group, The present invention relates to an impact modifier for a plastic resin and a thermoplastic polyamide resin composition having improved impact resistance.

[0002]

2. Description of the Related Art Polyamide resin is used for chemical resistance, moldability,
Due to its excellent properties such as wear resistance, it is used in a wide range of fields such as automobile parts and electric / electronic parts. However, since the impact resistance, especially the impact strength with a notch, is low, the application is considerably limited, and therefore various methods for improving the impact resistance of polyamide resins have been reported.

For example, a method of blending a polyamide resin with an ABS resin (Japanese Patent Publication No. 38-23476),
A method of blending a polyamide resin with a polymer obtained by graft-copolymerizing acrylonitrile and styrene on acrylic rubber (JP-B-51-36274), a modified ethylene copolymer having an active group capable of reacting with the polyamide resin and rubber elasticity, A method of blending a polymer type polymer (Japanese Patent Publication No. 54-4743, Japanese Patent Publication No. 55-44108, Japanese Patent Publication No. 58-23850) is known. However, although these methods improve the impact resistance of the polyamide resin at room temperature, the low temperature impact resistance is still unsatisfactory.

[0004]

SUMMARY OF THE INVENTION An object of the present invention is to provide a method capable of improving impact resistance at normal temperature and low temperature while maintaining the weather resistance of polyamide resin.
As a result of diligent research, the present inventors have found that by blending a mixture of epichlorohydrin-based rubber and maleic acid-modified polyethylene with nylon, it is possible to improve the impact resistance of nylon at normal temperature and low temperature without impairing weather resistance, The present invention has been completed based on this finding.

[0005]

According to the present invention, the following (1) to (3) are provided. (1) (A) Polyether rubber 5 to 95% by weight and (B)
A thermoplastic polymer composition comprising 95 to 5% by weight of a polyolefin containing a carboxylic acid group or an epoxy group. (2) An impact resistance modifier for thermoplastic resin, which comprises the thermoplastic polymer composition described in (1). (3) Thermoplastic polymer composition 3 to 7 described in (1)
0% by weight and thermoplastic polyamide resin 30 to 97% by weight
And a thermoplastic polyamide resin composition having improved impact resistance.

The embodiment of the present invention is as follows. 1. (A) is epichlorohydrin and has 2 to 10 carbon atoms
Is a copolymer of 90 to 100 mol% of at least one kind of monomer selected from the group consisting of alkyloxiranes having 1 to 10 mol% of an epoxy compound containing an unsaturated bond. 2. (B) consists of 70 to 99 mol% of α-olefin monomer, α, β-unsaturated carboxylic acid, anhydride of α, β-unsaturated carboxylic acid or metal salt thereof and unsaturated bond-containing epoxy compound. It is a copolymer composed of 1 to 30 mol% of at least one kind of monomer selected from the group. 3. (B) is at least one compound selected from the group consisting of α, β-unsaturated dicarboxylic acids, the carboxylic acid anhydrides and the carboxylic acid monoester compounds, based on 100 parts by weight of the poly α-olefin polymer. Is 0.05
10 to 10 parts by weight are added.

[0007]

BEST MODE FOR CARRYING OUT THE INVENTION

(Polyether Rubber) The polyether rubber used in the present invention is a polymer or copolymer of at least one monomer selected from the group consisting of epichlorohydrin and alkyloxirane having 2 to 10 carbon atoms,
And a copolymerization weight of up to 10 mol% of an unsaturated bond-containing epoxy compound copolymerizable with these monomers (the copolymerization composition of the monomer and the unsaturated bond-containing epoxy compound is 100 mol%). It is united.

Specific examples of the alkyloxirane having 2 to 10 carbon atoms include oxirane, methyloxirane,
Examples thereof include ethyloxirane, propyloxirane, butyloxirane, hexyloxirane, octyloxirane and the like. Of these, oxirane (ethylene oxide) and methyloxirane (propylene oxide) are preferable, and methyloxirane is particularly preferable.

Examples of unsaturated bond-containing epoxy compounds copolymerizable with these monomers include allyl glycidyl ether, vinyl glycidyl ether, glycidyl methacrylate, glycidyl acrylate, and glycidyl itaconate. Of these, allyl glycidyl ether is preferable.

(Polyolefin Containing Carboxylic Acid Group or Epoxy Group) The polyolefin containing a carboxylic acid group used in the present invention is an α-olefin and an α, β-unsaturated carboxylic acid, an acid anhydride of the carboxylic acid or Copolymer with the metal salt, or at least one or more α-
Obtained by reacting a polymer or copolymer of an olefin with at least one compound selected from the group consisting of α, β-unsaturated dicarboxylic acids, acid anhydrides of the dicarboxylic acids and monoesters of the dicarboxylic acids. Acid-modified polyolefin.

Specific examples of the α-olefin include ethylene, propylene, butene-1, pentene-1, hexene-1, 4-methylpentene-1, decene-1, octene-1 and the like. Of these, ethylene, propylene and butene-1 are preferable. These olefins may be used alone or in combination of two or more.

Specific examples of the α, β-unsaturated carboxylic acid or its acid anhydride include acrylic acid, methacrylic acid, maleic acid, fumaric acid, itaconic acid, citraconic acid, maleic anhydride, itaconic anhydride and citracone anhydride. Acid etc. are mentioned. Of these, maleic anhydride, acrylic acid and methacrylic acid are preferred.

Examples of the metal salt of α, β-unsaturated carboxylic acid or anhydride include salts of alkali metals such as Li and Na and salts of metals of Group 2 of the periodic table such as K, Mg, Ca and Zn. Can be mentioned. Of these, salts of polyvalent metals such as Mg and Zn are preferable.

Specific examples of the α, β-unsaturated carboxylic acid monoester include monomethyl ester, monoethyl ester, monopropyl ester, monobutyl ester, monohexyl ester and monooctyl ester of the above α, β-unsaturated carboxylic acid. Etc. Among them, maleic anhydride monomethyl ester or monoethyl ester is preferable.

The copolymer of an α-olefin with an α, β-unsaturated carboxylic acid, an acid anhydride of the carboxylic acid or a salt thereof is usually at least one or more α-olefin 70-
Polymerization of 99 parts by weight and 1 to 30 parts by weight of at least one kind of an α, β-unsaturated carboxylic acid, an anhydride of α, β-unsaturated carboxylic acid or a metal salt by a usual radical polymerization method. Is. The metal salt of the copolymer can also be obtained by a saponification reaction of a copolymer of an α-olefin with an α, β-unsaturated carboxylic acid or an acid anhydride of the carboxylic acid and an alkali compound.

The acid-modified polyolefin is usually a polymer or copolymer of at least one α-olefin.
0.05 to 10 parts by weight of at least one compound selected from the group consisting of α, β-unsaturated dicarboxylic acids, acid anhydrides of the dicarboxylic acids and monoesters of the dicarboxylic acids, relative to 00 parts by weight. It can be obtained by reacting.

The epoxy group-containing polyolefin used in the present invention is a copolymer of at least one α-olefin and an unsaturated bond-containing epoxy compound.
Specific examples of unsaturated bond-containing epoxy compounds include allyl glycidyl ether, vinyl glycidyl ether, glycidyl methacrylate, glycidyl acrylate, and glycidyl itaconate. Of these, glycidyl acrylate and glycidyl methacrylate are preferable.
These may be used alone or in combination of two or more.

The copolymer of α-olefin and epoxy compound containing an unsaturated bond is usually at least one α-olefin.
-Olefin 70 to 99% by weight and unsaturated bond-containing epoxy compound 1 to 30% by weight can be obtained by polymerization by an ordinary radical polymerization method.

(Thermoplastic Polymer Composition) The thermoplastic polymer composition of the present invention comprises (A) a polyether rubber of 5 to 95% by weight, preferably 10 to 60% by weight, and (B) a carboxylic acid group or an epoxy group. Group-containing polyolefin 95-5
The composition is composed of 90% by weight, preferably 90 to 40% by weight (however, the total of the components A and B is 100% by weight).

The method for preparing the composition is not particularly limited as long as the polyolefin component is melted, but is usually 150 to 250 ° C., preferably 170 to 200 ° C.
In, the mixture is prepared by melt-kneading the polyether rubber component and the polyolefin component. For melt kneading,
Various commonly used single-screw or twin-screw extruders,
A kneading device such as a Banbury mixer, a roll or various kneaders can be used.

(Impact modifier for thermoplastic resin) The thermoplastic polymer composition of the present invention exhibits excellent performance as an impact modifier for thermoplastic resin. That is, by adding the thermoplastic polymer composition of the present invention to a thermoplastic polyamide resin such as nylon, to improve the impact resistance at room temperature and low temperature without impairing the weather resistance of the thermoplastic polyamide resin. You can

(Thermoplastic Polyamide Resin) The polyamide resin used in the present invention is a ring-opening polymer of a lactam having three or more members, ω-amino acid capable of polymerizing with a lactam having three or more members, a dibasic acid, a diamine, etc. And a polycondensate obtained by polycondensation of an ω-amino acid with a diamine and a polycondensate obtained by polycondensation of a dibasic acid with a diamine. Specific examples of various polyamide resins include polymers such as ε-caprolactam, aminocaproic acid, enantolactam, 7-aminoheptanoic acid, 11-aminoundecanoic acid and 9-aminonanic acid; butanediamine, hexamethylenediamine, nonamethylene. Obtained by polycondensing diamines such as diamine, undecamethylenediamine, dodecamethylenediamine, metaxylenediamine and dicarboxylic acids such as terephthalic acid, isophthalic acid, adipic acid, sebacic acid, dodecane dibasic acid and glutaric acid. It is a copolymer or the like.

Specific examples are polyamide 4,6, polyamide 6, polyamide 6,6, polyamide 6,10, polyamide 11, polyamide 12, and aliphatic polyamide resins such as polyamide 6,12; polyhexamethylene diamine terephthalamide. And aromatic polyamide resins such as polyhexamethylene isophthalamide and xylene-containing polyamide. Among them, polyamide 6, polyamide 6,6, polyamide 11 and polyamide 12 are preferable.

When the thermoplastic polymer composition of the present invention is used as an impact modifier for a thermoplastic resin, the thermoplastic polymer composition is 3 to 70% by weight, preferably 5 to 40% by weight, a polyamide resin. 30 to 97% by weight, preferably 60 to
It can be used in the range of 95% by weight.

The method of mixing the thermoplastic polymer composition and the thermoplastic polyamide resin is not particularly limited as long as the polyolefin component and the polyamide resin are melted, but usually 150 to 250 ° C., preferably, 1
It is prepared by melt-kneading the polyether rubber component, the polyolefin component and the polyamide resin at 70 to 200 ° C. For the melt-kneading, generally-used kneading devices such as a single-screw or twin-screw extruder, a Banbury mixer, a roll, and various kneaders can be used. For the kneading method, after preparing a thermoplastic polymer composition by previously kneading a rubber component and a polyolefin component, a method of mixing this with a polyamide resin, or a rubber component and a polyolefin component and a polyamide resin at the same time. Any of the kneading methods can be adopted.

The thermoplastic polymer composition of the present invention and the composition of the thermoplastic polymer composition and the thermoplastic polyamide resin may include a filler, a dispersion aid, and a filler, as long as the moldability or the physical properties are not impaired. Plasticizer, softener, anti-aging agent,
Various commonly used compounding agents such as heat-resistant agents can be added. These compounding agents may be added in the process of producing the composition of the present invention or after the production of the composition, if necessary.

As the filler, carbon black, silica, calcium carbonate, mica, fine quartz powder, diatomaceous earth, basic magnesium carbonate, magnesium silicate, aluminum silicate, calcium metasilicate, talc, aluminum sulfate, calcium sulfate, Examples include barium sulfate, asbestos, glass fibers, organic reinforcing agents, organic fillers and the like.

Examples of the dispersion aid include higher fatty acids and their metal salts or amide salts. Examples of the plasticizer include polydimethylsiloxane oil, diphenylsilanediol, trimethylsilanol, phthalic acid derivatives, adipic acid derivatives, lactams, aminocarboxylic acids and the like. Examples of the softening agent include lubricating oil, process oil, coal tar, castor oil, calcium stearate and the like. Examples of the antiaging agent include phenylenediamines, phosphates, quinolines, cresols, phenols, and dithiocarbamate metal salts. As the heat-resistant agent, potassium hydroxide, iron naphthenate, potassium naphthenate and the like. Other colorants, ultraviolet absorbers, flame retardants, oil resistance improvers, scorch inhibitors, tackifiers, lubricants and the like can be optionally added.

[0029]

The present invention will be specifically described below with reference to examples and comparative examples, but the present invention is not limited to these examples. The parts and% in Examples, Comparative Examples and Reference Examples are based on weight unless otherwise specified. (1) Impact resistance test According to JIS K7110, it was performed by an Izod impact strength test method (with notch) at room temperature and -40 ° C (unit: Kg · cm / cm). (2) Weather resistance test method A test piece (30 × 50 × 2) of a thermoplastic polyamide resin composition prepared by injection molding was irradiated with ultraviolet rays (UV) under the following conditions (manufactured by Toyo Seiki Seisakusho: Atlas Wezao). Meter Ci4000), and the change in color tone of the test piece was evaluated according to the following criteria. ○: No yellowing ×: Yellowing UV (UV) irradiation conditions Temperature 63 ° C Humidity 50% RH Irradiance 80 W / m Irradiance ratio 320 nm or less is 300 to 400 nm
Less than 1.5% in the range of irradiation method continuous irradiation irradiation time 200 hours

(3) Polyamide resin used, polyolefin polyolefin resin Ube nylon 1 manufactured by Ube Industries
013B (Polyamide 6) Polyolefin-1 Mitsubishi Chemical Novatec AP
220L (maleic anhydride modified polyethylene) Polyolefin-2 Mitsui DuPont Nucler N1207C (Ethylene-methacrylic acid copolymer) Polyolefin-3 Mitsui DuPont Himilan 1652 (Ethylene-methacrylic acid zinc salt copolymer) Polyolefin-4 Sumitomo Chemical Bondfast E (Ethylene-glycidyl methacrylate copolymer)

Reference Example (Preparation of Polyether Rubber) 1.5 g of orthophosphoric acid was dispersed in 100 ml of ethyl ether in a glass container having an inner volume of 500 ml, the inside of which was replaced with nitrogen gas. (Triisobutylaluminum 200g
Was dissolved in benzene to make 1 l) and reacted with 50 ml. During this time, the reaction temperature was kept at 10 ° C. Then
1,8-diaza-bicyclo [5,4,0] undecene-
7 was added to 1 mol of triisobutylaluminum.
A catalyst was prepared by adding an amount corresponding to 3 mol and reacting for 1 hour. Next, in a stainless steel container having an internal volume of 5 liters whose interior was replaced with nitrogen gas, 25 g of epichlorohydrin, 191.3 g of propylene oxide, 12.5 g of allyl glycidyl ether, 3000 g of benzene and 8 g of triisobutylaluminum were prepared as catalysts prepared in advance. An amount corresponding to 0.5 g was added and a polymerization reaction was carried out at 60 ° C. for 5 hours. The reaction product was poured into hexane, the solvent and unreacted monomers were separated, and the obtained polymer was dried under reduced pressure at 50 ° C. for a whole day and night to obtain a polyether rubber. The polymer yield was 98.2%.

(Examples 1 to 6 and Comparative Examples 1 and 2) Pellet granulator (Moriyama Seisakusho, MS type feeder ruder F)
R-35 type) was used to granulate lumped polyether rubber into pellets. Next, using a 20 mmφ twin-screw extruder (2D25F2 type, manufactured by Toyo Seiki Seisaku-sho, Ltd.), the polyether rubber component and various polyolefin components were melt-kneaded at 180 ° C. in a composition shown in Table 1 to obtain a composition (I). It was
Further, using a 20 mmφ twin-screw extruder, the composition (I) and the polyamide resin were melt-kneaded at 240 ° C. in the formulation shown in Table 1 and granulated with a pelletizer to obtain a polyamide resin composition. Each polyamide resin composition was dried at 80 ° C. for 12 hours and then used as a molding machine using a vertical injection molding machine (Yamashiro Seiki Seisakusho, SAV-30 / 30).
A test piece for measuring physical properties was prepared at 240 ° C and a mold temperature of 50 ° C, and an impact resistance test and a weather resistance test were performed. The results are shown in Table 1.

Comparative Example 3 Polyether rubber and polyamide resin were melt-kneaded without blending with polyolefin.
An impact resistance test and a weather resistance test were performed in the same manner as in Example 1. The results are shown in Table 1.

Comparative Examples 4 to 7 Polyolefin and polyamide resin were melt-kneaded without blending the polyether rubber, and the impact resistance test and the weather resistance test were conducted in the same manner as in Example 1. The results are shown in Table 1.

(Comparative Examples 8 to 10) Instead of the thermoplastic polymer composition of the present invention, a conventionally used impact modifier for a polyamide resin and a polyamide resin were melt-kneaded, and the same as in Example 1. Then, an impact resistance test and a weather resistance test were performed. The results are shown in Table 1. The modifiers used are as follows. Polyacrylonitonyl-butadiene-styrene resin (A
BS) Polymethacrylonitrile-styrene resin (MBS) Maleic acid-modified ethylene-propylene rubber (maleated EPDM)

[0036]

[Table 1]

It can be seen from Table 1 that the thermoplastic polymer composition of the present invention can be used as an impact modifier for a thermoplastic resin so that the impact resistance at room temperature and low temperature can be obtained without impairing the weather resistance of the polyamide resin. It turns out that the sex can be improved.

[0038]

INDUSTRIAL APPLICABILITY The thermoplastic polymer composition of the present invention is not only useful as an impact modifier for thermoplastic resins, but also various polymer modifiers, adhesives for hot melts, wax modifiers, asphalt. It can be applied to modifiers, modifiers for ink coatings, adhesives for extrusion lamination, adhesives for coextrusion, extruded sheets and the like.

Claims (3)

[Claims] 1. (A) Polyether rubber 5 to 95% by weight
And (B) a thermoplastic polymer composition comprising 95 to 5% by weight of a carboxylic acid group- or epoxy group-containing polyolefin. 2. An impact modifier for a thermoplastic resin comprising the thermoplastic polymer composition according to claim 1. 3. The thermoplastic polymer composition according to claim 1 in an amount of 3 to 70% by weight, and a thermoplastic polyamide resin in an amount of 30 to 70% by weight.
A thermoplastic polyamide resin composition having an improved impact resistance of 97% by weight.