JPH0315942B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to thermoplastic elastomeric compositions that are stable to heat and ultraviolet light (sunlight). Polyether polyamide block copolymers, which have moderate amounts of polyamide and polyether parts in their molecular chains, are known as polymers with rubber-like elasticity, but when used alone, they deteriorate due to the action of oxygen and ozone in the air. However, undesirable phenomena such as coloring, surface cracking, opacity, and reduction in strength and elongation occur. In particular, this phenomenon is accelerated by heat and light. Therefore, various stabilizers are added to polyether polyamides for the purpose of preventing these deterioration phenomena. However, there is little knowledge regarding the stabilization of polyether polyamides, and no stabilizer has been found to be effective and satisfactory. In view of this, the inventors of the present invention conducted repeated research studies and found that a polyether polyamide containing a specific group of compounds as a stabilizer has extremely excellent thermal oxidation resistance and light resistance. This led to the completion of the . That is, in the present invention, 0.02 to 3% by weight of one or more compounds represented by the general formula (A) described below and 0.02% by weight of one or more compounds represented by the general formula (B) are added to the polyether polyamide elastomer polymer. ~3% by weight and one or more compounds represented by general formula (C)
The present invention relates to a thermoplastic elastomer composition characterized in that it contains 0.02 to 3% by weight and 0 to 3% by weight of one or more compounds represented by general formula (D). The polyether polyamide elastomer type polymer used in the present invention is 30 to 100 parts by weight of polyether polyamide elastomer, preferably 40 to 100 parts by weight.
It consists of 100 parts by weight, 70 to 0 parts by weight of polyamide resin, preferably 60 to 0 parts by weight, and 60 to 0 parts by weight of acid-modified olefin copolymer, for a total of 100 parts by weight. The polyether polyamide elastomer used in the present invention is a block copolymer having a hard segment made of polyamide such as nylon-6, nylon-66, nylon-11, nylon-12, etc. and a soft segment made of a polyether component. It is. The hard segment polyamide is made of a dicarboxylic acid such as terephthalic acid, isophthalic acid, oxalic acid, adipic acid, sebacic acid, 1,4-cyclohexyldicarboxylic acid, ethylene diamine, pentamethylene diamine, hexamethylene diamine, decamethylene diamine, 1 , 4-cyclohexyldiamine, m-xylene diamine; polymerization of cyclic lactams such as caprolactam, laurolactam; polycondensation of aminocarboxylic acids such as aminoenanthic acid, aminononanoic acid, aminoundecanoic acid, or the above-mentioned cyclic lactams; It is obtained by copolymerization of lactam, dicarboxylic acid, and diamine. In addition, the polyether component which is a soft segment has the general formula _H2N ( _-CH2 ) _-aO [-(- _CH2 ) _-bO ] _-c [-(-CH
₂ ) _-dO ] _-e ( _-CH2 ) _-f - _NH2 (wherein a, b, d and f are at least an integer of 2, preferably an integer of 2 to 4, and e is an integer of 2 to 30) , c is 0 or an integer from 2 to 30). For example, the general formula _H2N ( _-CH2 ) ₃ -O[-(- _CH2 ) ₄ -O] _-e ( _-CH2
) ₃ −
_NH2 (where e is an integer of ~30, preferably 6-30
is an integer. ) bis-(3-aminopropyl)
- mixture of polytetrahydrofuran, H ₂ N (-
CH ₂ ) ₃ −O [—(—CH ₂ ) ₃ −O] − _e (−CH ₂ ) ₃ −NH ₂ (
In the formula, e is an integer from 2 to 30, preferably from 6 to 30. ) bis-(3-aminopropyl)-polypropylene oxide, etc. Further, polyether glycols such as polyoxypropylene glycol and polyoxytetramethylene glycol can also be used. Such a polyether polyamide elastomer is usually produced by a condensation reaction between the polyamide component-forming compound and the polyether-containing diamine and dicarboxylic acid, and preferably the weight proportion of the polyether block is 8 to 60% by weight. . The dicarboxylic acid used in the polyether polyamide elastomer is the dicarboxylic acid exemplified as the raw material for the polyamide resin, a dimerized fatty acid having 36 carbon atoms, a mixture of a polymer resin containing the dimerized fatty acid as a main component, A compound represented by is used. Examples of polyether polyamide elastomers include M's
Marketed by Hemy (Switzerland)
GRILAMID ELY-60 and the like are preferably used. The polyamide resin used in the present invention includes dicarboxylic acids such as terephthalic acid, isophthalic acid, oxalic acid, adipic acid, sebacic acid, 1,4-cyclohexyldicarboxylic acid, and decanedicarboxylic acid, and ethylenediamine, pentamethylenediamine, hexamethylene Polycondensation of diamines such as diamine, decamethylenediamine, 1,4-cyclohexyldiamine, and m-xylenediamine; Polymerization of cyclic lactams such as caprolactam and laurolactam; Aminocarboxylic acids such as aminoenantoic acid, aminononanoic acid, and aminoundecanoic acid. or copolymerization of the above-mentioned cyclic lactam, dicarboxylic acid, and diamine. Preferred examples of these polyamides are 6 nylon, 66 nylon, 11 nylon, 12 nylon, 610 nylon, and 612 nylon.
Examples include nylon, 66/610 nylon, and 6/66 nylon. In the present invention, with respect to the acid-modified olefin copolymers, these are preferably at least 50 mol%
80 mol% of 1-olefins, such as ethylene, propylene, butene-1, isobutene, pentene-
1, hexene-1, decene-1, 4-methylbutene-1,4-methylpentene-1, 4,4-dimethylpentene-1, vinylcyclohexane, styrene, α-methylstyrene, substituted with lower alkyl substituent It should contain styrene or similar. It is also possible to use mixtures of the abovementioned olefins. Copolymers obtained from ethylene and butene-1 or propylene are preferred, and commercially available products include Tafmer A series (ethylene-butene-1 copolymers, Examples include the Tafmer P series (ethylene-propylene copolymer, manufactured by Mitsui Petrochemical Industries, Ltd.) such as Tafmer P0280, Tafmer P0480, Tafmer P0680, and Tafmer P0880 (products of Mitsui Petrochemical Industries, Ltd.). 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 acid components include acrylic acid, methacrylic acid, ethacrylic acid, itaconic acid, maleic acid (anhydride),
Examples include fumaric acid and monoesters of the above carboxylic acids. Suitable examples include acrylic acid, methacrylic acid and (anhydrous) maleic acid. Maleic acid (anhydride) is particularly preferred. Typical acid-modified olefin copolymers 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-
Methyl vinyl 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 Polymer, chlorinated ethylene-methacrylic acid copolymer, ethylene-butene-1-methacrylic acid copolymer, ethylene-butene-1-(anhydride) maleic acid copolymer, ethylene-propylene-(anhydride) maleic acid copolymer Polymer, propylene-acrylic acid copolymer, butene-1-acrylic acid copolymer, ethylene-isobutylene-acrylic acid copolymer, 3-methylbutene-1-acrylic acid copolymer, 4-methylpentene-1- Methacrylic acid copolymer, 4,4'-dimethylpentene-1-acrylic acid copolymer, propylene-undecacrylic acid copolymer, propylene-
α-methyl-styrene-maleic acid copolymer, propylene-butene-fumaric acid copolymer, ethylene-vinylcyclohexane-acrylic acid copolymer,
Chlorinated ethylene-acrylic acid copolymers and similar. Suitably ethylene-butene-1-(anhydrous) maleic acid copolymer, ethylene-propylene-(anhydrous)
Examples include maleic acid copolymers. Such an acid-modified olefin copolymer contains a monomer having an acidic group as a constituent component, and has a concentration of 0.01 to 20
It is important to contain 0.05% by weight, preferably 0.05% by weight.
~10% by weight. The amount of the acid-modified olefin copolymer to be blended is as described above, but if the amount is greater than the above range, the resulting molded product will become too flexible and its thermal properties will deteriorate, making it less than the original. deviate from the purpose. The group of stabilizers used in the present invention will be described in detail below. (1) Compound represented by general formula (A) However, in the above formula, R is -COO-, -NHCO-,

One or more carbon atoms having one or more of [Formula] in the molecular chain or at the end of the molecule or as a substituent
18 hydrocarbon groups, or -S-, -NHCO-,

[Formula], R' represents a hydrocarbon group having 1 to 18 carbon atoms which may be substituted with a hydroxyl group, and R ₁ , R ₂ is a hydrogen atom or 1 to 18 carbon atoms.
The alkyl groups may be the same or different, l is an integer of 0 or 2, m is 1 to
An integer of 4, n is an integer of 0 or 1. however,
The sum of l and m is equal to the total valence of R. The compound represented by the above general formula (A) usually acts as a radical scavenger, and examples thereof include the following. (a) Substituted monophenols 2,6-ditertiary-butyl-4-methylphenol, 2,6-ditertiary-butyl-4-octylphenol, 2-methyl-6-tertiary-butyl-4- Methylphenol, 2-methyl-
6-tert-butyl-4-octylphenol, 2-methyl-6-tert-butyl-4-nonylphenol. (b) Alkylidene bis (alkyl phenol)
Class 2,2'-methylenebis(4-methyl-6-
isopropylphenol), 2,2'-methylenebis(4-methyl-6-tertiary-butylphenol), 2,2'-methylenebis(4-ethyl-6-tertiary-butylphenol), 2,
2'-methylenebis(4-tert-butyl-6-
methylphenol), 2,2'-methylenebis(4,6-ditertiary-butylphenol), 4,
4'-methylenebis(2,6-ditertiary butylphenol), 4,4'-methylenebis(2-
methyl-6-tert-butylphenol), 4,
4'-methylenebis(2-tert-butyl-5-
methylphenol), 2,2'-ethylidene bis(4-methyl-6-tert-butylphenol), 2,2'-ethylidene bis(4,6-di-tert-butylphenol), 2,2'- Isopropylidene bis(4-methyl-6-isopropylphenol), 2,2'-isopropylidene bis(4-isopropyl-6-methylphenol), 2,2'-isopropylidene bis(4-methyl-6-tertiary) butylphenol), 4,4'-isopropylidene bis(2,
6-ditertiary butylphenol), 4,4'-
Isopropylidene bis(2-methyl-6-tertiary butylphenol), 4,4'-isopropylidene bis(2-tertiary butyl-5-methylphenol), 4,4'-butylidene bis(2-tertiary butylphenol) butyl-5-methylphenol), 4,4'-butylidenebis(2-methyl-6-tert-butylphenol), 4,4'-
Butylidene bis(2,6-di-tert-butylphenol), 4,4'-cyclohexylidene bis(6-tert-butylphenol), 4,
4'-cyclohexylidene bis(2-methyl-
6-tert-butylphenol), 4,4'-cyclohexylidene bis(2-tert-butyl-
5-methylphenol), 4,4'-cyclohexylidenebis(2,6-di-tert-butylphenol). (c) Polyphenols 1,1,3-tris(2-methyl-4-hydroxy-5-tertiary butylphenyl)butane,
2,4,6-tris(3,5-ditert-butyl-4-hydroxypenzyl)mesitylene. (2) Compound represented by general formula (B) (R ₃ )(-S-R ₄ )p...(B) In the formula, R ₃ is a hydrocarbon group having 1 to 18 carbon atoms, or a compound in the molecular chain. Represents a hydrocarbon group having 2 to 23 carbon atoms and having either -COO- or CONH- bond, R ₄ is a hydrogen atom or the same hydrocarbon group as R ₃ and may be the same as R ₃ . however
The total number of carbon atoms in R ₃ and R ₄ must be 7 or more. p is an integer from 1 to 4. The compound represented by the general formula (B) usually acts as a peroxide decomposer, and examples include the following. Di-n-hexyl sulfide, dilauryl sulfide, distearyl sulfide, dibenzyl sulfide, diphenyl sulfide, dioctyl odipropionate, dilaurylthiopropionate, distearylthiodipropionate, laurylstearyl thiodipropionate, thiodiethanol dilaurate,
Thiodiethanol distearate, bis(dodecylthio)methane, bis(stearylthio)methane, 1,1-bis(stearylthio)ethane, 1,1-bis(laurylthio)ethane,
1,1-bis(laurylthio)butane, 1,1
-Bis(stearylthio)butane, phenyl-
Bis(laurylthio)methane, 2,2-bis(dodecylthio)propane, 2,2-bis(stearylthio)propane, 1,1-bis(stearylthio)cyclohexane, 2,2-bis(dodecylthio)butane, 1- phenyl-1,
1-bis(dodecylthio)ethane, diphenyl-bis(octadecylthio)methane, dodecylcaptan, octadecylmethcaptan, thioglycolic acid lauryl ester, thioglycolic acid stearyl ester, thioglycolic acid para-tertiary butyl phenyl ester, 3-mercaptopropionic acid lauryl ester, 3-mercaptopropionic acid stearyl ester, 3-mercaptopropionic acid benzyl ester, 3-
Mercaptopropionic acid noniphenyl ester, 3-mercaptopropionic acid cyclohexyl ester, 4-mercaptobutyric acid lauryl ester, 4-mercaptobutyric acid stearyl ester, 6-mercaptocaproic acid lauryl ester, 6-mercaptocaproic acid stearyl ester, 6-mercaptocaproic acid Acid cyclohexyl ester, mercaptopropionate ethylene glycol ester, thioglycolic acid benzoquinone ester, glycerin tris(6-mercaptocaproic acid) ester, N-stearyl-mercaptoglycolic acid amide, thioglycolic acid anilide, N-cyclohexyl-thioglycolic acid amide , 3-mercaptocapropionic acid anilide, N,N-dicyclohexyl-3
-Mercaptopropionic acid amide, N-cyclohexyl-3-mercaptopropionic acid amide, 4-mercaptobutyric acid anilide, N-lauryl-4-mercaptobutyric acid amide, N-cyclohexyl-4-mercaptobutyric acid amide, N-stearyl-4-mercapto Butyric acid amide, 6-mercaptocaproic acid anilide, N-cyclohexyl-6-mercaptocaproic acid amide, N-lauryl-6-mercaptocaproic acid amide, N
-stearyl-6-mercaptocaproic acid amide, N,N'-bis(3-mercaptopropionyl)xylylenediamine, N,N'-bis(mercaptoacetyl)xylylenediamine. (3) Compound represented by general formula (C) In the formula, X is a halogen atom, n is an integer of 0 or 1, and R ₅ and R ₆ represent a hydrogen atom or a hydrocarbon group having 2 to 23 carbon atoms. The compound represented by the general formula (C) usually acts as an ultraviolet absorber, and examples include the following. 2-(2-oxy-3-tert-butyl-5-
methylphenyl)-5-chlorobenzotriazole, 2-(2-oxy-3,5-ditertiary-butylphenyl)-5-chlorobenzotriazole, 2-(2-oxy-5-methylphenyl)
Benzotriazole, 2-(2-oxy-3-
tertiary-butyl-5-methylphenyl)benzotriazole, 2-(2-oxy-3,5-ditertiary-butylphenyl)benzotriazole. (4) Compound represented by general formula (D) In the formula, X is -H or -O-, Y is -O-, -
Each represents N- or -N. The compound represented by the general formula (D) usually acts as an ultraviolet stabilizer, and examples include the following.

【formula】

【formula】

【formula】

【formula】

【formula】

【formula】

【formula】

【formula】

【formula】

【formula】

【formula】

【formula】

【formula】

【formula】

【formula】

【formula】 In particular, the following two types of compounds can be mentioned.

[Formula] and

[Formula] is preferred. As mentioned above, for the polyether polyamide elastomer polymer, the general formula
Blends of one or more compounds represented by (A), one or more compounds represented by general formula (B), and one or more compounds represented by general formula (C) are (A) to ( It has far superior thermal oxidation resistance and ultraviolet resistance compared to a mixture of only two of D).
The blending ratio of each of the stabilizers (A) to (C) in the composition of the present invention is suitably 0.02 to 3% by weight, particularly preferably 0.05 to 2%, based on the weight of the polymer. If the amount of each stabilizer added exceeds the above range, the physical properties of the resulting molded article will deteriorate and the original purpose will be missed. Furthermore, if the amount is small, the effect of the present invention is small and it is difficult to achieve the present invention. To achieve the purpose of the present invention, as shown above, the combination of the three components (A), (B), and (C) is essential, and (D) may be added as necessary. . If any one of stabilizer (A), stabilizer (B), or stabilizer (C) is absent, the object of the present invention cannot be achieved. The stabilizer (D) is blended in a proportion of 0 to 3% by weight based on the polymer. When blending these stabilizers with the polymer, even if both are blended before the latter polymerization, during the polymerization,
Although it may be blended after polymerization, it is desirable to blend it after polymerization. In addition to the above-mentioned components, the composition of the present invention may include inorganic fillers, graphite, glass fibers, metal fibers, carbon fibers, gypsum fibers, ceramic fibers, carbon black, titanium oxide, coupling agents, and other components within the scope of the present invention. , plasticizer, heat stabilizer,
A weathering stabilizer, a mold release agent, a lubricant, a coloring agent, an antistatic agent, a release agent such as an organic halogen compound, a combustion release aid such as antimony trioxide, a foaming agent, and the like may be added. Furthermore, the following polymers can be mixed and used as needed. These polymers include ethylene, propylene, butylene, pentene, butadiene, isoprene, chloroprene, styrene, α
- Homopolymers or copolymers of monomers such as methylstyrene, vinyl acetate, vinyl chloride, acrylic esters, methacrylic esters, (meth)acrylonitrile, polyurethane, polyamide, polyester, polyacetal, polycarbonate, polysulfone, polyallyl Sulfone, polyethersulfone, polyarylate, polyphenylene oxide, polyphenylene sulfide, polyetheretherketone, polyimide, polyamideimide, silicone resin, phenoxy resin,
Examples include homopolymers, random copolymers, block copolymers, graft copolymers, etc. of fluorocarbon resins and polyaryl ethers. The thermoplastic resin composition of the present invention can be prepared by various known methods. For example, there is a method in which the raw materials are uniformly mixed in advance in a mixer such as a tumbler or a Henschel mixer, and then fed into a single-screw or twin-screw extruder for melt-kneading and then prepared as pellets. The thermoplastic resin composition of the present invention can be used for various purposes due to its excellent properties, such as tubes, hoses, pipes, rods, films, sheets, electric wire coatings, wire coatings, optical fiber coatings, and various other applications. Plans, fishing nets, nets, hot melt adhesives, conveyor belts, V-belts, sports shoe soles for golf, baseball, soccer, track and field, ski boots, gear cam bearings, packing, gaskets, O-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, and other various automobiles. It can be used for parts, electronic/electrical equipment parts, precision machine parts, etc., and can also be used as powder coatings, solution-type adhesives, paints, etc. EXAMPLES The present invention will be specifically explained below with reference to Examples, but the present invention is not limited to these Examples. In addition, parts in the examples mean parts by weight. Examples 1 to 7, Comparative Examples 1 to 6 As polyether polyamide elastomer
GRILAMID ELY-60 (block copolymer with hard segment made of nylon 12 manufactured by EMS CHEMIE), GRILAMID as a polyamide resin
L20G (nylon 12 manufactured by the same company), GRILAMID
L25N150 (manufactured by the same company, plasticized nylon 12),
GRILON A28G (manufactured by the same company, nylon 6), acid-modified olefin copolymer [X] and [Y] below
was used. Such [X] is an ethylene-propylene copolymer (Tafmer P-0280, manufactured by Mitsui Petrochemical Industries, Ltd.
Co., Ltd., 0.5 parts by weight of 1,3-bis(tert-butylperoxypropyl)benzene and 1 part by weight of maleic anhydride were uniformly mixed with a Henschel mixer, and kneaded at 230°C with an extruder. An acid-modified copolymer [Y] was obtained by pelletizing and using ethylene-butene-1 copolymer (Tafmer A4090, manufactured by Mitsui Petrochemical Industries, Ltd.) in place of Tafmer P-0280. . In addition to the polymer, stabilizers were blended in the proportions shown in Table 1, mixed in a Henschel mixer, and kneaded at 180 to 240 °C in a 50 mmφ single screw extruder.The pellets obtained were then molded into pellets for physical property evaluation using an injection molding machine. I created a piece. Table 1 shows the physical property test results. However, the structural formulas and abbreviations of the stabilizers used in the examples are as follows.

【table】

【table】

[Table] Examples 8 and 9 GRILAMID as polyamide elastomer
Using ELY60 and using the following stabilizers in addition to (A)-1 to (D)-1 used in Examples 1 to 6 as stabilizers, the procedure was carried out in the same manner as in Example 1 according to the formulation shown in Table 2. Got pellets. Table 2 shows the physical property test results.

【table】

【table】

【table】

【table】

Claims (1)

[Claims] 1. Polyether polyamide elastomer 30~
General formula (A) 0.02 to 3% by weight of one or more of the compounds represented by
0.02 to 3% by weight of one or more compounds represented by the general formula (B) (R ₃ ) (-S-R ₄ )p...(B);
General formula (C) 0.02 to 3% by weight of one or more of the compounds represented by
General formula (D) 1. A thermoplastic elastomer composition containing 0 to 3% by weight of one or more of the following compounds. [However, in the above formula, R is -COO-, -NHCO-,
[Formula] A hydrocarbon group having 1 to 18 carbon atoms having one or more of the following in the molecular chain or at the end of the molecule or as a substituent,
or -S-, -NHCO-, [Formula], R' represents a hydrocarbon group having 1 to 18 carbon atoms which may be substituted with a hydroxyl group, and R ₁ , R ₂
are hydrogen atoms or alkyl groups having 1 to 18 carbon atoms, which may be the same or different, R ₃
represents a hydrocarbon group having 1 to 18 carbon atoms, or a hydrocarbon group having 2 to 23 carbon atoms having either -COO- or CONH- in the molecular chain, and R ₄ is a hydrogen atom or R ₃ and It is a similar hydrocarbon group and may be the same as R ₃ . However, the total number of carbon atoms in R ₃ and R ₄ must be 7 or more. l is 0~
m is an integer of 1 to 4, n is an integer of 0 or 1, and p is an integer of 1 to 4. X is a halogen atom, R ₅ and R ₆ are hydrogen atoms or have 2 to 23 carbon atoms
represents a hydrocarbon group, Z represents -H or -O-: Y represents -O-, -N- or -N<, respectively. ]