JPH0150339B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a polyetheresteramide resin composition having excellent heat resistance and weather resistance. Polyether ester amide, which has polyamide repeating units, polyether repeating units, and ester bonds in the polymer main chain, is well known, and like polyether ester or polyester amide, it has excellent impact resistance and rubber elasticity, so it is a new product in the elastomer field. It has been attracting attention as a material in recent years. In particular, polyether ester amide has excellent lightness, transparency, and low-temperature impact resistance, and is less likely to cause burrs, sink marks, etc. during molding, so it is promising for various molding applications. However, polyetheresteramide is extremely susceptible to oxidative deterioration, and as the degree of polymerization decreases, undesirable phenomena such as a decrease in mechanical properties, surface cracking, and coloration occur. In particular, this oxidative deterioration is accelerated by heat, light, etc., and its use is restricted when exposed outdoors or in a high-temperature atmosphere. Therefore, in order to prevent these deterioration phenomena, it has been considered to add various stabilizers to polyetheresteramide. However, there is little knowledge regarding the stabilization of polyether esteramides, and none has been found to be effective and satisfactory. In view of these points, the present inventors have made extensive studies and have found that by adding a specific group of compounds as stabilizers to polyether esteramide, heat resistance and The present invention was achieved by discovering that a polyetheresteramide resin composition having extremely excellent weather resistance can be obtained. That is, in the present invention, 0.01 to 3 parts by weight of the copper salt (B) and 0.05 parts by weight of the ultraviolet absorber represented by the following general formula (C) or (D) are added to 100 parts by weight of the polyether ester amide (A). ~5 parts by weight of each of the stabilized polyetheresteramide compositions. (However, R ₁ represents an alkyl group having 1 to 18 carbon atoms, R ₂ is a hydrogen atom or an alkyl group similar to R ₁ , and may be the same as R _1. X is a halogen atom, and l is 0 or 1.) In the polyether ester amide composition, a hindered amine light stabilizer represented by the following general formula (E) is added in an amount of 0.05 to 5 parts by weight per 100 parts by weight of the polyether ester amide (A). When added in a proportion of , the result is a polyether ester amide composition with even more outstanding heat resistance and weather resistance. (However, R ₃ is a hydrogen atom or has 1 to 12 carbon atoms.
The alkyl group, R ₄ is a straight chain or branched chain alkyl group having 1 to 6 carbon atoms, and R' ₄ is the same alkyl group as R ₄ , whether they are the same or different. good. Y is -O- or

[Formula], R ₅ is a hydrocarbon group having 1 to 23 carbon atoms which may be substituted with a hydroxyl group, or -S-

Indicates a hydrocarbon group having 1 to 18 carbon atoms and having any of the following formulas. l' is an integer from 1 to 4. ) The composition of the present invention will be specifically described below. Polyether ester amide (A) in the present invention
is a polymer composed of polyamide units and polyether ester units and having amide bonds, ether bonds, and ester bonds in the molecular chain. The polyamide units are derived from aminocarboxylic acids, lactams, salts of dicarboxylic acids and diamines, or combinations of dicarboxylic acids and diisocyanates. Polyether ester units have a number average molecular weight
It is derived from poly(alkylene oxide) glycols having 300 to 6000 carbon atoms and dicarboxylic acids having 4 to 20 carbon atoms. The copolymerization ratio of polyamide units and polyether ester units is approximately 5:90 to 95:95 by weight.
It is 10. The method for polymerizing polyether ester amide (A) is not particularly limited, and any known method can be used. For example, aminocarboxylic acids, lactams or dicarboxylic acid-diamine salts (a) and dicarboxylic acids
(c) is reacted in an approximately equimolar ratio to produce a polyamide prepolymer having carboxylic acid groups at both ends, and this is reacted with poly(alkylene oxide) glycol (b) under vacuum, or (a) above. The compounds (b) and (c) are charged into a reaction tank and reacted under pressure at high temperature in the presence or absence of water to produce a carboxylic acid-terminated polyamide prepolymer, and then under normal pressure or reduced pressure. A method of proceeding with polymerization is known. Alternatively, there is a method in which the compounds (a), (b), and (c) are simultaneously charged into a reaction tank, melt-mixed, and then polymerized all at once under high vacuum; this method is preferable since it causes less coloring of the polymer. In addition, we have developed a solution polymerization method in which poly(alkylene oxide) glycol is reacted with about twice the molar amount of dicarboxylic acid to create a prepolymer with carboxylic acid groups at both ends, and this is reacted with dicarboxylic acid and diisocyanate in an inert solvent. You can read it. Examples of the copper salt (B) which is another component constituting the composition of the present invention include copper chloride, copper bromide, copper fluoride,
Examples include copper iodide, copper thiocyanate, copper nitrate, copper sulfate, copper acetate, copper caprylate, copper caprate, copper laurate, copper myristate, copper palmitate, copper stearate, copper oleate, and the like. Among these, cuprous halides are particularly preferred. Further, the ultraviolet absorber, which is another component constituting the composition of the present invention, is represented by the above general formula (C) or (D). Examples of compounds represented by the general formula (C) include 2(2'-hydroxy-3',5'-di-tert-butylphenyl)benzotriazole, 2(2'-hydroxy-3'-tert-butyl-5 '-methylphenyl)-5
-chlorobenzotriazole, 2(2'-hydroxy-3',5'-di-tert-butylphenyl)-5-chlorobenzotriazole, 2(2'-hydroxy-3',
5′-ditertiary amyl phenyl)benzotriazole, 2(2′-hydroxy-5′-methylphenyl)
Benzotriazole, 2(2'-hydroxy-5'-
Examples include tetramethylbutyl)benzotriazole. Among these, 2(2'hydroxy-
3'-tert-butyl-5'-methylphenyl)benzotriazole is preferred. Examples of compounds represented by general formula (D) include 2-
Hydroxy-4-methoxybenzophenone, 2-
Hydroxy-4-benzyloxybenzophenone, 2-hydroxy-4-methoxy-4'-chlorobenzophenone, 2-hydroxy-4-dodecyloxy-benzophenone, 2-hydroxy-4-
Examples include n-octoxybenzophenone and 2-hydroxy-4-stearyloxy-benzophenone. Among these, 2-hydroxy-4
-n-octoxybenzophenone is preferred. Among these ultraviolet absorbers, 2(2'-hydroxy-3'-tert-butyl-5'-methylphenyl)benzotriazole is particularly preferred. When a hindered amine light stabilizer represented by the general formula (E) is further added to the polyether ester amide composition, the composition has even more outstanding heat resistance and weather resistance. general formula
Examples of the compound represented by (E) include 4-benzoyloxy-2,2,6,6-tetramethylpiperidine, bis(2,2,6,6-tetramethyl-4
-piperidinyl)adipate, bis(2,2,
6,6-tetramethyl-4-piperidinyl)suberate, bis(2,2,6,6-tetramethyl-
4-piperidinyl) sebacate, bis(2,2,
6,6-tetramethyl-4-piperidinyl) phthalate, bis(2,2,6,6-tetramethyl-
4-piperidinyl)isophthalate, bis(2,
2,6,6-tetramethyl-4-piperidinyl)
Terephthalate, bis(1,2,2,6,6-pentamethyl-4-piperidinyl) sebacate,
N,N'-bis(2,2,6,6-tetramethyl-4-piperidinyl)adipamide, bis(1,
2,2,6,6-pentamethyl-4-piperidinyl)-n-butyl(3,5-di-tert-butyl-4-
hydroxybenzyl)malonate, bis(1,
2,2,6,6-pentamethyl-4-piperidinyldibenzyl)malonate, bis(1,2,2,
6,6-pentamethyl-4-piperidinyl) diethylmalonate, bis(2,2,6,6-tetramethyl-4-piperidinyl)dibenzylmalonate, bis(2,2,6,6-tetramethyl-4 −
piperidinyl) benzylethyl malonate, bis(2,2,6,6-tetramethyl-4-piperidinyl)-n-butyl(3,5-di-tert-butyl-4
-hydroxybenzyl) malonate, tetra(2,2,6,6-tetramethyl-4-piperidinyl) ester of butanetetracarboxylic acid, and especially bis(2,2,6,6-
Tetra(2,2,
6,6-tetramethyl-4-piperidinyl) ester may be mentioned as a preferred compound. Each of these stabilizers contains an ultraviolet absorber and a hindered amine-based light stabilizer at a ratio of 0.01 to 3 parts by weight, preferably 0.05 to 1 part by weight of the copper salt (B) per 100 parts by weight of the polyether ester amide (A). The stabilizers are used in proportions of 0.05 to 5 parts by weight, preferably 0.1 to 2 parts by weight. If the amount of each stabilizer added is less than this, the effect will not be sufficiently expressed, and if the amount added is more than this, it will have a negative effect on the physical properties of the composition and may also cause undesirable phenomena such as blooming. Become. In addition, the polyether ester amide (A) of the present invention
In order to make the composition stable against both thermal oxidative deterioration and photooxidative deterioration, it is necessary to add a copper salt (B) and a compound represented by the general formula (C) or (D) to the polyether ester amide (A). It is necessary to add both ultraviolet absorbers, and if either of these is lacking, the composition will have significantly inferior heat resistance or weather resistance, or both, compared to the composition of the present invention. You can only get things. The method for adding each of these stabilizers to the polyether ester amide is not particularly limited and can be added during the polymerization of the polyether ester amide or at any time after the polymerization, but a particularly preferred embodiment is after the polymerization ( This is a method of melt-mixing (before molding). In addition, when preparing the composition of the present invention, other common additives such as hydrolysis resistance improvers, colorants (pigments, dyes), and electrostatic charges may be added as long as they do not impede the desired heat resistance and weather resistance stability. inhibitor,
Additives such as a conductive agent, a crystal nucleating agent, a lubricant, a filler, a reinforcing material, an adhesion aid, a plasticizer, a mold release agent, and a flame release agent can be optionally blended. The present invention will be explained below with reference to Examples. In the examples, all "parts" or "%" are expressed as weight ratios. In addition, the relative viscosities shown in the text and examples are values measured in orthochlorophenol at 25°C and a concentration of 0.5%.
(Perkin Elmer DSC-1B). Reference example Polymerization of polymer (A-1) 65.5 parts of aminododecanoic acid, number average molecular weight 680
33.6 parts of polytetramethylene oxide glycol and 8.2 parts of terephthalic acid are added to "Irganox".
1098 (antioxidant) and 0.05 part of tetrabutyl titanate catalyst into a reaction vessel equipped with a helical ribbon stirring blade, purged with _N2 ,
After heating and stirring at ℃ for 40 minutes to obtain an almost transparent homogeneous solution, it was heated to 270℃ and
The polymerization conditions were brought to below 0.5 mmHg. The polymerization reaction was carried out under these conditions for 3 hours and 50 minutes. The obtained polyether ester amide (A-
The melting point of 1) was 166°C, and the relative viscosity was 1.65. Polymerization of polymer (A-2) Aminododecanoic acid 43.6 parts, number average molecular weight 1000
Using 53.1 parts of polytetramethylene oxide glycol and 8.8 parts of terephthalic acid as starting materials, a polymerization reaction was carried out for 4 hours and 30 minutes in the same manner as in Example 1 to obtain a polymer (A-2). The melting point of the obtained polyether ester amide (A-2) is
At 142°C, the relative viscosity was 1.79. Stabilizer The structures and abbreviations of the stabilizers used in the examples are as follows.

[Table] Example After blending each stabilizer shown in Table 1 with polyether ester amide (A-1) and (A-2),
A-1 was melted and kneaded in a 30 mmφ extruder heated to 200°C and A-2 to 180°C, and then pelletized. After vacuum drying this pellet, if the polyether ester amide is (A-1), 200
In the case of polyether ester amide (A-2), it was pressed at 180°C to form a press sheet with a thickness of 0.9 to 1.1 mm, which was punched into JIS K-6301 No. 3 dumbbell-shaped test pieces. Heat resistance was investigated by aging the test piece in a hot air oven at 130°C, and the time when the elongation at break retention rate was 50% was defined as the heat resistance life. Weather resistance was examined by irradiating the test piece with light in a sunshine weather meter. The black panel temperature of the Sunshine Weather-Ometer is 63℃ for 2 hours.
Sprayed with water for 18 minutes. Weather resistance was evaluated by measuring the time at which the elongation retention rate reached 50% and the time at which cracks appeared on the irradiated surface. In addition, the measurement of elongation at break is
This was done in accordance with JIS K-6301. These results are shown in Table 1.

[Table] Comparative Example The stabilizer shown in Table 2 was blended with polyether ester amide (A-1) or (A-2), and then pelletized in the same manner as in the previous example to obtain a composition different from the composition of the present invention. I made it into a thing. These compositions, polymer (A-1) and polymer (A-2) were punched into test pieces in the same manner as in the above example. Table 2 shows the results of evaluating the heat resistance and weather resistance of each test piece.

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Claims (1)

[Claims] 1 0.01 to 3 parts by weight of copper salt (B) and the following general formula for 100 parts by weight of polyether ester amide (A)
Add 0.05 to 5 of the ultraviolet absorber shown by (C) or (D).
A polyether ester amide composition in which each proportion of parts by weight is added. (However, R ₁ represents an alkyl group having 1 to 18 carbon atoms, R ₂ is a hydrogen atom or an alkyl group similar to R ₁ , and may be the same as R _1. X is a halogen atom, and l is 0 or 1.) 2 For 100 parts by weight of polyether ester amide (A), add 0.01 to 3 parts by weight of copper salt (B) and an ultraviolet absorber represented by the following general formula (C) or (D). A polyether ester amide composition containing 0.05 to 5 parts by weight of a hindered amine light stabilizer represented by the following general formula (E) in respective proportions of 0.05 to 5 parts by weight. (However, R ₁ represents an alkyl group having 1 to 18 carbon atoms, R ₂ is a hydrogen atom or an alkyl group similar to R ₁ , and may be the same as R _1. X is a halogen atom, and l is (0 or 1) (However, R ₃ is a hydrogen atom or has 1 to 12 carbon atoms.
The alkyl group, R ₄ is a straight chain or branched chain alkyl group having 1 to 6 carbon atoms, and R' ₄ is the same alkyl group as R ₄ , whether they are the same or different. good. Y is -O- or [Formula], R ₅ is a hydrocarbon group having 1 to 23 carbon atoms which may be substituted with a hydroxyl group, or -S-,
Indicates a hydrocarbon group having 1 to 18 carbon atoms and having any of the following formulas. l' is an integer from 1 to 4. )