JPH0251461B2 - - 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 polyetheresteramide, and the effectiveness has not been satisfactory. In view of these points, the inventors of the present invention conducted extensive studies and found that by adding a specific group of compounds as stabilizers to polyether esteramide, heat resistance and weather resistance that could not be obtained conventionally were achieved. The inventors have discovered that a polyether ester amide resin composition having extremely excellent properties can be obtained, and have thus arrived at the present invention. That is, in the present invention, 0.05 parts by weight of an aromatic amine compound represented by the following general formula (B), (C), (D) or (E) is added to 100 parts by weight of polyether ester amide (A).
The present invention relates to a polyether ester amide composition in which 0.05 to 5 parts by weight of an ultraviolet absorber represented by the following general formula (F) or (G) are added. (However, R ₁ and R ₁ ' are hydrogen atoms, hydrocarbon groups having 1 to 18 carbon atoms, or 1 to 1 carbon atoms having an -O- bond.
They are any of the 18 hydrocarbon groups, and may be the same or different. R ₂ is carbon number 1
~12 alkyl groups. ) (However, R ₃ represents an alkyl group having 1 to 18 carbon atoms,
R ₄ is a hydrogen atom or an alkyl group similar to R ₃ , and may be the same as R ₃ . X is a halogen atom, and l is 0 or 1. ) A polyether ester amide composition in which a hindered amine light stabilizer represented by the following general formula (H) is added in the same ratio as above to the polyether ester amide composition has even more outstanding heat resistance and weather resistance. It becomes an amide composition. (However, R ₅ is a hydrogen atom or an alkyl group having 1 to 12 carbon atoms, R ₆ is a straight chain or branched alkyl group having 1 to 6 carbon atoms, and R ₆ ' is the same alkyl group as R ₆ . They may be the same or different.Y is -O- or H-N-, and _R7 is a hydrocarbon group having 1 to 23 carbon atoms which may be substituted with a hydroxyl group, or - S-,

It represents a hydrocarbon group having 1 to 18 carbon atoms and having any of the following formulas. m 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 of 300
~6000 poly(alkylene oxide) glycol and a dicarboxylic acid having 4 to 20 carbon atoms. The copolymerization ratio of polyamide units and polyether ester units is approximately 5:90 to 95:10 by weight.
It is. 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. There is also 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, a solution polymerization method is used in which poly(alkylene oxide) glycol is reacted with about twice the mole 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. It's good to wear. The aromatic amine compound, which is another component constituting the composition of the present invention, is represented by the general formula (B), (C), (D) or (E). Examples of the compound represented by the general formula (B) include phenyl-α-naphthylamine and phenyl-β-naphthylamine. Examples of compounds represented by general formula (C) include N,
N'-diphenyl-p-phenylenediamine, N,
N'-di-β-naphthyl-p-phenylenediamine, N,N'-bis((1-methylbutyl)-p-
Phenylenediamine, N,N'-bis(1-ethyl-3-methylheptyl)-p-phenylenediamine, N,N'-bis(1-ethyl-3-methylpentyl)-p-phenylenediamine, N, N'-
Bis(1,4-dimethylpentyl)-p-phenylenediamine, N-cyclohexyl-N'-phenyl-p-phenylenediamine, N-octyl-
N'-phenyl-p-phenylenediamine, p-
Examples include isopropoxydiphenylamine, N,N'-di-isopropyl-p-phenylenediamine, and dioctyl-p-phenylenediamine. Especially N,N'-di-β-naphthyl-p
-Phenylene diamine is preferred. Examples of compounds represented by general formula (D) are 4,
Examples include 4'-bis(4-α,α-dimethylbenzylphenylamine), p,p′-dioctyldiphenylamine, and p,p′-dimethoxyphenylamine. Among them, 4,4'-bis (4-α, α
-dimethylbenzyldiphenylamine) is preferred. Examples of compounds represented by general formula (E) include N,
Examples include N'-diphenylethylenediamine, N,N'-diphenylhexamethylenediamine, di-p-tolylethylenediamine, and di-p-tolylhexamethylenediamine. Among them, N.
N-diphenylethylenediamine is preferred. Among these aromatic amine compounds, 4,
Preference is given to using 4'-bis(4-α,α-dimethylbenzyldiphenylamine). Further, the ultraviolet absorber, which is another component constituting the composition of the present invention, is represented by the general formula (F) or (G). Examples of compounds represented by general formula (F) are 2
(2'-hydroxy-3',5'-di-tert-butyl-phenyl)benzotriazole, 2(2'-hydroxy-3'-tert-butyl-5'-methyl-phenyl)-5
-chloro-benzotriazole, 2(2'-hydroxy-3',5'-di-tert-butyl-phenyl)-5
-Chloro-benzotriazole, 2(2'-hydroxy-3',5'-di-tert-butyl-phenyl)benzotriazole, 2(2'-hydroxy-5'-methyl-phenyl)benzotriazole, 2(2 ′-Hydroxy-5′-tetramethylbutyl-phenyl)
Examples include benzotriazole. Among them, 2
(2'-hydroxy-3'-tert-butyl-5'-methyl-
Phenyl)-5-chloro-benzotriazole is preferred. Examples of compounds represented by formula (G) include 2-hydroxy-4-methoxy-benzophenone, 2,
4-di-hydroxy-benzophenone, 2-hydroxy-4-benzyloxy-benzophenone,
2-Hydroxy-4-methoxy-4'-chloro-benzophenone, 2-hydroxy-4-dodecyloxy-benzophenone, 2-hydroxy-4-n
-Octoxy-benzophenone and the like. Among them, 2-hydroxy-4-n-octoxy-benzophenone is preferred. Among these ultraviolet absorbers, 2(2'-hydroxy-3'-tert-butyl-5'-methyl-phenyl)-5-chloro-benzotriazole is particularly preferred. Further, the hindered amine light stabilizer which is another component constituting the composition of the present invention has the general formula (H).
It is indicated by. Examples of compounds represented by general formula (H) 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)benzylethylmalonate, bis(2,2,6,6-tetramethyl-4-
piperidinyl)-n-butyl(3,5-di-tertiary
butyl-4-hydroxybenzyl)malonate,
butanetetracarboxylic acid tetra(2,2,6,
6-tetramethyl-4-piperidinyl) ester, among others, bis(2,2,
6,6-tetramethyl-4-piperidinyl) sebacate and tetra(2,2,6,6-tetramethyl-4-piperidinyl) ester of butanetetracarboxylic acid may be mentioned as preferred compounds. Each of these stabilizers is used in an amount of 0.05 to 5 parts by weight, preferably 0.1 to 2 parts by weight, based on 100 parts by weight of the polyether ester amide (A). If the amount of each stabilizer added is less than this, the effect will not be sufficiently expressed, and if it is more than this, the physical properties of the composition will be adversely affected and undesirable phenomena such as blooming will occur. In addition, the polyether ester amide (A) of the present invention
In order to make the composition stable against both thermal oxidative deterioration and photo-oxidative deterioration, polyether ester amide (A) must be combined with the general formula (B), (C), (D) or
It is necessary to add both the aromatic amine compound represented by (E) and the ultraviolet absorber represented by the general formula (F) or (G), and if either of these is missing, Only compositions that have heat resistance and/or weather resistance that are significantly inferior to the compositions of the present invention can be obtained. The method of adding each of these stabilizers to the polyether ester amide is not particularly limited, and they 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), antistatic agents may be used as long as they do not impede the desired heat resistance and weather resistance stability. , a conductive agent, a crystal nucleating agent, a lubricant, a filler, a reinforcing material, an adhesion aid, a plasticizer, a mold release agent, a flame retardant, and other additives may 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℃ and 0.5% concentration, and the melting points are also measured by DSC unless otherwise specified.
(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".
0.20 parts of 1098 (antioxidant) and 0.05 parts of tetrabutyl titanate catalyst were charged into a reaction vessel equipped with a helical ribbon stirring blade, purged with _N2 , and heated to 240°C.
After heating and stirring for 40 minutes to obtain a nearly transparent homogeneous solution, it was heated to 270℃ according to the temperature increase and pressure reduction program.
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 structural formula and abbreviation of the stabilizer used in the examples are as follows.

【table】

[Table] Example After blending each stabilizer shown in Table 1 with polyether ester amide (A-1) and (A-2),
200℃ for (A-1), 180℃ for (A-2)
The mixture was melt-kneaded in a 30 mmφ extruder heated to ℃ and then pelletized. After drying this pellet in vacuum, it is pressurized at 200°C if the polyether ester amide is (A-1) or 180°C if the polyether ester amide is (A-2) to a thickness of 0.9 to 1.1 mm.
It was made into a press sheet of mm and punched into a No. 3 dumbbell-shaped test piece according to JIS K-6301. 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 was 63°C and water was sprayed for 18 minutes over a 2 hour period. 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. The elongation at break was measured in accordance with JIS K-6301. These results are shown in Table 1.

【table】

[Table] Comparative Example Polyether ester amide (A-1) or (A-2) was blended with either an aromatic amine compound or an ultraviolet absorber, and then pelletized in the same manner as in the previous example. These compositions, polymer (A-1) and polymer (A-2) were punched into test pieces in the same manner as in the above examples, and the heat resistance and weather resistance of each test piece were evaluated. Table 2 shows the results.

【table】

Claims (1)

[Claims] 1. 0.05 to 5 weight parts of an aromatic amine compound represented by the following general formula (B), (C), (D), or (E) to 100 parts by weight of polyether ester amide (A). and an ultraviolet absorber represented by the general formula (F) or (G) below.
0.05 to 5 parts by weight of each polyether ester amide composition. (However, R ₁ and R ₁ ' are hydrogen atoms, hydrocarbon groups having 1 to 18 carbon atoms, or 1 to 1 carbon atoms having an -O- bond.
They are any of the 18 hydrocarbon groups, and may be the same or different. R ₂ is carbon number 1
~12 alkyl groups. ) (However, R ₃ represents an alkyl group having 1 to 18 carbon atoms,
R ₄ is a hydrogen atom or an alkyl group similar to R ₃ , and may be the same as R ₃ . X is a halogen atom, and l is 0 or 1. ) 2 0.05 to 5 parts by weight of an aromatic amine compound represented by the following general formula (B), (C), (D) or (E) per 100 parts by weight of polyether ester amide (A), and the following general formula Add 0.05 of the ultraviolet absorber shown in (F) or (G)
5 parts by weight and a hindered amine light stabilizer represented by the following general formula (H) in respective proportions of 0.05 to 5 parts by weight. (However, R ₁ and R ₁ ' are hydrogen atoms, hydrocarbon groups having 1 to 18 carbon atoms, or 1 to 1 carbon atoms having an -O- bond.
They are any of the 18 hydrocarbon groups, and may be the same or different. R ₂ is carbon number 1
~12 alkyl groups. ) (However, R ₃ represents an alkyl group having 1 to 18 carbon atoms,
R ₄ is a hydrogen atom or an alkyl group similar to R ₃ , and may be the same as R ₃ . X is a halogen atom, and l is 0 or 1. ) (However, R ₅ is a hydrogen atom or an alkyl group having 1 to 12 carbon atoms, R ₆ is a straight chain or branched alkyl group having 1 to 6 carbon atoms, and R ₆ ' is the same alkyl group as R ₆ . They may be the same or different.Y is -O- or H-N-, and _R7 is a hydrocarbon group having 1 to 23 carbon atoms which may be substituted with a hydroxyl group, or -S-,
It represents a hydrocarbon group having 1 to 18 carbon atoms and having any of the following formulas. m is an integer from 1 to 4. )