JPH0150338B2 - - 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 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, 0.01 to 3 parts by weight of copper salt (B) is added to 100 parts by weight of polyether ester amide (A).
The present invention also relates to a stable polyetheresteramide composition in which a hindered amine light stabilizer represented by the following general formula (C) is added in a proportion of 0.05 to 5 parts by weight. (However, R ₁ is a hydrogen atom or has 1 to 12 carbon atoms.
an alkyl group, R ₂ is a straight chain or branched alkyl group having 1 to 6 carbon atoms, and R ₂ ' is the same alkyl group as R ₂ , which may be the same or different. Good too. X is -O- or

[Formula], R ₃ 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 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. 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 also a method in which the compounds (a), (b), and (c) above are charged into a reaction tank at the same time, melt-mixed, and then polymerized all at once under a high vacuum; this method is preferable because 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. Examples of the copper salt (B) which is another component constituting the composition of the present invention include copper chloride, copper bromide, copper fluoride, copper iodide, copper thiocyanate, copper nitrate, copper sulfate, and 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 hindered amine light stabilizer, which is another component constituting the composition of the present invention, is represented by the general formula (C). Examples of compounds represented by general formula (C) 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-ditert-butyl-4-hydroxybenzyl)malonate, bis(1,2,2,6,6-pentamethyl-4-piperidinylbenzyl)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-ditert-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 bis(1,2,2,6,6-pentamethyl-4-piperidinyl)-n-butyl(3,
5-ditert-butyl-4-hydroxybenzyl)malonate may be mentioned as a preferred compound. The copper salt (B) is used in a proportion of 0.01 to 3 parts by weight, preferably 0.05 to 1 part by weight, and the hindered amine light stabilizer is It is used in a proportion 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 hindered amine photostable compound represented by the general formula (C) to the polyether ester amide (A). It is necessary to add both of these agents, and if either of these is lacking, a composition that is significantly inferior in heat resistance or weather resistance, or both, compared to the composition of the present invention will be left. can't get it. There is no particular restriction on the method of adding each of these stabilizers to the polyether ester amide, 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). When preparing the composition of the present invention, other common additives, such as hydrolysis resistance improvers, colorants (pigments, dyes), antistatic agents, etc., may be used as long as they do not impede the desired heat resistance and weather stability. 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℃ and 0.5% concentration, and the melting points are also measured by DSC unless otherwise specified.
(Perkin Elmer DSC-1B). Reference example In the case of polymer (A-1): 65.5 parts of aminododecanoic acid, number average molecular weight is 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 obtained polyether ester amide (A-
The melting point of 2) was 142°C, and the relative viscosity was 1.79. Stabilizer The chemical formula or structural formula and its abbreviation of the stabilizer 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℃, polyether ester amide (A-2)
In the case of , the sheet was pressurized at 180°C to form a press sheet with a thickness of 0.9 to 1.1 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. Elongation retention rate is 50%
The weather resistance was evaluated by measuring the time required for this to occur and the time for cracks to occur on the irradiated surface. The measurement of elongation at break is
This was done in accordance with JIS K-6301. These results are shown in Table 1.

【table】

[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.

【table】

Claims (1)

[Claims] 1. 100 parts by weight of polyether ester amide (A), 0.01 to 3 parts by weight of copper salt (B), and a hindered amine light stabilizer represented by the following general formula (C).
Stable polyether ester amide compositions containing 0.05 to 5 parts by weight of each. (However, R ₁ is a hydrogen atom or has 1 to 12 carbon atoms.
an alkyl group, R ₂ is a straight chain or branched alkyl group having 1 to 6 carbon atoms, and R ₂ ' is the same alkyl group as R ₂ , which may be the same or different. Good too. X is -O- or [Formula], R ₃ 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. )