JPH0150341B2 - - 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, the hindered phenol radical scavenger represented by the following general formula (B) is added in an amount of 0.05 to 100 parts by weight of the polyether ester amide (A).
5 parts by weight, and the following general formula (C), (D), (E) or
This invention relates to a polyether ester amide composition in which a peroxide decomposer represented by (F) is added in a proportion of 0.05 to 5 parts by weight. (However, R ₁ is an alkyl group having 1 to 18 carbon atoms, and R ₁ ' is the same alkyl group as R ₁ and may be the same as R _1. R ₂ is a single bond, and 18
-COO-, in the hydrocarbon group or molecular chain of
CONH−,

[Formula] A hydrocarbon group having 1 to 18 carbon atoms and having any of the bonds, X is C,
S, a hydrocarbon group having 1 to 18 carbon atoms or

[Formula] is shown. l is an integer from 1 to 4. ) (However, R ₃ represents a hydrocarbon group having 1 to 18 carbon atoms or a hydrocarbon group having 1 to 23 carbon atoms having -COO-, -CONH- bonds in the molecular chain, and m is 1 to 4
is an integer. R ₄ is a hydrocarbon group similar to R ₃ and may be the same or different. However, the sum of the carbon numbers of R ₃ and R ₄ must be 12 or more. R ₃ ′, R ₃ ″, R ₃ are hydrocarbon groups similar to R ₃ and may be the same or different. Y represents -O- or -S-, and n is 0 (or 1.) The polyether ester amide composition further added with an ultraviolet absorber represented by the following general formula (G) or (H) in the same ratio as above has even more outstanding heat resistance. This results in a polyetheresteramide composition with weather resistance. (However, R ₅ represents an alkyl group having 1 to 18 carbon atoms, R ₆ is a hydrogen atom or an alkyl group similar to R ₅ , and may be the same as R _5. Z is a halogen atom, and p is 0 or 1.) 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 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. Examples of the hindered phenol radical scavenger (B), which is another component constituting the composition of the present invention, include 2,6-di-tert-butyl-p-cresol, 2,
5-di-tert-butyl-4-ethylphenol, 2,
2'-methylene-bis-4-methyl-6-tert-butylphenol, 2,2'-methylene-bis(4-ethyl-6-tert-butylphenol), 4,4'-methylene-bis(2, 6-di-tert-butylphenol), 4,4'-butylidene-bis(3-methyl-
6-tert-butylphenol), 4,4'-thiobis(6-tert-butyl-3-methylphenol), bis(3-methyl-4-hydroxy-5-tert-butylbenzyl) sulfide, 4,4' -thiobis(6-
tert-butyl-o-cresol)2,2'-thiobis(4-methyl-6-tert-butylphenol), 3,
Diethyl ester of 5-di-tert-butyl-4-hydroxybenzylphosphonic acid, n-octadecyl-3(3',5'-di-tert-butyl-4'-hydroxyphenyl)propionate, hexamethylene glycol-bis[ β-(3,5-di-tert-butyl-4-hydroxyphenol)propionate], N,
N'-hexamethylene-bis(3,5-di-tert-butyl-4-hydroxyhydrocinnamide), 2,
2'-thio[diethyl-bis-3(3,5-ditertiary)
butyl-4-hydroxyphenyl) propionate], dioctadecyl ester of 3,5-di-tert-butyl-4-hydroxybenzylphosphonic acid, tetraxy[methylene-3(3,5-di-tert-butyl-4-hydroxyphenyl)], [enyl)propionate] methane, 1,3,5-trimethyl-2,4,6-tris(3,5-di-tert-butyl-4-hydroxybenzyl)benzene, tris(3,5-di-tert-butyl-4 -hydroxyphenyl)isocyanurate, tris[β-(3,5-di-tert-butyl-4-
Examples include hydroxyphenyl)propionyl-oxyethyl]isocyanurate, and among these, those with a molecular weight of 500 or more are preferred because they are less likely to volatilize in a high-temperature atmosphere and can provide greater effects. Among these hindered phenol radical scavengers, N,N'-hexamethylene-bis(3,5-di-tert-butyl-4-hydroxyhydrocinnamide) is particularly suitable for use. The peroxide decomposer, which is another component constituting the composition of the present invention, is represented by the general formula (C), (D), (E) or (F). Examples of compounds represented by general formula (C) include dilauryl sulfide, distearyl sulfide,
Dibenzyl sulfite, diphenyl sulfide, dioctylthiodipropionate, dilaurylthiodipropionate, dimyristylthiodipropionate, distearylthiodipropionate, laurylstearylthiodipropionate, ditridecylthiodipropionate nate, distearyl-β,β′-thiodibutyrate, tetraxy[methylene-3(laurylthio)propionate]
Examples include methane. Among these, use of tetrakis[methylene-3(laurylthio)propionate]methane is particularly preferred. Examples of the compound represented by the general formula (D) include trilauryl phosphite, triisooctyl phosphite, trioleylphosphite, triphenyl phosphite, triotadecyl phosphite, triisodecyl phosphite, and trin-butyl phosphite. tris-2-ethylhexyl-phosphite, tris-stearyl phosphite, tris-2,4-di-tert-butylphenyl-phosphite, tris-tridecyl phosphite, tris-4-phenylphenol-phosphite,
Trisnonylphenylphosphite, phenyldiisodecylphosphite, phenyldioctylphosphite, diphenylnonylphenylphosphite, diphenylisodecylphosphite, diphenylisooctylphosphite, diphenyldecylphosphite, diphenyltri Examples include decyl phosphite, trilauryl trithiophosphite, tristearyl trithiophosphite, triphenyl trithiophosphite, trinonyl trithiophosphate, trilauryl trithiophosphate, among others, tris-2,
Preference is given to using 4-di-tert-butylphenyl phosphite, trilauryl trithiophosphite. Examples of compounds represented by general formula (E) include tetraphenyldipropylene glycol diphosphite, tetralauryl bisphenol A diphosphite, tetratridecyl bisphenol A diphosphite, tetraphenyltetratridecyl pentaerythritol tetraphosphite, etc. can be mentioned. Among them, tetralauryl bisphenol A
Diphosphites are preferred. Examples of the compound represented by the general formula (F) are diisodisyl pentaerythritol diphosphite, dilauryl pentaerythritol diphosphite,
Examples include distearyl pentaerythritol diphosphite and dinonyl phenyl pentaerythritol diphosphite. Among them, dinonylphenyl pentaerythritol diphosphite is preferred. A composition in which an ultraviolet absorber represented by the general formula (G) or (H) is further added to the polyether ester amide composition in the same proportion as above has even more outstanding heat resistance and weather resistance. It becomes a composition. An example of a compound represented by the general formula (G) is 2(2'-
Hydroxy-3',5'-di-tert-butylphenyl)benzotriazole, 2(2'-hydroxy-3'-tert-butyl-5'-methylphenyl)-5-chlorobenzotriazole, 2(2'-hydroxy-3 ′,5′−
ditertiary-butylphenyl)-5-chlorobenzotriazole, 2(2'-hydroxy-3',5'-ditertiary-amylphenyl)benzotriazole, 2(2'-hydroxy-5'-methylphenyl)benzotriazole, 2( Examples include 2'-hydroxy-5'-tetramethylbutyl)benzotriazole. Among these, 2(2'-hydroxy-3'-tert-butyl-5'-methylphenyl)benzotriazole is preferred. Examples of compounds represented by general formula (H) include 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-benzyloxybenzophenone,
2-Hydroxy-4-methoxy-4'-chlorobenzophenone, 2-hydroxy-4-dotesyloxy-benzophenone, 2-hydroxy-4-n-
Octoxybenzophenone, 2-hydroxy-4
-stearyloxy-benzophenone and the like. Among these, 2-hydroxy-4-n
-Octoxybenzophenone is preferred. Among these UV absorbers, it is particularly preferable to use 2(2'-hydroxy-3'-tert-butyl-5'-methylphenylbenzotriazole).
(A) 0.05 to 5 parts by weight per 100 parts by weight,
It is preferably used in a proportion of 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, the physical properties of the composition will be adversely affected, and undesirable phenomena such as blooming may occur. 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, a hindered phenol radical scavenger represented by the above general formula (B) and a hindered phenol radical scavenger represented by the above general formula (B) are added to the polyether ester amide (A).
It is necessary to add both of the peroxide decomposers shown in (C), (D), (E) or (F), and if either of these is lacking, the composition of the present invention Only compositions with significantly inferior heat resistance and/or weather resistance can be obtained compared to the conventional method. In addition, the ultraviolet absorber represented by the general formula (G) or (H) also includes the hindered phenol radical scavenger represented by the general formula (B) and the UV absorber represented by the general formula (C), (D), or (E).
Alternatively, the maximum effect can be obtained when both of the peroxide decomposers shown in (F) are added and further used. If either or both are lacking, the heat resistance and/or weather resistance will be significantly inferior to the composition of the present invention. 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 (molding). This is a method of melting and mixing. 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 agent, 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 structure 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),
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 in the Sunshine Weather-Ometer was 63°C and water was sprayed for 18 minutes over a 2 hour period. Elongation retention rate is 50
Weather resistance was evaluated by measuring the time at which the irradiation occurred and the time at which cracks appeared 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. The amount of each stabilizer added varies.
It is 0.4 parts.

[Table] Comparative Example 0.4 parts of each of the stabilizers shown in Table 2 were added to polyether ester amide (A-1) or (A-2), and then pelletized in the same manner as in the previous example.
The composition was different from the composition of the present invention. 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】

【table】

Claims (1)

[Claims] 1. 100 parts by weight of polyether ester amide (A), 0.05 to 5 parts by weight of a hindered phenol radical scavenger represented by the following general formula (B), and the following general formula (C). , (D), (E) or (F) in a proportion of 0.05 to 5 parts by weight. (However, R ₁ is an alkyl group having 1 to 18 carbon atoms, and R ₁ ' is the same alkyl group as R ₁ and may be the same as R _1. R ₂ is a single bond, and 18
−COO−, − in the hydrocarbon group or molecular chain of
CONH-, [Formula] is a hydrocarbon group having 1 to 18 carbon atoms, and X is C,
S, represents a hydrocarbon group having 1 to 18 carbon atoms or [Formula]. l is an integer from 1 to 4. ) (However, R ₃ represents a hydrocarbon group having 1 to 18 carbon atoms or a hydrocarbon group having 1 to 23 carbon atoms having -COO-, -CONH- bonds in the molecular chain, and m is 1 to 4
is an integer. R ₄ is a hydrocarbon group similar to R ₃ and may be the same or different. However, the sum of the carbon numbers of R ₃ and R ₄ must be 12 or more. R ₃ ′, R ₃ ″, R ₃ are hydrocarbon groups similar to R ₃ and may be the same or different. Y represents -O- or -S-, and n is 0 or 1.) 2 For 100 parts by weight of polyether ester amide (A), add 0.05 to 5 parts by weight of a hindered phenol radical scavenger represented by the following general formula (B), the following general formula (C), 0.05 to 5 parts by weight of a peroxide decomposer represented by (D), (E) or (F) and the following general formula (G)
Alternatively, a polyether ester amide composition containing an ultraviolet absorber represented by (H) in a proportion of 0.05 to 5 parts by weight. (However, R ₁ is an alkyl group having 1 to 18 carbon atoms, and R ₁ ' is the same alkyl group as R ₁ and may be the same as R _1. R ₂ is a single bond, and 18
−COO−, − in the hydrocarbon group or molecular chain of
CONH-, [Formula] is a hydrocarbon group having 1 to 18 carbon atoms, and X is C,
S, represents a hydrocarbon group having 1 to 18 carbon atoms or [Formula]. l is an integer from 1 to 4. ) (However, R ₃ represents a hydrocarbon group having 1 to 18 carbon atoms or a hydrocarbon group having 1 to 23 carbon atoms having -COO-, -NHCO- bonds in the molecular chain, and m is 1 to 4
is an integer. R ₄ is a hydrocarbon group similar to R ₃ and may be the same or different. However, the sum of the carbon numbers of R ₃ and R ₄ must be 12 or more. R ₃ ′, R ₃ ″, and R ₃ are hydrocarbon groups similar to R ₃ and may be the same or different. Y represents -O- or -S-, and n is 0 Or it is 1.) (However, R ₅ represents an alkyl group having 1 to 18 carbon atoms, R ₆ is a hydrogen atom or an alkyl group similar to R ₅ , and may be the same as R _5. Z is a halogen atom, and p is 0 or 1.)