JPH0150340B2 - - 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 have conducted intensive 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 to 5 parts of the hindered phenol radical scavenger represented by the following general formula (B) is added to 100 parts by weight of the polyether ester amide (A).
parts by weight, 0.05 to 5 parts by weight of a phosphite compound represented by the following general formula (C), (D) or (E), and 0.05 to 5 parts by weight of a hindered amine light stabilizer represented by the following general formula (F). The present invention relates to a polyamide elastomer composition prepared by adding each part of the polyamide elastomer composition. (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 , R ₃ ′, R ₃ ″ are hydrocarbon groups with 1 to 18 carbon atoms, or -COO-, -CONH in the molecular chain)
- represents a hydrocarbon group having 1 to 23 carbon atoms and may be the same or different. m is an integer from 1 to 4. ) (However, R ₄ is a hydrogen atom or has 1 to 12 carbon atoms.
an alkyl group, R ₅ is a straight chain or branched alkyl group having 1 to 6 carbon atoms, and R ₅ ' is the same alkyl group as R ₅ and may be the same or different. . Y is -O- or

[Formula], R ₆ 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. n is an integer from 1 to 4. ) A UV absorber represented by the following general formula (G) or (H) is further added to the polyether ester amide composition in the same proportion as above,
Furthermore, the composition has even more outstanding heat resistance and weather resistance. (However, R ₇ represents an alkyl group having 1 to 18 carbon atoms, R ₈ is a hydrogen atom or an alkyl group similar to R ₇ , and may be the same as R _7. 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.
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. 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-tertiary
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-butylphenol) 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-butylbenzyl) 3-butylphenol), diethyl ester of 3,5-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-hydroxyhydrocinnamic acid amide), 2,2'-thio[diethyl-bis-3(3,5
-di-tert-butyl-4-hydroxyphenyl)propionate], dioctadecyl ester of 3,5-di-tert-butyl-4-hydroxybenzylphosphonic acid, tetrakis[methylene-3(3,5-di-tert-butyl- 4-Hydroxyphenyl)propionate]methane, 1,3,5-trimethyl-2,
4,6-tris(3,5-di-tert-butyl-4-hydroxybenzyl)benzene, tris(3,5-
Examples include di-tert-butyl-4-hydroxyphenyl) isocyanurate, tris[β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionyl-oxyethyl] isocyanurate, among which the molecular weight is Those with a molecular weight of 500 or higher are preferred because they are less likely to volatilize in a high-temperature atmosphere and therefore 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. Further, the phosphite compound, which is another component constituting the composition of the present invention, is represented by the general formula (C), (D) or (E). Examples of the compound represented by the general formula (C) are trilauryl phosphite, triisooctyl phosphite, trioleylphosphite, triphenyl phosphite, triotadecyl phosphite,
Triisodecyl phosphite, tri-n-butyl phosphite, tris-2-ethylhexyl-
Phosphite, tristearyl phosphite, tris-2,4-di-tert-butylphenyl-phosphite, tris-tridecyl phosphite, tris-
4-phenylphenol phosphite, trisnonylphenyl phosphite, phenyl diisodecyl phosphite, phenyldioctyl phosphite, diphenylnonylphenyl phosphite,
Examples include diphenylisodecylphosphite, diphenylisooctylphosphite, diphenyldecylphosphite, diphenyltridecylphosphite, among others, tris-2,
Preference is given to using 4-di-tert-butylphenyl phosphite. Examples of compounds represented by general formula (D) 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 compounds represented by general formula (E) include diindecylpentaerythritol diphosphite, dilaurylpentaerythritol diphosphite,
Examples include distearyl pentaerythritol diphosphite and dinonyl phenyl pentaerythritol diphosphite. Among them, dinonylphenyl pentaerythritol diphosphite is preferred. Furthermore, the hindered amine light stabilizer which is another component constituting the composition of the present invention has the general formula (F).
It is indicated by. Examples of compounds represented by general formula (F) 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)sepacate, 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-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-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 tetra(2,2,6,6-tetramethyl-4-piperidinyl) ester of butanetetracarboxylic acid may be mentioned as preferred compounds. A composition in which an ultraviolet absorber represented by the general formula (G) or (H) is further added in the same ratio as above to the polyether ester amide composition has even more outstanding heat resistance and weather resistance. Become a thing. 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). Each stabilizer is used at a ratio of 0.05 to 5 parts by weight, preferably 0.1 to 2 parts by weight, per 100 parts by weight.If the amount of each stabilizer added is less than this, the effect will not be sufficiently expressed, and the amount added If the amount is more than this, the physical properties of the composition will be adversely affected, and undesirable phenomena such as blooming will also occur.
In order to make the composition stable against both thermal oxidative deterioration and photooxidative deterioration, it is necessary to use 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) for the polyether ester amide (A). It is necessary to add a phosphite compound represented by (C), (D) or (E) and a hindered amine stabilizer represented by the above general formula (F), and even if any one of these is If this is lacking, only a composition can be obtained which has significantly inferior heat resistance and/or weather resistance compared 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 at any time during or after the polymerization of the polyether ester amide, but a particularly preferred embodiment is after the polymerization (molding). This is a method of melting and mixing. When preparing the composition of the present invention, other common additives such as hydrolysis resistance improvers, colorants (pigments, dyes), and antistatic agents may be used as long as they do not impede the desired heat resistance and weather 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°C and a concentration of 0.5, 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".
1098 (antioxidant) 0.20 parts and tetrabutyl titanate catalyst 0.05 parts 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
The temperature was 142°C and the relative viscosity was 1.79. Stabilizer The structure and abbreviation of the stabilizer used in the examples are as follows.

【table】

【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-O-meter was 63°C and water was sprayed for 18 minutes for 2 hours. 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] 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 compound represented by the following general formula (B), the following general formula (C),
A phosphite compound represented by (D) or (E)
A polyamide elastomer composition containing 0.05 to 5 parts by weight of a hindered amine light stabilizer represented by the following general formula (F) in respective proportions 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 , R ₃ ′, R ₃ ″ are hydrocarbon groups with 1 to 18 carbon atoms, or -COO-, -CONH in the molecular chain)
- represents a hydrocarbon group having 1 to 23 carbon atoms and may be the same or different. m is an integer from 1 to 4. ) (However, R ₄ is a hydrogen atom or has 1 to 12 carbon atoms.
an alkyl group, R ₅ is a straight chain or branched alkyl group having 1 to 6 carbon atoms, and R ₅ ' is the same alkyl group as R ₅ and may be the same or different. . Y is -O- or [Formula], and R ₆ is a hydrocarbon group having 1 to 23 carbon atoms which may be substituted with a hydroxyl group, or -S- or [Formula] having 1 carbon number ~18 hydrocarbon groups are shown. n is an integer from 1 to 4. ) 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), and add the following general formula (C), (D) or ( 0.05 to 5 parts by weight of a phosphite compound represented by E), 0.05 to 5 parts by weight of a hindered amine light stabilizer represented by the following general formula (F), and 0.05 to 5 parts by weight of a phosphite compound represented by the following general formula (G) or (H). A polyamide elastomer composition containing an ultraviolet absorber 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 , R ₃ ′, R ₃ ″ are hydrocarbon groups with 1 to 18 carbon atoms, or -COO-, -CONH in the molecular chain)
- represents a hydrocarbon group having 1 to 23 carbon atoms and may be the same or different. m is an integer from 1 to 4. ) (However, R ₄ is a hydrogen atom or has 1 to 12 carbon atoms.
an alkyl group, R ₅ is a straight chain or branched alkyl group having 1 to 6 carbon atoms, and R ₅ ' is the same alkyl group as R ₅ and may be the same or different. . Y is -O- or [Formula], R ₆ 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. n is an integer from 1 to 4. ) (However, R ₇ represents an alkyl group having 1 to 18 carbon atoms, R ₈ is a hydrogen atom or an alkyl group similar to R ₇ , and may be the same as R _7. Z is a halogen atom, and p is 0 or 1.)