JPS6049060A - Polyamide elastomer composition - Google Patents

Abstract

PURPOSE:To provide the titled composition having remarkably improved heat resistance and weather resistance, by compounding a polyether ester amide with a hindered phenol compound, a phosphite compound and a hindered amine light stabilizer. CONSTITUTION:(A) 100pts.wt. of a polyether ester amide is compounded with (B) 0.05-5pts.wt. of a hindered phenol compound of formula I (R1 is 1-18C alkyl; R1' is same as R1; R2 is single bond, 1-18C hydrocarbon group, or 1- 18C hydrocarbon group containing -COO-, etc. in the molecular chain; X is C, S, etc.; l is 1-4), (C) 0.05-5pts.wt. of a phosphite compound of formula II, IIIor IV (R3, R3' and R3'' are 1-18C hydrocarbon group, etc.; m is 1-4) and (D) 0.05-5pts.wt. of a hindered amine light stabilizer of formula V (R4 is H or 1-12C alkyl; R5 and R5' are 1-6C alkyl; Y is -O- or -NH-; R6 is 1-23C hydrocarbon group, etc.; n is 1-4).

Description

[Detailed description of the invention]

The present invention relates to a polyether ester amide 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 main chain of the polymer, is well known and, like polyether ester or polyester amide, has excellent impact resistance and rubber elasticity, so it is widely used in the polyamide field. In recent years, it has attracted attention as a new material. In particular, polyether ester amide has excellent lightness, transparency, and low-temperature impact resistance, and is less likely to cause creases or sink marks during molding, so it is promising for various molding applications. However, polyetheresteramides are extremely susceptible to oxidative deterioration, resulting in a decrease in the degree of polymerization and resulting in undesirable phenomena such as a decrease in mechanical properties, surface cracking, and coloration. 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, attempts have been made to add various stabilizers to polyetheresteramides in order to prevent these deterioration phenomena. 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 extensive studies and found that the addition of a specific compound group as a stabilizer to polyether ester amide has achieved heat resistance and heat resistance that could not be obtained conventionally. The present invention was accomplished by discovering that a polyether ester amide resin composition having extremely excellent weather resistance can be obtained. That is, the present invention provides polyether ester amide (A)
0.005 to 5 parts by weight of a hingudphenol-based carcinogenic agent represented by the following general formula (E) per 100 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). This relates to a polyamide elastomer composition obtained by adding 5 parts by weight of each proportion.
1/ is the same alkyl group as R1, and may be the same as R. R2 is a single bond, a C1-C18 hydrocarbon group, or a C11 OR having -COO-1-CON H-5 -o-po-o- bond in the molecular chain. -18 hydrocarbon group, X is C, S, carbon number 1-1
8 hydrocarbon groups or 1. ) (However, R3, R1', B3tt have 1 to 18 carbon atoms.
hydrocarbon group or -COO-1-CO in the molecular chain
It represents a hydrocarbon group having 1 to 23 carbon atoms and having an NH- bond, and may be the same or different. m is 1
It is an integer of ~4. ] (However, R4 is a hydrogen atom or an alkyl group having 1 to 12 carbon atoms, 115 is a straight chain or branched alkyl group having 1 to 6 carbon atoms, and Rb2 is the same alkyl group as R5, and each is the same.) Y is 10- or -N-, and R
6 represents a hydrocarbon group having 1 to 23 carbon atoms which may be substituted with a hydroxyl group, or a -5-118 hydrogen ashing group,
, n is an integer from 1 to 4. ] The polyether ester amide composition described in θU is further added with an ultraviolet absorber represented by the following general formula fG) or (H) in the same ratio as described in DiJ, and has even more superior heat resistance. This results in a composition with improved weather resistance. HOR. (However, R7 represents an alkyl group having 1 to 18 carbon atoms, and R
8 is a hydrogen atom or an alkyl group similar to R7,
It may be the same as R7. 2 is a halogen atom, and p is 0 or 1. ) The composition of the present invention will be specifically described below. Polyether ester amide (Al) in the present invention is a polymer composed of polyamide units and polyether ester units and having amide bonds, ether bonds, 8 and ester bonds in the molecular chain. 7 derived from carboxylic acids, lactams, salts of dicarboxylic acids and diamines, or combinations of dicarboxylic acids and diincyanates.The polyether ester units have a number average molecular weight of 600 to 60.
The copolymerization ratio of polyamide units and polyether ester units is approximately 5:90 to 95:10 by weight.Polyether The method of polymerizing ester amide (Al) is not particularly limited and any known method can be used. For example, an aminocarboxylic acid, lactam or dicarboxylic acid-diamine salt (al and dicarboxylic acid (C) are mixed in an approximately equimolar ratio) A method of reacting to produce a polyamide prepolymer having carboxylic acid groups at both ends, and then reacting poly(alkylene oxide) glycol (b) once under vacuum, or adding the above compounds (al, fb+, (01) in a reaction tank. A method is known in which a yoricarboxylic acid-terminated polyamide prepolymer is produced by charging the mixture with water and reacting under pressure at high temperature in the presence or absence of water, and then proceeding with polymerization under normal pressure or reduced pressure. There is also a method of charging the above compounds (al, (bl, and A solution polymerization method in which Matapoly(alkylene oxide) glycol is reacted with about twice the mole of dicarboxylic acid to form a prepolymer with carboxylic acid groups at both ends, and this is reacted with dicarboxylic acid and diincyanate in an inert solvent. t
It's okay to overdo it. The other component of the composition of the present invention, hiftate-fer-based radical scavenger (BII:), includes, for example, 2,6-di5-butyl-p-creso-/l/;
2,5-tertiary phthyl-4-ethylphenol,
2.2'-methylene-bis-4-methyl-6-tert-butylphenol, 2.2'-methylene-bis(4-ethyl-6-5-tert-butylphenol), 4.41-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-hy)”
I"l xy-5-ffr, 3-butylbenzylnosulfide, 4,4-thiobis(6-5-butyl-0-cresol), 2,2'-thiobis(4-methyl-6-tert-butylphenol) ], 3,5-G'3 butyl 4
- diethyl ester of hydroxybenzylphosphonic acid,
n-octadecyl-3(3',5'-di-tert-butyl-4
'-Hydroxyphenyl)propionate, hexamethylene glycol-bis[β-(3,5-cy-31-thyl-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)propione)), 3,5-di-tert-butyl-4-hydroxyphenyl)
Dioctadecyl ester of butyl-4-hydroxybenzylphosphonic acid, tetraquine [methylene-3(3,5-
di-tert-butyl-4-hydroxyphel[propionate]methane, 1,3.5-trimethyl-2,4,6-)
Lis(3,5-ditert-butyl-4-hydroxybenzyl)benzene, Tris(3,5-ditert-butyl-4-hydroxyphenylcoin cyanurate, Tris[β-(3
, 5-di-tert-goutyl-4-hydroxyphenyl)propionyl-oxyethylcoin cyanurate, etc. Among these, those with a molecular weight of 500 or more are less likely to volatilize in a high-temperature atmosphere, so a greater effect can be obtained, and therefore 1 is preferred. . scavenging these hindered phenol radicals. Among the stimulants, N,N'-hexamethylene-bis(3
, 5-cyj33gtyl-4-hydroxyhydrocinnamic acid amide] is preferred. The phosphite compound, which is another component constituting the composition of the present invention, is represented by the general formula (C1, (D) or (El) in niJ. Examples of compounds represented by the general formula (C) is trilauryl phosphite, triisooctyl phosphite, trioleylphosphite, triphenyl phosphite, triotadecyl phosphite, triisodecyl phosphite, trin-butyl phosphite, tris-2-
Ethylhexyl phosphite, tristearyl phosphite, tris-2,4-di-tert-butylphenyl phosphite, tristridecyl phosphite, tris-4
-Phenylphenol-phosphite, trisnonylphenylphosphite, phenyldiisodecylphosphite, phenyldioctylphosphite, diphenylnonylphenylphosphite, zincenylisodecylphosphite, diphenylisooctyl7hs7phyl-, diphenyldecylphosphite l) 2i% of decyl phosphonoite and the like, among which tris-2,4-di-tert-butylphenyl phosphite is particularly preferred. Examples of the compound represented by the general formula (1)l include tetraphenyl dipropylene glycol diphosphite, tetratridecyl bisphenol A diphosphite, and tetraphenyltetratridecyl pentaerythritol tetraphosphite. Among them, tetralauryl bisphenol A diphosphite is preferred. Examples of compounds represented by the general formula (E) include C7 f
'/ Examples include lupentaerythritol diphosphite, dilauryl pentaerythritol diphosphite, distearyl pentaerythritol diphosphite, and zinnylphenyl pentaerythritol diphosphite. Among others. Dinonylphenylpentaerythritol diphosphite is preferred. Furthermore, the hindered aluminum/system element stabilizer, which is another component of the composition of the present invention, is represented by the general formula (F). Examples of compounds represented by the general formula ip) include 4-penzoyloxy-2.2,6.6-titramethylpiveridine, bis(2,2,6.6-tetramethyl-4-piperidinyl]adipate , bis(2.2,6.6-titramethyl-4-piperidinyl)suberate, bis<2.2
．． 6.6-Titramethyl-4-piperidinyl) Sepacu 1, Bis(2,2,6.6-Titramethyl-4-piperidinyl) Phthalate, Bis(2,2,6.6-Tetramethyl-4-piperidinyl) Inphthalate 1,, Bis( 2
, 2,6.6-tetramethyl-4-piperidinyl)tere7talate, bis(1.2.2,b,b-pentamethyl-4-piperidinyl)sebacate, N,N'-bis(2,2,6 .6-tetramethyl-4-piperidinyl)adipamide, bis(1.2,
2,6,6-bentamethyl-4-piperidinyl) -n
-butyl(3,5-ditert-butyl-4-hydro-7benzyl]malo, ?.-), bis(1.2.2.6.6-bentamethyl-4-piperidinyldibenzyl)malonate, bis(1 2,2,6.6-bentamethyl-4-piperidinyl)diethylmalonate, bis(2,2,6.6-tetramethyl-4-piperidinylnonbenzylmalonate, bis(2,2,6.6- Tetramethyl-4-piperidinyl)benzylethylmalonate, bis(2,2,6.6-
Tetramethyl-4-piperidinyl)-n-glutyl (3.
Examples include 5-di6-butyl-4-hydroxybenzyl]malonate, tetra(2,2,6.6-tetramethyl-4-piperidinyl)ester of butanetetracarboxylic acid, and especially bis(2.2, 6,6-tetramethyl-4-piperidinyl)sepacou)S and butanetetracarboxylic acid tetra(2,
2,6.6-tetramethyl-4-piperidinyl) ester is mentioned as a preferred compound. I can do that. The polyether ester amide composition is further added with an ultraviolet absorber of the general formula (Gl or (gl) in the same ratio as above) 1'8
The composition has heat resistance jiM and weather resistance exceeding 1+11. An example of a compound represented by the general formula (Gl) is 2(2'-
Hydroxy-s/. 57-Ditert-butylphenyl]benzotriazole, 2(2'-hydroxy-3'-tert-butyl-5'-methylphenyl)-5-chlorobenztriazole, 2(2'-hydroxy-X/.S/- Ji 3rd
butylphenyl]-5-chlorobensotho IJ 7zole, 2(2'-hydroxy-s/.51-di6th amyl phenyl]benzotriazole 2(27-hydroxy-
, 5'-Jf ruphenylfbenzotriazole, 2(2
Examples include '-hydroxy-5'-tetramethylbutylnobe/citriazole. Among these, 2 (2'
-Hydroxy-6'-5-y-thyl-5'-methylphenylbenzotriazole is preferred. Examples of compounds represented by formula ()11 include 2-hydroxy-4-methquine benzophenone, 2-hydroxy-4-penzyloxybenzophenone, and 2-hydroxy-4-methoxy/-4'-chlorobenzophenone. +2-hydroxy-4-totisyloxy-benzophenone, 2-
Hydroxy-4-n-octoxybenzophenone, 2-
Examples include hydroxy-4-stearyloxy-benzophenone. Among these, 2-hydroxy-4-
Preferred is n-octoxybenzophenone. Among these ultraviolet absorbers, especially 2(2'-hydroxy-3')
Preference is given to using -tert-butyl-5'-methylphenylbenzotriazole. Each of these stabilizers is composed of polyether ester amide and Al
005 to 5 parts by weight per 100 parts by weight, respectively;
Preferably, it is used in a ratio of 0.01 to 0.02 times. If the amount of each stabilizer added is less than the required amount, the effect will not be fully expressed.

[9 pieces added. If there is more than this, the physical properties of the composition will be affected.
It may cause irritation and may also cause undesirable urine discharge such as blooming. In addition, in order to make the polyether ester amide (Al) of the present invention a stable composition that is resistant to both heat aggregation degradation and photo-oxidative degradation, the polyether ester amide (A
1 ii J General formula (13) Hinodad phenolic carcasses ε and qtJ General formula te+, FD) or (E) phosphite compounds 16 and 1J J general It is necessary to add the king of hindered amine light stabilizers represented by formula (P), and if any one of them is lacking, the composition will have poor heat resistance or weather resistance compared to the composition of the present invention. Only compositions with significantly inferior properties or both can be obtained. The method of adding h5 to the polyether ester amide is not particularly limited, and it 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 ( Before molding) t
This is a method of melting and mixing. In addition, when preparing the m11 product of the present invention, other common additives such as hydrolysis resistance improvers, colorants (pigments, dyes), and antistatic additives may be used as long as they do not impede the desired heat resistance and weather resistance stability. Additives such as a conductive agent, a crystal nucleating agent, a lubricant, a filler, a reinforcing material, an adhesion aid, a 0■ plastic agent, a 1lill type agent, and a Y!11 fuel agent can be optionally blended. Examples below. The present invention will be explained by the following. In the examples, "parts" or "%" are all expressed in weight I^ ratios. In addition, the relative viscosity shown in g in the text and in the examples is orthochloro Values measured in phenol at 25°C% [L596
n Elmer DS+Nie IE). Reference Example Polymer (655 parts of polymerized aminododecanoic acid of A-IJ, polytetramethylene oxide glycol having a number average molecular weight of 680.
Iirganox” 1098 (antioxidant) 0.20
1 part and 0.05 part of tetrabutyl titanate catalyst were placed in a six-hole vessel equipped with a helical ribbon stirring blade, purged with N2, and heated and stirred at 240°C for 40 minutes to form an almost transparent homogeneous solution. After that, the proper conditions of 270° C. and 0.5 ml Hg or less were achieved according to a temperature increase and pressure reduction program. The polymerization reaction was carried out under these conditions for 3 hours and 50 minutes. The melting point of the obtained polyether ester amide (A-1) was 166°C, and the relative viscosity was 1.65.
Polymer (A-2) was obtained by carrying out a polymerization reaction in the same manner as in Example 1 using 53.1 parts g of polytetramethylene oxide glycol No. 0 and 8 parts of terephthalic acid A as starting materials. The obtained polyether ester amide (A-2) had a melting point of 142°C and a relative viscosity of 1
．． It was 79. The names and abbreviations of the stabilizers used in the stabilizer examples are as follows: Examples Polyetherester Amides (A-j'J and (A-
2) After comparing each of the stabilizers shown in Table 1, they were melted and kneaded in an extrusion mode with a diameter of 30 strokes heated to 200 °C in the case of A-1 and 180 °C in the case of A-2. Made into a beret. After drying this pellet in vacuum, the pellet was pressurized at 200°C for polyether ester amide (A-1J) and 180°C for polyether ester amide (A-2) to a thickness of 119 to 1.1 mm. As a press sheet, J-engine f
3 A No. 3 dumbbell-shaped test piece of K-6301 was punched out. The heat resistance was investigated by aging the test piece in a hot air open at 130°C, and the time when the elongation at break reached 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 for 2 hours and water was sprayed for 18 minutes. Weather resistance was evaluated based on the time at which the elongation body 11 ratio reached 50% and the time at which cracks appeared on the irradiated surface. The elongation at break was measured in the same manner as J-K5K-630+1. These results are shown in Table 1. Comparative Example Polyetheresteramide (A-IJ or (A-
After adding 4 parts each of the stabilizers shown in Table 2 to 2),
The pellets were pelletized in the same manner as in Examples to obtain a composition different from the composition of the present study. These compositions, polymer (A-1) and polymer (
A-2J was made into a punched test piece in the same manner as in the example described in MiJ. The results of evaluating the heat resistance and weather resistance of the dead test piece are shown in Table 2.Continued from page 1

Claims (1)

[Scope of Claims] 1. To 100 parts by weight of polyether ester amide (8), add 105 to 5 parts by weight of a hindered phenol compound represented by the following general formula (Bl) to 100 parts by weight of the following general formula (fcl).
, 0.05 to 5 parts by weight of a phosphite compound represented by (Dl or (Bi)), and the following general formula (F
) Hindered amine light stabilizer shown by 0.05~
5 parts by weight of each polyamide elastomer composition. R1 R, / (However, R1 is an alkyl group having 1 to 18 carbon atoms, and n
, / is the same alkyl group as R, and may be the same as R. R2 is simple. bond, a hydrocarbon group having 1 to 1B carbon atoms, and 0 is a carbon OR having any of -coo-1-0ONH-11 -o-po-o- bonds in the molecular chain. It is a hydrocarbon group of number 1 to 18, and X is C1S, carbon number 1
There are ~18 hydrocarbon groups or 1. ] (However, R3, R, / , R3// has 1 to 18 carbon atoms
hydrocarbon group or in the molecular chain e-COO-1-O
It represents a hydrocarbon group having 1 to 23 carbon atoms, such as an OIJH- bond, and may be the same or different. m
is an integer from 1 to 4. ) (However, R4 is a hydrogen atom or an alkyl group having 1 to 12 carbon atoms, R5 is a straight chain or branched alkyl group having 1 to 6 carbon atoms, and Rs' is the same alkyl group as R5, and each is the same.) Y is 10- or -N-, and R6 is water. A hydrocarbon group having 1 to 23 carbon atoms which may be substituted with an acid group, or -8-2 0, c, N\C 0 1 /N''C'ゝ\ Indicates a hydrocarbon group with a prime number of 1 to 18. n is an integer of 1 to 4.) 2. 0.05 to 5 parts of a hindered phenol radical scavenger represented by the following general formula fB to polyether ester amide (Al l 00 parts by weight), and the following general formula (C), CD + or (E ) 0.05 to 5 parts by weight of the phosphite compound represented by the following general formula (F
) 1 Hinder = Doamine light stabilizer 0,0
・5-5 parts by weight 1. A polyamide entomer composition containing an ultraviolet absorber represented by +3 and the following general formula iG) or (H) in a proportion of 005 to 5 parts by weight. (However, R, is an alkyl group having 1 to 18 carbon atoms, and R
1' is an alkyl group similar to R, and may be the same as R. ・R2 is a single bond, a hydrocarbon group having 1 to 18 carbon atoms, or -C00-, -CONH in the molecular chain. -1
1 carbon having any of the -o-p-o- bonds ■OR+ is a hydrocarbon group having numbers 1 to 18, and X is C1S, carbon number 1
~18 hydrocarbon groups or. ] 30 [However, R3, R3', B3// are hydrocarbon groups having 1 to 18 carbon atoms, or 1000-1-G O in the molecular chain
Ii represents a hydrocarbon group having 1 to 23 carbon atoms that forms an H-bond, and may be the same or different. m is an integer from 1 to 4. ] R6Ra' (where R4 is a hydrogen atom or an alkyl group having 1 to 12 carbon atoms, R5 is a straight chain or branched alkyl group having 1 to 6 carbon atoms, and R6' is the same alkyl group as R5. Y is 10- or -N-, and R6 is a hydrocarbon having 1 to 23 carbon atoms and optionally substituted with hydroxyl) group, or -S-1 ■ 1 1 to 18 hydrocarbon group. n is an integer of 1 to 4.] HOR. (However, R7 represents an alkyl having 1 to 18 carbon atoms, !l(, Ll is a hydrogen atom or 1 (an alkyl group similar to 7 and may be the same as R7; 2 is a halogen atom, and 511 is O or 1);