JPS6049061A - Polyether ester amide 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-type radical scavenger and a peroxide-decomposition agent. CONSTITUTION:The objective composition is produced by compounding (A) 100pts.wt. of a polyether ester amide with (B) 0.05-5pts.wt. of a hindered phenol-type radical scavenger 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-, -CONH-, etc. in the molecular chain; X is C, S, etc.; l is 1-4) and (C) 0.05-5pts.wt. of a peroxide-decomposition agent of formula II, III, IVor V (R3 is 1-18C hydrocarbon group or 1-23C hydrocarbon group containing -COO- or -CONH- in the molecular chain; m is 1-4; R4 is same as R3; the sum of the carbon numbers of R3 and R4 is >=12; R3', R3'' and R3''' are hydrocarbon group same as R3; Y is -O- or -S-; n is 0 or 1).

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a polyether ester amide resin composition having excellent heat resistance and weather resistance and a high property rj ratio.

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, and can be used as a flexible elastomer. R7 has been attracting attention in recent years as a new material in the field.

In particular, polyether ester amide is lightweight, transparent, has low-temperature impact resistance, and has excellent resistance to scratches during molding.
It is promising for various molding applications because it does not easily cause sink marks. However, polyetheresteramide is extremely susceptible to oxidative deterioration, and as the degree of polymerization decreases, mechanical properties decrease1.
Surface σ) Unfavorable phenomena such as 11 cracks and F timbre 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. Hence these deterioration phenomena.

In order to prevent this, the addition of various stabilizers to polyether ester amide has been studied. 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 present inventors have conducted intensive studies and found that by adding a specific compound Z (r-) as a stabilizer to polyether esteramide, heat resistance that could not be measured conventionally was achieved. The inventors have discovered that a polyether ester amide with extremely poor weather resistance can be obtained, and has arrived at the present invention.

That is, the present invention provides polyether ester amide
For 00 parts by weight of li, all of the hindered phenol radicals J+Il represented by the following general formula (B) are 0.
．． 0 5 to 5 parts, 8 and the following general formula FC+, (D
The present invention relates to a polyether ester amide composition in which a peroxide decomposer represented by +, (El or (F)) is added in a total percentage of 005 to 5.

(However, R, is an alkyl group having 1 to 18 carbon atoms, and R
1' is an alkyl group similar to R1;

may be the same as R2 is a single bond, carbon number 1-18
-000- in the molecular chain or a hydrocarbon group having 1 to 18 carbon atoms, and X is C, S, or a hydrocarbon group having 1 to 18 carbon atoms.
18 hydrocarbon groups (however, R3 has 1 to 1 carbon atoms)
8 carbon (arsenic group or e in the molecular chain co〇-,-
G ON represents a hydrocarbon group having 1 to 26 carbon atoms and having an H- bond, and m is an integer of 1 to 4. R4 is the same as R3
Soft σ] is a hydrocarbon group. They may be the same or different. However, the sum of the carbon numbers of R3 and R4 is 12
The above should be 7 good. R3, R3, rt3''
' is a hydrocarbon group similar to R3, and may be the same or different. Y [Yo-O- or -S-, n is 0 or 1, x) is 1. ] The above polyether ester amide tree composition further has an ultraviolet absorber represented by the following general formula (G) or (1') added thereto at a concentration of 41 as described in 1iii, and is even more refined. The resulting polyetheresteramide composition has heat resistance and weather resistance.

to R (however, R5 represents an alkyl group having 1 to 18 carbon atoms, R6 is a hydrogen atom or an alkyl group similar to R5, and R5
Even if it is the same as U\. 2 is a halogen atom, p
The composition of the present invention will be specifically described below.

The polyether ester amide (A) according to the present invention is composed of a polyamide unit and a polyether Nisder unit, and has V-amide bonds, ether bonds, and 3
It is a normal complex having an ester bond and an ester bond.

The polyamide unit is derived from an aminocarboxylic acid, a lactam, a salt of a dicarboxylic acid and a diamine, or a combination of a dicarboxylic acid and a diiso7amate.

Polyether ester units have an average molecular weight of 300 to 60
00 poly(alkylene oxide) glycol 8 and a dicarboxylic acid having 4 to 20 carbon atoms.

The copolymerization ratio of polyamide units and polyetherester J units is approximately 5:90 to 95:10 by weight.

The method of combining polyether ester amide + A) is not particularly limited, and any known method can be used. For example, aminocarboxylic acids, lactams or dicarboxylic acids
A polyamide prepolymer having carboxylic acid groups at both ends was prepared by reacting diamine salt fa) with dicarboxylic m (c) yx in an approximately equimolar ratio, and this was then reacted with poly(alkylene oxide) glycol (1+) under vacuum. how to make
Alternatively, the above compounds (al, (bl, (cl) are charged into a reaction tank and reacted under pressure at surface temperature in the presence or absence of water to produce a carboxylic acid-terminated polyamide prepolymer, and then, A method of proceeding with polymerization under normal pressure or reduced pressure is known.
There is also a method in which the compounds of
Rather, this method is preferable since it causes less coloring of the polymer.

Alternatively, 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 then reacted with dicarboxylic acid and diisocyanate in an inert solvent. It's okay to be legal F.

Examples of hindered phenol radical scavengers (g), which are other components that support 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-b-'t5s butylphenol +2,
2'-methylene.

-bis(4-ethyl-6-Xg 3-butylphenol), 4,4'-methylene-bis(2,6-di6-butylphenol), 4. Ru 6-1437-Terphenol 4,4
'-thiobis(6-tertiary glythyl-5-methylphenol), bis(3-,)'thiylcy4-human90xy5J
3-butylbenzyl] sulfite 114, 4'-thiobis(6-5-butyl-〇-cresol) + 2.2'-thiobis(4-methyl-6-tert-butylphenol), S,
Diethyl ester of 5-di-tert-butyl-4-hydroxypenzylphosphonic acid, 1-ocpfyl-3(
3'.

s' - tert-butyl-4'-hydroxyphenyl]
Propionate, hexamethylene glycol-bis[β
-(3.5-di-tert-butyl-4-hydroxyphenol-propione-)), N,N'-hexamethylene-bis(3.5-di-tert-butyl-4-hydroxyhydrocinnamic acid amide) , 2,2'-thio[diethyl-bis-3(3
．． 5-Di No. 37.

thyl-4-hydroxyphenyl)propionate), 3
．． Dioctadecyl ester of 5-ditert-butyl-4-hydroxybenzylphosphonic function, tetraxy[methylene-
3(3,5-ditert-butyl-4-hydroxyphenylnoprobionate)methane, 1,52.5-trimethyl-2,4,6-tris(3,5-ditert-butyl-4-
hydroxybenzyl)benzene, IJx(3,5-di-tert-butyl-4-hydroxyphenyl)isocyanur
]・, tris[β-(3,5-di6-butyl-4-hydroxyphenyl)propionyl-oxyethylcoin cyanurate, among which molecular weight is 50
0 or more is preferred because it volatilizes in a high-temperature atmosphere and is less dense, so a greater effect can be obtained.

Among the hindered phenol radical adjuvants of J'L et al., N,N'-hexamethylene-bis(3,5-Q
Preference is given to using 3-butyl-4-hydroxyhydrocinnamic acid amide).

In addition, the peroxide decomposer, which is one of the components of the composition of the present invention (14), has the following general formula (c), (o
), (+rJ・or fF).

Examples of compounds represented by the general formula (C) include dilauryl sulfide, distearyl sulfide, dibenzyl sulfide, diphenyl sulfide, dioctylthiodipropionate, dilaurylthiodipropionate, simiristylthiodipropionate, and distearyl. Examples include thiodipropionate, laurylzstearylthiodipropionate, dioctylthiodipropionate, distearyl-β, β'-thiodibutyrate, and tetraxy[methylene-3(laurylthio]propionate]methane. Among these, Particularly preferred is tetrakis[methylene-3(laurylthio)propionate]methane.

Examples of compounds represented by the general formula TDI include trilauryl phosphite, triinoctyl phosphite, trioleylphosphite, triphenyl phosphite,
Trioctadecyl phosphite, triindecyl phosphite, trin-butyl phosphite),) Lis-2
-Ethylhexyl-phosphite, tristearyl phosphite, tris-2,4-di-tert-butylphenyl-phosphite, tristritesyl phosphite, l-IJ
Sus--phenylphenol-phosphite, trisnonylphenylphosphite, phenyldiisodecylphosphite, phenyldioctylphosphite, diphenylnonylphenylphosphite, diphenylisodecylphosphite, diphenylisooctylphosphite,
Diphenyldecyl phosphite, diphenyltridecyl phosphite, trilauryltrithiophosphite, tristearyltrithiophosphite, triphenyltrithiophosphite, trinonyltrithiophosphate.

Examples include trilauryl trithiophosphate, among which tris-2,4-di-5-butylphenyl phosphite and trilauryl trithiophosphite are particularly preferred.

An example of the compound represented by the general formula (E) is tet.

Examples include raphenyldipropylene glycol diposphite, tetra2urylbisphenol A diphosphite, tetratridecylbisphenol A diphosphite, tetraphenyltetratridecylpentaerythritol tetraphosphite, and the like. Among them, tetralauryl bisphenol A diphosphite is preferred.

Examples of compounds represented by the general formula CF+ include diisodecylpentaerythritol diphosphite, dilaurylpentaerythritol diphosphite, distearylpentaerythritol diphosphite, dinonylphenylpentaerythritol diphosphite, and the like.

Among them, dinonylphenylpentaerythritol diphosphite is preferred.

ritJ A composition in which an ultraviolet absorber represented by the general formula (G) or (Hl) is further added in the same ratio as above to the polyneedle ester amide composition described above has even more outstanding heat resistance and weather resistance. becomes.

An example of a compound represented by the general formula (Gl) is 2(2'-
Hydroxy-s/,c,/-di5-buterphenylnopenzotriazole, 2(2'-hydroxy-"'-ff
i3 Goutyl-5'-methylphenyl-5-chloropenttriazole, 2(2'-hydroxy-31,5/-
ditertiarybutylphenyl, II/) -5-chloropenztriazole, 2(2'- and droxy-3/,5/-ditertiary amyl phenyl)penztriazole 2 < 2
/-hydroxy-5'-methylphenyl)benzotriazole, 2(2'-hydroxy-5'-tetramethylbutyl)benzotriazole, and the like.

Among these, 2(2'-hydroxy-3'J6butyl-5'-methylphenyl)benzotriazole is preferred.

Examples of compounds represented by the general formula +Fi+ include 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-benzyloxybenzophenone, 2-hydroxy-4-methoxy''-4'-chlorobenzophenone/, 2-
Hydroxy-4-.

Dodecyloxy-bencyphenone, 2-human 90x-
4-n-octoxybenzophenone, 2-hydroxy-
Contains 4-stearyloxy-benzophenone and the like. Among these, 2-hydroxy-4-n-octoxybenzophenone is preferred. These UV absorbers σ
) especially special 2 (2'-hydroxy-3'-45s)
Preference is given to using methylphenylbenzotriazole.

Each of these stabilizers is a positive ether ester amide iA)
100 parts by weight of each "C1 005~5 weight" 1
(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, this may occur. has a bad influence on the physical properties of the composition, and also comes to exhibit undesirable phenomena I7) such as blooming.

In addition, in order to make the polyether ester amide (tA) of the present invention a composition that is stable against both thermal oxidative deterioration and photo-oxidative deterioration, the polyether ester amide (Al
A pair of hindered phenol radical scavengers ε represented by the general formula (B) in 01j and the general formula (Cl
, (D+, (ic+) or (o°). It is necessary to plagiarize both of the peroxide decomposers, and if either of these is missing, the composition of the present invention Only compositions that are significantly inferior in heat resistance and/or weather resistance can be obtained compared to the conventional method.

Further, the ultraviolet absorbent represented by the general formula (G) or ()1) can also be used to combine a hindered phenol radical scavenger represented by the general formula (Bl) and the general formula (Cl, (D+,
(If both of the peroxide decomposers shown by El or fil are added, then if they are used in addition.)

If either the hindered enol carcinogen scavenger or the peroxide decomposer, or both are lacking, the heat resistance will be lower than that of the uninvented composition. Or weather resistance or both are greatly inferior.

There are no particular restrictions on the method of adding each of these stabilizers to the polyether ester amide.

-Although it can be added at any time (υ) during or after the polymerization of the thyl ester amide, a particularly preferred embodiment is a method in which it is melt-mixed after the polymerization (molding tJiJ).

In addition, in preparing the composition of the present invention, as long as it does not impede the desired heat resistance 3 and 1 weather resistance stability,
Other common additives, such as 11-inch hydrolysis improver,
Coloring agents (pigments, dyes), antistatic agents, conductive agents, crystal nucleating agents, lubricants, fillers, reinforcing materials, adhesion aids, plasticizers, mold release agents,
Additives such as flame retardants can be optionally added.

Hereinafter, the present invention will be explained with reference to Examples.

In Example A below, all items expressed in "parts" or "%" are expressed in weight ratios.

In addition, ε in the text and 4. Indicative viscosity shown in the examples are values measured in orthochlorophenol at 25°C and 0.5%.
Melting peak temperature measured with a Perkin Rlmer DSC-1B).

Reference Example Polymer (A-1) Polymerized aminododecane [65.5ill, number average molecular weight 68
36.6 parts of polytetramethylene oxide glycol and 2 parts of themphthalic acid a to 11yl)j/tsuk,
r, ” 1098 (, e, antioxidant) 020 parts J6
and tetrabutyl titanate catalyst [1L05 parts and 5 parts of helical ribbon were charged into a reaction vessel equipped with 14 stirring blades, and N
After 2 purges, the mixture was heated and stirred for 40 minutes at 24[deg.]C to obtain an almost transparent homogeneous solution, and the polymerization conditions were brought to 270[deg.]C, o, 5MH8 or less 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 obtained polyether ester amide (A-1) had a single point of 166° C. and a relative viscosity of 165.

Polymer (456 polymerized aminododecanoic acid of A-2J, number average molecular weight IGQ (l
Same as in Example 1 using 53.1 parts of polytetramethylene oxide glycol and &8' parts of terephthalic acid as the starting materials σ) Method Q: 4 hours.

A polymerization reaction was carried out for 30 minutes to obtain a polymer (A-2). The obtained polyether ester amide (IY-2
The melting point of J was 142°C, 4171°C.

The structures and abbreviations of the stabilizers used in the stabilizer examples are as follows: Example polyether ester amide (A-1) and (A-2)
After blending the stabilizers shown in Table 1e, A-+ was melted and kneaded in a 30 mφ extruder heated to 200°C and A-2 to 180°C, and then pelletized.

After drying this pellet in vacuum, it was pressurized at 200°C if the polyether ester amide was (A-1) and at 180°C if the polyether ester amide was (A-2) to give a thickness of 0.9 to 1. , 1st period press sheet, J Engineering S K
-6301 No. 3 dumbbell-shaped test piece was punched out. Heat resistance is 130C! The test piece was aged in an open wind environment, and the time at which the elongation at breakage retention rate reached 50% was defined as the heat-resistant life. Weather resistance was examined by irradiating the test piece with light using a Sunshine Weather-O-meter. Sunshine Weather-O-meter black panel temperature is 5 at 63'C
I sipped the water for 18 minutes for 2 hours.

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 J-Ko SK-6!101. These results are shown in Table 1. The amount of each stabilizer added was 0.4 parts.

Comparative example polyether ester amide (A-1) or (A-
04 parts of each of the stabilizers shown in Table 2f were added to Z) and pelletized in the same manner as in the previous example to obtain a composition different from the composition of the present invention.

These compositions, polymer (A-1) and polymer (
A-2) was made into a punched test piece 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.

Continuation of page 1

Claims (1)

[Claims] 1. 100 parts by weight of polyether ester amide (Δ), 0.05 to 5 parts by weight of hindered phenol radical scavenging tJl represented by the following general formula (Bl), and 10 parts by weight of the following general formula ( A polyether ester amide composition prepared by adding a peroxide decomposing agent represented by C1, FD+, (E) or (F) in a proportion of 0.05 to 5 parts by weight. R. R, / (where R , is an alkyl group having 1 to 1B carbon atoms, and U
, / is the same alkyl group as R1 and may be the same as R1. mR2 is a single bond, a hydrocarbon group having 1 to 18 carbon atoms, or -coo-% -CON H-1 in the molecular chain.
1 An alternative OR having any of the -o-po- bonds. It is a hydrocarbon group of number 1 to 18, and X is C151 carbon number 1
~18 hydrocarbon groups or 1 number. ) (R3) (-3-R4)... fC1 (however, R3
is a hydrocarbon group having 1 to 1B carbon atoms or -c in the molecular chain
oo-1-co old (- indicates a hydrocarbon group having 1 to 23 carbon atoms, m is an integer of 1 to 4. R4 is 1,
+ It is a hydrocarbon group similar to 3, and may be the same or 4. However, +1 (the sum of the carbon numbers of 3 and R4 must be 12 or more. R3/, R
3'', R3/// are the same hydrocarbon groups as R3, and may be the same or different. Y is 10-
Alternatively, it represents -8-, and n is 0 or 1. ) 2. Bosoether ester amide A) 100 f
005 to 5Ei of the hindered phenol carcinogenic agent represented by the following general formula FB+.
, Okibe, the peroxide decomposer represented by the following general formula (C1, (D+: +1!:) or (Fl) is 005
~5 parts by weight and the following general formula tG) or ++()
A polyether ester amide composition comprising 11 parts of ultraviolet absorbers represented by 005 to 5, respectively. 1 Ll (However, R1 is an alkyl group having 1 to 18 carbon atoms, and R
, / is the same alkyl group as R, and may be the same as R1. R2 is a single bond, a hydrocarbon group having 1 to 18 carbon atoms, or -(lioo -, -CONH-
11 - carbon 0I (+ is a hydrocarbon group having 1 to 18 carbon atoms, X is C1S, carbon number 1
~18 hydrogen ash,! I (or 1) (113) C-8-L””” +++ ・・・・・・(L
) (where R3 represents a hydrocarbon group having 1 to 18 carbon atoms or a hydrocarbon group having 1 to 23σ carbon atoms having a -Coo-, -NHOO- bond in the molecular chain, and m is 1 to 18 carbon atoms. 4
is an integer. R4) is a hydrocarbon group similar to R3, and may be the same or different. just. Shioka 3 and 1 (the number of carbon atoms in 4, 411, must be 12 or more. R3/, F3//, B3/// are R
J: is a hydrocarbon group similar to 3, and may be the same or different. Y represents 10- or -8-, and rl is 0 or 1. ] (However, R5 represents an alkyl group having 1 to 18 carbon atoms, and R
6 is a hydrogen atom or an alkyl group similar to R5,
Z may be the same as R5, and p is 0 or 1. ]