JPH0820711A - Polyetherester block copolymer composition - Google Patents

Abstract

PURPOSE:To provide the subject compsn. for a molding material excellent in wet aging resistance. CONSTITUTION:A polyetherester block copolymer in an amount of 100 pts.wt. having arom. polyester units as the hard segments and poly(alkylene oxide) glycol units as the soft segments is compounded with a both-side-hindered phenolic antioxidant (A), a one-side-hindered phenolic antioxidant (B), a thioether compd. (C), and a phosphorus compd. (D) in an amt. of the sum of A+B of 0.01-5 pts.wt. and in a wt. ratio of C/(A+B) of 0.2-4.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a polyetherester block copolymer resin composition, and more particularly to a thermoplastic polyetherester block copolymer resin composition excellent in heat aging resistance.

[0002]

2. Description of the Related Art A polyether polyester type block copolymer having an aromatic polyester as a hard segment and a poly (alkylene oxide) glycol as a soft segment is known to have cold resistance, heat resistance, oil resistance, flex fatigue resistance, mechanical resistance and mechanical resistance. As a saturated polyester elastomer with excellent dynamic strength, it is used for various purposes such as automobile parts, industrial parts, electric and electronic parts, etc., and its application range is expanding more and more in recent years. Saturated polyester elastomers for these molding materials are usually polycondensed at high temperature with a polyester-forming component composed of an aromatic dicarboxylic acid or its lower alkyl ester and an aliphatic glycol and a polyether such as poly (alkylene oxide) glycol. It is manufactured by

The polyetherester block copolymer produced by such a method has mechanical properties such as deterioration, softening, embrittlement and surface cracking due to the action of oxygen and heat during processing or use. There is a big problem in stability such as a remarkable decrease. Therefore, various methods have been studied in order to improve the heat aging resistance of the polyetherester block copolymer.

(A) Japanese Patent Application Laid-Open No. 4-332755 discloses a method of blending a specific one-hindered phenol compound, a thiopropionate compound and a phosphorus compound, (b) Japanese Patent Application Laid-Open No. 4-337349. The publication discloses a method of blending both hindered phenol compounds, one-hindered phenol compounds, hindered amine compounds and thioether compounds (C) JP-A-5-125262.
The publications disclose methods of blending tris (hydroxy-benzyl) benzene and bis (alkylphenyl) pentaerythritol diphosphite, respectively.

[0005]

However, in the above (a) to (c), although improvement in heat aging resistance is seen, it is still not sufficient, for example, (a),
In (b), although heat resistance at a high temperature of 160 to 170 ° C. is obtained, heat resistance for a long period of time such as heat treatment time of about 1 minute or 20 hours is not taken into consideration. Also in (c), the heat treatment period is about 7 days, and the heat resistant temperature is still 121 ° C, which is not satisfactory, and the polyether ester has excellent long-term heat aging resistance at a high temperature of 140 to 150 ° C. Copolymers are desired.

[0006]

Therefore, the present inventors have
As a result of earnest studies to solve such problems, a polyether polyester block copolymer having an aromatic polyester unit as a hard segment and a poly (alkylenetooxide) glycol unit as a soft segment is used for both hindered phenolic antioxidants. Agent (A), one-sided hindered phenolic antioxidant (B), thioether compound (C) and phosphorus compound (D),
When the compounding amount of (A) + (B) is 0.01 to 5 parts by weight with respect to 100 parts by weight of the copolymer, (C) / [(A) + (B)].
It was found that the polyether ester block copolymer having a compounding weight ratio of 0.2 to 4 is excellent in heat aging resistance, and has completed the present invention. The present invention will be described in detail below.

The polyether ester block copolymer of the present invention is obtained by polycondensing an aromatic dicarboxylic acid, an alkylene glycol and a poly (alkylene oxide) glycol, and the aromatic carboxylic acid is mainly terephthalic acid and its lower groups. An alkyl ester is used,
Other examples include isophthalic acid, phthalic acid, 2,5-norbonanedicarboxylic acid, 1,4-naphthalic acid, 1,5-naphthalic acid, 4,4-oxybenzoic acid and lower alkyl esters thereof. Among them, dimethyl terephthalate is particularly preferable in terms of availability of raw materials, high polyesterification rate, and influence on polyether (no acid decomposition).

Examples of the alkylene glycol include ethylene glycol, propylene glycol, 1,3-butylene glycol, 1,4-butanediol and 1,6-hexanediol, among which 1,4-butanediol is preferable. It has elastic properties and is particularly preferred. Furthermore,
Examples of the poly (alkylene oxide) glycol include polytetramethylene glycol, polyethylene glycol,
Polypropylene glycol etc. molecular weight 600-4000
Among them, the molecular weight is 1000 to 2000
Polytetramethylene glycol is particularly preferable because it exhibits good elastic properties.

The polyether ester block copolymer of the present invention can be obtained by a usual copolymerization method.
That is, as described above, the aromatic dicarboxylic acid, the alkylene glycol, and the poly (alkylene oxide) glycol are reacted, and the reaction mechanism is as follows. First, the aromatic dicarboxylic acid and the alkylene glycol, and the aromatic dicarboxylic acid and the poly (alkylene oxide). The ester reaction of (oxide) glycol occurs and then polycondensates to produce a polyether ester block copolymer (saturated polyester elastomer).

In the above esterification reaction step and polycondensation reaction step, a catalyst may be used if necessary, and the catalyst may be lithium, potassium, sodium, magnesium, calcium, barium, zinc, aluminum. , Titanium, cobalt, germanium, tin, lead,
Compounds such as antimony, cadmium and manganese are mentioned, and particularly preferably tetraisopropyl titanate,
Tetra-n-butyl titanate, dibutyltin oxide, calcium acetate, zinc acetate can be used, and two or more kinds of these catalysts may be used in combination.

The amount of the material charged in the present invention is 1 / 0.5 to 2.5 / 0.05 to 0. 0 in a molar ratio of aromatic dicarboxylic acid or its lower alkyl ester, alkylene glycol and poly (alkylene oxide) glycol. The ratio is preferably 6 and particularly preferably 1 / 1.0 to 2.0
/0.1 to 0.4. The addition amount of the catalyst to 1 mol of the aromatic dicarboxylic acid is preferably 0.0001 to 0.1 mol, and particularly preferably 1 / 0.001 to 0.01 mol. The catalyst may be added all at once at the beginning, but it is better to add it separately during the ester reaction and the polycondensation reaction, and the ratio of the addition amount is within the range of 1/1 to 10. preferable.

The greatest feature of the present invention is that the polyether ester block copolymer obtained as described above comprises both hindered phenolic antioxidants (A), one-hindered phenolic antioxidants (B) and thioether compounds. By blending (C) and the phosphorus compound (D), (A) is 2,
6-di-t-butyl-4-methylphenol (for example,
Sumitomo Chemical Co., Ltd .: trade name "Sumilyzer BHT", etc., n
-Octadecyl-3- (3,5-di-t-butyl-4-
Hydroxyphenyl) propionate (for example, manufactured by Sumitomo Chemical Co., Ltd .: trade name "Sumilyzer BP-76"), tetrakis [methylene-3- (3,5-di-t-butyl-4]
-Hydroxyphenyl) propionate] methane (for example, manufactured by Sumitomo Chemical Co., Ltd .: trade name "SUMILIZER BP-10"
1 "), 1,6-hexanediol-bis- [3-
(3,5-di-t-butyl-4-hydroxyphenyl)
Propionate] (for example, manufactured by Ciba-Geigy: trade name “Irganox 259”), 2,2-thio-diethylenebis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate (for example, Made by Ciba-Geigy: product name “Irganox 1035FF” and the like).

Tris- (3,5-di-t-butyl-4-
Hydroxybenzyl) -isocyanurate (for example, manufactured by Ciba Geigy: trade name “Irganox 3114”)
Etc.), 1,3,5-trimethyl-2,4,6-tris (3,5-di-t-butyl-4-hydroxybenzyl)
Benzene (for example, manufactured by Ciba Geigy: trade name "Irganox 1330"), pentaerythrityl-tetrakis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate] (for example, manufactured by Ciba Geigy) : Trade name “Irganox 1010”, etc., and preferably pentaerythrityl-tetrakis [3-
(3,5-di-t-butyl-4-hydroxyphenyl)
Propionate], 1,6-hexanediol-bis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate], 1,3,5-trimethyl-
2,4,6-Tris (3,5-di-t-butyl-4-hydroxybenzyl) benzene is used.

As (B), triethylene glycol-bis [3- (3-t-butyl-5-methyl-4-hydroxyphenyl) propionate] (for example, manufactured by Ciba-Geigy: trade name "Irganox 245") ), 3,
9-bis- [2- [3- (3-t-butyl-4-hydroxy-5-methylphenyl) -propionyloxy]-
1,1-Dimethylethyl] -2,4,8,10-tetraoxaspiro [5,5] undecane (for example, Sumitomo Chemical Co., Ltd .: trade name "Sumilyzer GA80"), 4,4 '
-Thiobis (3-methyl-6-t-butylphenol)
(For example, manufactured by Sumitomo Chemical Co., Ltd .: trade name "Sumilyzer WX-
R "), 4,4'-butylidene bis (3-methyl-6)
-T-butylphenol) (for example, manufactured by Sumitomo Chemical Co., Ltd .: trade name "SUMILIZER BBMS"), and preferably triethylene glycol-bis [3- (3-t-butyl-5-methyl-4-hydroxyphenyl). ) Propionate], 3,9-bis- [2- (3-t-butyl-4)
-Hydroxy-5-methylphenyl) -propionyloxy] -1,1-dimethylethyl-2,4,8,10-
Tetraoxaspiro [5,5] undecane is used.

The blending amount of (A) + (B) is 0, based on 100 parts by weight of the polyether ester block copolymer,
It is necessary to be 01 to 5 parts by weight, preferably 0.1 to 2.5 parts by weight, more preferably 0.2 to 2.0.
Parts by weight. If the blending amount of (A) + (B) is less than 0.01 parts by weight, the effect of the addition is extremely small, the heat aging resistance is not improved, and it is not suitable for practical use. On the other hand, if the amount exceeds 5 parts by weight, heat aging resistance is deteriorated, and bleed-out, blooming, and mechanical properties are deteriorated, which is a practical problem and is not suitable. The mixing ratio of (A) / (B) is not particularly limited, but from the viewpoint of further improving the effect of heat aging resistance, the number of moles of the phenolic hydroxyl group contained in each of (A) and (B) is (a), When it is referred to as (b), the molar ratio (a) / (b) is preferably 10/1 to 1/5, and more preferably 5/1 to 1/1 so that (A) and (B) are blended. It is desirable to adjust the ratio.

Examples of the thioether compound (C) include dioctylthiodipropionate, didodecylthiodipropionate, dodecylstearylthiodipropionate, distearylthiodipropionate, dimyristylthiodipropionate, didecylthiodipropionate. Pionate, didodecyl-β, β′-thiodibutyrate, distearyl-β, β′-thiodibutyrate, pentaerythritol-tetrakis (dodecylthiopropionate),
Pentaerythritol-tetrakis (dodecylthioacetate), pentaerythritol-tetrakis (dodecylthiobutyrate), pentaerythritol-tetrakis (octadecylthiopropionate), pentaerythritol-tetrakis (laurylthiopropionate), dilauryl 3,3 '. -Thiodipropionate, distearyl-3,3'-thiodipropionate, ditridecyl 3,3'-thiodipropionate, tetrakis [methylene-3- (dodecylthio) propionate] and the like are known. Preferably, distearyl-
3,3'-thiodipropionate is used.

Regarding the blending amount of (C), the above (A) +
(C) / [(A) + (B)] = with respect to the total weight of (B)
It is necessary to satisfy the relationship of 0.2 to 4 (weight basis), and if (C) / [(A) + (B)] is less than 0.2, the effect of improving long-term heat aging resistance is small and conversely 4 If it exceeds the range, problems such as bleeding, blooming of the sulfur compound and generation of sulfur odor occur. Preferably (C) /
[(A) + (B)] = 0.3 to 3.0, and more preferably (C) / [(A) + (B)] = 0.5 to 2.5.
As the phosphorus compound (D), a compound represented by the following chemical formula 1 is preferably used.

Embedded image (R ¹ ) ₃ PO _n R ¹ : alkyloxy group, alkenyloxy group, phenyloxy group, substituted phenyloxy group n: 0 or 1

Specific examples of the compound include triphenyl phosphate, triphenyl phosphine oxide, triethyl phosphine oxide, triethyl phosphate, triphenyl phosphite and triethyl phosphite. Further, the compound represented by the following chemical formula 2 is also preferably used.

Embedded image R ^2: an alkyl group, an alkenyl group, a phenyl group, a substituted phenyl group R ^3: C ₁ ~C ₆ specifically diethyl phosphite phosphono ethyl acetate in the alkyl group the compound, or 3,5-di -t- butyl - 4-hydroxybenzylphosphonate-diethyl ester and the like can be mentioned.

The blending amount of (D) is not particularly limited, but is 0.5 to 4.0 mmol / mole with respect to the polyether ester block copolymer before adding (A) to (D).
The copolymer is preferably kg, and more preferably 1.0 to 2.
If the amount is 0 mmol / copolymer, and the amount is too small, the heat resistance-improving effect is not sufficient. If the amount is too large, the hydrolysis resistance of the polyether ester block copolymer tends to be impaired.

The blending method of the blends (A) to (D) into the polyether ester block copolymer is not particularly limited as long as it is after the polycondensation reaction step of the polyether ester block copolymer, and the polymerization is not limited. Method of adding to the polyetherester block copolymer in a molten state before being dispensed in a can, melted polyetherester block when the formed polyetherester block copolymer is pelletized using an extruder or the like The method of adding to the copolymer is the method of adding the most effect. A method of adding at the time of molding can also be adopted.

The polyether ester block copolymer of the present invention may contain an alkali metal compound, a crystal nucleating agent such as talc, glass fiber, a flame retardant, a colorant and the like. The polyetherester block copolymer composition of the invention obtained by such a method is further subjected to post-treatment such as pellet processing, if necessary. In addition, conventionally, a polyester copolymer (polyester elastomer) obtained by polycondensing an aromatic dicarboxylic acid, an alkylene glycol and a poly (alkylene oxide) glycol has been used for medical applications by taking advantage of its stretch flexibility, moisture permeability and the like. (Base materials for medical aid tapes such as first-aid plasters, surgical tapes, rehabilitation tapes, base materials for treating diseases such as inflammation, pain relief, blood circulation promotion, surgical gloves, etc.), hygiene applications (base materials for tapes for fixing diapers) , Napkin fixing tape base material), sports clothing applications, etc., the polyether ester block copolymer composition of the present invention containing a specific compound is also used in the above-mentioned applications in the same manner as conventional polyester elastomers. Is also very useful.

[0022]

[Operation] In the present invention, a specific amount of a hindered phenolic antioxidant, a hindered phenolic antioxidant, a thioether compound and a phosphorus compound is blended in a polyether ester block copolymer composition. For,
A polyether ester block copolymer having excellent heat aging resistance can be obtained and can be used for automobile parts, industrial parts, electric and electronic parts and the like.

[0023]

EXAMPLES The present invention will be specifically described below with reference to examples. In the examples, “part” and “%” are based on weight unless otherwise specified. Example 1 Dimethyl terephthalate 2 in a nitrogen gas atmosphere in a reactor equipped with a stirrer, thermometer, gas blowing port and distillation port.
9.4 kg, 1,4-butanediol 16.0 kg, polytetramethylene glycol 1 having an average molecular weight of 1000
9.7 kg, tetrabutyl titanate 4.6 as catalyst
g at room temperature and reacted at 210 ° C. in nitrogen gas for 2 hours, after distilling out 9.6 kg of methanol, 11 g of tetrabutyl titanate was added and the temperature was raised from 210 ° C. to 250 ° C. in 90 minutes. Gradually reduced to 0.5
The reaction was performed at Torr for 2 hours. Then, set the temperature of the reaction system to 2
After cooling to 20 to 230 ° C., 200 g of Irganox 1330 (manufactured by Ciba Geigy) as both hindered phenolic antioxidants (A), and Sumilizer GA-80 (Sumitomo Chemical Co., Ltd.) as one-hindered phenolic antioxidants (B) 100 g and (C), 615 g of distearyl-3,3′-thiodipropionate as a component (D),
Irganox 1222 (Ciba Geigy) 31.0
After adding g and mixing for 1 hour, the mixture was cooled and pelletized with a pelletizer to obtain a polyether ester block copolymer composition of the present invention. Shore D of this pellet is A
According to STM D2240, it was 50 when measured by a D type durometer. Further, when the melt viscosity was measured according to the flow test method of thermoplastics of JIS K7210, it was 2300 poise.

The heat aging resistance of the polyether ester block copolymer was measured as follows.

(Heat-resistant aging resistance) Pellets after drying at 80 ° C. for 2 hours were left in a gear oven at 140 ° C. for 21 days, and then the tensile elastic modulus, tensile strength and elongation (JIS K 71
13 of each of the plastics (according to the tensile test method of plastic) was measured, and each retention rate (%) for each physical property before exposure treatment was determined. Examples 2 to 8 and Comparative Examples 1 to 8 Polyetherester block copolymers were produced according to Example 1 by changing the distribution composition of the components (A) to (D) as shown in Tables 1 and 2. The evaluation was performed in the same manner as in Example 1. Table 3 shows the results.

[0026]

[Table 1] Component (A) Component (B) Component (C) Component (D) Component Compounding amount Compounding compounding amount Compounding compounding compounding amount Compounding compounding amount Example 1 A-1 0.4 B-1 0.2 C-1 1.2 D-1 1.7 2 A-1 0.3 B-1 0.2 C-1 1.0 D-1 1.7 3 A-1 0.1 B-1 0.1 C-1 0.5 D-1 1.7 4 A-1 0.5 B-1 0.7 C- 1 0.6 D-1 1.7 5 A-1 0.6 B-1 1.2 C-1 1.8 D-1 1.7 6 A-2 0.2 B-1 0.1 C-1 0.6 D-2 1.7 7 A-2 0.6 B-2 0.3 C -2 1.5 D-3 1.7 8 A-3 0.5 B-3 0.3 C-1 1.5 D-4 1.7 Comparative Example 1 A-1 0.004 B-1 0.002 C-1 0.012 D-1 1.7 2 A-1 4.0 B- 1 2.0 C-1 12.0 D-1 1.7 3 A-1 0.4 B-1 0.2 C-1 0.09 D-1 1.7 4 A-1 0.4 B-1 0.2 C-1 3.0 D-1 1.7 5 − − B-1 0.6 C-1 1.2 D-1 1.7 6 A-1 0.6 --- C-1 1.2 D-1 1.7 7 A-1 0.4 B-1 0.2 --- D-1 1.7 8 A-1 0.4 B-1 0.2 C- 1 1.2 − −

Note) The blending amounts of the components (A) to (C) represent each part by weight with respect to 100 parts by weight of the polyether ester block copolymer. (D) represents the number of millimoles added to 1 kg of the polyether ester block copolymer. The abbreviations are as follows. A-1: Pentaerythritol-tetrakis [3-
(3,5-di-t-butyl-4-hydroxyphenyl)
Propionate] (trade name: Norganox 1010) A-2: 1,6-hexanediol-bis [3- (3,3
5-di-t-butyl-4-hydroxyphenyl) propionate] (trade name: Norganox 259) A-3: 1,3,5-trimethyl-2,4,6-tris (3,5-di-t-) Butyl-4-hydroxybenzyl)
Benzene (trade name: Norganox 1350) B-1: 3,9-bis- [2- (3-t-butyl-4-
Hydroxy-5-methylphenyl) propionyloxy] -1,1-dimethylethyl-2,4,8,10-tetraoxaspiro [5,5] undecane (trade name: Sumilizer GA-80) B-2: triethylene Glycol-bis [3- (3-t
-Butyl-5-methyl-4-hydroxyphenyl) propionate] (trade name: Irganox 245) C-1: distearyl-3,3'-thiodipropionate D-1: 3,5-di-t- Butyl-4-hydroxybenzylphosphonate-diethyl ester (trade name: Irganox 1222) D-2: Ethyl diethylphosphonoacetate D-3: Triphenylphosphine oxide D-4: Triphenyl phosphite

[0028]

[Table 2] (A) + (B) (C) (a) / (b) compounding amount (A) + (B) (molar ratio) Example 1 0.6 2.0 4.0 2 0.5 2.0 3.0 3 0.2 2.5 2.0 4.0 1.2 0.5 1.4 1.5 1.8 1.0 1.0 6.0 6 0.3 2.0 2.0 7 0.9 1.7 2.0 8 0.8 1.9 3.3 Comparative Example 1 0.006 2.0 4.0 2 6.0 2.0 2.0 3 0.6 0.15 4.0 4.0 40 .6 5.0 4.0 5.0 0.6 2.0 2.0 6 0.6 2.0 -7 0.6 0 4.0 4.0 8 0.6 2.0 4.0 (Note) (A) The blending amount of the + (B) component is parts by weight based on 100 parts by weight of the polyether ester block copolymer. (C) / [(A) + (B)] represents the blending weight ratio.
(A) / (b) represents the molar ratio of the phenolic hydroxyl groups of (A) and (B).

[0029]

[Table 3] Note) Heat aging resistance is indicated by the retention rate (%) of each physical property. *: Remarkable sulfur odor, bleed-out, blooming
Was observed.

[0030]

INDUSTRIAL APPLICABILITY In the present invention, a specific amount of both hindered phenolic antioxidants, one hindered phenolic antioxidants,
Since it contains a thioether compound and a phosphorus compound, a polyether ester block copolymer with excellent heat aging resistance can be obtained and can be used for automobile parts, industrial parts, electric / electronic parts, etc. .

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁶ Identification code Internal reference number FI Technical display area C08K 5/5317 // C08G 63/672 NNG

Claims (6)

[Claims] 1. A hindered phenolic antioxidant (A) based on 100 parts by weight of a polyether ester block copolymer having an aromatic polyester unit as a hard segment and a poly (alkylene oxide) glycol unit as a soft segment. , A hindered phenolic antioxidant (B), a thioether compound (C) and a phosphorus compound (D) are blended, and the blending amount of (A) + (B) is 0.01 to 5 parts by weight. And a blending ratio by weight of (C) / [(A) + (B)] is 0.2 to 4. A polyetherester block copolymer composition. 2. The mole number (a) of phenolic hydroxyl groups of both hindered phenolic antioxidants (A) and the mole number (b) of phenolic hydroxyl groups of one-hindered phenolic antioxidants (B). Ratio (a) / (b) is 10/1
It is 1/5, The polyether ester block copolymer composition of Claim 1 characterized by the above-mentioned. 3. Both hindered phenolic antioxidants (A) are pentaerythrityl-tetrakis [3- (3,
5-t-butyl-4-hydroxyphenyl) propionate], 1,6-hexanediol-bis [3- (3,3
5-di-t-butyl-4-hydroxyphenyl) propionate], 1,3,5-trimethyl-2,4,6-tris (3,5-di-t-butyl-4-hydroxybenzyl) benzene The polyether ester block copolymer composition according to claim 1 or 2, which is at least one selected from the group. 4. The one-hindered phenolic antioxidant (B) is triethylene glycol-bis [3- (3-t
-Butyl-5-methyl-4-hydroxyphenyl) propionate, 3,9-bis [2- (3-t-butyl-4)
-Hydroxy-5-methylphenyl) -propionyloxy] -1,1-dimethylethyl-2,4,8,10-
The polyether ester block copolymer composition according to any one of claims 1 to 3, which is at least one selected from the group consisting of tetraoxaspiro [5,5] undecane. 5. The polyetherester block copolymer composition according to claim 1, wherein the thioether compound (C) is distearyl-3,3′-thiodipropionate. . 6. The polyether ester block copolymer according to claim 1, wherein the phosphorus compound (D) is at least one selected from the group consisting of the following chemical formulas 1 and 2. Polymer composition. Embedded image (R ¹ ) ₃ PO _n R ¹ : alkyloxy group, alkenyloxy group, phenyloxy group, substituted phenyloxy group, alkyl group, alkenyl group, phenyl group, substituted phenyl group n: 0 or 1 2] R ² : alkyl group, alkenyl group, phenyl group, substituted phenyl group R ³ : C ₁ -C ₆ alkyl group