JPH03185053A - Polyether-ester block copolymer composition - Google Patents

Abstract

PURPOSE: To provide the subject composition excellent in weather-ability by incorporating therein a specific diol component and a three-component stabilizer comprising a phenolic antioxidant, a light stabilizer suitable for copolyesters and an amine-based light stabilizer as constituents.

CONSTITUTION: The desired polyether ester block copolymer composition comprises (A) a component comprising 5-25 (mol.)% of a polyalkylene oxide glycol and 75-95% of a low-molecular weight diol based on the total glycol content, and (B) a component comprising three components, in combination, of (i) one or more sterically hindered phenolic antioxidants, (ii) one or more light stabilizers suitable for copolyesters represented by formulae I-V, and (iii) one or more sterically hindered amine-based stabilizer represented by formula VI, and has a melt viscosity of 2,700-3,000 psi and an intrinsic viscosity of 1.0-1.5.

COPYRIGHT: (C)1991,JPO

Description

Detailed Description of the Invention (Industrial Field of Application) The present invention is characterized by the combination of a ternary stabilizer consisting of a specific phenolic antioxidant, a light stabilizer suitable for copolyester systems, and an amine light stabilizer. The present invention relates to a polyether ester elastomeric polymer with excellent weather resistance.

(Prior Art and Problems to be Solved by the Invention) Copolyetherester elastomeric polymers are commonly used in the form of sheets, films, or molded articles for a variety of applications such as hoses, belts, and sporting goods.

However, in order for polymeric substances in membranes to be successfully used for various purposes, there must be little or no change in external shape or physical properties due to use, but currently many molded products are exposed to air. It deteriorates due to the action of oxygen, ozone, moisture, ultraviolet rays, and heat, and when used exposed to the outside air, it has the drawback of causing undesirable phenomena such as discoloration, surface cracks, and a decrease in strength and elongation and degree of polymerization.

Although efforts have long been underway to improve the weatherability of such polymeric materials, no effective stabilizer has yet been found.

Regarding the effects of various stabilizers for improving the weather resistance of conventional copolyetherester elastomeric polymers, JP-A-50-91
No. 652 and European Patent No. 0003809, however, these methods do not give sufficient consideration to the use of stabilizers and their input amounts, and the decomposition of the resin is accelerated and the effects such as discoloration and staining occur. There were many problems in this respect.

As a result of research and study from multiple angles on decomposition and stabilizing effects caused by sunlight, the present inventors found that a product containing a specific 3$ splitting stabilizer that is suitable for polyester systems is resistant to exposure to light by adjusting the properties of the resin. The present invention has been completed by discovering that the resulting deterioration in physical properties can be significantly reduced.

(Means for Solving the Problems) The light-stabilized resin of the present invention meets American Industrial Standards Test G-2.
In the weather resistance test according to No. 3, the time for 50% decrease in tensile strength is 200 hours or more.

The polyether ester block copolymer of the present invention has 10
~75% by weight long chain ester units and 25-90% by weight
5-25 mol% of the total glycol content is polyalkylene oxide glycol, 75-95 mol% is composed of short-chain diols with a molecular weight of 250 or less, and 50-100% of the short-chain diol content is composed of short-chain ester units. mole%
is 1,4-cyclohexanedimethanol, 0-
50 mol% is A component composed of a third aliphatic diol and a specific three-component light stabilizer, which is sterically inhibited (
BFIi, which contains a sterically hindered phenolic stabilizer, an excellent light stabilizer suitable for copolyester resins, and a sterically hindered aqueous light stabilizer as shown in the general formula (!) below. Depending on the combination of

(However, in the formula, n is an integer of 3 to 30, R- to hydrogen,
R1 and R2 are a substituted or unsubstituted alkyl group having 1 to 25 carbon atoms, an allyl group having 6 to 25 carbon atoms, an alkylene group having 1 to 25 carbon atoms, a cycloalkylene group having 3 to 12 carbon atoms, and a cycloalkylene group having 1 to 12 carbon atoms; 18 hydroxyalkyl groups and ester groups thereof, alkylenecarboxylic acids having 2 to 18 carbon atoms, esters and amides thereof, and various other substituents. ) The photo-stabilized copolyether ester elastomer of the present invention has minimal decomposition due to sunlight, and as a result of a weather resistance test conducted in accordance with American Industrial Standard Test G-23, its physical properties, especially the rate of decrease in tensile strength, were confirmed. is so low that it takes more than 200 hours for the initial tensile strength to decrease by 50%.

The acid component of the copolyether ester is preferably an aromatic dicarboxylic acid having a molecular weight of 300 or less and two reactive groups.

The medium-long chain glycol of the long chain ester unit is a polyol with a hydroxyl terminal group, a molecular weight of 400 to 4,000, and a ratio of carbon atoms to oxygen atoms of 2.0 to 4,000.
4.3 polyalkylene oxide glycols, such as poly (ethylene oxide) glycol, poly (1,2- and 1,3-propylene oxide) glycol, poly (tetramethylene oxide) glycol, ethylene oxide and propylene oxide There are block copolymers, etc.

Furthermore, among the short-chain ester units, low-molecular-weight diols having a molecular weight of 250 or less can be used as the short-chain diol. For example, ethylene glycol, diethylene glycol, 1
．． Aliphatic diols such as 4-butanediol, 116-hexanediol and other cyclodiols can be used.

In particular, the present invention comprises dimethyl terephthalate, polyalkylene oxide glycol in an amount of 5 to 25 mol % based on the total glycol content, and 1 mol % in an amount of 50 to 100 mol % based on the total amount of short chain diols.
．． 4-cyclohexanedimethanol, 0 to 50 mol% of 1,4-butanediol or ethylene glycol can be used, but especially long-chain nosiols with a molecular weight of 600 to 50% can be used.
Polytetramethylene glycol having a molecular weight of 2,000 or a molecular weight of 1,500 to 2,000 and an ethylene oxide content of 15
~35% by weight poly(propylene oxide) glycol can be used.

Furthermore, as a composition that exhibits a photostabilizing effect, a sterically inhibited phenolic antioxidant is used as the first component, and a photostabilizer that has good compatibility with the copolyether esters represented by general formulas (n) to (Vl) is used. The agent is used as the second component, and the sterically inhibited amine light stabilizer represented by the general formula (1) is combined as the third component.

The phenolic antioxidant suitable for the copolyester system, which is the first component of the present invention, is preferably a sterically hindered, non-volatile polyolefin type antioxidant.

Suitable examples include the following.

1,3.5-,-tris(3,5-di-tart-butyl-4-hydroxybenzyl>-S-triazine-2°4.6-(1',3'5')-trione,
3.5-tert-butyl-4-hydroxyhydrocinnamic acid triester and 1.3.5. −) Squirrel−
(2-hydroxyethyl)-5-triazine-2゜4.
6- (1', 3', 5')-) combination of ions, 0, 0
-di-n-octadecyl-3,5-diEer t-butyl-4-hydroxybenzylphosphonate, octadecyl-3,5-diter t-butyl-4-
Hydroxyhydrocinnamide, thio-diethylene-bis(3,5-di-tert-butyl-4-hydroxy)hydrocinnamide, N,N'-
Hexamethylene-bis(3,5-di-tert-butyl-4-hydroxy)hydrocinnamide, 1,3,5-trimethyl-2,4,6-)lis-(3
゜5-';-tert-butyl-4-hydroxybenzyl)benzene, 2,4-bis(n-octylthio)-6-(4-hydroxy-3,5-di-tert-butylanilino)1,
3.5-) riazine, n-octadecyl-3,5-di-tert-butyl-
4-Hydroxyphenylacetate, 1,3.5-)lis-(4-tert-butyl-3hydroxy-2,6-dimethylbenzyl) -1,3゜5
-triazine-2,4,6-(1',3',5')-trione, 2.2'-methylene-bis(4-ethyl-6-tert
-butyl-phenol), 4.4′-methylene-bis(2,6-tart-butylphenol), 4.4′-thiobis(6-tert-butyl-2-methylphenol), etc., and these are “ Irganoxu 1
010'' antioxidant has already been commercialized by Ciba-Geigy and Cynamid in the United States.

As the second component, a light stabilizer, a compound represented by the following general formula is used among light stabilizers suitable for ester-based boat fishing.

p.

(However, in the above general formula (n), group, allyl group having 7 to 22 carbon atoms, alkylenylaryl group, etc., and in formula (I
~18 linear or branched alkyl groups, substituted or unsubstituted alkyl groups, alkylene/carbonyloxyalkyl groups having 3 to 18 carbon atoms, etc., and R of formula (rV)・, R9, R111, Ro are hydrogen,
each independently selected from linear or branched, substituted or unsubstituted alkyl groups having 1 to 18 carbon atoms, and X' in formula (V) is hydrogen, a methyl group, or a methoxy group; Y and Z are a cyano group and an alkyl ester group, and Lx
is a substituted or unsubstituted linear or branched alkyl or alkoxy group having 1 to 18 carbon atoms, and R13 in formula (Vl) is hydrogen, a substituted or unsubstituted linear or alkoxy group having 1 to 18 carbon atoms; It is a branched alkyl or alkoxy group. ) Light stabilizers of general formulas (II) to (Vl) include 2-hydroxybenzotriazole (II), 2-hydroxybenzophenol (■), and oxanilide (rV)
, an ester system of acrylic acid and malonic acid (■), and an aromatic ester system of salicylic acid (VI). For example,
The 2-hydroxybenzotriazole system includes 2-(2'-hydroxy-5'-methylphenyl)benzotriazole, 2-(2'-hydroxy-3', 5'-diter)
t-butylphenyl)benzotriazole, 2-(2'-hydroxy-3', 5'-di-tert
-butylphenyl)-5-chlorobenzotriazole,
2-(2'-hydroxy-3', 5'-ter
t-amyl phenyl)benzotriazole, 2-(2'-hydroxy-3'-tert-butyl-
5"-methylphenyl)-5-chlorobenzotriazole, 2-(2'-hydroxy-3'-5ec-butyl-5
゛-tert-butylphenyl)benzotriazole,
2-(2'-hydroxy-5-tert-octylphenyl)benzotriazole, 2-(2H-benzotriazol-2-yl)-4,6
-bis(1-methyl-1-phenylethyl)phenol and the like.

In addition, as a 2-hydroxybenzophenone type, 2.4
-dihydroxybenzophenone, 2-hydroxy-4-
Methoxybenzophenone, 2-hydroxy-4-ter
t-Butoxybenzophenone, 2-hydroxy-4-octoxybenzophenone, 2-
Hydroxy-4-dotecyloxybenzophenone, 2-hydroxy-4-stearooxybenzophenone, 2-hydroxy-4-phenoxybenzophenone, 2-
Hydroxy-4-(β-hydroxyethoxy)benzophenone, 2-hydroxy-4-(2'-hydroxy-3'-acryloxy-propoxy)benzophenone, 2-hydroxy-4-(2'-hydroxy-3°-methacrylic) oxypropoxy)benzophenone, 2.2"-dihydroxybenzophenone, 2.2'-dihydroxy-4-methoxybenzophenone, 2.2'-dihydroxy-4-lauroxybenzophenone, 2.2'-4,4'-tetrahydroxy Examples include benzophenone.

Oxanilides include 2-ethoxy-2°-ethyl oxanilide, 5-tert-butyl-2-ethoxy-2
”-ethyl oxanilide, etc.

As the acrylic ester, 2-ethylhexyl-2
-cyano-3,3-diphenylacrylate, 2-ethyl-2-cyano-3,3-diphenylacrylate, butyl-2-cyano-3-methyl-3-(p-methoxyphenyl)acrylate, and the like.

Examples of salicylic acid esters include p-tert-octylphenyl salicylate, phenyl salicylate, and carboxyphenyl salicylate. These are tinuvin P (T
inuvin P), tinuvin 326, tinuvin 114
, Cyasorb UV 531 (Cyasorb UV
531), Sheasolve UV 5411, etc., which have already been commercialized by Ciba Geigy and Cynamid in the United States.

The sterically inhibited amine light stabilizer, which is the third component represented by the above general formula (1), is known as “Chimasolp”.
asorb) 944" Sheasorb UV 3346".

The excellent weather resistance of the copolyether ester of the present invention is due to the 1. Based on the combination of 4-cyclohexanedimethanol and the above-mentioned three-branching system.

In particular, the amounts added are approximately 0.01 to 1.0 parts by weight of sterically inhibited phenolic antioxidant and 0.04 to 5.0 parts by weight of copolyether to 100 parts by weight of the elastomer resin. Since it is based on a light stabilizer suitable for esters and a sterically hindered amine light stabilizer represented by the general formula (1) in an amount of 0.01 to 2.0 parts by weight, if the amount added is less than the above range, , the effect is small, and if the amount exceeds the above range, the increase in effect with the input amount is not so large, which poses a problem in terms of economy. Further, the stabilizer, which causes problems such as deterioration of physical properties and contamination due to excessive addition, can be mixed during polymerization or in a molten state after polymerization, or can be mixed with the product after polymerization.

The functions of the added three-component stabilizer are as follows.

The first component, a sterically hindered phenolic antioxidant, binds to radicals (groups) that are generated within the polymer and promotes oxidation, suppresses radical reactions, and causes structural steric hindrance. The photostabilizers shown by general formulas (n) to (Vl) have the effect of suppressing oxidation reactions, and absorb ultraviolet rays to disperse energy in other forms that do not cause photodecomposition, that is, heat. play a role.

Although the sterically inhibited amine light stabilizer represented by general formula (1) does not have the function of absorbing ultraviolet rays, it is extremely effective because it reduces peroxides generated by decomposition. . In particular, since it is in the form of an oligomer, it has poor volatility and can maintain its photostabilizing effect for a long period of time. It also has the function of suppressing steric hindrance and creating an atmosphere for oxidation reactions.

Adding a phenolic antioxidant alone has only a low effect, but the combination of these three components can increase the effect, absorbing light and at the same time suppressing the production of peroxide due to photolysis. , various effects can be obtained.

(Effect of the invention) The copolyether ester according to the present invention has 0%
．． 01 mole % to 3 mole % of crosslinking agent can be used.

Depending on the purpose, pigments, dyes, phosphorus-based molding stabilizers, fillers, etc. may also be used. The copolyether ester stabilized in this way can be used by extrusion, blow extrusion, injection molding, etc. according to various uses and forms, and can be effectively used outdoors.

(Example) Hereinafter, the present invention will be specifically explained based on Examples.

Example 1 The following materials were placed in a flask equipped with a stainless steel stirrer and a distillation column, located at a height of about 3 increments from the bottom with the same radius as the internal radius of the flask.

Poly (tetramethylene oxide) glycol (molecular weight 1000) 46.73 parts by weight Dimethyl terephthalate 45.31 1,4-Butanediol 19.30 1,4-Cyclohexane dimethanol 16.19 (60 mol%) Trimerit Acid anhydride 0.45 parts by weight Tetrabutyl titanate 0.1 Irganox-10
100.1 (additional composition amounts are in parts by weight based on 100 parts by weight of final material polymer).

After placing the flask in a 160°C oil bath and stirring for 5 minutes,
A tetrabutyl titanate/1,4-butanediol solution was added. Methanol was evaporated from the reaction mixture by gradually increasing the temperature to 250°C over 1 hour, and when the temperature reached 250°C, the pressure was increased to about 2% in 20 minutes.
The pressure was gradually decreased to 70Pa. Polymerization reaction material at 250℃
The polycondensation reaction was stopped by bubbling nitrogen under vacuum for 55-90 minutes. The resulting viscous molten product was removed from the flask under a nitrogen atmosphere and then cooled.

The resulting polymer has a temperature of about 270°C at a temperature of 230°C.
having a melt viscosity of 0 to 3000 psi and 1.0 to 1.5
It had an intrinsic viscosity of . The copolyetherester elastomer was dried into a powder (approximately 30 meshes).

100 parts by weight of this powder contains 0 "Irganox-1010"
．． 1 part by weight, 0.05 parts by weight of ``Irgafuo-168'', 0.05 parts by weight of ``Chimasorpu 944'', and 0.2 parts by weight of ``Tinuvin-234'' were mixed, and a film with a thickness of 0.4 mm was obtained by blow extrusion. Ta. This film was prepared to fit the tensile strength test piece type 3 of the Korean Industrial Standard Test M651B, and a weathering test was conducted according to the E type method of the American Industrial Standard Test G23, and the tensile strength at each time was measured according to the Korean Industrial Standards. Measurement was performed using Test M651B, and the time required for the physical properties to reach 50% was measured.

Examples 2 to 4 Various stabilizers as shown in Table 1 were added to the copolyether ester polymer powder produced by polymerization according to the method of Example 1, and measurements were made according to the method of Example 1. The experimental results for each of the various light stabilizer components added are shown in Table 2.

Comparative Examples 1 to 3 Evaluation was conducted in the same manner as in Example 1, except that no stabilizer component was added. Table 1 shows the experimental results for each added light stabilizer component.

Table 1 *Additional compositions are in parts by weight based on 100 parts of copolymer.

*Irgafuos 168 is a phosphoric acid-based antioxidant (distearyl pentaerythrylol diphosphate, a Ciba Geigy product); *Timasolp 944 is a sterically inhibited amine-based light stabilizer [poly((6-( (1,1,3,3-tetramethylbutyl)amine) -1,3,5-triazine2.4-
diyl) ((2,2,6,6-tetramethyl-4-piperidinyl)imino) -1,6-hexanediyl((
2,2,6,6-tetramethyl-4-piperidinyl)imino)], a product of Ciba Geigy. *Tinuvin 234 is a light stabilizer (2-(2'-hydroxy-3', ter t-amylphenyl) benzotriazole], a product of Ciba Geigy.
7'chiru-4-hydroxyhydrocinnamate], a Ciba Geigy product; *Resorcinol stabilizer is a light stabilizer [3-hydroxyphenyl-4-(2-benzooxacylyl)benzoate)]; *Sheasorda UV 3346 is a sterically hindered amine light stabilizer [poly((6-((morpholine)-1゜3
．． 5-triazine-2,4-diyl) ((2,2,6
゜6-tetramethyl-4-piperidinyl)imino)-1
, 6-hexanediyl ((2,2,6,6-tetramethyl-4-piperidinyl)imino)〉], a product of Cynamide Co., Ltd. *Tinuvin 622 is a combination of the light stabilizer succinic acid and N-β-hydroxyethyl- A polyester bond of 2,2,6,6-butramethyl-4-hydroxypiperidine, a product of Ciba Geigy. be.

Comparative Examples 4 to 10 Elastic polymers were produced according to the method of Example 1, except that the following compositions were used.

Poly (tetramethylene oxide) glycol (molecular weight 1000) 47.71 parts by weight Dimethyl terephthalate 46.28 -1,4-butanediol 23.22 1,4-cyclohexanedimethanol 10.97 (40 mol%) Trimerit Acid anhydride 0.46 parts by weight Tetrabutyl titanate 0.1 Irganox-10
100.1 (Additional composition is in parts by weight based on 100 parts by weight of final material polymer).

After drying the produced polymeric elastomer powder with a melt viscosity of 2,500 to 2,700 psi and an intrinsic viscosity of 1.0 to 1.5, a stabilizer was added in the proportion shown in Table 2 below, and it was formed into a film with a thickness of 0.4 mm. After extrusion, weather resistance experiments were conducted in the same manner as in Examples 1 to 4 above. The results are shown in Table 2.

Table 2 The present invention is not limited to the above examples, but as evaluated in the examples above, the time at which the physical properties decrease by 50% with respect to the initial tensile strength after the weathering test is the same as that of the composition of the comparative example. It turns out that it takes much longer than that. Therefore, it can be said that the three-component composition of the present invention has excellent weather resistance.

Claims (3)

[Claims] (1) 5 to 25 mol% of the total glycol content is polyalkylene oxide glycol and 75 to 95 mol% of low molecular weight diol, especially 50 to 100 mol% of the low molecular weight diol is 1,4-cyclohexanedimethanol, and 0 ~50
The mol% is the A component composed of the third aliphatic diol,
The following general formulas (II) to (V
The following general formula ( I
) with at least one sterically hindered amine light stabilizer as the third component, and a combination of component B based on a combination of these three components, the melt viscosity is 270.
A polyetherester block copolymer composition having an intrinsic viscosity of 0 to 3000 psi and an intrinsic viscosity of 1.0 to 1.5. ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (I) (However, in the formula, n is an integer from 3 to 30, R_1 is hydrogen, R_1 and R_2 are substituted or unsubstituted alkyl groups having 1 to 25 carbon atoms, carbon Aryl group having 6 to 25 carbon atoms, 1 to 2 carbon atoms
5 alkylene group, a cycloalkylene group having 3 to 12 carbon atoms, a hydroxyalkyl group having 1 to 18 carbon atoms and its ester group, and an alkylenecarboxylic acid having 2 to 18 carbon atoms and its ester and amide. ) ▲There are mathematical formulas, chemical formulas, tables, etc.▼...(II) (However, in the formula, X is hydrogen or chlorine, and R_3, R_
4 is independent from hydrogen, a hydroxy group, a linear or branched alkyl group having 1 to 18 carbon atoms, a substituted or unsubstituted alkyl or alkoxy group, an aryl group having 7 to 22 carbon atoms, and an alkylenylaryl group. It was selected by ) ▲There are mathematical formulas, chemical formulas, tables, etc.▼...(III) (However, in the formula, R_5, R_6, and R_7 have carbon numbers of 1 to 18.
linear or branched alkyl groups, substituted or unsubstituted alkyl groups, and alkylenecarbonyloxyalkyl groups having 3 to 18 carbon atoms. ) ▲There are mathematical formulas, chemical formulas, tables, etc.▼...(IV) (However, in the formula, R_8, R_9, R_1_0, R_1_1
are independently selected from hydrogen, linear or branched, substituted or unsubstituted alkyl groups having 1 to 18 carbon atoms. ) ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼... (V) ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼... (VI) (However, in the formula, X' is hydrogen, methyl group, methoxy group, and Y , Z is a cyano group or an alkyl ester group,
R_1_2 is a substituted or unsubstituted linear or branched alkyl or alkoxy group having 1 to 18 carbon atoms, and R_1
_3 is hydrogen, a substituted or unsubstituted linear or branched alkyl or alkoxy group having 1 to 18 carbon atoms. ) (2) The polyalkylene oxide glycol of 5 to 25 mol% in the total glycol content has a molecular weight of 600 to 2000.
or polytetramethylene glycol with a molecular weight of 15
00-2000 and the ethylene oxide content is 15-2000
35 parts by weight of polypropylene oxide glycol and 75 to 95 mole % of low molecular weight diol.
100 mol% 1,4-cyclohexanedimethanol,
0 to 50 mol% aliphatic diol with a molecular weight of 250 or less,
2. A polyetherester block copolymer composition according to claim 1, characterized in that it is constituted in particular of ethylene glycol or diethylene glycol or 1,4-butanediol. (3) Component B of the three-component system is 0.01 to 0.01 to sterically inhibited phenolic antioxidant based on 100 parts by weight of resin.
1.0 parts by weight, 0 sterically hindered amine light stabilizers
．． The polyetherester block copolymer composition according to claim 1, wherein the composition ratio is maintained at 01 to 2.0 parts by weight.