JPH0260689B2 - - Google Patents

Description

[Detailed description of the invention]

By blending specific compounds, the present invention can
The present invention relates to a modified polyester composition with improved light resistance, and more particularly to a polyalkylene glycol-containing polyester composition with significantly improved light resistance by incorporating a specific substituted ethylene compound. Polyesters, represented by polyalkylene terephthalate, have excellent physical properties, so they can be used as fibers,
It is widely used in many fields such as films and other molded products. However, it has many drawbacks such as poor dyeability due to its hydrophobic nature, easy charging, and easy adsorption of dirt, and improvement of these problems has become a major issue. Conventionally, in order to solve these drawbacks, various attempts have been made to incorporate polyalkylene glycol or its derivatives into polyester either alone or in the form of copolymerization or blending with other auxiliaries. For example, a method of copolymerizing a small amount of polyalkylene glycol for easy dyeing, a method of blending polyalkylene glycols alone or in combination with metal salts, etc. to impart antistatic properties and hydrophilic properties, and a method of blending polyalkylene glycols alone or in combination with metal salts, etc. These methods include a method of producing an elastic body by copolymerizing a large amount, or a method of blending a polyester containing a large amount of polyalkylene glycol as a modifier with a fiber-forming polyester. Polyester inherently has good light fastness, and there are virtually no practical problems when using it for clothing or interior decoration.
However, if even a small amount of polyalkylene glycol is contained through the above-mentioned modification, the light fastness will sharply decrease, and the color fastness will be significantly reduced, and the polyester itself will deteriorate and discolor. It is preventing the development of Hitherto, methods for improving the light resistance of such modified polyesters, in particular, research on light stabilizers have been widely conducted. Typical examples include triazole light stabilizers,
Oxybenzophenone light stabilizers, salicylic acid light stabilizers, hindered amine light stabilizers, etc. may be used alone or in combination with oxidative decomposition inhibitors and the like. However, since polyester requires high manufacturing and molding temperatures, and also tends to react with various functional groups at high temperatures, many light-fastening agents have the disadvantage of causing coloration and deterioration of the physical properties of polyester, and have not been put into practical use. The reality is that it is not. The present inventors have arrived at the present invention as a result of intensive research into a method for improving the light fastness of polyester containing polyalkylene glycols. That is, the present invention involves adding 0.05 to 2.0% of a substituted ethylene compound represented by the following general formula [] to a modified polyester containing 0.5 to 80% by weight of one or more polyalkylene glycols or derivatives thereof.
It is characterized by containing % by weight. [However, R ¹ and R ² are a hydrogen atom or an alkyl group, an aryl group, an alkylaryl group, which may have a substituent substantially non-reactive with the modified polyester,
It is an arylalkyl group, R ³ is a hydrogen atom or a monovalent hydrocarbon group having 1 to 7 carbon atoms, R is a hydroxyl group, a carboxyl group or a salt or ester thereof, a sulfonic acid or a salt or ester thereof, a phosphonic acid or an ester thereof A (m+n)-valent organic group that may have a substituent such as a salt or ester, halogen, alkyl group, aryl group, alkylaryl group, or arylalkyl group (excluding a naphthalene ring. Here, hydroxyl group, etc. In the case of a group having reactivity with the modified polyester, the number l of functional groups is l+n≦2). Also m,
n is each independently an integer of 0 to 2, m+n≧1
It is. ] Compared to other light-resistant agents, the substituted ethylene compound used in the present invention has the characteristic that it does not cause particularly large discoloration or deterioration of physical properties when added during the production or molding of modified polyester; however, this does not necessarily mean that the compound This is not only due to excellent heat resistance. It is assumed that this is because when this compound is mixed with modified polyester at high temperature, it hardly reacts with modified polyester, or even if it does react, the reactant does not cause coloring compared to other light stabilizers. Ru. The acid components used in the modified polyester in the present invention include terephthalic acid, isophthalic acid,
P-oxybenzoic acid or esters thereof, etc., but aromatic dicarboxylic acids such as 5-sodium isophthalic acid, 5-potassium isophthalic acid, naphthalene dicarboxylic acid or esters thereof, adipic acid, Aliphatic dicarboxylic acids such as sebacic acid, azelaic acid, and dimer acid or their esters can also be used in combination. Further, as the glycol component, ethylene glycol, propylene glycol, 1,4-butanediol, 1,6-hexanediol, neopentyl glycol, etc. can be used. Furthermore, polyalkylene glycols or derivatives thereof used as modifiers include triethylene glycol, tetraethylene glycol, tripropylene glycol, polyethylene glycol,
Polypropylene glycol, polytetramethylene glycol (ethylene-propylene) block (or random) copolymer, poly(ethylene-propylene)
tetramethylene) block (or random) copolymers and the like. The polyalkylene glycol may be substituted at one or both ends with an organic group having a functional group that is more easily copolymerized with polyester, and if the polyalkylene glycol has a relatively high molecular weight, for example, 400 or more, one or both ends may be substituted. may be blocked with an organic group that is non-reactive with the polyester. Furthermore, polyalkylene glycols may be used, such as isopropylidene bisphenol, in which a divalent organic group exists in the molecular chain of a polyoxyalkylene compound, and an ether-bonded oxygen that bonds alkylene groups together in one molecule. A wide range of compounds can be mentioned. The amount of the polyalkylene glycol used varies depending on the use of the modified polyester, but is 0.5 to 80% by weight based on the modified polyester. It can be added at any stage from the production of polyester to the molding process, but in the case of copolymerization, it is added from the time of esterification or transesterification to the middle stage of polycondensation, while in the case of blends, it is added from the beginning of polycondensation to the time of molding. is desirable. The method for producing polyester in the present invention is not particularly limited, and is carried out according to a conventional method for producing polyester. At that time, stabilizers such as extinguishing agents, lubricating agents, dyes and pigments, crystallization promoters, and phosphorus compounds,
There is no problem in adding flame retardants, antistatic agents, etc. Specific examples of the compound represented by the general formula [] used in the present invention include the following compounds. They also contain the corresponding aldehydes,
It is synthesized by reacting ketones, polyaldehydes, polyketones, polyaldehyde ketones with malonitrile, cyanoacetic acid, esters thereof, or mixtures thereof in the presence of an appropriate catalyst by a dehydration condensation method. However, the substituted ethylene compound of the present invention is not limited to the specific examples below or the compounds obtained by the above synthesis method. (However, R ³ and R ⁴ are H, alkyl group, aryl group,
Alkylaryl group, alkoxy group, aryloxy group, etc., X ₁ is CN or COOR ⁶ , R ⁶ is H, alkyl group,
(aryl group, etc.) (However, R ⁷ is the same as [2] formula R ⁴ , R ⁸ is H, alkyl group, arylalkyl group, etc., and X ₁ is the same as [2] formula) (However, X ₁ is the same as above) (However, X ₂ and X ₃ are the same or different groups and are CN or
COOR ⁶ , R ⁶ are the same as above) (However, X ₂ and X ₃ are the same as above) (However, R ⁹ is COOR ¹⁰ , SO ₃ R ¹⁰ ,

[Formula] R ¹⁰ is H, alkyl group, aryl group, metal ion, R ¹¹ is an alkyl group, aryl group) The substituted ethylene compound is added during the production or molding of polyester. It can be added before, after, or simultaneously with the addition of polyalkylene glycols. Especially when the molecule contains cyanoacrylate or other functional groups that can react with polyester, during the production of polyester, especially after esterification reaction or transesterification reaction,
It is desirable to add it before the completion of polycondensation. The amount added is 0.05 to 2.0% by weight, preferably 0.1 to 1.0% by weight, based on the modified polyester. The present invention will be explained below with reference to Examples, but the present invention is not limited to the Examples. The structural formulas of the substituted ethylene compound and light stabilizer used in the examples are as follows. Example 1 A transesterification reaction is carried out from 960 g of dimethyl terephthalate, 640 g of ethylene glycol, 16 g of titanium oxide (20% ethylene glycol slurry), 0.4 g of zinc acetate, and 0.25 g of antimony trioxide. After the reaction was completed, 100 ppm of 2-carboethoxyethyl-diethylphosphonate was added as P, and after stirring for 5 minutes, polyethylene glycol 39 with a molecular weight of 4000 was added.
g was added, transferred to a polycondensation reactor, and heated at 280℃0.1mmHg.
Polycondensation is carried out with The resulting resin was white and had an intrinsic viscosity (measured at 30° C. in a 6/4 weight ratio of phenol/tetrachloroethane) of 0.63. This is called modified polyester A. Example 2 In Example 1, 5g of light stabilizers a, e, and f were added at the same time as polyethylene glycol, and polycondensation was performed in the same manner to obtain modified polyester compositions B, C, and D.
I got it. Table 1 shows the characteristic values of the obtained polymer.

[Table] The modified polyester composition shown in Table 1 was spun at a nozzle temperature of 293°C, stretched to make a double-sided knitted fabric, dyed under the following conditions, irradiated for 40 hours with a fade-o-meter, and tested for light resistance using a blue scale. I graded them. The results are shown in Table 2. However, modified polyester composition D had too strong coloring and was not practical at all, so spinning was not performed.

[Table] Dyeing conditions Resolin Blue FBL (Bayer disperse dye) 0.2% owf Acetic acid 1.0% owf Sodium acetate 0.5% owf Daysbar TL (Meisei Chemical Co., Ltd. leveling agent)
1g/bath ratio 1:100 120°C 60 minutes Example 3 In Example 1, a white polymer was obtained by using polyethylene glycol with a molecular weight of 20,000 instead of polyethylene glycol with a molecular weight of 4,000. The polymer was pulverized, mixed with a light resistance agent as shown in Table 3, and after spinning and knitting according to Example 2, the light resistance was evaluated. The results are shown in Table 3.

【table】

[Table] The fibers obtained from the composition of the present invention had good color tone and good light resistance.

Claims (1)

[Claims] 1. A modified polyester containing 0.5 to 80% by weight of one or more polyalkylene glycols or derivatives thereof, containing 0.05 to 2.0% by weight of a substituted ethylene compound represented by the following general formula [] A modified polyester composition. [However, R ¹ and R ² are hydrogen atoms, or an alkyl group, aryl group, arylalkyl group, or alkylaryl group that may have a substituent that is substantially non-reactive with the modified polyester, and R ³ is A hydrogen atom or a monovalent hydrocarbon group having 1 to 7 carbon atoms, R is a hydroxyl group, a carboxyl group, or a salt or ester thereof, a sulfonic acid or a salt or ester thereof, a halogen, an alkyl group, an aryl group, an alkylaryl group, It is an (m+n)-valent organic group (excluding a naphthalene ring) that may be substituted with an arylalkyl group. Furthermore, m and n are each independently an integer of 0 to 2, and m+n≧1]