JPH02133460A - Lightfast polyester composition - Google Patents

Abstract

PURPOSE:To obtain the title composition having an excellent synergistic effect and an excellent whiteness, improved mechanical properties and lightfastness of a dyed piece and useful for a fiber, a film or the like requiring high light by mixing a polyester with a specified manganous salt and a benzotriazole ultraviolet absorber. CONSTITUTION:A lightfast polyester resin composition is formed by mixing polyethylene terephthalate or a polyester based thereon with 0.005-0.5wt.%, desirably, 0.01-0.1wt.% (in terms of the Mn atoms) manganous salt (A) selected from among manganous borate, manganous chloride, (R<1>COO)<2>Mn, R<2>(COO)2Mn and [R<3>(OH)COO]2Mn (wherein R<1> is H or a 1-31C alkyl, R<2> is a 1-31C alkylene, and R<3> is a 1-31C alkyl) and 0.1-2.0wt.%, desirably, 0.2-1.0wt.% benzotriazole UV absorber (of a percentage weight loss <=5wt.% when heated at 310 deg.C for 20min) of the formula (wherein X is H or a halogen, R<4> and R<5> are each H, a 1-12C hydrocarbon group, an oxyalkyl group or a phthalimidoalkyl group) (B).

Description

DETAILED DESCRIPTION OF THE INVENTION (Field of Industrial Application) The present invention relates to a light-resistant polyester composition useful as molded articles such as fibers and films that require a high degree of light resistance.

(Prior Art) Polyesters represented by polyethylene terephthalate have excellent physical and chemical properties and are widely used as molded products. Polyester is a synthetic polymer with relatively good light resistance, but its physical properties deteriorate under harsh conditions such as when used as an automobile interior material, where it is exposed to high temperatures and ultraviolet rays.

There are problems such as fading of dyed products, and further improvement in light resistance is desired in fields where a high degree of light resistance is required.

Conventionally, as a means to improve the light resistance of polyester, it has been proposed to include a specific metal compound or ultraviolet absorber, but nothing satisfactory has been obtained due to coloring of the polyester, lack of light resistance, etc.

For example, the polyester kneaded with manganese hypophosphite or manganese sulfite disclosed in Japanese Patent Publication No. 32-10694 has the disadvantage of being colored gray.

It has little commercial value. Also, Special Publick Showa 52227
Although the hindered amine ultraviolet stabilizer disclosed in Japanese Patent No. 74 is effective for polyester ether copolymers having poor light resistance, it is not effective for polyesters mainly composed of polyethylene terephthalate.

Ultraviolet absorbers show a certain degree of light resistance improvement effect on polyester molded products, but they generally have poor heat resistance, and when polyester is exposed to high temperatures during melt molding, they sublimate and volatilize, leading to deterioration of the working environment.

It has the disadvantage of decreasing addition efficiency.

Therefore, Japanese Patent Publication No. 51-27788, Japanese Unexamined Patent Publication No. 59-
-192774 proposes a method of treating a molded product with an ultraviolet absorber, but the exhaustion rate of the ultraviolet absorber for polyester is low, and in order to increase light resistance, it is necessary to treat the molded product with an excessive amount of ultraviolet absorber. It has the disadvantage of being inferior in addition efficiency.

Note that the ultraviolet absorber 8 absorbs ultraviolet rays and prevents photodeterioration of substrate polymers and the like.

If the UV absorber does not have sufficient light resistance, it will gradually photodecompose upon irradiation with light, resulting in a decrease in effectiveness.

As described above, conventional light-resistant polyesters have problems such as insufficient light resistance under harsh conditions such as automobile interior materials, which are exposed to high temperatures and ultraviolet rays.

In addition, methods using dyes and pigments with excellent light resistance have been implemented as a means of suppressing discoloration of dyed products. However, there remains a strong need for measures to improve light resistance at the manufacturing stage of molded products such as fibers, rather than using post-processing methods.

(Problems to be Solved by the Invention) In view of the above-mentioned circumstances, the present invention has excellent whiteness, 9 mechanical properties, and light fastness of dyed products, which have an extremely excellent photodegradation inhibiting effect, and Dyes with excellent light resistance in post-processing methods,
The present invention aims to provide a versatile light-resistant polyester composition that can further enhance the effects of pigments.

(Means for solving problems) The present inventors aimed to solve the above problems.

Known light stabilizers 1, including manganous salts.

Hindered amine compounds, metal compounds such as copper and nickel, and benzotriazole compounds and hendphenone compounds as ultraviolet gA absorbers.

Oxalic acid anilide compounds, salicylate compounds.

As a result of careful studies on benzoate compounds, acrylonitrile compounds, etc., and their combinations, it was found that when a specific manganese salt and benzotriazole ultraviolet absorber are used together, a surprising synergistic effect is exhibited, and the conventional The inventors have discovered that it is possible to obtain a polyester composition that has superior performance compared to light-resistant polyester and also has excellent whiteness, and has thus arrived at the present invention.

That is, the gist of the present invention is as follows.

(A) 0.005 to 0.5% by weight of one or more manganese salts selected from group (A) as manganese atoms and -characteristic (
A light-resistant polyester composition containing 0.1 to 2.0% by weight of a benzotriazole ultraviolet absorber represented by B).

(A) Manganese borate, manganese chloride.

General formula (R' COO) z M n , R2(C
OO) 2 M n or [R”(OH)Coo)zMn
Manganese salt represented by 'lRS represents a hydrocarbon group having 1 hydrogen atom and 1 to 12 carbon atoms, an oxyalkyl group, or a phthalimide alkyl group.) The manganous salt used in the present invention is [selected from Group A3, but specific Examples include manganese borate, manganese chloride, manganese formate, manganese stearate, manganese lactate, and the like.

The content of the manganese salt is 0.005 to 0.5% by weight as manganese atoms based on the polyester composition.

Preferably it is 0.01 to 0.1% by weight. If the amount of manganese salt is less than this, the effect of improving the light resistance of the molded product will be poor, and if it is more than this, the moldability will be poor.

This is undesirable because it causes a decrease in mechanical properties.

In addition, the nizotriazole-based ultraviolet absorber in the present invention is represented by the formula (B), 31
It is preferable that the weight loss rate when heated at 0''C for 20 minutes is 5% by weight or less, since the amount of volatilization during molding is small.

Specific examples of such ultraviolet absorbers include 2-[2-
Hydroxy-3,5-bis(α,α-dimethylbenzyl)phenylcou 2H-benzotriazole, 2-(2'
-Hydroxy-3'-(3", 4".

5#, 6'-tetrahydrophthalimido-methyl)-5
'-Methylphenyl]-hensitriazole and the like.

The content of the benzotriazole ultraviolet absorber is 0.1 to 2.0% by weight, preferably 0.2 to 1.0% by weight based on the composition.
Weight%. If the amount of the ultraviolet absorber is less than this, the effect of improving the light resistance of the molded product is poor, and if it is more than this, the whiteness of the molded product is undesirably reduced.

The feature of the present invention is that a specific manganous salt and a benzotriazole ultraviolet absorber are used together, and when the mixing ratio of these is in the range of 1:400 to 5:1, an excellent mutual effect is obtained. Demonstrated.

The polyester in the present invention is not particularly limited, but polyethylene terephthalate is preferred, and may contain isophthalic acid, adipic acid, 5-sodium sulfoisophthalate, etc. as a copolymer component. It is also a commonly used disinfectant.

It may also contain antioxidants, flame retardants, n-materials, optical brighteners, and the like.

From the viewpoint of versatility, it is preferable to add the manganous salt and benzotriazole ultraviolet absorber of the present invention to the polyester before molding, and these additives may be added to the polyester simultaneously or separately. Alternatively, a polyester composition containing a large amount of manganous salt and a benzotriazole ultraviolet absorber is prepared, and this is diluted with a polyester that does not contain these. A so-called master punch method may also be employed.

(Function) The reason why the polyester composition of the present invention exhibits significantly superior light resistance compared to conventional compositions is 1. Not only does the benzotriazole-based ultraviolet absorber have an effect of suppressing photoexcitation of polyester molecules, but also the effect of suppressing photoexcitation of polyester molecules by the benzotriazole-based ultraviolet absorber. This is recognized to be due to the mutual effect of the benzotriazole compound molecules being preserved by the quenching action of the specific manganous salt.

(Example) Next, the present invention will be explained in more detail with reference to Examples and Comparative Examples.

Light resistance was determined by using a carbon arc fade-o-meter model F A L-3H manufactured by Suga Test Instruments Co., Ltd. for the yarn.
Light irradiation was performed for 1000 hours at a black panel temperature of 63±3''c, and the strength retention rate of the yarn before and after light irradiation was determined to determine the degree of photodeterioration of mechanical properties.

Light fastness was determined by processing the yarn into a tubular knitted fabric, dyeing it under the following conditions, irradiating it with light under the same conditions, and determining the degree of discoloration using a gray scale.

Staining liquid composition dye (manufactured by Ciba Geigy) ND AUTOBLUE No. 1, ND AU
TORED S-308 and ND AIJTO0RAN
GE F-201 mixed in a 2:1:1.7 weight ratio: 5.7% owf Dispersant (manufactured by NICCA Chemical Co., Ltd.) Nisoka Sunsalt RM 340: 5% OW [dying condition bath Ratio 1:50 130"C x 30 minutes In addition, the intrinsic viscosity is the value measured at 20°C using a mixture of equal amounts of phenol and tetrachloroethane as the solvent, and the carboxyl terminal group concentration is the value measured using a mixture of benzyl alcohol and chloroform as the solvent. This is a value measured by titration using an alcoholic solution of KOH as a solvent.

The heating loss rate of the ultraviolet absorber was 0.1±0.
01 g was heated at 310° C. for 20 minutes in nitrogen gas, and the IM concentration was measured.

Examples 1 to 4 and Comparative Examples 1 to 6 The viscosity was 1.02. Carboxyl end group concentration 15mm
ol/kg of polyethylene terephthalate tinobu.
Add the manganese salt shown in the table and the ultraviolet absorber below to the
Mix the amounts shown in the table and use a 401 mφ extruder type melt spinning machine at a spinning temperature of 300°C.
The yarn was spun from a spinneret with 36 spinning holes and wound at a speed of 450 m/min to obtain an undrawn yarn, which was drawn at a drawing temperature of 210° C. and a drawing ratio of 5.8. The obtained drawn yarn has a density of 500 a/
The zero strength was 8.3 ± 0.5 g/d and the elongation was 9-13% at 36 r.

Table 1 shows the results of measuring the light resistance and light fastness of the obtained drawn yarn.

Ultraviolet absorber OVA-1: 2-(2-hydroxy-3,5-bis(α
.

α-dimethylbenzyl)phenyl)-2H benzotriazole (heat loss rate 1%) OVA-2: 2- (5
-Methyl-2-hydroxyphenyl-to-benzotriazole (heating Mffi rate 85%) Table 1 (Effects of the invention) According to the present invention, the light resistance is useful as molded products such as fibers and films that require high light resistance. A polyester composition is provided.

Patent Applicant: Yu-Tei Riki Co., Ltd. Note: The addition level of the primary manganese salt is % by weight as manganese atoms, and the gravity 1 humidity of the ultraviolet absorber is 2% by weight.

In addition, in Comparative Example 3, the ultraviolet absorber easily volatilized, and a large amount of it was observed to volatilize during spinning. Furthermore, in Comparative Example 6, the yarn was colored gray.

Claims (3)

[Claims] (1) 0.005 to 0.5% by weight of one or more manganous salts selected from group [A] based on manganese atoms and 0.005 to 0.5% by weight of a benzotriazole ultraviolet absorber represented by general formula [B]. A light-resistant polyester composition containing 1 to 2.0% by weight. [A] Manganese borate, manganese chloride, general formula (R^1COO)_2Mn, R^2(COO)_
A manganese salt represented by 2Mn or [R^3(OH)COO)_2Mn (wherein R^1 is a hydrogen atom or an alkyl group having 1 to 31 carbon atoms, and R^2 is an alkylene group having 1 to 31 carbon atoms. , R^3
represents an alkyl group having 1 to 31 carbon atoms. ) [B]▲There are mathematical formulas, chemical formulas, tables, etc.▼ (In the formula, X is a hydrogen atom or a halogen atom, R^4, R^5
represents a hydrogen atom, a hydrocarbon group having 1 to 12 carbon atoms, an oxyalkyl group, or a phthalimidoalkyl group. ) (2) The polyester composition according to claim 1, wherein the polyester is polyethylene terephthalate or a polyester mainly composed of polyethylene terephthalate. (3) The benzotriazole ultraviolet absorber is heated to 310°C.
3. The polyester composition according to claim 1, wherein the polyester composition has a weight loss rate of 5% by weight or less when heated for 20 minutes.