JPS6019340B2 - thermoplastic resin composition - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a thermoplastic resin composition containing an ultraviolet absorber suitable for improving the light resistance of polymer molded articles.

The present invention relates to an ultraviolet absorber particularly suitable for improving the light resistance of molded products having a large surface area relative to their volume, such as polymer molded products, fibers, and films manufactured through high-temperature molding processes.
In general, polymeric materials tend to be degraded by light, and for example, when used outdoors for a long period of time, they have drawbacks such as verticalization and discoloration, which hinders their usefulness.

For this reason, conventionally, for example, 0-hydroxybenzophenone, 2
It has been attempted to incorporate small amounts of ultraviolet absorbers such as 1(2'-hydroxyphenyl)penzotriazole into polymers to improve light resistance. However, a major drawback of these commonly used ultraviolet absorbers is their compatibility. In other words, a polymer composition containing an ultraviolet absorber is formed into a molded product in a desired shape through a molding process such as extrusion molding, injection molding, and blow molding, as well as through processes such as stretching and heat treatment. In the process the polymer composition is 120
Since it is subjected to heat treatment at a high temperature of ~300 qo, a considerable amount of the added ultraviolet absorber is volatilized and desorbed, resulting in that it does not effectively improve light resistance. Furthermore, the UV absorber that has been volatilized and desorbed needs to be removed by exhaust air from a hygienic point of view. In addition, when a molded product made of a polymer to which such a UV absorber has been added is used outdoors for a long period of time, the additive gradually migrates to the surface of the molded product and desorbs over time, resulting in a decrease in light resistance. One of the disadvantages is that it causes a decline. The present inventors have conducted various studies to improve these drawbacks, and as a result, they have found that the ultraviolet absorber-containing thermoplastic resin composition of the present invention has excellent light resistance and can improve the above-mentioned drawbacks.

That is, the present invention relates to a thermoplastic resin composition containing an ultraviolet absorber made of a compound represented by the general formula (1) or (0) below.

R: hydroxy group 1, m: number of 0 or 1, but both cannot be 0.

R2, R3: selected from halogen, alkyl group or alkoxy group, which may be the same or different.

n, p: Represents an integer from 0 to 3.

R4: represents any one of alkyl, aryl, alkylene, and arylene group.

q: 1 or 2 The compound represented by the above general formula is, for example, a penzophenone derivative having two or more hydroxy groups or a penzotriazole derivative substituted with a phenyl group having two hydroxy groups, and various bases. It can be synthesized from acids, dibasic acids, or their acyl halides by conventional methods.

For example, it can be easily synthesized by heating and melting an acetylated product obtained by heating the penzophenone compound and acetic anhydride under reflux in the presence of a solvent and a monobasic acid or dibasic acid to perform an acetic acid removal reaction. It can also be easily synthesized by lacquering the above penzophenone compound in an alkaline solution and vigorously mixing it with an acyl halide to cause a reaction. That is, it is synthesized by an interfacial condensation reaction using a combination of water and a halide as a solvent. Examples of penzophenone derivatives and penzotriazole derivatives include 2
, 4-dihydroxybenzophenone, 2,2,4-trihydroxybenzophenone, 2,2',4-trihydroxy-3,5,5'-trimethylbenzophenone, 2,
4-dihydroxy-3,5,5'-trimethoxybenzophenone, 2,2',4-trihydroxy-5,5'-dichlorobenzophenone, 6-(2-day-benzotriazol-2-0yl) )-resorcin, 2-(5-chloro-
2H-penzotriazol-2-yl)-resorcin,
2,4-dimethyl-6-(2H-penzotriazol-2-yl)-resorcin, 2,4-dimethoxy-6-(
Examples include pan-penzotriazol-2-yl)-resorcin. In the penzophenone derivative, it is necessary that at least one hydroxy group is located at the ortho position with respect to the carbonyl group, and one hydroxy group is located at a position other than that. In the penzotriazole derivative, one of the two hydroxy groups must be at the ortho position to the nitrogen atom at position 2, and the other one must be at the other position. Monobasic acids used in the production of the ultraviolet absorber of the present invention include, for example, benzoic acid, bara, meta or J-orthomethylbenzoic acid, Q or B-naphthoic acid, anthracene-1-, 121- or 19-carboxylic acid,
Aromatic monobasic acids such as phenanthrene-1-1, 12-, 13- or 19-carboxylic acid, or C4 or higher aliphatic monobasic acids such as caproic acid, heptanoic acid, caprylic acid, belargonic acid, capric acid, n-undecylenic acid, lauric acid, n-tridecylenic acid, myristic acid, n-pentadecylenic acid, palmitic acid, margaric acid, stearic acid, n-nonadecylenic acid, arachidic acid, n-heneicodisanoic acid, behenic acid, n- tricosanoic acid, lig/seric acid, n-pentacosanoic acid, cerotic acid, n-heptacanoic acid, montanic acid, n-nonacosanoic acid, melisic acid,
n-Hentriacontanoic acid, n-Hentriacontanoic acid,
Seroplastic acid, n-2 hexatriacontanoic acid, n
-octatriacontanoic acid, n-hexatetracontanoic acid, Q-phenylacetic acid, etc.

Examples of dibasic acids include terephthalic acid, isophthalic acid, 2,2'- or 4,4-diphenyldicarboxylic acid,
Aromatic dibasic acids such as 2,6-, 2,73- or 1,5-naphthalene dicarboxylic acid, 1,2-bis(4-carboxylphenoxy)ethane, bis(4-carboxylphenyl)methane, or C3 The above aliphatic dibasic acids include propanedioic acid, butanedioic acid, betanedioic acid, trihexanedioic acid, heptanedioic acid, octanedioic acid, nonanedioic acid, decanedioic acid, undecanedioic acid, dodecanedioic acid, tridecane diacid, tetradecanedioic acid, bentadecanedioic acid, hexadecanoic acid, heptadecanedioic acid, octadecanedioic acid, /nadecanedioic acid, dicosanedioic acid, henicosanedioic acid, docosanedioic acid, tricosanedioic acid, tetracosanedioic acid, hexacosane Examples include diacid, triacontanedioic acid, tetratriacontanedioic acid, p-xylene dicarboxylic acid, and the like. The ultraviolet absorber of the present invention can be effectively used to improve the light resistance of thermoplastic resins that undergo photodeterioration.

Examples of thermoplastic resins include polyolefins such as polyethylene, polypropylene, and ethylenenopropylene copolymers, styrene homopolymers and copolymers, butadiene,
Homopolymers and copolymers derived from isoprene, etc., homopolymers and copolymers derived from vinyl chloride, vinylidene chloride, acrylate, etc., polyethylene terephthalate, polybutylene terephthalate, polyethylene terephthalate/isophthalate, polyalkylene Saturated polyesters such as naphthalates, and regular unsaturated polyesters, nylon 6, nylon 60, nylon 11
, nylon 12, nylon 6/10, nylon 6/66
Examples include, but are not limited to, aliphatic polyamides such as, aromatic polyamides containing xylylene groups, polyester/polyether flock polymers, and polyamide/polyether block polymers.
In addition, there are no restrictions on the form of molded products using the thermoplastic resin composition containing the ultraviolet absorber of the present invention, but fibers, films, sheets, paint films, hollow containers such as bolts, and various other plastic molded products can be used. can give.

The ultraviolet absorber of the present invention is particularly effectively used for polymeric materials whose processing temperatures are high, such as polypropylene, polyester, and polyamide, and for products that have a large surface area relative to their volume, such as fibers and films. It is. In order to improve the light resistance, it is necessary to blend the ultraviolet absorber of the present invention in an amount of 0.01 parts by weight or more per 10 parts by weight of the polymer material, but even if 5 parts by weight or more is used, the effect will not improve. not big.

A desirable range of blending amount is 0.5 to 3 parts by weight. There are no particular restrictions on the method of blending it into the thermoplastic resin, and it may be added during the polymerization process of the polymeric material or before the molding process. The ultraviolet absorber of the present invention not only has excellent ultraviolet absorption properties, but also has significantly improved volatilization and desorption properties. It increases the durability and usefulness of the polymeric material when used.

The present invention will be described below with reference to Examples, but the content of the present invention is not limited thereto.

The nuclear magnetic resonance spectra shown in the following examples were measured using Varian A-60 in deuterated chloroform.
Measured at a temperature of 60 qo.

Example 1 214 parts of 2,4-dihydroxybenzophenone, 10
Two parts of acetic anhydride were dissolved in 40 $ of nitrobenzene and heated to reflux for 2 hours.

After the reaction was completed, nitrobenzene was removed from the system. The residue was purified by repeating recrystallization three times from ethyl alcohol to obtain 2-hydroxy 4-acetoxybenzophenone. Furthermore, a mixture of 29.8 parts of 2-hydroxy 4-acetoxybenzophene, 20.2 parts of sebacic acid, and 0.05 parts of magnesium was heated at a temperature of 200° C. under a nitrogen atmosphere.

The reaction was carried out for 2 hours while acetic acid produced during the process was removed from the system. This reaction mixture was purified by recrystallizing twice from acetone to obtain bis(3-hydroxy-4-benzoylbenzene) sebacate. It was confirmed by NMR spectrum measurement that the hydroxy group at the 2-position of 2-hydroxy 4-acetoxybenzophenone and the hydroxy group at the 3-position of bis(3-hydroxy 4-benzoylbenzene) sebacate did not react. This spectrum is shown in [1] of FIG. That is, the structure was confirmed based on the fact that a signal based on the hydrogen bond between the carbonyl group and the hydroxyl group was observed near 7-2.1, and the proton relative intensity ratio of each signal showed good agreement with the theoretical value.

Example 2 25.3 parts of 2,4-dihydroxybenzophenone, 4
．． 7 parts of sodium hydroxide was dissolved in 30 parts of water, 12 parts of isophthalic acid chloride was further dissolved in 15 parts of chloroform, and this chloroform solution was added to the above aqueous solution and stirred vigorously for 0.3 hours. .

After the reaction was completed, the chloroform layer was separated and the chloroform was removed from it to obtain a pale yellow koji mixture. This was purified by recrystallization three times from a mixed solvent of chloroform:acetone=7:3 to obtain bis(3-hydroxy-4-penzoylbenzene) isophthalate. A signal was observed in the NMR spectrum of this compound in the vicinity of 2.1, and the front relative intensity ratio of each signal also showed good agreement with the theoretical value. This NM old spectrum is shown in Figure 1 (b). Example 3 Various synthetic products were obtained by the method shown in Example 1 or 2.

These properties are shown in Table 1. Example 4 Various compounds shown in Table 1 were mixed into polyethylene terephthalate resin 10.
Add 3 parts to Ikari Miyako and extrude at a temperature of 280℃,
This was stretched at a temperature of 9500 to obtain a film of 020.

This film was heated in air at a temperature of 200° C. for 30 seconds or at a vacuum level of 170° C. on 10-4 Wakihigo for 30 minutes.

The residual rate of the added composite compound was determined by measuring the change in absorbance at 330 (nm) in the ultraviolet region before and after heating these films. These results are shown in Table 2. The absorbance in the ultraviolet region was measured using a Hitachi 214 spectrophotometer. Example 5 3 parts of various compounds shown in Table 1 were added to 10 parts of polyethylene terephthalate resin and extruded at a temperature of 280 qo to obtain a film of 100 A.

This was further stretched at a temperature of 95 qo to obtain a 6 mm thin film. These films were irradiated for 300 hours with a xenon fade meter (manufactured by Toyo Rika Co., Ltd., 1.5 kW), changes in intrinsic viscosity were measured, and the effect of preventing photodeterioration was examined. These results are shown in Table 1. Note that the measurement of the intrinsic viscosity was carried out at a temperature of 30° C. using a mixed solvent of tetrachloroethane:phenol=4:6. 0 Comparative Example 1 Three commercially available compounds similar to those shown in Examples 4 and 5: 2-hydroxy-4-octoxybenzophenone, 2-(3
,5'-tenbutyl-2'-hydroxyenyl)-5
-chlorobenzotriazole and 21(4'-octoxy-2-hydroxyphenyl)penzotriazole (
The residual rate and photodegradation prevention effect of the structural formulas shown in Table 2) were investigated, and the results are shown in Tables 3 and 4.

All of the above three types of compounds exhibit the best residual rate among commercially available products and are among those exhibiting an excellent photodegradation prevention effect.

Comparative Example 2 In the same manner as shown in Examples 4 and 5, the residual rate and photodeterioration prevention effect of the compounds having the structures shown in Table 2, 4 and 4, were investigated, and the results are shown in Tables 3 and 4.

Table 4 shows that the known ultraviolet absorbers have almost the same ability to prevent photodeterioration as the compound synthesized according to the present invention.

However, Table 3 shows that all of them exhibited lower residual rates than the composites according to the present invention. Table 1 Various UV absorbers Table 2 Table 3 Residual rate of UV absorbers *Same as sample modification in Tables 1 and 2.

of / stop *Same as Osamu in Tables 1 and 2

[Brief explanation of drawings]

FIG. 1 shows the NMR spectrum of the compound used in the present invention. Figure 1

Claims (1)

[Scope of Claims] 1. A thermoplastic resin composition containing a compound represented by the general formula (I) or (II) below. ▲There are mathematical formulas, chemical formulas, tables, etc.▼ R_1: Hydroxy group 1, m: Number of 0 or 1, but both cannot be 0. R_2, R_3: selected from halogen, alkyl group or alkoxy group. They may be the same or different. n, p: Represents an integer from 0 to 3. R_4: represents any one of anylkyl, aryl, alkylene, and arylene group. q: Number of 1 or 2.