JPH045291A - Benzotriazole-based compound and use thereof - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

DETAILED DESCRIPTION OF THE INVENTION Industrial Application Field The present invention relates to a novel benzotriazole compound and its uses.

The novel benzotriazole compounds provided by the present invention have excellent ultraviolet absorption performance and are therefore useful as ultraviolet absorbers. Polymers containing the benzotriazole compound have excellent ultraviolet absorption properties based on the benzotriazole compound, and are therefore useful in food and drink products such as soft drinks, alcoholic beverages, and edible oils, cosmetics, and pharmaceuticals. It is useful as a material for containers for storing items that are susceptible to the harmful effects of ultraviolet light.

<Conventional technology> It is well known that many polymers such as polyolefins, polyesters, and polyamides deteriorate when exposed to ultraviolet rays contained in sunlight for a long time. A wide variety of products such as food and drink, cosmetics, and pharmaceuticals are sold and stored in transparent plastic containers. However, clear plastic containers are approximately 25
Since a considerable proportion of ultraviolet rays having a wavelength of 0 to 390 nm are transmitted, there is a risk that the contents may be affected by adverse effects such as deterioration, discoloration, and decomposition.

Therefore, in order to prevent the above-mentioned polymers from deteriorating from ultraviolet rays and to preserve the products in plastic containers, it is known to incorporate cyanoacrylate ultraviolet absorbers into these polymers (No. 62-501856). (See Publication SPX and Special Publication No. 1983-501857). In addition, benzotriazole-based ultraviolet absorbers such as 2-(2'-hydroxy-57-chlorophenyl)benzotriazole-3'-carboxylic acid and 4-(3-(benzotriazol-2-yl)-4-hydroxyphenyl]butyric acid) It is known that ultraviolet absorbing performance can be imparted to a polymer by incorporating an agent into the polymer through mixing or copolymerization (see Japanese Patent Publication No. 57-35221 and US Pat. No. 3,214,436).

<Problems to be Solved by the Invention> The above-mentioned cyanoacrylate-based ultraviolet absorbers have lower thermal stability and inferior ultraviolet absorption performance than benzotriazole-based ultraviolet absorbers. Also, special public service No. 57-35221
Even polymers containing benzotriazole-based ultraviolet absorbers described in the above publication or benzotriazole-based compounds specifically described in U.S. Pat. It's not something I can do.

Therefore, one object of the present invention is to provide a novel benzotriazole compound having excellent ultraviolet absorption performance. Another object of the present invention is to provide the use of the novel benzotriazole compound as an ultraviolet absorber. Furthermore, another object of the present invention is to obtain a polymer having excellent ultraviolet absorption performance containing the novel benzotriazole compound, particularly a polymer containing the novel benzotriazole compound as a copolymerization component. Our objective is to provide a polymer with excellent ultraviolet absorption performance.

<Means for Solving the Problems> According to the present invention, the above-mentioned object is achieved by providing a benzo)IJ azole compound shown in a ship's stock, and using the benzotriazole compound as an active ingredient. This is achieved by providing an ultraviolet absorber containing the benzotriazole compound, and the benzotriazole compound is
A polymer containing 10% by weight and the benzotriazole compound as a copolymerization component of 0.001 to 10% by weight.
This is achieved by providing a polymer containing % by weight.

Formula of R in general formula (1)! The bonding position on the benzotriazole skeleton is 4-
or 5-position. - Examples of the halogen atom represented by R in ship stock (1) include a chlorine atom, a bromine atom, etc., and examples of lower alkyl groups include a methyl group, an ethyl group, an n-propyl group, an isobutyl group, and an n-butyl group. group, isobutyl group, 1lee-butyl group, t
Examples of the lower alkoxyl group include ert-butyl group, methoxyl group, ethoxyl group, n
- globoxyl group, ingloboxyl group, n-butoxyl group, imbutoxyl group, 5ee-butoxyl group,
Examples include tert to butoxyl groups. - In the shipyard (1) - shipyard % formula %) (in the formula, m is as defined above) In the general formula of the group (wherein, n is as defined above) The bonding position on the benzene skeleton in the substituted 2-hydroxyphenyl group shown is the 3-position, the 4-position or the 6-position, and among these, the 3-position or the 4-position is preferable. −Funezo (
1) It is necessary that at least one of m and n in Unable to demonstrate performance. −Funezo (
%m of the benzotriazole compounds shown in 1)
and n is an integer from θ to 6, and the other is from 2 to
Those having an integer of 5 are advantageous in industrial production because they can be obtained from readily available raw materials.

The following compounds can be mentioned as representative examples of the benzo)IJ azole compounds represented by the general formula (1).

(a) 4-[3-(benzotriazol-2-yl)-
5-carboxy-2-hydroxyphenyl]butyric Wl: (b)4-[5-carboxy-3-(5-chlorobenzotriazol-2-yl)-2-hydroxyphenyl]
Butyric acid: (c) 4-[2-carboxy-4-hydroxy-5-(
5-methoxybenzotriazol-2-yl)phenyl]butyric acid: (d)5-[5-(benzotriazol-2-yl)3
-(3-carpoxyp-avir)-4-hydroxyphenyl]valeric acid: (e)4-[5-carpoxy-2-hydroxy-3-(
5-methylbenzotriazol-2-yl)phenyl]
Butyric acid: (II) (II) (F/) (to) 4-[5-carboxy-2-hydroxy-3-(
4-methylbenzotriazol-2-yl)phenyl]
The benzotriazole compound represented by the general formula (1) of butyric acid can be produced, for example, by the following synthesis method 1t or synthesis method 2.

<Synthesis method 1> (V) (1-1') (In each of the above formulas, R, m and n are as defined above.) That is, the side containing a carboxyl group represented by -Funazura (II) A phenolic compound having a chain in the para position, such as aluminum chloride, boron trifluoride, tin tetrachloride, 7
A substituted 7-ester compound into which two carboxyl groups represented by the general formula (Ill) are introduced by reacting it with a lactone such as γ-butyrolactone, δ-valerolactone, or C-caprolactone in the presence of Lewis acid such as hydrogen fluoride. /- Synthesize the files.

Furthermore, Lewis IL for the phenolic compound (If)
is usually used in an amount of 100 to 300 molti. Furthermore, after diazotizing the nitroaniline compound represented by Funazou (IV) using sodium nitrite in a conventional manner, the resulting diazotized product is converted into two carboxyl groups represented by the general formula (DI). For example, 10 to a substituted phenol into which
The nitroazo compound represented by the general formula (V) is obtained by coupling in a wt % aqueous sodium hydroxide solution at a temperature within the range of θ to 5°C. Here, the substituted phenol represented by - Funazura (1) into which two carboxyl groups have been introduced is usually used in an approximately equimolar amount to the nitroaniline compound represented by Funazura (■). By reducing the nitroazo compound (V) using a reducing agent such as zinc, tin, or zinc chloride in an aqueous solution of sodium hydroxide/rum at a temperature of 40°C or lower, the benzo compound (1) represented by A benzotriazole compound represented by general formula (1-1) included in triazole compounds can be obtained. The reducing agent is usually used in a molar amount of about 3 to 10 times the amount of the nitroazo compound represented by (V).

Synthesis Method 2〉 (■) (■) (In each of the above formulas, R, m, and n are as defined above.) That is, the side chain containing a carboxyl group represented by -Funazura (Vl) is Reaction with lactone in the same manner as in Synthesis method 1 except that a phenolic compound having a side chain containing a carboxyl group represented by general formula (n) in the rose position is used instead of a phenolic compound having a carboxyl group in the rose position. By diazotization, coupling and reduction, -
A benzotriazole compound represented by the general formula (1-2) included in the benzotriazole compound represented by the ship stock (1) can be obtained.

The benzotriazole compound represented by the general formula (1) has good ultraviolet absorption performance and good thermal stability, and is therefore useful as an ultraviolet absorber. - The benzotriazole compound shown in Funazou (1) can be used as an ultraviolet absorber for all types of polymers, but is particularly preferably used for condensation polymers such as polyester and polyamide.

The above-mentioned polyesters include polyesters composed of dicarboxylic acids and diols, such as polyesters composed of aromatic dicarboxylic acids and aromatic diols, polyesters composed of aromatic dicarboxylic acids and aliphatic diols, polyesters composed of aliphatic dicarboxylic acids and aliphatic diols, etc. polylactone, etc., but 50 or more moles of the dicarboxylic acid component is aromatic dicarboxylic acid, and 80 moles or more of the diol component is aliphatic or fc having 2 to 10 carbon atoms.
Polyesters made of Fi alicyclic diols are preferred. Examples of aromatic dicarboxylic acids include terephthalic acid, isophthalic acid, and 2,6-naphthalene dicarboxylic acid, and examples of aliphatic dicarboxylic acids include adipic acid, azelaic acid, and sebacic acid. Examples of aliphatic or alicyclic diols having 2 to 10 carbon atoms include ethylene glycol, propylene glycol, tetramethylene glycol, hexamethylene glycol,
Examples include decamethylene glycol, cyclohexane dimetatool, diethylene glycol, and the like. These dicarboxylic acids and diols are each used alone or in combination with 21
Used in combination of one or more. Polyesters also contain three or more hydroxyl groups or carboxyl groups, such as triols such as glycerin and trimethylolpropane; tetraols such as bentaerythritol; tricarboxylic acids such as trimellitic acid and trimesic acid; and tetracarboxylic acids such as pyromellitic acid. The polyfunctional compound may be contained as a copolymer component in an amount within a range that allows melt molding. Polyesters can be produced by, for example, a transesterification reaction between a lower alkyl ester such as methyl ester of a dicarboxylic acid and a diol, followed by a polycondensation reaction, or a dehydration esterification reaction between a dicarboxylic acid and a diol, followed by a polycondensation reaction. It is produced according to the method used for the production of ordinary polyester, such as the method used in the production of polyester. The polyester has an intrinsic viscosity of 0.3 to 1.5 dt/? measured at 30°C in a mixed solvent of equal weights of phenol and tetracumyl ethane. range, especially 0.4 to 1.2
dt/? It is desirable that it falls within the range of .

The above polyamides include polyamides consisting of aromatic dicarboxylic acids and aromatic diamines, polyamides consisting of aromatic dicarboxylic acids and aliphatic diamines, polyamides consisting of aliphatic dicarboxylic acids and aromatic diamines, and polyamides consisting of aliphatic dicarboxylic acids and aliphatic diamines. Polyamides made of dicarboxylic acids and diamines, such as polyamides made of dicarboxylic acids and diamines; examples include polylactams; polyamides made of aromatic dicarboxylic acids and aromatic diamines; polyamides made of aromatic dicarboxylic acids and aliphatic diamines; Preferred are polyamides made of group diamines, polyamides made of aliphatic dicarboxylic acids and aliphatic diamines, and the like.

Examples of aromatic dicarboxylic acids include terephthalic acid, isophthalic acid, and 2,6-naphthalene dicarboxylic acid, and examples of aliphatic dicarboxylic acids include adipic acid,
Examples include azelaic acid and sebacic acid. Examples of aromatic diamines include phenylene diamine and xylylene diamine, and examples of aliphatic diamines include tetramethylene diamine, hexamethylene diamine, and
Examples include octamethylene diamine. These dicarboxylic acids and diamines can be used alone or in Fi2
Used in combination of more than one species. In addition, polyamides are made by melting polyfunctional compounds having three or more 7-mino groups or carboxyl groups, such as triamines such as triaminobenzene; tricarboxylic acids such as trimellitic acid and trimesic acid; and tetracarboxylic acids such as pyromellitic acid. It may be included as a copolymer component in an amount within a moldable range. Polyamide can be manufactured using conventional methods such as a method of performing a nylon salt synthesis reaction with a dicarboxylic acid and a diamine followed by a polycondensation reaction, or a method of performing an interfacial polymerization reaction of a dicarboxylic acid halide such as dicarboxylic acid chloride and a diamine. Manufactured according to the method used. The polyamide has a relative viscosity of 1.4 to 3.5, particularly 1.8 to 3.5, as measured in 98% concentrated sulfuric acid at 25°C.
A value within the range of 3.0 is desirable.

The benzotriazole compound represented by the general formula (R) constituting the ultraviolet absorber of the present invention is generally contained in the polymer in an amount of 0.001 to 10% by weight, based on the polymer after containing it. Its content is 0.
It is preferably within the range of 01 to 5% by weight.
It is more preferable that the amount is in the range of 0.05 to 2.0 by weight. If the content is less than 0.0011, the ultraviolet absorbing effect of the polymer may be insufficient;
If it exceeds 0% by weight, the physical properties of the polymer may deteriorate. Furthermore, the ultraviolet absorber of the present invention can be used in combination with other additives such as colorants, antistatic agents, flame retardants, fillers, plasticizers, etc., as required.

The ultraviolet absorber of the present invention can be incorporated into the polymer at any stage of the polymer manufacturing process, and can also be incorporated in a conventional manner before or during molding of the polymer. The ultraviolet absorber of the present invention can be contained in a polymer in a mixed state;
It is preferable that the benzotriazole compound represented by 1) is contained in the polymer in a state where its carboxyl group is copolymerized with the main chain or side chain of the polymer through an ester bond, an amide bond, or the like. In addition, when using a polymer containing a benzotriazole compound shown in -Funazou (1) diluted with a polymer that is compatible with the polymer, -Funazou (1) containing a benzotriazole compound The compound is generally used in an amount such that the content of the benzotriazole compound in the diluted polymer is within the range of 0.001 to 10% by weight as described above. A polymer containing a benzotriazole compound represented by (1) has excellent ultraviolet absorption performance. Among the polymers provided by the present invention, a polymer containing a benzotriazole compound represented by the general formula (1) as a copolymerization component is particularly preferable because the ultraviolet absorbing component is not extracted from the polymer. The polymer of the invention can be #lil molded in the same way as ordinary polymers, and can be molded using known molding methods such as injection molding, blow molding, biaxial stretch blow molding,
Molded by vacuum forming, compression molding, etc.

Furthermore, the polymer L of the present invention can be blended or laminated with other polymers and molded.

Molded articles such as packaging materials and containers obtained from the polymer of the present invention have excellent ultraviolet absorption performance, and by blocking the transmission of ultraviolet rays, it is possible to effectively prevent the contents from deterioration and deterioration due to ultraviolet rays. can.

<Example> The present invention will be explained in more detail with reference to Examples below.
The present invention is not limited to these examples. Note that parts in the examples mean parts by weight. Further, each physical property fL in the examples is a value obtained by measurement according to the following method.

(1) Ultraviolet spectrum using a UV-2100 spectrophotometer manufactured by Takashi Seisakusho. Each weight was measured using a sample of a mixed solvent solution.

(2) Extractable polymer 1f Dissolved in phenol-tetrachloroethane equivalent weight mixed solvent of about 200 + d, added the obtained solution to about 2 tons of methanol, filtered out the precipitated polymer, and then measured the ultraviolet spectrum of the polymer. was measured and compared with the ultraviolet spectrum of the polymer before the extraction operation.

(Sl Intrinsic viscosity: A sample solution with a concentration of 10 W/L was prepared using a mixed solvent of equal weight of phenol and tetrachloroethane and measured at 30°C.

(4) Relative viscosity 10 using 98% concentrated sulfuric acid according to JIS K6810
A sample solution with a concentration of F/l was prepared and measured at 25°C.

(6) Melting point and glass transition temperature Measured at a heating rate of 10° C./min on a rapidly cooled amorphous sample using a TA-3000 DSC (differential scanning calorimeter) manufactured by Mettler. Example 1 p-Hydroxybenzoic acid 138.1? (1,0mo
t) and γ-butyrolactone 86.1? (1,0mo
t) was dissolved in 300% of ethanol, 145.7 f (1.1 mob) of aluminum chloride was added thereto little by little, and then stirred at room temperature overnight to obtain 4-
(5-carboxy-2-hydroxyphenyl) butyroe 7
3.Of (0.38 mot) was obtained (yield 38%).

O-nitroanilyy27.6f (200mmot)
and concentrated hydrochloric acid 60. Of (600 mmot) was added to the ice-cooled 0-nitroaniline hydrochloride aqueous solution, and 13.8 F (200 mmot) of sodium nitrite was added to the resulting aqueous solution of 0-nitroaniline hydrochloride.
A nitrobenzenediazonium salt aqueous solution was prepared by adding a solution prepared by dissolving 50- in water to the above 0-nide α-aniline hydrochloride aqueous solution and stirring for 1 hour. Next, 38.4 W (200 mmot) of 4-(5-carboxy-2-hydroxyphenyl)butyric acid was dissolved in a 10% by weight aqueous sodium hydroxide solution 200 E/L, and the temperature of the resulting solution was maintained at 0 to 5°C. Meanwhile, the previously prepared aqueous nitrobenzene diazonium salt solution was gradually added to the translation solution, followed by stirring for 2 hours. Concentrated hydrochloric acid was added to the resulting mixture to acidify the aqueous solution (1-2) IcL, and the precipitate was filtered off to obtain 52.9f of the corresponding di)o azo compound as a precipitate (yield: 68 h) 0 38.95'(10
0mmot) in 2N aqueous sodium hydroxide solution 10Q
Zinc powder 30, Of
(460 mmot) was gradually added to a suspension prepared by dispersing 25% sodium hydroxide in 50 d of an aqueous solution of sodium hydroxide while keeping the temperature of the suspension below 40°C.The resulting reaction mixture was heated to below 30°C. After cooling to temperature, the mixture was made acidic (F4-11-2) with concentrated hydrochloric acid, and then stirred for 2 hours. Next, the obtained reaction mixture was made alkaline using sodium hydroxide (Tables 13-14), filtered through a glass filter, and the obtained filtrate was acidified again with concentrated hydrochloric acid (...1-2
) KL, the deposited precipitate was separated by filtration. This precipitate was washed with cold water, dried, and then recrystallized from a mixed solvent of water and methanol to give pale yellow crystals (4-[3-(hensitriazol-2-yl)-5-carboxy-2-hydroxyphenyl). 11 tons and 25.6 f of dairy product were obtained (yield: 75 tons).

The obtained 4-(3-(benzotriazol-2-yl)
The physical properties of -5-carboxy-2-hydroxyphenyl]butyric acid are shown below.

Elemental analysis value Theoretical value Experimental value (as CI7HL505N3) Cchi 59;82 59.51Hchi
4.43 4.36N%
12.31 12.59 Mass spectrometry value 341 (
M'') Ultraviolet spectrum λmaz338nm Example 2 In Example 1, 4- was used instead of 0-nitroaniline.
Chloro-2-nitroaniline 34.5 f (200 mm
4-(5-carboxy-3-(5
-Chlorobenzotriazol-2-yl)-2-hydroxyphenyl]butyrozine (15.8 f) was obtained (yield: 21 g).

The physical properties of the obtained 4-[5-carboxy-3-(5-chlorobenzotriazol-2-yl)-2-hydroxyphenyl]butyric acid are shown below.

Elemental analysis value Theoretical value Experimental value (as C17H1405N3α) Cchi 54.34 53.98Hchi
3.76 3.61Nchi 1
1.18 11.02 Mass spectrometry value 37 s
(M+) Ultraviolet spectrum λmax 340 images Example 3 In Example 1, m-hydroxybenzoic acid 138.1 (1,0 mot) was used instead of p-hydroxybenzoic acid, and 4-methoxy instead of 0-nitroaniline. -2-nitroaniline 33.6 F (200 mmot)
By performing the reaction and separation operations in the same manner except that 4-(2-carboxy-4-hydroxy-5-(5-methoxyhenditriazol-2-yl)
10.4F of phenyl]butyric acid was obtained (yield: 14).0 Obtained 4-[2-carboxy-4-hydroxy-5-
The physical properties of (5-methoxybenzotriazol-2-yl)phenyl]butyric acid are shown below: 0 elemental analysis value theoretical value experimental value (as C1+sHryOgNs) C 58.22 57.88H%
4.61 4.56N%
11.32 11.47 Mass spectrometry value 371
(M”) Ultraviolet spectrum λmax 333nn1 Example 4 Phenol 141.29 (1,5 mot) and δ-valerolactone 150.2 f (1,5 mot) were dissolved in ethanol 5001E/, and aluminum chloride 213.4 t ( 1.6 mot) little by little,
Thereafter, 154.4f (0.80m
ot) obtained (yield 53cm) 0 followed by this 5-(4-hydroxyphenyl)valeric acid 154.4F (0.80mot
) and γ-butyrolactone 68.9F (0,80mot)
5-C3 was dissolved in 250-ml of ethanol, 120.0 f (0.9 mol) of aluminum chloride was added thereto little by little, and the mixture was stirred overnight at room temperature to obtain 5-C3.
78.5F (0.28 mot) of -(3-carboxypropyl)-4-hydroxyphenyl]valeric acid was obtained (yield: 35 mot).

0-nitroaniline 27.6 f (200 mmol
) with concentrated hydrochloric acid 60. Add Of (600mmot),
The obtained photo-0-nitroaniline hydrochloride aqueous solution was cooled on ice.

A nitrobenzenediazonium salt aqueous solution was prepared by adding a solution prepared by dissolving 13.8 f (200 mmot) of sodium nitrite in 150 d of water to the above 0-nitroanidihydrochloride aqueous solution and stirring for 1 hour.

Then 5-(3-(3-carboxypropyl)-4-hydroxyphenyl)valeric acid s6.tf (200 mmo
t) in 200 d of a 10% by weight aqueous sodium hydroxide solution, while maintaining the temperature of the resulting solution at 0 to 5°C,
The previously prepared aqueous nitrobenzene diazonium salt solution was gradually added to the solution, and the mixture was stirred for 2 hours. Concentrated hydrochloric acid was added to the resulting mixture to make the aqueous solution acidic (F4-11~2), and the precipitate was separated by filtration to obtain 51.5 of the corresponding nitroazo compound as a precipitate (yield: 60%). ).

Of the obtained nitroazo compounds, 42.9f (100
mmot) in 2N sodium hydroxide aqueous solution 100sE
/ and the resulting solution was dissolved in zinc powder 30, Of (
460 mmot) in a 25% by weight aqueous sodium hydroxide solution (50 JE/ml) to form a suspension.

The suspension was gradually added while keeping the temperature of the suspension below 40°C. After cooling the resulting mixture to a temperature below 30°C,
Acidified with concentrated hydrochloric acid (Table 1-2), then stirred for 2 hours. Next, the obtained reaction mixture was made alkaline (13-14 K) using sodium hydroxide, filtered through a glass filter, and the obtained filtrate was again made acidic (P) with concentrated hydrochloric acid.
H1-2), and the deposited precipitate was separated by filtration. This precipitate was washed with cold water, dried, and then recrystallized from a mixed solvent of water and methanol to form pale yellow crystals of 5-(5-(benzotriazol-2-yl)-3-(3-carboxypropyl)). -4-hydroxyphenyl]valeric acid 26.2
f (yield: 66 cm).

The obtained 5-[5-(benzotriazol-2-yl)
The physical properties of -3-(3-carboxypropyl)-4-hydroxyphenyl]valeric acid are shown below.0 Elemental analysis theoretical value Experimental value (as C21H2305N3) 0% 63.47 62.99H
5.83 5.88Nchi 1
0.57 10.28 Mass spectrometry value 379 (M
+) Ultraviolet spectrum λm, x336 nm Example 5 In Example 1, 4- was used instead of 0-nitroaniline.
Methyl-2-nitroaniline 30.4F (200mmo
4-(5-carboxy-2-hydroxy-3-(5-methylbenzotriazol-2-yl)phenyl)MJI was obtained by performing the same reaction and separation operations except for using 15.t). 8F was obtained (yield 21%).

The obtained 4-[5-carboxy-2-hydroxy-3-
The physical properties of (5-methylpenztriazol-2-yl)phenyl]butyric acid are shown below.

Elemental analysis value theory 1' [Experimental value (as C18H1705N3) 0% 60.84 60.37H
4.82 4.66Nchi 1
1.83 11.92 Mass spectrometry value 355 (
M'') Ultraviolet spectrum λ x 335 nm Example 6 1000 parts of dimethyl terephthalate, ethylene glycol 7209 (molar ratio of dimethyl terephthalate to ethylene glycol: lt 2.25) and 0.3 part of manganese acetate tetrahydrate were placed in a reactor at room temperature. After raising the temperature to 140°C, the temperature was gradually increased to 240°C over about 3 hours while stirring.
The theoretical amount of 99q6 or more methanol was distilled off while raising the temperature to °C. Next, 0.1 part of phosphorous acid, 0.5 part of germanium dioxide, and 4.9 parts of 4-(3-(benzotriazol-2-yl)-5-carboxyl 2-hydroxyphenyl)butyric acid obtained in Example 1 were added. 280℃
The polymerization reaction was carried out for about 2 hours under the conditions of a temperature of 0.5 or less and a pressure of 0.5 or less. The obtained polyester had an intrinsic viscosity of 0.82 d4/f, a melting point of 248.1°C, and a glass transition temperature of 80.2°C.

An extractability test was conducted on this polyester, and the ultraviolet absorption behavior of each sample before and after extraction was compared. As a result, the behavior of both samples was completely the same. Table 1 shows the ultraviolet absorption behavior of the sample after extraction.

Example 7 In Example 6, 14-(3-(penztriazole-
A polyester was obtained in the same manner except that the amount of 2-yl)-5-carboxy-2-hydroxyphenylbutyric acid used was changed from 4.9 parts to 0.5 parts. The resulting polyester had an intrinsic viscosity of 83 dz/l and a melting point of 25
The temperature was 0.1°C, and the glass transition temperature was 80.5°C.

An extractability test was conducted on this polyester, and the ultraviolet absorption behavior of each sample before and after extraction was compared. As a result, the behavior of both samples was completely the same. Table 1 shows the ultraviolet absorption behavior of the sample after extraction.

Example 8 Except for changing the amount of %4-[3-(benzotriazol-2-yl)-5-carboxy-2-hydroxyphenyl]butyushun from 4.9 parts to 73.5 parts in Example 6. Polyester was obtained in the same manner. The intrinsic viscosity of the obtained polyester was 0.74 dt/2, and the melting point was 2.
The temperature was 42.1°C, and the glass transition temperature was 78.9°C.

An extractability test was conducted on this polyester, and the ultraviolet absorption behavior of each sample before and after extraction was compared.5 The behavior of both samples was exactly the same. Table 1 shows the ultraviolet absorption behavior of the sample after extraction.

Example 9 A polyester was obtained in the same manner as in Example 6, except that 1000 parts of dimethyl isophthalate was used instead of 1000 parts of dimethyl terephthalate. The obtained polyester had an intrinsic viscosity 1j of 0.78647 g and a glass transition temperature of 64.5°C.

An extractability test was conducted on this polyester, and the ultraviolet absorption behavior of each sample before and after extraction was compared. As a result, the behavior of both samples was completely the same. The ultraviolet absorption behavior of the sample after extraction is shown in Table 1.0 Example 10 In Example 6 % 4-[3-(benzotriazol-2-yl)-5-carboxy-2-hydroxyphenyl]butyric acid 4.9 parts 4-[ obtained in Example 2 instead of
4.9 of 5-carboxy-3-(5-chlorobenzotriazol-2-yl)-2-humanmixyphenyl]butyric acid
A polyester was obtained in the same manner except that the same amount was used. The intrinsic viscosity of the obtained polyester is 0.78 dll? The melting point is 248.6°C and the glass transition temperature is 80°C.
．． The temperature was 3°C.

An extractability test was conducted on this polyester, and the ultraviolet absorption behavior of each sample before and after extraction was compared. As a result, the behavior of both samples was completely the same. The ultraviolet absorption behavior of the sample after extraction is shown in Table 1. Example 11 In Example 6, 4-[3-(benzotriazole-
In place of 4.9 parts of 2-yl)-5-carboxy-2-hydroxyphenyl]butyric acid, 4-[2
-4.9 of carboxy-4-hydroxy-5-(5-methoxybenzotriazol-2-yl)phenyl]butyric acid
A polyester was obtained in the same manner except that 0% was used. The intrinsic viscosity of the obtained polyester was 0.80d4/f, the melting point was 249.0°C, and the glass transition temperature Fi80
．． It died at 7℃.

An extractability test of this polyester was conducted and the ultraviolet absorption behavior of each sample before and after extraction was compared. As a result, the behavior of both samples was exactly the same.Table 1 shows the ultraviolet absorption behavior of the sample after zero extraction.

Example 12 In Example 6, 4-(3-(benzotriazole-
5-(5) obtained in Example 4 in place of 4.9 parts of 2-yl)-5-carboxy-2-hydroxyphenyl]butyric acid.
A polyester was obtained in the same manner as Fi except that 4.9 parts of -(benzotriazol-2-yl)-3-(3-carboxypropyl)-4-hydroxyphenyl]valeric acid was used. The intrinsic viscosity of the nine polyesters obtained is 0.83 dt
/f, the melting point was 249.5°C, and the glass transition temperature was 79.9°C.

An extractability test was conducted on this polyester, and the ultraviolet absorption behavior of each sample before and after extraction was compared. As a result, the behavior of both samples was completely the same. Table 1 shows the ultraviolet absorption behavior of the sample after extraction.

Example 13 In Example 6, 4-(3-(benzotriazole-
4-[5 obtained in Example 5 instead of 4.9 parts of 2-yl)-5-carboxy-2-hydroxyphenyl]butyric acid
A polyester was obtained in the same manner except that 4.9 parts of -carboxy-2-hydroxy-3-(5-methylbenzotriazol-2-yl]phenyl]butyric acid was used.The intrinsic viscosity of the obtained polyester was 0. 82 dz7r, the melting point is 248.5°C, and the glass transition temperature is 80.
The temperature was 6°C.

An extractability test was conducted on this polyester, and the ultraviolet absorption behavior of each sample before and after extraction was compared. As a result, the behavior of both samples was completely the same. Table 1 shows the ultraviolet absorption behavior of the sample after extraction.

Comparative Example 1 In Example 6, %4-[3(benzotriazole-2
-yl)-5-carboxy-2-hydroxyphenyl]
Polyester was obtained in the same manner except that butyric acid was not used.

The intrinsic viscosity of the obtained polyester is 0.75 dt/l
, the melting point is 252.9°C, and the glass transition temperature r
I'180.6°C. Table 1 shows the ultraviolet absorption behavior of this polyester.

Comparative Example 2 In Comparative Example 1, dimethyl terephthalate 1000@
A polyester was obtained in the same manner except that 1000 parts of dimethyl inphthalate was used instead of. The intrinsic viscosity of the nine polyesters obtained was 0.70 dt/f, and the glass transition temperature was 65.0°C. Table 1 shows the ultraviolet absorption behavior of this polyester.

Comparative Example 3 In Example 6, instead of 4.9 parts of 4-[:3-(benzotriazol-2-yl)-5-carboxy-2-hydroxyphenyl]butyric acid, 4 of the compound represented by the following structural formula was used. A polyester was obtained in the same manner except that .9 parts were used. The intrinsic viscosity of the obtained polyester is 0.78
dt/l, the melting point was 252.7°C, and the glass transition temperature was 80.3°C.

An extractability test was conducted on this polyester, and Table 1 shows the results of comparing the ultraviolet absorption behavior of each sample before and after extraction.

Comparative Example 4 In Example 6, 4-[3-(benzotriazole-
A polyester was obtained in the same manner except that 4.9 parts of a compound represented by the following structural formula was used instead of 4.9 s of 2-yl)-5-carboxy-2-hydroxyphenyl]acetic acid. Intrinsic viscosity of the obtained polyester #: t O, 7
5 dL/f, melting point was 250.3°C, and glass transition temperature was 80.3°C.

An extractability test was conducted on this polyester, and the ultraviolet absorption behavior of each sample before and after extraction was compared. As a result, the behavior of both samples was completely the same. Table 1 shows the ultraviolet absorption behavior of the sample after extraction.

Comparative Example 5 In Example 6, %4 [:3 (penztriazol-2-yl)-5-carboxy-2-human oxyphenyl]butyric i1! A polyester was obtained in the same manner except that 4.9 parts of the compound represented by the following structural formula was used instead of 4.9 parts. The resulting polyester had an intrinsic viscosity f of 0.74 dt/f, a melting point of 248.9°C, and a glass transition temperature of 79.5°C.

Table 1 An extractability test was conducted on this polyester, and the ultraviolet absorption behavior of each sample before and after extraction was compared.As a result, the behavior of both samples was exactly the same. The UV absorption behavior of the sample after extraction is shown in Table IK.

Comparative Example 6 In Example 8, 4-(3-(benzotriazole-
An attempt was made to produce a polyester in the same manner except that 73.5 parts of the same compound used in Comparative Example 4 was used instead of 3.5 parts of 2-yl)-5-carboxyl 2-hydroxyphenyl #197.

It was found that the molten product in the reactor immediately after the completion of the reaction had an extremely low viscosity, unlike the polyester obtained in Example 8, and therefore the degree of polymerization of the product was found to be extremely low.

Example 14 Too many parts of isophthalic acid, 429 parts of terephthal rR, 4-(3-(benzotriazole-2) obtained in Example 1
-yl)-5-carboxy-2-hydroxyphenyl]
10.6 parts of butyric acid, 1050 parts of hexamethylene diamine, 10.5 parts of benzoic acid, 614 parts of ion-exchanged water, and 1.8 parts of sodium hypophosphite were charged into an autoclave, and the atmosphere inside the autoclave was sufficiently replaced with nitrogen. did.

Heat the autoclave in a closed state and reduce the internal pressure to 9-1.
The reaction was carried out for 1 hour with stirring while controlling the internal temperature to 190°C to 200°C. Then, while stirring, the temperature was gradually raised from 200°C, and during the process, the internal pressure was increased to 18k.
The polymerization reaction was carried out by releasing the pressure so as to maintain the internal pressure from the time when it reached 1/aIi. Approximately 5 hours had passed since the start of the temperature increase, and when no more water was distilled out at 250°C, the pressure was released and the polyamide was taken out. The relative viscosity of the obtained polyamide was 2.26, and the glass transition temperature Fi
The temperature was 126.4°C.

An extractability test was conducted on this polyamide, and the ultraviolet absorption behavior of each sample was compared after 7 m of extraction. As a result, the behavior of both samples was completely the same. Table 2 shows the ultraviolet absorption behavior of the sample after extraction.

Example 15 In Example 14, the amount of 4-(3-(benzo)I)azol-2-yl)-5-carboxy-2-hydroxyphenyl]butyric acid used was changed from 10.6 parts to 1.1 part. A polyamide was obtained in the same manner except that the relative viscosity of the obtained polyamide was 2.10, and the glass transition temperature was 127.0°C.

An extractability test was conducted on this polyamide, and the ultraviolet absorption behavior of each sample before and after extraction was compared. As a result, the behavior of both samples was completely the same. Table 2 shows the ultraviolet absorption behavior of the sample after extraction.

Example 16 Same as Example 14 except that the amount of 4-(3-(benzotriazol-2-yl)-5-carboxy-2-hydroxyphenyl) used was changed from 10.6 parts to 106 parts. The polyamide obtained had a relative viscosity of 2.08 and a glass transition temperature of 12.
The temperature was 6.6°C.

An extractability test was conducted on this polyamide, and the ultraviolet a absorption behavior of each sample before and after extraction was compared. As a result, the behavior of both samples was completely the same. Table 2 shows the ultraviolet absorption behavior of the sample after extraction.

Example 17 1000 parts of adipic acid, 4-[3- obtained in Example 1
(benzotriazol-2-yl)-5-carboxy-
2-Hydroxyphenyl] 1°8.4 parts of butylene diamine, 955 parts of m-xylylene diamine, 7.0 parts of benzoic acid, 7.0 parts of ion-exchanged water, and 1.2 parts of sodium hypophosphite were charged into an autoclave. The atmosphere inside the autoclave was sufficiently replaced with nitrogen. Heat the autoclave in a closed state, and bring the internal pressure to 9~10]#/- and the internal temperature to 190℃.
The reaction was carried out for 1 hour while stirring and controlling the temperature to ~200°C. Next, the temperature was gradually raised from 200° C. while stirring, and during the process, when the internal pressure reached 18 kt/j, the pressure was released to maintain the internal pressure, thereby carrying out a polymerization reaction. Approximately 5 hours had passed since the start of the temperature increase, and when no water was distilled out at 270°C, the pressure was released and the polyamide was taken out. The relative viscosity of the obtained polyamide was 2.19, the glass transition temperature Vi was 86.1°C, and the melting point was 230°C.
．． The temperature was 2°C.

We conducted an extractability test on this polyamide and compared the ultraviolet absorption behavior of each sample before and after extraction, and found that the behavior of both samples was exactly the same9. Table 2 shows the ultraviolet absorption behavior of the sample after extraction.

Example 18 1000 parts of hexamethylene diamine, 125 parts of adipic acid
4 parts and 8.31S of 4-[3-(benzotriazol-2-yl)-5-carboxy-2-hydroxyphenyl]butyric acid obtained in Example 1 were each added to methanol for 25 minutes.
These methanol solutions were slowly mixed to give a weight percent concentration. The precipitate was filtered and recrystallized with a methanol-water mixed solvent to obtain 1,730 parts of nylon salt.The obtained nylon salt and its equivalent weight of water were charged into an autoclave, and the atmosphere in the autoclave was sufficiently filled with nitrogen. The internal temperature was raised to 200°C by heating a sealed autoclave with stirring.
The temperature was raised from 230°C over 4 hours. Meanwhile, the internal pressure rose from 10kF/- to 17.5kF/-. Next, the internal pressure was returned to normal pressure over 1 hour by gradually releasing the pressure, and during this time the internal temperature was raised to 270°C. The autoclave was cooled and the polyamide was taken out. The obtained polyamide had a relative viscosity of 2.43, a glass transition temperature d of 54.3°C, and a melting point of 260.
The extractability test of this polyamide was conducted and the ultraviolet absorption behavior of each sample before and after extraction was compared. As a result, the behavior of both samples was completely the same. The ultraviolet absorption behavior of the sample after extraction is shown in Table 2. Example 19 In Example 14, 10.6 parts of 4-(3-(benzotriazol-2-yl)-5-carboxy-2-hydroxyphenyl)butyric acid 4- obtained in Example 2 instead of
[5-carboxy-3-(5-chlorobenzotriazol-2-yl)-2-hydroxyphenyl]butyric acid 10,
A polyamide was obtained in the same manner except that 6 parts were used. The resulting polyamide had a relative viscosity of 2.18 and a glass transition temperature of 126.8°C.

An extractability test was conducted on this polyamide, and the ultraviolet absorption behavior of each sample before and after extraction was compared. As a result, the behavior of both samples was completely the same. Table 2 shows the ultraviolet absorption behavior of the sample after extraction.

Example 20 In Example 14, 10.6 parts of %4C3(benzotriazol-2-yl)-5-carboxy-2-hydroxyphenyl]butyric acid was replaced with 4-obtained in Example 3.
[2-carboxy-4-hydroxy-5-(5-methoxybenzotriazol-2-yl]phenyl]butyric acid 1O
A polyamide was obtained in the same manner except that 36 parts were used. The relative viscosity of the obtained polyamide was 2.34, and the glass transition temperature was 126.0°C.

As a result of conducting an extractability test on this polyamide and comparing the ultraviolet absorption behavior of each sample before and after extraction, the behavior of both F
The UV absorption behavior of the sample after zero extraction, which was exactly the same, is shown in Table 2.

Example 21 In Example 14, instead of 10.6 parts of 4-[3-(benzotriazol-2-yl)-5-carboxy-2-hydroxyphenyl]butyric acid! 5- obtained in Example 4
[5-(benzotriazol-2-yl)-3-(3-
A polyamide was obtained in the same manner except that 10.6 parts of carboxypropyl-4-hydroxyphenylvaleric acid was used. The relative viscosity of the obtained polyamide is U2.10,
The glass transition temperature Fi was 126.4° C. 0 This polyamide was subjected to an extractability test and the ultraviolet absorption behavior of each sample before and after extraction was compared. As a result, the behavior of both samples was completely the same. The ultraviolet absorption behavior of the sample after extraction is shown in Table 2. Example 22 In Example 14, instead of 106 parts of 4-(3-(benzotriazol-2-yl)-5-carboxy-2-hydroxyphenyl]butyric acid) 4-[ obtained in Example 5
5-carboxy-2-hydroxy-3-(5-methylbenzotriazol-2-yl)phenyl]butyric acid 10.6
A polyamide was obtained in the same manner except that the same amount was used. The resulting polyamide had a relative viscosity of 2.15 and a glass transition temperature of 126.6°C.

As a result of conducting an extractability test on this polyamide and comparing the ultraviolet absorption behavior of each sample before and after extraction, the behavior of both F
iIt was exactly the same. Table 2 shows the ultraviolet absorption behavior of the sample after extraction.

Comparative Example 7 A polyamide was obtained in the same manner as in Example 14, except that 4-(3-(benzotriazol-2-yl)-5-carboxy-2-hydroxyphenyl]butyric acid was not used. The relative viscosity was #'12.35, and the glass transition temperature was 126.7° C. The ultraviolet absorption behavior of this polyamide is shown in Table 2.

Comparative Example 8 A polyamide was obtained in the same manner as in Example 17, except that 4-(3-(bensito-1-noazol-2-yl)-5-carboxy-2-hydroxyphenyl]butyric acid was not used. The obtained polyamide The relative viscosity (d) is 2.22 °, the glass transition temperature is 86.3 °C, and the melting point is 233
．． The temperature was 2°C. Table 2 shows the ultraviolet absorption behavior of this polyamide.

Comparative Example 9 A polyamide was obtained in the same manner as in Example 18, except that 4-(3-(benzotriazol-2-yl)-5-carboxy-2-hydroxyphenyl]butyric acid was not used. Relative viscosity Fi2.42,
The glass transition temperature is 5466°C and the melting point is zM2.2
It was ℃. Table 2 shows the ultraviolet absorption behavior of this polyamide.
Shown below.

Comparative Example 10 In Example 14, 1000 parts of a compound represented by the following structural formula was used instead of 10.6 parts of 4-(3-(bensitoIJazol-2-yl)-5-carboxy-2-hydroxyphenyl]butyric acid. A polyamide was obtained in the same manner except that the relative viscosity of the obtained polyamide was U2.10.
The glass transition temperature was 126.4°C.

An extractability test was conducted on this polyamide, and Table 2 shows the results of comparing the ultraviolet absorption behavior of each sample before and after extraction.

The following margin <Effects of the Invention> The benzotriazole compound represented by the general formula (1) provided in the present invention has good ultraviolet absorption performance,
Useful as a UV absorber. In addition, the polymer containing the benzo)I/azole compound shown in -Funezo (1) effectively exhibits the excellent ultraviolet absorption performance derived from the benzotriazole compound, and has an excellent continuous ultraviolet light absorption property. Has performance.

Patent applicant RiRashi Co., Ltd.

Claims (1)

[Claims] 1. General formula ▲ Numerical formula, chemical formula, table, etc. ▼ In the formula, R represents a hydrogen atom, a halogen atom, a lower alkyl group or a lower alkoxyl group, and one of n and m is 0 to 16 represents an integer from 2 to 16, and the other represents an integer from 2 to 16. A benzotriazole compound represented by 2. An ultraviolet absorber containing the benzotriazole compound according to claim 1 as an active ingredient. 3. The benzotriazole compound according to claim 1 is added to 0.
Polymer containing 001 to 10% by weight. 4. A polymer containing 0.001 to 10% by weight of the benzotriazole compound according to claim 1 as a copolymerization component.