JP4369978B2 - Benzylformamidine compound and plastic product containing it as an ultraviolet absorber - Google Patents

Description

Detailed Description of the Invention

〔Technical field〕
The present invention relates to a benzylformamidine compound useful as an ultraviolet absorber, and more specifically, because it is extremely excellent in ultraviolet absorption and thermal safety, it requires high-temperature heat treatment and excellent thermal safety. The present invention relates to a benzylformamidine compound that can be usefully used as an ultraviolet absorber in various plastic products and a plastic product containing the same as an ultraviolet absorber.

[Background Technology]
In general, when various synthetic resin products, natural resin products and polymerizable polymer products (hereinafter referred to as 'plastic products') are exposed to ultraviolet rays, their physical properties deteriorate due to photodegradation and their durability is greatly reduced. This is well known. In particular, the photodegradation that occurs in plastic products causes problems such as product fading and discoloration, and the problem of making products easily broken by external impact. In order to eliminate this type of problem, an ultraviolet absorber is added during the manufacture of various plastic products.

  Many compounds are known in connection with UV absorbers. In particular, in US Pat. No. 4,021,471, which is a known technique related to the present invention, formamidine represented by the following general formula 1 An ultraviolet absorber is disclosed.

Here, R ¹ is selected from alkyl radicals having 1 to 5 carbon atoms, B is selected from H, OH, Cl and methoxy, and R ² is selected from alkyl radicals having 1 to 9 carbon atoms and phenyl radicals. A is selected from hydrogen, carboethoxy, carbobutoxy, methoxy, ethyl, dimethylamino and chlorine, and D is selected from H, OCH ₃ and Cl.

  Since the ultraviolet absorber having the structure of the general formula 1 has high light stability, it can be usefully used in the production of various synthetic resin products and polymerizable polymer products. However, most of the ultraviolet absorbers including the ultraviolet absorber having the structure of the general formula 1 have not obtained an effect that is sufficiently satisfactory in terms of thermal safety. It is a fact that the use to the required plastic products is greatly restricted.

  Therefore, in view of the fact that the processing temperature of most plastic products is high, there is an urgent need for an ultraviolet absorber that is not only ultraviolet absorbent but also very excellent in thermal safety. As a result of intensive studies on substances that are excellent not only in absorptivity but also in thermal safety and can be usefully used as ultraviolet absorbers, the present invention has been completed.

[Problems to be Solved by the Invention]
Accordingly, an object of the present invention is to provide a benzylformamidine compound that is extremely excellent in ultraviolet absorption and thermal safety and can be usefully used as an ultraviolet absorber in plastic products that require high-temperature heat treatment and thermal safety. There is.

  Another object of the present invention is to provide a plastic product containing the benzylformamidine compound as an ultraviolet absorber.

[Means for solving the problems]
In order to achieve the above object, the present invention provides a benzylformamidine compound represented by the following general formula 8 .

When the benzylformamidine compound represented by the above general formula 8 is used as an ultraviolet absorber, it has superior thermal safety and ultraviolet absorptivity compared to the conventional formamidine compound of the general formula 1 used as the ultraviolet absorber. can get. Therefore, the benzylformamidine compound having the structure of the general formula 8 can be usefully used as an ultraviolet absorber in the production of plastic products that require high-temperature heat treatment and thermal safety.

Further, the present invention was produced by adding the benzylformamidine compound represented by the above general formula 8 as an ultraviolet absorber in the process of molding a plastic raw material selected from a synthetic resin, a natural resin and a polymerizable polymer. A plastic product characterized by the above is provided.

The benzylformamidine compound represented by the above general formula 8 is very excellent in thermal safety and ultraviolet absorption, and this compound is used as an ultraviolet absorber in the manufacture of plastic products that require high-temperature heat treatment. In this case, the manufactured plastic product exhibits excellent ultraviolet absorption, and as a result, durability is improved.

  Hereinafter, the benzylformamidine compound according to the present invention will be described in more detail.

In the present invention, a benzylformamidine compound represented by the following general formula 8 is provided as a compound that can be usefully used as an ultraviolet absorber .

  The benzylformamidine compound according to the present invention having the above-described structure is superior not only in ultraviolet absorption but also in thermal safety as compared with existing formamidine compounds, and requires high-temperature heat treatment and thermal safety. It can be usefully used as an ultraviolet absorber when producing a synthetic resin product or a polymerized product.

The benzylformamidine compound of the general formula 8 according to the present invention can be easily produced through the reaction steps of the following reaction formulas 1 to 3.

In the above reaction formulas 1 to 3, R ¹ and R ² are ethoxycarbonyl groups, and L ¹ , L ² and L ³ are hydrogen .

  The above-mentioned benzylformamidine compound according to the present invention is superior in thermal safety and ultraviolet absorption to conventional formamidine compounds that have been generally used. It can be usefully used as an ultraviolet absorber when producing a required plastic product.

  The benzylformamidine compound according to the present invention can be added as an ultraviolet absorber in the process of producing a plastic product using a plastic raw material selected from a synthetic resin, a natural resin and a polymerizable polymer. Since it is very excellent in compatibility with polyol which is a raw material of polyurethane, it can be usefully used as an ultraviolet absorber for polyurethane which requires high-temperature heat treatment. Furthermore, the benzylformamidine compound can be used as an ultraviolet absorber in products such as cosmetics in addition to plastic products, if necessary.

  When the benzylformamidine compound is added as an ultraviolet absorber during the production of a plastic product, the addition amount may be within the normal addition range, and preferably 0.1% with respect to 100 parts by weight of the solid content of the plastic raw material. What is necessary is just to be -5.0 weight part.

[Best Mode for Carrying Out the Invention]
Hereinafter, the present invention will be described in more detail with reference to the following examples. The following examples are given to aid the understanding of the present invention and are not intended to limit the present invention.

<Example 1>
(Production of N, N′-bis (4-ethoxycarbonylphenyl) -N′-benzylformamidine)
Add 329.58 g of benzocaine to 800 ml of toluene, dissolve it with stirring at 43 ± 3 ° C., add 118.78 g of 85% formic acid dropwise thereto, and react at 100 ± 5 ° C. for 2 hours to give a solid product. Obtained.

  This solid product was dissolved in 500 ml of toluene while stirring, and then an aqueous solution prepared by stirring 8.12 g of t-butylammonium bromide and 150.04 g of NaOH in 200 ml of water was added dropwise. After the addition, 170.04 g of benzyl bromide was added and reacted with stirring for 1.5 hours. The organic layer was separated from the reaction mixture, dried and evaporated under reduced pressure to obtain a solid product.

The obtained solid product and benzocaine were added to 500 ml of toluene and dissolved while stirring at 30 ° C., and then 340.44 g of POCl ₃ was added dropwise and stirred at 70 ± 3 ° C. for 5 hours. The reaction is effected and added dropwise to 500 ml of 20% aqueous NaOH cooled to 20 ° C. The organic layer was separated from the reaction mixture, washed with 300 ml of saturated brine, subsequently dried over Na ₂ SO ₄ , filtered and evaporated under reduced pressure to obtain a crude product (Crude product).

  The obtained crude product was recrystallized with a 1: 1 solution of EA: Hex to obtain 325.5 g (yield 37.8%) of a solid product.

The result of ¹ H NMR (CDCl ₃ , 200 MHz) of the produced solid product is shown in FIG. Specific values thereof are as follows, and this solid purified product was identified as N, N′-bis (4-ethoxycarbonylphenyl) -N′-benzylformamidine of the general formula 8.

¹ H NMR (CDCl ₃ , 200 MHz): 1.36 to 1.43 (m, 6H), 4.29 to 4.40 (m, 4H), 7.06 (d, 2H, J = 6.8 Hz) 7.19 (d, 2H, J = 8.7 Hz), 7.31 to 7.34 (m, 5H), 7.98 (d, 2H, J = 2.2 Hz), 8.00 (d, 2H, J = 2.0 Hz), 8.37 (s, 1H)
< Reference Example 1 >
(Production of N-3,5-di-tert-butyl-4-hydroxybenzyl-N′-4-ethoxycarbonylphenyl-N-phenylformamidine)
2,2'-azobis with stirring while putting 40.00 g of 2,6-di-tert-butyl-4-methylphenol and 36.1 g of N-bromosuccinimide in 400 ml of chloroform. 2.90 g of isobutyronitrile are added and this is refluxed for 19 hours. The reaction mixture is cooled and then filtered, and the resulting filtrate is washed with 400 ml of water. The organic layer separated from the reaction mixture was dried using Na ₂ SO ₄ and evaporated under reduced pressure to obtain 51.50 g (yield: 94%) of the solid product (a).

  Add 14.6 ml of aniline to 80 ml of toluene, add 9.70 ml of formic acid dropwise, remove water while reacting at 100 ± 5 ° C for 2 hours, and after removing moisture, cool at room temperature and filter and wash with water. Thus, a solid product (b) was obtained.

This solid product (b) was dissolved in 80 ml of toluene while stirring, and 4.90 g of t-butylaminobromide and 5.60 g of NaOH were stirred in 100 ml of water. After the aqueous solution was added dropwise, 20.0 g of the solid product (a) was added and reacted with stirring for 2.0 hours. The organic layer was separated from the reaction mixture and dried using Na ₂ SO _4. After evaporation under reduced pressure, 12.1 g (yield: 53%) of a solid product (c) was obtained.

The obtained solid product (c) and 9.3 g of benzocaine were added to 200 ml of toluene and dissolved while stirring at 40 ° C. Then, 7.20 ml of POCl ₃ was added dropwise and 70 ± 3 ° C. for 6 hours. The solution is allowed to react with stirring, and the solution is added dropwise to 270 ml of a 10% aqueous NaOH solution cooled to 20 ° C. Thereafter, the organic layer separated from the reaction mixture was washed with 80 ml of saturated brine, subsequently dried over Na ₂ SO ₄ , and evaporated under reduced pressure after filtration to obtain a crude product (Crude product).

  The obtained crude product (Crude product) was recrystallized with a 1: 7 solution of EA: Hex to obtain 10.8 g (yield: 43%) of a solid product.

The results of ¹ H NMR (CDCl ₃ , 200 MHz) of the produced solid product are shown in FIG. Specific values thereof are as follows, and this solid purified product was obtained by using N-3,5-di-tert-butyl-4-hydroxybenzyl-N′-4-ethoxycarbonylphenyl-N-phenylformamidine. It was confirmed.

¹ H NMR (CDCl ₃ , 200 MHz): 1.35 to 1.42 (m, 21H), 4.35 (q, 2H, J = 7.0 Hz), 5.12 (s, 1H), 5.15 (S, 2H), 7.05 (d, 2H, J = 8.3 Hz), 7.12 (s, 2H), 7.15 to 7.34 (m, 5H), 7.99 (d, 2H) , J = 8.7 Hz), 8.15 (s, 1H)
< Reference Example 2 >
(Production of N, N′-bis (4-ethoxycarbonylphenyl) -N-3,5-di-tert-butyl-4-hydroxybenzylformamidine)
To 50 ml of toluene, 10.0 g of benzocaine was added and dissolved while stirring at 43 ± 3 ° C., and 7.2 ml of formic acid was added dropwise, and water was removed while reacting at 100 ± 5 ° C. for 2 hours. Upon completion of moisture removal, the product was cooled to room temperature, filtered and washed with water to obtain 10.2 g (yield: 88%) of the solid product (a).

The solid product (a) was dissolved in 20 ml of toluene while stirring, and an aqueous solution prepared by stirring 1.1 g of t-butylammonium bromide and 1.26 g of NaOH in 100 ml of water. Then, 4.5 g of 3,5-di-tert-butyl-hydroxybenzyl bromide was added and reacted with stirring for 2.0 hours, and the organic layer separated from the reaction mixture was dissolved in Na ₂ SO. ₄ dried with addition evaporated under reduced pressure, the solid product (b) 3.35 g (yield: 55%) was obtained.

The obtained solid product (b) and 1.4 g of benzocaine were added to 100 ml of toluene and dissolved while stirring at 40 ° C., and then 1.1 ml of POCl ₃ was added dropwise for 6 hours at 70 ± 3. The mixture was reacted with stirring at 0 ° C., and this solution was added dropwise to 75 ml of 10% aqueous NaOH cooled to 20 ° C., and then the organic layer separated from the reaction mixture was washed with 50 ml of saturated brine, followed by This was dried over Na ₂ SO ₄ , filtered and evaporated under reduced pressure to obtain a crude product (Crude product).

  The obtained crude product was recrystallized with a 1: 6 solution of EA: Hex to obtain 2.0 g (yield: 45%) of a solid product.

The result of ¹ H NMR (CDCl ₃ , 200 MHz) of the produced solid product is shown in FIG. Specific values thereof are as follows, and this solid purified product was obtained by using N, N′-bis (4-ethoxycarbonylphenyl) -N-3,5-di-tert-butyl-4-hydroxybenzylform. Confirmed as amidine.

¹ H NMR (CDCl ₃ , 200 MHz): 1.33-1.44 (m, 24H), 4.36 (q, 4H, J = 6.8 Hz), 5.14 (s, 1H), 5.23 (S, 2H), 7.05 (d, 2H, J = 12.9 Hz), 7.12 (s, 2H), 7.22 (d, 2H, J = 11.2 Hz), 7.98 (d , 4H, J = 9.9 Hz), 8.30 (s, 1H)
< Reference Example 3 >
(Production of N-4-butoxycarbonylphenyl-N′-4-ethoxycarbonylphenyl-N-3,5-di-tert-butyl-4-hydroxybenzylformamidine)
17.4 g of benzocaine was added to 20 ml of toluene and dissolved while stirring at 43 ± 3 ° C., and 5.4 ml of formic acid was added dropwise thereto, and then water was removed while reacting at 100 ± 5 ° C. for 2 hours. When the water removal was completed, the mixture was cooled to room temperature, filtered and washed with water to obtain 19.6 g of solid product (a) (yield: 98%).

12.6 g of this solid product (a) was dissolved in 150 ml of toluene while stirring, and 4.2 g of t-butylammonium bromide and 4.8 g of NaOH were added to 80 ml of water and stirred. After the dropwise addition of the aqueous solution, 17.0 g of 3,5-di-tert-4-hydroxybenzyl bromide was added and reacted while stirring for 2 hours. The organic layer separated from the reaction mixture was dissolved in Na ₂ SO ₄ dried with addition evaporated under reduced pressure, the solid product (b) 13.2 g (yield: 53%) was obtained.

The obtained solid product (b) and 5.5 g of benzocaine were added to 100 ml of toluene and dissolved while stirring at 40 ° C. Then, 4.2 g of POCl ₃ was added dropwise for 6 hours at 70 ± 3. The mixture was allowed to react with stirring at 0 ° C., and this solution was added dropwise to 250 ml of 10% aqueous NaOH cooled to 20 ° C., and then the organic layer separated from the reaction mixture was washed with 50 ml of saturated brine, followed by This was dried over Na ₂ SO ₄ , filtered and evaporated under reduced pressure to obtain a crude product (Crude product).

  The obtained crude product (Crude product) was recrystallized with a solution of EA: Hex 1: 5 to obtain 9.5 g (yield 53%) of a solid product.

The result of ¹ H NMR (CDCl ₃ , 200 MHz) of the produced solid product is shown in FIG. The specific values are as follows, the solid product, N-4-butoxycarbonylphenyl-N'-4-ethoxycarbonyl-phenyl -N-3,5-di -tert- butyl-4-hydroxy Identified as benzylformamidine.

¹ H NMR (CDCl ₃ , 200 MHz): 0.97 (t, 3H, J = 7.2 Hz), 1.36 to 1.53 (m, 23H), 1.64 to 1.82 (m, 2H) 4.28 to 4.42 (m, 4H), 5.14 (s, 1H), 5.23 (s, 2H), 7.06 (d, 2H, J = 8.5 Hz), 7.12 (S, 2H), 7.23 (d, 2H, J = 8.8 Hz), 8.01 (d, 4H, J = 9.1 Hz), 8.30 (s, 1H)
<Experimental example 1>
N, N′-bis (4-ethoxycarbonylphenyl) -N′-benzylformamidine of the general formula 8 produced in Example 1 and N- (having the structure of the following general formula 11 used as a conventional UV absorber: UV absorbance and thermal safety were measured for 4-ethoxycarbonylphenyl) -N′-methyl-N′-phenylformamidine, respectively.

Here, the absorbance was measured by dissolving 1 mg of each sample in 100 ml of chloroform solution and measuring the UV absorbance using a UV spectrum meter (Bechman Du-600), and the results are shown in FIG . The thermal safety was measured by heating the sample at 15 ° C. per minute under a nitrogen atmosphere with TGA (Thermal Gravimetric Analysis; Rerkin-Elmer TGA7), and the measurement results are shown in Table 1 and FIG .

From FIG. 6 , N, N′-bis (4-ethoxycarbonylphenyl) -N′-benzylformamidine of the present invention and conventional N- (4-ethoxycarbonylphenyl) -N′-methyl-N′-phenylform It can be seen that amidine is similar in ultraviolet absorption performance.

However, from Table 1 showing the results of the thermal stability test and FIG. 5 , N, N′-bis (4-ethoxycarbonylphenyl) -N′-benzylformamidine of the present invention is the conventional N- (4-ethoxycarbonyl). Compared with (phenyl) -N′-methyl-N′-phenylformamidine, it was confirmed that the thermal safety was remarkably excellent.

<Experimental example 2>
In the process of producing the polyurethaneurea elastic fiber, N, N′-bis (4-ethoxycarbonylphenyl) -N′-benzylformamidine of the general formula 8 produced in Example 1 and N having the structure of the general formula 11 Each of-(4-ethoxycarbonylphenyl) -N'-methyl-N'-phenylformamidine was added as an ultraviolet absorber.

  That is, 1.7 mol of 4,4-diphenylmethane diisocyanate was mixed with 1 mol of polytetramethylene glycol having a molecular weight of 1800 and then reacted at 90 ° C. for 90 minutes to synthesize a prepolymer having isocyanate at both ends. After this prepolymer was cooled to 40 ° C., N, N′-dimethylacetamide was added to produce a solution containing about 45% prepolymer. While this prepolymer solution was cooled to 5 ° C. and stirred vigorously, an N, N′-dimethylacetamide solution containing 96 equivalent% of ethylenediaman and 6 equivalent% of diethylamine was gradually added to the prepolymer. After the chain was extended and terminated to produce the final polyurethaneurea solution, the N, of formula 8 prepared in Example 1 as an ultraviolet absorber per 100 parts by weight of solids was added to the solution. N'-bis (4-ethoxycarbonylphenyl) -N'-benzylformamidine and N- (4-ethoxycarbonylphenyl) -N'-methyl-N'-phenylformamidine having the structure of general formula 11 The polyurethaneurea elastic fiber was produced by adding after radiating at a ratio shown in Table 2 below.

  The 40 denier polyurethaneurea elastic fibers thus produced were exposed to UV light for 40 hours using a fade-o-meter with a Zenon arc. At this time, the color change (Δb value) before and after processing by the color master (color master, Scinco, Korea) was measured, and the results are shown in Table 2.

  From Table 2 above, the benzylformamidine ultraviolet absorber according to the present invention shows superior performance even in the final product due to excellent heat resistance when compared with the conventional phenylformamidine ultraviolet absorber in the same amount. It was confirmed that it could be demonstrated.

[Industrial applicability]
Since the present invention is excellent in ultraviolet absorption and thermal safety, it can be usefully used as an ultraviolet absorber for plastic products that require high-temperature heat treatment and heat safety, and particularly requires high-temperature heat treatment. When used as an ultraviolet absorber during the manufacture of plastic products, the manufactured plastic product exhibits excellent ultraviolet absorption and has a useful effect of improving durability.

It is a diagram showing a _{^{1 H NMR (CDCl 3, 200MHz}} ) results of examples prepared compounds of the present invention. It is a diagram showing a _{^{1 H NMR (CDCl 3, 200MHz}} ) results of the compound prepared by Reference Example. It is a diagram showing a _{^{1 H NMR (CDCl 3, 200MHz}} ) results of the compound prepared by Reference Example. It is a diagram showing a _{^{1 H NMR (CDCl 3, 200MHz}} ) results of the compound prepared by Reference Example. It is the graph which compared the heat safety in the benzylformamidine compound by this invention, and the conventional formamidine compound. It is the graph which compared the ultraviolet-ray light absorbency in the benzylformamidine compound by this invention, and the conventional formamidine compound.

Claims (3)

The following general formula 8

A benzylformamidine compound represented by the formula: The following general formula 8

The ultraviolet absorber characterized by these. In the process of molding a plastic raw material selected from synthetic resins, natural resins and polymerizable polymers, the following general formula 8

It is manufactured by adding a benzylformamidine compound represented by
  A plastic product, wherein 0.1 to 5.0 parts by weight of the benzylformamidine compound is added to 100 parts by weight of a solid content of a plastic raw material.

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