KR20090006558A - Ultraviolet light absorber comprising acrylic benzotriazol copolymer and ultraviolet light absorber composition comprising the same - Google Patents

Abstract

A UV absorber is provided to be suitable for an automotive interior material, fiber product, plastic and coating agent due to low elution from a polymer, use at high concentration and stability at high temperature. A UV absorber comprises a benzotriazole-based acrylic copolymer manufactured by copolymerizing (A) a benzotriazole-based compound 10-30 mole % and (B) an acrylic compound 70-90 mole %. The benzotriazole-based compound has a structure expressed as the chemical formula 1. In the chemical formula 1, R1 is H or C1-C10 alkyl group and R2 is a methacryloyl group. The acrylic compound has a structure expressed as the chemical formula 2. In the chemical formula 2, R3 is H or CH3. R4 is C1~C10 alkyl group.

Description

Ultraviolet Light Absorber Comprising Acrylic Benzotriazol Copolymer And Ultraviolet Light Absorber Composition Comprising The Same}

The present invention relates to a UV absorber and a UV absorber composition, and more particularly, UV absorbers added to prevent decomposition of the synthetic resin by ultraviolet rays, such as interior and exterior materials or building materials of automobiles manufactured using synthetic resins and UV for the preparation thereof. It relates to an absorbent composition.

Films, fibers, building materials, furniture, films, interior and exterior materials of automobiles manufactured using synthetic resins are easily decomposed by light, especially ultraviolet rays. In order to prevent this, much research has been made on the method of stabilizing by introducing an ultraviolet stabilizer that absorbs or blocks ultraviolet rays to the synthetic resin. 2- (2-hydroxy aryl) benzotriazole is generally considered to be the most effective among ultraviolet absorbent compositions which can effectively prevent decomposition of the synthetic resin by ultraviolet rays.

As a conventional ultraviolet absorber, a benzotriazole-based compound having a small molecular weight is used. If the molecular weight of the benzotriazole-based compound is low, benzotriazole introduced into the synthetic resin is easily volatilized, which may cause process defects or contaminate the working environment. In addition, there is a problem that the product is easily deteriorated by the blooming (blooming) in which a compound having an ultraviolet absorbing function such as a benzotriazole-based compound is moved to the surface of the product, there is a problem that the life is shortened.

In order to improve this problem, various methods have been proposed to increase the molecular weight of the benzotriazole-based compound so that the benzotriazole-based compound can function stably in the synthetic resin without volatilization.

U.S. Patent No. 5,547,753 discloses a process for oligomerizing benzotriazole precursors to produce low volatility, high molecular weight materials. This method was effective in reducing the volatility of benzotriazole-based compounds used as UV absorbers, but was incompatible with synthetic resins.

US Pat. Nos. 5,237,071, 5,229,521, 4,937,348, 4,859,726 disclose methods of increasing the molecular weight of benzotriazole by combining two benzotriazole compounds into alkylene bridging groups. Bridging benzotriazole-based compounds have slightly reduced volatility but still do not solve the problem of incompatibility with synthetic resins.

U.S. Patent No. 4,319,016 discloses a process for preparing ultraviolet absorbent compositions by reacting sulfur-containing benzotriazole, formaldehyde and melamine. The presence of more than 0.5 moles of benzotriazole per mole of melamine is said to have a tendency to improve the compatibility of the ultraviolet absorber and the synthetic resin into which they are introduced. However, this method has a disadvantage in that the light absorption region of benzotriazole is shifted toward visible light, causing yellowing.

Technical problem of the present invention is to solve the problem that the ultraviolet absorber is easily volatilized, eluted and the problem of volatilizing at high temperature to contaminate the machine and the working environment. An object of the present invention is to provide a UV absorber and a UV absorber composition that can achieve such a technical problem.

In order to achieve the above object, the present invention provides a UV absorber comprising a benzotriazole-based acrylic copolymer and a UV absorber composition for producing the same.

The UV absorber of the present invention is characterized by comprising a benzotriazole-based acrylic copolymer prepared by copolymerizing the (A) benzotriazole compound and the (B) acrylic compound.

It is preferable to use the (A) benzotriazole type compound represented by following General formula (1).

[Formula 1]

In Formula 1, R ₁ is H or a C ₁ -C ₁₀ alkyl group and R ₂ includes acryloyl group or methacryloyl group.

It is preferable to use what is represented by following formula (2) for the said acryl-type compound.

[Formula 2]

In Formula 2, R ₃ is H or CH ₃ , and R ₄ is an alkyl group of C ₁ to C ₁₀ .

The UV absorber including the benzotriazole-based acrylic copolymer is 10 to 30 mol% of the (A) benzotriazole compound and (B) the acrylic compound relative to 100 mol% of the total of the (A) benzotriazole compound and the (B) acrylic compound. It is preferable to copolymerize 70 to 90 mol%.

Said UV absorber composition contains (A) benzotriazole type compound, (B) acryl type compound, and (C) solvent.

The (A) benzotriazole-based compound may be represented by the following formula (1).

[Formula 1]

In Formula 1, R ₁ is H or a C ₁ -C ₁₀ alkyl group and R ₂ includes acryloyl group or methacryloyl group.

It is preferable to use the thing represented by following General formula (2) as said (B) acryl-type compound.

[Formula 2]

In Formula 2, R ₃ is H or CH ₃ , and R ₄ is an alkyl group of C ₁ to C ₁₀ .

In the UV absorber composition of the present invention, the component ratio of the (A) benzotriazole compound and the (B) acryl compound is 100% by mole of the total of the (A) benzotriazole compound and the (B) acrylic compound (A) benzotria It is preferable that it is 70-90 mol% of (B) acrylic-type compound with respect to 10-30 mol% of a sol type compound.

The UV absorber composition may further include an initiator in the range of 1 to 15 mol% relative to 100 mol% of the (A) benzotriazole-based compound.

The UV absorber composition may further include a surfactant in the range of 2 to 20 mol% relative to 100 mol% of the (A) benzotriazole-based compound.

Hereinafter, the present invention will be described in more detail.

The UV absorber of the present invention is characterized by comprising a benzotriazole-based acrylic copolymer obtained by copolymerizing the (A) benzotriazole compound and the (B) acrylic compound.

Chemicals commonly used as ultraviolet absorbers include benzotriazole compounds, salicylate compounds, benzophenone compounds, hindered amine light stabilizers (HALS), and hindered amine compounds. amine), cyanoacrylate compounds, metal complex salt compounds, oxanilide compounds, and the like. Ultraviolet absorbers act to prevent the polymer from absorbing by absorbing ultraviolet rays and converting them into thermal energy, or oneself does not absorb ultraviolet rays, and the polymer and energy transfer are excited by light absorbed by the polymer. Serves to release. The benzotriazole-based compound, which is a typical ultraviolet absorber that absorbs ultraviolet rays and converts them into heat energy, is known to have excellent compatibility with other plastics, colorless transparency, and heat sublimation resistance.

However, when the molecular weight of the benzotriazole-based compound included in the ultraviolet absorbent is low, the ultraviolet absorbent component is easily eluted or volatilized to the outside of the synthetic resin, causing the ultraviolet absorbing ability to deteriorate or harmful chemicals volatilized to pollute the working environment. do.

The UV absorber of the present invention copolymerizes the (A) benzotriazole compound and the (B) acrylic compound to provide a UV absorber comprising a benzotriazole-based acrylic copolymer having a high molecular weight to effectively solve the above problems.

In the UV absorber containing the benzotriazole-based acrylic copolymer, (A) benzotriazole-based compound is preferably used represented by the following formula (1).

[Formula 1]

In Formula 1, R ₁ is H or a C ₁ -C ₁₀ alkyl group and R ₂ includes acryloyl group or methacryloyl group.

The acryloyl or methacryloyl group of the formula (1) includes a vinyl group, which acts to form a copolymer by radical polymerization reaction with the vinyl group included in the acrylic monomer.

In addition, it is preferable to use the thing represented by following formula (2) for the (B) acryl-type compound.

[Formula 2]

In Formula 2, R ₃ is H or CH ₃ , and R ₄ is an alkyl group of C ₁ to C ₁₀ .

Formula 2 includes an acrylate group. R ₃ in Formula 2 is H or CH ₃ . R ₄ is a C ₁ -C ₁₀ alkyl group, preferably 2-ethylhexyl acrylate, butyl acrylate, methyl methacrylate, butyl methacrylate.

The acryl-based compound of Formula 2 includes a vinyl group, and acts to finally form a copolymer by radical polymerization with the benzotriazole-based compound of Formula 1.

In the UV absorber comprising the benzotriazole-based acrylic copolymer of the present invention, the component ratio of the (A) benzotriazole-based compound is 10 to 30 compared to the total 100 mol% of the (A) benzotriazole-based compound and (B) acryl-based compound It is preferable that mol% and the component ratio of (B) acryl-type compound are 70-90 mol% with respect to 100 mol% of the sum total of (A) benzotriazole compound and (B) acryl-type compound.

If the content of the (A) benzotriazole-based compound is less than 10 mol%, the content of the benzotriazole group having UV absorbing ability is small, and thus the UV absorbing ability cannot be improved. The disadvantage of deterioration occurs.

Formula (3) below selects 2- [2`-hydroxy-3`-butyl-5` (methacrylooxyethyl) phenyl] -benzotriazole (Formula 4) from the (A) benzotriazole-based compound ( B) It is a chemical formula of the benzotriazole type acrylic copolymer which selected and copolymerized butyl methacrylate (formula 5) from an acryl-type compound. UV absorbers comprising the benzotriazole-based acrylic copolymer of the present invention may include a copolymer compound represented by the following formula.

[Formula 3]

In Formula 3, x and y represent the molar ratio of each monomer in the copolymer, and x + y = 1, and 0 <x <1 and 0 <y <1. x, y does not limit the binding order of each monomer.

[Formula 4]

Formula 4 is 2- [2′-hydroxy-3′-butyl-5 ′ (methacrylooxyethyl) phenyl] -benzotriazole.

[Formula 5]

Formula 5 is butyl methacrylate.

The UV absorber comprising the benzotriazole-based acrylic copolymer as described above may be prepared by heating and stirring the UV absorber composition containing the (A) benzotriazole-based compound, (B) acrylic compound and (C) solvent, followed by cooling have.

The process of heating and stirring the composition is preferably performed for 2 to 7 hours at 50 ℃ to 100 ℃.

In the UV absorber composition of the present invention, it is preferable to use the (A) benzotriazole-based compound represented by the formula (1). At this time, R ₁ is H or C ₁ ~ C ₁₀ Alkyl group. R2 is acryloyl group or methacryloyl group.

In addition, it is preferable to use the thing represented by the said General formula (2) for the (B) acryl type compound. In Formula 2, R ₃ is H or CH ₃ , R ₄ is a C ₁ -C ₁₀ alkyl group, preferably 2-ethylhexyl acrylate, butyl acrylate, methyl methacrylate, butyl methacrylate.

In the UV absorber composition, the component ratio of the (A) benzotriazole compound is 100 to 10 mol% of the sum of the component (A) and the component (B), and the component ratio of the (B) acrylic compound is the component (A) It is preferable that it is 70-90 mol% with respect to 100 mol% of sum of (B) component.

The solvent is added to the UV absorber composition of the present invention in an amount of 50 to 90 mol%, preferably 60 to 80 mol%, based on 100 mol% of the total of the (A) benzotriazole compound and the (B) acrylic compound. Water may be used as the solvent.

If the content of the solvent is 60 mol% or less, there is a difficulty in the reaction process due to the high viscosity, and if the content of the solvent is 80 mol% or more, the concentration of the UV absorber is low and needs to be dried for a long time.

In the UV absorber composition of the present invention, an initiator is added in an amount of 1 to 15 mol%, preferably 1 to 11 mol% based on 100 mol% of the (A) benzotriazole compound in addition to the (A) benzotriazole compound and the (B) acrylic compound. Can be. At this time, as an initiator used, potassium pulse sulfate is preferable.

In addition, the surfactant may be added to the UV absorber composition of the present invention 2 to 20 mol% compared to 100 mol% of the (A) benzotriazole-based compound. As the surfactant used at this time, sodium dodecylbenzenesulfonate is preferable.

The UV absorber and UV absorbent composition containing the benzotriazole-based acrylic copolymer according to the present invention is excellent in improving dispersibility with the polymer, and can solve the bleed out problem. In addition, it can eliminate the loss due to heat during processing and is stable at high temperatures. Therefore, it can be effectively used for automotive interiors, textiles, plastics and coatings.

Although the following examples are intended to illustrate the present invention in more detail, these examples are for illustrative purposes only and should not be construed as limiting the present invention.

Example  One

2- [2'-hydroxy-3'butyl-5 '(methacryloyloxyethyl) phenyl] -benzotriazole (61.37 g) and 2-ethylhexyl acrylate (237.72 g), sodium dodecylbenzenesulfur Nate (15 g) and 448.6 g of distilled water were placed in a reactor and made into a pre-emulsion using a homogenizer. A solution prepared by dissolving potassium pulse sulfate (2.61 g) in distilled water (84.5 g) was added dropwise to the pre-emulsion. Thereafter, the temperature was raised to 70 ° C., stirred for 3 hours, and cooled to terminate the reaction.

Example  2

2- [2'-hydroxy-3'butyl-5 '(methacryloyloxyethyl) phenyl] -benzotriazole (77.52 g) and butyl acrylate (209.17 g), sodium dodecylbenzenesulfonate (19 g ) And 430 g of distilled water were added to the reactor to make a pre-emulsion using a homogenizer. A solution prepared by dissolving potassium pearl sulfate (3.3 g) in distilled water (106.7 g) was added dropwise to the pre-emulsion. Thereafter, the temperature was raised to 70 ° C., stirred for 3 hours, and cooled to terminate the reaction.

Example  3

2- [2'-hydroxy-3'butyl-5 '(methacryloyloxyethyl) phenyl] -benzotriazole (77.52 g) and methyl methacrylate (163.4 g), sodium dodecylbenzenesulfonate ( 19 g) and 410.2 g of distilled water were added to the reactor to make a pre-emulsion using a homogenizer. A solution prepared by dissolving potassium pearl sulfate (3.3 g) in distilled water (106.7 g) was added dropwise to the pre-emulsion. The temperature was raised to 70 ° C., stirred for 3 hours, and cooled to terminate the reaction.

Example  4

2- [2'-hydroxy-3'butyl-5 '(methacryloyloxyethyl) phenyl] -benzotriazole (74.29 g) and butyl methacrylate (222.4 g), sodium dodecylbenzenesulfonate ( 18.2 g) and 445 g of distilled water were added to the reactor to make a pre-emulsion using a homogenizer. A solution of potassium sulphate (3.16 g) in distilled water (102.3 g) was added dropwise to the pre-emulsion. The temperature was raised to 70 ° C., stirred for 3 hours, and cooled to terminate the reaction.

Example  5

2- [2'-hydroxy-3'butyl-5 '(methacryloyloxyethyl) phenyl] -benzotriazole (129 g) and 2-ethylhexyl acrylate (11 g), sodium dodecylbenzenesulfonate ( 15 g) and 448.6 g of distilled water were added to the reactor to make a pre-emulsion using a homogenizer. A solution prepared by dissolving potassium pulse sulfate (2.61 g) in distilled water (84.5 g) was added dropwise to the pre-emulsion. Thereafter, the temperature was raised to 70 ° C., stirred for 3 hours, and cooled to terminate the reaction.

Example  6

2- [2'-hydroxy-3'butyl-5 '(methacryloyloxyethyl) phenyl] -benzotriazole (162 g) and butyl acrylate (10 g), sodium dodecylbenzenesulfonate (19 g) 430 g of distilled water was placed in a reactor and made into a pre-emulsion using a homogenizer. A solution prepared by dissolving potassium pearl sulfate (3.3 g) in distilled water (106.7 g) was added dropwise to the pre-emulsion. Thereafter, the temperature was raised to 70 ° C., stirred for 3 hours, and cooled to terminate the reaction.

Example  7

2- [2'-hydroxy-3'butyl-5 '(methacryloyloxyethyl) phenyl] -benzotriazole (130 g) and methyl methacrylate (6 g), sodium dodecylbenzenesulfonate (19 g) And 410.2 g of distilled water were added to the reactor to prepare a pre-emulsion using a homogenizer. A solution prepared by dissolving potassium pearl sulfate (3.3 g) in distilled water (106.7 g) was added dropwise to the pre-emulsion. The temperature was raised to 70 ° C., stirred for 3 hours, and cooled to terminate the reaction.

Example  8

2- [2'-hydroxy-3'butyl-5 '(methacryloyloxyethyl) phenyl] -benzotriazole (132 g) and butyl methacrylate (10 g), sodium dodecylbenzenesulfonate (18.2 g ) And 445 g of distilled water were added to the reactor to make a pre-emulsion using a homogenizer. A solution of potassium sulphate (3.16 g) dissolved in distilled water (102.3 g) was added dropwise to the pre-emulsion. The temperature was raised to 70 ° C., stirred for 3 hours, and cooled to terminate the reaction.

Table 1 below summarizes sample composition ratios (unit: mol%) of Examples 1 to 8.

Table 1 Composition of Sample

                                                          Unit: mol%

Benzotriazole compound Acrylic compound 2- [2'-hydroxy-3'butyl-5 '(methacryloyloxyethyl) phenyl] -benzotriazole 2-ethylhexyl acrylate Butyl acrylate Methyl methacrylate Butyl methacrylate Example 1 12.8 87.2 Example 2 12.8 87.2 Example 3 12.8 87.2 Example 4 12.8 87.2 Example 5 87.2 12.8 Example 6 87.2 12.8 Example 7 87.2 12.8 Example 8 87.2 12.8

UV absorbance of the UV absorber containing the benzotriazole-based acrylic copolymer prepared according to the above example was measured using a UV-Vis spectrometer (Shimadzu UV-160 1PC). As shown in the results in FIG. 1, the UV absorber containing the benzotriazole-based acrylic copolymer was found to absorb both ultraviolet rays in the UV A region and the UV B region.

In general, since the benzotriazole-based compound acts as a UV absorbing base, as the amount of the benzotriazole-based compound increases in the UV absorber, the UV absorption rate is improved, but the storage stability is lowered. In Examples 5 to 8, the ratio of the benzotriazole compound to the acrylic compound was 7: 1 (based on mole%) to prepare a UV absorber including the benzotriazole-based acrylic copolymer, which was stored at room temperature for 7 to 15 days. When the layer was separated and gelled it was observed that the storage stability was reduced. Figure 2 shows that after changing the UV absorber containing a benzotriazole-based acrylic copolymer prepared according to Example 7 at room temperature, the UV absorber was confirmed that the layer is separated and gelled. In addition, the unit cost of the UV absorber was increased by increasing the content of the benzotriazole compound.

3 is a result of NMR measurement of the compound prepared according to Example 4, it was confirmed that the benzotriazole-based compound and butyl methacrylate reacted to form a copolymer. Figure 4 shows a SEM photograph of the benzotriazole-based acrylic copolymer prepared according to Example 4. Through this, it was confirmed that the copolymer of the present invention was prepared in the form of spheres of nano size. Figure 5 shows the particle size distribution of the benzotriazole-based acrylic copolymer prepared according to Example 4. The benzotriazole-based acrylic copolymer of the present invention had an average particle diameter of about 84 nm, and the variation in particle diameter was not large, and thus it was confirmed that the particle size was even.

The copolymer of the present invention is spherical and the particle size is uniform, and the feel of the fiber prepared by using the polymer compound when the UV blocker containing the benzotriazole-based acrylic copolymer of the present invention is used as the UV absorber of the polymer compound. This means improved.

1 is a graph showing the results of measuring the UV absorbance of the UV absorber comprising the benzotriazole-based acrylic copolymer of Examples 1 to 4 using a UV-Vis spectrometer.

Figure 2 is a photograph showing the state after the UV absorber containing the benzotriazole-based acrylic copolymer prepared in Example 7 for 7 to 15 days at room temperature.

Figure 3 shows the NMR measurement results of the UV absorber comprising a benzotriazole-based acrylic copolymer prepared according to Example 4.

Figure 4 shows a SEM photograph of the benzotriazole-based acrylic copolymer prepared according to Example 4.

Figure 5 shows the distribution of the particle size of the benzotriazole-based acrylic copolymer prepared according to Example 4.

Claims (10)

A UV absorber containing the benzotriazole type acrylic copolymer manufactured by copolymerizing (A) benzotriazole type compound and (B) acrylic type compound. The method of claim 1, The (A) benzotriazole-based compound is a UV absorber, characterized in that represented by the following formula (1). [Formula 1]

In Formula 1, R ₁ is H or a C ₁ -C ₁₀ alkyl group, and R ₂ is a methacryloyl group. The method of claim 1, The acrylic compound (B) is a UV absorber, characterized in that represented by the following formula (2). [Formula 2]

In Formula 2, R ₃ is H or CH ₃ , and R ₄ is an alkyl group of C ₁ to C ₁₀ . The method of claim 1, The component ratio of (A) benzotriazole-based compound and (B) acrylic-based compound constituting the benzotriazole-based acrylic copolymer is (A) benzotria compared to 100 mol% of (A) benzotriazole-based compound and (B) acrylic-based compound. UV absorber, characterized in that 10 to 30 mol% of the sol-based compound, 70 to 90 mol% of the (B) acrylic compound. A UV absorber composition comprising (A) a benzotriazole compound, (B) an acrylic compound, and (C) a solvent. The method of claim 5, wherein The (A) benzotriazole-based compound is a UV absorber composition, characterized in that represented by the following formula (1). [Formula 1]

In Formula 1, R ₁ is H or a C ₁ -C ₁₀ alkyl group, and R ₂ is a methacryloyl group. The method of claim 7, wherein The acrylic compound (B) is a UV absorber composition, characterized in that represented by the formula (2). [Formula 2]

In Formula 2, R ₃ is H or CH ₃ , and R ₄ is an alkyl group of C ₁ to C ₁₀ . The method of claim 5, wherein The component ratio of the (A) benzotriazole compound and (B) acrylic compound is 10 to 30 mol% of (A) benzotriazole compound, based on 100 mol% of the total of (A) benzotriazole compound and (B) acrylic compound, ( B) 70 to 90 mol% of an acrylic compound, characterized in that the UV absorber composition. The method of claim 5, wherein (A) UV absorber composition further comprises an initiator in the range of 1 to 15 mol% relative to 100 mol% of the benzotriazole-based compound. The method of claim 5, wherein (A) UV absorber composition further comprises a surfactant in the range of 2 to 20 mol% relative to 100 mol% of the benzotriazole-based compound.

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