KR20200073020A - Cyanoacrylate-based ultraviolet absorbing compound and composition comprising the same as ultraviolet absorber - Google Patents

Abstract

The present invention relates to a cyanoacrylate-based ultraviolet absorbing compound represented by chemical formula 1 and a composition comprising the same as an ultraviolet absorber. (In the chemical formula 1, A1 is an ethyl group and A2 is a methyl group, a methoxy group, fluorine or a phenyl group.) The ultraviolet absorbing compound of the present invention has higher absorbency than conventional ultraviolet absorbers.

Description

A cyanoacrylate-based ultraviolet absorbent compound and a composition comprising the same as an ultraviolet absorber {CYANOACRYLATE-BASED ULTRAVIOLET ABSORBING COMPOUND AND COMPOSITION COMPRISING THE SAME AS ULTRAVIOLET ABSORBER}

The present invention relates to a composition containing an ultraviolet absorbent compound and the ultraviolet absorber.

Various products such as plastic, rubber, and paint used in industry face various problems. One of several problems is a problem caused by ultraviolet rays. It is caused by ultraviolet rays that pass through the ozone layer of the atmosphere and reach the Earth. The ultraviolet rays passed are UVA (320 ~ 400nm) and UVB (280 ~ 320nm), and these wavelengths of UV rays cause various problems such as aging, color change, peeling phenomenon, and decrease in strength. Problems caused by UV rays can cause the product to lose its original function or reduce its lifespan. Therefore, UV Absorber and Hindered Amine Light Stabilizer are added to the product to solve the problem.

Since the UV absorber has stronger UV absorbing ability than the product, it has the principle of absorbing UV instead and not affecting the product. It absorbs about 250~400nm of ultraviolet rays and the absorbed ultraviolet rays are released as thermal energy.

The operation principle of the ultraviolet absorber will be described in more detail with reference to FIG. 1. When absorbing ultraviolet rays, protons in the ground state (S ₀ = Ground state) move to the excited state (S ₁ = Singlet state). Protons that have moved to the excited state (S ₁ = Singlet state) due to absorption will have an excited state intramolecular proton transper = ESIPT in the excited state molecule. How easily the proton transfer phenomenon occurs in the excited state molecule plays a large role in the stability of the UV absorber. In this phenomenon, the proton moves slightly from the excited state to the excited state (S′ ₁ = Singlet state). At this time, the change in the structure of the molecule occurs, and the rate of change proceeds very quickly. The shape of the structure changes depending on which chromophore you have. After the structure change, it moves from the excited state (S′ ₁ = Singlet state) to the ground state (S′ ₀ = Ground state). In this process, the ultraviolet energy absorbed is released as thermal energy. The energy difference between the excited state (S′ ₁ = Singlet state) and the ground state (S′ ₀ = Ground state) has an energy difference small enough to be quickly and effectively dissipated as thermal energy. Therefore, the amount of energy released as thermal energy does not contribute to the deterioration of the thermal performance of the product. Energy is released, but the structure has been maintained. Finally, the structure is restored by returning to the original structure (S ₀ = Ground state) from the changed state (S′ ₀ = Ground state). This entire process takes place between picoseconds (10 ^-12 seconds) and nanoseconds (10 ^-9 seconds), and this cycle repeats itself as a UV absorber.

There are various types of UV absorbers such as Benzophenone, Benzotriazole, Triazine, Oxanilide, and Cyanoacrylate. Most of these ultraviolet absorbers are used by imports. The amount used in the product is small, but it is a fairly large part in terms of price. Therefore, it is urgent to develop a novel UV absorber that can maintain and maintain existing high absorbency.

Korean Patent Publication No. 10-2018-0109821 (Publication date: 2018.10.08) Korean Patent Publication No. 10-2017-0143096 (Publication date: 2017.12.29) Korean Patent Publication No. 10-2015-0097180 (Publication date: 2015.08.26)

Accordingly, an object of the present invention is to provide a UV absorbing compound that has a high absorbency of a conventional UV absorber or more and can replace the existing UV absorber and a composition paper comprising the same as an UV absorber.

The present invention provides a cyanoacrylate-based ultraviolet absorbent compound represented by the following Chemical Formula 1.

[Formula 1]

(In the above formula 1, A1 is ethyl, A2 is methyl, methoxy, fluorine or phenyl).

In addition, a cyanoacrylate-based ultraviolet absorbent compound represented by the following Chemical Formula 2 is provided:

[Formula 2]

.

.

In addition, a cyanoacrylate-based UV absorbing compound represented by Chemical Formula 3 is provided:

[Formula 3]

.

.

In addition, a cyanoacrylate-based UV absorbing compound represented by Chemical Formula 4 is provided:

[Formula 4]

.

.

In addition, a cyanoacrylate-based UV absorbing compound represented by Chemical Formula 5 is provided:

[Formula 5]

.

.

The ultraviolet absorbent compound according to the present invention is a dye, pigment, food, beverage, body-care product, vitamin, drug, ink, oil, fat, wax, surface coating agent, cosmetic, photographic material, fabric and dye thereof as an ultraviolet absorber, It can be applied to plastic materials, rubber, paint, polymer materials, polymer additives, and the like.

The ultraviolet absorbent compound according to the present invention may be used alone as an ultraviolet absorber, but is more preferably used as being included in a composition. The present invention provides a composition comprising the ultraviolet absorbent compound as an ultraviolet absorber in another aspect of the invention. And, the composition will be described in detail below.

Examples of the composition include dispersions, solutions, mixtures and coating materials.

First, the ultraviolet absorbent compound of the present invention can be used as a dispersion liquid dispersed in a dispersion medium. The medium for dispersing the ultraviolet absorbent compound according to the present invention includes water, an organic solvent, a resin, a resin solution, and the like, and these mediums may be used alone or in combination of two or more.

Examples of the organic solvent as a dispersion medium that can be used in the ultraviolet absorber of the present invention include hydrocarbon-based solvents (such as pentane, hexane and octane), aromatic solvents (such as benzene, toluene and xylene), and ether-based solvents (diethyl ether and methyl) -t-butyl ether, etc.), alcohol solvents (such as methanol, ethanol, and isopropanol), ester solvents (such as acetone, ethyl acetate, and butyl acetate), ketone solvents (such as methyl ethyl ketone), nitrile solvents (acetonitrile and Propionitrile, etc.), amide solvents (N,N-dimethylformamide, N,N-dimethylacetamide and N-methylpyrrolidone, etc.), sulfoxide solvents (such as dimethyl sulfoxide), amine solvents ( Triethylamine and tributylamine, etc., carboxylic acid solvents (such as acetic acid and propionic acid), halogen solvents (such as methylene chloride and chloroform), and heterocycle solvents (such as tetrahydrofuran and pyridine).

Examples of the resin as the dispersing medium include a number of known thermoplastic and thermosetting resins, which are commonly used in the production of molded articles, sheets, films, and the like.

Examples of thermoplastic resins include polyethylene-based resins, polypropylene-based resins, poly(meth)acrylic ester-based resins, polystyrene-based resins, styrene-acrylonitrile-based resins, acrylonitrile-butadiene-styrene-based resins, and polyvinyl chloride-based resins , Polyvinylidene chloride series resin, polyvinyl acetate series resin, polyvinyl butyral series resin, ethylene-vinyl acetate series copolymer, ethylene-vinyl alcohol series resin, polyethylene terephthalate resin (PET), polybutylene terephthalate resin (PBT), liquid crystal polyester resin (LCP), polyacetal resin (POM), polyamide resin (PA), polycarbonate resin, polyurethane resin, and polyphenylene sulfide resin (PPS) may be included, , As the thermosetting resin, epoxy resin, melamine resin, and unsaturated polyester resin may be used.

Meanwhile, the dispersion liquid containing the ultraviolet absorbent compound of the present invention as an ultraviolet absorber may contain other additives such as dispersants, antifoaming agents, preservatives, antifreeze agents and surfactants. The dispersion may further contain any other compound. Examples of other additives include dyes, pigments, ultraviolet absorbers, infrared absorbers, flavoring agents, polymerizable compounds, polymers, inorganic materials, metals, and the like.

In the composition in the form of a solution containing the ultraviolet absorbent compound according to the present invention as an ultraviolet absorber, the liquid dissolving the ultraviolet absorbent compound is not particularly limited, for example, water, organic solvents, resins, resin solutions, etc. . Such organic solvents, resins, and resin solutions include those described as the dispersion medium, and these may be used alone or in combination.

The solution of the ultraviolet absorbent compound according to the present invention may further contain any other compound. Examples of other additives include dyes, pigments, ultraviolet absorbers, infrared absorbers, flavoring agents, polymerizable compounds, polymers, inorganic materials, metals, and the like. At this time, components other than the ultraviolet absorbent compound according to the present invention need not be dissolved.

In addition, the ultraviolet absorbent compound of the present invention can be used as a composition in the form of a mixture with any other compound. The mixture containing the ultraviolet absorbent compound of the present invention is not limited in both its form and state.

That is, the composition in the form of a mixture may be in a liquid, solid or liquid crystal state, and in the case of a solid mixture, it may have various shapes such as film, powder, spherical, granular, granular, fibrous, tubular, and hollow fibrous. Can.

It is particularly preferable that the solid mixture is a polymer material containing the ultraviolet absorbing compound of the present invention. These polymer compositions are used in the manufacture of polymeric materials. The polymer composition may include the polymer material described below and the ultraviolet absorbent compound according to the present invention as an ultraviolet absorber.

At this time, the ultraviolet absorbent compound according to the present invention may be contained in the polymer material in various ways. When the ultraviolet absorbing compound according to the present invention is compatible with the polymer material, it can be added directly to the polymer material. Alternatively, the solution obtained by dissolving the ultraviolet absorbent compound according to the present invention in an auxiliary solvent compatible with the polymer material may be added to the polymer material. In addition, the dispersion obtained by dispersing the ultraviolet absorbing compound according to the present invention in a high boiling point organic solvent or polymer can be added to the polymer material.

On the other hand, the polymer material that can be used in the polymer composition may be a natural or synthetic polymer or copolymer, but among them, synthetic polymer, more preferably polyolefin, acrylic polymer, polyester, polycarbonate, or cellulose Esters, among others, polyethylene, polypropylene, poly(4-methylpentene), polymethyl methacrylate, polycarbonate, polyethylene terephthalate, polyethylene naphthalate, polybutylene terephthalate, and triacetylcellulose Is particularly preferred.

In addition, the polymer material containing the ultraviolet absorbent compound according to the present invention as an ultraviolet absorber may further include optional additives, for example, antioxidants, light stabilizers, processing stabilizers, decomposition inhibitors, and compatibilizers.

The novel cyanoacrylate-based ultraviolet absorbent compound according to the present invention exhibits superior efficiency compared to conventional ultraviolet stabilizers, and furthermore, it is excellent in processability and easy to process, and thus can be utilized in various technical fields as an ultraviolet stabilizer.

1 is a schematic view showing the principle of operation of the ultraviolet absorber.
2A and 2B are views showing a process of synthesizing ultraviolet absorbent compounds (ethyl 2-cyano-3,3-di-p-tolylacrylate) in Examples 1-1 and 1-2 of the present application, respectively.
3A and 3B are views showing a process of synthesizing an ultraviolet absorbing compound (ethyl 2-cyano-3,3-bis(4-methoxyphenyl)acrylate) in Examples 2-1 and 2-2 of the present application, respectively.
4A and 4B are views showing a process of synthesizing an ultraviolet absorbing compound (ethyl 2-cyano-3,3-bis(4-fluorophenyl)acrylate) in Examples 3-1 and 3-2 of the present application, respectively.
5A and 5B are ultraviolet absorbent compounds (ethyl 3,3-di([1,1'-biphenyl]-4-yl)-2-cyano acrylate) in Examples 4-1 and 4-2 of the present application, respectively. It is a diagram showing the process of synthesizing.

In the description of the present invention, when it is determined that detailed descriptions of related known functions or configurations may unnecessarily obscure the subject matter of the present invention, detailed descriptions thereof will be omitted.

The embodiments according to the concept of the present invention may be modified in various ways and have various forms, and thus, specific embodiments will be illustrated in the drawings and described in detail in the present specification or application. However, this is not intended to limit the embodiment according to the concept of the present invention to a specific disclosure form, and it should be understood to include all modifications, equivalents, or substitutes included in the spirit and scope of the present invention.

The terms used herein are only used to describe specific embodiments, and are not intended to limit the present invention. Singular expressions include plural expressions unless the context clearly indicates otherwise. In this specification, terms such as “include” or “have” are intended to indicate that a feature, number, step, action, component, part, or combination thereof described is present, and one or more other features or numbers. It should be understood that it does not preclude the presence or addition possibilities of, steps, actions, components, parts or combinations thereof.

Hereinafter, the present invention will be described in detail by way of examples.

The embodiments according to the present specification may be modified in various other forms, and the scope of the present specification is not interpreted to be limited to the embodiments described below. The embodiments of the present specification are provided to more fully describe the present specification to those skilled in the art.

<Example 1-1> Synthesis of ultraviolet absorbent compound (ethyl 2-cyano-3,3-di-p-tolylacrylate) according to the present invention

4,4'-Dimethylbenzophenone (10 g, 47.55 mmol), ethyl 2-cyanoacetate (6.45 g, 57.06 mmol), b-alanine (0.45 g, 4.75 mmol), acetic acid 20 ml, benzene 200 ml in 500 ml flask Dissolve. And heated to 105 ℃ with an oil bath and stirred for 30 hours. The generated water was removed by Dean-stark trap. After completion of the reaction, neutralize with NaHCO ₃ and repeat work-up with Ethyl acetate and water. The extracted organic layer is collected with a small amount of water using MgSO ₄ and the solvent is evaporated by distillation under reduced pressure. The evaporated residue is extracted with a compound using crystallization using EA and methanol (Fig. 2a).

<Example 1-2> Synthesis of ultraviolet absorbent compound (ethyl 2-cyano-3,3-di-p-tolylacrylate) according to the present invention

Dissolve 4,4'-Dimethylbenzophenone (10 g, 47.55 mmol), ethyl 2-cyanoacetate (6.45 g, 57.06 mmol), ammonium acetate (3.66 g, 47.55 mmol), acetic acid 20 ml, benzene 200 ml in 500 ml flask Order. And heated to 105 ℃ with an oil bath and stirred for 30 hours. The generated water was removed by Dean-stark trap. After completion of the reaction, neutralize with NaHCO ₃ and repeat work-up with ethyl acetate and water. The extracted organic layer is collected with a small amount of water using MgSO ₄ and the solvent is evaporated by distillation under reduced pressure. The evaporated residue is extracted with a crystallization using EA and methanol (Fig. 2b).

<Example 2-1> Synthesis of ultraviolet absorbent compound (ethyl 2-cyano-3,3-bis(4-methoxyphenyl)acrylate) according to the present invention

In a 250 mL reaction flask, 20 g (80.90 mmol) of 4,4'-Dimethoxybenzophenone, 12.14 g (105.17 mmol) of ethyl cyanoacetate, 0.8 g (8.8 mmol) of b-alanine, and 20 mL of acetic acid were dissolved in 100 mL of benzene. And while heating to 100 ℃ was stirred for 90 hours. Water generated during this process was removed by Dean Stark traps. When the reaction was completed after 90 hours, work-up was performed using water and EA. The EA layer was removed with MgSO ₄ and distilled under reduced pressure to evaporate the solvent. After evaporation, recrystallization was carried out using methanol to recover the residual starting material. After recovering the remaining starting material, it was recrystallized with Methanol to obtain a yellow solid (Fig. 3a).

<Example 2-2> Synthesis of ultraviolet absorbent compound (ethyl 2-cyano-3,3-bis(4-methoxyphenyl)acrylate) according to the present invention

In a 250 mL reaction flask, 4,4'-Dimethoxybenzophenone 20 g (80.90 mmol), ethyl cyanoacetate 12.14 g (105.17 mmol), ammonium acetate 6.43 g (80.90 mmol), and acetic acid 20 mL were dissolved in 100 mL of benzene. And stirred for 24 hours while heating to 100 ℃. During the reaction, 6.43 g (80.90 mmol) of ammonium acetate was added twice (2 hours after the reaction, 4 hours later). Water generated during this process was removed by Dean Stark traps. When the reaction was completed after 24 hours, work-up was performed using water and EA. The EA layer was removed with MgSO ₄ and distilled under reduced pressure to evaporate the solvent. After evaporation, recrystallization was carried out using methanol to recover the residual starting material. After recovering the remaining starting material, it was recrystallized with Methanol to obtain a yellow solid (Fig. 3b).

<Example 3-1> Synthesis of ultraviolet absorbent compound (ethyl 2-cyano-3,3-bis(4-fluorophenyl)acrylate) according to the present invention

In a 250 mL reaction flask, 20 g (89.83 mmol) of 4,4'-Difluorobenzophenone, 13.48 g (116.77 mmol) ethyl cyanoacetate, 0.8 g (8.8 mmol) b-alanine, and 20 mL acetic acid were dissolved in 100 mL benzene. And while heating to 100 ℃ was stirred for 90 hours. Water generated during this process was removed by Dean Stark traps. When the reaction was completed after 90 hours, work-up was performed using water and EA. The EA layer was removed with MgSO ₄ and distilled under reduced pressure to evaporate the solvent. After evaporation, recrystallization was performed using Methanol to obtain a solid. The obtained solid was recrystallized at a ratio of EA:Hex = 1:9 to obtain a white solid (Fig. 4A).

<Example 3-2> Synthesis of ultraviolet absorbent compound (ethyl 2-cyano-3,3-bis(4-fluorophenyl)acrylate) according to the present invention

In a 250 mL reaction flask, 20 g (89.83 mmol) of 4,4'-Difluorobenzophenone, 13.48 g (116.77 mmol) of ethyl cyanoacetate, 7.14 g (89.83 mmol) of ammonium acetate, and 20 mL of acetic acid were dissolved in 100 mL of benzene. And stirred for 24 hours while heating to 100 ℃. During the reaction, 7.14 g (89.83 mmol) of ammonium acetate was added twice (2 hours after the reaction, 4 hours later). Water generated during this process was removed by Dean Stark traps. When the reaction was completed after 24 hours, work-up was performed using water and EA. The EA layer was removed with MgSO ₄ and distilled under reduced pressure to evaporate the solvent. After evaporation, recrystallization was performed using Methanol to obtain a solid. The obtained solid was recrystallized at a ratio of EA:Hex = 1:9 to obtain a white solid (Fig. 4B).

<Example 4-1> Synthesis of ultraviolet absorbent compound (ethyl 3,3-di([1,1'-biphenyl]-4-yl)-2-cyano acrylate) according to the present invention

4,4'-Diphenylbenzophenone (10 g, 29.90 mmol), ethyl 2-cyanoacetate (4.06 g, 35.88 mmol), b-alanine (0.45 g, 4.75 mmol), acetic acid 20 ml, benzene 200 ml in 500 ml flask Dissolve. And heated to 120 ℃ with an oil bath and stirred for 36 hours. The generated water was removed by Dean-stark trap. After completion of the reaction, neutralize with NaHCO ₃ and repeat work-up with chloroform and water. The extracted organic layer is collected with a small amount of water using MgSO ₄ and the solvent is evaporated by distillation under reduced pressure. The evaporated residue is extracted with crystallization using chloroform and methanol (FIG. 5A).

<Example 4-2> Synthesis of ultraviolet absorbent compound (ethyl 3,3-di([1,1'-biphenyl]-4-yl)-2-cyano acrylate) according to the present invention

Dissolve 4,4'-Diphenylbenzophenone (10 g, 29.90 mmol), ethyl 2-cyanoacetate (4.06 g, 35.88 mmol), ammonium acetate (6.22 g, 80.73 mmol), acetic acid 20 ml, chloroform 200 ml in 500 ml flask Order. And heated to 120 ℃ with an oil bath and stirred for 36 hours. The generated water was removed by Dean-stark trap. After completion of the reaction, neutralize with NaHCO ₃ and repeat work-up with chloroform and water. The extracted organic layer is collected with a small amount of water using MgSO ₄ and the solvent is evaporated by distillation under reduced pressure. The evaporated residue was extracted with crystallization using chloroform and methanol (FIG. 5B).

Claims (6)

A cyanoacrylate-based UV absorbing compound represented by the following Chemical Formula 1:
[Formula 1]

(In the above formula 1, A1 is ethyl, A2 is methyl, methoxy, fluorine or phenyl). According to claim 1,
A cyanoacrylate-based UV absorbing compound represented by the following Chemical Formula 2:
[Formula 2]

. According to claim 1,
A cyanoacrylate-based UV absorbing compound represented by the following Chemical Formula 3:
[Formula 3]

. According to claim 1,
A cyanoacrylate-based UV absorbing compound represented by the following formula (4):
[Formula 4]

. According to claim 1,
A cyanoacrylate-based UV absorbing compound represented by the following Chemical Formula 5:
[Formula 5]

. A composition comprising the compound of any one of claims 1 to 5 as an ultraviolet absorber.

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