KR20200137199A - Novel 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 alkylene having 1 to 5 carbon atoms, and A2 is a methyl, methoxy, fluorine or phenyl group.) The novel cyanoacrylate-based ultraviolet absorbing compound according to the present invention exhibits excellent efficiency compared to conventional ultraviolet stabilizers.

Description

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

The present invention relates to an ultraviolet absorbing compound and a composition comprising the same as an ultraviolet absorber.

Various products such as plastics, rubber, and paints 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 passed ultraviolet rays are UVA (320 ~ 400nm) and UVB (280 ~ 320nm), and the ultraviolet rays of these wavelengths create various problems such as aging, color change, peeling, and intensity reduction of the product. Problems caused by ultraviolet rays can cause the product to lose its original function or reduce its lifespan. Therefore, in order to solve the problem, UV Absorber and Hindered Amine Light Stabilizer are added to the product.

Since UV absorbers have a stronger UV absorption ability than products, they have the principle of absorbing UV rays instead of affecting the product. It absorbs approximately 250 to 400 nm of ultraviolet rays, and the absorbed ultraviolet rays are released as thermal energy.

The principle of action of the ultraviolet absorber will be described in more detail with reference to FIG. 1 as follows. When absorbing ultraviolet rays, the proton in the ground state (S ₀ = Ground state) moves to the excited state (S ₁ = Singlet state). Protons that have moved to an excited state (S ₁ = Singlet state) due to absorption undergo an excited state intramolecular proton transper (ESIPT). How easily the proton transfer phenomenon occurs in the excited state molecule plays a big 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, a phenomenon in which the structure of the molecule changes, and the rate of change proceeds very quickly. The shape in which the structure changes appears differently depending on which chromophore it has. After the structural change, it moves from the excited state (S′ ₁ = Singlet state) to the ground state (S′ ₀ = Ground state). The ultraviolet energy absorbed in this process 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 a small enough energy difference to quickly and effectively dissipate as heat energy inside. Therefore, the amount of energy released as thermal energy does not contribute to the thermal degradation of the product. It releases energy but keeps the changed structure. Finally, the structure is restored by returning to the original structure (S ₀ = Ground state) from the ground state (S′ ₀ = Ground state), which is the changed structural state. This whole process takes place between picoseconds (10 ^-12 seconds) and nanoseconds (10 ^-9 seconds), and this cycle is repeated to act as an ultraviolet absorber.

There are various types of UV absorbers such as Benzophenone, Benzotriazole, Triazine, Oxanilide, and Cyanoacrylate. Most of these UV absorbers are being used by importers. Although the amount used in the product is small, it occupies a fairly large part in terms of price. Therefore, it is urgent to develop a novel UV absorber that can be replaced while maintaining high absorbency.

Korean Patent Application Publication No. 10-2018-0109821 (Publication date: 2018.10.08) Korean Patent Application Publication No. 10-2017-0143096 (Publication date: 2017.12.29) Japanese Patent Application Publication No. 2008-184463 (Publication date: (2008.08.14)

Accordingly, it is an object of the present invention to provide an ultraviolet absorbing compound capable of replacing an existing ultraviolet absorber and a composition comprising the same as an ultraviolet absorber having higher absorption properties than the conventional ultraviolet absorber.

The present invention provides a cyanoacrylate-based ultraviolet absorbing compound represented by the following formula (1).

[Formula 1]

(In Chemical Formula 1, A1 is alkylene having 1 to 5 carbon atoms, and A2 is methyl, methoxy, fluorine or phenyl).

In addition, it provides a cyanoacrylate-based ultraviolet absorbing compound represented by the following Formula 2:

[Formula 2]

.

.

In addition, it provides a cyanoacrylate-based ultraviolet absorbing compound represented by the following Formula 3:

[Formula 3]

.

.

In addition, it provides a cyanoacrylate-based ultraviolet absorbing compound represented by the following Formula 4:

[Formula 4]

.

.

In addition, it provides a cyanoacrylate-based ultraviolet absorbing compound represented by the following Formula 5:

[Formula 5]

.

.

The UV-absorbing compound according to the present invention is a UV-absorbing agent, including dyes, pigments, foods, beverages, body-care products, vitamins, drugs, inks, oils, fats, waxes, surface coating agents, cosmetics, photographic materials, fabrics and dyes thereof, It can be applied to plastic materials, rubber, paints, polymer materials, polymer additives, etc.

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

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

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

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

Examples of resins as the dispersion medium include a number of known thermoplastic and thermosetting resins that are commonly used in the manufacture of molded articles, sheets, films, and the like.

Examples of thermoplastic resins include polyethylene resins, polypropylene resins, poly(meth)acrylic ester resins, polystyrene resins, styrene-acrylonitrile resins, acrylonitrile-butadiene-styrene resins, and polyvinyl chloride resins. , Polyvinylidene chloride-based resin, polyvinyl acetate-based resin, polyvinyl butyral-based resin, ethylene-vinyl acetate-based copolymer, ethylene-vinyl alcohol-based 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). , As the thermosetting resin, an epoxy resin, a melamine resin, and an unsaturated polyester resin may be used.

On the other hand, the dispersion containing the ultraviolet absorbing compound of the present invention as an ultraviolet absorber may contain other additives such as a dispersing agent, an antifoaming agent, a preservative, an antifreezing agent, and a surfactant. 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 substances, metals, and the like.

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

The solution of the ultraviolet absorbing 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 substances, metals, and the like. At this time, components other than the ultraviolet absorbing compound according to the present invention need not be dissolved.

In addition, the ultraviolet absorbing 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 absorbing compound of the present invention is not limited to 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 type, powder type, spherical particle type, granular particle type, fiber type, tubular type, hollow fiber type, etc. I can.

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

At this time, the ultraviolet absorbing compound according to the present invention may be contained in the polymer material in various ways. If the ultraviolet absorbing compound according to the present invention is compatible with the polymeric material, it can be added directly to the polymeric material. Alternatively, a solution obtained by dissolving the ultraviolet absorbing compound according to the present invention in a co-solvent compatible with the polymer material may be added to the polymer material. In addition, a dispersion obtained by dispersing the ultraviolet absorbing compound according to the present invention in a high boiling point organic solvent or a polymer may 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 these, preferably a synthetic polymer, more preferably a polyolefin, an acrylic polymer, polyester, polycarbonate, or cellulose It may be an ester, and among others, polyethylene, polypropylene, poly(4-methylpentene), polymethyl methacrylate, polycarbonate, polyethylene terephthalate, polyethylene naphthalate, polybutylene terephthalate, and triacetylcellulose Is particularly preferred.

In addition, the polymeric material containing the ultraviolet absorbing compound according to the present invention as an ultraviolet absorber may further include optional additives such as antioxidants, light stabilizers, processing stabilizers, decomposition inhibitors and compatibilizers, if necessary.

The novel cyanoacrylate-based ultraviolet absorbing compound according to the present invention exhibits excellent efficiency compared to the conventional ultraviolet stabilizer, and further, it has excellent processability and is easy to process, so it can be used in various technical fields as an ultraviolet stabilizer.

1 is a schematic diagram showing the principle of operation of an ultraviolet absorber.
2A and 2B are diagrams showing a process of synthesizing an intermediate compound (methyl 2-cyano-3,3-bis(4-fluorophenyl)acrylate) in Example 1 of the present application.
Figure 2c The ultraviolet absorbing compound in Example 1 of the present application (2,2-bis(((2-cyano-3,3-bis(4-fluorophenyl)acryloyl)oxy)methyl)propane-1,3-diyl bis(2- It is a diagram showing the process of synthesizing cyano-3,3-bis(4-fluorophenyl)acrylate)).
3A and 3B are diagrams showing a process of synthesizing an intermediate compound (methyl 2-cyano-3,3-bis(4-methoxyphenyl)acrylate) in Example 2 of the present application.
3C is a UV-absorbing compound (2,2-bis(((2-cyano-3,3-bis(4-methoxyphenyl)acryloyl)oxy)methyl)propane-1,3-diyl bis(2) in Example 2 of the present application. -cyano-3,3-bis(4-methoxyphenyl)acrylate)) is a diagram showing the synthesis process.

In describing the present invention, if it is determined that a detailed description of a related known function or configuration may unnecessarily obscure the subject matter of the present invention, a detailed description thereof will be omitted.

Since the embodiments according to the concept of the present invention can apply various changes and have various forms, 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 embodiments according to the concept of the present invention to a specific form of disclosure, and it should be understood that all changes, equivalents, and substitutes included in the spirit and scope of the present invention are included.

The terms used in the present specification 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 the present specification, terms such as "comprise" or "have" are intended to designate the presence of a set feature, number, step, action, component, part, or combination thereof, but one or more other features or numbers It is to be understood that the possibility of addition or presence of, steps, actions, components, parts, or combinations thereof is not preliminarily excluded.

Hereinafter, the present invention will be described in detail with reference to examples.

The embodiments according to the present specification may be modified in various forms, and the scope of the present specification is not construed as being limited to the embodiments described below. The embodiments of the present specification are provided to more completely describe the present specification to those of ordinary skill in the art.

<Example 1> UV-absorbing compound according to the present invention (2,2-bis(((2-cyano-3,3-bis(4-fluorophenyl)acryloyl)oxy)methyl)propane-1,3-diyl bis( 2-cyano-3,3-bis(4-fluorophenyl)acrylate)) synthesis

(1) Synthesis of methyl 2-cyano-3,3-bis(4-fluorophenyl)acrylate

An intermediate compound (methyl 2-cyano-3,3-bis(4-fluorophenyl)acrylate) was synthesized as described in 1) or 2) below.

1) In a 250 mL reaction flask, 4,4'-Difluorobenzophenone 20g (89.83mmol), methyl cyanoacetate 11.81g (116.77mmol), b-alanine 0.8g (8.8 mmol), and acetic acid 20mL were dissolved in benzene 100mL. And it was stirred for 90 hours while heating to 100 ℃. Water generated during this process was removed by a Dean Stark trap. When the reaction was complete after 90 hours, work-up was performed using water and EA. Water was removed from the EA layer using 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 in a ratio of EA:Hex =1:9 to obtain a white solid (FIG. 2A).

2) In a 250 mL reaction flask, 4,4'-Difluorobenzophenone 20g (89.83mmol), methyl cyanoacetate 11.81g (116.77mmol), ammonium acetate 7.14g (89.83mmol), and acetic acid 20mL were dissolved in benzene 100ml. And it was stirred for 24 hours while heating to 100 ℃. During the reaction, 7.14 g (89.83 mmol) of ammonium acetate was added twice (reaction 2 hours, after 4 hours). Water generated during this process was removed by a Dean Stark trap. When the reaction was completed after 24 hours, work-up was performed using water and EA. Water was removed from the EA layer using 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 in a ratio of EA:Hex = 1:9 to obtain a white solid (Fig. 2b).

(2)2,2-bis(((2-cyano-3,3-bis(4-fluorophenyl)acryloyl)oxy)methyl)propane-1,3-diyl bis(2-cyano-3,3-bis( Synthesis of 4-fluorophenyl)acrylate)

Pentaerythritol 1g (7.20 mmol), Compound No. 5 12.93g (43.2mmol), and DBTO 0.11g (0.432mmol) were dissolved in a 250mL reaction flask in IG (ISOPAR G) (Exxon mobile), a non-polar solvent. And it was stirred for 48 hours while heating to 160 ℃. The reaction was terminated after reaction check using TCL. After completion of the reaction, a solid that was not dissolved in IG was dissolved in EA, and work-up was performed with water. Water was removed from the EA layer using MgSO ₄ and distilled under reduced pressure to evaporate the solvent. After evaporation, recrystallization was performed using EA/Hex to obtain a white solid (Fig. 2c).

<Example 2> UV-absorbing compound according to the present invention (2,2-bis(((2-cyano-3,3-bis(4-methoxyphenyl)acryloyl)oxy)methyl)propane-1,3-diyl bis( 2-cyano-3,3-bis(4-methoxyphenyl)acrylate)) synthesis

(1) Synthesis of methyl 2-cyano-3,3-bis(4-methoxyphenyl)acrylate

An intermediate compound (methyl 2-cyano-3,3-bis(4-methoxyphenyl)acrylate) was synthesized as described in 1) or 2) below.

1) In a 250mL reaction flask, 4,4'-Dimethoxybenzophenone 20g (80.90mmol), methyl cyanoacetate 10.63g (105.17mmol), b-alanine 0.8g (8.8 mmol), and acetic acid 20mL were added and dissolved in benzene 100mL. And it was stirred for 90 hours while heating to 100 ℃. Water generated during this process is removed by the Dean Stark trap. When the reaction was complete after 90 hours, work-up was performed using water and EA. Water was removed from the EA layer using MgSO ₄ and distilled under reduced pressure to evaporate the solvent. After evaporation, recrystallization was performed using methanol to recover the residual starting material. After recovering the residual starting material, it was recrystallized with methanol to obtain a yellow solid (Fig. 3a).

2) In a 250 mL reaction flask, 4,4'-Dimethoxybenzophenone 20g (80.90mmol), methyl cyanoacetate 10.63g (105.17mmol), ammonium acetate 6.43g (80.90mmol), and acetic acid 20mL were added and dissolved in benzene 100ml. And it was stirred for 24 hours while heating to 100 ℃. During the reaction, 6.43 g (80.90 mmol) of ammonium acetate was added twice (reaction 2 hours, after 4 hours). Water generated during this process is removed by the Dean Stark trap. When the reaction was completed after 24 hours, work-up was performed using water and EA. Water was removed from the EA layer using MgSO ₄ and distilled under reduced pressure to evaporate the solvent. After evaporation, recrystallization was performed using methanol to recover the residual starting material. After recovering the residual starting material, it was recrystallized with methanol to obtain a yellow solid (Fig. 3b).

(2)2,2-bis(((2-cyano-3,3-bis(4-methoxyphenyl)acryloyl)oxy)methyl)propane-1,3-diyl bis(2-cyano-3,3-bis( Synthesis of 4-methoxyphenyl)acrylate)

In a 250 mL reaction flask, 1 g (7.20 mmol) of Pentaerythritol, 13.97 g (43.2 mmol) of Compound No. 8, and 0.11 g (0.432 mmol) of DBTO were dissolved in IG (ISOPAR G) (Exxon mobile), a non-polar solvent. And it was stirred while heating to 180 ℃. The reaction was terminated after reaction check using TCL. After completion of the reaction, a solid that was not dissolved in IG was dissolved in EA, and work-up was performed with water. Water was removed from the EA layer using MgSO ₄ and distilled under reduced pressure to evaporate the solvent. After evaporation, recrystallization was performed using methanol to obtain a white solid (Fig. 3c).

Claims (6)

Cyanoacrylate-based ultraviolet absorbing compound represented by the following formula (1):
[Formula 1]

(In Chemical Formula 1, A1 is alkylene having 1 to 5 carbon atoms, and A2 is methyl, methoxy, fluorine or phenyl). The method of claim 1,
Cyanoacrylate-based ultraviolet absorbing compound represented by the following formula (2):
[Formula 2]

. The method of claim 1,
Cyanoacrylate-based ultraviolet absorbing compound represented by the following formula (3):
[Formula 3]

. The method of claim 1,
Cyanoacrylate-based ultraviolet absorbing compound represented by the following Formula 4:
[Formula 4]

. The method of claim 1,
Cyanoacrylate-based ultraviolet absorbing compound represented by the following 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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