KR102345990B1 - UV-absorbing paint and film coated with the paint - Google Patents

Abstract

[상기 화학식에서, R¹이 수소원자 또는 알킬기, R²가 알킬기, R³가 아크릴로일옥시알킬기 또는 메타크릴로일옥시알킬기]A benzotorazole type formed by polymerizing a raw material containing a metoquinone type benzotorazole type monomer of the following formula as a polymer having absorption performance in a wide range of ultraviolet wavelengths from 300 to 400 nm while absorbing light in the short wavelength region of visible light up to around 450 nm (co)polymers are provided.

[In the above formula, R ¹ is a hydrogen atom or an alkyl group, R ² is an alkyl group, R ³ is an acryloyloxyalkyl group or a methacryloyloxyalkyl group]

Description

UV-absorbing paint and film coated with the paint

The present invention relates to a benzotriazole-based (co)polymer having ultraviolet absorption performance and absorbing ultraviolet light in a broad wavelength region and light in a short visible light wavelength region, a paint containing the same, and a film coated with the paint.

Conventionally, for the purpose of absorbing and blocking ultraviolet rays, preventing elution or bleeding out of ultraviolet absorbing components from the coating film, preventing crystallization of ultraviolet absorbing components in the coating film, improving the weather resistance of the coating film, and improving compatibility with other resins and compounding materials. Ultraviolet-absorbing (co)polymers are used.

A benzotriazole-based copolymer formed by copolymerizing a monomer composition containing one or more types of alkanolphenol-type benzotriazole-based UV-absorbing monomers having UV-absorbing properties in a relatively short region centered around 300 nm to 360 nm is mainly It is used (for example, patent documents 1-2).

A benzotriazole-type benzotriazole-based copolymer having absorption near 400 nm in a relatively long wavelength region, which was insufficient for an alkanolphenol-type benzotriazole-based copolymer, is formed by copolymerizing a monomer composition containing one or several sesamol-type benzotriazole-based UV-absorbing monomers. A triazole-type copolymer is used (for example, patent document 3).

These benzotriazole-based UV-absorbing monomers are generally used, for example, in display display devices by adding a UV-absorbing agent to optical films such as polarizing plate protective films to prevent discoloration of these optical films. Moreover, in order to prevent deterioration by the ultraviolet-ray of the near-infrared absorber contained in an antireflection film, the ultraviolet absorber is added to the antireflection film. Moreover, various organic substances, such as a fluorescent material and a phosphorescent material, are used for the light emitting element of organic electroluminescent display, In order to prevent deterioration by the ultraviolet-ray of these organic substances, an ultraviolet absorber is added to the surface film of a display, etc.

In addition, in the human body, it is well known that the skin and eyes are tanned by ultraviolet rays and cause various diseases. It is generally practiced to prevent contact with the eyes.

In addition, in recent years, it has been pointed out that not only ultraviolet light of 400 nm or less but also light in the visible light short wavelength range of 400 to 450 nm damages organic matter or the human body, and in specific uses including the above use, There is a demand for a light absorber capable of absorbing light in the short wavelength range of visible light.

In each of the above uses, a light absorber for efficiently absorbing light in the short wavelength region of ultraviolet and visible light has been proposed, and as a compound having absorption in such a wavelength region, for example, as described in Patent Documents 4 to 5, and indole derivatives, pyrrolidine-amide derivatives and xanthone derivatives. However, these compounds generally have low light resistance, and cannot be used for a long period of time because they deteriorate due to exposure to sunlight, resulting in a decrease in light absorption ability. Moreover, there is no description of light resistance in Patent Documents 4 to 5.

Although the sesamol-type benzotriazole-based copolymer generally known as having high light resistance in Patent Document 3 can absorb light in the short wavelength region of ultraviolet and visible light, absorption of 420 nm or more is weak, and in the ultraviolet region near 300 to 330 nm There is a problem that absorption is rather weak.

Japanese Patent Laid-Open No. 2006-021402 Japanese Patent Laid-Open No. 2006-264312 Japanese Patent Laid-Open No. 2012-25811 Japanese Patent Laid-Open No. 2012-58643 Japanese Patent Laid-Open No. 2007-284516

The alkanolphenol-type benzotriazole-based polymers and sesamol-type benzotriazole-based polymers described in these publications did not have absorption performance in the short visible light wavelength region of 420 to 450 nm, and the paint using them and the visible light short wavelength region of the film coated with the paint. The blocking performance was insufficient.

In addition, even if a monomer absorbing a visible light short wavelength region of 400 nm to 450 nm is added to the coating material and the coated film and used in a blended state, the elution of the ultraviolet absorbing component from the coating film, bleeding out, or in the coating film There were problems with the crystallization of the absorbent component or compatibility with other compounding materials.

Therefore, the subject of the present invention is a benzotriazole-based (co)polymer having absorption performance in a wide range of ultraviolet wavelengths from 300 to 400 nm while absorbing light in the short-wavelength region of visible light up to around 450 nm, a paint containing the same, and the paint To provide a film coated with.

In order to solve the above problems, the present inventors have studied the UV-absorbing benzotriazole-based copolymer, the paint containing the same, and furthermore the film coated with the paint, having a novel molecular structure different from that of the conventional benzotriazole-based monomer A benzotriazole-based (co)polymer formed by polymerizing or copolymerizing a raw material monomer including a benzotriazole-based monomer was discovered, and the present invention was reached.

That is, the present invention is the most important feature of using a benzotriazole-based UV-absorbing polymer formed by polymerizing a raw material containing a metoquinone-type benzotriazole-based monomer represented by Formula 1 as a polymerizable monomer.

[Formula 1]

In Formula 1, R ¹ is a hydrogen atom or an alkyl group having 1 to 8 carbon atoms. R ² is an alkyl group having 1 to 8 carbon atoms. R ³ is an acryloyloxyalkyl group having 1 to 2 alkyl carbon atoms or a methacryloyl oxyalkyl group having 1 to 2 alkyl carbon atoms.

In addition, the "methoquinone-type benzotriazole-based monomer" as used herein is a derivative from a compound in which a phenol having alkoxy is bonded to the meta position of the 2nd nitrogen atom of the benzotriazole ring, as represented by the above formula (1). , also refers to a molecular structure in which a polymerizable double bond is introduced into the carboxyl group introduced into the benzene moiety of the benzotriazole ring.

In addition, as the polymerizable monomer, the alkanolphenol-type benzotriazole-based monomer represented by Formula 2 is further included as a raw material, and it is preferable to use a benzotriazole-based UV-absorbing polymer formed by copolymerizing it.

[Formula 2]

In Formula 2, R ⁴ is a hydrogen atom or a methyl group, R ⁵ is a linear or branched alkylene group having 1 to 6 carbon atoms, R ⁶ is a hydrogen atom or a hydrocarbon group having 1 to 18 carbon atoms, and R ⁷ is a hydrogen atom, a halogen group, a hydrocarbon group having 1 to 8 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, a cyano group or a nitro group.

In addition, the "alkanolphenol-type benzotriazole monomer" as used herein is a derivative of a compound in which an alkanolphenol is bonded to the 2nd nitrogen atom of the benzotriazole ring as represented by the above formula (2), and the alkanol It refers to a molecular structure in which a polymerizable double bond is introduced into the phenol moiety.

The metoquinone-type benzotriazole-based monomer represented by Formula 1 has two of the maximum absorption wavelengths λ max in the vicinity of 310 nm and 380 nm, and a wide range of ultraviolet wavelengths and short visible wavelengths covering the wavelength range of 300 to 450 nm. It has an absorption spectrum in the region and has the ability to absorb short wavelengths of visible light up to 450 nm.

Therefore, the benzotriazole-based (co)polymer of the present invention, a paint containing the same, and a film coated therewith, have a broad wavelength range of 300 to 450 nm and a short wavelength range of visible light that can respond to the spectral irradiance distribution of the solar ultraviolet part on the ground. The absorption performance is excellent, and the coating material including the same and the film coated with the coating material are excellent in the absorption performance of ultraviolet and visible light wavelengths and the ultraviolet blocking performance.

The alkanolphenol-type benzotriazole-based monomer represented by the above formula (2) is a known benzotriazole-based monomer that is generally used in existing, benzotriazole-based UV-absorbing polymers, and a representative industrial product is 2-[2-hydroxy -5-(methacryloyloxyethyl)phenyl]-2H-benzotriazole. The maximum absorption wavelength λ max has an ultraviolet absorption spectrum of 338 nm and a range covering 250 to 380 nm, but the ultraviolet absorption ability in a long wavelength region of 380 nm or more is extremely low.

Therefore, in a preferred embodiment of the benzotriazole-based (phase) polymer of the present invention, a metoquinone-type benzotriazole-based monomer represented by Formula 1 and an alkanolphenol-type benzotriazole-based monomer represented by Formula 2 are included as raw material monomers. By copolymerizing with the raw material monomer, the absorption performance is excellent in a wider range of UV rays of 250 to 450 nm, and the paint including the same and the film coated with the coating material have even more excellent UV absorption performance and UV blocking performance.

In addition, since the benzotriazole-based (co)polymer of the present invention is a polymer, it is possible to form a coating film by itself. Therefore, the problem of the elution of the ultraviolet-absorbing component from the coating film, or a bleed-out does not arise. Furthermore, by appropriately selecting monomers other than the UV-absorbing monomer constituting the polymer to form a copolymer, the polymer polarity can be freely changed. Therefore, crystallization of the ultraviolet-absorbing component in the coating film and the problem of compatibility with other resins and compounding materials do not arise.

1 is an ultraviolet absorption spectrum of the compound of Example 1 of the present invention.
2 is an ultraviolet absorption spectrum of the compound of Example 2 of the present invention.
3 is an ultraviolet absorption spectrum of the compound of Example 3 of the present invention.
4 is an ultraviolet absorption spectrum of the compound of Example 4 of the present invention.
5 is an ultraviolet absorption spectrum of the compound of Comparative Example 1.
6 is an ultraviolet absorption spectrum of the compound of Comparative Example 2.

The details of the present invention will be described below. The benzotriazole-based UV-absorbing polymer of the present invention is formed by polymerizing or copolymerizing a raw material containing the metoquinone-type benzotriazole-based monomer represented by Formula 1 as a polymerizable monomer. In addition, it is formed by copolymerizing a raw material further including an alkanolphenol-type benzotriazole-based monomer represented by Formula 2 as a polymerizable monomer. Moreover, you may contain the polymerizable monomer other than that in the said raw material as needed.

In the metoquinone-type benzotriazole-based monomer represented by Formula 1, in Formula 1, ^{the substituent represented by R 1 is} composed of a hydrogen atom or an alkyl group having 1 to 8 carbon atoms, and ^{the substituent represented by R 2} has 1 to 8 carbon atoms. and ^{benzotriazoles composed of an alkyl group of R 3} , an acryloyloxyalkyl group having 1 to 2 alkyl carbon atoms, or a methacryloyloxyalkyl group having 1 to 2 alkyl carbon atoms.

As a specific material name of the metoquinone-type benzotriazole-based unit, 2-methacryloyloxyethyl 2-(2-hydroxy-5-methoxyphenyl)-2H-benzotriazole-5-carboxylate, 2- Acryloyloxyethyl 2-(3-tert-butyl-2-hydroxy-5-methoxyphenyl)-2H-benzotriazole-5-carboxylate, 2-methacryloyloxyethyl 2-(3- tert-butyl-2-hydroxy-5-methoxyphenyl)-2H-benzotriazole-5-carboxylate, etc. are mentioned, but it is not limited to the said specific example. In addition, these metoquinone type benzotriazole type monomers may be used by 1 type, and may use 2 or more types.

The alkanolphenol-type benzotriazole-based monomer represented by Formula 2 is always, in Formula 2, ^{a substituent represented by R 4} is a hydrogen atom or a methyl group, ^{and a substituent represented by R 5} is a linear or branched alkyl having 1 to 6 carbon atoms. Rene group, ^{a substituent represented by R 6} is a hydrogen atom or a hydrocarbon group having 1 to 18 carbon ^{atoms, a substituent represented by R 7} is a hydrogen atom, a halogen group, a hydrocarbon group having 1 to 8 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, cya Benzotriazoles composed of no group or nitro group.

Specific material names of alkanolphenol-type benzotriazole units include 2-[2-hydroxy-5-(methacryloyloxymethyl)phenyl]-2H-benzotriazole, 2-[2-hydroxy-5 -(acryloyloxymethyl)phenyl]-2H-benzotriazole, 2-[2-hydroxy-5-(methacryloyloxyethyl)phenyl]-2H-benzotriazole, 2-[2-hydro Roxy-5-(acryloyloxyethyl)phenyl]-2H-benzotoriazole, 2-[2-hydroxy-5-(methacryloyloxypropyl)phenyl]-2H-benzotriazole, 2-[ 2-hydroxy-5-(acryloyloxypropyl)phenyl]-2H-benzotriazole, 2-[2-hydroxy-5-(methacryloyloxybutyl)phenyl]-2H-benzotriazole; 2-[2-hydroxy-5-(acryloyloxybutyl)phenyl]-2H-benzotriazole, 2-[2-hydroxy-5-(methacryloyloxyhexyl)phenyl]-2H-benzo Triazole, 2-[2-hydroxy-5-(acryloyloxyhexyl)phenyl]-2H-benzotriazole, 2-[2-hydroxy-3-t-butyl-5-(methacrylo Iloxyethyl)phenyl]-2H-benzotriazole, 2-[2-hydroxy-3-t-butyl-5-(acryloyloxyethyl)phenyl]-2H-benzotriazole, 2-[2- Hydroxy-5-(methacryloyloxyethyl)phenyl]-5-chloro-2H-benzotriazole, 2-[2-hydroxy-5-(acryloyloxyethyl)phenyl]-5-chloro- 2H-benzotriazole, 2-[2-hydroxy-5-(methacryloyloxyethyl)phenyl]-5-methoxy-2H-benzotriazole, 2-[2-hydroxy-5-(acryl) Royloxyethyl)phenyl]-5-methoxy-2H-benzotriazole, 2-[2-hydroxy-5-(methacryloyloxyethyl)phenyl]-5-cyano-2H-benzotriazole , 2-[2-hydroxy-5-(acryloyloxyethyl)phenyl]-5-cyano-2H-benzotriazole, 2-[2-hydroxy-5-(methacryloyloxyethyl) Phenyl]-5-t-butyl-2H-benzotriazole, 2-[2-hydroxy-5-(acryloyloxyethyl)phenyl]-5-t-butyl-2H-benzotriazole, 2-[ 2-hydroxy-5-(methacryloyloxyethyl)phenyl]-5-nitro-2H-benzotriazole, 2-[2-hydroxy-5-(acryloyloxyethyl)phenyl]-5- nitro-2H-benzotriazole, and the like, but are not limited thereto. In addition, these alkanol phenol type benzotriazole type monomers may be used by 1 type, and may use 2 or more types.

In the benzotriazole-type copolymer of this invention, you may copolymerize with polymerizable monomers other than the said benzotriazole-type monomer as a polymerizable monomer which is the raw material. Other polymerizable monomers that can be copolymerized with the benzotriazole-based monomer are not particularly limited, and can be appropriately selected and used. For example, methyl (meth) acrylate, ethyl (meth) acrylate, propyl ( Meth) acrylate, isopropyl (meth) acrylate, butyl (meth) acrylate, isobutyl (meth) acrylate, t-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, octyl ( (meth)acrylic acid alkyl esters such as meth)acrylate, nonyl (meth)acrylate, lauryl (meth)acrylate, and stearyl (meth)acrylate. and hydroxyl group-containing unsaturated monomers such as hydroxyethyl (meth) acrylate, hydroxypropylethyl (meth) acrylate, hydroxybutyl (meth) acrylate, and caprolactone-modified hydroxy (meth) acrylate. Furthermore, oxide ring containing unsaturated monomers, such as glycidyl (meth)acrylate and oxetane (meth)acrylate, are mentioned. Further (meth)acrylamide, N,N'-dimethylaminoethyl (meth)acrylate, (meth)acrylonitrile, (meth)acryloylmorpholine, vinylpyridine, vinylimidazole, N-vinylpyrrol Nitrogen-containing unsaturated monomers, such as money, are mentioned. Furthermore, halogen-containing unsaturated monomers, such as vinyl chloride and vinylidene chloride, are mentioned. Furthermore, aromatic unsaturated monomers, such as styrene and (alpha)-methylstyrene, are mentioned. Furthermore, carboxyl group-containing unsaturated monomers, such as (meth)acrylic acid, a crotonic acid, itaconic acid, a maleic acid, and maleic anhydride, are mentioned. Furthermore, sulfonic acid group containing unsaturated monomers, such as vinyl sulfonic acid and styrene sulfonic acid, are mentioned. Furthermore, 2-(meth)acryloyloxyethyl acid phosphate, 2-(meth)acryloyloxypropyl acid phosphate, 2-(meth)acryloyloxy-3-chloropropyl acid phosphate, 2-(meth)acryl Phosphoric acid group-containing unsaturated monomers, such as royloxyethylphenyl phosphoric acid, are mentioned.

A known method can be used for the method of adjusting the raw material, such as a method of mixing the raw material containing the benzotriazole-based monomer, and is not particularly limited.

Although the radical polymerization initiator used in the polymerization reaction is not particularly limited, for example, 2,2'-azobis-(4-methoxy-2,4-dimethylvaleronitrile), 2,2'-azobis- (2,4-dimethylvaleronitrile), dimethyl 2,2'-azobis-(2-methylpropionate), 2,2'-azobisisobutyronitrile, 2,2'-azobis-( 2-methylbutyronitrile), 1,1'-azobis(cyclohexane-1-carbonitrile), 2,2'-azobis[N-(2-propenyl)-2-methyl propionamide], 1-[(1-cyano-1-methylethyl)azo]formamide, 2,2'-azobis(N-butyl-2-methyl propionamide), , 2,2'-azobis(N-cyclo and azo radical polymerization initiators such as hexyl-2-methyl propionamide, etc. Further, hydrogen peroxide, dibenzoyl peroxide, dilauroyl peroxide, diisobutyryl peroxide, bis(3,5, 5-) Trimethylhexanoyl) peroxide, methyl ethyl ketone peroxide, methyl isobutyl ketone peroxide, cyclohexanone peroxide, methyl cyclohexanone peroxide, t-butyl hydro peroxide, cumene hydro peroxide, diiso Propylbenzene hydroperoxide, p-mentane hydroperoxide, 1,1,3,3-tetramethylbutylhydroperoxide, di-t-butylhydroperoxide, t-butyl-α-cumylperoxide, di-t -Butyl-α-cumyl peroxide, di-α-cumyl peroxide, 1,1-bis(t-butylperoxy)-3,3,5-trimethylcyclohexane, 2,2-bis(t-butylperoxy) and organic peroxide radical polymerization initiators such as oxy)butane, t-butylperoxyacetate, t-butylperoxybenzoate, and bis-(2-ethylhexyl)peroxydicarbonate. Furthermore, persulfate radical polymerization initiators, such as potassium persulfate, ammonium persulfate, and sodium persulfate, etc. are mentioned. Moreover, the usage-amount of a polymerization initiator is not specifically limited, either.

In an aqueous polymerization method such as an emulsion polymerization method, sodium sulfite, L-ascorbic acid, longalite, or the like is used as a reducing agent, so that it may be used as a redox initiator.

When carrying out the copolymerization reaction, you may use a chain transfer agent and a polymerization regulator as needed. Chain transfer agents and polymerization modifiers include n-dodecyl mercaptan, β-mercaptopropionate methyl-3-mercaptopropionate, 2-ethylhexyl-3-mercaptopropionate, n-octyl-3-mer Captopropionate, methoxybutyl-3-mercaptopropionate, stearyl-3-mercaptopropionate, thioglycolic acid, ammonium thioglycolate, thioglycolic acid monoethanolamine, alpha methyl styrene dimer, etc. However, it is not particularly limited. In addition, the usage-amount of a chain transfer agent and a polymerization regulator is not specifically limited.

Examples of the solvent that can be used in the solution polymerization method include toluene, xylene, ethyl acetate, butyl acetate, serosolve acetate, dimethyl ketone, methyl ethyl ketone, methyl isobutyl ketone, and the like, but is not particularly limited. Moreover, the usage-amount of a solvent is not specifically limited, either.

Surfactants that can be used in the emulsion polymerization method include sodium lauryl sulfate, ammonium lauryl sulfate, sodium polyoxyethylene lauryl ether acetate, polyoxyethylene lauryl ether ammonium acetate, sodium polyoxyethylene lauryl ether sulfate, polyoxyethylene Ammonium lauryl ether sulfate, sodium dodecylbenzene sulfonate, ammonium dodecylbenzene sulfonate, polyoxyethylene lauryl ether, polyoxyethylene cetyl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene Octyldodecyl ether, lauryl trimethylammonium chloride, stearyl trimethylammonium chloride, cetyl trimethylammonium chloride, octadecyoxypropyl trimethylammonium chloride, distearyl dimethylammonium chloride, partially saponified polyvinyl alcohol, fully saponified polyvinyl alcohol, poly Sodium acrylate, ammonium polyacrylate, styrene-sodium acrylate copolymer, styrene-ammonium acrylate copolymer, styrene-alphamethylstyrene-sodium acrylate copolymer, styrene-alphamethylstyrene-ammonium acrylate copolymer, styrene-sodium maleate copolymer , styrene-ammonium maleate copolymer, polyvinylpyrrolidone, and the like, but is not particularly limited thereto. Moreover, the usage-amount of surfactant is not specifically limited, either.

Examples of the dispersing agent that can be used in the suspension polymerization method include, but are not particularly limited to, partially saponified polyvinyl alcohol, fully saponified polyvinyl alcohol, sodium polyacrylate, methyl cellulose, carboxymethyl cellulose, and polyethylene oxide. Also, the amount of the dispersant used is not particularly limited.

The polymerization reaction temperature is preferably in the range of room temperature to 200°C, more preferably in the range of 40°C to 140°C, but is not particularly limited to these ranges. The reaction time is not particularly limited, and conditions may be appropriately set so that the polymerization reaction is completed depending on the composition of the monomer composition used, the kind of polymerization initiator, and the like.

As described above, the benzotriazole-based UV-absorbing polymer of the present invention has a configuration formed by (co)polymerizing a raw material containing the metoquinone-type benzotriazole-based monomer represented by Formula 1 as a polymerizable monomer. More preferably, it has a configuration formed by (co)polymerizing a raw material further comprising an alkanolphenol-type benzotriazole-based monomer represented by Formula 2 as a polymerizable monomer. That is, since it is (co)polymerized with a raw material containing a UV-absorbing monomer having UV-absorbing ability over the entire wavelength range of 280 to 400 nm, a wide range of UV wavelengths covering the entire wavelength range of 280 to 450 nm and short wavelengths of visible light It has absorption in the region and has the ability to absorb short wavelengths of visible light up to around 450 nm.

The paint containing the benzotriazole-based (co)polymer of the present invention is a benzotriazole-based (co)polymer formed by (co)polymerizing a raw material containing the metoquinone-type benzotriazole-based monomer represented by Formula 1 above. . More preferably, it has a configuration including a benzotriazole-based copolymer formed by copolymerizing the raw material further including an alkanolphenol-type benzotriazole-based monomer represented by Chemical Formula 2. The form of the paint may include a water-based paint, a solvent-based paint, an ultraviolet curable paint, a thermosetting paint, a clear paint, a pigment paint, a dye paint, and the like, but is not particularly limited. In addition, materials other than the benzotriazole-based (co)polymer constituting the paint, a solvent, a crosslinking agent, a curing agent, a catalyst, a filler, a leveling agent, a plasticizer, a stabilizer, a dye, a pigment, etc. are not particularly limited, and may be appropriately selected can be used

The film coated with a paint containing the benzotriazole-based (co)polymer of the present invention is a benzotriazole-based (co)polymer formed by (co)polymerizing a raw material containing the metoquinone-type benzotriazole-based monomer represented by Formula 1 above. It is a film coated with a paint composition including More preferably, it is a film coated with a paint having a composition including a benzotriazole-based copolymer formed by copolymerizing a raw material further containing an alkanolphenol-type benzotriazole-based monomer represented by Chemical Formula 2. The types of films are polyester film, cellulose film, polyolefin film, polyamide film, polystyrene film, vinyl chloride film, vinylidene chloride film, polyvinyl alcohol film, polycarbonate film, polyE Although a mid-type film etc. are mentioned, It is not specifically limited.

As a method of coating the film with a paint containing a benzotriazole-based (co)polymer, the paint containing the benzotriazole-based (co)polymer is roll-coated, reverse roll-coated, gravure coating, knife coating, blade coating, rod coating , air doctor coating, curtain coating, fountain coating, kiss coating, screen coating, spin coating, cast coating, spray coating, electrodeposition coating, extrusion coating, Langmuir Blotjet (LB) method, etc. no. Furthermore, as a site|part of the coating film containing the benzotriazole type (co)polymer of this invention, although the surface of a film, the back surface, both surfaces, and between lamination|stacking, etc. are mentioned, it is not specifically limited.

Example

Hereinafter, the present invention will be described in more detail with reference to Examples and Comparative Examples of benzotriazole-based (co)polymers, paints and films coated with them, but the present invention is not limited to these forms. In addition, "%" described in a synthesis example, an Example, and a comparative example shows "weight%", and "part" shows a "weight part".

〔One. Synthesis of benzotriazole-based monomers]

(Synthesis Example 1)

[Compound (a); Synthesis of 2-methacryloyl oxyethyl 2-(3-tert-butyl-2-hydroxy-5-methoxyphenyl)-2H-benzotriazole-5-carboxylate]

[Formula 3]

. . . compound (a)

Attach a beaded condenser, thermometer, and stirrer to a 200 mL four-necked flask, add 100 mL of water, 6.5 g (0.061 mol) of sodium carbonate, and 20.0 g (0.110 mol) of 4-amino-3-nitrobenzoic acid to dissolve, 36 % aqueous sodium nitrite solution 22.7 g (0.118 mol) was added. To a 500 mL four-necked flask, attach a condenser with a bead, a thermometer, and a stirrer, add 100 mL of water, 43.0 g (0.274 mol) of 62.5% sulfuric acid, mix, and add dropwise to cooled to 3 to 7 ° C. Aqueous solution of diazonium salt was obtained by stirring at the same temperature for 2 hours. Attach a beaded condenser, thermometer, and stirring device to a 1000 mL four-neck flask, add 18.0 g (0.100 mol) of 2-tert-butyl-4-methoxyphenol, 10 mL of isopropyl alcohol, and 140 mL of water and mix, Aqueous solution of diazonium salt is added dropwise at 5 to 10°C, stirred at 5 to 10°C for 2 hours, and then stirred at 10 to 15°C for 12 hours, 2-tert-butyl-6-(4-carboxy-2-nitro A phenylazo)-4-methoxyphenol slurry liquid was obtained. 27.8 g (0.222 mol) of 32% sodium hydroxide aqueous solution and 200 mL of isopropyl alcohol were added, and the lower aqueous layer was separated and removed at 70 degreeC. 30.0 g (0.222 mol) of 32% aqueous sodium hydroxide solution, 200 mL of water, and 0.4 g of hydroquinone were added, and 6.0 g (0.072 mol) of 60% hydrazine hydrate was added dropwise at 40 to 50° C. over 1 hour, at the same temperature. Stirred for 2 hours. The pH was adjusted to 4 with 62.5% sulfuric acid, and the resulting precipitate was filtered, washed with water and dried, and 5-carboxy-2-(3-tert-butyl-2-hydroxy-5-methoxy phenyl)-2H-benzo 23.6 g of triazole N-oxide was obtained.

Attach a beaded condenser, thermometer, and stirrer to a 500 mL four-necked flask, and add 5-carboxy-2-(3-tert-butyl-2-hydroxy-5-methoxyphenyl)-2H-benzotriazole N - 23.6 g (0.066 mol) of the oxide, 100 mL of isopropyl alcohol, 100 mL of water, 24.0 g (0.192 mol) of a 32% aqueous sodium hydroxide solution, and 12.0 g (0.111 mol) of thiourea dioxide at 70 to 80 ℃ 3 added over time. The mixture was stirred at the same temperature for 1 hour, the lower aqueous layer was separated and removed, and the pH was adjusted to 4 with 62.5% sulfuric acid, and the resulting precipitate was filtered, washed with water, and dried, and 5-carboxy-2-(3-tert). 20.3 g of -butyl-2-hydroxy-5-methoxyphenyl)-2H-benzotriazole was obtained.

Attach a beaded condenser, thermometer, and stirrer to a 300 mL four-necked flask, and add 20.3 of 5-carboxy-2-(3-tert-butyl-2-hydroxy-5-methoxyphenyl)-2H-benzotriazole g (0.059 mol), 100 mL of toluene, 13.0 g (0.109 mol) of thionyl chloride, and 2.0 mL of N,N-dimethylformamide were added, and the mixture was stirred at 60 to 70°C for 3 hours. The solvent was recovered under reduced pressure, 100 mL of toluene, 14.0 g (0.108 mol) of 2-hydroxyethyl methacrylate, and 8.3 g (0.105 mol) of pyridine were added, and the mixture was stirred at 60 to 70°C for 1 hour. 20 mL of water and 9.0 g (0.057 mol) of 62.5% sulfuric acid are added, and the lower aqueous layer is separated and removed at 60 to 70 ° C., further 20 mL of water is added, and the lower aqueous layer is separated and removed at 60 to 70 ° C. , toluene was recovered under reduced pressure, 90 mL of isopropyl alcohol was added, and the resulting precipitate was filtered, washed and dried to obtain 23.1 g of crude crystals. This crude crystal was recrystallized from isopropyl alcohol to obtain 22.2 g of compound (a). Yield 49% (from 2-tert-butyl-4-methoxyphenol).

In addition, the purity of compound (a) was measured by HPLC analysis.

<Measurement conditions>

Device: L-2130 (manufactured by Hitachi High-Technologies Co., Ltd.)

Column used: SUMIPAX ODS A-212 6.0Х150 mm 5 μm

Column temperature: 40℃

Mobile phase: methanol/water=95/5 (phosphoric acid 3 ml/L)

Flow rate: 1.0 mL/min

Detection: UV 250 nm

<Measurement result>

HPLC cotton 100% purity 98.5%

Moreover, as a result of performing NMR measurement of compound (a), the result which supported the said structure was obtained. The measurement conditions are as follows.

<Measurement conditions>

Device: JEOL JNM-AL300

Resonant frequency: 300 MHz (1H-NMR)

Solvent: chloroform-d

As an internal standard of 1H-NMR, tetramethylsilane was used, and the chemical shift value was expressed as δ value (ppm), and the coupling constant was expressed as Hertz. Also, s stands for singlet, d stands for doublet, and m stands for multiplet. The same applies to the following examples. Further, Examples 2 to 6 below were also subjected to NMR measurement under the same measurement conditions as in this Example. The contents of the obtained NMR spectrum are as follows.

δ=11.44(s, 1H, phenol-OH), 8.73(s, 1H, benzotriazol-H), 8.13(d, 1H, J=9.0Hz, benzotriazol-H), 7.98(d, 1H, J=11.1Hz) , benzotriazol-H), 7.82(s, 1H, phenol-H), 7.05(s, 1H, phenol-H), 6.18(s, 1H, C=CH ₂ -H), 5.62(s, 1H, C= CH ₂ -H), 4.65(m, 2H, methacryloyl-O-CH ₂ -H), 4.56(m, 2H, benzotriazol-CO-O-CH ₂ -H), 3.93(s, 3H, phenol-O- CH ₃ -H), 1.98 (s, 3H, CH ₂ =C-CH ₃ -H), 1.56 (s, 9H, tert-butyl-H)

(Synthesis Example 2)

[Compound (b); Synthesis of 2-methacryloyl oxyethyl 2-(2-hydroxy-5-methoxyphenyl)-2H-benzotriazole-5-carboxylate]

[Formula 4]

. . . compound (b)

Compound (b) was obtained in a yield of 5% (from 4-methoxyphenol) in the same manner as in Synthesis Example 1 except that 2-tert-butyl-4-methoxyphenol was used as 4-methoxyphenol. The melting point was 94°C, the maximum absorption wavelength λ max was 309.8 nm and 373.2 nm, and the molar extinction coefficient ε of the wavelength was 14700 and 13100, respectively.

In addition, the purity of compound (b) was measured by HPLC analysis.

<Measurement conditions>

Device: L-2130 (manufactured by Hitachi High-Technologies Co., Ltd.)

Column used: Inertsil ODS-3 4.6Х150 mm 5 μm

Column temperature: 25℃

Mobile phase: acetonitrile/water=9/1 (phosphoric acid 3 mL/L)

Flow rate: 1.0 mL/min

Detection: UV 250 nm

<Measurement result>

HPLC cotton whiteness 93.4%

Moreover, as a result of performing NMR measurement of compound (b), the result which supported the said structure was obtained. The contents of the obtained NMR spectrum are as follows.

δ=10.71(s, 1H, phenol-OH), 8.73(s, 1H, benzotriazole-H), 8.12(d, 1H, J=9.6Hz, benzotriazole-H), 7.98(d, 1H, J=9.6Hz) , benzotriazole-H), 7.15 (m, 3H, phenol-H), 6.18 (s, 1H, C=CH ₂ -H), 5.62 (s, 1H, C=CH ₂ -H), 4.65 (m, 2H) , methacryloyl-O-CH ₂ -H), 4.57(m, 2H, benzotriazole-CO-O-CH ₂ -H), 3.89(s, 3H, phenol-O-CH ₃ -H), 1.98(s, 3H) , CH ₂ =C-CH ₃ -H)

〔2. Benzotriazole-based monomer commercially available]

As the alkanolphenol-type benzotriazole-based monomer, commercially available 2-[2-hydroxy-5-(methacryloyloxyethyl)phenyl]-2H-benzotriazole (Otsuka Chemical RUVA-93) was used. Hereinafter, 2-[2-hydroxy-5-(methacryloyloxyethyl)phenyl]-2H-benzotriazole is written as "compound (c)".

[3. Sesamol-type benzotriazole-based monomer commercially available]

Sesamol-type benzotriazole-based monomer is a commercially available 2-[2-(6-hydroxy-1,3-benzodioxol-5-yl)-2H-1,2,3-benzotriazol-5-yl]ethyl= Methacrylate (Cypro Chemical R26) was used. Hereinafter, 2-[2-(6-hydroxy-1,3-benzodioxol-5-yl)-2H-1,2,3-benzotriazol-5-yl]ethyl = methacrylate is referred to as “compound ( d) Write ”.

〔4. Benzotriazole-based (co)polymer synthesis]

(Example 1)

A dimroth cooler, mercury thermometer, nitrogen gas injection tube, and stirring device are attached to a four-neck flask, and 20 parts of compound (a) as a monomer composition, methyl methacrylate (hereinafter referred to as “MMA”) 20 parts, and 60 parts of methyl ethyl ketone (hereinafter, referred to as "MEK") as a solvent, and 2,2'-azobis-methylbutyronitrile as a polymerization initiator (hereinafter, referred to as "AMBN") 1.5 Part was added, and the inside of the flask was purged with nitrogen for 1 hour at a nitrogen gas flow rate of 10 mL/min while stirring, followed by polymerization at a reaction solution temperature of 80 to 86° C. under reflux for 10 hours. After completion of the polymerization reaction, 101.5 parts of a UV-absorbing copolymer solution was obtained.

(Example 2)

The monomer composition in Example 1 was described as 20 parts of compound (a), 8 parts of MMA, styrene (hereinafter referred to as “St”), and 2-hydroxyethyl methacrylate (hereinafter referred to as “HEMA”). ) The polymerization reaction operation was the same as in Example 1 except that it was set to 8 parts, and a UV-absorbing copolymer solution was obtained.

(Example 3)

In Example 1, the monomer composition was mixed with 10 parts of compound (a), 10 parts of compound (c), 18 parts of cyclohexyl methacrylate (hereinafter referred to as “CHMA”), and 1,2,2,6,6 -Pentamethyl piperidyl methacrylate (hereinafter referred to as "HALS") The polymerization reaction operation was the same as in Example 1 except that it was used in 2 parts to obtain a UV-absorbing copolymer solution.

(Example 4)

The same polymerization reaction as in Example 1 was performed except that the monomer composition in Example 1 was 1 part of compound (b) and 19 parts of MMA, 80 parts of MEK as a solvent and 0.8 parts of AMBN as a polymerization initiator. , to obtain a UV-absorbing copolymer solution.

(Comparative Example 1)

A polymerization reaction operation was carried out as in Example 1 except that the monomer composition in Example 1 was 20 parts of compound (c) and 20 parts of MMA, to obtain a UV-absorbing copolymer solution.

(Comparative Example 2)

A polymerization reaction operation was carried out as in Example 1 except that the monomer composition in Example 1 was 20 parts of compound (d) and 20 parts of MMA, to obtain a UV-absorbing copolymer solution.

〔4. evaluation〕

The non-volatile content, solution viscosity, molecular weight, and maximum absorption wavelength λ max of the UV-absorbing copolymer solutions obtained in Examples 1 to 4 and Comparative Examples 1 and 2 of the UV-absorbing copolymer were measured. Furthermore, by producing a paint containing a UV-absorbing copolymer, and making a coating film coated with it on a polyester film, a UV blocking function confirmation test for the purpose of confirming the protective performance of the dye used for sublimation transfer printing, UV rays from the coating film Dissolution of the absorbent component, bleed-out, crystallization, and confirmation of compatibility of the compounding material were tested.

The non-volatile content was calculated from the residual resin amount after weighing 0.5 g of the UV-absorbing copolymer solution obtained in an aluminum dish, drying at 100°C for 1 hour, and further drying at 150°C for 5 hours.

The viscosity was measured for the solution viscosity at 25 ° C. using an EH-type viscometer (TV-22, Donggi Industries, Ltd.).

Molecular weight was determined using GPC system HLC-8320GPC EcoSEC (Dongso Co., Ltd.), tetrahydrofuran as the eluent, and TSKgelGMHXL-L (Dongso Co., Ltd.) as the separation column, and the weight average molecular weight (Mw) in terms of polystyrene using a polystyrene calibration curve, number average Molecular weight (Mn) and polydispersity (Mw/Mn) were measured.

The maximum absorption wavelength λ max and the ultraviolet absorption spectrum were measured using a spectrophotometer (Hitachi High-Technologies Co., Ltd. U-3900H) after desolving the obtained ultraviolet absorbing copolymer solution by drying under reduced pressure, making it a 40 ppm chloroform solution. did.

In the UV protection function test, using the UV-absorbing copolymer solutions obtained in Examples 1 to 3 and Comparative Examples 1 and 2, a UV-absorbing copolymer-containing paint was prepared, and sublimation transfer printing using the coating film of the paint The UV absorption blocking performance of the dye used for Write the order below.

5 parts of toluene and 5 parts of MEK were added to 10 parts of the UV-absorbing copolymer solutions obtained in Examples 1 to 3 and Comparative Examples 1 and 2 to prepare a paint including the UV-absorbing copolymer, and a glass plate (TP base, thickness) 2 mm), after applying the above paint with a bar coater #20, dried at 80° C. for 1 minute, and further dried at 100° C. for 30 seconds, to obtain a coating film containing a UV-absorbing copolymer. The film thickness of the coating film containing the UV-absorbing copolymer using a film thickness meter (FILMETRICS F20) was approximately 3 µm, respectively.

Then, yellow paint, cyan paint, magenta paint, and three-color transfer film used in a commercially available sublimation transfer compact photo printer (Canon SELPHY CP600) were obtained. In accordance with JISK5701-1:2000, the deterioration of the transfer film due to UV irradiation of dye was measured using a xenon weathermeter (Suga Tester SX-75), irradiance of 180W, black panel temperature 63±3℃, and UV continuous irradiation for 100 hours. From this result, fading deterioration of dye was made into the ultraviolet-ray function evaluation standard.

Similarly, using the transfer film of the dye, the transfer film was protected with a glass plate coated with a paint containing each of the ultraviolet absorbing copolymers prepared above, and similarly, according to JISK5701-1:2000, deterioration of ultraviolet fading of the dye was confirmed. The evaluation is made into 5 stages in consideration of the degree of fading by visual confirmation, level 5 is no change, level 4 can confirm slight ink fading, level 3 can confirm ink fading, and level 2 is mostly ink Discoloration and level 1 were taken as ink decomposition and disappearance.

Elution of UV-absorbing components from the coating film, bleed-out, crystallization, and change of the coating film state of compounding material compatibility were tested using an optical microscope to measure the change over time of the coating film containing each of the UV-absorbing copolymers prepared above. observed. Evaluation was made into the visual sensitivity evaluation of the state of a coating film for 1 month from film production.

In Examples 1 to 4 and Comparative Examples 1 and 2, the non-volatile content, molecular weight, maximum absorption wavelength λ max, wavelength range 300 nm, 360 nm, 400 nm, 420 nm, 450 nm of the UV absorbing copolymer solutions obtained in Comparative Examples 1 and 2 As a result of the absorbance and UV blocking function test evaluation results, the UV absorption spectrum is shown in FIGS. .

Synthetic No.
Raw materials Example comparative example One 2 3 4 One 2 compound (a) 20 20 10 compound (b) One compound (c) 10 20 compound (d) 20 MMA 20 8 19 20 20 St 8 HEMA 2 CHMA 18 HALS 2 AMBN 1.5 1.5 1.5 0.8 1.5 1.5 MEK 60 60 60 80 60 60 Sum 101.5 101.5 101.5 100.8 101.5 101.5 Non-volatile content (%) 43.4 43.1 43.7 22.9 41.5 40.9 polymer solution viscosity
(mPa s/25°C) 100 36 66 4 242 58 polymer
Molecular Weight Mw 20356 12413 17898 12539 15077 18844 Mn 5271 4585 5184 4175 6896 6328 Mw/Mn 3.862 2.707 3.452 3.003 2.186 2.978 Maximum absorption wavelength λ max 314.0 nm 314.0 nm 326.4 nm 314.0 nm 338.8 nm 369.2 nm 383.6 nm 383.8 nm - 383.8 nm - - UV absorption spectrum Figure 1 Figure 2 Fig. 3 Fig. 4 Fig. 5 Fig. 6 Absorbance at each wavelength 300 nm 0.7280 0.7232 0.9475 0.8568 1.2970 0.5620 360 nm 0.6421 0.6380 0.7663 0.8171 0.9630 1.5720 400 nm 0.7218 0.7257 0.3510 0.5866 0.0010 0.6890 420 nm 0.3833 0.3912 0.1836 0.1865 0.0000 0.0660 450 nm 0.0327 0.0342 0.0138 0.0058 0.0000 0.0000 UV protection function test result 5 5 4 - 3 5 state of the film Early Transparency Transparency Transparency Transparency Transparency Transparency 1 month later no change no change no change no change no change no change

The meanings of the symbols in Table 1 are as follows.

"Compound (a)": 2-methacryloyl oxyethyl 2-(3-tert-butyl-2-hydroxy-5-methoxyphenyl)-2H-benzotriazole-5-carboxylate

"Compound (b)": 2-methacryloyl oxyethyl 2-(2-hydroxy-5-methoxyphenyl)-2H-benzotriazole-5-carboxylate

“Compound (c)”: 2-[2-hydroxy-5-(methacryloyloxyethyl)phenyl]-2H-benzotriazole

"Compound (d)": 2-[2-(6-hydroxy-1,3-benzodioxol-5-yl)-2H-1,2,3-benzotriazol-5-yl]ethyl = methacryl rate

「MMA」: methyl methacrylate

「St」 : Styrene

"HEMA": 2-hydroxyethyl methacrylate

"CHMA": cyclohexyl methacrylate

"HALS": 4-methacryloyloxy-1,2,2,6,6-pentamethylpiperidine

「AMBN」: 2,2'-azobis-methylbutyronitrile

「MEK」: methyl ethyl ketone

As is clear from the results of Examples 1 to 4, the benzotriazole-based (co)polymer of the present invention has a broad ultraviolet absorption wavelength region for the ultraviolet wavelength region 300 nm to 400 nm of the solar irradiance distribution reaching from the sun on the ground. have In addition, it has absorption in the short wavelength range of visible light of about 400 to 450 nm, which is pointed out to cause damage to organic matter or the human body. Accordingly, a paint using the same and a film coated with the same also have a broad range of ultraviolet and visible light absorption wavelength ranges from 300 nm to 450 nm. Therefore, it was found that, when used as a UV absorption blocking protective material, the object to be protected can be protected from UV rays at a very high level. It was also found that there were no problems with elution or bleed-out of the ultraviolet absorbing component from the coating film, crystallization of the ultraviolet absorbing component within the coating film, or compatibility with other compounding materials.

Industrial Applicability

The benzotriazole-based (co)polymer of the present invention can absorb a wide wavelength range of 300 to 400 nm, which can correspond to the spectral irradiance distribution of the solar ultraviolet part, among the ultraviolet region of sunlight, which has been difficult to absorb conventionally, and also organic substances However, it is a material capable of absorbing visible light in the short wavelength region of 400 to 450 nm, which is pointed out to cause damage to the human body. In addition, in the benzotriazole-based (co)polymer of the present invention, which can be obtained by copolymerizing the conventionally known benzotriazole-based monomer that absorbs an ultraviolet region of 250 nm to 380 nm as a raw material monomer, absorption performance in a wider ultraviolet region this is excellent It can also be coated by using it as a paint. Therefore, it can be suitably used for protecting the human body or materials deteriorated by light in the short wavelength range of ultraviolet and visible light, and among them, it can be suitably used for display optical films, spectacle lenses, and the like.

Claims (4)

Benzotriazole-based (co)polymer, characterized in that it is formed by polymerizing a raw material containing a metoquinone-type benzotriazole-based monomer represented by Formula 1 as a polymerizable monomer:
[Formula 1]

In Formula 1, R ¹ is a hydrogen atom or an alkyl group ^{having 1 to 8 carbon atoms, R 2} is an alkyl group having 1 to 8 carbon atoms, and R ³ is an acryloyloxyalkyl group having 1 to 2 alkyl carbon atoms or an alkyl group having 1 to 2 alkyl carbon atoms. of a methacryloyl oxyalkyl group. The benzotriazole-based (co)polymer according to claim 1, further comprising an alkanolphenol-type benzotriazole-based monomer represented by Formula 2 as the polymerizable monomer as a raw material:
[Formula 2]

In Formula 2, R ⁴ is a hydrogen atom or a methyl group, R ⁵ is a linear or branched alkylene group having 1 to 6 carbon atoms, R ⁶ is a hydrogen atom or a hydrocarbon group having 1 to 18 carbon atoms, and R ⁷ is a hydrogen atom, a halogen group, a hydrocarbon group having 1 to 8 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, a cyano group or a nitro group. A UV-absorbing paint containing the benzotriazole-based (co)polymer of claim 1 or 2. The film coated with the UV-absorbing paint of claim 3.

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