KR20190132534A - UV absorbing paint and film coated - Google Patents

Abstract

[상기 화학식에서, R¹이 수소원자 또는 알킬기, R²가 알킬기, R³가 아크릴로일옥시알킬기 또는 메타크릴로일옥시알킬기]A benzotriazole-based polymer formed by polymerizing a raw material containing a methoquinone type benzotriazole-based monomer of the formula Provide a (co) polymer.

[Wherein 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

The present invention relates to a benzotriazole-based (co) polymer having ultraviolet absorbing performance and absorbing ultraviolet light in a broad wavelength range and light in a short wavelength range of visible light, 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 coatings, preventing crystallization of ultraviolet absorbing components in coatings, improving weather resistance of coatings, and improving compatibility with other resins and blending materials. Ultraviolet absorbing (co) polymers are used.

A benzotriazole copolymer mainly formed by copolymerizing a monomer composition comprising one or more kinds of alkanolphenol-type benzotriazole-based ultraviolet absorbent monomers having ultraviolet absorbance in a relatively short region around 300 nm to 360 nm is mainly used. It is used (for example, patent documents 1-2).

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

These benzotriazole type ultraviolet absorbing monomers are generally used in a display display apparatus, for example, adding a ultraviolet absorber to optical films, such as a polarizing plate protective film, and preventing 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, an ultraviolet absorber is added to an antireflection film. In addition, various organic materials such as fluorescent materials and phosphorescent materials are used for the light emitting elements of the organic EL display, and ultraviolet absorbers are added to the surface film of the display in order to prevent deterioration due to the ultraviolet rays of these organic materials.

In addition, in the human body, it is well known that the skin and the eyeballs are tanned by ultraviolet rays and cause various diseases. In order to prevent various diseases of the eyeballs caused by ultraviolet rays, an ultraviolet absorber is added to the spectacle lens or the contact lens to prevent ultraviolet rays. It is generally done to prevent eye contact.

In addition, in recent years, it has been pointed out that not only ultraviolet rays of 400 nm or less in sunlight, but also light in the visible wavelength short wavelength region of about 400 to 450 nm damage organic matters and the human body. There is a need for a light absorber capable of absorbing even visible light in the short wavelength range.

In each of the above applications, a light absorbing agent for efficiently absorbing light in the ultraviolet and visible short wavelength ranges has been proposed, and as a compound having absorption in such a wavelength region, for example, as described in Patent Documents 4 to 5, Indole derivatives, pyrrolidine-amide derivatives, and xanthone derivatives. However, these compounds generally have low light resistance, deteriorate due to exposure to sunlight, and thus have a low light absorption ability, and therefore cannot be used for a long time. Moreover, patent documents 4-5 do not have description of light resistance.

Although the sesamol type benzotriazole type copolymer of patent document 3 generally known as high light resistance can absorb the ultraviolet-ray and the visible light short wavelength region, absorption of 420 nm or more is weak and it is the thing of the ultraviolet region of 300-330 nm vicinity. There is a problem of weak absorption.

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

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

Moreover, even if it adds the monomer which absorbs the visible light short wavelength region 400 nm-450 nm region to a coating material and it is used in a compounding state, elution, bleed out of the ultraviolet absorption component from a coating film, and the inside of a coating film There were problems of crystallization of the absorbent components and compatibility with other compounding materials.

Therefore, the subject of this invention is the benzotriazole-type (co) polymer which has absorption capability in 300-400 nm of wide ultraviolet wavelength range, absorbing the light of the visible light short wavelength region to 450 nm vicinity, the coating material and the said coating material It is to provide a film coated with.

MEANS TO SOLVE THE PROBLEM In order to solve the said subject, the present inventor examined the ultraviolet-absorbing benzotriazole type copolymer, the coating material containing this, and also the film which coated the said paint, As a result, it has a novel molecular structure different from the conventional benzotriazole type monomer. The benzotriazole type (co) polymer formed by superposing | polymerizing or copolymerizing the raw material monomer containing a benzotriazole type monomer was discovered, and the present invention was reached.

That is, the main feature of the present invention is to make a benzotriazole-based ultraviolet absorbent polymer formed by polymerizing a raw material containing a methoquinone type benzotriazole-based monomer represented by the formula (1) as the 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 acryloyl oxyalkyl 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 type monomer" as used in this specification is a derivative | guide_body from the compound which couple | bonded the phenol which has alkoxy to the meta position of the nitrogen atom of the 2nd nitrogen atom of a benzotriazole ring as shown by the said Formula (1). And a molecular structure in which a polymerizable double bond is introduced into a carboxyl group introduced into the benzene site of the benzotriazole ring.

The polymerizable monomer further includes an alkanolphenol type benzotriazole monomer represented by the formula (2) as a raw material, and is preferably a benzotriazole ultraviolet absorbent polymer formed by copolymerization.

[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, R ⁷ is It is a hydrogen atom, a halogen group, a C1-C8 hydrocarbon group, a C1-C4 alkoxy group, a cyano group, or a nitro group.

In addition, the "alkanol phenol type benzotriazole type monomer" as used in this specification is a derivative of the compound which couple | bonded the alkanol phenol to the 2nd nitrogen atom of a benzotriazole ring as shown by the said Formula (2), and said alkanol The molecular structure which introduce | transduced a polymerizable double bond into a phenol part is said.

Metoquinone-type benzotriazole-based monomer represented by the formula (1), the maximum absorption wavelength λ max is two around 310 nm and 380 nm, a wide range of ultraviolet wavelength range and visible light short wavelength covering 300 to 450 nm wavelength range It has an absorption spectrum in the region and a short wavelength absorption of visible light up to around 450 nm.

Therefore, the benzotriazole-based (co) polymer of the present invention and the paint and the coated film including the same have a broad wavelength range of 300 to 450 nm and a short wavelength range of visible light, which correspond to the spectral irradiance distribution of the solar ultraviolet portion. The absorption performance is excellent, the paint and the coating film containing the same, the absorption of ultraviolet and short wavelength of visible light and excellent UV blocking performance.

The alkanolphenol type benzotriazole monomer represented by the above formula (2) is an existing known benzotriazole monomer generally used for the existing benzotriazole ultraviolet absorbing polymer, 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 in a range covering 338 nm and 250 to 380 nm, but the ultraviolet absorption ability in the long wavelength region of 380 nm or more is extremely low.

Therefore, in the preferable form of the benzotriazole type (phase) polymer of this invention, the metoquinone type benzotriazole type monomer represented by General formula (1) and the alkanol phenol type benzotriazole type monomer represented by said Formula (2) are contained as a raw material monomer. By copolymerizing with the raw material monomer, it is excellent in the absorbing performance in a broader ultraviolet region of 250 to 450 nm, and the coating and the film coated with the same have further excellent ultraviolet absorbing performance and UV blocking performance.

In addition, since the benzotriazole-based (co) polymer of the present invention is a polymer, a coating film can be formed per se. Therefore, there is no problem of elution or bleed out of the ultraviolet absorbing component from the coating film. Furthermore, polymer polarity can be changed freely by selecting monomers other than the ultraviolet absorbing monomer which comprises a polymer timely and making it into a copolymer. Therefore, there is no problem of crystallization of the ultraviolet absorbing component in the coating film and compatibility with other resins and compounding materials.

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

The detail of this invention is demonstrated below. The benzotriazole-based ultraviolet absorbent polymer of the present invention is formed by polymerizing or copolymerizing a raw material including a metoquinone type benzotriazole-based monomer represented by the formula (1) as a polymerizable monomer. In addition, the polymerizable monomer is formed by copolymerizing a raw material further comprising an alkanolphenol type benzotriazole monomer represented by the formula (2). Moreover, the said raw material may also contain the other polymerizable monomer as needed.

In the metoquinone type benzotriazole-based monomer represented by Formula 1, in Formula 1, the substituent represented by R ¹ is a hydrogen atom or an alkyl group having 1 to 8 carbon atoms, and the substituent represented by R ² is 1 to 8 carbon atoms. Benzotriazoles composed of an alkyl group having 1 to 2 acryloyl oxyalkyl group represented by R ³ or an alkyl group having 1 to 2 methacryloyl oxyalkyl group represented by R ³ .

Specific name of the metoquinone type benzotriazole-based unit is 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 and the like, but are not limited to the above specific examples. In addition, these metoquinone type benzotriazole type monomers may be used by one type, and may use two or more types.

Alkanol phenol type benzotriazole-based monomer represented by Formula 2 is at all times Formula 2, R substituent is R ⁴ is represented by ⁴ is a hydrogen atom or a methyl group, a straight or branched of the substituents represented by R ⁵ having 1 to 6 carbon atoms The chain alkylene group, the substituent represented by R ⁶ is a hydrogen atom or a hydrocarbon group of 1 to 18 carbon atoms, the substituent represented by R ⁷ is a hydrogen atom, a halogen group, a hydrocarbon group of 1 to 8 carbon atoms, alkoxy of 1 to 4 carbon atoms Benzotriazoles composed of a group, a cyano group or a nitro group.

Specific material names of the alkanolphenol type benzotriazole-based monomers include 2- [2-hydroxy-5- (methacryloyloxymethyl) phenyl] -2H-benzotriazole and 2- [2-hydroxy-5 -(Acryloyloxymethyl) phenyl] -2H-benzotriazole, 2- [2-hydroxy-5- (methacryloyloxyethyl) phenyl] -2H-benzotriazole, 2- [2-hydroxy Hydroxy-5- (acryloyloxyethyl) phenyl] -2H-benzotriazole, 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-benzotria , 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 Hydroxy-5- (methacryloyloxyethyl) phenyl] -5-methoxy-2H-benzotriazole, 2- [2-hydroxy-5- (acryloyloxyethyl) 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-benzo Triazole, 2- [2-hydroxy-5- (acryloyloxyethyl) phenyl] -5-t-butyl-2H-benzotriazole, 2- [2-hydroxy-5- (methacryloyl Oxyethyl) phenyl] -5-nitro-2H-benzotriazole, 2- [2-hydroxy-5- (acryloyloxyethyl) phenyl] -5-ni Tro-2H-benzotriazole etc. are mentioned, It is not limited to the said specific example. In addition, these alkanolphenol type benzotriazole type monomers may be used by one type, and may use two 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. The other polymerizable monomer which can be copolymerized with the benzotriazole-based monomer is not particularly limited and may be appropriately selected and used. For example, methyl (meth) acrylate, ethyl (meth) acrylate, propyl ( Meta) acrylate, isopropyl (meth) acrylate, butyl (meth) acrylate, isobutyl (meth) acrylate, t-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, octyl ( (Meth) acrylic-acid alkylesters, such as a meta) acrylate, a nonyl (meth) acrylate, a lauryl (meth) acrylate, and a stearyl (meth) acrylate. And hydroxyl group-containing unsaturated monomers such as hydroxyethyl (meth) acrylate, hydroxy propylethyl (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. Furthermore, (meth) acrylamide, N, N'-dimethylaminoethyl (meth) acrylate, (meth) acrylonitrile, (meth) acryloyl morpholine, vinylpyridine, vinylimidadol, N-vinylpyrroli Nitrogen-containing unsaturated monomers, such as don, 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, crotonic acid, itaconic acid, 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 well-known method can be used for the method of adjusting the said raw material, such as the mixing method of the raw material containing the said benzotriazole type monomer, and is not specifically limited.

The radical polymerization initiator used in the polymerization reaction is not particularly limited, but 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 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, methylethylketone peroxide, methyl Sobutyl ketone peroxide, cyclohexanone peroxide, methylcyclohexanone peroxide, t-butylhydro peroxide, cumenehydro peroxide, diisopropylbenzene hydroperoxide, p-mentane hydroperoxide, 1,1, 3,3-tetramethylbutylhydroperoxide, di-t-butylhydroperoxide, t-butyl-α-cumylperoxide, di-t-butyl-α-cumylperoxide, di-α-cumylperoxide, 1,1-bis (t-butylperoxy) -3,3,5-trimethylcyclohexane, 2,2-bis (t-butylperoxy) butane, t-butylperoxy acetate, t-butylperoxybenzo Organic peroxide radical polymerization initiators such as ate 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 aqueous polymerization methods, such as emulsion polymerization method, it is good also as a redox initiator by using sodium sulfite, L-ascorbic acid, rongalit, etc. as a reducing agent.

When making a copolymerization reaction, you may use a chain transfer agent and a polymerization regulator as needed. As a chain transfer agent and a polymerization regulator, n-dodecyl mercaptan, n-dodecyl mercaptan, (beta)-mercapto propionic acid methyl-3- mercapto propionate, 2-ethylhexyl-3- mercapto propionate, n-octyl-3-mercaptopropionate, methoxy butyl-3-mercaptopropionate, stearyl-3-mercaptopropionate, thioglycolic acid, thioglycolic acid ammonium, thioglycolic acid monoethanolamine , Alpha methyl styrene dimer and the like, but is not particularly limited. Moreover, the usage-amount of a chain transfer agent and a polymerization regulator is not specifically limited, either.

Examples of the solvent that can be used in the solution polymerization method include toluene, xylene, ethyl acetate, butyl acetate, cervical acetate, dimethyl ketone, methyl ethyl ketone, and methyl isobutyl ketone, but are 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, lauryl ammonium sulfate, polyoxyethylene lauryl ether sodium acetate, polyoxyethylene lauryl ether ammonium acetate, polyoxyethylene lauryl ether sodium sulfate, polyoxyethylene Ammonium lauryl 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, octadecyloxy propyl trimethylammonium chloride, distearyl dimethylammonium chloride, partially saponified polyvinyl alcohol, fully saponified polyvinyl alcohol, poly Sodium acrylate, polyacrylic acid Monium, styrene-sodium acrylate copolymer, styrene-ammonium acrylate copolymer, styrene-alphamethylstyrene-sodium acrylate copolymer, styrene-alphamethylstyrene-ammonium acrylate copolymer, styrene-sodium maleate copolymer, styrene-maleic acid Ammonium copolymer, polyvinylpyrrolidone, and the like, but are not particularly limited. Moreover, the usage-amount of surfactant is not specifically limited, either.

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

The polymerization reaction temperature is preferably in the range of room temperature to 200 ° C, and more preferably in the range of 40 ° C to 140 ° C, but is not particularly limited to these ranges. Reaction time is not specifically limited, What is necessary is just to set conditions suitably so that a polymerization reaction may be completed according to the composition of the monomer composition to be used, the kind of polymerization initiator, etc.

As mentioned above, the benzotriazole type ultraviolet absorbing polymer of this invention is a structure formed by (co) polymerizing the raw material containing the metoquinone type benzotriazole type monomer represented by the said Formula (1) as a polymerizable monomer. More preferably, it is a structure formed by (co) polymerizing the raw material which further contains the alkanolphenol-type benzotriazole-type monomer represented by General formula (2) as a polymerizable monomer. That is, since it is (co) polymerized with a raw material containing an ultraviolet absorbing monomer having ultraviolet absorbance in the entire wavelength region of 280 to 400 nm, a wide range of ultraviolet wavelength region and visible light short wavelength covering the entire wavelength region of 280 to 450 nm. It has absorption in the region and has a short wavelength absorption capability of visible light up to around 450 nm.

The coating material containing the benzotriazole-based (co) polymer of the present invention is a composition including a benzotriazole-based (co) polymer formed by (co) polymerizing a raw material containing a methoquinone-type benzotriazole-based monomer represented by the formula (1). . More preferably, it is the structure containing the benzotriazole type copolymer formed by copolymerizing the said raw material which further contains the alkanol phenol type benzotriazole type monomer represented by General formula (2). The form of the paint may include an aqueous paint, a solvent 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, such as resin, a solvent, a crosslinking agent, a hardening | curing agent, a catalyst, a filler, a leveling agent, a plasticizer, a stabilizer, a dye, and a pigment other than the benzotriazole type (co) polymer which comprise a coating material, are not specifically limited, Can be used.

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

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

Example

Hereinafter, although an Example and a comparative example of a benzotriazole-type (co) polymer, the coating material and the coating film which contain the same, this invention are demonstrated in detail, but this invention is not limited to these forms. In addition, "%" described in the synthesis example, the Example, and the comparative example represents "weight%", and "part" represents "weight part".

〔One. Benzotriazole monomer synthesis]

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 condenser with a bead, a thermometer, and a stirring device to a 200 mL four-necked flask, dissolve in 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. 22.7 g (0.118 mol) of% aqueous sodium nitrite solution was added. This solution was attached to a 500 mL four-necked flask with a condenser with a bead, a thermometer, and a stirring device. Then, 100 mL of water and 43.0 g (0.274 mol) of 62.5% sulfuric acid were added to the solution, and the mixture was cooled to 3 to 7 ° C. It stirred at the same temperature for 2 hours, and obtained the diazonium salt aqueous solution. Attach a condenser with a bead, a thermometer, and a stirring device to a 1000 mL four-neck flask, add 18.0 g (0.100 mol) of 2-tert-butyl-4-methoxy phenol, 10 mL of isopropyl alcohol, and 140 mL of water, and mix, The diazonium salt aqueous solution was dripped at 5-10 degreeC, and it stirred at 5-10 degreeC for 2 hours, and then stirred at 10-15 degreeC for 12 hours, and 2-tert- butyl-6- (4-carboxy-2-nitro A phenylazo) -4-methoxy phenol slurry liquid was obtained. 27.8 g (0.222 mol) of 32% aqueous sodium hydroxide solutions and 200 mL of isopropyl alcohol were added, and the lower aqueous layer was isolate | 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 DEG C over 1 hour, and at the same temperature. Stir for 2 hours. PH 6 with 62.5% sulfuric acid, the resulting precipitate was filtered, washed with water, dried and 5-carboxy-2- (3-tert-butyl-2-hydroxy-5-methoxy phenyl) -2H-benzo 23.6 g of triazole N-oxide was obtained.

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

A condenser with a bead, a thermometer, and a stirring device are attached to a 300 mL four neck flask, and 20.3 5-carboxy-2- (3-tert-butyl-2-hydroxy-5-methoxyphenyl) -2H-benzotriazole is added. g (0.059 mol), 100 mL of toluene, 13.0 g (0.109 mol) of thionyl chloride, 2.0 mL of N and N-dimethylformamide were added thereto, 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 methacrylic acid, and 8.3 g (0.105 mol) of pyridine were added, followed by stirring at 60 to 70 ° C for 1 hour. 20 mL of water and 9.0 g (0.057 mol) of 62.5% sulfuric acid were added to separate and remove the lower aqueous layer at 60 to 70 ° C. Furthermore, 20 mL of water was added to separate and remove the lower aqueous layer at 60 to 70 ° C. Toluene was recovered under reduced pressure, 90 mL of isopropyl alcohol was added, and the produced 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 the compound (a) was measured by HPLC analysis.

<Measurement conditions>

Equipment: L-2130 (manufactured by Hitachi High Technologies)

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

Column Temperature: 40 ℃

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

Flow rate: 1.0 mL / min

Detection: UV 250 nm

<Measurement result>

HPLC cotton whiteness 98.5%

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

<Measurement conditions>

Device: JEOL JNM-AL300

Resonant frequency: 300 MHz (1H-NMR)

Solvent: Chloroform-d

Tetramethylsilane was used as an internal standard of 1H-NMR, and the chemical shift value was δ (ppm), and the coupling constant was Hertz. S stands for singlet, d stands for doublet, and m stands for multiplet. The same applies to the following examples. In addition, the following Examples 2-6 also performed NMR measurement on the same measurement conditions as this Example. The content of the obtained NMR spectrum is as follows.

δ = 11.44 (s, 1H, phenol-OH), 8.73 (s, 1H, benzotriazol-H), 8.13 (d, 1H, J = 9.0 Hz, benzotriazol-H), 7.98 (d, 1H, J = 11.1 Hz , 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 yield 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. Melting | fusing point was 94 degreeC, the maximum absorption wavelength (lambda) max was 309.8 nm and 373.2 nm, and the molar extinction coefficient (epsilon) of those wavelengths was 14700 and 13100, respectively.

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

<Measurement condition>

Equipment: L-2130 (manufactured by Hitachi High Technologies)

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 supports the said structure was obtained. The content of the obtained NMR spectrum is as follows.

δ = 10.71 (s, 1H, phenol-OH), 8.73 (s, 1H, benzotriazole-H), 8.12 (d, 1H, J = 9.6 Hz, benzotriazole-H), 7.98 (d, 1H, J = 9.6 Hz , 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 monomer commercially available product]

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

[3. Sesamol type benzotriazole monomer commercial item]

Sesamol type benzotriazole-based monomers are commercially available 2- [2- (6-hydroxy-1,3-benzodioxol-5-yl) -2H-1,2,3benzotriazol-5-yl] ethyl = Methacrylate (ciprochemical R26) was used. Hereinafter, 2- [2- (6-hydroxy-1,3-benzodioxol-5-yl) -2H-1,2,3benzotriazol-5-yl] ethyl = methacrylate is referred to as "compound ( d) 」.

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

(Example 1)

A dimroth cooler, a mercury thermometer, a nitrogen gas blowing tube, and a stirring apparatus were attached to the four-necked flask, and 20 parts of compound (a) and methyl methacrylate (hereinafter referred to as "MMA") were written as the monomer composition. Part 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 After the addition, the flask was purged with nitrogen in a flask at a nitrogen gas flow rate of 10 mL / min for 1 hour while stirring, followed by polymerization at reflux for 10 hours at a reaction solution temperature of 80 to 86 ° C. After completion | finish of a polymerization reaction, 101.5 parts of ultraviolet absorbing copolymer solutions were obtained.

(Example 2)

The monomer composition in Example 1 is described as 20 parts of compound (a), 8 parts of MMA, styrene (hereinafter referred to as "St"), and 2-hydroxy ethyl methacrylate (hereinafter referred to as "HEMA"). A polymerization reaction operation was performed in the same manner as in Example 1 except that 8 parts were used), thereby obtaining a UV absorbing copolymer solution.

(Example 3)

In Example 1, the monomer composition is 10 parts of the compound (a), 10 parts of the compound (c), cyclohexyl methacrylate (hereinafter referred to as "CHMA") 18 parts, and 1,2,2,6,6 -Pentamethyl piperidyl methacrylate (hereinafter referred to as "HALS") except that it was made into 2 parts, the polymerization reaction operation similar to Example 1 was performed, and the ultraviolet absorbing copolymer solution was obtained.

(Example 4)

The monomer composition in Example 1 was used as the compound (b) 1 part and 19 parts of MMA, and the polymerization reaction operation similar to Example 1 was performed except having made 80 parts of MEK as a solvent, and 0.8 parts of AMBN as a polymerization initiator. , Ultraviolet absorbing copolymer solution was obtained.

(Comparative Example 1)

Except having made the monomer composition in Example 1 into 20 parts of compounds (c) and 20 parts of MMA, the polymerization reaction operation was performed like Example 1 and the ultraviolet absorbing copolymer solution was obtained.

(Comparative Example 2)

Except having made the monomer composition in Example 1 into 20 parts of compounds (d) and 20 parts of MMA, the polymerization reaction operation similar to Example 1 was performed and the ultraviolet absorbing copolymer solution was obtained.

〔4. evaluation〕

The non volatile matter, solution viscosity, molecular weight, and maximum absorption wavelength λ max of the ultraviolet absorbent copolymer obtained in Examples 1 to 4 and Comparative Examples 1 and 2 were measured. Furthermore, a coating material containing an ultraviolet absorbent copolymer was prepared, and a coating film coated on the polyester film was produced to check the UV blocking function for the purpose of confirming the protective performance of the dye used for sublimation transfer printing, and ultraviolet rays from the coating film. The elution, bleed out, crystallization, and confirming compatibility of the blended materials of the absorbent component were carried out.

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

The viscosity measured the solution viscosity in 25 degreeC using the EH type | mold viscosity meter (Synthetic Industry Co., Ltd. TV-22).

The molecular weight was obtained by using the GPC system HLC-8320GPC EcoSEC (Esoso Co., Ltd.) as the eluent as tetrahydrofuran and the separation column as TSKgelGMHXL-L (Dongso Co., Ltd.). Molecular weight (Mn) and polydispersity (Mw / Mn) were measured.

The maximum absorption wavelength λ max and the ultraviolet absorption spectrum were measured by using a spectrophotometer (Hitachi High Technologies U-3900H) as a 40 ppm chloroform solution after desolvation of the obtained ultraviolet absorbent copolymer solution by vacuum drying. did.

In the ultraviolet ray blocking function test, a UV absorbing copolymer-containing paint was produced using the ultraviolet absorbing copolymer solution obtained in Examples 1 to 3, Comparative Examples 1 and 2, and the sublimation transfer printing by the coating film of the coating material. The ultraviolet absorption blocking performance of the dye used for was confirmed. Write the sequence below.

5 parts of toluene and 5 parts of MEK were added to 10 parts of the ultraviolet absorbent copolymer solutions obtained in Examples 1 to 3, Comparative Examples 1 and 2, and a paint containing the ultraviolet absorbent copolymer was produced to obtain a glass plate (TP vapor, thickness). 2 mm) was coated with the bar coater # 20, and then dried at 80 ° C. for 1 minute, and then dried at 100 ° C. for 30 seconds to obtain a coating film containing an ultraviolet absorbent copolymer. The film thickness of the coating film containing the ultraviolet absorbing copolymer using the film thickness meter (FILMETRICS F20) was about 3 micrometers, respectively.

Subsequently, yellow paints, cyan paints, magenta paints, and three-color transfer films used in commercially available sublimation transfer method compact photo printers (Canon SELPHY CP600) were obtained. Degradation by dye ultraviolet irradiation of the transfer film according to JISK5701-1: 2000 was irradiated with 180W of irradiance using a xenon weather meter (Suga tester SX-75), a black panel temperature of 63 ± 3 ° C, and 100 hours of ultraviolet irradiation. From this result, the fading deterioration of the dye was used as the evaluation criteria of the ultraviolet ray function.

Similarly, the transfer film was protected by the glass plate coated with the coating material containing each ultraviolet absorbent copolymer produced above using the transfer film of dye, and similarly the ultraviolet-ray fading deterioration of the dye was confirmed according to JISK5701-1: 2000. The evaluation was carried out in five stages by considering the degree of visual inspection of the fading, the level 5 is unchanged, the level 4 can see some ink fading, the level 3 can identify the ink fading, and the level 4 is mostly ink Discoloration and level 1 were made into ink dissipation loss.

The elution, bleed out, crystallization of the ultraviolet absorbing component from the coating film and the change of the coating state of the compounding material compatibility test were conducted by using an optical microscope to determine the change over time of the coating film containing each of the ultraviolet absorbing copolymers prepared above. Observed. Evaluation was made into the visual sensitivity evaluation of the coating film state for 1 month from film manufacture.

Non-volatile content, molecular weight, maximum absorption wavelength λ max of the ultraviolet absorbing copolymer solution obtained in Examples 1 to 4, Comparative Examples 1 and 2 in the wavelength range 300 nm, 360 nm, 400 nm, 420 nm, 450 nm The absorbance and ultraviolet ray screening test evaluation results of the results of the elution, bleed out, crystallization, and change of coating state of the compatibility of the compounding material of the ultraviolet absorbing component from the coating film are shown in Table 1, and the ultraviolet absorption spectrum is shown in Tables 1 to 6. .

Synthesis 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 Nonvolatile matter (%) 43.4 43.1 43.7 22.9 41.5 40.9 Polymer solution viscosity
(mPas / 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 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 1 2 3 4 5 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 test results 5 5 4 - 3 5 Coating state 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- (methacryloyl oxyethyl) phenyl] -2H-benzotriazole

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

`` MMA '': Methyl methacrylate

「St」: Styrene

`` HEMA '': 2-hydroxyethyl methacrylate

`` CHMA '': cyclohexyl methacrylate

"HALS": 4--methacryloyl oxy-1,2,2,6,6-pentamethylpiperidine

"AMBN": 2,2'-azobis-methylbutyronitrile

「MEK」: Methyl ethyl ketone

As is evident from the results of Examples 1-4, the benzotriazole-based (co) polymers of the present invention cover a broad range of ultraviolet absorption wavelengths for the 300-400 nm ultraviolet wavelength region of the solar irradiance distribution reaching from the sun on the ground. Have It also has absorption in the visible light short wavelength region of about 400 to 450 nm, which is pointed out to damage organic matter or the human body. Therefore, the paint and the film coated with the same also have an absorption wavelength region of a wide range of ultraviolet and visible light short wavelengths of 300 nm to 450 nm. Therefore, it was found that the protection target can be protected from ultraviolet rays at a very high level when used as an ultraviolet absorption blocking protective material. Moreover, it turned out that neither the elution of the ultraviolet absorbing component from a coating film, the breeding out, the crystallization of the ultraviolet absorbing component in a coating film, or the compatibility with another compounding material arise.

Industrial availability

The benzotriazole-based (co) polymer of the present invention can absorb a wide range of wavelengths from 300 to 400 nm, which can correspond to the spectral irradiance distribution of the solar ultraviolet portion, among the ultraviolet region of sunlight, which has been difficult to absorb in the past. It is an absorbable material in the visible light short wavelength region of about 400 to 450 nm, which has been pointed out to damage the human body. In addition, in the benzotriazole-based (co) polymer of the present invention, which can be obtained by further copolymerizing a benzotriazole-based monomer absorbing the ultraviolet region of 250 nm to 380 nm as a raw material monomer, absorption performance in a wider ultraviolet region. This is excellent. It may also be coated as a paint. Therefore, it can use suitably for the protection of the material deteriorated by the light of ultraviolet-ray and visible-light short wavelength region, and a human body, and can use suitably for the optical film for display, spectacle lens, etc. especially.

Claims (4)

A benzotriazole-based (co) polymer, characterized in that formed by polymerizing a raw material containing a methoquinone type benzotriazole-based monomer represented by the general 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 acryloyl oxyalkyl group having 1 to 2 alkyl carbon atoms or 1 to 2 alkyl carbon atoms Is a methacryloyl oxyalkyl group. The benzotriazole copolymer according to claim 1, further comprising, as a raw material, an alkanolphenol type benzotriazole monomer represented by Formula 2 as a polymerizable monomer.
[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, R ⁷ is It is a hydrogen atom, a halogen group, a C1-C8 hydrocarbon group, a C1-C4 alkoxy group, a cyano group, or a nitro group. The ultraviolet absorbent coating containing the benzotriazole type (co) polymer of Claim 1 or 2. The film coated with the ultraviolet absorbent paint of claim 3.

Images