JP5132218B2 - Ultraviolet absorber and resin composition containing the same - Google Patents

Description

  The present invention relates to an ultraviolet absorber and a resin composition containing the same, and more particularly to an ultraviolet absorber that exhibits high absorption in the ultraviolet region of 380 nm or less and transmits a wavelength of 400 nm or more and a resin composition containing the same. .

  In display devices that have been developed in recent years, anti-reflection used in polarizing plate protective films, retardation films, viewing angle widening films, optical correction films, brightness enhancement films, and plasma displays used in liquid crystal display devices. Optical films made of resin having various functions such as films, optical correction films used in organic EL displays, and light emitter protective films are used.

  Resin is a material that is lighter in weight, better in processability and easier to handle than glass, and therefore is used in many optical fields such as optical lenses, prisms, and optical fibers in addition to the optical film. However, the resin has a problem that it deteriorates due to ultraviolet rays, and the influence of this problem is particularly remarkable in an optical film that directly receives light from a light source.

Therefore, the optical film made of resin is provided with a measure not to be exposed to ultraviolet rays, and as a general countermeasure example, a method for suppressing deterioration of the optical film by blending an optical film with an ultraviolet absorber is known. . For example, Patent Document 1 blends an olefin resin having a maleimide component with an ultraviolet absorber selected from the group consisting of a triazine ultraviolet absorber, a benzotriazole ultraviolet absorber, and a benzophenone ultraviolet absorber. A method has been proposed, and Patent Document 2 proposes the use of an ultraviolet absorber selected from benzophenone-based and benzotriazole-based ultraviolet absorbers for an optical film.
JP 2003-026942 A JP 2003-043259 A

  However, the conventional ultraviolet absorber has a problem that the absorption shifts to the lower wavelength side and the absorption near 380 nm is insufficient, so that a large amount of blending is required, and a bleedout is caused by a large amount of blending. In addition, the optical film must have a property of transmitting light in the visible light region. However, the conventional ultraviolet absorber has a slight absorption in the visible light region, and the optical film is colored.

  Accordingly, an object of the present invention is to provide an ultraviolet absorber that cuts ultraviolet rays of 380 nm or less and transmits visible light of 400 nm or more without causing bleed-out, and a resin composition containing the same.

  As a result of intensive studies to solve the above-mentioned problems, the present inventors have found that an ultraviolet absorber comprising a specific carbazole compound can achieve the above object, and have completed the present invention.

〔（式（１）中、ｎは１又は２を表し、ｎが１の場合、Ａは、水素原子、置換基を有してもよく分岐を有していてもよい炭素原子数１〜１２のアルキル基、置換基を有していてもよい炭素原子数６〜１２のアリール基、置換基を有していてもよい炭素原子数５〜１２のシクロアルキル基又はこれらの組み合わせを表し、ｎが２の場合、Ａは、置換されていてもよく分岐を有していてもよい炭素原子数１〜１２のアルキレン基、置換基を有していてもよい炭素原子数６〜１２のアリーレン基、置換基を有していてもよい炭素原子数５〜１２のシクロアルキレン基又はこれらの組み合わせを表し、Ｂは下記一般式（２）、

（式（２）中、Ｒは水素原子、置換基を有してもよく分岐を有していてもよい炭素原子数１〜１２のアルキル基、置換基を有してもよく分岐を有していてもよい炭素原子数２〜１８のアルケニル基、置換基を有してもよい炭素原子数５〜１２のシクロアルキル基又は置換基を有してもよい炭素原子数６〜１２のアリール基を表し、Ｘは酸素原子又は−ＮＨ−を表し、ｎが２の場合、Ｒ及びＸは各々独立である）の構造の化合物を表す〕で表されるカルバゾール化合物であることを特徴とするものである。 That is, the ultraviolet absorber of the present invention has the following general formula (1),

[In the formula (1), n represents 1 or 2, and when n is 1, A is a hydrogen atom, may have a substituent and may have 1 to 12 carbon atoms. And an alkyl group having 6 to 12 carbon atoms that may have a substituent, a cycloalkyl group having 5 to 12 carbon atoms that may have a substituent, or a combination thereof, and n When A is 2, A is an alkylene group having 1 to 12 carbon atoms which may be substituted or branched and an arylene group having 6 to 12 carbon atoms which may have a substituent. Represents a cycloalkylene group having 5 to 12 carbon atoms which may have a substituent or a combination thereof, and B represents the following general formula (2),

(In Formula (2), R may have a hydrogen atom, a substituent, or a C1-C12 alkyl group that may have a branch, a substituent, or a branch. An alkenyl group having 2 to 18 carbon atoms, a cycloalkyl group having 5 to 12 carbon atoms which may have a substituent, or an aryl group having 6 to 12 carbon atoms which may have a substituent Wherein X represents an oxygen atom or —NH—, and when n is 2, it represents a compound having a structure of R and X are independent from each other)] It is.

（式（３）中、Ｒは、水素原子又は置換基を有してもよく分岐を有していてもよい炭素原子数１〜１２のアルキル基を表し、Ｘは前記と同じものを表し、Ａは置換基を有してもよく分岐を有していてもよい炭素原子数１〜１２のアルキル基を表す）で表される構造のカルバゾール化合物、または、下記一般式（４）、

（式（４）中、Ｒは、各々独立して、水素原子又は置換基を有してもよく分岐を有していてもよい炭素原子数１〜１２のアルキル基を表し、Ａは置換基を有してもよく分岐を有していてもよい炭素原子数１〜１２のアルキレン基又は置換基を有してもよい炭素原子数６〜１２のアリーレン基を表し、Ｘは、各々独立して、前記と同じものを表す）で表される構造のカルバゾール化合物である。 The ultraviolet absorber represented by the general formula (1) is preferably the following general formula (3),

(In Formula (3), R represents a hydrogen atom or a C1-C12 alkyl group which may have a substituent and may have a branch, X represents the same thing as the above, A represents a C 1-12 alkyl group which may have a substituent or may have a branch), or a carbazole compound having a structure represented by the following general formula (4),

(In Formula (4), R represents a hydrogen atom or a C1-C12 alkyl group which may have a hydrogen atom or a substituent, and may have a branch, A is a substituent. Represents an alkylene group having 1 to 12 carbon atoms which may have a branch or an arylene group having 6 to 12 carbon atoms which may have a substituent, and each X is independently The carbazole compound has a structure represented by the same formula as above.

  In addition, the resin composition of the present invention is characterized by containing 0.1 to 10 parts by mass of the above-described ultraviolet absorber with respect to 100 parts by mass of the synthetic resin component.

  According to the present invention, it is possible to provide an ultraviolet absorber that cuts out ultraviolet rays of 380 nm or less and transmits visible light of 400 nm or more without causing bleed out, and a resin composition containing the same.

Hereinafter, the ultraviolet absorbent and the resin composition of the present invention will be described in detail based on preferred embodiments.
The ultraviolet absorber of the present invention is a compound having a carbazole group represented by the general formula (1), and the carbazole group is represented by a structure of the general formula (2).

Examples of the alkyl group having 1 to 12 carbon atoms which may have a branch represented by A in the general formula (1) and R in the general formula (2) may have a substituent. For example, methyl, ethyl, propyl, isopropyl, butyl, sec-butyl, tert-butyl, isobutyl, amyl, isoamyl, tert-amyl, hexyl, 2-hexyl, 3-hexyl, heptyl, 2-heptyl, 3-heptyl , Isoheptyl, tertiary heptyl, n-octyl, isooctyl, tertiary octyl, 2-ethylhexyl, nonyl, isononyl, dodecyl and the like. —CH ₂ — in the alkyl group may be substituted with —O—, —CO—, —COO— or —OCO—, and the hydrogen atom in the alkyl group is a halogen atom, alkenyl group, alkenyl It may be substituted with an oxy group, an alkanoyloxy group, an alkoxycarbonyl group, a nitrile group or a cyano group.

Examples of the alkenyl group having 2 to 18 carbon atoms which may have a branch represented by R in the general formula (2) and may have a substituent include vinyl, 1-methylethenyl, 2-methylethenyl, propenyl, butenyl, isobutenyl, pentenyl, hexenyl, heptenyl, octenyl, decenyl, Bae Ntadeseniru, octadecenyl and the like, _-CH 2 in the alkenyl group - is, -O -, - CO -, - COO- or -OCO -The hydrogen atom in the alkenyl group may be a halogen atom, an alkyl group, an alkoxy group, an alkenyl group, an alkenyloxy group, an alkoxyalkyl group, an alkanoyloxy group, an alkoxycarbonyl group, a nitrile group or a cyano group. It may be substituted with a group.

  Examples of the cycloalkyl group having 5 to 12 carbon atoms which may have a substituent represented by A in the general formula (1) and R in the general formula (2) include cyclopentyl, cyclohexyl, cyclononyl, And saturated carbocycles such as cyclodecyl, and the hydrogen atoms in the saturated carbocycle are halogen atoms, alkyl groups, alkoxy groups, alkenyl groups, alkenyloxy groups, alkoxyalkyl groups, alkanoyloxy groups, alkoxycarbonyl groups, nitrile groups. Alternatively, it may be substituted with a cyano group.

  Examples of the aryl group having 6 to 12 carbon atoms which may have a substituent represented by A in the general formula (1) and R in the general formula (2) include 1,2-phenyl, 1 , 3-phenyl, 1,4-phenyl, 2,5-dimethyl-1,4-phenyl, biphenyl, naphthyl and the like, and the hydrogen atom in the aromatic ring is a halogen atom, an alkyl group, It may be substituted with an alkoxy group, alkenyl group, alkenyloxy group, alkoxyalkyl group, alkanoyloxy group, alkoxycarbonyl group, nitrile group or cyano group.

  Examples of A in the case where n in the general formula (1) is 2 include those exemplified above in the case where n is 1, and those in which one of hydrogen atoms is substituted with a connector.

  As a preferable specific structure of the compound represented by the general formula (1) in the present invention, the following compound No. 1-No. 9 is mentioned. However, the present invention is not limited by the following compounds.

  Among the compounds exemplified here, in particular, Compound No. 3 and no. The compound No. 4 is particularly preferably used because it has an effect of being excellent in high heat resistance, low volatility and compatibility.

  The usage-amount with respect to the synthetic resin of the ultraviolet absorber of this invention is 0.001-10 mass parts with respect to 100 mass parts of synthetic resin components, Preferably, it is 0.01-5 mass parts. When the amount is less than 0.001 part by mass, the light absorption ability is not sufficiently exhibited. On the other hand, when the amount exceeds 10 parts by mass, bleeding out may occur in the molded product of the resin composition, This is not preferable because there is a risk of deteriorating characteristics.

  Examples of the synthetic resin in which the ultraviolet absorber of the present invention can be used include α-olefins such as polypropylene, high density polyethylene, low density polyethylene, linear low density polyethylene, polybutene-1, and poly-3-methylpentene. Polymer or ethylene-vinyl acetate copolymer, ethylene-ethyl acrylate copolymer, ethylene-methyl acrylate copolymer, ethylene-acrylic acid copolymer, ethylene-methacrylic acid copolymer, ethylene-vinyl alcohol copolymer , Polyolefins such as ethylene-propylene copolymer and copolymers thereof, polyvinyl chloride, polyvinylidene chloride, chlorinated polyethylene, chlorinated polypropylene, polyvinylidene fluoride, rubber chloride, vinyl chloride-vinyl acetate copolymer, chloride Vinyl-ethylene copolymer Vinyl chloride-vinylidene chloride copolymer, vinyl chloride-vinylidene chloride-vinyl acetate terpolymer, vinyl chloride-acrylic acid ester copolymer, vinyl chloride-maleic acid ester copolymer, vinyl chloride-cyclohexyl maleimide copolymer Halogen-containing resins such as coalescence, petroleum resin, coumarone resin, polystyrene, polyvinyl acetate, acrylic resin, styrene and / or α-methylstyrene and other monomers (for example, maleic anhydride, phenylmaleimide, methyl methacrylate, Copolymer (eg, AS resin, ABS resin, MS resin, MBS resin, heat-resistant ABS resin, etc.), polymethyl methacrylate, polyvinyl alcohol, polyvinyl formal, polyvinyl butyral, polyethylene terephthalate, and polybutylene. Linear polyester such as terephthalate, polyamide such as polyphenylene oxide, polycaprolactam and polyhexamethylene adipamide, polycarbonate, polycarbonate / ABS resin, branched polycarbonate, polyacetal, polyphenylene sulfide, polyurethane, triacetyl cellulose, cycloolefin, fiber resin And thermosetting resins such as phenol resins, urea resins, melamine resins, epoxy resins and unsaturated polyester resins. Furthermore, elastomers such as isoprene rubber, butadiene rubber, acrylonitrile-butadiene copolymer rubber, and styrene-butadiene copolymer rubber may be used. Further, it may be polymerized by adding the ultraviolet absorbent of the present invention to a monomer having an ethylenically unsaturated bond. These synthetic resins may be used alone or in combination of two or more.

  Among these resins, AS resin, MS resin, polymethyl methacrylate, polycarbonate, triacetyl cellulose, and cycloolefin are preferably used because they are excellent in transparency, workability, and physical properties.

  In addition, the resin composition of the present invention includes various additives generally used in the above synthetic resins, such as other ultraviolet absorbers, phosphorus antioxidants, phenolic antioxidants different from the present invention. An oxidizing agent or a sulfur-based antioxidant can also be used.

  Examples of the other ultraviolet absorbers include 2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-octoxybenzophenone, 2-hydroxy-4-tert-butyl-4′- 2-hydroxybenzophenones such as (2-methacryloyloxyethoxyethoxy) benzophenone and 5,5′-methylenebis (2-hydroxy-4-methoxybenzophenone); 2- (2-hydroxy-5-methylphenyl) benzotriazole; 2- (2-hydroxy-5-tert-octylphenyl) benzotriazole, 2- (2-hydroxy-3,5-ditert-butylphenyl) -5-chlorobenzotriazole, 2- (2-hydroxy-3- Tert-butyl-5-methylphenyl) -5-chlorobenzotria 2- (2-hydroxy-3-dodecyl-5-methylphenyl) benzotriazole, 2- (2-hydroxy-3-tert-butyl-5-C7-9 mixed alkoxycarbonylethylphenyl) triazole, 2- 2- (2-hydroxyphenyl) such as (2-hydroxy-3,5-dicumylphenyl) benzotriazole, polyethylene glycol ester of 2- (2-hydroxy-3-tert-butyl-5-carboxyphenyl) benzotriazole Benzotriazoles; 2- (2-hydroxy-4-hexyloxyphenyl) -4,6-diphenyl-1,3,5-triazine, 2- (2-hydroxy-4-methoxyphenyl) -4,6-diphenyl -1,3,5-triazine, 2- (2-hydroxy-4-octoxyphenyl) -4,6- (2,4-dimethylphenyl) -1,3,5-triazine, 2- (2-hydroxy-4-acryloyloxyethoxyphenyl) -4,6-bis (2,4-dimethylphenyl) -1,3 2,5-triazine, 2- (2-hydroxy-4- (2-ethylhexyloxyloyloxyethoxyphenyl) -4,6-bis (2,4-dimethylphenyl) -1,3,5-triazine, etc. -(2-hydroxyphenyl) -1,3,5-triazines; phenyl salicylate, resorcinol monobenzoate, 2,4-ditert-butylphenyl-3,5-ditert-butyl-4-hydroxybenzoate, 2, 4-ditert-amylphenyl-3,5-ditert-butyl-4-hydroxybenzoate, hexadecyl-3,5-ditert-butyl-4-hydroxybenzoate Benzoates such as ethates; substituted oxanilides such as 2-ethyl-2′-ethoxy oxanilide, 2-ethoxy-4′-dodecyl oxanilide; ethyl-α-cyano-β, β-diphenyl acrylate, methyl- And cyanoacrylates such as 2-cyano-3-methyl-3- (p-methoxyphenyl) acrylate.

  Examples of the phosphorus antioxidant include triphenyl phosphite, tris (2,4-ditert-butylphenyl) phosphite, tris (nonylphenyl) phosphite, tris (dinonylphenyl) phosphite, tris ( Mono-, di-mixed nonylphenyl) phosphite, bis (2-tert-butyl-4,6-dimethylphenyl) -ethyl phosphite, diphenyl acid phosphite, 2,2'-methylene bis (4,6-di-tert-butyl) Phenyl) octyl phosphite, diphenyl decyl phosphite, phenyl diisodecyl phosphite, tributyl phosphite, tris (2-ethylhexyl) phosphite, tridecyl phosphite, trilauryl phosphite, dibutyl acid phosphite, dilauryl acid phosphite, G Lauryl trithiophosphite, bis (neopentylglycol) 1,4-cyclohexanedimethyldiphosphite, bis (2,4-ditert-butylphenyl) pentaerythritol diphosphite, bis (2,6-ditert-butyl) -4-methylphenyl) pentaerythritol diphosphite, distearyl pentaerythritol diphosphite, tetra (C12-15 mixed alkyl) -4,4'-isopropylidene diphenyl phosphite, bis [2,2'-methylenebis (4 , 6-Diamylphenyl)]-isopropylidene diphenyl phosphite, hydrogenated-4,4'-isopropylidenediphenol polyphosphite, tetratridecyl 4,4'-butylidenebis (2-tert-butyl-5- Methylphenol) diphosphite, hexa ( Tridecyl) -1,1,3-tris (2-methyl-5-tert-butyl-4-hydroxyphenyl) butanetriphosphonite, 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10 -Oxide, 2-butyl-2-ethylpropanediol-2,4,6-tritert-butylphenol monophosphite and the like.

  The usage-amount of the said phosphorus antioxidant is 0.001-10 mass parts with respect to 100 mass parts of synthetic resins, Preferably, it is 0.01-5 mass parts.

  Examples of the phenol-based antioxidant include 2,6-ditert-butyl-p-cresol, 2,6-diphenyl-4-octadecyloxyphenol, stearyl (3,5-ditert-butyl-4- Hydroxyphenyl) propionate, distearyl (3,5-ditert-butyl-4-hydroxybenzyl) phosphonate, tridecyl-3,5-ditert-butyl-4-hydroxybenzylthioacetate, thiodiethylenebis [(3,5 -Di-tert-butyl-4-hydroxyphenyl) propionate], 4,4'-thiobis (6-tert-butyl-m-cresol), 2-octylthio-4,6-di (3,5-di-tert-butyl) -4-hydroxyphenoxy) -s-triazine, 2,2'-methylenebis (4-methyl-6-tert-butylphenol), bis [3,3- (4-hydroxy-3-tert-butylphenyl) butyric acid] glycol ester, 4,4′-butylidenebis (4,6-ditert-butylphenol), 2,2′-ethylidenebis (4,6-di) Tert-butylphenol), 1,1,3-tris (2-methyl-4-hydroxy-5-tert-butylphenyl) butane, bis [2-tert-butyl-4-methyl-6- (2-hydroxy-3) -Tert-butyl-5-methylbenzyl) phenyl] terephthalate, 1,3,5-tris (2,6-dimethyl-3-hydroxy-4-tert-butylbenzyl) isocyanurate, 1,3,5-tris ( 3,5-ditert-butyl-4-hydroxybenzyl) isocyanurate, 1,3,5-tris (3,5-ditert-butyl-4-hydroxybenzyl) -2,4,6-to Limethylbenzene, 1,3,5-tris [(3,5-ditert-butyl-4-hydroxyphenyl) propionyloxyethyl] isocyanurate, tetrakis [methylene-3- (3,5-ditert-butyl- 4-hydroxyphenyl) propionate] methane, 2-tert-butyl-4-methyl-6- (2-acryloyloxy-3-tert-butyl-5-methylbenzyl) phenol, 3,9-bis [2- ( 3-tert-butyl-4-hydroxy-5-methylhydrocinnamoyloxy) -1,1-dimethylethyl] -2,4,8,10-tetraoxaspiro [5.5] undecane], triethylene glycol bis [Β- (3-tert-butyl-4-hydroxy-5-methylphenyl) propionate] and the like.

  The usage-amount of the said phenolic antioxidant is 0.001-10 mass with respect to 100 mass parts of synthetic resins, Preferably, it is 0.01-5 mass parts.

  Examples of the sulfur-based antioxidant include dialkylthiodipropionates such as dilauryl, dimyristyl, myristyl stearyl, and distearyl esters of thiodipropionic acid and polyols such as pentaerythritol tetra (β-dodecyl mercaptopropionate). And β-alkyl mercaptopropionic acid esters.

  The usage-amount of the said sulfur type antioxidant is 0.001-10 mass parts with respect to 100 mass parts of synthetic resins, Preferably, it is 0.01-5 mass parts.

  In particular, phenol-based and phosphorus-based antioxidants are preferably used because they prevent coloring of the synthetic resin.

  In addition, additives that are usually used as necessary, for example, fillers, coloring agents, crosslinking agents, antistatic agents, plate-out prevention agents, surface treatment agents, lubricants, flame retardants, fluorescent agents, antifungal agents , Fungicides, metal deactivators, release agents, pigments, processing aids, antioxidants, light stabilizers, foaming agents, and the like can be used.

  In addition, as an addition method of the above-mentioned other additives used as necessary, a method of adding to the synthetic resin separately from the ultraviolet absorber of the present invention, a mixture previously mixed with the ultraviolet absorber of the present invention, The method of adding the mixture to a synthetic resin, the ultraviolet absorber of the present invention is used as needed, and is mixed with a granulating aid such as a binder, wax, solvent, silica, etc. in advance at a desired ratio, and then granulated. To make a one-pack composite additive, a method of adding the one-pack composite additive to the synthetic resin, or a masterbatch containing the above-mentioned other additives including an ultraviolet absorber, and adding this to the synthetic resin A method or the like can be used.

  Since the ultraviolet absorber of the present invention has the property of absorbing ultraviolet light in the vicinity of 380 nm and transmitting wavelengths of 400 nm or longer, for example, a retardation plate (1/2 wavelength plate, 1/4 wavelength plate, etc.), polarized light, etc. It can be suitably used for an organic glass such as an optical film such as an element, a dichroic polarizing plate, a liquid crystal alignment film, an antireflection film, a selective reflection film, and a viewing angle compensation film, or a spectacle lens film. In addition, building materials such as wall materials, floor materials, window frames, wallpaper, etc. using ultraviolet absorbing ability; wire covering materials; automotive interior and exterior materials; agricultural materials such as houses and tunnels; wraps, trays, etc. Fish food packaging materials; can be used as miscellaneous goods such as paints, hoses, pipes, sheets and toys.

  Examples of the organic glass that can be used include polymethyl methacrylate, polycarbonate, aliphatic allyl carbonate, aromatic allyl carbonate, and polythiourethane.

  Next, the present invention will be described in more detail with reference to production examples and examples, but the present invention is not limited by the following examples. In addition, the following thermal analysis was measured on the conditions shown below.

[Measuring method of thermal analysis (TG-DTA)]
A sample was weighed 10 mg, set on a differential thermal balance (manufactured by RIGAKU; Thermo Plus TG8120), heated in a nitrogen atmosphere (200 ml / min) from room temperature to 400 ° C. at a rate of 10 ° C./min, and the melting point of the sample Asked.

[Production Example 1] (Production of Compound No. 1)
In a nitrogen atmosphere, 2.35 g (10.5 mmol) of ethyl diethylphosphonoacetate and 5 ml of N, N-dimethylformamide were mixed, and then 2.03 g (10.5 mmol) of 28% sodium methoxide solution was added with stirring. The mixture was kept at room temperature for 30 minutes and then cooled on ice. Next, a solution prepared by dissolving 2.33 g (10 mmol) of 9-ethyl-3-carbazole carbaldehyde in N, N-dimethylformamide was added dropwise thereto while cooling with ice.

  After stirring for 1 hour, analysis by gas chromatography confirmed the disappearance of the aldehyde form, so toluene was added to perform oil-water separation. Thereafter, the oil phase was washed with water, dehydrated by adding anhydrous sodium sulfate, the solvent was distilled off, and the residue was added to a 1.4% sodium methoxide solution and stirred at room temperature for 1 hour.

After stirring, water is added and neutralized with formic acid, toluene is added again to separate the oil and water, the oil phase is washed with water, dehydrated with anhydrous sodium sulfate, the solvent is distilled off, and a pale yellow powder is obtained. 2.3 g of compound was obtained. The obtained compound was analyzed by ¹ H-NMR and IR. 1 was identified. Further, when the compound was subjected to thermal analysis (TG-DTA), the melting point of the compound was 76.9 ° C. The results of these analyzes are shown below.

(1) ¹ H-NMR [CDCl ₃ ] (ppm)
1.42 (t; 3H), 3.82 (s; 3H), 4.34 (q; 2H), 6.47 (d; 1H), 7.1-8.3 (m; 8H)

(2) IR (cm ⁻¹ ) [KBr tablet method]
1165, 1620, 1713, 2947, 2978, 3051

[Production Example 2] (Production of Compound No. 2)
Under a nitrogen atmosphere, 2.35 g (10.5 mmol) of ethyl diethylphosphonoacetate and 4 ml of N, N-dimethylformamide were mixed, and then 3.57 g (10.5 mmol) of 20% sodium ethoxide solution was added, After holding for a minute, it was ice-cooled. Next, a solution prepared by dissolving 3.07 g (10 mmol) of 9-octyl-3-carbazolecarbaldehyde in 5 ml of N, N-dimethylformamide was added dropwise thereto while cooling with ice.

  The mixture was stirred for 1 hour from the end of the dropping and analyzed by gas chromatography. As a result, disappearance of the aldehyde was confirmed, and toluene was added to separate the oil and water. The oil phase was washed with water, dehydrated with anhydrous sodium sulfate, the solvent was distilled off, and the residue was washed with hexane to obtain 1.88 g of a white powder. When the obtained compound was analyzed by IR, the target compound No. 2 was identified. Further, when the compound was subjected to thermal analysis (TG-DTA), the melting point of the compound was 73.8 ° C. The results of these analyzes are shown below.

(1) IR (cm ⁻¹ ) [KBr tablet method]
1265, 1620, 1701, 2924, 2955, 3048

[Production Example 3] (Production of Compound No. 3)
Compound No. obtained in [Production Example 1] above. 1 was added to 11.6 g (41.5 mmol), 1.78 g (19.8 mmol) of 1,4-butanediol, 30 g of xylene, and 0.19 g (0.99 mmol) of 28% sodium methoxide solution. The reaction was carried out for 14 hours while warming and distilling methanol.

  After the reaction, the mixture was cooled to room temperature, and the precipitate formed by adding hexane was filtered off, and the residue was washed with a solvent of water, isopropanol, and acetone to obtain 2.05 g of a white powder compound. When the compound was analyzed by IR, the target compound No. 3 was identified. Further, when the compound was subjected to thermal analysis (TG-DTA), the melting point of the compound was 148.5 ° C. The results of these analyzes are shown below.

(1) IR (cm ⁻¹ ) [KBr tablet method]
1165, 1624, 1705, 2889, 2936, 3055

[Production Example 4] (Production of Compound No. 4)
This was carried out in the same manner as in [Production Example 3] except that 1.78 g (19.8 mmol) of 1,4-butanediol was changed to 2.33 g (19.8 mmol) of 1,6-hexanediol. Compound No. 4 was obtained. The results of IR and thermal analysis of the compound are shown below.

(1) IR (cm ⁻¹ ) [KBr tablet method]
1173, 1624, 1690, 2862, 2936, 3058

(2) Thermal analysis (TG-DTA)
177.3 ° C

[Production Example 5] (Production of Compound No. 5)
Compound No. produced in [Production Example 1] above. 1 with 14.2 g (50.9 mmol), 1,4-diaminobutane 2.13 g (24.2 mmol), heavy aromatic hydrocarbon solvent 40 g and 28% sodium methoxide solution 0.47 g (24.2 mmol) After mixing, the mixture was heated and reacted in the range of 130 to 180 ° C. for 15 hours while distilling methanol. After completion of the reaction, the mixture was neutralized with formic acid, the formed precipitate was filtered off, and the residue was washed with methanol and acetone to obtain 3.32 g of a white powder compound. When the compound was analyzed by IR, the target compound No. 5 was identified. Further, when the compound was subjected to thermal analysis (TG-DTA), the melting point of the compound was 219.4 ° C. The results of these analyzes are shown below.

(1) IR (cm ⁻¹ ) [KBr tablet method]
1535, 1612, 1647, 2939, 2970, 3047, 3290

[Production Example 6] (Production of Compound No. 6)
Compound No. 5 was prepared in the same manner as in [Example 5] except that 2.13 g (24.2 mmol) of 1,4-diaminobutane was changed to 2.81 g (24.2 mmol) of 1,6-diaminohexane. . 6 was obtained. The results of IR and thermal analysis of the compound are shown below.

(1) IR (cm ⁻¹ ) [KBr tablet method]
1551, 1593, 1651, 2858, 2932, 3067, 3260

(2) Thermal analysis (TG-DTA)
231.9 ° C

[Production Example 7] (Production of Compound No. 7)
The same procedure as in Example 5 above was carried out except that 2.13 g (24.2 mmol) of 1,4-diaminobutane was changed to 3.29 g (24.2 mmol) of meta-xylylenediamine. 7 was obtained. The results of IR and thermal analysis of the compound are shown below.

(1) IR (cm ⁻¹ ) [KBr tablet method]
1535, 1593, 1651, 2932, 2974, 3055, 3245

(2) Thermal analysis (TG-DTA)
263.9 ° C

[Evaluation Example 1] (Absorbance at 380 nm and transmittance at 400 nm)
The compounds shown in Table 1 below were each dissolved in chloroform to form 0.1% chloroform solutions, and transmittances at wavelengths of 380 nm and 400 nm were obtained with a spectrophotometer (manufactured by JASCO Corporation; V-560). These results are shown in Table 1 below.

[Evaluation Example 2] (Film coloring)
Dissolve 10 g of polymethylmethacrylate (Mitsubishi Rayon Co., Ltd .: Acrypet V) in chloroform, add 0.3 g of the compound shown in Table 2 below, and create a film with a thickness of 100 μm by the casting method. The yellowness (YI) was measured. These results are shown in Table 2 below.

＊１）比較化合物１：２，２’−メチレンビス〔４−（１，１，３，３−テトラメチルブチル）−６−（２Ｎ−ベンゾトリアゾール−２−イル）フェノール〕

* 1) Comparative compound 1: 2,2′-methylenebis [4- (1,1,3,3-tetramethylbutyl) -6- (2N-benzotriazol-2-yl) phenol]

  As is clear from Table 1 above, it can be seen that the ultraviolet absorber that is not a compound of the present invention (Comparative Example 1-1) has a poor ability to absorb ultraviolet light at 380 nm and low visible light transmittance at 400 nm. On the other hand, it was confirmed that the ultraviolet absorbents (Examples 1-1 to 1-4) of the present invention have a high ultraviolet absorption ability of 380 nm and excellent visible light transmittance of 400 nm.

  From Table 2 above, in the film (Comparative Example 2-2) prepared with the UV absorber that is not the UV absorber of the present invention, coloring was observed, whereas the film prepared with the UV absorber of the present invention (implementation) In Examples 2-1 to 2-4), almost no coloring was observed.

  As described above, the ultraviolet absorber of the present invention is a polarizing plate protective film, a retardation film, a viewing angle widening film, an optical correction film, a brightness enhancement film, a plasma display as an ultraviolet absorber excellent in ultraviolet absorbing ability and visible light transmission. Can be suitably used for resin optical film applications having various functions, such as an antireflection film used in the present invention, an optical correction film used in an organic EL display, and a light emitter protective film.

Claims (4)

The following general formula (1),

[(In the formula (1), n represents 1 or 2, when n is 1, A is a hydrogen atom, an alkyl group optionally having 1 to 12 carbon atoms which may have a branch, carbon atom number 6-12 aryl group, a cycloalkyl group, or a combination of these carbon atom number 5-12, and when n is 2, a is carbon atoms which may have a branch 1-12 alkylene group, an arylene group of carbon atom number 6-12, represents a cycloalkylene group or a combination of these carbon atom number 5 to 12, B is represented by the following general formula (2),

(In the formula (2), R is a hydrogen atom, branch alkyl group having 1 to 12 carbon atoms which may have a branch an alkenyl group having 2 to 18 carbon atoms which may have a, or a cycloalkyl group carbon atom number 5-12 or an aryl group of carbon atom number 6 to 12, X represents an oxygen atom or -NH-, when n is 2, R and X are each independently A compound having the structure of (I))]. The ultraviolet absorber represented by the general formula (1) is represented by the following general formula (3),

(In the formula (3), R is, or hydrogen atom is an alkyl group optionally having 1 to 12 carbon atoms which may have a branch, X represents the same meanings as defined above, A is have a branch The ultraviolet absorber according to claim 1, which is a carbazole compound having a structure represented by (which represents an optionally substituted alkyl group having 1 to 12 carbon atoms). The ultraviolet absorber represented by the general formula (1) is represented by the following general formula (4),

(In the formula (4), R each independently represent a hydrogen atom or a good 1 to 12 carbon atoms which may have a branch alkyl group, A also has have a branch alkylene group or 1 to 12 carbon atoms represents an arylene group carbon atom number 6 to 12, X are each independently a carbazole compound having a structure represented by the representative) the same as the The ultraviolet absorber according to claim 1.   A resin composition comprising 0.1 to 10 parts by mass of the ultraviolet absorber according to any one of claims 1 to 3 with respect to 100 parts by mass of the synthetic resin component.