JP2014227533A - Ultraviolet absorber and novel carbazole compound - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an ultraviolet absorber which has excellent heat resistance and can retain ultraviolet absorbency for a long time, and a novel carbazole compound that can be used for the ultraviolet absorber.SOLUTION: An ultraviolet absorber is a carbazole compound represented by the general formula (I) in the figure.

Description

  The present invention relates to an ultraviolet absorber and a novel carbazole compound. Specifically, the present invention relates to an ultraviolet absorbent having excellent heat resistance and high ultraviolet absorbing ability, and a novel carbazole compound that can be used for the ultraviolet absorbent.

  Conventionally, it is known to add an ultraviolet absorber in order to impart an ultraviolet absorbing ability to a polymer film used for various applications such as an optical film and a protective film to prevent yellowing and a decrease in transparency.

  For example, Patent Document 1 discloses a resin composition containing an ultraviolet absorber that is a carbazole compound. Patent Document 2 discloses a laminate formed by laminating a surface layer made of a polycarbonate resin composition containing an ultraviolet absorber. Furthermore, Patent Document 3 discloses a hard coat film containing an ultraviolet absorber.

JP 2009-035698 A JP 2011-202090 A JP 2012-118305 A

  However, none of the ultraviolet absorbers known so far has a sufficient heat resistance, and the ultraviolet absorption ability has been reduced over time.

  Accordingly, an object of the present invention is to provide an ultraviolet absorber excellent in heat resistance and excellent in ultraviolet absorbing ability in a wide wavelength range from UVA to UVB, and a novel carbazole compound that can be used for the ultraviolet absorber.

  As a result of intensive investigations to solve the above problems, the present inventors have found that a carbazole compound represented by the following general formula (I) is suitable as an ultraviolet absorber, and complete the present invention. It came.

  That is, the ultraviolet absorbent according to the present invention is a carbazole compound represented by the following general formula (I).

（式中、Ｒ^１及びＲ^２は、それぞれ独立に、Ｒ^１１、ＯＲ^１１、ＣＯＲ^１１、ＳＲ^１１、ＣＯＮＲ^１２Ｒ^１３又はＣＮを表し、Ｒ^２は隣接するベンゼン環と一緒になって環を形成していてもよく、
Ｒ^１１、Ｒ^１２及びＲ^１３は、それぞれ独立に、炭素原子数１〜２０のアルキル基、炭素原子数２〜２０のアルケニル基若しくはアルキニル基、炭素原子数６〜３０のアリール基、炭素原子数７〜３０のアリールアルキル基又は炭素原子数２〜２０の複素環基を表し、
前記アルキル基、アルケニル基又はアルキニル基は分岐側鎖があっても、環状アルキル基であってもよく、これらアルキル基、アルケニル基、アルキニル基、アリール基、アリールアルキル基及び複素環基の水素原子は、更にＲ^２１、ＯＲ^２１、ＣＯＲ^２１、ＳＲ^２１、ＮＲ^２２Ｒ^２３、ＣＯＮＲ^２２Ｒ^２３、ＮＲ^２２ＯＲ^２３、ＣＮ、ハロゲン原子、炭素原子数２〜２０の不飽和結合含有基、カルボキシル基又はエポキシ基で置換されていてもよく、
Ｒ^２１、Ｒ^２２、及びＲ^２３は、それぞれ独立に、水素原子、炭素原子数１〜２０のアルキル基、炭素原子数２〜２０のアルケニル基若しくはアルキニル基、炭素原子数６〜３０のアリール基、炭素原子数７〜３０のアリールアルキル基又は炭素原子数２〜２０の複素環基を表し、
Ｒ^１１、Ｒ^１２、Ｒ^１３、Ｒ^２１、Ｒ^２２、及びＲ^２３で表されるアルキル基、アルケニル基、アルキニル基、又はアリールアルキル基のアルキレン部分のメチレン基は、不飽和結合、エーテル結合、チオエーテル結合、エステル結合、チオエステル結合、−Ｃ（＝Ｎ−ＯＲ^２１）−、アミド結合又はウレタン結合により一回もしくは複数回中断されていてもよく、また、Ｒ^１２とＲ^１３及びＲ^２２とＲ^２３はそれぞれ一緒になって環を形成していてもよく、
Ｒ^３、Ｒ^４、Ｒ^５及びＲ^６は、それぞれ独立に、Ｒ^１１、ＯＲ^１１、ＳＲ^１１、ＣＯＲ^１１、ＣＯＮＲ^１１Ｒ^１２、ＯＣＯＲ^１１、ＣＯＯＲ^１１、ＳＣＯＲ^１１、ＯＣＳＲ^１１、ＣＯＳＲ^１１、ＣＳＯＲ^１１、ＣＮ、ハロゲン原子又は水酸基を表し、ａは０〜３の整数であり、複数あるＲ^３は、それぞれ同じでも異なっていてもよい。）

(In the formula, R ¹ and R ² each independently represent R ¹¹ , OR ¹¹ , COR ¹¹ , SR ¹¹ , CONR ¹² R ¹³ or CN, and R ² forms a ring together with the adjacent benzene ring. May be formed,
R ¹¹ , R ¹² and R ¹³ are each independently an alkyl group having 1 to 20 carbon atoms, an alkenyl group or alkynyl group having 2 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, or the number of carbon atoms. Represents a 7-30 arylalkyl group or a C2-C20 heterocyclic group,
The alkyl group, alkenyl group or alkynyl group may have a branched side chain or a cyclic alkyl group, and hydrogen atoms of these alkyl group, alkenyl group, alkynyl group, aryl group, arylalkyl group and heterocyclic group R ²¹ , OR ²¹ , COR ²¹ , SR ²¹ , NR ²² R ²³ , CONR ²² R ²³ , NR ²² OR ²³ , CN, halogen atom, unsaturated bond-containing group having 2 to 20 carbon atoms, carboxyl group Or may be substituted with an epoxy group,
R ²¹ , R ²² , and R ²³ are each independently a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an alkenyl group or alkynyl group having 2 to 20 carbon atoms, or an aryl group having 6 to 30 carbon atoms. Represents an arylalkyl group having 7 to 30 carbon atoms or a heterocyclic group having 2 to 20 carbon atoms,
The methylene group of the alkyl group, alkenyl group, alkynyl group, or arylalkyl group represented by R ¹¹ , R ¹² , R ¹³ , R ²¹ , R ²² , and R ²³ is an unsaturated bond, an ether bond, It may be interrupted one or more times by a thioether bond, an ester bond, a thioester bond, —C (═N—OR ²¹ ) —, an amide bond or a urethane bond, and R ¹² and R ¹³ and R ²² and R ²³ may be combined together to form a ring,
R ³ , R ⁴ , R ⁵ and R ⁶ are each independently R ¹¹ , OR ¹¹ , SR ¹¹ , COR ¹¹ , CONR ¹¹ R ¹² , OCOR ¹¹ , COOR ¹¹ , SCOR ¹¹ , OCSR ¹¹ , COSR ¹¹ , CSOR ¹¹ , CN, a halogen atom or a hydroxyl group, a is an integer of 0 to 3, and a plurality of R ³ may be the same or different. )

  The present invention also provides a novel carbazole compound represented by the following general formula (II).

（式中、Ｒ^１は、炭素原子数１〜１０のアルキル基、炭素原子数６〜２０のアリール基、炭素原子数７〜２０のアリールアルキル基又は炭素原子数２〜２０の複素環基を表し、
Ｒ^３、Ｒ^４、Ｒ^５及びＲ^６は、それぞれ独立に、炭素原子数１〜１０のアルキル基、炭素原子数１〜１０のアルコキシ基、炭素原子数６〜２０のアリール基、炭素原子数６〜２０のアリールオキシ基、炭素原子数７〜２０のアリールアルキル基、炭素原子数２〜２０の複素環基、水酸基、ハロゲン原子又はＣＮを表し、
Ｒ^７、Ｒ^８、Ｒ^９、Ｒ^１０及びＲ^１１は、それぞれ独立に、水素原子、炭素原子数１〜１０のアルキル基、炭素原子数１〜１０のアルコキシ基、炭素原子数６〜２０のアリール基、炭素原子数６〜２０のアリールオキシ基、炭素原子数７〜２０のアリールアルキル基又は炭素原子数２〜２０の複素環基を表し、前記アルキル基及びアリールアルキル基中のアルキレン部分のメチレン基は、−Ｏ−又は−Ｓ−により１〜５回中断されていてもよく、Ｒ^７、Ｒ^８、Ｒ^９、Ｒ^１０及びＲ^１１のうち少なくとも１つは水素原子でない。）

(In the formula, R ¹ represents an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 20 carbon atoms, an arylalkyl group having 7 to 20 carbon atoms, or a heterocyclic group having 2 to 20 carbon atoms. Represent,
R ³ , R ⁴ , R ⁵ and R ⁶ are each independently an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, an aryl group having 6 to 20 carbon atoms, or the number of carbon atoms. An aryloxy group having 6 to 20 carbon atoms, an arylalkyl group having 7 to 20 carbon atoms, a heterocyclic group having 2 to 20 carbon atoms, a hydroxyl group, a halogen atom or CN;
R ⁷ , R ⁸ , R ⁹ , R ¹⁰ and R ¹¹ are each independently a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, or 6 to 20 carbon atoms. Represents an aryl group, an aryloxy group having 6 to 20 carbon atoms, an arylalkyl group having 7 to 20 carbon atoms, or a heterocyclic group having 2 to 20 carbon atoms, wherein the alkyl group and the alkylene moiety in the arylalkyl group The methylene group may be interrupted 1 to 5 times by —O— or —S—, and at least one of R ⁷ , R ⁸ , R ⁹ , R ¹⁰ and R ¹¹ is not a hydrogen atom. )

  ADVANTAGE OF THE INVENTION According to this invention, it is excellent in heat resistance and can provide the novel carbazole compound which can be used for the ultraviolet absorber which is excellent in ultraviolet-ray absorption ability in the wide wavelength range from UVA to UVB, and this ultraviolet absorber.

Hereinafter, preferred embodiments of the ultraviolet absorbent and the novel carbazole compound of the present invention will be described.
The ultraviolet absorber of the present invention is a carbazole compound represented by the above general formula (I).

In the general formula (I), examples of the alkyl group having 1 to 20 carbon atoms represented by R ¹¹ , R ¹² , R ¹³ , R ²¹ , R ²² and R ²³ include, for example, methyl, ethyl, propyl, isopropyl , Butyl, isobutyl, s-butyl, t-butyl, pentyl, isopentyl, t-pentyl, hexyl, heptyl, octyl, isooctyl, 2-ethylhexyl, t-octyl, nonyl, isononyl, decyl, isodecyl, undecyl, dodecyl, tetradecyl , Hexadecyl, octadecyl, icosyl, cyclopentyl, cyclohexyl, cyclohexylmethyl and the like,
Examples of the alkenyl group or alkynyl group having 2 to 20 carbon atoms include vinyl, allyl, butenyl, ethynyl, propynyl and the like,
OR ¹¹ , COR ¹¹ , SR ¹¹ , CONR ¹² R ¹³ , OR ²¹ , COR ²¹ , SR ²¹ , NR ²² R ²³ , CONR ²² R ²³ , NR ²² OR ²³ correspond to the above alkyl group, alkenyl group or alkynyl group Such as methoxyethyl, ethoxyethyl, propoxyethyl, pentyloxyethyl, octyloxyethyl, methoxyethoxyethyl, ethoxyethoxyethyl, propoxyethoxyethyl, methoxypropyl, 2-methoxy-1-methylethyl and the like,
Examples of the aryl group having 6 to 30 carbon atoms represented by R ¹¹ , R ¹² , R ¹³ , R ²¹ , R ²² and R ²³ include phenyl, tolyl, xylyl, ethylphenyl, chlorophenyl, naphthyl, anthryl, Phenanthrenyl, phenyl, biphenylyl, naphthyl, anthryl substituted with one or more of the above alkyl groups,
Examples of the arylalkyl group having 7 to 30 carbon atoms represented by R ¹¹ , R ¹² , R ¹³ , R ²¹ , R ²² and R ²³ include benzyl, chlorobenzyl, α-methylbenzyl, α, α- Dimethylbenzyl, phenylethyl, phenylethenyl and the like,
Examples of the heterocyclic group having 2 to 20 carbon atoms represented by R ¹¹ , R ¹² , R ¹³ , R ²¹ , R ²² and R ²³ include pyridyl, pyrimidyl, furyl, thienyl, tetrahydrofuryl, dioxolanyl, benzo Preferred examples include 5- to 7-membered heterocycles such as oxazol-2-yl, tetrahydropyranyl, pyrrolidyl, imidazolidyl, pyrazolidyl, thiazolidyl, isothiazolidyl, oxazolidyl, isoxazolidyl, piperidyl, piperazyl, morpholinyl,
The ring that R ¹² and R ¹³ can form together, the ring that R ²² and R ²³ can form together, and the ring that R ² can form together with an adjacent benzene ring include: For example, a 5- to 7-membered ring such as a cyclopentane ring, cyclohexane ring, cyclopentene ring, benzene ring, piperidine ring, morpholine ring, lactone ring, lactam ring, etc.
R ¹¹ , R ¹² , R ¹³ , R ²¹ , R ²² and the halogen atom that may be substituted for R ²³ and the halogen atom represented by R ^{3 to} R ⁶ include a fluorine atom, a chlorine atom, a bromine atom, iodine Atom.

Among the oxime ester compounds of the present invention, R ¹ and R ² in the general formula (I) each independently represent R ¹¹ , COR ¹¹ or CN, and R ² is combined with the adjacent benzene ring. R ¹¹ may be an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, an arylalkyl group having 7 to 30 carbon atoms, or 2 to 2 carbon atoms. Those having 20 heterocyclic groups are preferred because they are easy to synthesize and have high heat resistance, and when used as an ultraviolet absorber, ε is high and a small amount can be added.
In addition, when R ² in the general formula (I) is an aryl group having 6 to 30 carbon atoms or an arylalkyl group having 7 to 30 carbon atoms substituted with an electron-donating group, the raw material can be obtained. It is more preferable because it is easy. Examples of the electron donating group include an alkyl group, an alkoxy group, a hydroxyl group, an amino group, an alkylamino group, and a dialkylamino group.

  As a preferable specific structure of the carbazole compound represented by the general formula (I) in the present invention, the following compound No. 1-No. 72 can be mentioned. However, the present invention is not limited by the following compounds.

  The method for producing the carbazole compound represented by the general formula (I) is not particularly limited. For example, according to the following reaction formula, nitrocarbazole compound 1 and acid chloride 2 are reacted in the presence of zinc chloride for acylation. Thus, the carbazole compound represented by the general formula (I) can be obtained.

  Since the ultraviolet absorber of the present invention comprising the carbazole compound represented by the above general formula (I) absorbs ultraviolet rays of 290 to 380 nm and transmits visible light of 400 nm or more, it is preferably used as an ultraviolet absorber. it can. For example, it can be suitably used for optical films such as retardation plates, polarizing elements, dichroic polarizing plates, liquid crystal alignment films, antireflection films, selective reflection films, viewing angle compensation films, and organic glasses such as eyeglass lens films. . 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. Food packaging materials; solar cells; can be used as hoses, pipes, sheets, toys, etc.

  The novel carbazole compound of the present invention corresponds to the compound represented by the following general formula (II) among the compounds used in the ultraviolet absorber of the present invention described above.

（式中、Ｒ^１は、炭素原子数１〜１０のアルキル基、炭素原子数６〜２０のアリール基、炭素原子数７〜２０のアリールアルキル基又は炭素原子数２〜２０の複素環基を表し、
Ｒ^３、Ｒ^４、Ｒ^５及びＲ^６は、それぞれ独立に、炭素原子数１〜１０のアルキル基、炭素原子数１〜１０のアルコキシ基、炭素原子数６〜２０のアリール基、炭素原子数６〜２０のアリールオキシ基、炭素原子数７〜２０のアリールアルキル基、炭素原子数２〜２０の複素環基、水酸基、ハロゲン原子又はＣＮを表し、
Ｒ^７、Ｒ^８、Ｒ^９、Ｒ^１０及びＲ^１１は、それぞれ独立に、水素原子、炭素原子数１〜１０のアルキル基、炭素原子数１〜１０のアルコキシ基、炭素原子数６〜２０のアリール基、炭素原子数６〜２０のアリールオキシ基、炭素原子数７〜２０のアリールアルキル基又は炭素原子数２〜２０の複素環基を表し、前記アルキル基及びアリールアルキル基中のアルキレン部分のメチレン基は、−Ｏ−又は−Ｓ−により１〜５回中断されていてもよく、Ｒ^７、Ｒ^８、Ｒ^９、Ｒ^１０及びＲ^１１のうち少なくとも１つは水素原子でない。）

(In the formula, R ¹ represents an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 20 carbon atoms, an arylalkyl group having 7 to 20 carbon atoms, or a heterocyclic group having 2 to 20 carbon atoms. Represent,
R ³ , R ⁴ , R ⁵ and R ⁶ are each independently an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, an aryl group having 6 to 20 carbon atoms, or the number of carbon atoms. An aryloxy group having 6 to 20 carbon atoms, an arylalkyl group having 7 to 20 carbon atoms, a heterocyclic group having 2 to 20 carbon atoms, a hydroxyl group, a halogen atom or CN;
R ⁷ , R ⁸ , R ⁹ , R ¹⁰ and R ¹¹ are each independently a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, or 6 to 20 carbon atoms. Represents an aryl group, an aryloxy group having 6 to 20 carbon atoms, an arylalkyl group having 7 to 20 carbon atoms, or a heterocyclic group having 2 to 20 carbon atoms, wherein the alkyl group and the alkylene moiety in the arylalkyl group The methylene group may be interrupted 1 to 5 times by —O— or —S—, and at least one of R ⁷ , R ⁸ , R ⁹ , R ¹⁰ and R ¹¹ is not a hydrogen atom. )

Among the compounds represented by the general formula (II), those in which R ⁹ is an alkoxy group having 1 to 10 carbon atoms are preferable because of easy production.

  When the ultraviolet absorbent according to the present invention is used in the above various applications, it is mixed with a binder resin, a visible light absorbent, a near infrared absorbent, a solvent or the like to obtain a resin composition. , Bar coater, dip coater, air knife coater, gravure coater, die coater, curtain coater, various kinds of printing, dipping and the like can be applied onto the transparent support. Moreover, after once applying on transparent supports, such as a film, it can also be transcribe | transferred on another transparent support body, There is no restriction | limiting in the application method.

  Examples of the binder resin include natural polymer materials such as gelatin, casein, starch, cellulose derivatives, and alginic acid, or polymethyl methacrylate, polyvinyl butyral, polyvinyl pyrrolidone, polyvinyl alcohol, polyvinyl chloride, styrene-butadiene copolymer, polystyrene. , Synthetic polymer materials such as polyester, polyether, polycarbonate, polyamide, polyimide, polyurethane, melamine resin, and cyclic olefin resin, and pressure-sensitive adhesives.

  Examples of the visible light absorber include trimethine cyanine derivatives such as trimethine indolium compounds, trimethine benzoxazolium compounds, and trimethine benzothiazolium compounds; pentamethine oxazolium compounds, pentamethine thiazolium compounds, and the like Pentamethine cyanine derivatives; squarylium dye derivatives; azomethine dye derivatives; xanthene dye derivatives; azo dye derivatives; pyromethene dye derivatives; azo metal complex derivatives: rhodamine dye derivatives; phthalocyanine derivatives; porphyrin derivatives; dipyrromethene metal chelate compounds.

  Examples of the near infrared absorber include pentamethine cyanine derivatives such as pentamethine benzoindolium compound, pentamethine benzoxazolium compound, pentamethine benzothiazolium compound; heptamethine indolium compound, heptamethine benzoindolium compound, Heptamethine cyanine derivatives such as heptamethine oxazolium compound, heptamethine benzoxazolium compound, heptamethine thiazolium compound, heptamethine benzothiazolium compound; diimonium compound; aminium compound; squarylium derivative; ) Compounds, nickel complexes such as bis (benzenedithiolato) nickel compounds, bis (camphagethiolato) nickel compounds; squarylium derivatives; azo dye derivatives; phthalocyanines Derivatives; porphyrin derivatives; dipyrromethene metal chelate compounds, and the like.

  Examples of the solvent include ketones such as methyl ethyl ketone, methyl amyl ketone, diethyl ketone, acetone, methyl isopropyl ketone, methyl isobutyl ketone, cyclohexanone, and 2-heptanone; ethyl ether, dioxane, tetrahydrofuran, 1,2-dimethoxyethane, Ether solvents such as 1,2-diethoxyethane and dipropylene glycol dimethyl ether; methyl acetate, ethyl acetate, n-propyl acetate, isopropyl acetate, n-butyl acetate, cyclohexyl acetate, ethyl lactate, dimethyl succinate, texanol, etc. Ester solvent of: cellosolve solvent such as ethylene glycol monomethyl ether and ethylene glycol monoethyl ether; methanol, ethanol, iso- or n-propanol, iso- or n Alcohol solvents such as butanol and amyl alcohol; ethylene glycol monomethyl acetate, ethylene glycol monoethyl acetate, propylene glycol-1-monomethyl ether-2-acetate (PGMEA), dipropylene glycol monomethyl ether acetate, 3-methoxybutyl acetate, ethoxy Ether ester solvents such as ethyl propionate; BTX solvents such as benzene, toluene and xylene; Aliphatic hydrocarbon solvents such as hexane, heptane, octane and cyclohexane; Terpenes such as terpine oil, D-limonene and pinene Hydrocarbon oils; mineral spirits, parasols such as Swazol # 310 (Cosmo Matsuyama Oil Co., Ltd.), Solvesso # 100 (Exxon Chemical Co., Ltd.); carbon tetrachloride, chloroform Halogenated aliphatic hydrocarbon solvents such as chlorobenzene, halogenated aromatic hydrocarbon solvents such as chlorobenzene, carbitol solvents, aniline, triethylamine, pyridine, acetic acid, acetonitrile, Examples thereof include carbon disulfide, N, N-dimethylformamide, N, N-dimethylacetamide, N-methylpyrrolidone, dimethyl sulfoxide, water, and the like. These solvents may be used as one or a mixture of two or more. it can.

  In addition, the resin composition includes an adhesion imparting agent; a softening agent; a light resistance imparting agent; an ultraviolet absorber other than the compound represented by the general formula (I); an antioxidant; a polymerization initiator; Polymeric compound having a bond; Plasticizer; Antifoaming agent; Leveling agent; Dispersant; Curing agent; Flame retardant; Lubricant; Antistatic agent; Inorganic fine particle; Dispersant; Dispersing aid; p-anisole, hydroquinone , T-butylcatechol, phenothiazine, and other thermal polymerization inhibitors; adhesion promoters; fillers; surface modifiers; anti-aggregation agents; catalysts; effect promoters; cross-linking agents; Conventional additives such as surfactants can be added.

  Examples of the material for the transparent support include inorganic materials such as glass; cellulose esters such as diacetylcellulose, triacetylcellulose (TAC), propionylcellulose, butyrylcellulose, acetylpropionylcellulose, and nitrocellulose; polyamide; polyimide; polyurethane Epoxy resin; polycarbonate; polyethylene terephthalate, polyethylene naphthalate, polybutylene terephthalate, poly-1,4-cyclohexanedimethylene terephthalate, polyethylene-1,2-diphenoxyethane-4,4′-dicarboxylate, polybutylene terephthalate Polyester such as polystyrene; Polyolefin such as polyethylene, polypropylene, polymethylpentene; polyvinyl acetate, polyvinyl chloride, Polymer compounds such as vinyl compounds such as vinyl fluoride; acrylic resins such as polymethyl methacrylate and polyacrylate; polycarbonates; polysulfones; polyether sulfones; polyether ketones; polyether imides; Can be mentioned.

  EXAMPLES Hereinafter, although an Example etc. are given and this invention is demonstrated further in detail, this invention is not limited to these Examples.

Examples 1 to 3 Compound No. 1 1-No. Synthesis of 3 To a 100 mL four-necked flask, nitrocarbazole (1 equivalent) and chlorobenzene (30 equivalents) were added and stirred. Zinc chloride (0.1 equivalent) was added thereto, the atmosphere was replaced with nitrogen, and the temperature was raised to 80 ° C. Thereafter, at 80 ° C., Compound No. 1-No. Acid chloride (1.2 equivalents) corresponding to 3 was added dropwise under nitrogen. After completion of the dropwise addition, the mixture was heated to reflux and reacted for 32 hours under reflux.
Thereafter, the mixture was air-cooled to room temperature and separated into two phases with ethyl acetate / water. The organic phase was extracted and washed with an aqueous sodium hydrogen carbonate solution. The washed organic phase was washed with water until pH = 7, dehydrated with magnesium sulfate, and then desolvated to take out a crude product. Thereafter, the crude product was recrystallized with an ethyl acetate solvent to obtain the respective desired products. The target product was confirmed by ¹ H-NMR and IR. The yield and yield are shown in Table 1 below, and the analysis results are shown in Table 2 and Table 3 below.

_{^{<1 H-NMR (CDCl 3}} )>

[Evaluation Examples 1 to 3 and Comparative Examples 1 to 2] Evaluation of UV absorbing ability Compound No. 1-No. 3 of Evaluation Examples 1 to 3 and the following Comparative Compound No. 1-No. For Comparative Evaluation Examples 1 to 3 of 3, the extinction coefficient per unit weight (ε / g) was examined, and this was defined as the ultraviolet absorption ability. The results obtained are shown in Table 4 below.

Comparative Compound No. 1

Comparative Compound No. 2

Comparative Compound No. 3

  From the results shown in Table 4 above, it is clear that the ultraviolet absorber of the present invention has a high ε / g at a specific wavelength, particularly in the ultraviolet region, that is, a high ability to absorb ultraviolet rays.

  From the above results, the ultraviolet absorbent of the present invention is excellent in ultraviolet absorbing ability in a wide wavelength range from UVA (400 to 315 nm) to UVB (315 to 280 nm), and is useful as an ultraviolet absorbent.

Claims (5)

The ultraviolet absorber characterized by being a carbazole compound represented by the following general formula (I).

(In the formula, R ¹ and R ² each independently represent R ¹¹ , OR ¹¹ , COR ¹¹ , SR ¹¹ , CONR ¹² R ¹³ or CN, and R ² forms a ring together with the adjacent benzene ring. May be formed,
R ¹¹ , R ¹² and R ¹³ are each independently an alkyl group having 1 to 20 carbon atoms, an alkenyl group or alkynyl group having 2 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, or the number of carbon atoms. Represents a 7-30 arylalkyl group or a C2-C20 heterocyclic group,
The alkyl group, alkenyl group or alkynyl group may have a branched side chain or a cyclic alkyl group, and hydrogen atoms of these alkyl group, alkenyl group, alkynyl group, aryl group, arylalkyl group and heterocyclic group R ²¹ , OR ²¹ , COR ²¹ , SR ²¹ , NR ²² R ²³ , CONR ²² R ²³ , NR ²² OR ²³ , CN, halogen atom, unsaturated bond-containing group having 2 to 20 carbon atoms, carboxyl group Or may be substituted with an epoxy group,
R ²¹ , R ²² , and R ²³ are each independently a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an alkenyl group or alkynyl group having 2 to 20 carbon atoms, or an aryl group having 6 to 30 carbon atoms. Represents an arylalkyl group having 7 to 30 carbon atoms or a heterocyclic group having 2 to 20 carbon atoms,
The methylene group of the alkyl group, alkenyl group, alkynyl group, or arylalkyl group represented by R ¹¹ , R ¹² , R ¹³ , R ²¹ , R ²² , and R ²³ is an unsaturated bond, an ether bond, It may be interrupted one or more times by a thioether bond, an ester bond, a thioester bond, —C (═N—OR ²¹ ) —, an amide bond or a urethane bond, and R ¹² and R ¹³ and R ²² and R ²³ may be combined together to form a ring,
R ³ , R ⁴ , R ⁵ and R ⁶ are each independently R ¹¹ , OR ¹¹ , SR ¹¹ , COR ¹¹ , CONR ¹¹ R ¹² , OCOR ¹¹ , COOR ¹¹ , SCOR ¹¹ , OCSR ¹¹ , COSR ¹¹ , CSOR ¹¹ , CN, a halogen atom or a hydroxyl group, a is an integer of 0 to 3, and a plurality of R ³ may be the same or different. ) In the general formula (I), R ¹ and R ² each independently represent R ¹¹ , COR ¹¹ or CN, and R ² may be combined with an adjacent benzene ring to form a ring. ,
R ¹¹ represents an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, an arylalkyl group having 7 to 30 carbon atoms, or a heterocyclic group having 2 to 20 carbon atoms. The group may have a branched side chain or may be a cyclic alkyl. The hydrogen atom of these alkyl group, aryl group, arylalkyl group and heterocyclic group may be further R ²¹ , OR ²¹ , COR ²¹ , halogen atom, May be substituted with an unsaturated bond-containing group,
R ²¹ represents an alkyl group having 1 to 20 carbon atoms,
The methylene group of the alkylene part of the substituent represented by R ¹¹ and R ²¹ may be interrupted once or a plurality of times by an ether bond or a thioether bond,
R ³ , R ⁴ , R ⁵ and R ⁶ each independently represent R ¹¹ , OR ¹¹ , CN or a halogen atom, a and b are each independently 0 to 3, and a plurality of R ³ are The ultraviolet absorber according to claim 1, which may be the same or different. The general formula (I), wherein R ² is an aryl group having 6 to 30 carbon atoms or an arylalkyl group having 7 to 30 carbon atoms substituted with an electron donating group. The ultraviolet absorber according to any one of 2 above. A carbazole compound represented by the following general formula (II).

(In the formula, R ¹ represents an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 20 carbon atoms, an arylalkyl group having 7 to 20 carbon atoms, or a heterocyclic group having 2 to 20 carbon atoms. Represent,
R ³ , R ⁴ , R ⁵ and R ⁶ are each independently an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, an aryl group having 6 to 20 carbon atoms, or the number of carbon atoms. An aryloxy group having 6 to 20 carbon atoms, an arylalkyl group having 7 to 20 carbon atoms, a heterocyclic group having 2 to 20 carbon atoms, a hydroxyl group, a halogen atom or CN;
R ⁷ , R ⁸ , R ⁹ , R ¹⁰ and R ¹¹ are each independently a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, or 6 to 20 carbon atoms. Represents an aryl group, an aryloxy group having 6 to 20 carbon atoms, an arylalkyl group having 7 to 20 carbon atoms, or a heterocyclic group having 2 to 20 carbon atoms, wherein the alkyl group and the alkylene moiety in the arylalkyl group The methylene group may be interrupted 1 to 5 times by —O— or —S—, and at least one of R ⁷ , R ⁸ , R ⁹ , R ¹⁰ and R ¹¹ is not a hydrogen atom. ) The carbazole compound according to claim 4, wherein, in the general formula (II), R ⁹ is an alkoxy group having 1 to 10 carbon atoms.