WO2011071183A1 - Composition photochrome - Google Patents

Composition photochrome Download PDF

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Publication number
WO2011071183A1
WO2011071183A1 PCT/JP2010/072593 JP2010072593W WO2011071183A1 WO 2011071183 A1 WO2011071183 A1 WO 2011071183A1 JP 2010072593 W JP2010072593 W JP 2010072593W WO 2011071183 A1 WO2011071183 A1 WO 2011071183A1
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group
photochromic
formula
ring
photochromic composition
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PCT/JP2010/072593
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English (en)
Japanese (ja)
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潤治 竹中
潤ニ 百田
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株式会社トクヤマ
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    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
    • G03C1/00—Photosensitive materials
    • G03C1/72—Photosensitive compositions not covered by the groups G03C1/005 - G03C1/705
    • G03C1/73—Photosensitive compositions not covered by the groups G03C1/005 - G03C1/705 containing organic compounds
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K9/00—Tenebrescent materials, i.e. materials for which the range of wavelengths for energy absorption is changed as a result of excitation by some form of energy
    • C09K9/02—Organic tenebrescent materials
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
    • G03C1/00—Photosensitive materials
    • G03C1/685—Compositions containing spiro-condensed pyran compounds or derivatives thereof, as photosensitive substances
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
    • C09K2211/10—Non-macromolecular compounds
    • C09K2211/1018—Heterocyclic compounds
    • C09K2211/1025—Heterocyclic compounds characterised by ligands
    • C09K2211/1088—Heterocyclic compounds characterised by ligands containing oxygen as the only heteroatom

Definitions

  • the present invention relates to a photochromic composition excellent in repeated durability against light exposure.
  • Photochromism is a reversible action that quickly changes color when a compound is irradiated with light containing ultraviolet light, such as sunlight or mercury lamp light, and returns to its original color when the light is stopped and left in the dark. Yes, it is used for various purposes.
  • fulgimide compounds, spirooxazine compounds, chromene compounds and the like have been found. These compounds can be made into an optical article having photochromic properties by compounding with a plastic. Therefore, many studies have been made on the compounding of the above compound and plastic. Photochromism is also used in the field of spectacle lenses.
  • Photochromic eyeglass lenses that use photochromic compounds function as sunglasses when they are exposed to light containing ultraviolet rays, such as sunlight, and function as sunglasses. It functions as normal and normal glasses, and its demand is increasing in recent years.
  • photochromic eyeglass lenses those made of plastic are particularly preferred from the viewpoint of lightness and safety.
  • the photochromic property is imparted to such plastic lenses by combining the above photochromic compound and plastic. It is done by.
  • the surface of a lens having no photochromic property is impregnated with a photochromic compound (hereinafter referred to as impregnation method), or the photochromic compound is dissolved in a polymerizable monomer and directly polymerized.
  • a method of obtaining a photochromic lens (hereinafter referred to as a kneading method), and a method of coating a surface of a lens with a photochromic compound dissolved in a polymerizable monomer (hereinafter referred to as a coating method) are known. ing. About these photochromic compounds and plastic optical articles having photochromic properties containing them, from the viewpoint of their function, (I) the degree of coloring in the visible light region before irradiation with ultraviolet rays (hereinafter referred to as initial coloring) is low.
  • indeno [2,1-f] naphtho [1,2-b] pyran As a chromene compound having excellent characteristics, a compound having indeno [2,1-f] naphtho [1,2-b] pyran as a basic skeleton (hereinafter referred to as indeno [2,1-f] naphtho [1,2-b] ] (Also referred to as a pyran compound) (see International Publication No. 96/014596, International Publication No. 01/019813, International Publication No. 01/060811, and International Publication No. 05/028465). . Since these compounds have excellent photochromic properties, they are widely used in current photochromic eyeglass lenses.
  • an object of the present invention is to provide a photochromic composition having excellent repeated durability against light exposure.
  • Another object of the present invention is to provide a photochromic cured product or a photochromic molded article, such as a photochromic spectacle lens, containing the photochromic composition of the present invention.
  • the above objects and advantages of the present invention are as follows. First, 100 parts by mass of an indeno [2,1-f] naphtho [1,2-b] pyran compound and a maximum absorption wavelength in the longest wavelength range. This is achieved by a photochromic composition comprising 1 to 300 parts by mass of an ultraviolet absorber present in the range of 280 to 330 nm. According to the present invention, the above objects and advantages of the present invention are, secondly, a polymerization curable photochromic composition comprising 100 parts by weight of the polymerizable monomer and 0.01 to 20 parts by weight of the photochromic composition of the present invention. And a photochromic cured product obtained by polymerizing and curing the product.
  • the above objects and advantages of the present invention thirdly comprise 100 parts by weight of a polymeric material and 0.01-20 parts by weight of the photochromic composition described above, and the photochromic composition comprises This is achieved by a photochromic molded product dispersed in a polymer material.
  • FIG. 1 is an ultraviolet / visible absorption spectrum diagram of the indeno [2,1-f] naphtho [1,2-b] pyran compound (PC1) used in Example 1.
  • FIG. 2 is an ultraviolet absorption spectrum diagram of an ultraviolet absorber, ethyl-2-cyano-3,3-diphenyl acrylate.
  • the indeno [2,1-f] naphtho [1,2-b] pyran compound used in the present invention has the following formula (1):
  • R 6 Is a hydroxyl group, an alkyl group, a haloalkyl group, a cycloalkyl group, an alkoxy group, an amino group, a heterocyclic group that contains a ring nitrogen atom and is directly bonded to the benzene ring to which it is bonded, a cyano group, a nitro group, It represents a formyl group, a hydroxycarbonyl group, an alkylcarbonyl group, an alkoxycarbonyl group, a halogen atom, an aralkyl group, an aryl group, an aryloxy group, a heteroaryl group or an alkylthio group.
  • the alkyl group is preferably an alkyl group having 1 to 6 carbon atoms.
  • suitable alkyl groups include methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, n-pentyl, n-hexyl and the like.
  • the haloalkyl group is preferably a haloalkyl group having 1 to 6 carbon atoms substituted with 1 to 13 halogen atoms such as a fluorine atom, a chlorine atom or a bromine atom.
  • haloalkyl groups include trifluoromethyl group, pentafluoroethyl group, chloromethyl group, 2-chloroethyl group, bromomethyl group and the like.
  • the cycloalkyl group is preferably a cycloalkyl group having 3 to 8 carbon atoms.
  • suitable cycloalkyl groups include cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group and the like.
  • the alkoxy group is preferably an alkoxy group having 1 to 6 carbon atoms.
  • alkoxy groups examples include methoxy group, ethoxy group, n-propoxy group, isopropoxy group, n-butoxy group, sec-butoxy group, tert-butoxy group and the like.
  • the amino group can be, for example, an unsubstituted amino group, a mono- or di-substituted amino group.
  • substituent of the amino group include an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, a cycloalkyl group having 3 to 8 carbon atoms, an aryl group having 6 to 14 carbon atoms, and 4 to 12 heteroaryl groups and the like can be mentioned.
  • R 6 It is a group similar to the group described in 1.
  • the aryl group having 6 to 10 carbon atoms include a phenyl group, a 1-naphthyl group, and a 2-naphthyl group.
  • the heteroaryl group having 4 to 12 carbon atoms includes, for example, a 5- to 7-membered aromatic ring containing 1 to 2 oxygen atoms, nitrogen atoms or sulfur atoms, or a condensed ring of these with a benzene ring. A heteroaryl group is preferred.
  • Illustrative examples include thienyl group, furyl group, pyrrolinyl group, pyridyl group, benzothienyl group, benzofuranyl group, benzopyrrolinyl group and the like.
  • suitable amino groups include amino groups, methylamino groups, dimethylamino groups, ethylamino groups, diethylamino groups, phenylamino groups, diphenylamino groups, and the like.
  • a heterocyclic group containing a ring nitrogen atom and directly bonded to the benzene ring to which the nitrogen atom is bonded includes 1 to 2 ring nitrogen atoms and 0 to 1 ring oxygen atom or sulfur atom.
  • a 5- to 7-membered ring or a condensed ring of these with a benzene ring is preferred.
  • suitable ones include morpholino group, piperidino group, pyrrolidinyl group, piperazino group, N-methylpiperazino group, indolinyl group and the like.
  • the heterocyclic group may have an alkyl group having 1 to 6 carbon atoms as a substituent.
  • Specific examples of the substituent include an alkyl group such as a methyl group.
  • Preferred examples of the heterocyclic group having a substituent include 2,6-dimethylmorpholino group, 2,6-dimethylpiperidino group, 2,2,6,6-tetramethylpiperidino group and the like. Is mentioned.
  • the alkylcarbonyl group preferably includes an alkyl group having 1 to 6 carbon atoms. Examples of suitable ones include acetyl group and ethylcarbonyl group.
  • the alkoxycarbonyl group preferably contains an alkoxy group having 1 to 6 carbon atoms. Examples of suitable ones include methoxycarbonyl group, ethoxycarbonyl group and the like. Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.
  • the aralkyl group is preferably an aralkyl group having 7 to 11 carbon atoms.
  • Suitable aralkyl groups include benzyl group, phenylethyl group, phenylpropyl group, phenylbutyl group, naphthylmethyl group and the like.
  • the aryl group is preferably an aryl group having 6 to 10 carbon atoms. Specific examples of suitable aryl groups include phenyl, 1-naphthyl and 2-naphthyl groups.
  • the aryloxy group is preferably an aryloxy group having 6 to 10 carbon atoms. Examples of suitable aryloxy groups include phenoxy group, 1-naphthoxy group, 2-naphthoxy group and the like.
  • the above aralkyl group, aryl group and aryloxy group have 1 to 7 hydrogen atoms, particularly preferably 1 to 4 hydrogen atoms such as benzene or naphthalene ring, as a hydroxyl group, an alkyl group, a haloalkyl group, a cycloalkyl group. , Alkoxy group, amino group, heterocyclic group containing a ring nitrogen atom and directly binding to the aryl ring to which it is bonded, cyano group, nitro group, formyl group, hydroxycarbonyl group, alkylcarbonyl group, alkoxycarbonyl The group may be substituted with a halogen atom. Specific examples of these groups are the same as the above specific examples.
  • the heteroaryl group is preferably a 5- to 7-membered aromatic ring containing 1 to 2 ring oxygen atoms, nitrogen atoms or sulfur atoms, or a condensed ring of these with a benzene ring.
  • the heteroaryl group is bonded to the benzene ring to which the heteroaryl group is bonded with a carbon atom.
  • suitable heteroaryl groups include thienyl group, furyl group, pyrrolinyl group, pyridyl group, benzothienyl group, benzofuranyl group, benzopyrrolinyl group and the like.
  • the heteroaryl group is a 5- to 7-membered aromatic ring containing 1 to 2 ring member oxygen atoms, nitrogen atoms or sulfur atoms, or 1 to 7 hydrogen atoms in a bond ring with the benzene ring, Preferably 1 to 4 hydrogen atoms are directly bonded to a heteroaryl ring containing a hydroxyl group, alkyl group, haloalkyl group, cycloalkyl group, alkoxy group, amino group, ring member nitrogen atom to which it is attached
  • the alkylthio group is preferably an alkylthio group having 1 to 6 carbon atoms.
  • suitable alkylthio groups include methylthio group, ethylthio group, n-propylthio group, isopropylthio group, n-butylthio group, sec-butylthio group, tert-butylthio group, n-pentylthio group, n-hexylthio group and the like. be able to.
  • p is an integer of 0 to 4, and when p is 2 to 4, a plurality of R 6 May be the same as or different from each other.
  • alkylenedioxy group is preferably an alkylenedioxy group having 1 to 8 carbon atoms.
  • suitable alkylenedioxy groups include methylenedioxy groups and ethylenedioxy groups.
  • R 7 Is a hydroxyl group, an alkyl group, a haloalkyl group, a cycloalkyl group, an alkoxy group, an amino group, a heterocyclic group directly containing a ring nitrogen atom and a benzene ring to which the nitrogen atom is bonded, a cyano group, a nitro group Represents a formyl group, a hydroxycarbonyl group, an alkylcarbonyl group, an alkoxycarbonyl group, a halogen atom, an aralkyl group, an aryl group, or an aryloxy group.
  • Preferred groups and specific examples of these groups include R 6 And the same groups as described above.
  • R 8 And R 9 are each independently a hydrogen atom, a hydroxyl group, an alkyl group, a haloalkyl group, a cycloalkyl group, an alkoxy group, an amino group, a heterocyclic ring containing a ring nitrogen atom and directly attached to the indene ring to which it is attached.
  • Preferred groups and specific examples of these groups include R 6 And the same groups as described above.
  • R 8 And R 9 Can bond together to form a ring together with the carbon atoms to which they are bonded.
  • Examples of such a ring structure include an aliphatic hydrocarbon ring having 3 to 20 carbon atoms, a condensed polycycle in which an aromatic hydrocarbon ring or an aromatic heterocycle is condensed to the aliphatic hydrocarbon ring, and a ring. And a heterocyclic ring having 3 to 20 atoms, or a condensed polycycle in which an aromatic hydrocarbon ring or an aromatic heterocyclic ring is condensed to the heterocyclic ring. These rings may be substituted with 1 to 10 alkyl groups having 1 to 6 carbon atoms or halogen atoms.
  • R 8 And R 9 Examples of suitable rings formed by bonding to each other include the following.
  • R 10 And R 11 Each independently represents a group represented by the following formula (5), a group represented by the following formula (6), an aryl group, a heteroaryl group, or an alkyl group.
  • R in the formula (5) 12 Is an aryl group or a heteroaryl group.
  • specific examples of the aryl group and heteroaryl group include R 6 The same group as already explained in the explanation part of.
  • a heteroaryl group is a group having 1 to 7 hydrogen atoms, particularly preferably 1 to 4 hydrogen atoms, preferably an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, or 3 to 3 carbon atoms. It may be substituted with 8 cycloalkyl groups, halogen atoms, amino groups, mono- or di-substituted amino groups. Examples of the substituent of the mono- or di-substituted amino group include an alkyl group, a phenyl group, a morpholino group, a piperidino group, a mono- or di-alkyl piperidino group, and the like.
  • R 13 Is a hydrogen atom, an alkyl group or a halogen atom.
  • the alkyl group and the halogen atom include R 6
  • the same groups as those described above for. m is an integer of 1 to 3.
  • suitable groups as the group represented by the formula (5) include phenyl-ethenyl group, (4- (N, N-dimethylamino) phenyl) -ethenyl group, (4-morpholinophenyl) -ethenyl group, (4-piperidinophenyl) -ethenyl group, (4-methoxyphenyl) -ethenyl group, (2-methoxyphenyl) -ethenyl group, phenyl-1-methylethenyl group, (4-methoxyphenyl) -1-methylethenyl group , Phenyl-1-fluoroethenyl group, (4- (N, N-dimethylamino)
  • R 14 Is an aryl group or a heteroaryl group. These examples are R 12 Is the same as described above.
  • N is an integer of 1 to 3.
  • suitable groups as the group represented by the formula (6) include phenyl-ethynyl group, (4- (N, N-dimethylamino) phenyl) -ethynyl group, (4-morpholinophenyl) -ethynyl group, (4-piperidinophenyl) -ethynyl group, (4-methoxyphenyl) -ethynyl group, (4-methylphenyl) -ethynyl group, (2-methoxyphenyl) -ethynyl group, 2-thienyl-ethynyl group, 2 -Furyl-ethynyl group, 2- (N-methyl) pyrrolinyl-ethynyl group, 2-benzothieny
  • R 10 And R 11 Specific examples of the aryl group, heteroaryl group, and alkyl group of 12 , R 14 And the same groups as those already described.
  • R 10 And R 11 May be bonded to each other to form a ring structure together with the carbon atoms to which they are bonded.
  • Examples of such a ring structure include an aliphatic hydrocarbon ring or an aromatic hydrocarbon ring.
  • an aliphatic hydrocarbon ring an aliphatic hydrocarbon ring having 6 to 12 carbon atoms is preferable.
  • suitable rings include an adamantane ring, a bicyclononane ring, and a norbornane ring.
  • the aromatic hydrocarbon ring is preferably an aromatic hydrocarbon ring having 9 to 15 carbon atoms. Suitable rings include fluorene rings.
  • R above 10 And R 11 In particular, in order to exhibit excellent photochromic properties, at least one, preferably both groups are preferably aryl groups or heteroaryl groups. In addition, R 10 And R 11 It is particularly preferable that at least one of these groups, preferably both groups, is any group represented by the following (i) to (iii).
  • substitution position of the substituent of the aryl group in the above (i) to (iii) is not particularly limited, and the total number is not particularly limited. Still, in order to exhibit excellent photochromic properties, the substitution position is preferably the 3-position or the 4-position when the aryl group is a phenyl group.
  • the number of substituents at that time is preferably 1 to 2.
  • suitable aryl group include 4-methylphenyl group, 4-methoxyphenyl group, 3,4-dimethoxyphenyl group, 4-n-propoxyphenyl group, 4- (N, N-dimethylamino) phenyl.
  • the position at which the substituent is substituted is not particularly limited, and the total number is not particularly limited, but the number is preferably 1.
  • suitable heteroaryl groups include 4-methoxythienyl group, 4- (N, N-dimethylamino) thienyl group, 4-methylfuryl group, 4- (N, N-diethylamino) furyl.
  • an indeno [2,1-f] naphtho [1,2-b] pyran compound having an absorption edge defined below of 400 nm or more, preferably 410 nm or more is particularly preferably used.
  • the absorption edge here is measured under dark conditions using a solution in which 0.1 part by weight of an indeno [2,1-f] naphtho [1,2-b] pyran compound is dissolved in 100 parts by weight of tetrahydrofuran.
  • the tangent at the point where the absorbance on the spectrum curve is 1.5 is defined as the wavelength at the point where the X-axis intersects. .
  • FIG. 1 shows an absorption edge of an indeno [2,1-f] naphtho [1,2-b] pyran compound (PC1 in Examples) that can be suitably used in the present invention.
  • the absorption edge largely depends on the type of substituent at the 6-position of indeno [2,1-f] naphtho [1,2-b] pyran.
  • the 6th position is the position indicated by 6 in the following formula.
  • the indeno [2,1-f] naphtho [1,2-b] pyran having an absorption edge of 400 nm or more includes a hydroxyl group among the above-mentioned groups in which the 6-position is a hydrogen atom and the 6-position group
  • the substituents that they may have are the same as those described above.
  • the 6-position group includes a hydroxyl group, an alkyl group, a cycloalkyl group, an alkoxy group, an amino group, and a ring member nitrogen atom among the above-described groups because the absorption edge is 410 nm or more.
  • a heterocyclic group, an aralkyl group, an aryl group, an aryloxy group, a heteroaryl group, or an alkylthio group in which an atom is directly bonded to a benzene ring to which the atom is bonded is particularly preferable.
  • indeno [2,1-f] naphtho [1,2-b] pyran compound Among the above-described indeno [2,1-f] naphtho [1,2-b] pyran compounds, specific examples of suitable compounds include compounds of the following formula.
  • the indeno [2,1-f] naphtho [1,2-b] pyran compound used in the present invention is used alone or in combination of two or more for the purpose of adjusting the color tone.
  • photochromic compounds having a structure other than indeno [2,1-f] naphtho [1,2-b] pyran can be appropriately mixed and used as long as the effects of the present invention are not impaired.
  • the ratio of the indeno [2,1-f] naphtho [1,2-b] pyran compound in all the photochromic compounds is 50% by mass or more, preferably 70% by mass or more.
  • UV absorber The present invention combines the above-mentioned indeno [2,1-f] naphtho [1,2-b] pyran compound with an ultraviolet absorber having a maximum absorption wavelength in the longest wavelength region in the range of 280 to 330 nm.
  • Ultraviolet absorber having a maximum absorption wavelength in the longest wavelength range of less than 280 nm, for example, benzoate ultraviolet absorption represented by 2,4-di-t-butylphenyl-3,5-di-t-butyl-4-hydroxybenzoate With the agent, the effect of improving the repeated durability against light exposure cannot be obtained.
  • an ultraviolet absorber having a longest maximum wavelength of more than 330 nm for example, benzotriazole ultraviolet rays represented by 2- (3-tert-butyl-2-hydroxy-5-methylphenyl) -5-chlorobenzotriazole
  • an absorber or a triazine ultraviolet absorber represented by tri (pn-hexyloxyphenyl) triazine an effect of improving the repeated durability against light exposure can be obtained, but the color density is remarkably lowered.
  • the maximum absorption wavelength in the longest wavelength region will be described with reference to FIG.
  • FIG. 2 shows an ultraviolet absorption spectrum of ethyl-2-cyano-3,3-diphenyl acrylate that can be suitably used in the present invention.
  • This ultraviolet absorber usually has maximum absorption wavelengths at a plurality of locations. Among these, the maximum absorption wavelength existing in the longest wavelength range is referred to as the maximum absorption wavelength in the longest wavelength range.
  • the ultraviolet absorber used in the present invention is an ultraviolet absorber having a maximum absorption wavelength in the longest wavelength range in the range of 280 to 330 nm.
  • a cyanoacrylate compound represented by the following formula (2) can be preferably used.
  • R 1 Is an aryl group which may have a substituent
  • R 2 Is an organic group having 1 to 12 carbon atoms
  • x is 1 or 2.
  • R 1 The number of carbon atoms of the aryl group represented by is not particularly limited, but is preferably 6 to 14.
  • aryl group examples include a phenyl group, a naphthyl group, an anthryl group, and a phenanthryl group.
  • the above aryl group may have a substituent.
  • Preferred examples of such a substituent include an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, and an alkylenedioxy group having 1 to 4 carbon atoms.
  • an alkyl group having 1 to 6 carbon atoms such as a methyl group, an ethyl group, a propyl group, a butyl group; a methoxy group, an ethoxy group, a propoxy group, a butoxy group, a hexyloxy group, a 2-ethylhexyloxy group, Examples thereof include alkoxy groups having 1 to 12 carbon atoms such as octyloxy group and dodecyloxy group; alkylene dioxy groups having 1 to 4 carbon atoms such as methylenedioxy group and ethylenedioxy group.
  • R 1 Preferable specific examples of the aryl group which may have a substituent include phenyl group, methoxyphenyl group, methylenedioxyphenyl group, tolyl group, xylyl group, anthryl group, phenanthryl group and the like.
  • R 2 The organic group having 1 to 12 carbon atoms is preferably an alkyl group having 1 to 12 carbon atoms. Specifically, a methyl group, ethyl group, propyl group, butyl group, hexyl group, 2-ethylhexyl group, octyl group, dodecyl group and the like are preferable.
  • a preferred cyanoacrylate compound used in the present invention is R in the above formula (2). 1 Is an aryl group having 6 to 14 carbon atoms and R 2 Is an alkyl group having 1 to 12 carbon atoms and x is 2. Specific examples of the cyanoacrylate compound used in the present invention include ethyl-2-cyano-3,3-diphenyl acrylate, 2′-ethylhexyl-2-cyano-3,3-diphenyl acrylate, and ethyl-2-cyano-3.
  • ethyl-2-cyano-3,3-diphenyl acrylate and methyl-2-cyano-3,3-diphenyl acrylate are preferable, and ethyl-2-cyano-3,3-diphenyl acrylate is most preferable.
  • These cyanoacrylate compounds may be used alone or in combination of two or more.
  • a benzophenone compound represented by the following formula (3) can also be suitably used in the present invention.
  • R 3 ⁇ R 5 Are each independently a hydrogen atom, a hydroxyl group, an alkoxy group or an aralkoxy group.
  • alkoxy group examples include alkoxy groups having 1 to 12 carbon atoms such as a methoxy group, an ethoxy group, a propoxy group, a butoxy group, a hexyloxy group, a 2-ethylhexyloxy group, an octyloxy group, and a dodecyloxy group. .
  • alkoxy groups having 1 to 12 carbon atoms such as a methoxy group, an ethoxy group, a propoxy group, a butoxy group, a hexyloxy group, a 2-ethylhexyloxy group, an octyloxy group, and a dodecyloxy group.
  • aralkoxy group a benzyloxy group can be mentioned, for example.
  • benzophenone compound used in the present invention examples include 2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-octyloxybenzophenone, 2-hydroxy-4-benzyloxybenzophenone, 2 2,2′-dihydroxy-4-methoxybenzophenone, 2,2 ′, 4,4′-tetrahydroxybenzophenone, 2,2′-dihydroxy-4,4′-dimethoxybenzophenone, 2-hydroxy-4-dodecyloxybenzophenone, etc. Is mentioned. These benzophenone compounds may be used alone or in combination of two or more. Moreover, you may mix and use the cyanoacrylate compound demonstrated previously.
  • the ultraviolet absorber having a maximum absorption wavelength in the longest wavelength range of 280 to 330 nm with respect to 100 parts by mass of the indeno [2,1-f] naphtho [1,2-b] pyran compound. 1 to 300 parts by mass, preferably 3 to 100 parts by mass, and more preferably 5 to 50 parts by mass to obtain a photochromic composition. If the amount is less than 1 part by mass, the effect of improving the repeated durability is small. If the amount exceeds 300 parts by mass, the effect of improving the repeated durability is large, but the color density is insufficient.
  • the photochromic composition of the present invention develops a good reversible photochromic effect in a polymer material by color development upon irradiation with sunlight or ultraviolet light, and quickly returns to a transparent state when the light is blocked. Therefore, the photochromic composition of the present invention can be made into a photochromic spectacle lens by uniformly dispersing in a polymer material (polymer solid matrix) exemplified below and molding it.
  • the polymer solid matrix to be used is not particularly limited as long as the photochromic composition of the present invention is uniformly dispersed, and optically preferably, for example, polymethyl acrylate, polyethyl acrylate, polymethyl methacrylate, Mention may be made of thermoplastic resins such as polyethyl methacrylate, polystyrene, polyacrylonitrile, polyvinyl alcohol, polyacrylamide, poly (2-hydroxyethyl methacrylate), polydimethylsiloxane and polycarbonate.
  • thermoplastic resins such as polyethyl methacrylate, polystyrene, polyacrylonitrile, polyvinyl alcohol, polyacrylamide, poly (2-hydroxyethyl methacrylate), polydimethylsiloxane and polycarbonate.
  • the indeno [2,1-f] naphtho [1,2-b] pyran compound used in the present invention is mixed with various polymerizable monomers before forming a polymer, whereby a curable photochromic composition. It can also be set as a photochromic hardening body by polymerizing and hardening this. That is, by curing the photochromic composition of the present invention and the curable photochromic composition containing various polymerizable monomers, a cured product in which the photochromic composition is uniformly dispersed can be obtained.
  • polymerizable monomer examples include ethylene glycol diacrylate, diethylene glycol dimethacrylate, triethylene glycol dimethacrylate, tetraethylene glycol dimethacrylate, ethylene glycol bisglycidyl methacrylate, bisphenol A dimethacrylate, and 2,2-bis (4 -Methacryloyloxyethoxyphenyl) propane, 2,2-bis (3,5-dibromo-4-methacryloyloxyethoxyphenyl) propane, trimethylolpropane trimethacrylate, polyester acrylate, urethane acrylate, etc.
  • Acid esters diallyl phthalate, diallyl terephthalate, diallyl isophthalate, diallyl tartrate, epoxy succinic acid
  • Polyvalent allyl compounds such as allyl, diallyl fumarate, diallyl chlorendate, diallyl hexaphthalate, diallyl carbonate, allyl diglycol carbonate, trimethylolpropane triallyl carbonate; 1,2-bis (methacryloylthio) ethane, bis (2- (Acryloylthioethyl) ether, 1,4-bis (methacryloylthiomethyl) benzene and other polyvalent thioacrylates or polyvalent thiomethacrylates; glycidyl acrylate, glycidyl methacrylate, ⁇ -methylglycidyl methacrylate, bisphenol A-monoglycidyl Ether-methacrylate, 4-glycidyloxymethacrylate, 3- (glycidyl-2
  • Examples of a method for obtaining a photochromic eyeglass lens containing the photochromic composition of the present invention include a method in which a photocatalytic composition is dissolved in the above polymerizable monomer, and then a polymerization catalyst is added and polymerized by heat or light. It is done.
  • the curable photochromic composition is prepared by mixing the photochromic composition of the present invention and the polymerizable monomer, the mixing ratio of the photochromic composition and the polymerizable monomer is the photochromic composition of the present invention.
  • the photochromic composition is usually 0.001 to 20 masses per 100 mass parts of the polymerizable monomer. Part, preferably 0.01 to 5 parts by weight.
  • a cured product of a curable photochromic composition mainly containing bisphenol A and a skeleton that does not contain a skeleton similar thereto tends to have a particularly large effect of improving repeated durability. Particularly preferred.
  • the refractive index of the lens as the cured body is about 1.48 to 1.52.
  • various stabilizers such as antioxidants, ultraviolet stabilizers, dyes, pigments, anti-coloring agents, antistatic agents, and fluorescent dyes, and additives may be added as necessary.
  • the UV stabilizer a hindered amine light stabilizer, a hindered phenol light stabilizer, a sulfur-based antioxidant, and the like can be suitably used.
  • the amount of the UV stabilizer used is not particularly limited, but is usually in the range of 1 to 1,000 parts by mass, more preferably 10 to 300 parts by mass with respect to 100 parts by mass of the photochromic composition.
  • a known method can be adopted as a method of polymerization and curing.
  • the polymerization means can be carried out by using polymerization initiators such as various peroxides and azo compounds, or by irradiation with ultraviolet rays, ⁇ rays, ⁇ rays, ⁇ rays, etc., or in combination with both.
  • a typical polymerization method is exemplified by injecting a polymerization composition comprising a polymerization initiator, the photochromic composition of the present invention and a polymerizable monomer between molds held by an elastomer gasket or a spacer, and a heating furnace. Cast polymerization that is removed after polymerization in can be employed.
  • a well-known thing can be used as a polymerization initiator.
  • Typical examples are benzoyl peroxide, p-chlorobenzoyl peroxide, decanoyl peroxide, diallyl peroxide such as lauroyl peroxide, acetyl peroxide; t-butylperoxy-2-ethylhexanate, t -Butylperoxyneodecanate, cumylperoxyneodecanate, t-butylperoxybenzoate, t-butylperoxyisobutyrate, 1,1,3,3-tetramethylbutylperoxy-2-ethylhexanate And peroxyesters such as diisopropyl peroxycarbonate and di-sec-butylperoxydicarbonate; and azo compounds such as azobisisobutyronitrile.
  • t-butyl peroxyneodecanate t-butylperoxyneodecanate / t-butylperoxyisobutyrate
  • a combination of oxy-2-ethylhexanate is preferable in terms of polymerization efficiency and hardness of the cured product.
  • a polymerization catalyst is added, and applied to the surface of a lens made of a thermoplastic resin or a thermosetting resin.
  • a photopolymerization initiator exemplified below as a polymerization catalyst.
  • photopolymerization initiator examples include benzoin, benzoin methyl ether, benzoin butyl ether, benzophenol, acetophenone, 4,4′-dichlorobenzophenone, diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one.
  • Benzyl methyl ketal 1- (4-isopropylphenyl) -2-hydroxy-2-methylpropan-1-one, 1-hydroxycyclohexyl phenyl ketone, 2-isopropylthioxanthone, bis (2,6-dimethoxybenzoyl-2, 4,4-trimethyl-pentylphosphine oxide, bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide, 2,4,6-trimethylbenzoyldiphenyl-phosphine oxide, 2- And benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1.
  • Seasorb 502 2′-ethylhexyl-2-cyano-3,3-diphenyl acrylate (maximum absorption wavelength in the longest wavelength range is 300 nm, manufactured by Sipro Kasei Co., Ltd.). 4).
  • Seesorb 107 2,2′-dihydroxy-4,4′-dimethoxybenzophenone (maximum absorption wavelength in the longest wavelength range is 320 nm, manufactured by Sipro Kasei Co., Ltd.) 5.
  • UV absorber Sumisorb 400: 2,4-di-t-butylphenyl-3,5-di-t-butyl-4-hydroxybenzoate (benzoate UV absorber; maximum absorption wavelength in the longest wavelength range is 255 nm, Sumika Chemitex Corporation).
  • ADK STAB LA36 2- (3-tert-butyl-2-hydroxy-5-methylphenyl) -5-chlorobenzotriazole (benzotriazole ultraviolet absorber; maximum absorption wavelength in the longest wavelength range is 355 nm, manufactured by Adeka Corporation ). 6).
  • Polymerizable monomer 3PG tripropylene glycol dimethacrylate.
  • 4G Tetraethylene glycol dimethacrylate.
  • A400 Polyethylene glycol diacrylate (average molecular weight 532).
  • THHA urethane acrylate obtained by reacting trimethylhexamethylene diisocyanate with 2-hydroxyethyl acrylate.
  • TMPT Trimethanolpropane trimethacrylate
  • EB-1830 Polyester oligomer hexaacrylate.
  • BPE-100N 2,2-bis (4-methacryloyloxyethoxyphenyl) propane.
  • BPE-500 2,2-bis (4-methacryloyloxypentaethoxyphenyl) propane.
  • GMA glycidyl methacrylate.
  • MS ⁇ -methylstyrene.
  • MSD ⁇ -methylstyrene dimer. 7).
  • Polymerization initiator perbutyl ND t-butyl peroxyneodecanate.
  • Perocta O 1,1,3,3-tetramethylbutyl peroxy-2-ethylhexanate.
  • CGI1800 A mixture of 1-hydroxycyclohexyl phenyl ketone and bis (2,6-dimethoxybenzoyl) -2,4,4-trimethyl-pentylphosphine oxide (mass ratio 3: 1).
  • Example 1 A photochromic composition comprising 0.04 part of PC1 as an indeno [2,1-f] naphtho [1,2-b] pyran compound and 0.01 part of Seesorb 501 as a cyanoacrylate ultraviolet absorber, 3 parts of 50 parts of THPG, THHA 25 Part, TMPT 10 parts, A400 12 parts, GMA 1 part and MSD 2 parts were dissolved in 100 parts of polymerizable monomer, and 1 part perbutyl ND and 0.1 part peroctaO were added and mixed well. This mixed solution was poured into a mold composed of a glass plate and a gasket made of an ethylene-vinyl acetate copolymer, and cast polymerization was performed.
  • the polymerization an air furnace was used, and the temperature was gradually raised from 30 ° C. to 90 ° C. over 18 hours and maintained at 90 ° C. for 2 hours. After completion of the polymerization, the polymer was removed from the mold glass mold.
  • the obtained photochromic cured product (thickness 2 mm) was used as a sample, and a xenon lamp L-2480 (300 W) SHL-100 manufactured by Hamamatsu Photonics Co., Ltd. was added to the sample at 20 ° C.
  • the cured product was measured for photochromic characteristics by irradiating with 120 ° C.
  • ⁇ max This is the maximum absorption wavelength after color development obtained by a spectrophotometer (instant multichannel photodetector MCPD1000) manufactured by Otsuka Electronics Co., Ltd. The maximum absorption wavelength is related to the color tone at the time of color development.
  • Color density ⁇ (120) ⁇ (0) ⁇ the difference between the absorbance ⁇ (120) ⁇ after the light irradiation for 120 seconds and the above ⁇ (0) at the maximum absorption wavelength.
  • the higher the residual rate, the higher the repetition durability, and the yellowness degree ⁇ YI YI (200) ⁇ YI (0) using a color difference meter (SM-4) manufactured by Suga Test Instruments Co., Ltd. The value was determined.
  • Example 2 Except for using 0.03 part of PC3 as the indeno [2,1-f] naphtho [1,2-b] pyran compound and 0.04 part of Seasorb 502 as the cyanoacrylate UV absorber, the same as in Example 1.
  • Example 4 0.02 part of PC2 and 0.01 part of PC3 as indeno [2,1-f] naphtho [1,2-b] pyran compounds, 0.02 part of PC4 as other photochromic compounds, and Seasorb 501 as a cyanoacrylate ultraviolet absorber
  • a lens was prepared and evaluated in the same manner as in Example 1 except that 0.01 part was used. The composition is shown in Table 1, and the evaluation results are shown in Table 2.
  • Example 5 A lens was prepared and evaluated in the same manner as in Example 1 except that 50 parts of BPE-100N, 7 parts of TMPT, 30 parts of 4G, 3 parts of GMA, 8 parts of MS and 2 parts of MSD were used as the polymerizable monomer. went. The composition is shown in Table 1, and the evaluation results are shown in Table 2.
  • Example 6 Except for using 0.04 part of PC1 as indeno [2,1-f] naphtho [1,2-b] pyran compound and 0.005 part of Seasorb 501 and 0.005 part of Adeka Stub 1413 as cyanoacrylate ultraviolet absorber. Were prepared in the same manner as in Example 1 and evaluated. The composition is shown in Table 1, and the evaluation results are shown in Table 2.
  • Example 7 A photochromic composition comprising 2 parts of PC3 as an indeno [2,1-f] naphtho [1,2-b] pyran compound and 0.5 part of Seasorb 501 as a cyanoacrylate UV absorber, 56 parts of BPE-500, A400 11 1 part of TMPT, 11 parts of TMPT, 11 parts of EB-1830 and 11 parts of GMA and dissolved in 100 parts of polymerizable monomer, 0.3 parts by weight of CGI1800 as a photopolymerization initiator, and bis (1, 2,2,6,6-pentamethyl-4-piperidyl) sebacate, 7 parts by mass of ⁇ -methacryloyloxypropyltrimethoxysilane as a silane coupling agent and 3 parts by mass of N-methyldiethanolamine were added.
  • This surface-coated lens was irradiated with a metal halide lamp with an output of 120 mW / cm 2 in a nitrogen gas atmosphere for 3 minutes to be cured (indeno [2,1-f] naphtho [1,2-b]
  • An optical article (photochromic plastic lens) covered with a polymer film in which a pyran compound was dispersed was prepared (thickness of polymer film: 40 ⁇ m). The obtained lens was used as a sample, and the same evaluation as in Example 1 was performed.
  • the composition is shown in Table 1, and the results are shown in Table 2.
  • Comparative Example 1 A lens was prepared in the same manner as in Example 1 except that 0.04 part of PC1 was used as the indeno [2,1-f] naphtho [1,2-b] pyran compound and no ultraviolet absorber was used. And evaluated. The composition is shown in Table 1, and the evaluation results are shown in Table 2. Compared to Example 1, it can be seen that the repeated durability is inferior. Comparative Example 2 A lens was prepared in the same manner as in Example 5 except that 0.04 part of PC1 was used as the indeno [2,1-f] naphtho [1,2-b] pyran compound and no ultraviolet absorber was used. And evaluated. The composition is shown in Table 1, and the evaluation results are shown in Table 2. Compared to Example 5, it can be seen that the repetition durability is inferior.
  • Comparative Example 4 Example 1 except that 0.04 part of PC1 was used as the indeno [2,1-f] naphtho [1,2-b] pyran compound and 0.01 part of sorbate 400 of benzoate compound was used as the UV absorber.
  • a lens was prepared and evaluated in the same manner as described above. The composition is shown in Table 1, and the evaluation results are shown in Table 2. It can be seen that when the ultraviolet absorber having the shortest maximum absorption wavelength of 255 nm is used, the effect of improving the repeated durability is not observed.
  • Comparative Example 5 Example except that 0.04 part of PC1 was used as the indeno [2,1-f] naphtho [1,2-b] pyran compound and 0.01 part of Adekastab L36 of benzotriazole compound was used as the UV absorber.
  • a lens was prepared and evaluated in the same manner as in 1. The composition is shown in Table 1, and the evaluation results are shown in Table 2. It can be seen that when the ultraviolet absorber having the longest maximum absorption wavelength of 355 nm is used, the color density is significantly lowered although the repetition durability is good.
  • Examples 8 to 16 Using indeno [2,1-f] naphtho [1,2-b] pyran compounds and ultraviolet absorbers listed in Table 3, lenses were prepared and evaluated in the same manner as in Example 1. The results are shown in Table 4.
  • Comparative Example 6 A lens was prepared in the same manner as in Example 11 except that 0.04 part of PC2 was used as the indeno [2,1-f] naphtho [1,2-b] pyran compound and no ultraviolet absorber was used. And evaluated. The composition is shown in Table 3, and the evaluation results are shown in Table 4. Compared with Example 11, it turns out that it is inferior to repeated durability. In addition, it turns out that the fall of the coloring density by addition of a ultraviolet absorber is slightly large compared with the system using the polymerizable monomer of Example 1 and Comparative Example 1.
  • Comparative Example 7 A lens was prepared in the same manner as in Example 15 except that 0.04 part of PC7 was used as the indeno [2,1-f] naphtho [1,2-b] pyran compound, and no ultraviolet absorber was used. Evaluation was performed. The composition is shown in Table 3, and the evaluation results are shown in Table 4. Compared to Example 15, it can be seen that the repetition durability is inferior. Effects of the Invention According to the present invention, a photochromic composition that provides a photochromic eyeglass lens excellent in repeated durability can be obtained.

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Abstract

La présente invention concerne une composition photochrome comprenant 100 parts en masse d'un indéno[2,1-f]naphto[1,2-b]pyranne dont le squelette est représenté par la formule (I) et 1 à 300 parts en masse d'un agent absorbant les ultraviolets dont l'absorption maximale se situe dans la gamme de longueurs d'onde de 280-330 nm, l'absorption maximale étant obtenue pour la longueur d'onde la plus élevée.
PCT/JP2010/072593 2009-12-10 2010-12-09 Composition photochrome WO2011071183A1 (fr)

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JP2021134330A (ja) * 2020-02-28 2021-09-13 株式会社トクヤマ フォトクロミック化合物、及び該フォトクロミック化合物を含む硬化性組成物

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JP6763138B2 (ja) * 2015-12-24 2020-09-30 コニカミノルタ株式会社 温度時間積算型インジケータ用組成物、温度時間積算型インジケータ、及び温度時間積算量の測定方法
WO2018078770A1 (fr) * 2016-10-27 2018-05-03 伊藤光学工業株式会社 Element photochromique et procede de fabrication correspondant

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JPH0446333A (ja) * 1990-06-13 1992-02-17 Toray Ind Inc フォトクロミック組成物および積層体
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WO2001060811A1 (fr) * 2000-02-21 2001-08-23 Tokuyama Corporation Compose de chromene
WO2005075193A1 (fr) * 2004-02-03 2005-08-18 Tokuyama Corporation Stratifie et son procede de production
WO2007032127A1 (fr) * 2005-09-15 2007-03-22 Hoya Corporation Composition durcissable et élément optique faisant usage de celle-ci
JP2007507569A (ja) * 2003-09-29 2007-03-29 チバ　スペシャルティ　ケミカルズ　ホールディング　インコーポレーテッド 光互変系の安定化

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JPH0446333A (ja) * 1990-06-13 1992-02-17 Toray Ind Inc フォトクロミック組成物および積層体
JPH11511199A (ja) * 1996-04-19 1999-09-28 トランジションズ・オプティカル・インコーポレイテッド 改良された疲労抵抗性のホトクロミックナフトピラン組成物
WO2001060811A1 (fr) * 2000-02-21 2001-08-23 Tokuyama Corporation Compose de chromene
JP2007507569A (ja) * 2003-09-29 2007-03-29 チバ　スペシャルティ　ケミカルズ　ホールディング　インコーポレーテッド 光互変系の安定化
WO2005075193A1 (fr) * 2004-02-03 2005-08-18 Tokuyama Corporation Stratifie et son procede de production
WO2007032127A1 (fr) * 2005-09-15 2007-03-22 Hoya Corporation Composition durcissable et élément optique faisant usage de celle-ci

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JP2021134330A (ja) * 2020-02-28 2021-09-13 株式会社トクヤマ フォトクロミック化合物、及び該フォトクロミック化合物を含む硬化性組成物

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