JPH11116565A - Photochromic compound, photochromic liquid composition, photochromic sheet and camera - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain the subject new compound capable of being rapidly dispersed in an aqueous phase and useful for printing materials, dimming lenses, color- changeable fibers for clothes, UV light checkers, and photosensitive inks. SOLUTION: A photochromic compound of formula I [X<1> ,X<2> are each O or the like; R<1> ,R<2> are each a 3-20C alkyl; (m), (n) are each an integer; the sum of (m) and (n) is 1 to 4]. For example, a compound of formula II. The compound of formula I is preferably used in an amount of 0.1-5 g/m<2> as a coating amount on a photochroic sheet. The combined employment of several photochromic compounds is effective for obtaining an especially desired developed color tone. An oil phase comprising the compound of formula I and an organic solvent (e.g. dibutyl phthalate), if necessary, containing a decoloration-accelerating agent (preferably tridodecyloxyphosphine or the like) can be mixed with the aqueous solution (aqueous phase) of a hydrophilic polymer (preferably gelatin and its derivative) to disperse the oil phase in an oil drop-like state. A polymer is preferably added to the oil drops to prevent the generation of haze.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

TECHNICAL FIELD The present invention relates to a photochromic compound, a liquid composition prepared using the photochromic compound, a sheet produced using the photochromic liquid composition, and a photochromic sheet as a substitute for a conventional camera diaphragm mechanism. The camera used.

[0002]

2. Description of the Related Art A photochromic compound is a compound having a property of developing a color when irradiated with light (usually UV light), and decoloring by means of stopping light irradiation or heating or irradiation with light of different wavelengths. For an overview of photochromic compounds, see Photochromism, Molecule and Syst
ems (Ed by H. Durrr; H. Bouas-Laurent Elsevier, NewY
ork 1989). Photochromic compounds include inorganic compounds such as silver halide containing inorganic glasses. However, an inorganic photochromic compound has a very low color erasing speed. Therefore, recently, mainly fulgide compounds, indolinospiropyran compounds,
Research and development of organic photochromic compounds such as thioindolinospiropyran compounds and spiropyran compounds are underway. Organic photochromic compounds are described in JP-B-45-28892 and JP-B-48-892.
No. 23787, No. 49-48631, No. 55-362
No. 84, JP-A-58-113203 and JP-A-61-263
No. 935, No. 61-267578, No. 63-6617
No. 8, JP-A-1-52783, JP-A-2-42084,
2-69471, 3-11075, 3-12
No. 118, No. 3-133988, No. 3-252453
Nos. 3,252,493 and 5,273,692, U.S. Pat.
8A2, East German Patent Nos. 0153-690 and 1563-
No. 72 is described in each specification.

[0003] Applications of photochromic compounds include:
Printing materials, dimming lenses (eg, correction lenses, sunglass lenses, goggle lenses), discoloring fibers for clothing, ultraviolet checkers, and photosensitive inks have been proposed. Currently, practical applications are particularly advanced in applications of sunglasses and goggles. Japanese Utility Model Application No. 61-100481 (Japanese Utility Model Application Laid-Open No. 63-6426) and Japanese Patent Application No. 61-1004.
No. 83 (JP-A-63-6427) and JP-A-64-49026 disclose a camera using a sheet containing a photochromic compound (photochromic sheet) in place of an ordinary camera diaphragm mechanism. Has been proposed. The photochromic sheet is disposed so as to block an optical path from the photographing opening to the photo film loading unit. Specifically, a photochromic sheet is arranged on the optical path in front of the lens (Japanese Utility Model Application No. 61-1004).
No. 81) or a lens and a photochromic sheet are integrally formed (Japanese Utility Model Application No. 61-100483).
Alternatively, the lens itself is formed from a photochromic sheet (JP-A-64-49026).

[0004] In any application, the speed of coloring and decoloring of the photochromic compound is important. Organic photochromic compounds have a faster decoloring rate than inorganic photochromic compounds, but still require further improvement. The color erasing speed of the organic photochromic compound largely depends on the temperature condition, and there is a problem that the color erasing speed at a low temperature is low. Sunglasses and goggles, which are the main uses of photochromic compounds, are often used under low-temperature conditions such as snowy mountains. In addition, since the photochromic compound has a property of coloring in a bright place and decoloring in a dark place, the photochromic sheet should theoretically substitute for the mechanism of the aperture of the camera. However, at the state of the art at the time of filing the above document (about 1987 to 1987), practical use of such a camera was impossible at all. Photochromic compounds at that time have very slow color development and color erasure. Therefore, a waiting time of several minutes was required for the photochromic compound to develop or decolor to a concentration suitable for the brightness at the time of photographing. Cameras that need to wait a few minutes before shooting are less than practical.

[0005] Japanese Patent Publication No. 7-26095 discloses a method for greatly improving the coloring and decoloring speed of an organic photochromic compound. The organic photochromic compound is generally used by being dispersed in a matrix made of an organic polymer. In this case, the photochromic compound is fixed to the matrix, and there has been a problem that it takes time to change the molecular structure of the photochromic compound in a color-forming reaction or a decoloring reaction. In the invention described in the above publication, an organic photochromic compound is added to oil droplets composed of a high-boiling organic solvent, and the oil droplets are dispersed in a layer containing a hydrophilic polymer. Thereby, the molecular structure of the photochromic compound can be freely changed, and the coloring speed and the decoloring speed are remarkably improved.

[0006]

[Problems to be Solved by the Invention] Japanese Patent Publication No. Hei 7-26095
In order to obtain the effects of the invention described in Japanese Patent Application Laid-Open No. H10-209, it is necessary to disperse oil droplets containing an organic photochromic compound finely and uniformly in an aqueous phase containing a hydrophilic polymer. Many conventional organic photochromic compounds require a very long time (several hours) for dispersion. If stirring for several hours is required for the preparation, the production efficiency is too low, and it becomes difficult to carry out the invention described in JP-B-7-26095. It is an object of the present invention to provide a photochromic compound that can be rapidly dispersed in an aqueous phase. Another object of the present invention is to provide a photochromic liquid composition that is easy to prepare. Still another object of the present invention is to provide a photochromic sheet having an improved decoloring speed. Still another object of the present invention is to enable the practical use of a photochromic sheet as a substitute for an aperture mechanism of a camera.

[0007]

The above objects are achieved by the following photochromic compound, photochromic liquid composition,
Achieved by photochromic sheet and camera. (1) A photochromic compound represented by the following formula (Ia).

[0008]

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Wherein X ¹ and X ² are each independently an oxygen or sulfur atom; R ¹ and R ²
Are each independently a branched alkyl group having 3 to 20 carbon atoms; and m and n are each an integer, and the sum of m and n is 1, 2, 3, or 4, is there. (2) A photochromic liquid composition in which oil droplets containing the photochromic compound represented by the formula (Ia) and an organic compound are dispersed in an aqueous phase containing a hydrophilic polymer. (3) A photochromic sheet having a hydrophilic layer containing a hydrophilic polymer on a transparent support, wherein oil droplets containing the photochromic compound represented by the formula (Ia) and an organic solvent are dispersed in the hydrophilic layer. (4) A camera in which a photochromic sheet is disposed in front of or behind a lens, or in which a lens and a photochromic sheet are integrally formed,
The photochromic sheet has a hydrophilic layer containing a hydrophilic polymer on a transparent support, and oil droplets containing the photochromic compound represented by the formula (Ia) are dispersed in the hydrophilic layer. A camera characterized by the following.

[0010]

According to the study of the present inventors, the above formula (I)
The photochromic compound represented by a) has good dispersibility in an aqueous phase, and a fine and uniform emulsion (photochromic liquid composition) can be obtained by stirring for a short time. Furthermore, the photochromic compound represented by the above formula (Ia) also has excellent properties normally required for a photochromic compound, such as the color development and decoloration rates. By using the phorochromic compound of the present invention,
The problem of the invention described in Japanese Patent Publication No. Hei 7-26095, which takes a long time to disperse the conventional organic photochromic compound, is solved. Therefore, in the photochromic liquid composition of the present invention, the effect of improving the coloring and decoloring rates by using oil droplets of an organic solvent (the effect of the invention described in JP-B-7-26095) can also be obtained. Furthermore, since the problem that the coloration and decoloration speed of the organic photochromic compound is slow is solved, the photochromic sheet can be put to practical use as a substitute for the aperture mechanism of a camera.

[0011]

BEST MODE FOR CARRYING OUT THE INVENTION

(Photochromic compound of the present invention) In the present invention, a photochromic compound represented by the following formula (Ia) is used.

[0012]

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In the formula (Ia), X ¹ and X ² are
Each is independently an oxygen atom or a sulfur atom. Oxygen atoms are preferred over sulfur atoms. The position where X ¹ and X ² are bonded to the benzene ring is not particularly limited. In the formula (Ia), R ¹ and R ² are each independently a branched alkyl group having 3 to 20 carbon atoms. A chain branched alkyl group is more preferable than a cyclic branched alkyl group. The number of carbon atoms in the alkyl group is 3
It is preferably from 15 to 15, more preferably from 3 to 10, still more preferably from 3 to 8, and most preferably from 3 to 6. The carbon atom causing the branch may be a tertiary carbon atom or a quaternary carbon atom. The branched carbon atom is preferably at the 1- to 6-positions of the alkyl group, more preferably at the 1- to 4-positions, still more preferably at the 1- to 3-positions, at the 1- or 2-positions. Is most preferred. It may have a plurality of branches. Examples of branched alkyl groups include isopropyl, isobutyl, sec-butyl, ter
Includes t-butyl, isopentyl, neopentyl, tert-pentyl, 1-methylbutyl, 2-methylbutyl, 1-ethylpropyl, 1,2-dimethylpropyl, isohexyl and 1-methyl-1-ethylpropyl.

In the formula (Ia), m and n are each an integer (0 to 4), and the sum of m and n is 1,
2, 3 or 4. When m or n is 2 to 4, X
¹ a plurality of groups represented by -R ¹ or X ² -R ² may be different from each other. Hereinafter, specific examples of the photochromic compound represented by the formula (Ia) will be shown.

[0015]

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[0016]

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[0017]

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[0018]

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[0019]

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[0020]

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The amount of the photochromic compound used is preferably 0.05 to 10 g / m ² , more preferably 0.1 to 5 g, as a coating amount on the photochromic sheet.
/ M ² is more preferable. Two or more photochromic compounds may be used in combination. In particular, a combination of a plurality of photochromic compounds is effective for obtaining a desired color hue (for example, black). You may use together with another photochromic compound.

(Other Photochromic Compounds That Can Be Used in Combination) Examples of the photochromic compound include indolinospiropyran compounds, fulgide compounds, pyran compounds, spirooxazine compounds, spironaphthoxazine compounds, diarylethene compounds, chromene compounds, thio-forms of these compounds, stilbenes. Derivatives and azo compounds are included. The photochromic compound generally has the following cyclic structure as a partial skeleton.

[0023]

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In the above formula, X ¹⁰ is a carbon atom or a nitrogen atom; Y ¹⁰ is an oxygen atom or a sulfur atom;
One or two substituents may be attached to the atoms contained in the ring; and two or more substituents may be attached to
A fused ring or spiro ring may be formed.

Examples of the substituent include an alkyl group (eg, methyl, ethyl, propyl, iso-propyl, butyl, sec-butyl, pentyl, iso-pentyl, hexyl, heptyl,
Octyl, dodecyl, stearyl), substituted alkyl groups (eg, trifluoromethyl, N- (p-propylphenyl) carbamoylmethyl, N-iso-pentylcarbamoylmethyl, 2-hydroxyethyl, 2-methoxyethyl, 2-propoxycarbonyl Ethyl), an alkoxy group (eg, methoxy, ethoxy, butoxy, octyloxy), a substituted alkoxy group (eg, 2-hydroxyethoxy, 3-hydroxypropoxy), an alkoxycarbonyl group (eg, ethoxycarbonyl), an alkylthio group (eg, Methylthio), aralkyl groups (eg, benzyl),
Substituted aralkyl groups (eg, n-pentadecylbenzyl),
An aralkylthio group (eg, benzylthio), an alkenyl group, (eg, 1-propenyl, allyl), an aryl group (eg, phenyl), a substituted aryl group (eg, diisopropylnaphthyl), an aryloxy group (eg, phenoxy),
Aryloxycarbonyl group (eg, phenoxycarbonyl), arylthio group (eg, phenylthio, naphthylthio), halogen atom (eg, fluorine atom, chlorine atom, bromine atom), substituted amino group (eg, dimethylamino, ethylamino, diethylamino, Dibutylamino, ethylbutylamino, phenylamino), amide group (eg, acetamide, propionamide, butylamide, benzamide,
Methacrylamide, 2-furancarboxamide), acyl group (eg, acetyl, benzoyl, acryloyl), acyloxy group (eg, acetoxy, acryloyloxy), alkylsulfonyl group (eg, methanesulfonyl,
Butanesulfonyl), substituted carbamoyl groups (eg, N-methylcarbamoyl, N-ethylcarbamoyl, N-iso-
Pentylcarbamoyl, N-butylcarbamoyl, N-
Phenylcarbamoyl, N-cyclohexylcarbamoyl, N-hydroxy-N-methylcarbamoyl, N-hydroxycarbamoyl), substituted sulfamoyl groups (eg,
Butanesulfamoyl), substituted carbamoyloxy groups (eg, N, N-diethylcarbamoyloxy), heterocyclic groups (eg, piperidino, pyrrolidino, furyl), ureido, hydroxy, cyano and nitro.

The number of carbon atoms of the substituent is preferably 30 or less, more preferably 20 or less, and 1
It is more preferably 5 or less, and most preferably 10 or less. The condensed ring and spiro ring formed by the bonding of the substituents are exemplified in the specific examples described later. Preferred nuclei of the photochromic compound are represented by the following formulas (I) and (II).

[0027]

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In the above formulas (I) and (II),
X ¹¹ , X ¹² and X ¹³ are each independently a carbon atom or a nitrogen atom; Y ¹¹ is an oxygen atom or a sulfur atom; R ¹¹ is a hydrogen atom or a substituent; May further have one or two substituents attached thereto; and two or more substituents may be attached to form a condensed ring or a spiro ring. Examples of substituents are
As described above. The condensed ring and spiro ring formed by the bonding of the substituents are exemplified in the specific examples described later. More preferred photochromic compounds are represented by the following formulas (VI) and (VII).

[0029]

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In the above formula (VI), X ¹⁴ , X ¹⁵ ,
X ¹⁶ , X ¹⁷ and X ¹⁸ are each independently a carbon atom or a nitrogen atom;
One or two substituents may be attached; and
Two or more substituents may combine to form a fused or spiro ring. Examples of the substituent are as described above.
The condensed ring and spiro ring formed by the bonding of the substituents are exemplified in the specific examples described later. Formula (VII)
Wherein X ¹⁹ and X ²⁰ are each independently a carbon atom or a nitrogen atom; Y is an oxygen atom or a sulfur atom; R ¹² and R ¹³ are each independently a hydrogen atom or a substituent; The atoms in the ring further include:
One or two substituents may be attached; two or more substituents may be joined to form a fused or spiro ring; and at least one of R ¹² and R ¹³ is
A substituent containing a hydroxy, amide bond or sulfonamide bond. Examples of the substituent are as described above.

Examples of the substituent containing a hydroxy, amide bond or sulfonamide bond include carbamoyl-substituted alkyl groups (eg, N- (p-propylphenyl) carbamoylmethyl, N-iso-pentylcarbamoylmethyl), hydroxy-substituted alkyl Group (eg, 2-hydroxyethyl), hydroxy-substituted alkoxy group (eg, 2-hydroxyethoxy, 3-hydroxypropoxy), amide group (eg, acetamide, propionamide, butylamide, benzamide, methacrylamide, 2-furancarboxamide) A substituted carbamoyl group (eg, N-methylcarbamoyl, N-ethylcarbamoyl, N-iso-pentylcarbamoyl, N-butylcarbamoyl, N-phenylcarbamoyl, N-cyclohexylcarbamoyl,
-Hydroxy-N-methylcarbamoyl, N-hydroxycarbamoyl), substituted sulfamoyl groups (eg, butanesulfamoyl), substituted carbamoyloxy groups (eg,
N, N-diethylcarbamoyloxy) and ureido. The condensed ring and spiro ring formed by the bonding of the substituents are exemplified in the following specific examples. Hereinafter, specific examples of other photochromic compounds that can be used in combination will be described.

[0032]

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[0033]

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──────────────────────────────────── Specific examples Substituents (R without description is hydrogen Atom) Ｉ Ib-01 R ¹ , R ² = dimethylamino Ib −02 R ¹ , R ² = methoxy Ib-03 R ¹ , R ² = butoxy Ib-04 R ¹ , R ² = butyroyl ＩIc-01 R ³ = butoxy, R ⁵ = acetamide Ic-02 R ² , R ³ = methyl, R ⁵ = methoxy, R ⁹ = propyl Ic-03 R ¹ = fluoro, R ⁴ = trifluoromethyl, R ⁵ = methoxy Ic-04 R ³ = dimethylamino Ic-05 R ³ = butoxy, R ⁵ = butyramide Ic-06 R ² = methyl, R ³ = ethyl, ⁵ = methoxy, R ⁹ = methoxy Ic-07 R ¹ = fluoro, R ⁴ = trifluoromethyl, R ⁵ = phenoxy ^{Ic-08 R 3, R 5} = methoxy, R ⁷ = hydroxy Ic-09 R ⁵ = methyl, R ⁷ = methoxy Ic-10 R ³ = methoxy, R ⁶ = methyl, R ⁸ = propionamide ────────

[0035]

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──────────────────────────────────── Specific examples Substituents (R without description is hydrogen Atom) ────────────────────────────────────Id-01 R ¹ = methyl, R ² = butyl Id-02 R ² = octyl────────────────────────────────────Ie-01 R ¹ = methyl , R ² = butyl Ie-02 R ² = acetyl

[0037]

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──────────────────────────────────── Specific examples Substituents (R without description is hydrogen Atom) ──────────────────────────────────── If-00 unsubstituted If-01 R ¹ = butoxy ──────────────────────────────────── Ig-00 unsubstituted ───────── ───────────────────────────

[0039]

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──────────────────────────────────── Specific examples Substituents (R without description is hydrogen Atom) ──────────────────────────────────── Ih-00 unsubstituted Ih-01 R ¹ = methoxy Ih-02 R ² = octyloxy ──────────────────────────────────── Ii-00 Unsubstituted Ii -01 R ⁷ = bromo Ii-02 R ² = dibutylamino, R ³ = methyl, R ⁴ = phenylamino, R ⁶ = octyloxy Ii-03 R ² = methoxy Ii-04 R ² , R ³ = chloro Ii- 05 R ² , R ³ = methoxy Ii-06 R ¹ , R ² = methyl, R ³ = methoxy, R ⁸ = propyl Ii-07 R ³ = acetamide, R ⁵ = methoxy Ii-08 R ² = methyl, R ³ = Butoxy, R ⁸ = propyl Ii-09 R ² = diethylamino, R ³ = butyl, R ⁴ = anilino Ii-10 R ² = dibutylamino, R ³ = methyl, R ⁴ = toluidino Ii-11 R ² = methoxy, R ³ = butoxy, R ⁶ = pentyloxy Ii-12 R ² = dihexylamino, R ³ = ethyl, R ⁴ = anilino, R ⁶ = butyl, R ⁸ = methyl ^{Ii-13 R 2, R 3} , R 8 = butoxy ────────────────────────────────────

[0041]

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──────────────────────────────────── Specific examples Substituents (R without description is hydrogen Atom) ──────────────────────────────────── Ij-01 R ¹ , R ⁴ = methoxy, R ² = ethyl, R ³ = methyl Ij-02 R ² = methyl, R ³ = acetamide Ik-01 R ² , R ⁴ = methoxy, R ³ = dimethylamino Ik-02 R ¹ , R ² , R ⁴ = methoxy, R ³ = dimethylamino ───────────────────────────

[0043]

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──────────────────────────────────── Specific examples Substituents (R without description is hydrogen Atom) ──────────────────────────────────── Il-01 R ² = dibutylamino, R ³ = Methyl, R ⁴ = anilino II-02 R ¹ = butoxy, R ² = dibutylamino, R ³ , R ⁴ = methyl, R ⁵ = methoxy 01Im-01 R ¹ = methoxy, R ² = ethoxy, R ³ = acetoxy Im-02 R ¹ = butoxy, R ² = acetamide ─────────────────────────────────

[0045]

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──────────────────────────────────── Specific examples Substituents (R without description is hydrogen Atom) ──────────────────────────────────── In-00 unsubstituted In-01 R ³ = hydroxy , R ⁵ = chloro, R ⁸ = acetyl In-02 R ¹ = fluoro, R ⁴ = trifluoromethyl, R ⁶ = methoxy ^{In-03 R 3, R 6} = dimethylamino, R ⁹ = propyl In-04 R ³ = Hydroxy, R ⁶ = chloro, R ⁷ = methyl, R ⁸ = acetyl In-05 R ¹ = fluoro, R ⁴ = trifluoromethyl, R ⁶ = phenoxy In-06 R ² , R ³ = methyl, R ⁶ = methoxy ^{In-07 R 3, R 6} = dimethylamino In-08 R ³ = dimethylamino ───────────────────── ────────────── Io-01 R ¹ = methyl, R ² = methoxy ──────────────────────── ────────────

[0047]

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──────────────────────────────────── Specific examples Substituents (R without description is hydrogen Atom) ──────────────────────────────────── Ip-00 unsubstituted ─────── ＩIq-01 R ¹ , R ² = methyl Iq-02 R ¹ , R ² = phenyl Iq −03 R ¹ , R ² = methyl, R ³ , R ⁴ = methoxy ───

[0049]

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──────────────────────────────────── Specific examples Substituents (R without description is hydrogen Atom) {Ir-01 R ¹ , R ² = dimethylamino} {Is-01 R ¹ = methyl, R ² = methoxy} ─────────────────────────────────

[0051]

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──────────────────────────────────── Specific examples Substituents (R without description is hydrogen Atom) ──────────────────────────────────── It-01 R ¹ = methyl, R ² = butyl ────────────────────────────────────IIa-01 R ² , R ⁹ , R ¹⁰ = methyl, R ⁶ = hexyl IIa-02 R ² = methylthio, R ⁶ = sec-butyl, R ⁹ , R ¹⁰ = methyl IIa-03 R ² = benzoyl, R ⁶ = benzyl, R ⁹ , R ¹⁰ = methyl IIa-04 R ² = phenylthio, R ⁶ = iso-pentyl, R ⁸ = methoxy, R ⁹ , R ¹⁰ = methyl IIa-05 R ¹ , R ² , R ⁶ , R ⁹ , R ¹⁰ = methyl, R ⁴ = acetyl, R ⁷ = Methoxy, IIa-06 R ⁴ , R ⁶ , R ⁹ , R ¹⁰ = Methyl IIa-07 R ¹ = acetoxy, R ⁴ , R ⁶ , R ⁹ , R ¹⁰ = methyl IIa-08 R ² = methoxy, R ⁴ = piperidino, R ⁶ , R ⁹ , R ¹⁰ = methyl IIa-09 R ² = hydroxy, R ⁴ = ^{cyano, R 6, R 9, R} 10 = methyl IIa-10 R ² = methoxy, R ⁴ = trifluoromethyl, R ⁶ = hexyl, R ^9, R ¹⁰ = methyl IIa-11 R ¹ = ^{phenoxy, R 6, R 9, R} 10 = ethyl IIa-12 R ¹ = methacrylamide, R ³ = ethyl butylamino R ⁶ = heptyl, R ^9, R ¹⁰ = methyl IIa-13 R ³ = acryloyloxy, R ⁴ = 1-propenyl, R ⁶ = propyl, R ⁷ = chloro, R ⁹ , R ¹⁰ = methyl IIa-14 R ² = N-butylcarbamoyl, R ⁶ , R ⁹ , R ¹⁰ = methyl IIa-15 R ¹ = ethylamino, R ⁴ = trifluoromethyl, R ⁶ = 2-propoxy Ruboniruechiru, R ^9, R ¹⁰ = ethyl ────────────────────────────────────

(Continued) ──────────────────────────────────── IIa-51 R ⁵ = N− Phenylcarbamoyl, R ⁶ = butyl, R ⁹ , R ¹⁰ = methyl IIa-52 R ⁵ = 2-hydroxyethoxy, R ⁶ , R ⁹ , R ¹⁰ = ethyl IIa-53 R ⁶ = 2-hydroxyethyl, R ⁹ , R ¹⁰ = methyl IIa-54 R ⁵ = butylamide, R ⁶ = propyl, R ⁹ , R ¹⁰ = methyl IIa-55 R ⁵ = hydroxy, R ⁶ = butyl, R ⁸ = methoxy, R ⁹ , R ¹⁰ = methyl IIa -56 R ² = bromo, R ⁶ = 2-hydroxyethyl, R ⁹ , R ¹⁰ = methyl IIa-57 R ² = ethoxycarbonyl, R ⁶ = 2-hydroxyethyl, R ⁹ , R ¹⁰ = methyl IIa-58 R ⁵ = ureido, R ⁶ = hexyl, R ⁹ , R ¹⁰ = methyl IIa-59 R ⁵ = N-phenylcarbamoy Le, R ⁶ = benzyl IIa-60 R ⁵ = N- phenylcarbamoyl, R ⁶ = 2-ethylhexyl IIa-61 R ⁵ = N- tolylcarbamoyl, R ⁶ = octyl, R ⁷ = dibutylamino ────── ──────────────────────────────

[0054]

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──────────────────────────────────── Specific examples Substituents (R without description is hydrogen Atom) IIb-01 R ² , R ⁵ , R ⁷ , R ⁸ = ethyl IIb-02 R ² = methoxy, R ³ = ethoxy, R ⁵ = dodecyl, R ^7, R ⁸ = methyl IIb-03 R ¹ = ^{acetyl, R 2, R 6, R} 7, R 8 = methyl , R ³ = chloro, R ⁵ = octyl チ ル IIb-51R ⁴ = N-phenylcarbamoyl, R ⁵ = butyl, R ⁷ , R ⁸ = methyl ───── IIc-01 R ¹ = nitro, R ² = propyl, R ^3, R ⁴ = methylate ────────────────────────────────────

[0056]

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──────────────────────────────────── Specific examples Substituents (R without description is hydrogen Atom) ──────────────────────────────────── IId-01 R ¹ = ethyl, R ² , R ³ , R ⁴ = methyl────────────────────────────────────IId-51 R ² = N- (P-propylphenyl) carbamoylmethyl, R ³ , R ⁴ = methyl IIe-01 R ¹ = methoxy, R ² = ethoxy, R ³ , R ⁵ , R ⁶ = methyl IIe-02 R ¹ = acetyl, R ² , R ⁴ = methoxy, R ³ , R ⁵ , R ⁶ = Methyl ─────────────────────────────── ────

[0058]

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──────────────────────────────────── Specific examples Substituents (R without description is hydrogen Atom) IIf-01 R ¹ = butanesulfonyl, R ² = Chloro, R ³ , R ⁴ , R ⁵ = methyl ────────────────────────────────────IIg- 01 R ¹ = methoxy, R ² = diethylamino, R ³ , R ⁴ , R ⁵ = methyl {IIg-51 R ² = N-cyclohexylcarbamoyl, R ³ , R ⁴ , R ⁵ = methyl} ──────────────

[0060]

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──────────────────────────────────── Specific examples Substituents (R without description is hydrogen Atom) ──────────────────────────────────── IIh-01 R ⁵ = hexyl, R ⁸ , R ⁹ = methyl ^{IIh-02 R 5, R 9} , R 10 = methyl ^{IIh-03 R 5, R 9} , R 10 = ethyl IIh-04 R ⁵ = benzyl, R ^9, R ¹⁰ = methyl IIh-05 R ^5, R ⁹ , R ¹⁰ = methyl, R ⁷ = chloro IIh-06 R ⁵ , R ⁹ , R ¹⁰ = methyl, R ⁷ = methoxy IIh-07 R ³ = ethoxy, R ⁵ , R ⁹ , R ¹⁰ = methyl IIh- 08 R ² = nitro, R ⁵ , R ⁹ , R ¹⁰ = methyl IIh-09 R ² = butyl, R ⁵ , R ⁹ , R ¹⁰ = methyl IIh-10 R ² = ethyl, R ⁴ = methanesulfonyl, R ⁵ , R ⁹ , R ¹⁰ = ethyl IIh-11 R ² = Methoxy, R ³ = ethoxy, R ⁵ = dodecyl, R ⁹ , R ¹⁰ = methyl IIh-12 R ¹ = acetyl, R ² , R ⁶ , R ⁹ , R ¹⁰ = methyl, R ³ = chloro, R ⁵ = Octyl IIh-13 R ⁴ = N-phenylcarbamoyl IIh-14 R ⁴ = N-xylylcarbamoyl, R ⁵ = isopropyl, R ⁷ = dimethylamino IIh-15 R ⁴ = N-butoxyphenylcarbamoyl, R ⁵ = 2-ethylhexyl , R ⁹ , R ¹⁰ = methyl

(Continued) IIi-01 R ⁴ , R ⁶ , R ^7, R ⁸ = methyl IIi-02 R ¹ = acetyl, R ² = trifluoromethyl, R ⁴ = ^{ethyl, R 5, R 6, R} 7, R 8 = methyl ^{IIi-03 R 1, R 6} = Methoxy, R ² = ethoxy, R ⁴ , R ⁷ , R ⁸ = methyl IIi-04 R ¹ , R ⁴ , R ⁷ , R ⁸ = methyl, R ² = trifluoromethyl, R ⁵ , R ⁶ = methoxy IIi- 05 R ¹ = methoxy, R ² = ethoxy, R ⁴ , R ⁷ , R ⁸ = methyl IIi-06 R ¹ = acetyl, R ² , R ⁵ = methoxy, R ³ = N-methylcarbamoyl, R ⁴ , R ⁷ , R ⁸ = methyl ────────────────────────────────────

[0063]

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──────────────────────────────────── Specific examples Substituents (R without description is hydrogen Atom) IIj-01 R ¹ = acetoxy, R ⁵ , R ⁸ , R ⁹ = methyl IIj-02 R ⁴ = piperidino, R ⁵ , R ⁸ , R ⁹ = methyl IIj-03 R ¹ , R ⁷ = methoxy, R ² = ethoxy, R ⁵ , R ⁸ , R ⁹ = methyl IIj-04 R ² , R ⁴ = trifluoromethyl, R ⁵ = hexyl, R ⁸ , R ⁹ = methyl IIj-05 R ³ = phenyl, R ⁴ = 1-propenyl, R ⁵ = propyl, R ⁶ , R ⁷ = Chloro, R ⁸ , R ⁹ = methyl IIj-06 R ¹ = methyl, R ² = trifluoromethyl, R ⁵ , R ⁸ , R ⁹ = propyl, R ⁶ , R ⁷ = methoxy ────── ────────────────────── IIk-01 R ¹ = ^{nitro, R 2, R 3, R} 4 = methyl ────────── ──────────────────────────

[0065]

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──────────────────────────────────── Specific examples Substituents (R without description is hydrogen Atom) ────────────────────────────────────IIl-01 R ¹ , R ³ , R ⁴ = Methyl, R ² = chloro────────────────────────────────────IIm-01 R ¹ , R ² , R ³ = methyl ────────────────────────────────────

[0067]

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──────────────────────────────────── Specific examples Substituents (R without description is hydrogen Atom) ──────────────────────────────────── IIn-01 R ¹ = phenyl, R ² = tri Fluoromethyl, R ³ , R ⁴ , R ⁵ = ethyl ────────────────────────────────────IIo -01 R ⁸ = hexyl, R ¹³ , R ¹⁴ = methyl IIo-02 R ⁸ , R ¹³ , R ¹⁴ = methyl IIo-03 R ⁸ , R ¹³ , R ¹⁴ = ethyl IIo-04 R ⁸ = benzyl, R ¹³ , R ¹⁴ = methyl IIo-05 R ⁸ , R ¹¹ , R ¹³ , R ¹⁴ = methyl IIo-06 R ⁸ , R ¹³ , R ¹⁴ = methyl, R ¹¹ = chloro IIo-07 R ⁸ , R ¹³ , R ¹⁴ = methyl, R ¹¹ = methoxy IIo-08 R ³ = acetoxy, R ⁸ R ^13, R ¹⁴ = methyl IIo-09 R ⁶ = ^{ethoxy, R 8, R 13, R} 14 = methyl IIo-10 R ⁶ = ^{piperidino, R 8, R 13, R} 14 = methyl IIo-11 R ⁴ = nitro R ⁸ , R ¹³ , R ¹⁴ = methyl, R ¹¹ = chloro IIo-12 R ⁴ , R ⁶ = trifluoromethyl, R ⁸ = hexyl, R ¹³ , R ¹⁴ = methyl IIo-13 R ⁴ = butyl, R ^8, R ^13, R ¹⁴ = methyl IIo-14 R ³ = ethyl, R ⁵ = butyl, R ⁸ = heptyl, R ^13, R ¹⁴ = methyl IIo-15 R ³ = acetyl, R ⁴ = trifluoromethyl, R ⁸ = ethyl, R ¹⁰ , R ¹¹ , R ¹³ , R ¹⁴ = methyl ───

(Continued) ────────────────────────────────────IIo-16 R ⁵ = phenyl, R ⁶ = 1-propenyl, R ⁸ = propyl, R ^10, R ¹¹ = chloro, R ^13, R ¹⁴ = methyl IIo-17 R ⁴ = methyl, R ⁸ = hexyl, R ^13, R ¹⁴ = methyl IIo-18 R ⁴ = methylthio, R ⁸ = sec-butyl, R ¹² = methoxy, R ¹³ , R ¹⁴ = methyl IIo-19 R ⁴ = phenylthio, R ⁸ = iso-pentyl, R ¹³ , R ¹⁴ = methyl IIo-20R ^{3, R 8, R 13,} R 14 = methyl, R ⁴ = methanesulfonyl, R ⁶ = acetyl, R ¹⁰ = methoxy, R ¹² = ethyl ^{IIo-21 R 6, R 8} , R 13, R 14 = methyl IIo -22 R ³ = acetoxy, R ⁶ , R ⁸ , R ¹³ , R ¹⁴ = methyl IIo-23 R ⁴ = acetyl, R ⁶ = piperidino, R ⁸ , R ¹³ , R ¹⁴ = Methyl IIo-24 R ⁴ = hydroxy, R ⁶ = cyano, R ⁸ , R ¹³ , R ¹⁴ = methyl IIo-25 R ⁴ = methoxy, R ⁶ = trifluoromethyl, R ⁸ = hexyl, R ¹³ , R ¹⁴ = Methyl IIo-26 R ³ = phenoxy, R ⁸ , R ¹³ , R ¹⁴ = ethyl IIo-27 R ³ = methacrylamide, R ⁵ = ethylamino, R ⁶ = butyl, R ⁸ = heptyl, R ¹³ , R ¹⁴ = Methyl IIo-28 R ¹ = piperidino, R ⁵ = acryloyloxy, R ⁶ = 1-propenyl, R ⁸ = propyl, R ¹⁰ = chloro, R ¹³ , R ¹⁴ = methyl IIo-29 R ⁴ = N-butylcarbamoyl ^{, R 8, R 13, R} 14 = methyl IIo-30 R ³ = ethylamino, R ⁶ = trifluoromethyl, R ⁸ = 2-propoxycarbonyl ethyl, R ^13, R ¹⁴ = ethyl IIo-31 R ⁸ = octyl , R ^13, R ¹⁴ = methyl ──── ───────────────────────────────

(Continued) ──────────────────────────────────── IIo-51 R ⁷ = N- Phenylcarbamoyl, R ⁸ , R ¹³ , R ¹⁴ = methyl IIo-52 R ⁷ = N-butylcarbamoyl, R ⁸ = ethyl, R ¹³ , R ¹⁴ = methyl IIo-53 R ⁷ = N-iso-pentylcarbamoyl, R ^8, R ^13, R ¹⁴ = ethyl, R ¹¹ = methyl IIo-54 R ⁴ = methoxy, R ⁷ = N-hydroxy -N- methylcarbamoyl, R ⁸ = hexyl, R ¹¹ = chloro, R ^13, R ¹⁴ = Methyl IIo-55 R ⁷ = N-cyclohexylcarbamoyl, R ⁸ = benzyl, R ¹¹ = methoxy, R ¹³ , R ¹⁴ = methyl IIo-56 R ⁷ = N-hydroxycarbamoyl, R ⁸ = 2-methoxyethyl, R ¹³ , R ¹⁴ = methyl IIo-57 R ⁴ , R ⁷ = butanesulfamoyl, R ⁸ = Iso-propyl, R ¹³ = methyl, R ¹⁴ = ethyl IIo-58 R ⁷ = acetamide, R ⁸ = propyl, R ¹³ , R ¹⁴ = methyl IIo-59 R ⁷ = hydroxyl, R ⁸ = hexyl, R ¹³ , R ¹⁴ = methyl IIo-60 R ⁷ = benzamide, R ⁸ = pentyl, R ¹³ , R ¹⁴ = methyl IIo-61 R ⁷ = 2-furancarboxamide, R ⁸ = allyl, R ¹³ , R ¹⁴ = methyl IIo-62 R ⁷ = 2-hydroxyethoxy, R ⁸ = ethyl, R ^13, R ¹⁴ = methyl IIo-63 R ¹ = 3- hydroxypropoxy, R ⁸ = propyl, R ^13, R ¹⁴ = methyl IIo-64 R ⁸ = 2 - hydroxyethyl, R ^13, R ¹⁴ = methyl ^{IIo-65 R 8 = N-} iso- pentylcarbamoyl methyl, R ^13, R ¹⁴ = methyl IIo-66 R ⁷ = N- phenylcarbamoyl, R ⁸ = N-iso- Pentylcarbamoylmethyl, R ¹³ , R ^{1 4} = methyl IIo-67 R ² = methoxy, R ⁷ = N-ethylcarbamoyl, R ⁸ = ethyl, R ⁹ , R ¹¹ = chloro, R ¹³ , R ¹⁴ = methyl ─────────────────────────

[0071]

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──────────────────────────────────── Specific examples Substituents (R without description is hydrogen Atom) IIp-01 R ¹ , R ³ , R ⁴ = Methyl, R ² = methoxy────────────────────────────────────IIq-01 R ¹ = phenyl, R ² = trifluoromethyl, R ³ , R ⁴ , R ⁵ = ethyl ───

[0073]

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──────────────────────────────────── Specific examples Substituents (R without description is hydrogen Atom) IIr-51 R ¹ = N-cyclohexylcarbamoyl, R ^2, R ^3, R ⁴ = methyl ──────────────────────────────────── IIs-01 R ¹ = Acetyl, R ² = diethylamino, R ³ , R ⁴ , R ⁵ = methyl {IIs-51 R ² = 3-hydroxypropoxy, R ³ = propyl, R ⁴ , R ⁵ = methyl} ─────────────

[0075]

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──────────────────────────────────── Specific examples Substituents (R without description is hydrogen Atom) IIt-51 R ¹ = benzamide, R ² = N -Ethylcarbamoyl, R ³ = methyl IIu-51 R ¹ = Methoxy, R ² = N-ethylcarbamoyl, R ³ = propyl, R ⁴ , R ⁵ = methyl IIu-52 R ¹ = methyl, R ² = N-phenylcarbamoyl, R ³ = ethyl, R ⁴ , R ⁵ = methyl IIu-53 R ¹ = methyl, R ² = acetamide, R ³ = allyl, R ⁴ , R ⁵ = methyl ───────────

[0077]

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──────────────────────────────────── Specific examples Substituents (R without description is hydrogen Atom) ──────────────────────────────────── IIv-01 R ¹ = nitro, R ² , R ³ , R ⁴ = methyl {IIw-01 R ² , R ⁴ , R ⁵ = methyl IIw-02 R ² , R ⁴ , R ⁵ = methyl, R ³ = methoxy IIw-03 R ¹ = ethyl, R ² , R ⁴ , R ⁵ = methyl ───────────────────────────

[0079]

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──────────────────────────────────── Specific examples Substituents (R without description is hydrogen Atom) IIx-01 R ¹ = phenyl, R ² = tri Fluoromethyl, R ³ , R ⁴ , R ⁵ = ethyl ────────────────────────────────────IIy -01 R ¹ = phenoxycarbonyl, R ² = benzoyl, R ³ = benzyl, R ⁴ , R ⁵ = methyl ───────────

[0081]

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──────────────────────────────────── Specific examples Substituents (R without description is hydrogen Atom) IIz-01 R ¹ = nitro, R ² = propyl , R ^3, R ⁴ = methyl ──────────────────────────────────── IIA-01 R ¹ = Pyrrolidino, R ² = butanesulfonyl, R ³ = chloro, R ⁴ , R ⁵ , R ⁶ = methyl ─────────

(Organic Solvent) An organic solvent is used for forming oil droplets containing a photochromic compound. As the organic solvent, a solvent having a high boiling point (190 ° C. or higher) is preferably used. Preferably, the high boiling organic solvent is substantially insoluble in water. Examples of high boiling organic solvents include carboxylic esters (eg, dibutyl phthalate, diisooctyl phthalate, dicyclohexyl phthalate, dimethoxyethyl phthalate, dibutyl adipate, diisooctyl azelenate, tributyl citrate, butyl laurate, sebacine Dibutyl acid), phosphates (eg, tricyclohexyl phosphate, tributyl phosphate, triisooctyl phosphate), carboxylic amides (eg, N, N-diethylcaprylic amide, N, N-dimethylpalmitic acid) Amide, butyl- (m-pentadecyl) phenyl ether,
Ethyl- (2,4-di-tert-butyl) phenyl ether), phenols (eg, 2,5-di-tert-amylphenol), aromatic amines (eg, 2-butoxy-5-)
tert-octylaniline), halogen-substituted hydrocarbons (eg, paraffin chloride), and hydrophobic organic polymers that are inactive at the surface (eg, polymethyl methacrylate, polyethyl methacrylate, polyethyl acrylate, polycyclohexyl methacrylate, poly-N-tert) -Butylacrylamide, poly-N-tert-octylacrylamide).

Instead of or in addition to the high boiling organic solvent,
An organic solvent having a low boiling point (130 ° C. or lower) may be used. As the low boiling point organic solvent, a solvent miscible with water may be used. Examples of low boiling organic solvents include esters (eg, propylene carbonate, methyl acetate, ethyl acetate, isopropyl acetate, butyl acetate, ethyl propionate), alcohols (eg, se
c-butyl alcohol), ketones (eg, methyl ethyl ketone, 2-pentanone, 3-pentanone, cyclohexanone), amides (eg, dimethylformamide), and sulfoxides (eg, dimethyl sulfoxide). The organic solvent is preferably used in the range of 0.1 to 100 parts by weight, more preferably 0.2 to 10 parts by weight, per 1 part by weight of the photochromic compound.

(Color Loss Accelerator) It is preferable to use a phosphine compound as a color loss accelerator. Examples of the phosphine compound include tridodecyloxyphosphine,
Tridecyloxyphosphine, trinonyloxyphosphine, trihexyloxyphosphine, tridodecylthiophosphine, tridecylthiophosphine,
Trinonylthiophosphine, trihexylthiophosphine, tridodecylphenyloxyphosphine, tributylphenyloxyphosphine, triethyloxyphosphine, trimethoxybutylphenyloxyphosphine, tripropenyloxyphosphine, tridecenyloxyphosphine , Tripropylphenoxyphosphine, trihexenyloxyphosphine, tridodecenyloxyphosphine, tridecenylthiophosphine and tributenyloxyphenyloxyphosphine. The phosphine compound is preferably used in the range of 5 to 90% by weight of the organic solvent, more preferably 10 to 80% by weight, and more preferably 1 to 80% by weight.
It is more preferably from 5 to 70% by weight, most preferably from 20 to 60% by weight.

(Oil Droplet Dispersion) An oil phase comprising a photochromic compound and an organic solvent (a solution containing other components such as a decolorizing accelerator, if necessary) is converted into an aqueous solution (aqueous phase) of a hydrophilic polymer described later. By mixing with, the oil phase containing the photochromic compound can be dispersed in the form of oil droplets. Instead of the aqueous solution of the hydrophilic polymer, water and an oil phase may be mixed to form oil droplets, and then the hydrophilic polymer may be added. The particle size of the oil droplets is 0.02
To 10 μm, preferably 0.05 to 2 μm.
m, more preferably 0.05 to 1 μm, and most preferably 0.05 to 0.5 μm. In mixing the oil phase and the aqueous phase, a forward mixing method in which the oil phase is added to the stirred aqueous phase may be used. However, the phase inversion method, which is a kind of the reverse mixing method, is particularly preferable because fine oil droplet particles can be formed. In the phase inversion method, an aqueous phase is added to an oil phase under stirring to form a W / O emulsion, which is then phase inverted to form an O / W emulsion.

In order to reduce the particle size of the oil droplet,
It is preferable to use a disperser. A high-speed stirring type disperser having a large shearing force or a disperser using high-intensity ultrasonic energy can be used. In a high-speed stirring type disperser,
The part that acts to disperse at a high speed in the liquid (500 to 20,000)
(rpm). Examples of high-speed stirring type dispersers include dissolvers, polytrons, homomixers,
Includes homo-blender, kedi mill and jet agitator. Dissolvers (also called high speed impeller dispersers) are preferred. It is particularly preferable to use a dissolver (described in Japanese Patent Application Laid-Open No. 55-129136) in which a shaft rotating at high speed is provided with an impeller in which saw-toothed plates are alternately bent vertically. In the oil droplet dispersion, it is preferable to use a surfactant. After a large amount of the surfactant is used to form fine oil droplets, an excess amount of the surfactant may be removed by washing with water (WO-93 / 3420).
No.). Cosolvents may be used in the oil-like dispersion. Methods for removing surfactants and cosolvents are described in U.S. Pat. Nos. 2,322,027, 2,801,171 and 294.
Nos. 6360, 3396027 and 423339
No. 7 is described in each specification. An outer shell may be formed at the interface between the water phase and the oil phase of the emulsion to make the oil droplets microcapsules. Various conventionally known methods for producing microcapsules can be employed. The “oil droplet” in the present invention includes a microcapsule having an outer shell formed on the surface of the oil droplet.

(Hydrophilic polymer) The hydrophilic polymer preferably has a wavelength longer than 350 nm, more preferably 35 nm.
It is desirable not to have absorption at wavelengths longer than 0 nm. Generally, a colorless and transparent hydrophilic polymer is used.
It is particularly preferred that the hydrophilic polymer is water-soluble.
Examples of hydrophilic polymers include proteins (eg, gelatin,
Gelatin derivatives, graft polymers of gelatin and other polymers, albumin, casein), polysaccharides (eg, hydroxyethylcellulose, carboxymethylcellulose, cellulose sulfate, sodium alginate)
And synthetic hydrophilic polymers (eg, polyvinyl alcohol, partially acetalized polyvinyl alcohol, poly-N
-Vinylpyrrolidone, polyacrylic acid, polymethacrylic acid, polyacrylamide, polyvinylimidazole, polyvinylimidazole). As the synthetic hydrophilic polymer, a copolymer of the above polymers may be used.

[0089] Particularly preferred hydrophilic polymers are gelatin and its derivatives. As gelatin, acid-processed gelatin may be used in addition to general lime-processed gelatin. A gelatin derivative is generally obtained by reacting gelatin with a specific compound. Examples of compounds to be reacted with gelatin include acid halides, acid anhydrides, aldehydes, isocyanates, bromoacetic acid, alkane sultones, vinylsulfonamides, maleimide compounds, polyalkylene oxides and epoxy compounds. It is.
Gelatin derivatives also include gelatin hydrolysates.
The hydrolyzate is usually obtained by enzymatic degradation of gelatin. The amount of the hydrophilic polymer used is generally 1 to 10 g.
/ M ² .

(Polymer for Adjusting Refractive Index) In an emulsion in which oil droplets containing a photochromic compound are dispersed, the refractive indices of the oil droplets and the hydrophilic polymer are usually different, and as a result, haze is generated. To prevent haze,
It is preferable to add a polymer to the oil droplets so as to adjust the refractive indices of the oil droplets and the hydrophilic polymer to be substantially the same. The difference between the refractive indices is preferably less than 0.05, more preferably less than 0.04, and 0.0
Most preferably, it is less than 3. For adjusting the refractive index of the oil droplet, it is preferable to use a polymer obtained by polymerization of an ethylenically unsaturated monomer. Examples of ethylenically unsaturated monomers include acrylic esters, methacrylic esters, crotonic esters, vinyl esters,
Includes maleic diester, fumaric diester, itaconic diester, acrylamides, methacrylamides, vinyl ethers and styrenes.

The polymer is preferably used as a latex. Specifically, an emulsion in which oil droplets containing a photochromic compound are dispersed and a polymer latex are mixed, and the oil droplets are impregnated or dissolved and coalesced with polymer particles in the latex. The amount and molecular weight of the polymer used are
It is determined in consideration of the difference in the refractive index between the oil droplet and the hydrophilic polymer. The amount of the latex used is preferably from 1 to 500% by weight, more preferably from 10 to 200% by weight, and even more preferably from 50 to 150% by weight of the amount of the oil droplets.

(Other Additives) The emulsion in which the oil droplets containing the photochromic compound are dispersed may further contain an antioxidant, a color development accelerator, a decolorization accelerator or a reducing agent. As the color development accelerator, compounds having an acetal group or a ketal group or zinc salicylates can be used.

(Transparent Support) As the transparent support, a synthetic polymer sheet or a glass plate can be used. Examples of synthetic polymers include polyethylene terephthalate, polyethylene naphthalate, polycarbonate, polyvinyl chloride, polystyrene, polypropylene, polyimide, and cellulose derivatives (eg, triacetyl cellulose). An antistatic layer may be provided on one or both sides of the transparent support. The antistatic layer can be formed by applying a semiconductor metal oxide (eg, alumina sol, tin oxide) together with a hydrophilic binder. Note that the transparent support may function as a lens depending on the application. The thickness of the transparent support is generally from 10 μm to 10 mm. In order to continuously apply a layer containing a photochromic compound (photochromic coloring layer), 10 to 20
It is preferable to apply a photochromic color-forming layer on a transparent film having a thickness of 0 μm, and to laminate it on a transparent substrate as necessary.

(Layer Structure of Photochromic Sheet) A photochromic sheet is produced by applying and drying an emulsion in which oil droplets containing a photochromic compound are dispersed on a transparent support. The thickness of the layer containing the photochromic compound is preferably 0.5 to 30 μm, more preferably 1 to 10 μm.
Two or more layers (up to about six layers) containing a photochromic compound may be provided on the transparent support. The photochromic sheet may be further provided with a protective layer and an ultraviolet absorbing layer.

The protective layer is provided as a layer containing a polymer on the layer containing a photochromic compound. As the polymer, both a hydrophilic polymer and a hydrophobic polymer are used. Examples of the hydrophilic polymer are the same as the examples of the hydrophilic polymer used in the layer containing the photochromic compound. Examples of the hydrophobic polymer, in addition to the example of the polymer used for adjusting the refractive index described above, polyvinyl butyral, polyvinyl formal, ethylene-vinyl acetate copolymer, ethylene-acrylic acid copolymer, polyvinyl chloride, polymethyl methacrylate, Includes acrylate-methacrylate copolymers, polyesters, vinyl acetate-vinyl chloride copolymers, polycarbonates, styrene-maleic anhydride maleimide copolymers, styrene-vinyl toluene copolymers, chlorosulfonated polyethylene, nitrocellulose, polyolefins and polyimides. Further, a protective layer may be formed as a cumulative film by the Langmuir-Blodgett method. When a cumulative film is formed, a compound other than a polymer such as a silane coupling agent, ω-tricosanoic acid, dioctadecyldimethylammonium chloride, or methyl stearate can be used as a matrix of the protective layer. The compound used as the matrix of the protective layer is preferably a wavelength longer than 350 nm, more preferably 35 nm.
It is desirable not to have absorption at wavelengths longer than 0 nm. The thickness of the protective layer is preferably from 0.1 to 10 μm, more preferably from 0.2 to 5 μm.

The photochromic sheet may be provided with an ultraviolet absorbing layer. In the use of the conventional photochromic compound, use of an ultraviolet absorber or installation of an ultraviolet absorbing layer has not been considered at all. Photochromic compounds are
It develops color by absorbing ultraviolet light. Therefore, the ultraviolet absorber cannot coexist with the photochromic compound, and the ultraviolet absorbing layer cannot be provided on the light source side of the layer containing the photochromic compound. In addition, the fact that the photochromic compound absorbs a certain amount of ultraviolet light has been definitely proved by its coloring reaction. However, research by the present inventors has revealed that the layer containing the photochromic compound unexpectedly transmits a large amount of ultraviolet light. In order to prevent transmission of harmful ultraviolet rays, it is preferable to provide an ultraviolet absorbing layer on the side farther from the light source than the layer containing the photochromic compound.

As the ultraviolet absorber, organic ultraviolet absorbing dyes or inorganic fine particles can be used. Examples of ultraviolet absorbing dyes include aryl-substituted benzotriazole compounds, 4-thiazolidone compounds, benzophenone compounds,
Includes cinnamate compounds, butadiene compounds and benzo-shell azole compounds. As inorganic fine particles, such as zinc oxide, cesium oxide and titanium dioxide,
Ultrafine metal oxide particles are used. Further, an ultraviolet absorbing polymer may be used as the ultraviolet absorbing agent. The amount of the ultraviolet absorber in the ultraviolet absorption layer is 0.02 to 10 g /
m ² , more preferably 0.1 to 5 g / m ² . As the binder of the ultraviolet absorbing layer, the same polymer as the polymer added to the layer containing the photochromic compound or the protective layer described above can be used. When the ultraviolet absorber is oil-soluble, it may be dispersed in the form of oil droplets. The organic solvent used for the oil droplet is the same as the organic solvent used for the layer containing the photochromic compound.

(Applications) The photochromic liquid composition and the photochromic sheet of the present invention include a printing material, a dimming lens (eg, a correcting lens, a sunglass lens,
It can be applied to various uses such as lenses for goggles), discolored fibers for clothing, UV checkers and photosensitive inks. The use of photochromic compounds is described in various documents. Further, as described in the specification of Japanese Utility Model Application No. 61-100485 (Japanese Utility Model Application Laid-Open No. 63-6431), a photochromic sheet is attached to a camera so that a warning mark is displayed when the amount of light is insufficient. You may. Further, as described in the specification of Japanese Utility Model Application No. 61-100487 (Japanese Utility Model Application Laid-Open No. 63-6428), a photochromic sheet may be used for a light amount measuring device attached to a camera. Further, a photochromic sheet can be used as a substitute for an ordinary camera aperture mechanism.

(Camera) The camera will be described with reference to the drawings. FIG. 1 is a perspective view of a camera body and a cover. In FIG. 1, a rectangular parallelepiped camera body (10)
And a rectangular parallelepiped cover (12) in which the camera body is closely housed. The camera body (10) includes a photographing lens (14) and a finder light blocking tube (1).
6), a shutter release button (18) and a film winding knob (20) are provided. Camera body (1
The imaging light-shielding cylinder (22) formed in 0) is formed so as to be concentric and spread stepwise. The light-shielding cylinder (22) having the step-like steps prevents unnecessary diffuse reflection during photographing. Similarly, a stepped step is formed in the finder light-shielding cylinder (16), so that irregular reflection of light is prevented and the subject can be easily observed. The cover (12) is formed from printable cardboard or a thin plastic sheet. Camera body (1
Even if the surface of 0) is formed as a rough surface, it is hidden by the cover (12) and is invisible to human eyes. Therefore, by using the cover (12), the camera body (10) can be formed of an inexpensive material. The cover (12) is provided with an opening (13).

FIG. 2 is a perspective view of the camera body viewed from the rear side, and FIG. 3 is an exploded perspective view showing a state in which the film is taken out from the camera body. FIG. 2 shows the back of the camera body (10) loaded with a 110-type film (ASA 400 to 1600). As shown in FIGS. 2 and 3, the rear surface of the camera body (10) is configured as an open surface (28), and a 110-type film cartridge (30) is inserted into the open surface (28). A film storage chamber is formed. A rectangular shooting opening (32) is formed around the shooting lens (14).
When the film cartridge (30) is loaded into the camera body (10), the exposure surface of the film cartridge (30) is positioned at the photographing opening (32). As is well known, a winding gear (not shown) is formed on the film cartridge (30). When the film cartridge (30) is loaded into the camera body (10), the gear is moved to the camera body (10). ) Lower gear (3
4) It is designed to engage. This gear (34)
Is linked with the film winding knob (20). Therefore, by rotating the hoisting knob (20), the film in the film cartridge (30) can be wound up every time the photographing is completed.

The back surface of the camera body (10) is formed as an open surface (28) as described above. A film cartridge (30) is loaded therein, and a pressure plate (36) is provided from the back surface of the film cartridge (30). Even with (28), the film exposure surface is completely shielded from light. Pressure plate (36)
Projections (40) and (41) are formed at a predetermined interval at the upper end of. A projecting piece (42) is formed at the center of the lower end of the pressure plate (36). Protruding piece (40) at the upper end,
(41) is inserted into the rectangular gaps (46) and (47) on the back of the camera body (10). The projection (42) at the lower end is provided at the lower end (4) of the camera body (10).
8) is inserted. The pressure plate (36) is made of sheet metal having some elasticity. A screw (50) is inserted into the screw hole of the projecting piece (42), and the screw (50) is screwed into the screw hole (52) in the concave portion (48). In the opening for shooting (3
It is pressed against the periphery (38) of 2), and is completely shielded from light.

FIG. 4 is an exploded perspective view of the camera from the front of the camera. As shown in FIG. 4, the camera body (1)
0) consists of a first half (60) and a second half (62). The first half (60) and the second half (62) are each formed by injection molding. As described above, the finder light-shielding tube (16) and the photographing lens light-shielding tube (22) are integrally formed on the first half (60) by injection molding. The front part (33) of the photographing opening (32) of the rear half (62)
An optical path hole (66) for photographing is formed at a position facing the light blocking cylinder (22) for photographing lens of the first half (60). A shutter blade (68) is provided in front of the imaging optical path hole (66). The shutter blade (68) includes a support plate (70).
The photographing optical path (66) can be opened and closed in the gap between the camera and the front part (33). In the camera shown in FIG.
No mechanism for adjusting the aperture diameter and shutter speed of 2) is provided, for example, brightness f11, shutter speed 1 /
Exposure is provided to a base value, such as 100 seconds. The support plate (70) is attached to the rear body (62) by screws (72) and (73) as shown in FIG.

FIG. 5 is a sectional view showing a main part of the camera. As shown in FIG. 5, the support plate (70) is
A hole (74) is formed opposite to the light shielding tube (22) of (0). A step is provided at the periphery of the hole (74) to form a concave portion (75). The annular groove-shaped concave portion (75)
This corresponds to the size of the taking lens (14). The photographing lens (14) has a flange formed on the peripheral edge (15), is placed in the concave portion (75) of the stepped hole (74), and is accurately arranged at a position facing the light shielding tube (22). Both halves (60),
When (62) is joined to form the main body (10),
The lens (14) is formed by the light-shielding cylinder (22)
Is pressed down, and the lens (14) is fixed. In addition, screws are used for joining the two halves (61) and (62). As shown in FIG. 5, a photochromic sheet (78) is provided in front of the lens (14) (subject side or light source side) in the light shielding tube (22) for photographing.
Is arranged. Photochromic sheet (78)
Means that the light transmittance changes proportionally from 10% to 50% depending on the luminance under the sunlight of the outdoors, and almost 1 indoors.
It shows a light transmittance of 00%.

FIG. 6 is a schematic sectional view of a photochromic sheet (78 in FIG. 5). As shown in FIG. 6, a preferred embodiment of the photochromic sheet is a transparent support (78).
0), a photochromic coloring layer (781), an intermediate layer (782), a UV absorbing layer (783), and a protective layer (78).
4) in order. Photochromic coloring layer (781)
Is a hydrophilic layer in which oil droplets containing an organic photochromic compound and a phosphine compound are dispersed in a hydrophilic binder. As shown in FIG. 6, it is preferable that the back side (transparent support side) of the photochromic sheet is the subject side (or the light source side), and the front side (photochromic coloring layer = hydrophilic layer side) is opposed to the lens. . By using the photochromic sheet in this way, exposure control is automatically performed when shooting outdoors. That is, in the outdoors, the photochromic sheet develops color according to the intensity of sunlight and the light transmittance is reduced. Therefore, it is possible and preferable to use a high-sensitivity film for the camera. Since the photochromic sheet hardly develops a color indoors, a high-sensitivity film enables photographing with room light such as a fluorescent lamp without an auxiliary light source.

As shown in FIG. 5, the photochromic sheet (78) is most preferably arranged in front of the lens (14) (object side or light source side). It is also possible to form the lens integrally. When disposing the photochromic sheet in front of the lens, the photochromic sheet may be attached to the back of the opening (13) of the cover (12). However, if the photochromic sheet is mounted in the light-shielding cylinder as shown in FIG. 5, it is possible to prevent the transmittance of the photochromic sheet from excessively decreasing due to direct sunlight. Although FIGS. 1 to 6 illustrate an example of a film-integrated camera having no exposure adjustment function such as an aperture, the present invention is also effective for an inexpensive camera having one or two exposure adjustment stages. 1 to 6, 11
Although the type 0 cartridge has been described as an example, a 126 type cartridge (instatic cartridge), a 35 mm size cartridge or an APS type cartridge may also be used.
The present invention is effective.

[0106]

【Example】

[Example 1] "Preparation of photochromic liquid composition (coloring layer coating solution)" photochromic compound (IIo-31) 0.37
g, photochromic compound (Ia-0) 0.37 g,
0.37 g of photochromic compound (Ia-1) and 0.55 of tridodecylthiophosphine (color fading accelerator)
5 g was dissolved in 1.44 g of the high boiling organic solvent (1), and this was added to 20 g of a 14% by weight aqueous gelatin solution.
Sodium dodecylbenzenesulfonate (surfactant)
Was added and 10 ml of a 5% by weight aqueous solution was added and emulsified and dispersed by a microhomogenizer at a rotation speed of 20,000 rpm. After further adding 40 ml of water and 20 g of a 14% by weight aqueous solution of gelatin to the emulsion, 4.44 g of latex (1) corresponding to a solid content was added thereto, followed by stirring for about 1 hour to prepare a coating solution. The refractive index of the oil droplet before adding the latex (1) was 1.50, and the refractive index of gelatin as a hydrophilic binder was 1.53. By adding latex having a refractive index of 1.55, the refractive index of the oil droplet was adjusted to 1.52. The time required for this emulsification and dispersion was 20 minutes.

[0107]

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[0108]

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[Preparation of Photochromic Sheet (Light Control Filter)] A photochromic sheet having the following layer structure was prepared.

(784) Protective layer Gelatin 1.0 g / m ² Sodium dodecylbenzenesulfonate (surfactant) 0.08 g / m ² (783) UV absorbing layer Gelatin 1.5 g / m ² UV absorber (A) below 0.75 g / m ² High boiling organic solvent (1) 0.8 g / m ² Sodium dodecylbenzenesulfonate (interface (Activator) 0.08 g / m ² (782) Intermediate layer gelatin 1.0g / m ² ──────────────────────────────────── (781) a photochromic coloring layer Zera Down 3.0 g / m ² photochromic compound (IIo-31) 0.2g / m 2 photochromic compound (Ia-0) 0.2g / m 2 photochromic compound (Ia-1) 0.2g / m 2 High-boiling organic solvent (1) 0.8 g / m ² tridodecylthiophosphine (color facilitator) 0.3 g / m ² latex (1) 2.4 g / m ² sodium dodecyl benzene sulfonate (surfactant) 0.05 g / m ² ──────────────────────────────────── (780) 100 μm thick transparent support of polyethylene terephthalate ────────────────────────────────────

[0111]

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[Preparation of Photochromic Sunglasses] A photochromic sheet (light control filter) prepared in the same manner as above, except that the protective layer was not provided, was cut into a sunglass lens shape. The surface of the ultraviolet absorbing layer of the photochromic sheet and the outer surface of the lens of sunglasses are bonded with a reactive adhesive (Bond UV670, Toa Gosei Co., Ltd.)
). When the prepared sunglasses were worn, the color density of the photochromic compound rapidly changed in accordance with the brightness even at a low temperature condition of about -10 to 0 ° C.

[Preparation of Camera] The photochromic sheet (light control filter) prepared as described above was
The film was cut according to the shape of the light-shielding cylinder of the film-integrated camera shown in FIG. The periphery of the cut photochromic sheet and the light-shielding cylinder of the film-integrated camera were bonded using a reactive adhesive (Bond UV670, manufactured by Toa Gosei Co., Ltd.). When the prepared camera was used, the color density of the photochromic compound rapidly changed in accordance with the brightness even under a low temperature condition of about −10 to 0 ° C., and a clear photograph could be taken.

Examples 2 to 10 and Comparative Example 1 In preparing the photochromic sheet liquid composition of Example 1, the same amount of the photochromic compound shown in Table 1 below was used in place of the photochromic compound (Ia-1). A liquid composition for a photochromic sheet was prepared in the same manner as described above. Table 1 shows the time required for emulsification and dispersion.

[0115]

[Table 1] Table 1 試 料 Sample No. Photochromic compound Emulsification required Time ──────────────────────────────────── Example 1 (Ia-1) 20 minutes Example 2 (Ia-2) 30 minutes Example 3 (Ia-3) 20 minutes Example 4 (Ia-4) 25 minutes Example 5 (Ia-5) 25 minutes Example 6 (Ia-6) 20 minutes Example 7 (Ia-7) 40 minutes Example 8 (Ia-8) 45 minutes Example 9 (Ia-9) 40 minutes Example 10 (Ia-12) 50 minutes Comparative Example 1 (Ia-x) 4 hours ─────────────────────────────────

[0116]

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[Brief description of the drawings]

FIG. 1 is a perspective view of a camera body and a cover.

FIG. 2 is a perspective view of the camera body as viewed from the rear side.

FIG. 3 is an exploded perspective view showing a state where a film is taken out from a camera body.

FIG. 4 is an exploded perspective view of the camera from the front of the camera.

FIG. 5 is a sectional view showing a main part of the camera.

FIG. 6 is a schematic sectional view of a photochromic sheet.

[Explanation of symbols]

 DESCRIPTION OF SYMBOLS 10 Camera main body 12 Cover 13 Opening 14 Shooting lens 15 Peripheral part 16 Finder light-shielding tube 18 Shutter release button 20 Film winding knob 22 Shooting light-shielding tube 28 Opening surface 30 Film cartridge 32 Shooting opening 33 Front part 34 Gear 36 Pressure plate 38 Peripheral edge of opening 40, 41, 42 Protruding piece 46, 47 Rectangular gap 48 Depression 50 Screw 52 Screw hole 60 First half 62 Second half 66 Optical path hole for imaging 68 Shutter blade 70 Support plate 72, 73 Screw 74 Hole 75 Ring groove-shaped recess 78 Photochromic sheet 780 Transparent support 781 Photochromic coloring layer 782 Intermediate layer 783 UV absorption layer 784 Protective layer

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Claims (4)

[Claims] 1. A photochromic compound represented by the following formula (Ia): Embedded image Wherein X ¹ and X ² are each independently an oxygen atom or a sulfur atom; R ¹ and R ² are each independently a branched alkyl group having 3 to 20 carbon atoms; , M and n are integers, respectively, and the sum of m and n is 1, 2, 3 or 4. 2. A photochromic liquid composition in which oil droplets containing a photochromic compound represented by the following formula (Ia) and an organic compound are dispersed in an aqueous phase containing a hydrophilic polymer. Embedded image Wherein X ¹ and X ² are each independently an oxygen atom or a sulfur atom; R ¹ and R ² are each independently a branched alkyl group having 3 to 20 carbon atoms; , M and n are integers, respectively, and the sum of m and n is 1, 2, 3 or 4. 3. A photochromic having a hydrophilic layer containing a hydrophilic polymer on a transparent support, wherein oil droplets containing a photochromic compound represented by the following formula (Ia) and an organic solvent are dispersed in the hydrophilic layer. Sheet. Embedded image Wherein X ¹ and X ² are each independently an oxygen atom or a sulfur atom; R ¹ and R ² are each independently a branched alkyl group having 3 to 20 carbon atoms; , M and n are integers, respectively, and the sum of m and n is 1, 2, 3 or 4. 4. A camera in which a photochromic sheet is disposed in front of or behind a lens, or in which a lens and a photochromic sheet are integrally formed, wherein the photochromic sheet has a hydrophilic polymer on a transparent support. A sheet comprising a hydrophilic layer containing: and a sheet in which oil droplets containing a photochromic compound represented by the following formula (Ia) are dispersed in the hydrophilic layer. Embedded image Wherein X ¹ and X ² are each independently an oxygen atom or a sulfur atom; R ¹ and R ² are each independently a branched alkyl group having 3 to 20 carbon atoms; , M and n are integers, respectively, and the sum of m and n is 1, 2, 3 or 4.