JPH05273692A - Photochromic composite - Google Patents

Abstract

PURPOSE:To enable easy expression with any colors at the time of coloration simply by preparing at least three kinds of photochromic materials. CONSTITUTION:This photochromic composite is a photochromic material having the max. of the light absorption spectra within the ranges respectively of (a) >=350nm and <490nm, (b) >=490nm and <580nm, (c) >=580nm and <=750nm. This photochromic composite consists of the polymer, the copolymer component of which is the photochromic material having the max. of the light absorption spectra within the ranges respectively of (d) >=350nm and <490nm, (e) >=490nm and <580nm, (f) >=580nm and <=750nm and having a polymerizable substitutent, as a constituting component.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a photochromic composite, which is particularly suitable for use as a printing material, an optical device, a recording material, a display material, a light control material, a photosensitive element, clothing, and a decorative material.

[0002]

2. Description of the Related Art Conventionally, many materials are known as photochromic materials. For example, in JP-A-2-42084 and JP-A-1-52783, a spirooxazine-based photochromic material is disclosed in JP-A-63-661.
No. 78 discloses a chromene-based photochromic material,
JP-A-61-263935 discloses a diarylethene-based photochromic material and JP-A-61-267757.
No. 8 discloses a fulgide-based photochromic material, and JP-A No. 58-113203 discloses a spiropyran-based photochromic material.

In Japanese Patent Laid-Open No. 3-12118 and Japanese Patent Laid-Open No. 3-252493, a combination of a chromene derivative and a fulgide compound or a fulgimide compound is combined with gray,
Methods for obtaining photochromic materials that exhibit colors such as brown and amber have been shown.

[0004]

However, in these materials, although the hue at the time of coloring changes depending on the kind of the substituent and the mixing ratio of the two kinds of photochromic materials, the kind of the color is substantially limited. was there. That is, there are innumerable subtle shades of color depending on the strength of redness, blueness, yellowness, etc., but in order to express those subtle shades by the conventional method, a large number of photochromic materials are used. It had to be prepared, and it was very difficult and practically impossible to handle all colors.
Therefore, if the user cannot obtain a photochromic material capable of expressing the intended delicate color, he has to put up with a similar color.

The present invention is intended to solve the drawbacks of the prior art, and an object of the present invention is to provide a photochromic composite which can easily express any delicate color tone at the time of coloring.

[0006]

In order to solve the above-mentioned problems, the photochromic composite of the present invention has the following constitution.

"(1) A photochromic composite comprising the following photochromic materials (a), (b) and (c) as constituent components.

(A) 350 nm or more in a colored state, 490
A photochromic material having a maximum light absorption spectrum in the range of less than nm.

(B) 490 nm or more in a colored state, 580
A photochromic material having a maximum light absorption spectrum in the range of less than nm.

(C) 580 nm or more in a colored state, 750
A photochromic material having a maximum light absorption spectrum in the range of nm or less.

(2) A photochromic composite comprising a polymer having a photochromic material of the following (d), (e) and (f) as a copolymerization component as a constituent component.

(D) 350 nm or more in a colored state, 490
has a maximum of the light absorption spectrum in the range of less than nm,
A photochromic material having a polymerizable substituent.

(E) 490 nm or more in a colored state, 580
has a maximum of the light absorption spectrum in the range of less than nm,
A photochromic material having a polymerizable substituent.

(F) Colored state: 580 nm or more, 750
has a maximum of the light absorption spectrum in the range of nm or less,
A photochromic material having a polymerizable substituent. In the photochromic composite according to claim 1 of the present invention, (a) 350 nm or more and 490 n or more in a colored state.
a photochromic material having a maximum light absorption spectrum in a range of less than m, (b) 490 nm or more in a colored state,
A photochromic material having a maximum light absorption spectrum in the range of less than 580 nm, (c) 580 n in a colored state
A photochromic material having a maximum light absorption spectrum in the range of m or more and 750 nm or less is used.
The photochromic material of (a) is preferably a photochromic material that exhibits a yellow color, and the photochromic material of (b) is preferably a photochromic material that exhibits a magenta color in a colored state, and
The photochromic material (c) is preferably a photochromic material that exhibits a cyan color in a colored state.

Further, in the case of claim 2, (d) in a colored state
The light absorption spectrum is within the range of 350 nm or more and less than 490 nm.
A photopolymerizable substituent having a maximum C
Tochromic material, (e) 490 nm or more in a colored state,
It has a maximum light absorption spectrum within the range of less than 580 nm.
A photochromic material having a polymerizable substituent
Material, (f) colored state of 580 nm or more and 750 nm or less
It has a maximum light absorption spectrum within the range of
Photochromic material with various substituents as a copolymerization component
The polymer is a constituent component, but the photochromic of (d)
As a colorant material, it can be polymerized to show a yellow color when colored.
A photochromic material having a substituent is preferably used.
As the photochromic material (e), the colored state
With a polymerizable substituent that exhibits a magenta color at room temperature
A chromic material is preferably used, and the (f) flux is used.
As a photochromic material, it exhibits a cyan color in the colored state.
Photochromic material having a polymerizable substituent
It is preferably used.

In these cases, by using a combination of the three primary colors of yellow, magenta and cyan photochromic materials, all colors can be easily expressed by preparing at least three types of photochromic materials.

The photochromic composite of the present invention, which is represented by the maximum position of the light absorption spectrum, has the following features:
(A) A photochromic material having a maximum light absorption spectrum in the range of 390 nm to 480 nm in a colored state,
(B) a photochromic material having a maximum light absorption spectrum in the range of 510 nm to 570 nm in a colored state,
And (c) the photochromic material having the maximum of the light absorption spectrum in the range of 590 nm to 710 nm in the colored state is preferably used as a constituent component. In the case of claim 2, (d) a photochromic material having a polymerizable substituent having a maximum of the light absorption spectrum in the range of 390 nm to 480 nm in the colored state, and (e) 51 in the colored state.
A photochromic material having a polymerizable substituent, which has a maximum light absorption spectrum in the range of 0 nm to 570 nm, and (f) 590 nm to 710 nm in a colored state.
It is preferable to use, as a constituent component, a polymer having a photochromic material having a polymerizable substituent and having a maximum of the light absorption spectrum within the above range as a copolymerization component.

In the photochromic composite of the present invention, the constituents or copolymerization constituents (a), (b),
The measurement of the optical absorption spectrum of the photochromic material of (c) or (d), (e), (f) is preferably performed under the same or similar conditions as the actual use conditions.

In the photochromic composite of the present invention, the components or copolymerization components (a), (b),
Examples of the photochromic material of (c) or (d), (e), (f) include the following.

Examples thereof include spirooxazine-based compounds represented by the following formula (I) or spirooxazine-based polymers obtained by copolymerizing the compound represented by the following formula (I) with other monomers.

[0021]

[Chemical 1] [In the formula (I), the α ring represents a ring selected from a benzene ring, a naphthalene ring, a quinoline ring, and a pyridine ring, and the α ring may be substituted.

The β ring represents a ring selected from a benzene ring, a naphthalene ring, a phenanthrene ring, an anthracene ring, a quinoline ring, an isoquinoline ring and a dibenzofuran ring, and the β ring may be substituted.

X represents S or CR ² R ³ .

R ¹ has 1 to 2 carbon atoms which may be substituted.
0 alkyl group, optionally substituted carbon number 2-20
Alkenyl group, optionally substituted carbon number 2-20
Alkynyl group, optionally substituted carbon number 7 to 20
Aralkyl group and optionally substituted carbon number 6 to
It is selected from 19 aryl groups.

If X represents CR ² R ³ , then R ² , R ³
Are independent, an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, an alkynyl group having 2 to 20 carbon atoms, an aralkyl group having 7 to 20 carbon atoms and a carbon number of 6 to 1
9 represents a substituent selected from the aryl groups of 9 and when they are not independent, R ² and R ³ may share a carbon atom with each other to form a ring having 3 to 20 carbon atoms.

R ⁴ is a hydroxy group, an amino group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, and 7 to 1 carbon atoms.
5 aralkoxy groups, C 6-14 aryloxy groups, C 1-20 acyloxy groups, C 1-20
An alkyl group having 2 to 20 carbon atoms, an alkynyl group having 2 to 20 carbon atoms, an aralkyl group having 7 to 15 carbon atoms, an aryl group having 6 to 14 carbon atoms, a halogeno group, a cyano group, a carboxylic acid group, Nitro group, C1-20 acyl group, C2-20 alkoxycarbonyl group, C1-20 carbamoyl group, sulfonic acid group, C1
Represents a substituent selected from an alkoxysulfonyl group having 20 to 20 carbon atoms, a sulfamoyl group having 0 to 20 carbon atoms and hydrogen.

When the α ring, β ring and R ¹ are substituted, the substituent is selected from the same substituents as R ⁴ except hydrogen.

A substituent on the α ring, a substituent on the β ring, a substituent on R ¹ , and at ^{least one of} R ¹ , R ² , R ³ and R ⁴ is a polymerizable substituent. Good. ] In addition, the following formula (I
Examples thereof include spiropyran-based compounds represented by I) or spiropyran-based polymers obtained by copolymerizing the compound represented by the following formula (II) with other monomers.

[0029]

[Chemical 2] [In the formula (II), the α ring has the same meaning as the α ring in the formula (I).

The β ring has the same meaning as the β ring in formula (I).

Y represents S, O, or CR ² R ³ .

Z represents O or S.

[0033] R ¹ has the same meaning as R ¹ in formula (I).

When X represents CR ² R ³ , R ² , R ³
Represents the same meaning as R ² and R ^{3 in} formula (I).

R ⁵ and R ⁶ are selected from the same substituents as R ⁴ in the formula (I).

When the α ring, β ring and R ¹ are substituted, the substituent is selected from the same substituents as R ⁴ in the formula (I) except hydrogen.

The α ring on substituents, substituents on the β ring, the substituents on ^{R 1, R 1, R 2} , R 3, R 5, 1 or more is polymerizable substituent of the R ⁶ May be Further, a chromene or oxazine-based compound represented by the following formula (III) or a chromene or oxazine-based polymer obtained by copolymerizing the compound represented by the following formula (III) with another monomer.

[0038]

[Chemical 3] [In the formula (III), the β ring has the same meaning as the β ring in the formula (I).

L represents CR ⁹ or N.

M represents CR ¹⁰ or N.

R ⁷ and R ⁸ are, independently of each other, an optionally substituted alkyl group having 1 to 20 carbon atoms, an optionally substituted alkenyl group having 2 to 20 carbon atoms, or an optionally substituted one. Represents a substituent selected from a good alkynyl group having 2 to 20 carbon atoms, an optionally substituted aralkyl group having 7 to 20 carbon atoms, and an optionally substituted aryl group having 6 to 19 carbon atoms, which is not independent In the case of, R ⁷ and R ⁸ may share a carbon atom with each other to form an optionally substituted ring having 3 to 20 carbon atoms.

When L represents CR ⁹ , R ⁹ is of formula (I)
Selected from the same substituents as R ⁴ therein.

When M represents CR ¹⁰ , R ¹⁰ is of the formula (I)
Selected from the same substituents as R ⁴ therein.

When the β ring, R ⁷ , R ⁸ , and the ring formed by R ⁷ and R ⁸ are substituted, the substituents are the same as those of R ⁴ in the formula (I) except hydrogen. Selected from substituents.

A substituent on the β ring, a substituent on R ⁷ , a substituent on R ⁸ , a substituent on the ring formed by R ⁷ and R ⁸ , R ⁷ ,
One or more of R ⁸ , R ⁹ and R ¹⁰ may be a polymerizable substituent. ] Further, a fulgide or fulgimide-based compound represented by the following formula (IV), or the following formula (IV)
Examples include fulgide or fulgimide-based polymers obtained by copolymerizing the compound represented by

[0046]

[Chemical 4] [In the formula (IV), G represents NR ¹¹ or O.

R ¹² is selected from the same substituents as R ⁴ in formula (I).

R ¹³ is an optionally substituted carbon atom of 3 to
Represents 20 aryl groups.

R ² and R ³ have the same meanings as R ² and R ³ in formula (I).

If G represents NR ¹¹ , then R ¹¹ is of the formula (I)
Selected from the same substituents as R ¹ therein.

When R ¹¹ and R ¹³ are substituted, the substituent is selected from the same substituents as R ⁴ in the formula (I) except hydrogen.

Substituent on R ¹¹ , Substituent on R ¹³ , R ¹¹ ,
One or more of R ¹² , R ² and R ³ may be a polymerizable substituent. ] Others, diarylethene series, thioindigo series, dihydropyrene series, bipyridine series, aziridine series, azobenzene series, salicylideneaniline series,
Photochromic materials such as xanthene-based, triphenylmethane-based, viologen-based, norbornadiene-based, and silver halide can be cited as examples, but the present invention is not limited thereto.

R ¹ in the formula (I) is an optionally substituted alkyl group having 1 to 20 carbon atoms, an optionally substituted alkenyl group having 2 to 20 carbon atoms, or an optionally substituted carbon atom 2 To an alkynyl group having 20 to 20 carbon atoms, an aralkyl group having 7 to 20 carbon atoms which may be substituted, and an aryl group having 6 to 19 carbon atoms which may be substituted, and preferable specific examples thereof include a methyl group and an ethyl group. Group, propyl group,
Chain alkyl groups such as butyl group, pentyl group, hexyl group, octyl group, dodecyl group, octadecyl group, icosyl group; branched alkyl groups such as isopropyl group, tert-butyl group, 2-ethylhexyl group; cyclohexyl group, Cycloalkyl groups such as norbornyl group and adamantyl group; vinyl group, allyl group, isopropenyl group, 1,
An alkenyl group such as a 3-butadienyl group; an ethynyl group,
Examples thereof include an alkynyl group such as a 2-propynyl group; an aralkyl group such as a benzyl group, a phenethyl group, and a naphthylmethyl group; and an aryl group such as a phenyl group and a naphthyl group.

When X in the formula (I) represents CR ² or R ³ , when R ² and R ³ are independent, an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, and a carbon number Two
Represents a substituent selected from an alkynyl group having 20 to 20 carbon atoms, an aralkyl group having 7 to 20 carbon atoms, and an aryl group having 6 to 19 carbon atoms. Specific examples thereof include the same substituents as the specific examples of R ^1. A group can be mentioned. When R ² and R ³ are not independent, R ² and R ³ may share a carbon atom with each other to form a ring having 3 to 20 carbon atoms. Can include a cyclopropane ring, a cyclopentane ring, a cyclohexane ring, a bicyclononane ring, a norbornane ring, an adamantane ring, and the like, including the 3-position carbon of the indoline ring.

R ⁴ in the formula (I) is a hydroxy group, an amino group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, an aralkoxy group having 7 to 15 carbon atoms, and 6 to 14 carbon atoms.
Aryloxy group, an acyloxy group having 1 to 20 carbon atoms,
C1-C20 alkyl group, C2-C20 alkenyl group, C2-C20 alkynyl group, C7-1
5 aralkyl groups, C 6-14 aryl groups, halogeno groups, cyano groups, carboxylic acid groups, nitro groups, 1 carbon atoms
To an acyl group having 2 to 20 carbon atoms, an alkoxycarbonyl group having 2 to 20 carbon atoms, a carbamoyl group having 1 to 20 carbon atoms, a sulfonic acid group, an alkoxysulfonyl group having 1 to 20 carbon atoms, a sulfamoyl group having 0 to 20 carbon atoms, and hydrogen. Specific examples of the selected substituents include hydroxy group; amino group, dibenzylamino group, diethylamino group, morpholino group, piperidino group, 1-pyrrolidyl group,
Thiomorpholino group, methacryloylamino group, acryloylamino group, N- (2-methacryloyloxyethyl) amino group, N- (2-acryloyloxyethyl)
Amino group, N- (4-vinylbenzyl) amino group, amino group such as glycidylamino group; methoxy group, ethoxy group, propoxy group, butoxy group, isopropoxy group, t
ert-butoxy group, dodecyloxy group, octadecyloxy group, icosyloxy group, glycidyloxy group, vinyloxy group, allyloxy group, 2-methacryloyloxyethyloxy group, 2-acryloyloxyethyloxy group, and other alkoxy groups; benzyloxy group, phenethyloxy group Four
An aralkoxy group such as a vinylbenzyloxy group; an aryloxy group such as a phenoxy group and a naphthyloxy group; an acyloxy group such as a formyloxy group, an acetoxy group, a propanoyloxy group, a benzoyloxy group, an acryloyloxy group, a methacryloyloxy group; a methyl group, an ethyl group, Propyl group, butyl group, hexyl group, dodecyl group, octadecyl group, icosyl group, N-methacryloylaminomethyl group, N-acryloylaminomethyl group, N- (4-vinylbenzyl) aminomethyl group, N-glycidylaminomethyl group , Alkyl groups such as glycidyl group; branched alkyl groups such as isopropyl group, tert-butyl group, 2-ethylhexyl group; cycloalkyl groups such as cyclohexyl group, norbornyl group, adamantyl group; vinyl group, allyl group, isoproton group Alkenyl groups such as nyl group and 1,3-butadienyl group; alkynyl groups such as ethynyl group and 2-propynyl group; aralkyl groups such as benzyl group, phenethyl group, naphthylmethyl group and 4-vinylbenzyl group; phenyl group, naphthyl group Aryl groups such as groups; halogeno groups such as chloro groups and bromo groups; cyano groups; carboxylic acid groups such as carboxylic acid groups and sodium carboxylic acid groups; nitro groups; formyl groups, acetyl groups, benzoyl groups, acryloyl groups, methacryloyl groups An acyl group such as; an ethoxycarbonyl group, an (2,2,6,6-tetramethyl-4-piperidyl) oxycarbonyl group, a vinyloxycarbonyl group, an allyloxycarbonyl group, a glycidyloxycarbonyl group, or another alkoxycarbonyl group; N-methylcarbamoyl group, N-phenylcarbamoyl group Carbamoyl group; sodium sulfonate group, a sulfonic acid group such as a sulfonic acid group; a sulfamoyl group, a sulfamoyl group, such as N- ethyl-sulfamoyl group; and hydrogen.

R ⁷ and R ⁸ in the formula (III) are, independently of each other, an optionally substituted alkyl group having 1 to 20 carbon atoms, an optionally substituted alkenyl group having 2 to 20 carbon atoms, A substituent selected from an optionally substituted alkynyl group having 2 to 20 carbon atoms, an optionally substituted aralkyl group having 7 to 20 carbon atoms, and an optionally substituted aryl group having 6 to 19 carbon atoms. In the case of non-independence, R ²
And R ³ may share a carbon atom with each other to form an optionally substituted ring having 3 to 20 carbon atoms. Specific examples thereof include R ² in the formula (I), The same as specific examples of R ³ can be mentioned.

R ¹³ in the formula (IV) represents an optionally substituted aryl group having 3 to 20 carbon atoms, and specific examples thereof include a phenyl group, a naphthyl group, a phenanthryl group, an anthryl group, Examples thereof include furyl group, thienyl group, benzothienyl group, benzofuryl group, pyrrolyl group and indolyl group.

Among these photochromic materials, the spirooxazine-based compound represented by the formula (I) or the spirooxazine-based polymer obtained by copolymerizing the compound represented by the formula (I) with another monomer is a color-erasing agent. It is preferable that at least one kind is contained as a constituent component of the photochromic composite of the present invention, because it has excellent color repetition durability and a relatively high coloring density.

The composite form of the photochromic composite of the present invention is not particularly limited, but examples thereof include a uniform mixture, a laminate of each component layer, and an arrangement of minute dots of each component. Many forms are conceivable, such as a combination of these forms.

As the composition of the photochromic composite of the present invention, in the case of the invention of claim 1, (a) 1 × 10 ^-9 to 1
000 parts by weight, (b) 1 × 10 ^{−9 to} 1000 parts by weight,
(C) It is preferably 1 × 10 ^{−9 to} 1000 parts by weight. However, at least one of these is used in an amount of 1 part by weight. This composition ratio should be determined in accordance with the intended color shade of the colored state under the use conditions. Any color can be expressed by changing the composition ratio. Also, (a), (b),
In the form of arranging the minute dots of each component in (c), the ultraviolet ray is squeezed to the size of the dot for irradiation, and the light amount or irradiation time of this ultraviolet ray applied to each dot is also changed arbitrarily. Any color can be expressed.

In the case of the invention of claim 2, (d),
In a polymer containing (e) and (f) as a copolymerization component,
The copolymerization ratio of (d), (e) and (f) is (d)
1 × 10 ^{−9 to} 1000 parts by weight, (e) 1 × 10 ⁻⁹ to 10
It is preferably 00 parts by weight and (f) 1 × 10 ^{−9 to} 1000 parts by weight. However, at least one of these is used in an amount of 1 part by weight. These copolymerization ratios should be determined in accordance with the intended hue for the hue of the colored state under the conditions of use. Any color can be expressed by changing the copolymerization ratio. The polymer may have one or more copolymerization components other than (d), (e) and (f). (D),
The copolymerization component other than (e) and (f) may be any compound having a polymerizable substituent, and the number of polymerizable substituents may be plural, Specific examples are acrylic acid, methacrylic acid; acrylic acid esters, methacrylic acid esters; acrylonitrile, methacrylonitrile; styrene-based monomers such as styrene, divinylbenzene, α-methylstyrene;
Vinyl acetate monomers; olefin monomers such as ethylene, propylene, butadiene, vinyl chloride, vinylidene chloride, ethylene glycol bisallyl carbonate; epoxy monomers such as bisglycidyl ether of bisphenol A; silane monomers having polymerizable substituents, etc. Is mentioned. These copolymer components may play a role such as an ultraviolet absorber, a radical trap agent, an antioxidant, and a singlet oxygen quencher. It is preferable to use 0.01 to 10000 parts by weight of these copolymerization components.

Other constituents of the photochromic composite of the present invention include optically transparent or translucent polymers, solvents, inorganic glasses, ultraviolet absorbers, radical traps, antioxidants, singlet oxygen quenchers, etc. Can be mentioned. One or more of each of these may be used,
It may not be used. When used, it is preferable to use 0.01 to 10000 parts by weight of each of the optically transparent or translucent polymer, the solvent, and the inorganic glass.
It is preferable to use 0.0001 to 1 part by weight of each of the ultraviolet absorber, the antioxidant, the singlet oxygen quencher and the like.

Specific examples of the optically transparent or translucent polymer include diethylene glycol bisallyl carbonate polymer; acrylic ester polymer;
Methacrylic acid ester-based polymers; Cellulose; Olefin-based polymers such as polyvinyl acetate, polyvinyl alcohol, polyvinyl butyral, polystyrene, polyethylene, poly (4-methylpentene), polyvinyl chloride, polyvinylidene chloride, polyvinyl fluoride; polyethylene terephthalate Polyester resin such as; Polycarbonate resin; Epoxy resin; Nylon resin; Polyurethane resin; (Halogenated) bisphenol A di (meth) acrylate polymer, (Halogenated) bisphenol A urethane-modified di (meth) acrylate polymer; Melamine resin; Examples thereof include phenol resins, and copolymers and alloys of these resins are also preferably used.

Applications of the photochromic material of the present invention include ink, printed matter, sunglasses lenses, various goggles, protective eyeglass lenses, camera light control filters, helmet shields, recording materials for writing by light, repetition of display and erasing. Display materials that can be used, windshields, automobile windows such as sunroofs, curtains, light control films, light control laminated glass, photosensitive elements that convert changes in light intensity into changes in refractive index, electrical resistance, absorbance, etc. , Toys, cosmetics, writing instruments, etc. are preferred examples.

[0065]

EXAMPLES The present invention will now be described with reference to examples, but the present invention is not limited thereto. Example 1 Compound of the following formula (V) (λmax 600 nm at the time of coloring,
Polybutylmethacrylate), a compound of the following formula (VI) (λmax at coloring 540 nm, in polybutylmethacrylate), a compound of the following formula (VII) (λmax at coloring)
440 nm in polybutyl methacrylate), and Ciasorb UV1084 (trade name of American Cyanamide Co.) were dissolved in a 30 wt% toluene solution of polybutyl methacrylate in an arbitrary ratio. The total weight of each compound was 10% by weight based on polybutyl methacrylate.

[0066]

[Chemical 5] After coating this solution on a slide glass, toluene was removed by heating to produce a colorless transparent film.
When the film was irradiated with ultraviolet light, it was colored. This colored film returned to the original colorless state when the irradiation of ultraviolet light was stopped and the film was left under room light. This change could be repeated any number of times. The color at the time of coloring could express any color such as red, orange, yellow, green, blue, indigo, purple, brown, and gray based on the ratio of each compound.

Example 2 A polymer obtained by copolymerizing 10% by weight of a compound of the following formula (VIII) with 90% by weight of butyl methacrylate (λma when colored)
x 600 nm), a polymer obtained by copolymerizing 10% by weight of a compound of the following formula (IX) with 90% by weight of butyl methacrylate (λmax of 540 nm when colored), the formula (VII of Example 1).
The compound of 1) and polybutyl methacrylate were dissolved in toluene at an arbitrary ratio to obtain a 30 wt% solution.

[0068]

[Chemical 6] After coating this solution on a slide glass, toluene was removed by heating to produce a colorless transparent film.
When the film was irradiated with ultraviolet light, it was colored. This colored film returned to the original colorless state when the irradiation of ultraviolet light was stopped and the film was left under room light. This change could be repeated any number of times. The color at the time of coloring could be expressed in any color depending on the ratio of each constituent.

Example 3 A polymer obtained by copolymerizing 10% by weight of the compound of the following formula (X) with 90% by weight of 2-ethylhexyl methacrylate (λmax 620 nm at the time of coloring), and 10% by weight of the compound of the formula (IX) of Example 2 were used. 2-ethylhexyl methacrylate 90
Polymers copolymerized with wt% (λmax540 when colored
nm), a polymer obtained by copolymerizing 10% by weight of the compound of the following formula (XI) with 90% by weight of 2-ethylhexyl methacrylate (λmax 400 nm when colored), and tinuvin 7
65 (trade name of Ciba-Geigy) was dissolved in toluene at an arbitrary ratio to obtain a 30% by weight solution.

[0070]

[Chemical 7] After coating this solution on a slide glass, toluene was removed by heating to produce a colorless transparent film.
When the film was irradiated with ultraviolet light, it was colored. This colored film returned to the original colorless state when the irradiation of ultraviolet light was stopped and the film was left under room light. This change could be repeated any number of times. The color at the time of coloring could be expressed in any color depending on the ratio of each constituent.

Example 4 Compound of formula (X) of Example 3, compound of formula (IX) of Example 2, compound of formula (XI) of Example 3, Mark LA-87
(Adeka Argus Co., Ltd. trade name), Mark LA-82 (Adeka Argus Co., Ltd. trade name), and 2-ethylhexyl methacrylate were dissolved in toluene at an arbitrary ratio to obtain a 50 wt% solution. 2, as a polymerization initiator in this solution
0.3% by weight of 2′-azobis (2,4-dimethylvaleronitrile) was added, and polymerization was carried out at 75 ° C. for 7 hours.

After completion of the polymerization, the reaction solution was applied on a slide glass, and then toluene was removed by heating to produce a colorless transparent film. When the film was irradiated with ultraviolet light, it was colored. This colored film returned to the original colorless state when the irradiation of ultraviolet light was stopped and the film was left under room light. This change could be repeated any number of times. The color at the time of coloring could be expressed in any color depending on the ratio of each copolymerization component.

[0073]

By using the photochromic composite of the present invention, it is possible to easily express any color at the time of coloring by preparing at least three types of photochromic materials.

Continuation of the front page (51) Int.Cl. ⁵ Identification number Office reference number FI technical display location C07D 513/10 8415-4C G03C 7/20

Claims (2)

[Claims] 1. A photochromic composite comprising the following photochromic materials (a), (b) and (c) as constituent components. (A) A photochromic material having a maximum light absorption spectrum in the range of 350 nm or more and less than 490 nm in a colored state. (B) A photochromic material having a maximum light absorption spectrum in the range of 490 nm or more and less than 580 nm in a colored state. (C) A photochromic material having a maximum light absorption spectrum in the range of 580 nm to 750 nm in a colored state. 2. A photochromic composite comprising a polymer containing the following photochromic materials (d), (e) and (f) as a copolymerization component. (D) A photochromic material having a polymerizable substituent, which has a maximum light absorption spectrum in the range of 350 nm or more and less than 490 nm in a colored state. (E) A photochromic material having a polymerizable substituent, which has a maximum light absorption spectrum within a range of 490 nm or more and less than 580 nm in a colored state. (F) A photochromic material having a polymerizable substituent, which has a maximum light absorption spectrum within a range of 580 nm to 750 nm in a colored state.