JPH0931453A - Microcapsule and element using the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a microcapsule, containing a photochromic compound and a high-boiling solvent, having a specific average particle diameter and a high speed of response, excellent in transparency, color development density and repetitive developing and decoloring resistances and useful for dimming, displaying, etc. SOLUTION: This microcapsule is obtained by including (A) a photochromic compound such as a compound of formula I [R1 to R8 are each a halogen, a (substituted)alkyl, a (substituted)aryl, a (substituted)alkoxy, etc.; Ar1 and Ar3 are each a (condensed)aromatic ring] or a compound of formula II [R15 to R22 are each R1 ; Ar3 and AP4 are each Ar1 ; X is an atomic group required to form a 5-to an 8-membered (un)saturated ring comprising nonmetallic atomsl and (B) a high-boiling solvent (e.g. a solvent having 160-260 deg.C boiling point), regulating the particle diameter to <=2.0μm and forming the wall from a synthetic polymer.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a microcapsule using a photochromic compound and an element useful for various transparent light control, display, coloring and recording using the microcapsule.

[0002]

2. Description of the Related Art In recent years, photochromic compounds have attracted attention as optical recording, display or light modulating materials. Attempted. For these compounds and their uses, see Photoc, for example.
hromism, Molecule and Systems (Ed.by H.Durr, H.Bouas
-Laurent, Elsevier, New York 1989) or the like, or JP-A-5-273692, 3-252453, 3-133988, 3-11075,
Same 2-69471, same 2-42084, same 1-52783, same 3-12118, same
3-252493, JP-A-63-66178, 61-263935, 61-26757
8, 58-113203, Japanese Examined Sho 45-28892, 49-48631, 48
-23787, 55-36284, or European Patent 401958A2, US Patent 4980089, US Patent 3270639, East German Patent 0153-690, US Patent 1563-7.
2, etc., and application examples for various uses are described.

As described in these documents, various photochromic compounds are melted by heating together with a hydrophobic polymer to form a film or a three-dimensional object, or dissolved together with a hydrophobic polymer in an organic solvent and coated on a substrate. It has been proposed to install them and use them for various purposes. Among these applications, it is necessary to satisfy some requirements when used as a light control material. For example, it is required to develop a color depending on the amount of light applied to the material, whether it is a low temperature outdoors in a snowy country or a high temperature on the beach in summer. Also, if you stop the exposure,
It is desired to quickly erase the color. In addition, when used as a display and recording material, it is desired to quickly react to the light irradiation required for display and recording.

However, since the coloring and decoloring reaction of the photochromic compound is accompanied by a structural change of the photochromic compound, the coloring and / or decoloring rate thereof is extremely slow when fixed in the hydrophobic polymer as described above. There was a problem. Particularly when used at a temperature of room temperature or higher, depending on the type of photochromic compound used, it usually takes several tens of minutes to several hours or more for sufficient coloring and decoloring. Further, for the purpose of adjusting various hues, when a plurality of types of photochromic compounds exhibiting different hues are provided as a multilayer on the support, the color development of the photochromic compound in the lower layer is suppressed by the filter effect of the photochromic compound used in the upper layer. However, it is difficult to adjust and control a preferable hue. In order to solve these problems, the present inventors have made detailed studies on the structure, color-developing characteristics and usage of the photochromic compound, and have completed the present invention.

[0005]

SUMMARY OF THE INVENTION Accordingly, it is an object of the present invention to provide a photosensitive composition having novel properties and novel properties which are useful for light control, coloring and recording materials. Secondly, it is to provide a photosensitive composition having photochromic properties that can withstand the use of light control, coloring and recording even at room temperature or higher. Thirdly, it is to provide a useful element for transparent light control, coloring and recording or display material having the composition supported on a substrate. Fourthly, it is to provide a photosensitive composition having photochromic properties that develops color in a well-balanced manner even when a plurality of types of photochromic compounds are used. Fifth, it is to provide a light control, coloring and recording or display material having a low haze carried on a substrate of a transparent support. Sixth, light control in which this composition is carried on a substrate,
It is to provide a useful element for coloring and recording or displaying materials. Seventh, an element useful for dimming, coloring and recording or displaying materials, which comprises a transparent substrate on which a plurality of layers containing the composition having different coloring wavelengths are substantially supported and which is further provided with a transparent protective layer. Is to provide.

Various studies have been conducted for a long time with regard to the use of a photochromic compound in a coacervation method or encapsulation using a polymer such as polystyrene as a wall material. For example, JP-A-3-67240, 7-15992
See 4th grade. However, the methods proposed in these are sufficient in performance in response to the requirements such as responsiveness (colorability and decoloring property), transparency, diversity of coloring hue, and repetition resistance, which are important for photochromic compounds. It wasn't something. Further, it was not suitable for fields requiring high haze and transparent properties.

[0007]

Means for Solving the Problems As a result of earnest studies by the present inventors, the purpose of the present invention is: 1. A photopolymerizable compound containing a photochromic compound and a high boiling point solvent, having an average particle diameter of 2.0 μm or less and having a wall of a synthetic polymer. Is a microcapsule. 2. An element in which two or more kinds of the microcapsules described in 1 above are carried on a substrate, the walls of the microcapsules are made of polyurethane-urea, and the two or more kinds of microcapsules each have an absorption maximum at the color development wavelength of the photochromic compound. An element characterized by different values of 50 nm or more. 3. An element in which the microcapsules described in 1 above are substantially one-layered on a transparent substrate using a polymer binder and further provided with a protective layer. It was found that this can be achieved by developing the above, and the present invention has been completed.

Further, preferred embodiments of the present invention will be mentioned. 4. A photosensitive composition in which a capsule containing a compound having a photochromic property and a high boiling point solvent has an average particle diameter of 1.2 μm or less and a wall is a synthetic polymer. 5. The photosensitive composition as described in 1 above, which contains a photochromic compound and a high boiling point solvent and has a wall made of polyurethane-urea. 6. The photosensitive composition as described in 1 above, which contains a photochromic compound, a high boiling point solvent and an oil-soluble salicylic acid derivative, and has a wall made of polyurethane-urea. 7. The photosensitive composition as described in 1 above, which is a fine particle containing a substantially colorless photochromic compound and a high boiling point solvent, and the particle size of the emulsion and the size of the capsule are substantially within 1.5 times. 8. A plurality of types of photosensitive compositions according to claim 1 are applied onto a substrate by using a combination of a high boiling point solvent and a core substance such that the oil phase in the capsule has a refractive index of 1.51 to 1.60 and a polymer binder. Carried elements. 9. The photosensitive composition as described in 1 above, which contains a photochromic compound, an oil-soluble salicylate and a high boiling point solvent, and has a wall made of polyurethane-urea.

Further, the preferred embodiments of the present invention are as follows. 1. Contains photochromic compound and average particle size is 2μ
m or less, particularly preferably 1.2 μ from the viewpoint of improving transparency.
A photosensitive composition containing capsules having a wall of synthetic polymer and having a size of m or less. 2. 2. The photosensitive composition as described in 1 above, which contains a photochromic compound and a solvent having a boiling point of 150 ° C. or higher and has a wall made of polyurethane-urea. 3. A transparent element comprising a plurality of types of the photosensitive composition according to the above 1 supported on a substrate by using a polymer binder. 4. A photosensitive composition in which the photochromic compound contains at least one selected from benzopyran and naphthopyran. 5. An element comprising a plurality of types of the photosensitive composition as described in 1 above, which contains a photochromic compound, a high boiling point solvent and an oil-soluble salicylic acid derivative, and has a wall made of polyurethane-urea. 6. A photosensitive composition, wherein the oil-soluble salicylic acid derivative is a compound having 10 or more total carbon atoms. 7. A high-boiling solvent containing a photochromic compound that develops yellow to red and a high-boiling solvent, and a photosensitive composition characterized in that the wall is polyurethane-urea and a photochromic compound that develops blue to purple and a high-boiling solvent different from the above. An element comprising a photosensitive composition containing at least two types of capsules, the composition containing the composition and a photosensitive composition characterized in that the wall is polyurethane-urea.

Further, the following can be mentioned as preferred embodiments. 8. In the above 1), the photochromic compound has at least one absorption wavelength maximum in the colored state of 380 to 480 mμ and at least one absorption wavelength maximum of 450 to 550 mμ.
A photosensitive composition, which is a mixture of at least one compound exhibiting 0 to 680 mμ. 9. In 1) above, the high boiling point solvent has a boiling point of 150 to 380 ° C.
A light-controlling, coloring and recording or display material having a photosensitive composition as described above carried on a substrate. 10. A transparent laminated material in which the photosensitive composition shown in 1) to 3) above is uniformly carried on a transparent support, and a scratch-resistant transparent protective layer is further provided.

11. A laminated material in which the composition represented by the above (1) to (3) is uniformly carried as a substantially single layer on a transparent support. 12. The photosensitive composition as described above, wherein the oil-soluble salicylic acid derivative is a zinc salt having an alkyl group and / or an aryl group at the 3-position or the 5-position. 13. A photosensitive composition in which the pyran compound is a photochromic compound having a diarylbenzo or naphthopyran skeleton. The pyran compound is represented by the following general formula

[0012]

Embedded image

The general formulas (1) and (2) will be further described. The organic group of R _{1 to} R ₂₄ is a halogen atom, an optionally substituted alkyl group such as an ethyl group, a methyl group, a butyl group, an amyl group, a cyclooctyl group, a dodecyl group, a methoxybutyl group, a chlorobutyl group, a phenoxypropyl group. Etc., an optionally substituted aryl group, for example, a phenyl group, a naphthyl group, a furyl group, an indolyl group, a methanesulfonylphenyl group, a trifluoromethylphenyl group, etc., an optionally substituted alkoxy group, for example, an ethoxybutoxy group, Phenoxypropoxy group, acyl group such as acetyl group, butyroyl group, benzoyl group, cinnamoyl group, sulfonyl group, optionally substituted amino group such as acylamino group, alkylamino group, arylamino group, dialkylamino group, ureido group , Urethane group, etc. Sill group, sulfo group, a cyano group, a perfluoroalkyl group, an alkane sulfonyl group, selected from such as thioalkyl group. Further, they may be cyclized to each other at adjacent positions to form a saturated or unsaturated ring composed of a 5- to 8-membered non-metal atom. Ar ₁
To Ar ₄ represents an aromatic ring. These are not limited to benzene rings, but are preferably aromatic rings which may be condensed. For example, cyclohexene, cyclopentene, azulene, benzene, naphthalene, pyridine, pyrimidine, quinoline, imidazole, indole, furan, thiophene, indazole, benzimidazole,
Examples thereof include cyclic structures such as naphthothiophene, naphthopyran, pyrene, anthracene, and naphthoquinoline. X represents an atomic group necessary for forming a saturated or unsaturated ring composed of a 5- to 8-membered non-metal atom, and a 5- to 6-membered ring is particularly preferable. These substituents are selected from the viewpoints of durability, solubility, handling and the like.

The photochromic compound used in the present invention includes spiropyran compounds, indolinospiropyran compounds, fulgide compounds, pyran compounds, spirooxazine compounds, spironaphthoxazine compounds, spirophenanthrooxazine compounds, diarylethene compounds, chromene compounds, and these. Various compounds known as photochromic compounds such as thio compounds, stilbene derivatives, azo compounds, spirobenzopyran derivatives, triarylmethane compounds, salicylideneaniline compounds and dithizone compounds can be used. Among them, spiropyran-based derivatives, oxazine-based derivatives, pyran-based derivatives, spirobenzopyran-based derivatives, etc. are particularly convenient because of their photoresponse speed, decolorization suitability, hue diversity, ease of introduction of oil-soluble substituents, handling suitability, etc. Is.
Other photochromic compounds are represented by the general formula:

[0015]

Embedded image

The above general formulas (3) and (4) will be further described. The organic group of R _{25 to} R ₄₃ is a halogen atom, an optionally substituted alkyl group, an optionally substituted aryl group, an optionally substituted alkoxy group, an acyl group,
It is selected from a sulfonyl group, an optionally substituted amino group, a carboxyl group, a sulfo group, a cyano group, a perfluoroalkyl group, an alkanesulfonyl group, a thioalkyl group and the like. An example of the specific example is shown above. Further, they may be cyclized to each other at adjacent positions to form a saturated or unsaturated ring composed of a 5- to 8-membered non-metal atom. Ar
_{1 to} Ar ₄ represent an aromatic ring. These are not limited to benzene rings, but are preferably aromatic rings which may be condensed. X is a substituted alkylene, NR, O, S
Represents R is selected from a hydrogen atom, an alkyl group, an aryl group, an acyl group and the like and may further have a substituent. Y
Represents O or S.

The compound represented by the general formula (1) shown above is particularly useful as a photochromic compound which develops yellow to red to black. The compound represented by the general formula (2) shown above is particularly useful as a photochromic compound that develops blue to red to black. The total number of aromatic rings in the compound is preferably 3 to 7, and particularly 4 to 6 compounds have solubility, color-decoloration reproducibility, durability, storage stability, sublimation resistance, crystallinity, etc. Is preferred. In particular, it is also preferable that the spiropyran compound has an aromatic ring having a large planar structure on the side different from the pyran ring, and that the spiro compound has an electron donating substituent at a conjugated position with respect to the central carbon atom of the spiro compound. . Furthermore, it has two different substituents on the central carbon atom of the spiro compound,
It is also preferred that one is a substituted amino group. These may be used as a mixture of several kinds. There is an advantage that black or gray can be easily assembled. General formula (1),
Some specific examples of the compound represented by (2) are shown below. In the formula, Me represents a methyl group.

[0018]

Embedded image

[0019]

Embedded image

Some specific examples of the compounds represented by formulas (3) and (4) are shown below. In the formula, Me represents a methyl group and Et
Represents an ethyl group, Bu represents a butyl group, and Ac represents an acetyl group.

[0021]

Embedded image

When a plurality of kinds are used in combination, the spiropyran compound, the indolinospiropyran compound, the fulgide compound, the pyran compound, the spirooxazine compound and the spironaphtho described in the above-mentioned patents and literatures are used depending on the hue, solubility and the like. Oxazine compounds, spirophenanthrooxazine compounds, diarylethene compounds, chromene compounds,
Also, thio compounds and stilbene derivatives thereof are preferably used. In particular, when a plurality of types of capsules are used, there is an advantage that the photochromic compound and the high boiling point solvent can be changed in kind and concentration or additives used together to bring out preferable characteristics. Preferably, it is convenient to use microcapsules using a compound having a maximum absorption wavelength difference of 50 nm or more at the time of color development of the photochromic compound. In particular, an element composed of microcapsules using the compounds represented by the general formulas (1) and (2) and microcapsules using the compounds represented by the general formulas (3) and (4) is preferable. For example, stabilizers, color development accelerators, decolorization accelerators, high temperature color development agents,
It is possible to change the auxiliary materials such as UV absorbers and dyes as desired, and adjust to a desired balance according to the desired color development characteristics of the capsule. Regarding the photochromic compound, it can be easily synthesized in accordance with the methods described in the above-mentioned specification or texts.

For example, the aforementioned book, H. Durr, Photochromi
It is described in sm, GPEllis, Chromans., etc., and the synthesis of related compounds is also summarized. For other compounds, these methods and U.S. Pat.
1645, 5066818, JP-A-7-48362, 7-48363, 7
It can be synthesized with reference to the synthetic method described in -48566 and the like. Also, various leuco dye compounds may be used in combination in the capsule. For the leuco dye, see Japanese Patent Application Laid-Open No. 1-211591,
For details, refer to 1-190484,5-59060, 6-128497, JP-A-63-17077, or the previous publication. The addition amount, hue, and type can be selected according to the purpose. It is safe to aim for multiple colors as another layer.

The microcapsules of the present invention preferably contain an oil-soluble salicylate at the same time. The oil-soluble salicylates include those containing derivatives having so-called substituents such as various alkyl groups and aralkyl groups. It does not matter whether it is a low molecule or a polymer. When forming a salt, a counter ion is selected from metals such as Ca, Mg, Al, Zn, Fe, Co and Ni and bases. Ni, Al, Zn, Ca, Mg.Ba and the like are preferable.
Among them, the Zn salt is most preferable from the viewpoints of effect, handleability and whiteness. In some cases, Ni salt may be used to improve the storage stability. Among these combinations, a combination which is colorless and has excellent stability, color-promoting effect, decoloring speed and the like is preferable from the viewpoint of application to a recording system. They are,
By making a simple formulation and trying the color development at 40 ° C to 50 ° C and observing the subsequent process, a person skilled in the art can make a relative comparison, and easily promote the color development promoting effect and the color erasing promoting effect. Can be optimized.

As the substituent of the oil-soluble salicylic acid derivative, various substituents such as a halogen atom, an alkyl group, an aralkyl group, an acyl group, an aryl group and an amide group are conveniently used. These may further have a substituent. Examples of the substituent include an alkyl group (methyl group, ethyl group, isopyryl group, butyl group, hexyl group, lauryl group, cyclohexyl group, methylbenzyl group, dimethylbenzyl group, α-ethyl, α-methylbenzyl group, naphthoxybutyl group. Group, dicyclopentadienyl group), aryl group (phenyl group, biphenyl group, dimethylphenyl group), substituted carbamoyl group, substituted sulfamoyl group, acyl group (acetyl group, benzoyl group, toluenesulfonyl group), chloro atom, alkoxy Group (ethoxy group, phenoxyethoxy group, methoxyphenoxyethoxy group,
Chloropropoxyethoxy group, benzyloxypropoxy group, naphthoxyethoxy group), aryloxy group (phenoxy group, naphthoxy group, p-methoxyphenoxy group), substituted ureido group, substituted urethane group, carboxyl group, alkoxycarbonyl group, sulfo group , A trimethoxysilyl group, a glycidyl group and the like.

In addition to the substituted benzyl group and the like, derivatives obtained by reacting xylylene dihalide, xylylene glycol and the like with salicylic acid are also included. The substitution position of these substituents is preferably 3-position or / and 5-position from the viewpoint of availability of raw materials. Particularly, those having a total number of carbon atoms of about 2 to 18 are convenient. Those substituted at the 6-position with alkyl are also preferable in terms of performance. From the viewpoint of solubility, compounds having 12 or more and 60 or less total carbon atoms are preferable. An oil-soluble zinc salt of salicylic acid having two α-methyl-substituted benzyl groups at the 3-position and the 5-position is easy to synthesize and is particularly preferable in terms of safety and handling of the composition.

For example, zinc 3,5-dibutylsalicylate, 3,
Zinc 5-dihexylsalicylate, Zinc 3,5-diamylsalicylate, Zinc 3,5-didecylsalicylate, 3,5-Dibutyl-6-
Zinc methosalicylate, 3,5-dibutyl-6-butylsalicylate aene, 3-amyl-6-methylsalicylate zinc, 3-benzyl-5-α, α-dimethylbenzylsalicylate zinc,
Zinc 3,5-diα-ethylbenzyl salicylate, 3,5-diα-
Zinc methylbenzyl salicylate, zinc 5-pentadecyl salicylate, zinc 5-lauryl salicylate, 3,5-diα, α-
Zinc dimethylbenzyl salicylate, zinc 3,5-diα-butylbenzyl salicylate, zinc 5-lauryl-3-methylsalicylate, 5-lauryl-3-acetamidosalicylic acid zinc salt, 5- (p-butylphenoxy)- Zinc α-butylacetamidosalicylic acid zinc salt, a mixture of zinc 5-p- (2-ethylhexyloxy) phenylureidosalicylate and zinc oxide, and the like are preferable. These are 0.001 to 500 parts by weight, preferably 0.1 to 500 parts by weight, relative to 1 part by weight of the photochromic compound.
About 10 parts by weight is used.

In encapsulating the photosensitive composition containing the photochromic compound of the present invention, it is convenient to use a solvent having a high boiling point, particularly a solvent having a boiling point of about 150 to 380 ° C., particularly about 160 to 260 ° C. The solvent used is one that dissolves the photochromic compound in an amount of 10 wt% or more, preferably 20 wt% or more. It is useful for forming a recording system in which high density color development and transparency are maintained with a small coating amount. As the solvent,
Those that are virtually insoluble in water and safe are preferred. For example, solubility and refractive index are selected from carboxylic acid esters, phosphoric acid esters, carboxylic acid amides, ethers, phenols, anilines, substituted hydrocarbons and hydrophobic organic polymers which are inert to the surface. It can be easily selected by those skilled in the art in consideration of the boiling point. Specific examples thereof include dibutyl phthalate, diisooctyl phthalate, dicyclohexyl phthalate, dimethoxyethyl phthalate, di-n-butyl adipate, diisooctyl azelenate, tributyl citrate, butyl laurate, dibutyl sebacate,
Tricyclohexyl phosphate, tributyl phosphate, triisooctyl phosphate, isopropylated triphenyl phosphate, N, N-diethylcaprylic acid amide, N, N-dimethylpalmitic acid amide, toeicresyl phosphate, diisopropylnaphthalene, phenylxylyl Ethane, dibutyl maleate,

Butyl- (m-pentadecyl) phenyl ether, ethyl- (2,4-di-t-butyl) phenyl ether, 2,5-diamylphenol, 2-n-butoxy-5-tert-octylaniline, Ditolylethane,
There are isopropyl naphthalene, xylyl phenyl ethane, ditolyl ether, butyl anisole, pentaerythritol diethyl acetal, benzyl morpholine, oligobutylene oxide and the like, and a plurality of these can be used. The compound known as a plasticizer has an advantage that it is easily available and easy to handle.

In preparing a photosensitive composition containing the microencapsulated photochromic compound of the present invention, among the usual encapsulation methods, those having a wall forming a polyurethane-polyurea are conveniently used. To be The present inventors have already summarized these as literatures, and the materials and methods described therein can be conveniently used. See, for example, Organic Materials for Imaging, Bushin Publishing, Tokyo, 1993, Chapter 4. Upon encapsulation, various polyvalent isocyanate compounds, alcohol-modified polyvalent isocyanate compounds, mixtures of polyvalent isocyanate compounds and polyhydric alcohols, combined use of polyvalent isocyanate compounds and polyamines, reaction of polyvalent isocyanate compounds with water, etc. The means and materials of are used. Examples of the polyvalent isocyanate compound include hexane diisocyanate, tolylene diisosonate, xylylene diisocyanate, polyphenylene diisocyanate, m-xylylene diisocyanate, naphthylene diisocyanate, diphenylmethylene diisocyanate and isophorone diisocyanate. Examples of the polyol include glycerol, ethylene glycol, diethylene glycol, diglyceryl, hemicellulose, hexanetriol, pentaerythritol, trimethylolpropane and cyclohexanetriol. Furthermore, if necessary, a polyvalent amine compound such as triethylenediamine or butylenediamine can be used in combination. These can be selected by those skilled in the art in consideration of the required particle size and strength of the capsule. Above all, it is convenient to use a microcapsule made of a synthetic polymer having a polyurea / urethane as a wall material, which uses polyurethane isocyanate, from the viewpoint of stability, color developability, handling suitability and transparency of the photochromic compound. In the present invention, when the photochromic compound is dissolved, in addition to the above-mentioned high-boiling-point organic substance, water-soluble polar solvent or low-boiling-point organic solvent (having a boiling point of about 130 ° C. or less), etc. are made into fine particles and promotion of dissolution. You may plan and use together. Examples of those organic solvents include propylene carbonate, methyl acetate, ethyl acetate, isopropyl acetate, dichloromethane, butyl acetate,
Examples thereof include ethyl propionate, butyl alcohol, methyl ethyl ketone, pentanone, cyclohexanone, dimethylformamide, dimethyl sulfoxide and the like. The preferable amount of the high boiling point solvent used is 0.1 to 100 times the weight of the photochromic compound to be dispersed. The low boiling point solvent is in the composition in the microcapsules,
It is desirable that the amount is 0.2% or less by weight so that it does not substantially remain. Further, in emulsifying and dispersing before the encapsulation step of the present invention, as described in International Patent Publication WO93 / 3420, after increasing the amount of the surfactant and finely dispersing it, the excess surfactant is removed by washing with water. The method of doing is also effective.
If necessary, the size of the dispersion particles can be changed from the micron level to the sub-micron level, especially 0.01 μ size to further improve the transparency. At this time, in order to make the particles finer, the following disperser may be used.

As the disperser, there are a high-speed stirring type disperser having a large shearing force, a disperser giving high-strength ultrasonic energy, and the like. Specifically, there are a colloid mill, a homogenizer, a capillary type emulsifying device, a liquid siren, an electromagnetic distortion type ultrasonic generator, and an emulsifying device having a Paulman whistle. The co-solvent or surfactant can be removed by a known method, for example, US Pat.
801171, 2946360, 339602
7 and 4233397.

Various processes can be followed in preparing the emulsified dispersion of the photochromic compound. When the spiropyran compound is dissolved in an organic solvent, it is dissolved in one or two or more arbitrary multi-component mixtures selected from the above high boiling organic substances or low boiling organic solvents, and then the presence of a hydrophilic polymer. Below, a method of emulsifying and dispersing in water or an aqueous solution of a hydrophilic polymer is general. The oily liquid containing the photochromic compound and the aqueous liquid may be mixed by a so-called forward mixing method in which the oily liquid is added to the aqueous liquid while stirring.

When dispersed in water during encapsulation, it is preferable to add an aqueous hydrophilic polymer solution at the time of dispersion or at the time of coating. Gelatin is advantageously used as the hydrophilic polymer, but other hydrophilic polymers can also be used. For example, gelatin derivatives, graft polymers of gelatin and other polymers, proteins such as albumin and casein; cellulose derivatives such as hydroxyethyl cellulose, carboxymethyl cellulose, cellulose sulfates, sodium alginate,
Sugar derivatives such as starch derivatives; polyvinyl alcohol, polyvinyl alcohol partial acetals, polyvinylpyrrolidone, polyacrylic acid, polymethacrylic acid, polyacrylamide, polyvinylimidazole, polyvinylpyrazole, etc. Molecular substances can be used.

As the gelatin, besides lime-processed gelatin, acid-processed gelatin may be used, and gelatin hydrolyzate and gelatin enzyme dispersion may also be used. Examples of the gelatin derivative include gelatin such as acid halide, acid anhydride, isocyanates, bromoacetic acid, alkane sultones, vinyl sulfonamides, maleimide compounds,
Those obtained by reacting various compounds such as polyalkylene oxides and epoxy compounds are used. Furthermore,
In order to stabilize the composition containing the photochromic compound, it is preferable to use the polymer compound together with the hydrophilic polymer.

Modified PVA is particularly preferred. Among them, a random or block copolymer of vinyl alcohol and vinyl ester in which the terminal is modified with a hydrophobic group such as a decylthio group is conveniently used. These hydrophilic polymers can be used alone, or can be used as a mixture of two or more kinds with other hydrophilic polymers. The hydrophilic polymer is 350 nm, more preferably 320 n.
Polymers that do not have absorption in the longer wavelengths than m are useful.

An example of a method of supporting the above-mentioned microcapsule and an element using the same on a substrate will be described. As the high boiling organic solvent used in this method, the high boiling organic solvent described above can be used. The microcapsules of the present invention are preferably used by dispersing them in a binder. A material with a refractive index of 1.40 to 1.60 is desirable as the binder. Prevents scattering and maintains transparency. As the binder, for example, polyvinyl butyral resin, polyvinyl formal resin, ethylene-vinyl acetate copolymer, ethylene-acrylic acid copolymer, vinyl chloride resin, polymethylmethacrylate, acrylic ester-methacrylic acid ester copolymer Coalesce, polyester resin, vinyl acetate-vinyl chloride copolymer, polycarbonate resin, polystyrene, styrene-acrylic acid ester copolymer, styrene-methacrylic acid ester copolymer,
Examples thereof include polysulfone, phenoxy resin, styrene-butadiene copolymer, and silicone resin. From these, the refractive index, binder strength, water resistance, solubility, etc. are selected as criteria.

The photochromic photosensitive composition of the present invention includes various additives such as a photopolymerization initiator, a photocurable compound, a vinyl monomer, a singlet oxygen quencher typified by a Ni salt, and a nitroxyl radical. Compounds, ultraviolet absorbers, triplet quenchers, radical scavengers,
An appropriate amount of various materials selected from antioxidants, viscosity reducers, decolorization accelerators, color development accelerators, stabilizers, HALS, oxidizing agents or reducing agents can be contained according to the purpose.
The spiropyran compound, the oil-soluble salicylic acid derivative and the organic solvent used in the present invention can be used as a mixture of two or more kinds. The layer containing the photosensitive composition of the present invention may be composed of two or more layers that develop different colors.

These layers may contain a polymer latex in order to improve the film quality and curling characteristics. As the monomer constituting the polymer latex,
For example, acrylic acid ester, methacrylic acid ester,
Crotonic acid ester, vinyl ester, maleic acid diester, fumaric acid diester, itaconic acid diester,
Examples thereof include acrylamides, methacrylamides, vinyl ethers and styrenes.

The glass transition point of the polymer composed of these monomers is preferably 40 ° C. or lower. It may be a homopolymer or a copolymer. Preferred are acrylic esters, copolymers of acrylic esters and methacrylic esters, and copolymers of acrylic esters and acrylic acid or methacrylic acid. As the polymer, a compound having a refractive index of about 1.45 to 1.60 is preferable.

Radical polymerization of ethylene monomers is already well known. For example, the usage of the initiator is described in F.
A. Bovey "Emulsion Polymerization" Interscienc
e Publishers Inc. New York, 1955, pp. 59-93.

A compound having a surface activity is used as the emulsifier in the latex formation, and preferred examples thereof include soaps, sulfonates, phosphates and sulfates, cationic compounds, amphoteric compounds and polymeric protective colloids. Examples of these and their usage can be found in Belgische Chemisch
e Industrie Volume 28, 16 to 20 (1963), etc.

In the present invention, a polymer latex having a glass transition point of 20 ° C. or lower is particularly preferable. Specific examples of the polymer latex are described below, but the present invention is not limited thereto. Polyethyl acrylate, polypropyl acrylate, polyethoxyethyl acrylate, propyl acrylate / styrene copolymer, ethyl acrylate / styrene copolymer, propyl acrylate / acrylic acid (95: 5) copolymer, polybutyl acrylate, polyphenoxyethyl Acrylate, polydiethylene glycol monoacrylate methyl ether, nonaethylene glycol methacrylate methyl ether polymer, propyl acrylate / methacrylic acid (95: 5)
There are copolymers, ethylhexyl acrylate / diacetone acrylamide copolymers, methyl acrylate / butyl methacrylate copolymers, hexyl methacrylate / methacrylic acid (9: 1) copolymers and the like.

It is useful to provide a protective layer on these coating layers (outermost layer). It is important to prevent scattering due to minute irregularities and improve transparency. As a material used for the protective layer, an ultraviolet curable resin, an electron beam curable resin, a hydrophilic polymer and a hydrophobic polymer, latex or the like can be used. As the hydrophilic polymer and latex, the hydrophilic polymer and polymer latex as the above-mentioned dispersion medium can be used. Examples of the hydrophobic polymer include organopolysiloxane, polyvinyl butyral resin, polyvinyl formal resin, ethylene-vinyl acetate copolymer, ethylene-acrylic acid copolymer, vinyl chloride resin, polymethylmethacrylate, acrylic ester-methacrylic acid ester copolymer. Examples include polymers, polyester resins, vinyl acetate-vinyl chloride copolymers, polycarbonate resins, styrene-maleimide anhydride copolymers, styrene-vinyltoluene copolymers, polyolefins and polyimides. In addition, organic substances such as polysiloxane and silane coupling agent, pentaerythritol tetraacrylate, acrylic modified polyurethane, silicone modified curable resin, ω-tricosanoic acid,
A cumulative film formed by the Langmuir-Projet method (LB method) such as dioctadecyldimethylammonium chloride and methyl stearate can also be used. A metal vapor deposition film such as silicon oxide or aluminum may be used. Further, in the protective layer, transparent pigments, dyes, metal soaps, waxes, antistatic agents and the like can be used for the purpose of improving water resistance, adhesion and scratch resistance. For the pigment, colloidal silica with a refractive index of 1.4 to 1.55-silicon modified PV
A, calcium carbonate, aluminum hydroxide, Si resin, fluororesin, amorphous silica, etc. are used. An emulsion of zinc stearate or aluminum is useful as the metal soap. Examples of the wax include paraffin wax, microcrystalline wax, and emulsion of silicone. As described above, the material used for the protective layer is preferably one that does not have absorption in a long wave of preferably 350 nm, more preferably 320 nm.

The thickness of the photosensitive layer containing the photochromic compound of the present invention depends on the purpose, but is preferably about 150 μm or less, particularly preferably 20 μm or less, such as a support, a coating layer, a photosensitive layer and a protective layer. It may be laminated in 2 to 6 layers. The thickness of the coating film of the protective layer is preferably 10 μm or less, particularly preferably 5 μm or less. The refractive index of the protective layer is preferably 1.40 to 1.60.

Hardeners optionally used in the binder or protective layer in which microcapsules are dispersed are described in US Pat. No. 4,678,739, column 41, JP-A-59-11.
No. 6655, No. 62-245261, No. 61-189.
42 and the hardeners described in JP-A-62-234157 and the like. More specifically, aldehyde type hardener (formaldehyde etc.), aziridine type hardener, epoxy type hardener, vinyl sulfone type hardener (N, N'-ethylene-bis (vinylsulfonylacetamide)) Compounds such as ethane), N-methylol hardeners (dimethylol urea, etc.), polymer hardeners and the like. Among the above-mentioned hardeners, from the viewpoint of coatability (that is, stability of coating solution over time and reactivity with an adjacent layer during coating) and film quality (stability of raw sample and hardenability). Epoxy hardeners are particularly preferred. Specific examples of the epoxy hardener include hardeners described in JP-A-62-91942.

Uses of the composition or element of the present invention include printed matter, dyes, transfer agents, sunglasses, protective glasses,
Optical recording materials, light control materials, light control filters, display materials, interior products, toys, light meters, clothes, cosmetics, writing instruments,
Examples thereof include inks, and they are particularly useful for applications such as light control filters or sunglasses, which quickly control the intensity of sunlight including UV light to control the amount of color development.

As the substrate used in the present invention, various substrates can be selected according to the above-mentioned applications. Specifically,
Synthetic resin, glass or various plastic films,
Plastic lenses can be used. Processability, weight,
A plastic product is preferable because it has both strength and transparency. For example, diethylene glycol bisallyl carbonate, methyl polymethacrylate, polyethylene terephthalate, polyethylene-2,6-naphthalate, polycarbonate, polyurethane, nylon, triacetyl cellulose, polyacrylate, polysulfone, polyether sulfone, polyolefin, polyimide, triacetyl cellulose. Etc. or a laminated material of a plurality of these or glass can be effectively used. If necessary, the surface of the support itself may be treated with such a support before the undercoat layer is applied to improve the adhesiveness and transparency. For example, it is within the scope of those skilled in the art to set the conditions that the corona treatment, the glow treatment, and the like are used under appropriate conditions. For example, US Patents 2715075, 2846727, 3549406,
Descriptions such as 3590107 are valid. A transparent coating layer and a transparent substrate are particularly preferable when the composition or element containing the photochromic compound is used as a light control material for spectacles or cameras (especially films with high-sensitivity lenses).

The layer containing the photosensitive composition of the present invention and the protective layer are formed as thin layers on the substrate by any coating method such as vapor deposition, curtain coating, blade coating, spin coating, dip coating, and extrusion coating. it can. For example, U.S. Patents 2761791, 3508947, 2941898,
3526528, Harasaki, "Coaching Engineering" Asakura, Tokyo, 1973
See also. If necessary, U.S. Patents 2761791 and 383709
It is also possible to apply two or more layers simultaneously by the method described in 5.

The capsule containing the photochromic compound of the present invention is stable and colorless when it is not irradiated with UV light, but develops color immediately when it is irradiated with light containing UV light. The same applies whether the light source is UV light or sunlight, room temperature or low temperature. Further, if irradiation is stopped, there is an advantage that the material becomes colorless immediately. Moreover, it is excellent in transparency and is preferable as a light control material. Repeats coloring and colorlessness stably and with good durability.

[0050]

EXAMPLES The present invention will be described in more detail based on examples.

Example 1 6 g of diisopropylnaphthalene was mixed with 4 g of photochromic compound (1,3,3-trimethylspiroindolinonaphtho).
[2,1-b] [1,4] oxazine) is dissolved, and as a wall agent, 0.4 g of aromatic polyisocyanate (MDI-LK), 0.4 g of aliphatic polyisocyanate (N-3200) and Polyol (RT-40
4) A total of 10.96g of 0.16g is used as the capsule wall and core. This is emulsified with 30 g of 12% PVA 205 aqueous solution as a protective colloid at 25 ° C. to prepare a dispersion having a particle size of 1.1 μm, and a capsule wall made of polyurethane-urea is formed. Then, 0.7g of 5% polyamine for wall reinforcement
To obtain strong capsules by treating at 80 ° C for 60 minutes. The obtained capsule particle size was 1.1 μm. Water 10
ml to make a capsule liquid having a solid content concentration of 28%.

Example 2 1,3,3-Trimethylspiroindolinonaphtho of Example 1
[2,1-b] [1,4] Oxazine replaced with 1-hexyl-3,3-dimethylspiroindolinonaphtho [2,1-b] [1,4] oxazine Was added to obtain a photosensitive composition.

Example 3 An example in which the oil is changed in Example 1 will be described. A capsule dispersion having a particle size of 1.0 μm was obtained in the same manner except that isopyrylated triphenyl phosphate was used instead of diisopropylnaphthalene (KMC oil).

Example 4 In Example 3, the photochromic compound was changed to 1,3,3-trimethylspironaphthoxazine (coloring wavelength: 610n).
m) and 3,3-di (4-methoxyphenyl) naphtho [2,1-
b] An example of changing to a 1: 1 mixture of pyran (coloring wavelength: 470 nm) is shown. A capsule dispersion having a particle size of 1.0 μm was obtained in the same manner as above.

Example 5 In Example 4, in place of 2 g of 3,3-di (4-methoxyphenyl) naphthopyran, 3,3-di (4-methoxyphenyl) naphthopyran and 3,3-diphenylnaphthopyran (color development) were used. A photosensitive composition containing a capsule dispersion liquid was obtained in the same manner except that the mixture (2: 1) having a wavelength of 430 nm was used.

Example 6 To 24 g of isopropylated triphenyl phosphate, 6 g of the photochromic compound used in Example 5 was dissolved, and 20 g of a modified trimethylolpropane-m-xylylene diisocyanate (D-110N) and 25 g of methylene chloride were added. It was This was used as a wall and a core substance by an emulsification treatment to give a value of 0.
The size was 7 microns. 50% 8% PVA when dispersed
g, 15 ml of a 1.2% aqueous solution of dioctyl Na sulfosuccinate was used. A high speed homogenizer was used for stirring. Then, the mixture was kept at 40 ° C. for 3 hours to obtain a capsule dispersion liquid containing a photochromic compound having a capsule size of 0.7 micron. No methylene chloride remained in the capsule.

Example 7 A photosensitive composition dispersion liquid was obtained in the same manner as in Example 1 except that 3,3-di (4-butoxyphenyl) naphthopyran was used instead of the photochromic compound.

Example 8 The liquid of Example 1 and the liquid of Example 7 were mixed so that the weight ratio of the photochromic compound was 1: 1 to prepare a coating composition containing two types of capsules. Example 9 As an oil-soluble salicylic acid derivative, 0.7 g of zinc 3,5-di-α-methylbenzylsalicylate was used as a high-boiling-point organic solvent, and isopropylated triphenyl phosphate (0.1%) was used.
It was dissolved in 2 g and 0.4 g of ethyl acetate to obtain an oil phase (A). To 2 g of a 10% aqueous solution of lime-processed gelatin, 0.2 cc of a 5% aqueous solution of dodecylbenzenesulfonic acid was added as a surfactant. The oil phase and the aqueous phase were mixed and emulsified and dispersed for 5 minutes at 10,000 rpm with a mini homogenizer.
Add 3 cc of water and 2 g of 14% gelatin aqueous solution to this emulsified dispersion.
Was added. The dispersion liquid of Example 8 was added to this to prepare a photosensitive layer coating composition.

Example 10 The photosensitive composition dispersion prepared in Examples 6, 7, 8 and 9 was added to 100 parts.
Thickness of 12 μm on polyethylene terephthalate film
It was applied so as to have a thickness of μm and dried. Further, modified PVA was applied to a thickness of 2 μm to form a protective layer. When this photosensitive composition-coated film was exposed to sunlight, it showed vivid coloring and became colorless in the dark.

Example 11 The photochromic compound of Example 5 was mixed with 3,5-di-α.
-A photosensitive dispersion liquid containing capsules was obtained in the same manner except that 0.9 g of zinc methylbenzylsalicylate was added. Example 12 To 3.6 g of isopropylated triphenyl phosphate, 2 g of the photochromic compound used in Example 7 and 10 g of ethyl acetate were mixed, and 6 g of a modified trimethylolpropane-m-xylylene diisocyanate (D-110N) was added. This was emulsified as wall and core material to a size of 0.7 microns. 47 g of 10% carboxy-modified PVA when dispersed,
Pionine 0.1 g was used as an emulsifier. A high speed homogenizer was used for stirring. Then, the mixture was kept at 40 ° C. for 3 hours to obtain a capsule dispersion liquid containing a photochromic compound having a capsule size of 0.32 micron. No ethyl acetate remained in the capsule.

[0061]

The capsule containing the photochromic compound prepared under the specific conditions specified in the present invention and the element using the same have high transparency, high response speed, and high color density even at room temperature or higher. Has a high resistance to repeated coloring / decoloring.

Front Page Continuation (72) Inventor Mitsugu Tanaka, 210 Nakanuma, Minamiashigara City, Kanagawa Prefecture, Fuji Photo Film Co., Ltd. (72) Toshiaki Aono, 210, Nakanuma, Minami Ashigara City, Kanagawa Prefecture, Fuji Photo Film Co., Ltd.

Claims (3)

[Claims] 1. A microcapsule containing a photochromic compound and a high-boiling solvent, having an average particle diameter of 2.0 μm or less and having a wall made of a synthetic polymer. 2. An element in which two or more kinds of the microcapsules according to claim 1 are supported on a substrate, wherein the walls of the microcapsules are made of polyurethane-urea, and the two or more kinds of microcapsules each develop a color of a photochromic compound. An element characterized by having absorption maximum values of wavelengths different by 50 nm or more. 3. An element comprising substantially one layer of the microcapsule according to claim 1 supported on a transparent substrate using a polymer binder, and further provided with a protective layer.