JP2000328039A - Light absorber - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a light absorber which can effectively intercept light in a desired region, having any one of a chalcone structure, a base styryl structure, a cyanine structure, a merocyanine structure, a phenylmethane structure, a coumarin structure, a pyrylium structure and a nickel complex structure and containing one or more organic colorant compounds applicable to clothes. SOLUTION: This absorber comprises a chalcone-structure-containing organic colorant compound represented by formula I (wherein Ar1 and Ar2 are each independently a monovalent group of a mono- or poly-cyclic aromatic hydrocarbon compound or heterocyclic compound such as phenyl, naphthyl, quinolyl, thienyl, or phenyl. A desirable example of the chalcone-structure-containing organic colorant compound is a compound of formula II (wherein λmax=344 nm, and ε=29,000) or formula III (λmax=345 nm; and ε=29,000).

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a light absorber, and more particularly, to a light absorber containing an organic dye compound.

[0002]

2. Description of the Related Art Living organisms are exposed to various types of light, including natural light. Natural light consists of light in the ultraviolet, visible, and infrared regions, and is indispensable for living organisms.However, when looking at light in individual areas, some are useful for living things. Some are not. For example, light in the ultraviolet and visible regions is an essential component of photosynthesis in plants and vitamin D in animals, but overexposure can cause skin cell death or, in some cases, DNA damage. ,
Induces skin cancer. On the other hand, although light in the infrared region has the effect of warming living organisms, there are some that cause burns or exacerbate cataracts, such as light in the near-infrared region, after the exposure. In addition, in certain immune diseases and viral diseases, natural light may directly or indirectly cause the disease to develop or the symptoms to worsen. Such a problem associated with exposure is included not only in natural light but also in ambient light including artificial light in general. Modern medicine, which is undergoing remarkable progress, has revealed various obstacles and inconveniences associated with exposure, together with the useful effects of light on living organisms. Thus, various types of light shielding means have been conventionally proposed in various fields.

[0003] The light blocking means can be broadly classified into physical means for blocking light with an object and chemical means for blocking light by absorbing light with a light absorbing agent. Looking at chemical means using an organic dye compound as a light absorber, for example, in the field of clothing,
As disclosed in JP-A-018 and JP-A-9-255890, conventionally, an organic dye compound having an ultraviolet absorbing ability such as a benzotriazole derivative or a benzophenone derivative is kneaded into fibers to impart ultraviolet absorbing ability to clothing. And a method of imparting infrared absorbing power to clothing by dyeing fibers with an organic dye compound having infrared absorbing power such as an aminium derivative. However, when the former method is used among these methods, there is a problem that although the light in the ultraviolet region can be blocked, the light in other regions cannot be blocked at all. On the other hand, in the latter method, light other than in the infrared region cannot be blocked at all, and the light absorbing agent itself develops a color.Therefore, depending on clothing, it is difficult to adjust the desired color, color tone, and texture. Was.

[0004]

In recent years, as obstacles and inconveniences caused by natural light and artificial light have become widely known, in the field of clothing as well as other fields, infrared rays have been used. In a wide range of light up to a region, a light absorber capable of efficiently blocking light in a desired region has been desired. In view of such a situation, an object of the present invention is to provide a light absorber capable of efficiently shielding light in a desired region in a wide range of light from the ultraviolet region to the infrared region, particularly, light useful in clothing. It is an object to provide an absorbent and its use.

[0005]

Means for Solving the Problems As a result of diligent research conducted by the present inventors, light absorbers used for articles such as clothing are:
(1) It exhibits a very small amount of light-blocking ability in the ultraviolet, visible, and / or infrared regions, and when used in articles such as clothing, the desired color, color tone, and texture of the article (2) When used for articles such as clothing that come into direct or indirect contact with the skin, it does not cause substantial damage to the skin. (3) When using a plurality of components having a light-shielding ability, The plurality of components exhibit good compatibility with each other while satisfying the two requirements, and (4) temporarily supporting the article by, for example, spraying or applying while satisfying the three requirements. It has been found that a material which can be easily removed by washing, washing or the like as required is desirable.

Accordingly, the present inventor has conducted intensive studies and researched on organic dye compounds that are artificially created.
Chalcone structure, base styryl structure, cyanine structure, merocyanine structure, phenylmethane structure, coumarin structure,
Each of the organic dye compounds having a pyrylium structure and a nickel complex structure has a large molecular extinction coefficient in an ultraviolet region, a visible region, and / or an infrared region, and efficiently absorbs light in these regions. Have been found to be able to efficiently block light in a desired region in a wide range of light from the ultraviolet region to the infrared region by using as a light absorber. In addition, such organic dye compounds, in addition to having good compatibility, even when used in clothing, cause substantial damage to the skin, or produce the desired color, color tone, and texture in clothing. It has been confirmed that the desired light-shielding ability can be temporarily or semi-permanently imparted to clothing without substantially impairing it, and that the clothing can be used with confidence.

[0007] That is, the present invention solves the above problem by having any of a chalcone structure, a base styryl structure, a cyanine structure, a merocyanine structure, a phenylmethane structure, a coumarin structure, a pyrylium structure, or a nickel complex structure,
The problem is solved by providing a light absorber containing one or more organic dye compounds that can be used in clothing.

[0008] Further, the present invention solves the above-mentioned problems by providing clothing containing such a light absorbing agent.

[0009]

BEST MODE FOR CARRYING OUT THE INVENTION The organic dye compound referred to in the present invention is an organic dye compound that is artificially created and has a chalcone structure, a base styryl structure, a cyanine structure, a merocyanine structure, a phenylmethane structure, It means one having any of a coumarin structure, a pyrilium structure or a nickel complex structure and can be blended into clothing. The organic dye compound generally has one or a plurality of absorption maxima (hereinafter sometimes referred to as “λ _max ”) in an ultraviolet region, a visible region, and / or an infrared region. In the present invention, what is desirable is a molecular extinction coefficient at the absorption maximum (hereinafter, referred to as “absorption coefficient”).
It may be described as “ε”. ) Is a large organic dye compound, and in particular, those having a molecular extinction coefficient of 10,000 or more, more preferably 20,000 or more, at the absorption maximum are suitable.

[0010] Shown in Formula 1 is an organic dye compound having a chalcone structure at Formula 1, Ar ₁ and Ar
₂ is each independently a monovalent group of a monocyclic or polycyclic aromatic hydrocarbon compound such as a phenyl group, a naphthyl group, a quinolyl group, a thienyl group, a furyl group, or a hetero compound; Is a halogen atom, a hydroxyl group, a nitro group, a cyano group, a carboxyl group, a carboxylic ester group, a carboxylic acid amide group,
It may have one or more substituents such as an alkyl group, an alkoxy group, an alkylamino group and a dialkylamino group. Examples of the individual alkyl groups include linear or branched lower alkyl groups such as a methyl group, an ethyl group, a propyl group, and a butyl group. Desirable organic dye compounds having a chalcone structure include, for example,
(Λ _max = 344 nm, ε = 29,000)
(Λ _max = 345 nm, ε = 29,000).

[0011]

Embedded image

[0012]

Embedded image

[0013]

Embedded image

Chemical formula 4 shows an organic dye compound having a base styryl structure. In chemical formula 4, Z ₁ contains a nitrogen atom, for example, a benzooxazolyl group,
Represents a monovalent group of a polycyclic hetero compound such as a naphthooxazolyl group, a quinolyl group, a benzothiazolyl group, a naphthothiazolyl group, an indolenyl group, and the monovalent group is, for example, a halogen atom, a nitro group, a cyano group, an alkoxy group. It may have one or more substituents such as a group, a hydroxyl group, a carboxyl group, a carboxylic acid ester group, a carboxylic acid amide group, and an alkyl group. Examples of the alkyl group included in Z ₁ include a linear or branched lower alkyl group such as a methyl group, an ethyl group, a propyl group, and a butyl group. As R ₁ , for example, a halogen atom, a nitro group, a cyano group, an alkyl group, an alkoxy group,
Examples thereof include an alkylamino group, a dialkylamino group, a hydroxyl group, a carboxyl group, and a carboxylic acid ester group. Of these, an alkylamino group and a dialkylamino group are preferable. n is a natural number selected from 1 and 2, and usually an organic dye compound in which n is 1 is desirable. Desirable organic dye compound having a base styryl structure, for example, of _{5 (λ ma x = 392nm,} ε = 46,
600) and 6 (λ _max = 395 nm, ε = 39,5)
00). Each of the organic dye compounds represented by Chemical Formula 2, Chemical Formula 3, Chemical Formula 5, and Chemical Formula 6 has one or more absorption maximums in an ultraviolet region and a large molecular extinction coefficient at the absorption maximum. It is extremely useful as an ultraviolet absorber for absorbing and blocking light in the ultraviolet region of ambient light such as natural light and artificial light.

[0015]

Embedded image

[0016]

Embedded image

[0017]

Embedded image

Chemical formula 7 shows an organic dye compound having a cyanine structure. In chemical formula 7, Z ₂ and Z _{3 each} contain a nitrogen atom. For example, benzothiazolyl group, benzooxazolyl group, benzoin It represents a monovalent group or a divalent group of the same or different polycyclic hetero compound such as a denyl group and a quinolyl group. The monovalent group and the divalent group may have, for example, one or more substituents such as a halogen atom, a cyano group, a nitro group, an alkyl group, and an alkoxy group.
For example, a linear or branched lower alkyl group such as a methyl group, an ethyl group, a propyl group, and a butyl group may be mentioned. R ₂ and R ₃ each independently represent an alkyl sulfate group or a linear or branched lower alkyl group such as a methyl group, an ethyl group, a propyl group, a butyl group, an octyl group, and a decyl group; Represents R ₄ represents a hydrogen atom or a linear or branched lower alkyl group such as a methyl group, an ethyl group, a propyl group, and a butyl group. n is zero or a natural number, usually
It is selected from the range of 0 to 2. X ⁻ is an appropriate counter ion, and has a site where R ₂ and / or R ₃ is negatively charged;
It is not present when forming an intramolecular salt. Desirable organic dye compounds having a cyanine structure include, for example, Chemical formula 8 (λ _max = 423 nm, ε = 86,600), Chemical formula 9
(Λ _max = 497 nm, ε = 126,000),
(Λ _max = 582 nm, ε = 122,000)
1 (λ _max = 638 nm, ε = 250,000). Each of the organic dye compounds represented by Chemical formulas 8 to 11 has one or more absorption maxima in the visible region and a large molecular extinction coefficient at the absorption maxima. It is extremely useful as a visible absorber for absorbing and blocking light in the visible region of ambient light.

[0019]

Embedded image

[0020]

Embedded image

[0021]

Embedded image

[0022]

Embedded image

[0023]

Embedded image

A desirable organic dye compound having a merocyanine structure is, for example, a compound represented by the formula (12) (λ _max = 426 n
m, ε = 57,800), Formula 13 (λ _max = 461n)
m, ε = 74,000) and Formula 14 (λ _max = 589 n)
m, ε = 213,000),
As a desirable organic dye compound having a phenylmethane structure, for example, a compound represented by Chemical formula 15 (λ _max = 530 nm, ε = 1
10,000 (λ _max = 552 nm, ε = 1
0,000), Formula 17 (λ _max = 554 nm, ε = 1)
20,000) and Formula 18 (λ _max = 588 nm, ε =
112,000). Examples of the organic dye compound having a coumarin structure include, for example, Chemical formula 19 (λ _max = 458 nm, ε = 55,300), Chemical formula 2
0 (λ _max = 479 nm, ε = 60,500) and
Compounds represented by 1 (λ _max = 487 nm, ε = 80,200) are preferred. All of these organic dye compounds have one or more absorption maxima in the visible region and a large molecular extinction coefficient at the absorption maximum. Is very useful as a visible light absorber for absorbing and shielding light.

[0025]

Embedded image

[0026]

Embedded image

[0027]

Embedded image

[0028]

Embedded image

[0029]

Embedded image

[0030]

Embedded image

[0031]

Embedded image

[0032]

Embedded image

[0033]

Embedded image

[0034]

Embedded image

Chemical formula 22 is an organic dye compound having a pyrylium structure. In Chemical formula 22, Ar _{3 to} Ar ₆ are, for example, monocyclic or phenyl, naphthyl, pyridyl, quinolyl or the like. A monovalent group of a polycyclic aromatic hydrocarbon compound, and the monovalent group is, for example,
It may have one or more linear or branched lower alkyl groups such as a methyl group, an ethyl group, a propyl group, and a butyl group. According to the ordinary synthesis method, Ar
₃ and Ar ₆ , and Ar ₄ and Ar ₅ have the same structure, respectively. R ₅ and R ₆ represent a hydrogen atom or the same linear or branched lower alkyl group such as a methyl group, an ethyl group, a propyl group, and a butyl group. n is an integer selected from 0 to 2, and
X ^- is a counter ion as appropriate. Desirable organic dye compounds having a pyrylium structure include, for example,
_max = 1,060 nm, ε = 173,000) and
_{4 (λ m ax = 943nm,} ε = 124,000) a compound represented by the like.

[0036]

Embedded image

[0037]

Embedded image

[0038]

Embedded image

Chemical formula 25 is an organic dye compound having a nickel complex structure. In Chemical formula 25, R _{7 to} R ₁₀ are hydrogen atoms or, for example, halogen atoms.
Alkyl group, alkoxy group, alkoxyalkoxy group,
Represents a substituent such as a secondary amino group. According to the ordinary synthesis method, R ₇ and R ₁₀ , and R ₈ and R ₉ each have the same structure. Desirable organic dye compounds having a nickel complex structure include, for example, Chemical formula 26 (λ _max =
886 nm, ε = 26,100) and Formula 27 (λ _max =
1,068 nm, ε = 29,600). Each of the organic dye compounds represented by Chemical Formulas 23, 24, 26 and 27 has one or more absorption maxima in the infrared region and a large molecular extinction coefficient at the absorption maxima. It is extremely useful as an infrared absorber for absorbing and blocking light in the infrared region of environmental light such as natural light and artificial light.

[0040]

Embedded image

[0041]

Embedded image

[0042]

Embedded image

In the light absorbing agent of the present invention, an organic dye compound may be used alone, or a plurality of organic dye compounds may be used in combination. The light absorbing agent of the present invention comprising an organic dye compound that absorbs light in the ultraviolet region, for example, when used in clothing, natural light, ultraviolet light contained in environmental light such as artificial light is blocked by the light absorbing agent, the skin Since the ultraviolet rays reaching the attenuator are reduced, it is possible to prevent or reduce skin damage and inconvenience caused by the ultraviolet rays. Further, the light absorbing agent of the present invention comprising an organic dye compound that absorbs light in the infrared region, for example, when used in clothing, the light absorbing agent can be applied to environmental light such as heat due to body temperature, natural light, and artificial light. Since it absorbs the infrared rays contained therein, it gives a refreshing feeling when worn, and can prevent or reduce unnecessary sweating and stuffiness.

On the other hand, when a light absorbing agent is used in combination of a plurality of organic dye compounds, it is easy to efficiently block light in a desired region in a wide range of light from the ultraviolet region to the infrared region. Become. For example, in the ultraviolet region and / or
Alternatively, the light absorbing agent of the present invention using a combination of one or more organic dye compounds that absorb light in the visible region and one or more other organic dye compounds that absorb light in the infrared region is applicable to clothing. Then, while shielding ultraviolet rays and visible light harmful to the human body, it is possible to effectively absorb heat due to body temperature and infrared rays included in environmental light such as natural light and artificial light. In particular, chemical formula 2, chemical formula 3, chemical formula 5, chemical formula 6, chemical formula 8 to chemical formula 2
The organic dye compounds represented by Chemical Formula 1, Chemical Formula 23, Chemical Formula 24, Chemical Formula 26 and Chemical Formula 27 have high light resistance and stability, and also have excellent compatibility and even in a state where no solvent is present,
Since they are well mixed with each other and do not form crystals, they are most suitable for using a plurality of organic dye compounds in combination.
Incidentally, all of these organic dye compounds can be obtained from Hayashibara Biochemical Laboratory Co., Ltd.

In the light absorber of the present invention, usually, 1
Alternatively, a supporting material for supporting the organic dye compound on the article is used together with the plurality of organic dye compounds. The support material is
Usually, it is composed mainly of an inorganic polymer substance and / or an organic polymer substance. As the individual inorganic polymer substance, for example,
Glass, ceramics, silane, polysiloxane, polyorganosiloxane, silicone oil, and the like, and examples of the organic polymer substance include polyester, polyamide, polycarbonate, polyester, polystyrene,
Polypropylene, polyethylene, polymethylpentene,
Polysulfone, polyether sulfone, polyarylate, polyetherimide, polymethyl methacrylate,
Polyolefin, acrylic, nylon, acetate, Bemberg, rayon, cotton, hemp, wool, silk, cellulose, cellulose ester, pullulan, starch, amylose, amylopectin and other synthetic resins, semi-synthetic resins, recycled resins, natural resins, and more Mixing, kneading, blending, blending,
These mixed materials by knitting, knitting, lamination and the like can be mentioned. These support materials may be liquid, solid or semi-solid, depending on the article to which the light absorber of the present invention is applied.
The shape, for example, powder, granules, beads, film,
It may be a sheet, paper, board, panel, thread, cotton, woven fabric, non-woven fabric or the like, or a mixture thereof. In supporting the organic dye compound on such a supporting material, if necessary, for example, a general-purpose solvent, a microencapsulating agent, a binder, a monomer, an oligomer, a polyfunctional reagent, a sizing agent, an adhesive, and a propellant And a surfactant.

In the light absorber of the present invention, as a compounding component other than the organic dye compound and the carrier, for example, a general-purpose colorant,
Flame retardant, wrinkle remover, deodorant, water repellent, oil repellent, antistatic agent, conductive agent, water absorbing agent, moisture proofing agent, fragrance, antioxidant, insect repellent, fungicide, antibacterial, antiallergic Agents, blood circulation enhancers,
Surfactants, emulsion stabilizers, chelating agents and the like can be used as appropriate.

Now, the use of the light absorbing agent of the present invention will be described. Most of the organic dye compounds exhibit a remarkable light-shielding ability in a very small amount. In addition, the desired color, color tone and feeling of the article are not substantially impaired. Therefore, one of the important applications of the light absorber of the present invention is clothing, and as individual clothing, for example, business suits, sack suits, three sets, blazer, cardigan jacket, blouson, Jackets and vests such as boleros and sacks, shirts such as shirts, dress shirts, formal shirts, sports shirts, aloha shirts, cutter shirts, open collar shirts, polo shirts, tee shirts, slacks, rappa trousers, nicker bockers,
Trousers such as gaucho pants, pedal pushers, jeans, ties such as ties, bow ties, cravats, sailor ties, windsor ties, underwear such as undershirts, briefs, looses, scanties, shorts, trunks, lingerie, Petticoat, camisole, bra, stockings, pantyhose, foundations such as girdle, body suit, blouses such as chori, midi blouse, set-in blouse, divided skirt, midi skirt, mini skirt, trumpet skirt, wrap skirt, etc. Skirts, apron dress, basic dress, camisole dress, chemise dress, coat dress, house dress, jumper dress, sack dress, Sudoresu, dress such as shift dress, pullover, cardigan, boat neck sweaters, bulky sweater, crew neck sweaters, sweater such as turtleneck, Barumakan,
Duffel coat, duster coat, Inverness, raglan, trench coat, lane coat and other coats, tailcoat, tuxedo and other dresses, tengallon hat, beret, rimless hat, alpine, boater, busby, derby, fedora, fes, Hunting cap, opera hat,
Sombrero, Breton, Cloche, Pillbox, Picture Hat, Snood, Tamoshunter, Talk,
Hats such as turban, bonnet, casquette, ankle socks, bobby socks, crew socks, knee socks, over knee socks, sweat socks, three quarter socks, tube socks, etc. , Hand towel, fur, gloves, mittens, scarf, scarf, ribbon, belly band, uniform, jersey, kimono, swimwear, wetsuit, workwear, firefighting suit, military uniform, flying suit, diving suit, space suit, etc. And all garment materials such as interlinings and linings for preparing such garments.

The application of the light absorbing agent of the present invention is not limited to clothing, and it can be advantageously applied to various kinds of articles other than clothing which needs to block environmental light such as natural light and artificial light. Individual articles other than clothing include, for example, drapes, laces, casements, prints, venetian blinds, roll screens, shutters, goodwill, blankets, futons, futon sideways, futon covers, futon cotton, sheets, cushions, pillows , Pillowcases, cushions, mats, carpets, sleeping bags, tents, car interior materials, window glass,
Bedclothes such as window glass, paper diapers, diaper covers,
Sanitary goods such as glasses, monocles, lownets, etc., shoe insoles, shoe linings, luggage, furoshiki, umbrellas, parasols, stuffed animals, lighting equipment, and, for example, CRT displays, liquid crystal displays, electric fields Light-emitting display,
Filters, panels and screens for image display devices such as television receivers and personal computers using plasma displays, etc., sunglasses, sunroofs, sun visors, PET bottles, storages, plastic houses, chillers, optical fibers, prepaid cards, electronics Ranges, viewing windows such as ovens, and even natural light,
It can be used very advantageously also in packaging materials, filling materials, containers, and the like for packaging, filling, or storing articles that do not want to be exposed to environmental light such as artificial light.

When the light absorbing agent of the present invention is used in such an article, it can not only prevent or reduce obstacles and inconveniences in living things and articles, but also adjust light transmitted / reflected through the article to a desired color balance. There are benefits that can be done. When the light absorber of the present invention is used for the purpose of adjusting the color balance of transmitted light or reflected light, an organic dye compound that absorbs light in the infrared region, in particular, 1 or 2 that absorbs light in the near infrared region Along with blending one or more of the organic dye compounds that absorb light in the ultraviolet region and / or the visible region with a plurality of organic dye compounds, a light absorber as a composition may include, for example,
A component having a wavelength of 500 nm or less in incident light and 620 n
m or more, while substantially shielding each of the components, so that the spectrum at a wavelength of 500 to 620 nm in transmitted light or reflected light is similar to that of sunlight, the amount of each organic dye compound blended in the light absorber, What is necessary is just to adjust the amount of the light absorber applied to the article.

In order to apply the light absorbing agent of the present invention to the above-mentioned articles, ordinary methods such as mixing, coating, spraying, dipping, and fixing are applied according to the shape, size, purpose of use, etc. of the article. do it. In order to allow the light absorber of the present invention to be temporarily or semi-permanently supported on various kinds of articles such as clothing, for example, one or more of the organic dye compounds may be optionally used as a carrier, a microencapsulating agent. ,binder,
Monomer, oligomer, polyfunctional reagent, glue, adhesive, colorant, flame retardant, wrinkle remover, deodorant, water repellent, oil repellent,
Antistatic agent, conductive agent, water absorbing agent, moisture proofing agent, fragrance, antioxidant, insect repellent, fungicide, antibacterial, antiallergic, blood circulation promoter, surfactant, emulsion stabilizer, chelating agent, etc. One or more, for example, water, pentane, hexane, cyclohexane, petroleum ether, petroleum benzene, isooctane, octane, benzene, toluene, xylene, carbon tetrachloride, chloroform, 1,2-dichloroethane, trichloroethylene, tetrachloroethylene, chlorobenzene, bromo Benzene, dichlorobenzene, methanol,
Ethanol, 1-propanol, 2-propanol,
2,2,2-trifluoroethanol, 1-butanol, 2-butanol, isobutyl alcohol, isopentyl alcohol, cyclohexanol, ethylene glycol, propylene glycol, 2-methoxyethanol, 2-ethoxyethanol, phenol, benzyl alcohol, cresol , Diethylene glycol, triethylene glycol, glycerin, diethyl ether, diisopropyl ether, tetrahydrofuran, tetrahydropyran, 1,4-dioxane, anisole, 1,2
-Dimethoxyethane, diethylene glycol dimethyl ether, dicyclohexyl-18-crown-6, methyl carbitol, ethyl carbitol, furfural,
Acetone, methyl ethyl ketone, cyclohexanone, formic acid, acetic acid, acetic anhydride, trichloroacetic acid, trifluoroacetic acid, ethyl acetate, butyl acetate, ethylene carbonate, propylene carbonate, formamide, N-methylformamide, N,
N-dimethylformamide, N-methylacetamide,
N, N-dimethylacetamide, N-methylpyrrolidone, hexamethylphosphoric triamide, triethylphosphate, acetonitrile, propionitrile, succinonitrile,
Dissolve or suspend in a general-purpose solvent such as benzonitrile, nitromethane, nitrobenzene, ethylenediamine, pyridine, piperidine, morpholine, dimethylsulfoxide, sulfolane or a mixture thereof, and if necessary, house in a closed container together with a general-purpose propellant. . The solutions and suspensions thus obtained are applied or sprayed on various kinds of articles or immersed in the articles to impart a desired part or whole of the articles with light-shielding ability. Can be. Among the light absorbers of this type, those that can be easily removed by washing or washing include, for example, horticulture, picnics, hiking, trekking, mountain climbing, swimming, skiing, in addition to ordinary going out and athletic sports. When going to places exposed to strong ultraviolet rays such as golf, cycling, clamming, fishing, etc., temporarily light-shield clothing beforehand, and after wearing, wash or wash as necessary to remove the light absorber. It can be easily detached.

To allow the light absorber of the present invention to be semipermanently carried on clothing or the like, one or more organic dye compounds may be used as they are, or may be, for example, silica having a fine porous structure, activated carbon, or melamine. In a micro-encapsulated state using fine particles of resin, acrylate resin, urea resin, etc., together with a binder made of urethane resin, acrylic resin, aminoplast resin, epoxy resin, glyoxal resin, ethylene urea resin, silicon resin, etc., if necessary To disperse in an aqueous medium containing a higher alcohol or a surfactant. The cloth or sewn product is immersed in this dispersion, and the excess dispersion is removed by centrifugation or the like, and dried at 180 ° C. or less, preferably 140 ° C. or less. Set or set to moist heat. According to this method, the light absorbing agent of the present invention can be carried semipermanently on clothing, and washing resistance is improved. The light absorber of the present invention can be used, for example, in clothing, bedclothes, sanitary goods, filters such as lighting devices and image display devices, panels and screens, sunroofs, PET bottles, tents,
When blended in an article such as a greenhouse, an appropriate amount of the light absorber of the present invention may be contained in an appropriate step until the preparation of the article is completed.

The amount of the light absorbing agent of the present invention to be applied to the article depends on the type of the organic dye compound and the article and the purpose of applying the light absorbing agent, but is usually calculated in terms of the weight of the organic dye compound. 0.0001% or more, preferably 0.001% or more per weight. The light blocking ability of the article
Naturally, the coloring of the article by the organic dye compound itself may become conspicuous depending on the amount of the light absorbing agent to be added, though depending on the amount of the organic dye compound used. So, for example, in the case of clothing,
In terms of the weight of the organic dye compound, the blending amount per weight is preferably 5% or less.

Hereinafter, embodiments of the present invention will be described based on examples.

[0054]

Example 1 <Apparel> Two kinds of organic dye compounds represented by Chemical Formulas 2 and 5 having an absorption maximum in the ultraviolet region and Chemical Formulas 23 and 26 having an absorption maximum in the infrared region. Two kinds of organic dye compounds are mixed at a weight ratio of 2: 2: 1: 1, and N-methylpyrrolidone is added to the mixture at a weight ratio of 1: 100. Particles having a porous structure (particle size 2 to 6 μm)
To microencapsulate the organic dye compound.

This microcapsule in which a plurality of organic dye compounds are mixed with one another is mixed with an acrylic acid ester-based binder (trade name “Blimar HA-16”,
(Nippon Reichhold Co., Ltd.) at a weight ratio of 1: 1 to give a 120 g / l aqueous dispersion. A stocking made of nylon 6 processing yarn is immersed in the dispersion, and the microcapsules are adhered by 3% by dry weight, dehydrated by a centrifugal dehydrator, dried at 120 ° C., and heat-set at 140 ° C. for 3 minutes. did. Thereafter, the stockings to which the organic pigment compound microcapsules are attached are arranged on the right leg (Example 1), and the same stockings without the organic pigment compound are attached to the left leg (Comparative Example 1). Thus, pantyhose was prepared.

For this pantyhose, 15
A trial test of 20 women aged ４０40 years for one month showed significantly less sunburn on the right leg than on the left leg. Also, when a questionnaire was sent to all the subjects about the trial findings, the pantyhose in this example
Many respondents said that when worn, the right leg had a noticeable refreshing sensation compared to the left leg, and it was hard to get stuffy and the light-shielding effect was not reduced even after repeated washing.

[0057]

Example 2 <Apparel supplies> In Example 1, the organic dye compounds represented by Chemical Formulas 3, 6, and 27 are used instead of the organic dye compounds represented by Chemical Formulas 2, 5, and 23, respectively. Microcapsules were prepared in the same manner as in Example 1 except that was used. This microcapsule, in which a plurality of organic dye compounds are mixed together with one another, is called a polyetherester block copolymer (trade name “SR-1”).
000 ”manufactured by Takamatsu Yushi Co., Ltd.) and 30 parts by weight of a melamine-based fiber processing resin (trade name“ Sumitex Resin ”manufactured by Sumitomo Chemical Co., Ltd.) in a weight ratio of 1: 1. After mixing in proportions, 1
An aqueous dispersion of 00 g / l was obtained.

The right sleeve (Example 2) of a long-sleeved polo shirt made of processed cotton was immersed in this dispersion liquid, and 5% of the microcapsules were adhered by dry weight, and then set at 120 ° C. for 3 minutes by moist heat. The left sleeve of the polo shirt was untreated and used as a control (Comparative Example 2).

The polo shirt was worn by a man 18 to 46 years old.
When a trial test was conducted on 0 subjects for one month, sunburn of the right arm was significantly less than that of the left arm. Also,
After a questionnaire survey of all participants regarding trial findings,
When wearing the polo shirt of this example, compared to the left arm,
Many answered that the right arm had a remarkable refreshing sensation, was hardly stuffy, and did not diminish the light-shielding ability even after repeated washing.

[0060]

Example 3 <Coating Agent> Two kinds of organic dye compounds represented by Chemical Formulas 3 and 6 having an absorption maximum in an ultraviolet region in an isopropanol / dimethylformamide mixed solution (volume ratio 5: 1), and absorbing in a visible region Chemical formula 8 and chemical formula 1 having the maximum
4, the organic dye compounds represented by Chemical Formulas 18 and 19, and Chemical Formulas 26 and 27 having an absorption maximum in the infrared region
Each of the two types of organic dye compounds represented by.
After dissolving to a concentration of 2% (w / w), a urethane-based coating resin (trade name "Olester NL2249E", manufactured by Mitsui Toatsu Chemicals, Inc.) having a thin film forming ability having a concentration of 6 according to a conventional method. % (W / w), uniformly mixed and dissolved to prepare a coating agent.

The coating agent of this example is absorbed by a sponge, a brush, a spatula or the like, and is applied to the surface of the article, or is applied by dipping the article. This product has excellent spreadability, quick-drying properties and excellent color balance of transmitted light and reflected light.Multiple organic dye compounds are mixed together with each other without any crystallization, and this product does not produce crystals. tent,
The present invention can be advantageously applied to a wide variety of articles such as PET bottles, plastic greenhouses, cold gauze, filters for lighting devices and video display devices, panels and screens, and viewing windows such as microwave ovens and ovens.

[0062]

Example 4 <Aerosol> According to a conventional method, an appropriate amount of a mixed solution of ethanol / 1,1,1,2-tetrafluoroethane (volume ratio 2: 1) was applied to a fluorine-based water-repellent base material (trade name “Defenser MCF”). -323 ", manufactured by Dainippon Ink and Chemicals, Inc., so that the final concentration becomes 0.5% (w / w), and further represented by Chemical Formulas 2 and 5 having an absorption maximum in the ultraviolet region. The two kinds of organic dye compounds are added so that the final concentration becomes 0.2% (w / w), and the organic dye compounds have an absorption maximum in the visible region.
The final concentration of each of the four organic dye compounds represented by Chemical Formulas 7 and 20 and the two organic dye compounds represented by Chemical Formulas 23 and 24 having an absorption maximum in the infrared region is 0.1%.
% (W / w), uniformly mixed and dissolved, and then filled into an aerosol can. Thereafter, the same ethanol / 1,1,1,1,2-tetrafluoroethane mixed solution as described above was added until the filling amount in the aerosol can became 100 ml, and then carbon dioxide was used as a propellant and the internal pressure of the aerosol can was 4.5 kg /. An aerosol was prepared by filling to a volume of cm ² .

The aerosol of the present example is used by spraying on articles such as clothing, and is removed by washing, washing, etc. after wearing. Excellent a light-shielding property, easy to handle, a plurality of organic dye compounds are mixed together with each other, no crystal is generated, and the aerosol of this example which can be easily removed by washing, washing, etc. is, for example, clothing, Bedclothes,
It is extremely useful as an aerosol for providing temporary light-shielding ability to sanitary articles.

[0064]

As described above, the present invention provides an organic dye compound having a chalcone structure, a base styryl structure, a cyanine structure, a merocyanine structure, a phenylmethane structure, a coumarin structure, a pyrylium structure and a nickel complex structure. It is based on the unique finding that it is useful as a light absorber for various articles such as clothing. That is, all of these organic dye compounds efficiently absorb light in an ultraviolet region, a visible region, and / or an infrared region, and are large in light resistance, stable, excellent in compatibility, and excellent in each other. They do not mix and form crystals, and do not cause substantial damage upon contact with skin. In addition, since these organic dye compounds exhibit remarkable light-shielding ability in a trace amount, they can be used for articles such as clothing.
It does not substantially impair the desired color, color tone, or texture of the article. The light absorbing agent of the present invention comprising one or more of such organic dye compounds can be used in a wide variety of articles such as clothing and other than clothing, for example, bedclothes and sanitary goods. In a wide range of light ranging from the infrared to the infrared region, light in a desired region can be freely blocked, so there is a real benefit that obstacles and inconveniences of living things and articles due to environmental light such as natural light and artificial light can be prevented or reduced. .

In particular, the light absorbing agent of the present invention comprising a plurality of coloring compounds can be used in addition to clothing, bedclothes and sanitary goods, as well as lighting devices and, for example, cathode ray tube displays, liquid crystal displays, electroluminescent displays, Filters for video display devices such as TV receivers and personal computers using plasma displays, etc.
Panels and screens, sunglasses, sunroofs,
By applying it to articles such as sun visors, plastic greenhouses, cold gauze, and optical fibers, it is possible not only to prevent obstacles and inconvenience of living things and articles due to environmental light such as natural light and artificial light, but also to obtain light that transmits and reflects through articles. There is a benefit that can be adjusted to the color balance.

The present invention having such remarkable effects can be said to be a significant invention that greatly contributes to the art.

────────────────────────────────────────────────── ───

[Procedure amendment]

[Submission date] September 21, 1999 (September 9, 1999
1)

[Procedure amendment 1]

[Document name to be amended] Statement

[Correction target item name] 0047

[Correction method] Change

[Correction contents]

Now, the use of the light absorbing agent of the present invention will be described. Most of the organic dye compounds exhibit a remarkable light-shielding ability in a very small amount. In addition, the desired color, color tone and feeling of the article are not substantially impaired. Thus, this one important Applicable target of the light absorbing agent of the invention will be referred to as garments, as the individual garment, for example, business suit, sack suit, three-justified, blazer, cardigan jackets, Jackets , Bolero, jackets and vests such as sack, shirts, dress shirts, formal shirts, sports shirts, aloha shirts, cutter shirts, open collar shirts, polo shirts, tee shirts and other shirts, slacks, rappa pants, nicker bockers,
Trousers such as gaucho pants, pedal pushers, jeans, ties such as ties, bow ties, cravats, sailor ties, windsor ties, underwear such as undershirts, briefs, looses, scanties, shorts, trunks, lingerie, Petticoat, camisole, bra, stockings, pantyhose, foundations such as girdle, body suit, blouses such as chori, midi blouse, set-in blouse, divided skirt, midi skirt, mini skirt, trumpet skirt, wrap skirt, etc. Skirts, apron dress, basic dress, camisole dress, chemise dress, coat dress, house dress, jumper dress, sack dress, Sudoresu, dress such as shift dress, pullover, cardigan, boat neck sweaters, bulky sweater, crew neck sweaters, sweater such as turtleneck, Barumakan,
Duffel coat, duster coat, Inverness, raglan, trench coat, lane coat and other coats, tailcoat, tuxedo and other dresses, tengallon hat, beret, rimless hat, alpine, boater, busby, derby, fedora, fes, Hunting cap, opera hat,
Sombrero, Breton, Cloche, Pillbox, Picture Hat, Snood, Tamoshunter, Talk,
Hats such as turban, bonnet, casquette, ankle socks, bobby socks, crew socks, knee socks, over knee socks, sweat socks, three quarter socks, tube socks, etc. , Hand towel, fur, gloves, mittens, scarf, scarf, ribbon, belly band, uniform, jersey, kimono, swimwear, wetsuit, workwear, firefighting suit, military uniform, flying suit, diving suit, space suit, etc. And all garment materials such as interlinings and linings for preparing such garments.

[Procedure amendment 2]

[Document name to be amended] Statement

[Correction target item name] 0048

[Correction method] Change

[Correction contents]

The application of the light absorbing agent of the present invention is not limited to clothing, and it can be advantageously applied to various kinds of articles other than clothing which needs to block environmental light such as natural light and artificial light. Individual articles other than clothing include, for example, drapes, laces, casements, prints, venetian blinds, roll screens, shutters, goodwill, blankets, futons, futon sideways, futon covers, futon cotton, sheets, cushions, pillows , Pillowcases, cushions, mats, carpets, sleeping bags, tents, car interior materials, window glass,
Bedclothes such as window glass, paper diapers, diaper covers,
Sanitary goods such as glasses, monocles, lownets, shoe insoles, shoe linings, luggage, furoshiki, umbrellas, umbrellas, stuffed animals, lighting equipment, and, for example, CRT displays, liquid crystal displays, electroluminescent displays , Filters for image display devices such as television receivers and personal computers using plasma displays, etc.
Panels and screens, sunglasses, sunroofs,
Packaging, filling or storage of sun visors, PET bottles, storages, greenhouses, cold gauze, optical fibers, prepaid cards, microwave ovens, viewing windows such as ovens, and other items that do not want to be exposed to environmental light such as natural light and artificial light. It can also be used very advantageously in packaging materials, filling materials, containers and the like.

[Procedure amendment 3]

[Document name to be amended] Statement

[Correction target item name] 0061

[Correction method] Change

[Correction contents]

The coating agent of this example is applied by sucking or scooping on a sponge, a brush, a spatula or the like , and applying it to the surface of an article, or immersing the article. This product has excellent spreadability, quick-drying properties and excellent color balance of transmitted light and reflected light.Multiple organic dye compounds are mixed together with each other without any crystallization, and this product does not produce crystals. Tent, PET bottle, plastic greenhouse, cold gauze,
It can be advantageously applied to a wide variety of articles such as filters, panels and screens for lighting devices and video display devices, and viewing windows such as microwave ovens and ovens.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) C09B 65/00 C09B 65/00 69/00 69/00 C09D 5/32 C09D 5/32 7/12 7 / 12 Z D06M 13/335 D06M 13/335 // C08K 5/00 C08K 5/00 F term (reference) 4H056 BA02 BB05 BF02E BF21 BF26F BF29F BF34 CA01 CA02 CA03 CC02 CC08 CD02 CE02 CE03 CE06 CE07 DD03 DD04 DD06 DD07 DD12 DD12 DD28 DD29 EA13 EA14 FA05 4J002 BG031 CC161 CC181 CD001 EE026 EJ016 EL086 EL096 EN086 EU026 EU036 EU066 EU106 EV306 EV326 EV346 EZ006 FD096 4J038 EA011 JA65 JB28 JB38 JC18 KA08 4L033 AA00 BA04 AC04

Claims (5)

[Claims] 1. a chalcone structure, a base styryl structure, a cyanine structure, a merocyanine structure, a phenylmethane structure,
A light absorber having one or more organic dye compounds that have any of a coumarin structure, a pyrylium structure, and a nickel complex structure and can be used for clothing. 2. The light absorbent according to claim 1, which absorbs light in an ultraviolet region, a visible region, and / or an infrared region. 3. The light absorber according to claim 1, further comprising a support material for supporting an organic dye compound. 4. The light absorber according to claim 1, wherein the support material is mainly composed of a polymer substance. 5. A garment comprising any one of the light absorbers according to claim 1.