WO2019074008A1 - Irreversible ultraviolet colour developing composition, and technology related thereto - Google Patents

Irreversible ultraviolet colour developing composition, and technology related thereto Download PDF

Info

Publication number
WO2019074008A1
WO2019074008A1 PCT/JP2018/037767 JP2018037767W WO2019074008A1 WO 2019074008 A1 WO2019074008 A1 WO 2019074008A1 JP 2018037767 W JP2018037767 W JP 2018037767W WO 2019074008 A1 WO2019074008 A1 WO 2019074008A1
Authority
WO
WIPO (PCT)
Prior art keywords
compound
irreversible
ultraviolet
coloring composition
composition according
Prior art date
Application number
PCT/JP2018/037767
Other languages
French (fr)
Japanese (ja)
Inventor
陽介 北川
正三 末福
達広 高井
智浩 水原
Original Assignee
株式会社松井色素化学工業所
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by 株式会社松井色素化学工業所 filed Critical 株式会社松井色素化学工業所
Publication of WO2019074008A1 publication Critical patent/WO2019074008A1/en

Links

Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
    • B41M1/00—Inking and printing with a printer's forme
    • B41M1/26—Printing on other surfaces than ordinary paper
    • B41M1/30—Printing on other surfaces than ordinary paper on organic plastics, horn or similar materials
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
    • G03C1/00—Photosensitive materials
    • G03C1/72—Photosensitive compositions not covered by the groups G03C1/005 - G03C1/705
    • G03C1/73—Photosensitive compositions not covered by the groups G03C1/005 - G03C1/705 containing organic compounds

Definitions

  • the present invention relates to an irreversible ultraviolet coloring composition which irreversibly develops color upon irradiation with ultraviolet light, an irreversible ultraviolet coloring material using the composition, an ultraviolet irradiation recording material, a recording method, and a coloring composition colored by the composition.
  • a diallyl ethene compound is known as one that causes a quasi-irreversible change, and this compound exhibits an irreversible coloration after irradiation with ultraviolet light, but it loses color when irradiated with visible light, so to leave a record after irradiation with ultraviolet light.
  • Inappropriate Japanese Patent No. 4238075.
  • UV-sensitive sheets using leuco dyes capable of oxidative coloration and photooxidants (Japanese Patent Laid-Open No. 2014-163798), photooxidants and leuco dyes capable of oxidative coloration and reducing agents are used as those that irreversibly change color.
  • An ultraviolet detection sheet Japanese Patent Laid-Open No. 2014-174505 is known. They have high color development speed and irreversibly develop color at low illuminance, but at the same time the stability in the initial state is poor, and even in the initial colorless state they will develop color even if left for a short time in a daily indoor environment It had a drawback.
  • a first layer containing a photoactive agent that generates free radicals by ultraviolet irradiation and a color change agent that exhibits a visible color change due to the action of the free radicals is laminated in this order on a second layer that contains an ultraviolet absorber.
  • Measure the amount of ultraviolet light by changing the color by making the color change gentle by absorbing a part of the irradiated ultraviolet light by the second layer and reducing the amount of free radicals generated from the photoactive agent in the first layer It is known to improve the accuracy (JP-B 7-54269).
  • this method is complicated in construction, still fast in color development speed, and poor in initial stability.
  • the present invention relates to an irreversible ultraviolet coloring composition and an irreversible ultraviolet coloring material using the composition, which irreversibly develops color by ultraviolet irradiation, has a high coloring density, and good stability in the initial state before ultraviolet irradiation, It is an object of the present invention to provide an ultraviolet radiation recording material, a recording method, and a color forming composition in which the above-mentioned composition develops a color.
  • the irreversible ultraviolet coloring composition of the present invention the irreversible ultraviolet coloring material using the composition, the ultraviolet irradiation recording material, the recording method, and the coloring composition colored by the composition can be represented as follows.
  • a composition comprising a compound A represented by the formula (I) and a compound B capable of dissolving the compound A, Irreversible ultraviolet coloring composition in which compound A is dissolved in compound B and X is detached from the compound A when irradiated with ultraviolet light to cause an irreversible color development.
  • R 1 to R 4 each independently represent a linear or branched alkyl group having 1 to 4 carbon atoms, Q represents oxygen, nitrogen or sulfur, and X represents a benzoyl group or toluene] A sulfonyl group is shown. ]
  • the compound A is colored as a composition before X is desorbed from the above compound A by irradiation with ultraviolet light, and X is desorbed from the compound A by irradiation with ultraviolet light to produce an irreversible color.
  • the irreversible ultraviolet coloring composition according to any one of (6).
  • non-reversible ultraviolet coloring composition which is colored before X is eliminated from compound A by ultraviolet irradiation
  • the composition is colored according to the color of compound A and / or compound B itself
  • What colored as a composition can be mentioned by containing thing, dye, a pigment, and another coloring matter.
  • a coloring material comprising the irreversible ultraviolet coloring composition according to any one of (1) to (10).
  • the irreversible ultraviolet coloring composition according to any one of the above (1) to (10) is contained in a required part which is a part or the whole, and the desired position in the required part is irradiated with ultraviolet light
  • the material containing the irreversible ultraviolet coloring composition according to any one of the above (1) to (10) in a required part that is a part or the whole is irradiated with ultraviolet light at a desired position in the required part
  • the irreversible ultraviolet coloring composition, the irreversible ultraviolet coloring material, the ultraviolet irradiation recording material, the recording method, and the color forming composition colored by the composition of the present invention irreversibly develop color by ultraviolet irradiation, and the coloring density is high.
  • the stability of the initial state before ultraviolet irradiation is good.
  • the compound A is represented by the above general formula (I).
  • R 1 to R 4 in the formula (I) include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl and tert-butyl.
  • the compound A examples include benzoyl leuco methylene blue, hydroxybenzoyl leuco methylene blue, meta-amino benzoyl leuco methylene blue, methoxy benzoyl leuco methylene blue, ethoxy benzoyl leuco methylene blue, para-toluenesulfonyl leuco methylene blue and the like, but are not limited thereto. It is not a thing.
  • the irreversible ultraviolet coloring composition of the present invention can contain one kind of compound A, and can also contain two or more kinds of compound A.
  • Compound B is capable of dissolving Compound A.
  • dissolution means that a substance (solute) which is a gas, liquid or solid is mixed with other liquid or solid to form a homogeneous mixture of phases, that is, a solution.
  • the compound B can be, for example, at least one selected from esters, alcohols, ketones, ethers, polyethylene resins, polypropylene resins, other polymer compounds and oligomers.
  • compound B Stearate laurate, myristate laurate, cetyl caprate, palmitate stearate, laurate laurate, palmitate laurate, stearyl caprate, myristyl caprate, docosyl caprate, 2-ethylhexyl laurate, n-decyl laurate, myristic acid 3-Methylbutyl, cetyl myristate, isopropyl palmitate, neopentyl palmitate, nonyl palmitate, cyclohexyl palmitate, n-butyl stearate, 2-methylbutyl stearate, n-undecyl stearate, pentadecyl stearate, stearyl stearate, Cyclohexyl methyl stearate, isopropyl behenate, hexyl behenate, lauryl behenate, hexyl behenate, lauryl behenate, lau
  • the irreversible UV-coloring composition of the present invention is a composition comprising Compound A and Compound B, and Compound A is dissolved in Compound B, and the compound A to X are irradiated with ultraviolet rays. C. is eliminated to cause an irreversible color development, and can be obtained, for example, by dissolving compound A in compound B under heating (for example, 50 to 250.degree. C.).
  • the irreversible ultraviolet coloring composition of the present invention may be solid or liquid at normal temperature.
  • the irreversible ultraviolet coloring composition of the present invention does not require that the entire amount of Compound A contained in the compound B be dissolved in the compound B, but substantially all of the compound A contained in the compound B be dissolved in the compound B.
  • a considerable amount of the compound A contained in the compound A is dissolved in the compound B, and the remainder can be exemplified as one uniformly dispersed in the compound B.
  • the compound A can be added to the compound B It can be dissolved stably.
  • the compound B can be, for example, 1 to 2000 in weight ratio to the compound A.
  • the resulting composition is irradiated with ultraviolet light (for example, ultraviolet light of 3000 mJ / cm 2 or more) to cause chemical decomposition in which X is eliminated from compound A as shown next, and compound A from which X is eliminated Becomes a coloring composition in which an irreversible color is developed. That is, for example, a composition whose initial state is colorless becomes a color forming composition which irreversibly changes to a color after ultraviolet irradiation.
  • ultraviolet light for example, ultraviolet light of 3000 mJ / cm 2 or more
  • the irreversible ultraviolet coloring composition of the present invention is such that irreversible coloring is less likely to occur by irradiation with an amount of ultraviolet light lower than 100 to 500 mJ / cm 2 . Even if some irreversible color development occurs by irradiation with an ultraviolet light amount lower than 100 to 500 mJ / cm 2 , the color difference ⁇ E before and after the irreversible color development is preferably 1.6 or less.
  • the irreversible ultraviolet coloring composition of the present invention By blending the irreversible ultraviolet coloring composition of the present invention in, for example, a polyethylene resin, a polypropylene resin, or a polypropylene oligomer by heating and mixing, various molded articles and films containing the irreversible ultraviolet coloring composition of the present invention You can get (4) Bisphenols
  • the irreversible ultraviolet coloring composition of the present invention preferably contains bisphenols (bisphenol or its derivative) in order to increase the coloring density by ultraviolet irradiation.
  • bisphenols include bisphenol A, bisphenol F, bisphenol AF, 2,2'-biphenol, 4,4 '-(1-phenylethylidene) bisphenol, 1,1-bis (4-hydroxyphenyl) -2- Ethyl hexane, 2-bis (4-hydroxy-3-methylphenyl) propane, 2-2-bis (4-hydroxy-3-methylphenyl) butane, 2,2-bis (4-hydroxyphenyl) -4 -Methylpentane, 2,2-bis (4-hydroxyphenyl) -4-methylhexane and the like, but it is not limited thereto.
  • the irreversible ultraviolet coloring composition of the present invention can contain one kind of bisphenol, and can also contain two or more kinds of bisphenol.
  • the reason why the bisphenols effectively act to increase the coloring density by ultraviolet irradiation in the irreversible ultraviolet coloring composition of the present invention is that the above compound A is dissolved in compound B (preferably under heating) It is presumed that the hydroxyl group in the compound B and the bisphenol interacts with the compound A to enhance the stability of the dissolved state of the compound A with respect to the compound B and increase the concentration of irreversible color development by ultraviolet light.
  • the content of bisphenols relative to compound A in the irreversible UV-coloring composition of the present invention is preferably 0.2 to 10 in weight ratio.
  • the irreversible ultraviolet coloring composition of the present invention can contain a photosensitizer D.
  • the photosensitizer D in the present invention refers to a substance that promotes elimination of the X group in compound A. It is also possible to contain bisphenols together.
  • Irreversible UV coloring composition of the present invention containing a photosensitizer D can be one wherein X is detached from the above compound A by irradiation with a relatively low amount of UV light to cause irreversible color development, The stability of the previous initial condition may be reduced.
  • the content of the photosensitizer D can be determined in consideration of, for example, the relationship between the ultraviolet irradiation amount and the coloring density.
  • photosensitizer D in the present invention include p-nitrobenzotribromide, bromotrichloromethane, pencitrichloride, hexabromoethane, 1,1,1-tribromo-2-methyl-2-propanol, 1 1,2,2-Tetrabromoethane, 2,2,2-Tribromoethanol, 1,1,1-Trichloro-2-methyl-2-Bropanol, o-Nitro- ⁇ , ⁇ , ⁇ -Tribromoacetophenone , M-nitro- ⁇ , ⁇ , ⁇ -tribromoacetophenone, p-nitro- ⁇ , ⁇ , ⁇ -tribromoacetophenone, ⁇ , ⁇ , ⁇ -tribromo 3,4-cycloacetophenone, 2,4-dinitrobenzenesulfonyl Chloride, o-nitrobenzenesulfonyl chloride, m-nitrobenzenesulfonyl chloride, 3,
  • the irreversible ultraviolet coloring composition of the present invention can contain one photosensitizer, and can also contain two or more photosensitizers.
  • the irreversible ultraviolet coloring composition of the present invention can contain the ultraviolet absorber E.
  • the irreversible ultraviolet coloring composition of the present invention containing the ultraviolet absorber E, a part of the irradiated ultraviolet rays is absorbed by the ultraviolet absorber E, so the amount of ultraviolet rays (energy light amount) acting on the compound A is reduced Do. Therefore, in the above composition, the rate at which X is desorbed from compound A to cause an irreversible color development can be delayed, and the stability of the initial state before ultraviolet irradiation can be improved.
  • the ultraviolet light absorber E further contributes to the improvement of the light resistance of the color product from which X is desorbed from the compound A in the composition.
  • the content of the ultraviolet absorber E can be, for example, 0.1 to 10 with respect to the compound A in a weight ratio.
  • ultraviolet light absorber E in the present invention examples include benzophenone based ultraviolet light absorbers, benzotriazole based ultraviolet light absorbers, triazine based ultraviolet light absorbers, salicylate based ultraviolet light absorbers and the like.
  • Specific examples include 2,4-hydroxy-4-methoxy-5-sulfobenzophenone, 2- (5-chloro-2H-benzotriazol-2-yl) -4-methyl-6-tert-butylphenol, 2- (2 -Hydroxy-5-methylphenyl) benzotriazole, 2- (2-hydroxy-5-tert-butylphenyl) benzotriazole, 2- (4-((2-hydroxy-3-dodecyloxypropyl) oxy) -2-) Hydroxyphenyl) -4,6-bis (2,4-dimethylphenyl) -1,3,5-triazine, 2,4-bis (2-hydroxy-4-propyloxyphenyl) -6- (2,4-) Dimethylphenyl) -1
  • the irreversible ultraviolet coloring composition of the present invention can contain one type of ultraviolet absorber E, and can also contain two or more types.
  • the irreversible ultraviolet coloring composition of the present invention is substantially colorless before X is desorbed from compound A by ultraviolet irradiation, and other than those which irreversibly develop color by desorbing X from compound A by irradiation of ultraviolet rays
  • the compound is colored as a composition before X is desorbed from compound A by ultraviolet irradiation, and X is desorbed from compound A by irradiation with ultraviolet light to further cause an irreversible color development, and the combined colors are It can also be presented.
  • the coloring of the composition before X is eliminated from compound A by ultraviolet irradiation is realized, for example, by containing a dye, a pigment and other coloring substances in addition to the color of compound A and / or compound B itself. It can.
  • the irreversible ultraviolet coloring composition of the present invention can be encapsulated in a microcapsule.
  • the irreversible ultraviolet coloring composition of the present invention in which the compound A is dissolved in the compound B is added to microcapsules in the state further containing bisphenols, photosensitizer D, ultraviolet absorber E, etc., if necessary.
  • the stability becomes higher. That is, when the irreversible ultraviolet coloring composition of the present invention is used without encapsulating it in microcapsules, discoloration inhibition due to various external factors, for example, printing ink used for printing or being contained in a synthetic resin etc.
  • the compound B and the bisphenols may be bled out of the system to lose the ultraviolet coloring function or to change the ultraviolet coloring rate, which is effectively prevented by being contained in the microcapsule.
  • the particle diameter of the microcapsule is preferably 0.5 to 50 ⁇ m, more preferably 1 to 10 ⁇ m. If it is smaller than 0.5 ⁇ m, sufficient coloring density may not be obtained, and if it is larger than 50 ⁇ m, the smoothness of the surface is lowered when it is used for printing ink and contained in a synthetic resin etc. And the microcapsules may be easily broken.
  • the wall film of the microcapsule it is preferable to select a material having no reactivity with the compound A and compound B, bisphenol, photosensitizer D, ultraviolet absorber E, etc.
  • melamine Resin compounds or isocyanate compounds and their curing agents can be preferably used. More preferably, they are melamine resin compounds.
  • the microcapsules are preferably colorless and transparent, but are not necessarily limited thereto.
  • melamine resin compound examples include urea-formaldehyde compounds, melamine-formaldehyde compounds, methylolmelamine, methylated melamine and the like.
  • Examples of the isocyanate compound include m-phenylene diisocyanate, p-phenylene diisocyanate, 2-4-tolylene diisocyanate, di-phenylmethane-4,4-diisocyanate, xylylene-1,4-diisocyanate and hexamethylene diisocyanate.
  • Examples of the curing agent for forming a wall film by crosslinking include polyamines such as ethylenediamine, trimethylenediamine, tetramethylenediamine, hexamethylenediamine, and diethylenetriamine compounds.
  • the wall film material of the microcapsules is not necessarily limited to these.
  • the microencapsulation of the irreversible ultraviolet coloring composition of the present invention can be carried out, for example, as follows.
  • Compound A and Compound B and, if necessary, bisphenols, photosensitizer D, UV absorber E and the like are further dissolved (preferably under heating) to make Compound A dissolved in Compound B, preferably Is introduced into water with heating and stirring in the presence of a dispersing agent to form an objective oil particle diameter of 1 to 10 ⁇ m, and a melamine resin compound as a wall film material in the bath, or an isocyanate compound and a curing agent
  • the compound is charged and reacted at 95 to 100 ° C. for 1 to 5 hours to obtain a microcapsule encapsulating the irreversible ultraviolet coloring composition of the present invention in which the compound A is dissolved in the compound B.
  • microcapsules can be used, for example, in the form of an aqueous slurry containing microcapsules, or can be used as a powder by drying through spray drying, natural drying, and dehydration steps. It is.
  • microcapsules containing the irreversible ultraviolet coloring composition of the present invention are contained in a printing ink or the like containing various binders in the form of an aqueous slurry or in the form of a powder, so that paper, cloth, synthetic resin film, or the like
  • the article can be applied and fixed by means of screen printing, coating or the like.
  • microcapsules containing the irreversible ultraviolet coloring composition of the present invention in the form of an aqueous slurry, it is possible to obtain a writing instrument ink containing the microcapsules, and obtain a writing instrument using the writing instrument ink Can.
  • a master batch for coloring synthetic resins and the like by blending the powdered microcapsules containing the irreversible ultraviolet coloring composition of the present invention.
  • the masterbatch is compounded into various synthetic resins for injection molding or extrusion molding, or the microcapsuled powder is directly compounded into the synthetic resin to encapsulate the irreversible ultraviolet coloring composition of the present invention.
  • Various molded articles, films and the like containing microcapsules can be obtained.
  • the coloring material of the present invention contains the irreversible ultraviolet coloring composition of the present invention.
  • the irreversible ultraviolet coloring composition of the present invention can be used as a printing ink, an ink for writing instruments, water or oil It can be contained in coloring materials such as paints, various paints, pencils, crayons, Contes, and pastels.
  • Such a coloring material is, for example, attached or fixed to an object by writing, drawing, coating or the like, and then the desired position of the coloring material adhered or fixed to the object is irradiated with ultraviolet light and the position is
  • the compound A can be used to perform desired color recording by removing X from compound A to cause irreversible color development.
  • the UV-irradiated recording material of the present invention contains the irreversible UV-coloring composition of the present invention in the required part, which is a part or the whole, paper, synthetic resin film, cloth, plate made of various materials, wall , Molded articles, and various other articles.
  • the various articles that constitute the ultraviolet irradiation recording material contain the irreversible ultraviolet coloring composition in the article itself (for example, in a synthetic resin molding or a synthetic resin film) or a coating film on the article Or other attachments or bonds (eg, those fixedly contained by printing, writing, coating, etc. or contained in a non-fluid state), and various articles themselves or attachments to them UV irradiation is performed at a desired position of the compound A, and X is desorbed from the compound A at that position to cause irreversible color development, whereby the material can be used as a UV irradiation recording material for performing desired color recording such as characters and patterns. .
  • an ultraviolet irradiation recording material for example, a molded article or a film
  • the irreversible ultraviolet coloring composition in the article unlike the ink adhered to or adhered to the article such as the ink for writing instruments or printing ink, peeling etc.
  • the recording material is excellent in durability.
  • the color forming aspect such as the color of the color developed by the ultraviolet irradiation and the color density can be made different depending on the part.
  • the color development mode of the irreversible ultraviolet color development composition can be made to correspond to the position by changing the ultraviolet irradiation mode such as the ultraviolet irradiation dose according to the position.
  • the ultraviolet irradiation is applied to the desired position at the required position with respect to the ultraviolet irradiation recording material of the present invention containing the irreversible ultraviolet coloring composition in the required portion which is a part or the whole.
  • the ultraviolet irradiation recording material of the present invention containing the irreversible ultraviolet coloring composition in the required portion which is a part or the whole.
  • a means for automatically controlling the position and the irradiation amount of the ultraviolet light by a computer etc. a means for controlling the position and the irradiation amount of the ultraviolet light manually, a masking film or other masking is applied.
  • a means etc. which irradiate an ultraviolet ray can be suitably used except the part which carried out.
  • parts and% mean parts by weight and% by weight, respectively.
  • Composition 1 in which 1.8 parts of benzoyl leuco methylene blue as compound A and 200 parts of decyl laurate (ester compound having a melting point of 20 ° C.) as compound B are heated and dissolved at 150 ° C. is added to the reaction bath of 95 ° C. The mixture was gradually introduced while stirring to disperse Composition 1 into oil droplets of 2 to 3 ⁇ m in diameter.
  • Sumitex resin M-3 (trade name of melamine resin; manufactured by Sumitomo Chemical Co., Ltd.) was added to the reaction bath at 95 ° C. with stirring, and the pH of the reaction bath was adjusted with oxalic acid 4.
  • the obtained microcapsules and slurry are substantially colorless before ultraviolet irradiation, and develop a blue-purple color by a predetermined amount of ultraviolet irradiation, and the color development is an irreversible one that the blue-purple color does not disappear even after the completion of the ultraviolet irradiation. there were.
  • microcapsules having an average particle diameter of 2.3 ⁇ m can be obtained by treating in the same manner as in Example 1 except that composition 2 is used in place of composition 1 and 25 parts of bisphenol A as bisphenols is added. It was obtained in the state of 1000 g of aqueous slurry containing a large amount of the microcapsules.
  • the obtained microcapsules and the slurry are substantially colorless before ultraviolet irradiation, and develop a darker blue color than that of Example 1 by irradiation with a predetermined amount of ultraviolet light, and the color development is irreversible that the blue color does not disappear even after the completion of ultraviolet irradiation. It was
  • the aqueous slurry containing a large amount of microcapsules obtained in Example 1 is diluted 10 times with water and spray dried using a spray dryer to obtain an average particle size of secondary aggregation of primary particles. 380 g of 12.0 ⁇ m microcapsule powder was obtained.
  • the obtained microcapsule powder is substantially colorless before ultraviolet irradiation, and develops a blue-purple color upon irradiation with a predetermined amount of ultraviolet light, and the color development is irreversible such that the blue-purple color does not disappear even after the completion of ultraviolet irradiation.
  • a 95 ° C. reaction bath prepared by heating and dissolving 25 parts of Ganzlets AN-179 as a dispersant, 10 parts of caustic soda, and 500 parts of water in a 2 liter flask was prepared.
  • the obtained microcapsules and the slurry were substantially colorless before ultraviolet irradiation, and developed a blue color by irradiation with a predetermined amount of ultraviolet light, and the color development was irreversible such that the blue color did not disappear even after the completion of ultraviolet irradiation. .
  • a 95 ° C. reaction bath prepared by heating and dissolving 25 parts of Ganzlets AN-179 as a dispersant, 10 parts of caustic soda, and 500 parts of water in a 2 liter flask was prepared.
  • the obtained microcapsules and the slurry were substantially colorless before ultraviolet irradiation, and developed a blue color by irradiation with a predetermined amount of ultraviolet light, and the color development was irreversible such that the blue color did not disappear even after the completion of ultraviolet irradiation. .
  • the mixture was charged into a molding machine, heated to 200 ° C., and melt-kneaded to orient benzoyl leuco methylene blue (compound A) molecularly to the polyethylene resin (compound B), and to cool the mixture.
  • compound A benzoyl leuco methylene blue
  • compound B polyethylene resin
  • the obtained masterbatch was substantially colorless before ultraviolet irradiation, and developed a blue color upon irradiation with a predetermined amount of ultraviolet light, and the color development was irreversible such that the blue color did not disappear even after the completion of ultraviolet irradiation.
  • the obtained Japanese paper is substantially colorless before ultraviolet irradiation, and a blue flower pattern appears by irradiation with a predetermined amount of ultraviolet light, and the color development of the blue flower pattern is irreversible which does not disappear even after the completion of ultraviolet irradiation.
  • Printing ink prepared by blending 30 parts of the microcapsule slurry obtained in Example 2 with 70 parts of binder 50S (trade name of binder for aqueous screen printing; manufactured by Matsui Dyeing & Chemical Co., Ltd.) It was screen printed on Japanese paper using a plate.
  • binder 50S trade name of binder for aqueous screen printing; manufactured by Matsui Dyeing & Chemical Co., Ltd.
  • the Japanese paper obtained is substantially colorless before ultraviolet irradiation, and a blue flower pattern appears by overlapping a black masking film of flower pattern and irradiating a predetermined amount of ultraviolet light, and the color development of the blue flower pattern is ultraviolet irradiation It was irreversible which did not fade even after the end.
  • binder 50S trade name of binder for aqueous screen printing; manufactured by Matsui Dyeing & Chemical Co., Ltd.
  • the Japanese paper obtained is substantially colorless before ultraviolet irradiation, and a blue flower pattern appears by irradiating ultraviolet light so as to draw a flower pattern with an ultraviolet laser marker by computer control, and the color of the blue flower pattern is It was irreversible which did not lose color even after the end of irradiation.
  • the molded object A was obtained by injection-molding at 180 degreeC using the injection molding machine which set (1).
  • the obtained molded product A is substantially colorless before irradiation with ultraviolet light, and is covered with an aluminum masking material for flower pattern and irradiated with ultraviolet light to reveal a blue flower pattern, and the color of the blue flower pattern is irradiated with ultraviolet light. It was irreversible which did not fade even after the end. Also in the case of the rattan, the blue color developed not only on the surface of the molded product A but also on the inward part, so that the blue flower pattern did not disappear even if the surface of the molded product A was rubbed.
  • the molded object A was obtained by injection-molding at 180 degreeC using the injection molding machine which set (1).
  • the obtained molded product A is substantially colorless before ultraviolet irradiation, and a blue flower pattern appears by irradiating ultraviolet light so as to draw a flower pattern with an ultraviolet laser marker by computer control, and the color of the blue flower pattern is After the completion of the ultraviolet irradiation, the color was irreversible. Also in the case of the rattan, the blue color developed not only on the surface of the molded product A but also on the inward part, so that the blue flower pattern did not disappear even if the surface of the molded product A was rubbed.
  • Example 3 19 parts of the microcapsule powder obtained in Example 3 and 40% Byron 300 solution (Byron 300 [trade name of a saturated polyester resin; manufactured by Toyobo Co., Ltd.]) to PGMAc (trade name of an ester solvent; manufactured by Kuraray Co., Ltd.) 150 parts of a printing ink consisting of 65 parts of dissolved, 15 parts of ethyl acetate, and 1 part of TSE-350 (trade name of silicone antifoamer; manufactured by Toshiba Silicon Co., Ltd.), all over a solid pattern, 150 mesh screen Printed on polyester film.
  • Byron 300 solution Byron 300 [trade name of a saturated polyester resin; manufactured by Toyobo Co., Ltd.]
  • PGMAc trade name of an ester solvent; manufactured by Kuraray Co., Ltd.
  • TSE-350 trade name of silicone antifoamer; manufactured by Toshiba Silicon Co., Ltd.
  • the obtained polyester film is substantially colorless before irradiation with ultraviolet light, and a blue flower pattern appears by irradiating ultraviolet light so as to draw a flower pattern with an ultraviolet laser marker by computer control, and the color of the blue flower pattern is It was irreversible which did not lose color even after the end of ultraviolet irradiation.
  • HDI trade name of isocyanate: manufactured by Tosoh Corp.
  • the dispersion is added to an aqueous solution containing 2000 parts of an aqueous solution containing 10 parts of colloidal tricalcium phosphate and 0.2 parts of sodium dodecylbenzenesulfonate as a dispersion stabilizer, and the dispersion is added to the aqueous solution in an amount of 2 to 3 ⁇ m It was dispersed to be the diameter.
  • microcapsules having an average particle diameter of 2.6 ⁇ m, in which Composition 1 is coated with an isocyanate resin It was obtained in the form of a 1000 g aqueous slurry containing a large amount of microcapsules.
  • the obtained microcapsules and slurry are substantially colorless before ultraviolet irradiation, and develop a blue-purple color by a predetermined amount of ultraviolet irradiation, and the color development is an irreversible one that the blue-purple color does not disappear even after the completion of the ultraviolet irradiation. there were.
  • the resulting Japanese paper was substantially colorless before ultraviolet irradiation and hardly developed even when irradiated with ultraviolet light.
  • Example 8 About the Japanese paper obtained in Example 8, the molded object A obtained in Example 11, and the Japanese paper obtained in Comparative Example 1, the result of having measured ultraviolet coloring property is shown.
  • UV light source a black light of 15 W and a main peak of 352 nm was used, and a metal halide lamp of 120 w and a main peak of 250 to 450 nm was used. Further, the color difference ( ⁇ E) was measured by CHECK II PLUS manufactured by Datacolor, and the integrated ultraviolet light quantity was measured by UVR-36 manufactured by Topcon Corporation.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Inks, Pencil-Leads, Or Crayons (AREA)
  • Printing Methods (AREA)
  • Non-Silver Salt Photosensitive Materials And Non-Silver Salt Photography (AREA)

Abstract

Provided are: an irreversible ultraviolet colour developing composition which irreversibly develops colour with a high colour development concentration as a result of being irradiated with ultraviolet, and which exhibits excellent initial state stability; an irreversible ultraviolet colour developing material which uses said composition; an ultraviolet irradiation recording material; a recording method; and a colour developing composition in which said composition develops colour. This irreversible ultraviolet colour developing composition includes compound A which is represented by formula (I), and compound B which is capable of dissolving compound A. Compound A is dissolved in compound B. X is detached from compound A and irreversibly develops colour as a result of irradiation with ultraviolet. (In formula (I): R1 to R4 each independently represent C1-4 straight-chain or branched-chain alkyl groups; Q represents oxygen, nitrogen, or sulfur; and X represents a benzoyl group or a toluenesulfonyl group.)

Description

不可逆性紫外線発色組成物及びその関連技術Irreversible UV coloring composition and related technology
　本発明は、紫外線照射により不可逆的に発色する不可逆性紫外線発色組成物並びにその組成物を用いる不可逆性紫外線発色材料、紫外線照射記録用材料、記録方法及び前記組成物が発色した発色組成物に関する。 The present invention relates to an irreversible ultraviolet coloring composition which irreversibly develops color upon irradiation with ultraviolet light, an irreversible ultraviolet coloring material using the composition, an ultraviolet irradiation recording material, a recording method, and a coloring composition colored by the composition.
　初期状態は無色で、紫外線を照射する事で有色に変化する材料は、例えばスピロピラン、スピロオキサジン、クロメン化合物を用いたフォトクロミック材料が知られているが、これらの化合物は可逆的な色変化を呈するものであり、紫外線照射後の色変化を記録することができるものではない（特開２００７－８９８２３号公報）。 Materials which are colorless in the initial state and change color by irradiation with ultraviolet light are known, for example, photochromic materials using spiropyran, spirooxazine and chromene compounds, but these compounds exhibit reversible color change It is not possible to record the color change after ultraviolet irradiation (Japanese Patent Application Laid-Open No. 2007-89823).
　また、準不可逆的変化をするものとしてジアリルエテン化合物が知られており、この化合物は紫外線照射後に不可逆の発色を呈するが、可視光を照射すると消色するため、紫外線照射後の記録を残すには不適当である（特許第４２３８０７５号公報）。 In addition, a diallyl ethene compound is known as one that causes a quasi-irreversible change, and this compound exhibits an irreversible coloration after irradiation with ultraviolet light, but it loses color when irradiated with visible light, so to leave a record after irradiation with ultraviolet light. Inappropriate (Japanese Patent No. 4238075).
　一方、不可逆的に変色するものとしては、酸化発色可能なロイコ染料と光酸化剤を用いた紫外線感知シート（特開２０１４－１６３７９８）、光酸化剤と酸化発色可能なロイコ染料と還元剤を用いた紫外線感知シート（特開２０１４－１７４５０５）が知られている。これらは、発色速度が速く、低照度において不可逆的に発色するが、その反面、初期状態での安定性が悪く、初期無色状態で日常の室内環境に短時間放置しても発色してしまうという欠点を有していた。 On the other hand, UV-sensitive sheets using leuco dyes capable of oxidative coloration and photooxidants (Japanese Patent Laid-Open No. 2014-163798), photooxidants and leuco dyes capable of oxidative coloration and reducing agents are used as those that irreversibly change color. An ultraviolet detection sheet (Japanese Patent Laid-Open No. 2014-174505) is known. They have high color development speed and irreversibly develop color at low illuminance, but at the same time the stability in the initial state is poor, and even in the initial colorless state they will develop color even if left for a short time in a daily indoor environment It had a drawback.
　また、紫外線照射により遊離基が生成する光活性剤と、この遊離基の作用により可視的な色変化を示す変色剤とを含む第一層及び紫外線吸収剤を含む第二層をこの順に積層し、照射される紫外線の一部を第二層により吸収して第一層で光活性剤から発生する遊離基の量を少なくすることで色の変化を緩やかにして色の変化による紫外線量の測定精度を高める事が知られている（特公平７－５４２６９）。しかしこの方法は、構成が複雑であると共に、いまだ発色速度が速く、初期の安定性が良くないものであった。 In addition, a first layer containing a photoactive agent that generates free radicals by ultraviolet irradiation and a color change agent that exhibits a visible color change due to the action of the free radicals is laminated in this order on a second layer that contains an ultraviolet absorber. Measure the amount of ultraviolet light by changing the color by making the color change gentle by absorbing a part of the irradiated ultraviolet light by the second layer and reducing the amount of free radicals generated from the photoactive agent in the first layer It is known to improve the accuracy (JP-B 7-54269). However, this method is complicated in construction, still fast in color development speed, and poor in initial stability.
特開２００７－８９８２３号公報JP 2007-89823 A 特許第４２３８０７５号公報Patent 4238075 gazette 特開２０１４－１６３７９８号公報JP 2014-163798 特開２０１４－１７４５０５号公報JP, 2014-174505, A 特公平７－５４２６９号公報Japanese Examined Patent Publication 7-54269
　本発明は、紫外線照射により不可逆的に発色し、その発色濃度が高く、紫外線照射前の初期状態の安定性が良好な、不可逆性紫外線発色組成物並びにその組成物を用いる不可逆性紫外線発色材料、紫外線照射記録用材料、記録方法及び前記組成物が発色した発色組成物を提供することを目的とする。 The present invention relates to an irreversible ultraviolet coloring composition and an irreversible ultraviolet coloring material using the composition, which irreversibly develops color by ultraviolet irradiation, has a high coloring density, and good stability in the initial state before ultraviolet irradiation, It is an object of the present invention to provide an ultraviolet radiation recording material, a recording method, and a color forming composition in which the above-mentioned composition develops a color.
　本発明の不可逆性紫外線発色組成物並びにその組成物を用いる不可逆性紫外線発色材料、紫外線照射記録用材料、記録方法及び前記組成物が発色した発色組成物は、次のように表わすことができる。 The irreversible ultraviolet coloring composition of the present invention, the irreversible ultraviolet coloring material using the composition, the ultraviolet irradiation recording material, the recording method, and the coloring composition colored by the composition can be represented as follows.
　(1) 式（Ｉ）で表わされる化合物Ａと、化合物Ａを溶解し得る化合物Ｂを含有してなる組成物であって、
化合物Ａが化合物Ｂに溶解しており、紫外線が照射されることにより、前記化合物ＡからＸが脱離して不可逆発色する不可逆性紫外線発色組成物。 (1) A composition comprising a compound A represented by the formula (I) and a compound B capable of dissolving the compound A,
Irreversible ultraviolet coloring composition in which compound A is dissolved in compound B and X is detached from the compound A when irradiated with ultraviolet light to cause an irreversible color development.
Figure JPOXMLDOC01-appb-I000002
・・・（Ｉ）
［式（Ｉ）中、Ｒ１乃至Ｒ４はそれぞれ独立的に炭素数１乃至４の直鎖又は分岐鎖のアルキル基を示し、Ｑは酸素、窒素又は硫黄を示し、Ｘはベンゾイル基又はトルエンスルホニル基を示す。］
Figure JPOXMLDOC01-appb-I000002
... (I)
[In formula (I), R 1 to R 4 each independently represent a linear or branched alkyl group having 1 to 4 carbon atoms, Q represents oxygen, nitrogen or sulfur, and X represents a benzoyl group or toluene] A sulfonyl group is shown. ]
　(2) 化合物Ｂがエステル類、アルコール類、ケトン類、エーテル類、ポリエチレン樹脂、ポリプロピレン樹脂から選ばれる少なくとも１種である上記(1)記載の不可逆性紫外線発色組成物。 (2) The irreversible ultraviolet coloring composition according to the above (1), wherein the compound B is at least one selected from esters, alcohols, ketones, ethers, polyethylene resin and polypropylene resin.
　(3) 重量比において化合物Ａに対し化合物Ｂが１乃至２０００である上記(1)又は(2)に記載の不可逆性紫外線発色組成物。 (3) The irreversible ultraviolet coloring composition according to the above (1) or (2), wherein the weight ratio of the compound B to the compound A is 1 to 2,000.
　(4) ビスフェノール類を含有する上記(1)乃至(3)の何れか１項に記載の不可逆性紫外線発色組成物。 (4) The irreversible ultraviolet coloring composition according to any one of the above (1) to (3), which contains a bisphenol.
　(5) 光増感剤Ｄを含有する上記(1)乃至(4)の何れか１項に記載の不可逆性紫外線発色組成物。 (5) The irreversible ultraviolet coloring composition according to any one of the above (1) to (4), which comprises a photosensitizer D.
　(6) 紫外線吸収剤Ｅを含有する上記(1)乃至(5)の何れか１項に記載の不可逆性紫外線発色組成物。 (6) The irreversible ultraviolet coloring composition according to any one of the above (1) to (5), which contains the ultraviolet absorber E.
　(7) 紫外線照射により上記化合物ＡからＸが脱離する前より組成物として着色しており、紫外線が照射されることにより、前記化合物ＡからＸが脱離して不可逆発色する上記(1)乃至(6)の何れか１項に記載の不可逆性紫外線発色組成物。 (7) The compound A is colored as a composition before X is desorbed from the above compound A by irradiation with ultraviolet light, and X is desorbed from the compound A by irradiation with ultraviolet light to produce an irreversible color. The irreversible ultraviolet coloring composition according to any one of (6).
　このような、紫外線照射により化合物ＡからＸが脱離する前より着色している不可逆性紫外線発色組成物の例としては、化合物Ａおよび／または化合物Ｂ自体の色により組成物として着色しているものや、染料、顔料、その他の着色性物質を含有することにより組成物として着色しているものを挙げることができる。 As an example of such a non-reversible ultraviolet coloring composition which is colored before X is eliminated from compound A by ultraviolet irradiation, the composition is colored according to the color of compound A and / or compound B itself What colored as a composition can be mentioned by containing thing, dye, a pigment, and another coloring matter.
　(8) マイクロカプセルに内包されてなる上記(1)乃至(7)の何れか１項に記載の不可逆性紫外線発色組成物。 (8) The irreversible ultraviolet coloring composition according to any one of the above (1) to (7), which is encapsulated in a microcapsule.
　(9) マイクロカプセルの平均粒子径が０．５乃至１０μｍであり、２０μｍ未満の粒子を９０％以上含む上記(8)記載の不可逆性紫外線発色組成物。 (9) The irreversible ultraviolet coloring composition according to the above (8), wherein the microcapsules have an average particle size of 0.5 to 10 μm and 90% or more of particles smaller than 20 μm.
　(10) マイクロカプセルの壁膜がメラミン樹脂又はイソシアネート樹脂からなる上記(8)又は(9)記載の不可逆性紫外線発色組成物。 (10) The irreversible ultraviolet coloring composition according to the above (8) or (9), wherein the wall film of the microcapsule is made of melamine resin or isocyanate resin.
　(11) 上記(1)乃至(10)の何れか１項に記載の不可逆性紫外線発色組成物を含有する着色用材料。 (11) A coloring material comprising the irreversible ultraviolet coloring composition according to any one of (1) to (10).
　(12) 上記(1)乃至(10)の何れか１項に記載の不可逆性紫外線発色組成物を部分又は全体である所要箇所に含有し、前記所要箇所における所望位置に紫外線を照射してその位置における化合物ＡからＸを脱離させて不可逆発色させることにより所望の着色記録を行うための紫外線照射記録用材料。 (12) The irreversible ultraviolet coloring composition according to any one of the above (1) to (10) is contained in a required part which is a part or the whole, and the desired position in the required part is irradiated with ultraviolet light A UV irradiation recording material for performing desired color recording by eliminating X from compound A at the position to cause irreversible color development.
　(13) 上記(1)乃至(10)の何れか１項に記載の不可逆性紫外線発色組成物を部分又は全体である所要箇所に含有する材料に対し、前記所要箇所における所望位置に紫外線を照射してその位置における化合物ＡからＸを脱離させて不可逆発色させることにより所望の着色記録を行う記録方法。 (13) The material containing the irreversible ultraviolet coloring composition according to any one of the above (1) to (10) in a required part that is a part or the whole is irradiated with ultraviolet light at a desired position in the required part A recording method of performing desired color recording by causing X to be released from compound A at that position and causing irreversible color development.
　(14) 上記(1)乃至(10)の何れか１項に記載の不可逆性紫外線発色組成物において上記化合物ＡからＸが脱離して不可逆発色した発色組成物。 (14) A coloring composition in which X is eliminated from the compound A in the irreversible ultraviolet coloring composition according to any one of the above (1) to (10) to cause an irreversible color formation.
　本発明の不可逆性紫外線発色組成物、不可逆性紫外線発色材料、紫外線照射記録用材料、記録方法及び前記組成物が発色した発色組成物は、紫外線照射により不可逆的に発色し、その発色濃度が高く、紫外線照射前の初期状態の安定性が良好である。 The irreversible ultraviolet coloring composition, the irreversible ultraviolet coloring material, the ultraviolet irradiation recording material, the recording method, and the color forming composition colored by the composition of the present invention irreversibly develop color by ultraviolet irradiation, and the coloring density is high. The stability of the initial state before ultraviolet irradiation is good.
　本発明の実施の形態を説明する。 An embodiment of the present invention will be described.
　尚、本明細書において"乃至"の前後に数値が記載されている場合は、"乃至"の前後の数値を下限値及び上限値として含む数値範囲を表わすものとする。
　(1) 化合物Ａ In addition, when numerical values are described before and after “to” in the present specification, a numerical range including the numerical values before and after “to” as the lower limit value and the upper limit value will be represented.
(1) Compound A
　化合物Ａは上記一般式（Ｉ）で表わされる。式（Ｉ）中のＲ１乃至Ｒ４の例としては、メチル、エチル、ｎ－プロピル、イソプロピル、ｎ－ブチル、イソブチル、sec－ブチル、tert－ブチルを挙げることができる。 The compound A is represented by the above general formula (I). Examples of R 1 to R 4 in the formula (I) include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl and tert-butyl.
　化合物Ａの具体例としては、ベンゾイルロイコメチレンブルー、ヒドロキシベンゾイルロイコメチレンブルー、メタアミノベンゾイルロイコメチレンブルー、メトキシベンゾイルロイコメチレンブルー、エトキシベンゾイルロイコメチレンブルー、パラトルエンスルホニルロイコメチレンブルーなどを挙げることができるが、これらに限定されるものではない。 Specific examples of the compound A include benzoyl leuco methylene blue, hydroxybenzoyl leuco methylene blue, meta-amino benzoyl leuco methylene blue, methoxy benzoyl leuco methylene blue, ethoxy benzoyl leuco methylene blue, para-toluenesulfonyl leuco methylene blue and the like, but are not limited thereto. It is not a thing.
　本発明の不可逆性紫外線発色組成物は、化合物Ａを１種含有するものとすることができる他、化合物Ａを２種以上含有するものとすることもできる。 The irreversible ultraviolet coloring composition of the present invention can contain one kind of compound A, and can also contain two or more kinds of compound A.
　(2) 化合物Ｂ (2) Compound B
　化合物Ｂは、化合物Ａを溶解し得るものである。 Compound B is capable of dissolving Compound A.
　本明細書中、溶解とは、気体、液体、固体である物質（溶質）が、ほかの液体や固体と混合して均一な相の混合物、すなわち溶体（solution）をつくることを言う。 In the present specification, dissolution means that a substance (solute) which is a gas, liquid or solid is mixed with other liquid or solid to form a homogeneous mixture of phases, that is, a solution.
　化合物Ｂとしては、化合物Ａとの間に反応性がないものが望ましい。 As the compound B, one not having reactivity with the compound A is desirable.
　化合物Ｂは、例えば、エステル類、アルコール類、ケトン類、エーテル類、ポリエチレン樹脂、ポリプロピレン樹脂、その他の高分子化合物及びオリゴマーから選ばれる少なくとも１種とすることができる。 The compound B can be, for example, at least one selected from esters, alcohols, ketones, ethers, polyethylene resins, polypropylene resins, other polymer compounds and oligomers.
　化合物Ｂの具体例としては、
ステアリン酸ラウレート、ミリスチン酸ラウレート、カプリン酸セチル、ステアリン酸パルミテート、ラウリン酸ラウレート、ラウリン酸パルミテート、カプリン酸ステアリル、カプリン酸ミリスチル、カプリン酸ドコシル、ラウリン酸２－エチルヘキシル、ラウリン酸ｎ－デシル、ミリスチン酸３－メチルブチル、ミリスチン酸セチル、パルミチン酸イソプロピル、パルミチン酸ネオペンチル、パルミチン酸ノニル、パルミチン酸シクロヘキシル、ステアリン酸ｎ－ブチル、ステアリン酸２－メチルブチル、ステアリン酸ｎ－ウンデシル、ステアリン酸ペンタデシル、ステアリン酸ステアリル、ステアリン酸シクロヘキシルメチル、ベヘン酸イソプロピル、ベヘン酸ヘキシル、ベヘン酸ラウリル、ベヘン酸ヘキシル、ベヘン酸ラウリル、ベヘン酸ラウリル、ベヘン酸ベヘニル、安息香酸セチル、ブチル安息香酸ステアリル、フタル酸ジミリスチル、マロン酸ジセチル、グルタル酸ジラウリル、アジピン酸ジウンデシル、アゼライン酸ジラウリル、４，４’－（ヘキサフルオロイソプロピリデン）ビフェノールジカプテート、４，４’－（ヘキサフルオロイソプロピリデン）ビフェノールジラウレート、４，４’－（ヘキサフルオロイソプロピリデン）ビフェノールジミリステート、４，４’－（ヘキサフルオロイソプロピリデン）ビフェノールジパルミエート、４，４’－（ヘキサフルオロイソプロピリデン）ビフェノールジウンデカノエート、４，４’－（ヘキサフルオロイソプロピリデン）ビフェノールジトリデカエートなどのエステル類；
セチルアルコール、ステアリルアルコール、ベンジルアルコール、ラウリルアルコール、オクチルアルコール、ミリスチルアルコール、パルミチルアルコール、デシルアルコール、ウンデシルアルコール、ドデシルアルコール、トリデシルアルコール、テトラデシルアルコール、ペンタデシルアルコール、ヘキサデシルアルコール、オクタデシルアルコール、エイコシルアルコール、ドコシルアルコールなどのアルコール類；
ジオクチルケトン、ジノニルケトン、ジウンデシルケトン、ジトリデシルケトン、ジペンタデシルケトン、フェニルトリデシルケトン、２－テトラデカノン、２－ペンタデカノン、８－ペンタデカノン、３－ヘキサデカノン、９－ヘプタデカノン、２－ペンタデカノン、２－オクタデカノン、１０－ノナデカノン、２－エイコサノン、２－ヘンエイコサノン、２－ドコサノンなどのケトン類；
ジエイコシルエーテル、ジオクタデシルエーテル、ジペンタデシルエーテル、ジドコシルエーテル、ジテトラデシルエーテル、ジトリデシルエーテルなどのエ－テル類；
ポリエチレン樹脂、ポリプロピレン樹脂等の高分子化合物又はオリゴマーとして、低密度ポリエチレン樹脂、高密度ポリエチレン樹脂、超低密度ポリエチレン樹脂、ポリプロピレン樹脂、ポリプロピレンオリゴマー等が挙げられる。但し、これらに限定されるものでなく、本発明の不可逆性紫外線発色組成物は、化合物Ｂを１種含有するものとすることができる他、化合物Ｂを２種以上含有するものとすることもできる。 As specific examples of compound B,
Stearate laurate, myristate laurate, cetyl caprate, palmitate stearate, laurate laurate, palmitate laurate, stearyl caprate, myristyl caprate, docosyl caprate, 2-ethylhexyl laurate, n-decyl laurate, myristic acid 3-Methylbutyl, cetyl myristate, isopropyl palmitate, neopentyl palmitate, nonyl palmitate, cyclohexyl palmitate, n-butyl stearate, 2-methylbutyl stearate, n-undecyl stearate, pentadecyl stearate, stearyl stearate, Cyclohexyl methyl stearate, isopropyl behenate, hexyl behenate, lauryl behenate, hexyl behenate, lauryl behenate, Lauryl phosphate, behenyl behenate, cetyl benzoate, stearyl butylbenzoate, dimyristyl phthalate, dicetyl malonate, dilauryl glutarate, diundecyl adipate, dilaudecyl azelate, 4,4 '-(hexafluoroisopropylidene) biphenol di Captate, 4,4 ′-(hexafluoroisopropylidene) biphenol dilaurate, 4,4 ′-(hexafluoroisopropylidene) biphenol dimyristate, 4,4 ′-(hexafluoroisopropylidene) biphenol dipalmiate, 4 Esters such as 4,4 '-(hexafluoroisopropylidene) biphenol diundecanoate, 4,4'-(hexafluoroisopropylidene) biphenol ditridecaate;
Cetyl alcohol, stearyl alcohol, benzyl alcohol, lauryl alcohol, octyl alcohol, myristyl alcohol, palmityl alcohol, decyl alcohol, undecyl alcohol, dodecyl alcohol, tridecyl alcohol, tetradecyl alcohol, pentadecyl alcohol, hexadecyl alcohol, octadecyl alcohol , Alcohols such as eicosyl alcohol, docosyl alcohol;
Dioctyl ketone, dinonyl ketone, diundecyl ketone, ditridecyl ketone, dipentadecyl ketone, phenyl tridecyl ketone, 2-tetradecanone, 2-pentadecanone, 8-pentadecanone, 3-hexadecanone, 9-heptadecanone, 2-pentadecanone, 2-octadecanone Ketones such as 10-nonadecanone, 2-eicosanone, 2-haeneicosanone, 2-docosanone;
Ethers such as dieicosyl ether, dioctadecyl ether, dipentadecyl ether, didocosyl ether, ditetradecyl ether, ditridecyl ether;
As high molecular compounds or oligomers such as polyethylene resin and polypropylene resin, low density polyethylene resin, high density polyethylene resin, ultra low density polyethylene resin, polypropylene resin, polypropylene oligomer and the like can be mentioned. However, the present invention is not limited to these, and the irreversible ultraviolet coloring composition of the present invention may contain one kind of compound B, and may also contain two or more kinds of compound B. it can.
　(3) 不可逆性紫外線発色組成物 (3) Irreversible UV coloring composition
　本発明の不可逆性紫外線発色組成物は、化合物Ａと化合物Ｂを含有してなる組成物であり、化合物Ａが化合物Ｂに溶解しており、紫外線が照射されることにより、前記化合物ＡからＸが脱離して不可逆発色するものであって、例えば、化合物Ａを化合物Ｂ中に加熱下（例えば５０乃至２５０℃）で溶解させることにより得ることができる。 The irreversible UV-coloring composition of the present invention is a composition comprising Compound A and Compound B, and Compound A is dissolved in Compound B, and the compound A to X are irradiated with ultraviolet rays. C. is eliminated to cause an irreversible color development, and can be obtained, for example, by dissolving compound A in compound B under heating (for example, 50 to 250.degree. C.).
　本発明の不可逆性紫外線発色組成物は、常温で固体であっても液体であってもよい。また本発明の不可逆性紫外線発色組成物は、含有する化合物Ａの全量が化合物Ｂに溶解していることを要するものではなく、含有する化合物Ａの実質上全量が化合物Ｂに溶解しているものの他、含有する化合物Ａのうち相当量が化合物Ｂに溶解し、残部は化合物Ｂに均一状に分散しているものを、その例として挙げることができる。 The irreversible ultraviolet coloring composition of the present invention may be solid or liquid at normal temperature. The irreversible ultraviolet coloring composition of the present invention does not require that the entire amount of Compound A contained in the compound B be dissolved in the compound B, but substantially all of the compound A contained in the compound B be dissolved in the compound B. In addition, a considerable amount of the compound A contained in the compound A is dissolved in the compound B, and the remainder can be exemplified as one uniformly dispersed in the compound B.
　例えば、化合物Ｂとして、化合物Ａとの間に反応性がないエステル類、アルコール類、ケトン類、エーテル類、ポリエチレン樹脂、ポリプロピレン樹脂から選ばれる少なくとも１種を用いることにより、化合物Ａを化合物Ｂに安定的に溶解させることができる。 For example, by using at least one selected from an ester, an alcohol, a ketone, an ether, a polyethylene resin, and a polypropylene resin having no reactivity with the compound A as the compound B, the compound A can be added to the compound B It can be dissolved stably.
　本発明の不可逆性紫外線発色組成物においては、重量比において化合物Ａに対し化合物Ｂは例えば１乃至２０００であるものとすることができる。 In the irreversible ultraviolet coloring composition of the present invention, the compound B can be, for example, 1 to 2000 in weight ratio to the compound A.
　得られた組成物に対し、紫外線（例えば３０００ｍＪ／ｃｍ２以上の紫外線）を照射することにより、次に示すように化合物ＡからＸが脱離する化学分解が生じ、Ｘが脱離した化合物Ａが不可逆発色した発色組成物となる。すなわち例えば、初期状態が無色の組成物が紫外線照射後は有色に不可逆的に変化した発色組成物となる。 The resulting composition is irradiated with ultraviolet light (for example, ultraviolet light of 3000 mJ / cm 2 or more) to cause chemical decomposition in which X is eliminated from compound A as shown next, and compound A from which X is eliminated Becomes a coloring composition in which an irreversible color is developed. That is, for example, a composition whose initial state is colorless becomes a color forming composition which irreversibly changes to a color after ultraviolet irradiation.
Figure JPOXMLDOC01-appb-I000003
Figure JPOXMLDOC01-appb-I000003
　本発明の不可逆性紫外線発色組成物は、１００乃至５００ｍＪ／ｃｍ２を下回る紫外線量の照射によっては不可逆発色が生じにくいものであることが好ましい。１００乃至５００ｍＪ／ｃｍ２を下回る紫外線量の照射により何らかの不可逆発色が生じるとしても、その不可逆発色の前後の色差ΔＥは、１．６以下であるものであることが好ましい。 It is preferable that the irreversible ultraviolet coloring composition of the present invention is such that irreversible coloring is less likely to occur by irradiation with an amount of ultraviolet light lower than 100 to 500 mJ / cm 2 . Even if some irreversible color development occurs by irradiation with an ultraviolet light amount lower than 100 to 500 mJ / cm 2 , the color difference ΔE before and after the irreversible color development is preferably 1.6 or less.
　本発明の不可逆性紫外線発色組成物を、例えば、ポリエチレン樹脂、ポリプロピレン樹脂、又はポリプロピレンオリゴマー中に加熱混合等により配合することにより、本発明の不可逆性紫外線発色組成物を含有する各種成形物やフィルムを得ることができる。
　(4) ビスフェノール類 By blending the irreversible ultraviolet coloring composition of the present invention in, for example, a polyethylene resin, a polypropylene resin, or a polypropylene oligomer by heating and mixing, various molded articles and films containing the irreversible ultraviolet coloring composition of the present invention You can get
(4) Bisphenols
　本発明の不可逆性紫外線発色組成物は、紫外線照射による発色濃度を高める上で、ビスフェノール類（ビスフェノール又はその誘導体）を含有するものとすることが望ましい。 The irreversible ultraviolet coloring composition of the present invention preferably contains bisphenols (bisphenol or its derivative) in order to increase the coloring density by ultraviolet irradiation.
　ビスフェノール類の具体例としては、ビスフェノールＡ、ビスフェノールＦ、ビスフェノールＡＦ、２，２’ビフェノール、４，４’－（１－フェニルエチリデン）ビスフェノール、１，１－ビス（４－ヒドロキシフェニル）－２－エチルヘキサン、２－２－ビス（４－ヒドロキシ－３－メチルフェニル）プロパン、２－２－ビス（４－ヒドロキシ－３－メチルフェニル）ブタン、２，２－ビス（４－ヒドロキシフェニル）－４－メチルペンタン、２，２－ビス（４－ヒドロキシフェニル）－４－メチルヘキサンなどが挙げられるが、これらに限定されるものではない。 Specific examples of bisphenols include bisphenol A, bisphenol F, bisphenol AF, 2,2'-biphenol, 4,4 '-(1-phenylethylidene) bisphenol, 1,1-bis (4-hydroxyphenyl) -2- Ethyl hexane, 2-bis (4-hydroxy-3-methylphenyl) propane, 2-2-bis (4-hydroxy-3-methylphenyl) butane, 2,2-bis (4-hydroxyphenyl) -4 -Methylpentane, 2,2-bis (4-hydroxyphenyl) -4-methylhexane and the like, but it is not limited thereto.
　本発明の不可逆性紫外線発色組成物は、ビスフェノール類を１種含有するものとすることができる他、ビスフェノール類を２種以上含有するものとすることもできる。 The irreversible ultraviolet coloring composition of the present invention can contain one kind of bisphenol, and can also contain two or more kinds of bisphenol.
　なお、ビスフェノール類が、本発明の不可逆性紫外線発色組成物において紫外線照射による発色濃度を高める上で有効に作用する理由は、上記化合物Ａを化合物Ｂ中に（好ましくは加熱下で）溶解させる場合に、化合物Ｂとビスフェノール類における水酸基が化合物Ａと相互作用して化合物Ｂに対する化合物Ａの溶解状態の安定性を高め、紫外線による不可逆性発色の濃度を高めるものと推定される。 The reason why the bisphenols effectively act to increase the coloring density by ultraviolet irradiation in the irreversible ultraviolet coloring composition of the present invention is that the above compound A is dissolved in compound B (preferably under heating) It is presumed that the hydroxyl group in the compound B and the bisphenol interacts with the compound A to enhance the stability of the dissolved state of the compound A with respect to the compound B and increase the concentration of irreversible color development by ultraviolet light.
　本発明の不可逆性紫外線発色組成物における化合物Ａに対するビスフェノール類の含有量は、重量比において０．２乃至１０であることが好ましい。 The content of bisphenols relative to compound A in the irreversible UV-coloring composition of the present invention is preferably 0.2 to 10 in weight ratio.
　(5) 光増感剤Ｄ (5) Photosensitizer D
　本発明の不可逆性紫外線発色組成物は、光増感剤Ｄを含有するものとすることができる。本発明における光増感剤Ｄは、化合物ＡにおけるＸ基の脱離を助長する物質を言う。ビスフェノール類を併せて含有するものとすることもできる。 The irreversible ultraviolet coloring composition of the present invention can contain a photosensitizer D. The photosensitizer D in the present invention refers to a substance that promotes elimination of the X group in compound A. It is also possible to contain bisphenols together.
　光増感剤Ｄを含有する本発明の不可逆性紫外線発色組成物は、比較的に低い紫外線量の照射により上記化合物ＡからＸが脱離して不可逆発色するものとすることができるが、紫外線照射前の初期状態の安定性が低下するおそれがある。 Irreversible UV coloring composition of the present invention containing a photosensitizer D can be one wherein X is detached from the above compound A by irradiation with a relatively low amount of UV light to cause irreversible color development, The stability of the previous initial condition may be reduced.
　光増感剤Ｄの含有量は、例えば、紫外線照射量と発色濃度等の関係を考慮して決めることができる。 The content of the photosensitizer D can be determined in consideration of, for example, the relationship between the ultraviolet irradiation amount and the coloring density.
　本発明における光増感剤Ｄの具体例としては、ｐ－ニトロベンゾトリブロマイド、ブロモトリクロロメタン、ペンシトリクロライド、ヘキサブロモエタン、１，１，１－トリブロモ－２－メチル－２－プロパノール、１，１，２，２－テトラブロモエタン、２，２，２－トリブロモエタノール、１，１，１－トリクロロ－２－メチル－２－ブロパノール、ｏ－ニトロ－α，α，α－トリブロモアセトフェノン、ｍ－ニトロ－α，α，α－トリブロモアセトフェノン、ｐ－ニトロ－α，α，α－トリブロモアセトフェノン、α，α，α－トリブロモ３，４－シクロアセトフェノン、２，４－ジニトロベンゼンスルホニルクロライド、ｏ－ニトロベンゼンスルホニルクロライド、ｍ－ニトロベンゼンスルホニルクロライド、３，３－ジフェニルスルフォンジスルホニルクロライド、エタンスルホニルクロライド、ｐ－ブロモベンゼンスルホニルクロライド、ヘキサブロモジメチルスルホオキサイド、ペンタブロモジメチルスルホオキサイド、ヘキサブロモジメチルスルフォン、トリクロロメチルフェニルスルフォン、トリブロモメチルフェニルスルフォン、トリクロロメチルフェニルスルフォン、トリクロロ－ｐ－クロロフェニルスルフォン、トリ－ｐ－トリスルフォニウムトリフルオロメタンスルホナート、トリブロモキナルジン、２－トリブロモメチル－４－メチルキノリン、４－トリブロモメチルピリミジン、４－フェニル－６－トリブロモメチルピリミジン、２－トリクロロメチル－６－ニトロベンゾチアゾールなどを挙げることができるが、これらに限られるものではない。 Specific examples of the photosensitizer D in the present invention include p-nitrobenzotribromide, bromotrichloromethane, pencitrichloride, hexabromoethane, 1,1,1-tribromo-2-methyl-2-propanol, 1 1,2,2-Tetrabromoethane, 2,2,2-Tribromoethanol, 1,1,1-Trichloro-2-methyl-2-Bropanol, o-Nitro-α, α, α-Tribromoacetophenone , M-nitro-α, α, α-tribromoacetophenone, p-nitro-α, α, α-tribromoacetophenone, α, α, α-tribromo 3,4-cycloacetophenone, 2,4-dinitrobenzenesulfonyl Chloride, o-nitrobenzenesulfonyl chloride, m-nitrobenzenesulfonyl chloride, 3,3-diphenyl sulfone Disulfonyl chloride, ethane sulfonyl chloride, p-bromobenzene sulfonyl chloride, hexabromodimethyl sulfo oxide, pentabromo dimethyl sulfo oxide, hexabromo dimethyl sulfone, trichloromethyl phenyl sulfone, tribromo methyl phenyl sulfone, trichloromethyl phenyl sulfone, trichloro- p-Chlorophenylsulfone, tri-p-trissulfonium trifluoromethanesulfonate, tribromoquinaldine, 2-tribromomethyl-4-methylquinoline, 4-tribromomethyl pyrimidine, 4-phenyl-6-tribromomethyl pyrimidine And 2-trichloromethyl-6-nitrobenzothiazole, but not limited thereto.
　本発明の不可逆性紫外線発色組成物は、光増感剤を１種含有するものとすることができる他、光増感剤を２種以上含有するものとすることもできる。 The irreversible ultraviolet coloring composition of the present invention can contain one photosensitizer, and can also contain two or more photosensitizers.
　(6) 紫外線吸収剤Ｅ (6) UV absorber E
　本発明の不可逆性紫外線発色組成物は、紫外線吸収剤Ｅを含有するものとすることができる。 The irreversible ultraviolet coloring composition of the present invention can contain the ultraviolet absorber E.
　紫外線吸収剤Ｅを含有する本発明の不可逆性紫外線発色組成物においては、照射された紫外線の一部が紫外線吸収剤Ｅにより吸収されるので、化合物Ａに作用する紫外線量（エネルギー光量）が低減する。そのため、前記組成物において化合物ＡからＸが脱離して不可逆発色する速度を遅らせることができ、また紫外線照射前の初期状態の安定性を向上させることができる。紫外線吸収剤Ｅは、更には、前記組成物中の化合物ＡからＸが脱離した発色物の耐光性の向上にも資する。 In the irreversible ultraviolet coloring composition of the present invention containing the ultraviolet absorber E, a part of the irradiated ultraviolet rays is absorbed by the ultraviolet absorber E, so the amount of ultraviolet rays (energy light amount) acting on the compound A is reduced Do. Therefore, in the above composition, the rate at which X is desorbed from compound A to cause an irreversible color development can be delayed, and the stability of the initial state before ultraviolet irradiation can be improved. The ultraviolet light absorber E further contributes to the improvement of the light resistance of the color product from which X is desorbed from the compound A in the composition.
　紫外線吸収剤Ｅの含有量は、例えば、重量比において化合物Ａに対して０．１乃至１０とすることができる。 The content of the ultraviolet absorber E can be, for example, 0.1 to 10 with respect to the compound A in a weight ratio.
　本発明における紫外線吸収剤Ｅの具体例としては、ベンゾフェノン系紫外線吸収剤、ベンゾリアゾール系紫外線吸収剤、トリアジン系紫外線吸収剤、サリチレート系紫外線吸収剤などが挙げられる。具体例としては、２，４ヒドロキシ－４－メトキシ－５－スルホベンゾフェノン、２－（５－クロロ－２Ｈ－ベンゾトリアゾール－２－イル）－４－メチル－６－ｔｅｒｔ－ブチルフェノール、２－（２－ヒドロキシ－５－メチルフェニル）ベンゾトリアゾール、２－（２－ヒドロキシ－５－ターシャリーブチルフェニル）ベンゾトリアゾール、２－（４－（（２－ヒドロキシ－３－ドデシルオキシプロピル）オキシ）－２－ヒドロキシフェニル）－４，６－ビス（２，４－ジメチルフェニル）－１，３，５－トリアジン、２，４－ビス（２－ヒドロキシ－４－プロピルオキシフェニル）－６－（２，４－ジメチルフェニル）－１，３，５トリアジン、２，４－ビス（（２－ヒドロキシ－４－ブトキシフェニル）－６－（２，４－ブトキシフェニル）－１，３，５－トリアジン、２，４－ビス（２－ヒドロキシ－４－（１－（イソオクチルオキシカルボニル）エトキシ）フェニル）－６－（２，４－ビス（１－（イソオクチルオキシカルボニル）エトキシ）フェニル）－１，３，５－トリアジン、フェニルサリチレートなどを挙げることができるが、これらに限られるものではない。 Specific examples of the ultraviolet light absorber E in the present invention include benzophenone based ultraviolet light absorbers, benzotriazole based ultraviolet light absorbers, triazine based ultraviolet light absorbers, salicylate based ultraviolet light absorbers and the like. Specific examples include 2,4-hydroxy-4-methoxy-5-sulfobenzophenone, 2- (5-chloro-2H-benzotriazol-2-yl) -4-methyl-6-tert-butylphenol, 2- (2 -Hydroxy-5-methylphenyl) benzotriazole, 2- (2-hydroxy-5-tert-butylphenyl) benzotriazole, 2- (4-((2-hydroxy-3-dodecyloxypropyl) oxy) -2-) Hydroxyphenyl) -4,6-bis (2,4-dimethylphenyl) -1,3,5-triazine, 2,4-bis (2-hydroxy-4-propyloxyphenyl) -6- (2,4-) Dimethylphenyl) -1,3,5 triazine, 2,4-bis ((2-hydroxy-4-butoxyphenyl) -6- (2,4-butoxy) Nyl) -1,3,5-triazine, 2,4-bis (2-hydroxy-4- (1- (isooctyloxycarbonyl) ethoxy) phenyl) -6- (2,4-bis (1- (iso)) Examples include, but are not limited to, octyloxycarbonyl) ethoxy) phenyl) -1,3,5-triazine, phenyl salicylate and the like.
　本発明の不可逆性紫外線発色組成物は、紫外線吸収剤Ｅを１種含有するものとすることができる他、２種以上含有するものとすることもできる。 The irreversible ultraviolet coloring composition of the present invention can contain one type of ultraviolet absorber E, and can also contain two or more types.
　(7) 着色組成物 (7) Colored composition
　本発明の不可逆性紫外線発色組成物は、紫外線照射により化合物ＡからＸが脱離する前は実質上無色で、紫外線が照射されることにより、化合物ＡからＸが脱離して不可逆発色するものの他、紫外線照射により化合物ＡからＸが脱離する前より組成物として着色しており、紫外線が照射されることにより、化合物ＡからＸが脱離して更に不可逆発色し、それらが総合された色を呈するものとすることもできる。 The irreversible ultraviolet coloring composition of the present invention is substantially colorless before X is desorbed from compound A by ultraviolet irradiation, and other than those which irreversibly develop color by desorbing X from compound A by irradiation of ultraviolet rays The compound is colored as a composition before X is desorbed from compound A by ultraviolet irradiation, and X is desorbed from compound A by irradiation with ultraviolet light to further cause an irreversible color development, and the combined colors are It can also be presented.
　紫外線照射により化合物ＡからＸが脱離する前の組成物の着色は、例えば、化合物Ａおよび／または化合物Ｂ自体の色によるもののほか、染料、顔料、その他の着色性物質を含有させることにより実現し得る。 The coloring of the composition before X is eliminated from compound A by ultraviolet irradiation is realized, for example, by containing a dye, a pigment and other coloring substances in addition to the color of compound A and / or compound B itself. It can.
　(8) マイクロカプセル化 (8) Microencapsulation
　本発明の不可逆性紫外線発色組成物は、マイクロカプセルに内包されたものとすることができる。 The irreversible ultraviolet coloring composition of the present invention can be encapsulated in a microcapsule.
　(8-1) 化合物Ａが化合物Ｂに溶解した本発明の不可逆性紫外線発色組成物は、必要に応じ更にビスフェノール類、光増感剤Ｄ、紫外線吸収剤Ｅ等を含有した状態でマイクロカプセルに内包されることにより、より安定性が高いものとなる。すなわち、本発明の不可逆性紫外線発色組成物をマイクロカプセルに内包しない状態で用いた場合における各種外部要因による変色阻害、例えは印刷インキに用いて印刷したり合成樹脂等に含有させて成形物とした場合に、化合物Ｂやビスフェノール類等が系外にブリードして紫外線発色機能を喪失したり紫外線発色速度が変化することが、マイクロカプセルに内包することにより有効に防止される。 (8-1) The irreversible ultraviolet coloring composition of the present invention in which the compound A is dissolved in the compound B is added to microcapsules in the state further containing bisphenols, photosensitizer D, ultraviolet absorber E, etc., if necessary. By being contained, the stability becomes higher. That is, when the irreversible ultraviolet coloring composition of the present invention is used without encapsulating it in microcapsules, discoloration inhibition due to various external factors, for example, printing ink used for printing or being contained in a synthetic resin etc. In such a case, the compound B and the bisphenols may be bled out of the system to lose the ultraviolet coloring function or to change the ultraviolet coloring rate, which is effectively prevented by being contained in the microcapsule.
　(8-2) マイクロカプセルの粒子径は、好ましくは０．５乃至５０μｍ、より好ましくは１乃至１０μｍである。０．５μｍより小さいと、十分な発色濃度が得られない恐れがあり、５０μｍより大きいと印刷インキに用いて印刷したり合成樹脂等に含有させて成形物とした場合に表面の平滑性が低下したりマイクロカプセルの破壊が生じ易くなる恐れがある。 (8-2) The particle diameter of the microcapsule is preferably 0.5 to 50 μm, more preferably 1 to 10 μm. If it is smaller than 0.5 μm, sufficient coloring density may not be obtained, and if it is larger than 50 μm, the smoothness of the surface is lowered when it is used for printing ink and contained in a synthetic resin etc. And the microcapsules may be easily broken.
　(8-3) マイクロカプセルの壁膜としては、化合物Ａ及び化合物Ｂ並びにビスフェノール類、光増感剤Ｄ、紫外線吸収剤Ｅ等との反応性のない材料を選択することが好ましく、例えば、メラミン樹脂化合物、又は、イソシアネート化合物とその硬化剤を、好ましく使用し得る。より好ましくはメラミン樹脂化合物である。マイクロカプセルは、無色透明であることが好ましいが、必ずしもこれに限るものではない。 (8-3) As the wall film of the microcapsule, it is preferable to select a material having no reactivity with the compound A and compound B, bisphenol, photosensitizer D, ultraviolet absorber E, etc. For example, melamine Resin compounds or isocyanate compounds and their curing agents can be preferably used. More preferably, they are melamine resin compounds. The microcapsules are preferably colorless and transparent, but are not necessarily limited thereto.
　メラミン樹脂化合物としては、尿素－ホルムアルデヒド化合物、メラミン－ホルムアルデヒド化合物、メチロールメラミン、メチル化メラミンなどが挙げられる。 Examples of the melamine resin compound include urea-formaldehyde compounds, melamine-formaldehyde compounds, methylolmelamine, methylated melamine and the like.
　イソシアネート化合物としては、ｍ－フェニレンジイソシアネート、ｐ－フェニレンジイソシアネート、２－４－トリレンジイソシアネート、ジ－フェニルメタン－４，４－ジイソシアネート、キシリレン－１，４－ジイソシアネート、ヘキサメチレンジイソシアネートが挙げられ、これらを架橋により壁膜とするための硬化剤としては、エチレンジアミン、トリメチレンジアミン、テトラメチレンジアミン、ヘキサメチレンジアミン、ジエチレントリアミン化合物等のポリアミン類を挙げることができる。但し、マイクロカプセルの壁膜材料は、必ずしもこれらに限定されるものではない。 Examples of the isocyanate compound include m-phenylene diisocyanate, p-phenylene diisocyanate, 2-4-tolylene diisocyanate, di-phenylmethane-4,4-diisocyanate, xylylene-1,4-diisocyanate and hexamethylene diisocyanate. Examples of the curing agent for forming a wall film by crosslinking include polyamines such as ethylenediamine, trimethylenediamine, tetramethylenediamine, hexamethylenediamine, and diethylenetriamine compounds. However, the wall film material of the microcapsules is not necessarily limited to these.
　(8-4) 本発明の不可逆性紫外線発色組成物のマイクロカプセル化は、例えば次のように行い得る。 (8-4) The microencapsulation of the irreversible ultraviolet coloring composition of the present invention can be carried out, for example, as follows.
　化合物Ａ及び化合物Ｂ並びに必要に応じ更にビスフェノール類、光増感剤Ｄ、紫外線吸収剤Ｅ等を（好ましくは加熱下で）溶解させて、化合物Ａが化合物Ｂに溶解したものとした後、好ましくは分散剤の存在下で、加熱・撹拌しながら水中に投入し、目的の１乃至１０μｍの粒子径の油滴とし、当該浴中に壁膜材料であるメラミン樹脂化合物、またはイソシアネート化合物と硬化剤化合物を投入し、９５乃至１００℃で１乃至５時間反応させることにより、化合物Ａが化合物Ｂに溶解した本発明の不可逆性紫外線発色組成物を内包したマイクロカプセルが得られる。 Compound A and Compound B and, if necessary, bisphenols, photosensitizer D, UV absorber E and the like are further dissolved (preferably under heating) to make Compound A dissolved in Compound B, preferably Is introduced into water with heating and stirring in the presence of a dispersing agent to form an objective oil particle diameter of 1 to 10 μm, and a melamine resin compound as a wall film material in the bath, or an isocyanate compound and a curing agent The compound is charged and reacted at 95 to 100 ° C. for 1 to 5 hours to obtain a microcapsule encapsulating the irreversible ultraviolet coloring composition of the present invention in which the compound A is dissolved in the compound B.
　(8-5) 得られたマイクロカプセルは、例えば、マイクロカプセルを含有する水性スラリーの態様で用いること、或いは、噴霧乾燥、自然乾燥、脱水工程を経て乾燥させることによりパウダー化して用いることも可能である。 (8-5) The obtained microcapsules can be used, for example, in the form of an aqueous slurry containing microcapsules, or can be used as a powder by drying through spray drying, natural drying, and dehydration steps. It is.
　本発明の不可逆性紫外線発色組成物を内包するマイクロカプセルは、水性スラリーの態様又はパウダーの態様で、各種バインダーを配合した印刷インキ等に含有させて、紙、布、合成樹脂フィルム、又はその他の物品に対し、スクリーン印刷やコーティング等の手段により適用して固着させることができる。 The microcapsules containing the irreversible ultraviolet coloring composition of the present invention are contained in a printing ink or the like containing various binders in the form of an aqueous slurry or in the form of a powder, so that paper, cloth, synthetic resin film, or the like The article can be applied and fixed by means of screen printing, coating or the like.
　また、本発明の不可逆性紫外線発色組成物を内包するマイクロカプセルを水性スラリーの態様で配合することにより、そのマイクロカプセルを含有する筆記具用インキを得、その筆記具用インキを用いた筆記具を得ることができる。 In addition, by blending microcapsules containing the irreversible ultraviolet coloring composition of the present invention in the form of an aqueous slurry, it is possible to obtain a writing instrument ink containing the microcapsules, and obtain a writing instrument using the writing instrument ink Can.
　また、本発明の不可逆性紫外線発色組成物を内包するマイクロカプセルをパウダー化したものを配合して合成樹脂等着色用のマスターバッチを得ることができる。このマスターバッチを、インジェクション成形や押し出し成形用の各種合成樹脂等に配合し、又はマイクロカプセルをパウダー化したものを直接に合成樹脂に配合して、本発明の不可逆性紫外線発色組成物を内包するマイクロカプセルを含有する各種成形体やフィルムなどを得ることができる。 In addition, it is possible to obtain a master batch for coloring synthetic resins and the like by blending the powdered microcapsules containing the irreversible ultraviolet coloring composition of the present invention. The masterbatch is compounded into various synthetic resins for injection molding or extrusion molding, or the microcapsuled powder is directly compounded into the synthetic resin to encapsulate the irreversible ultraviolet coloring composition of the present invention. Various molded articles, films and the like containing microcapsules can be obtained.
　また、本発明の不可逆性紫外線発色組成物を内包するマイクロカプセルをパウダー化したものを、塩化ビニル樹脂やアクリル樹脂からなるゾルインキに配合してスラッシュ成形やローテーション成形などにより樹脂成形物を得ることができる。 In addition, it is possible to obtain a resin molded product by slush molding, rotation molding, etc. by blending the powdered microcapsules containing the irreversible ultraviolet coloring composition of the present invention into a sol ink composed of a vinyl chloride resin or an acrylic resin. it can.
　(9) 本発明の着色用材料は、本発明の不可逆性紫外線発色組成物を含有するものであり、例えば、本発明の不可逆性紫外線発色組成物を、印刷インキ、筆記具用インキ、水性又は油性ペイント、各種絵の具、鉛筆、クレヨン、コンテ、パステル等の着色用材料に含有させたものとすることができる。 (9) The coloring material of the present invention contains the irreversible ultraviolet coloring composition of the present invention. For example, the irreversible ultraviolet coloring composition of the present invention can be used as a printing ink, an ink for writing instruments, water or oil It can be contained in coloring materials such as paints, various paints, pencils, crayons, Contes, and pastels.
　このような着色用材料は、例えば、対象物に筆記、描画、塗布等により付着又は固着等させた後、対象物に付着又は固着等した着色用材料の所望位置に紫外線を照射してその位置における化合物ＡからＸを脱離させて不可逆発色させることにより所望の着色記録を行うために用いることができる。 Such a coloring material is, for example, attached or fixed to an object by writing, drawing, coating or the like, and then the desired position of the coloring material adhered or fixed to the object is irradiated with ultraviolet light and the position is The compound A can be used to perform desired color recording by removing X from compound A to cause irreversible color development.
　(10) 本発明の紫外線照射記録用材料は、本発明の不可逆性紫外線発色組成物を、部分又は全体である所要箇所に含有する、紙、合成樹脂フィルム、布帛、各種材料からなる板、壁、成形物、その他の各種物品である。 (10) The UV-irradiated recording material of the present invention contains the irreversible UV-coloring composition of the present invention in the required part, which is a part or the whole, paper, synthetic resin film, cloth, plate made of various materials, wall , Molded articles, and various other articles.
　前記紫外線照射記録用材料を構成する各種物品は、前記不可逆性紫外線発色組成物を、その物品自体に含有するもの（例えば合成樹脂成形物や合成樹脂フィルムに含有するもの）又はその物品に対する塗膜若しくはその他の付着若しくは固着物等に含有するもの（例えば印刷、筆記、塗布等により固定的に含有するもの又は非流動状態で含有するもの）とすることができ、各種物品自体又はそれらに対する固着物の所望の位置に紫外線を照射してその位置における化合物ＡからＸを脱離させて不可逆発色させることにより文字や図柄等の所望の着色記録を行うための紫外線照射記録用材料とすることができる。 The various articles that constitute the ultraviolet irradiation recording material contain the irreversible ultraviolet coloring composition in the article itself (for example, in a synthetic resin molding or a synthetic resin film) or a coating film on the article Or other attachments or bonds (eg, those fixedly contained by printing, writing, coating, etc. or contained in a non-fluid state), and various articles themselves or attachments to them UV irradiation is performed at a desired position of the compound A, and X is desorbed from the compound A at that position to cause irreversible color development, whereby the material can be used as a UV irradiation recording material for performing desired color recording such as characters and patterns. .
　物品自体に前記不可逆性紫外線発色組成物を含有する紫外線照射記録用材料（例えば成形物やフィルム）の場合、筆記具用インキや印刷インキのように物品に付着又は固着したものとは異なり、剥離等による記録の消失のおそれが低く、耐久性に優れた記録用材料となる。 In the case of an ultraviolet irradiation recording material (for example, a molded article or a film) containing the irreversible ultraviolet coloring composition in the article itself, unlike the ink adhered to or adhered to the article such as the ink for writing instruments or printing ink, peeling etc. There is a low risk of loss of recording due to the above, and the recording material is excellent in durability.
　前記所要箇所における不可逆性紫外線発色組成物の種類を、部分によって異なるものとすることにより、部分によって紫外線照射による発色の色や発色濃度等の発色態様を異なるものとすることができる。 By making the type of the irreversible ultraviolet ray coloring composition at the required portion different depending on the part, the color forming aspect such as the color of the color developed by the ultraviolet irradiation and the color density can be made different depending on the part.
　また、位置に応じて紫外線照射量等の紫外線照射態様を変えることにより、不可逆性紫外線発色組成物の発色態様を位置に応じたものとすることもできる。 In addition, the color development mode of the irreversible ultraviolet color development composition can be made to correspond to the position by changing the ultraviolet irradiation mode such as the ultraviolet irradiation dose according to the position.
　(11) 本発明の記録方法は、不可逆性紫外線発色組成物を部分又は全体である所要箇所に含有する本発明の紫外線照射記録用材料に対し、前記所要箇所における所望位置に紫外線を照射してその位置における化合物ＡからＸを脱離させて不可逆発色させることにより文字や図柄等の所望の着色記録を行うものである。 (11) In the recording method of the present invention, the ultraviolet irradiation is applied to the desired position at the required position with respect to the ultraviolet irradiation recording material of the present invention containing the irreversible ultraviolet coloring composition in the required portion which is a part or the whole. By desorbing X from compound A at that position and causing irreversible color development, desired color recording of characters, patterns and the like is performed.
　所望位置に紫外線を照射するには、コンピュータ等により紫外線照射の位置や照射量等を自動制御する手段、手動で紫外線照射の位置や照射量等を制御する手段、マスキングフィルム又はその他のマスキングを施した部分以外に紫外線を照射する手段等を適宜用いることができる。 In order to irradiate the ultraviolet light to the desired position, a means for automatically controlling the position and the irradiation amount of the ultraviolet light by a computer etc., a means for controlling the position and the irradiation amount of the ultraviolet light manually, a masking film or other masking is applied. A means etc. which irradiate an ultraviolet ray can be suitably used except the part which carried out.
　以下、本発明を実施例を挙げて説明するが、本発明はこれらに限定されるものではない。なお、以下の説明中、部及び％はそれぞれ重量部及び重量％を意味する。 Hereinafter, the present invention will be described by way of examples, but the present invention is not limited thereto. In the following description, parts and% mean parts by weight and% by weight, respectively.
　（実施例１） Example 1
　２リットルのフラスコに、分散剤としてのガンツレッツＡＮ－１７９（メチルビニルエーテル・無水マレイン酸共重合樹脂の商品名；株式会社ＩＳＰ製）２５部を苛性ソーダ１０部及び水５００部からなる水溶液に加熱溶解させた９５℃の反応浴を用意した。 In a 2 liter flask, 25 parts of Ganzlets AN-179 (trade name of methyl vinyl ether / maleic anhydride copolymer resin; made by ISP Co., Ltd.) as a dispersant is dissolved by heating in an aqueous solution consisting of 10 parts of caustic soda and 500 parts of water. A 95 ° C. reaction bath was prepared.
　化合物Ａとしてのベンゾイルロイコメチレンブルー１．８部と化合物Ｂとしてのラウリン酸デシル（融点２０℃のエステル化合物）２００部を１５０℃で加熱溶解させた組成物１を、前記９５℃の反応浴に対し撹拌しながら徐々に投入して、その組成物１を２乃至３μｍ径の油滴状に分散させた。 Composition 1 in which 1.8 parts of benzoyl leuco methylene blue as compound A and 200 parts of decyl laurate (ester compound having a melting point of 20 ° C.) as compound B are heated and dissolved at 150 ° C. is added to the reaction bath of 95 ° C. The mixture was gradually introduced while stirring to disperse Composition 1 into oil droplets of 2 to 3 μm in diameter.
　次いで、スミテックスレジンＭ－３（メラミン樹脂の商品名；株式会社住友化学製）１６０部を、前記９５℃の反応浴に対し撹拌しながら投入し、その反応浴のｐＨをシュウ酸により４．０乃至４．５に調整して５時間反応を行わせることにより、組成物１をメラミン樹脂で被覆した平均粒子径２．４μｍのマイクロカプセルが、そのマイクロカプセルを多量に含有する１０００ｇの水性スラリーの状態で得られた。 Next, 160 parts of Sumitex resin M-3 (trade name of melamine resin; manufactured by Sumitomo Chemical Co., Ltd.) was added to the reaction bath at 95 ° C. with stirring, and the pH of the reaction bath was adjusted with oxalic acid 4. An aqueous slurry containing 1000 g of microcapsules having an average particle diameter of 2.4 μm, in which Composition 1 is coated with melamine resin and adjusted to 0 to 4.5 and allowed to react for 5 hours, contains a large amount of the microcapsules. It was obtained in the condition of
　得られたマイクロカプセル及びスラリーは、紫外線照射前は実質上無色で、所定量の紫外線照射により青紫色に発色し、その発色は、紫外線照射終了後も青紫色が消色しない不可逆的なものであった。 The obtained microcapsules and slurry are substantially colorless before ultraviolet irradiation, and develop a blue-purple color by a predetermined amount of ultraviolet irradiation, and the color development is an irreversible one that the blue-purple color does not disappear even after the completion of the ultraviolet irradiation. there were.
　（実施例２） (Example 2)
　組成物１に替えて、組成物１にビスフェノール類としてビスフェノールＡ２５部を加えた組成物２を用いる以外は、実施例１と同様に処理することにより、平均粒子径２．３μｍのマイクロカプセルが、そのマイクロカプセルを多量に含有する１０００ｇの水性スラリーの状態で得られた The microcapsules having an average particle diameter of 2.3 μm can be obtained by treating in the same manner as in Example 1 except that composition 2 is used in place of composition 1 and 25 parts of bisphenol A as bisphenols is added. It was obtained in the state of 1000 g of aqueous slurry containing a large amount of the microcapsules.
　得られたマイクロカプセル及びスラリーは、紫外線照射前は実質上無色で、所定量の紫外線照射により実施例１よりも濃い青色に発色し、その発色は、紫外線照射終了後も青色が消色しない不可逆的なものであった。 The obtained microcapsules and the slurry are substantially colorless before ultraviolet irradiation, and develop a darker blue color than that of Example 1 by irradiation with a predetermined amount of ultraviolet light, and the color development is irreversible that the blue color does not disappear even after the completion of ultraviolet irradiation. It was
　（実施例３） (Example 3)
　実施例１で得られた、マイクロカプセルを多量に含有する水性スラリーを、水で１０倍に希釈し、それをスプレードライヤーを用いて噴霧乾燥させることにより、一次粒子が二次凝集した平均粒子径１２．０μｍのマイクロカプセルパウダー３８０ｇが得られた。 The aqueous slurry containing a large amount of microcapsules obtained in Example 1 is diluted 10 times with water and spray dried using a spray dryer to obtain an average particle size of secondary aggregation of primary particles. 380 g of 12.0 μm microcapsule powder was obtained.
　得られたマイクロカプセルパウダーは、紫外線照射前は実質上無色で、所定量の紫外線照射により青紫色に発色し、その発色は、紫外線照射終了後も青紫色が消色しない不可逆的なものであった。 The obtained microcapsule powder is substantially colorless before ultraviolet irradiation, and develops a blue-purple color upon irradiation with a predetermined amount of ultraviolet light, and the color development is irreversible such that the blue-purple color does not disappear even after the completion of ultraviolet irradiation. The
　（実施例４） (Example 4)
　２リットルのフラスコに、分散剤としてのガンツレッツＡＮ－１７９を２５部、苛性ソーダ１０部及び水５００部からなる水溶液に加熱溶解させた９５℃の反応浴を用意した。 A 95 ° C. reaction bath prepared by heating and dissolving 25 parts of Ganzlets AN-179 as a dispersant, 10 parts of caustic soda, and 500 parts of water in a 2 liter flask was prepared.
　化合物Ａとしてのベンゾイルロイコメチレンブルー２．０部、化合物Ｂとしてのパルミチン酸ステアリル（融点４４℃のエステル化合物）２００部、ビスフェノール類としての４，４’－（１－フェニルエチリデン）ビスフェノール３０部を１５０℃で加熱溶解させた組成物２を、前記９５℃の反応浴に対し撹拌しながら徐々に投入して、その組成物２を２乃至３μｍ径の油滴状に分散させた。 2.0 parts of benzoyl leuco methylene blue as compound A, 200 parts of stearyl palmitate (ester compound having a melting point of 44 ° C.) as compound B, 150 parts of 30 parts of 4,4 '-(1-phenylethylidene) bisphenol as bisphenols The composition 2 heated and dissolved at 0 ° C. was gradually added to the 95 ° C. reaction bath with stirring to disperse the composition 2 into oil droplets of 2-3 μm diameter.
　次いで、１６０部のスミテックスレジンＭ－３を、前記９５℃の反応浴に対し撹拌しながら投入し、その反応浴のｐＨをシュウ酸により４．０乃至４．５に調整して５時間反応を行わせることにより、組成物２をメラミン樹脂で被覆した平均粒子径２．４μｍのマイクロカプセルが、そのマイクロカプセルを多量に含有する１０００ｇの水性スラリーの状態で得られた。 Next, 160 parts of Sumitex resin M-3 was added to the 95 ° C. reaction bath with stirring, and the pH of the reaction bath was adjusted to 4.0 to 4.5 with oxalic acid, and the reaction was carried out for 5 hours. As a result, microcapsules having an average particle diameter of 2.4 μm, in which the composition 2 was coated with a melamine resin, were obtained in the form of a 1000 g aqueous slurry containing a large amount of the microcapsules.
　得られたマイクロカプセル及びスラリーは、紫外線照射前は実質上無色で、所定量の紫外線照射により青色に発色し、その発色は、紫外線照射終了後も青色が消色しない不可逆的なものであった。 The obtained microcapsules and the slurry were substantially colorless before ultraviolet irradiation, and developed a blue color by irradiation with a predetermined amount of ultraviolet light, and the color development was irreversible such that the blue color did not disappear even after the completion of ultraviolet irradiation. .
　（実施例５） (Example 5)
　２リットルのフラスコに、分散剤としてのガンツレッツＡＮ－１７９を２５部、苛性ソーダ１０部及び水５００部からなる水溶液に加熱溶解させた９５℃の反応浴を用意した。 A 95 ° C. reaction bath prepared by heating and dissolving 25 parts of Ganzlets AN-179 as a dispersant, 10 parts of caustic soda, and 500 parts of water in a 2 liter flask was prepared.
　化合物Ａとしてのベンゾイルロイコメチレンブルー２．０部、化合物Ｂとしてのセチルアルコール（融点４９℃のアルコール類）２００部、ビスフェノール類としての４，４’－（１－フェニルエチリデン）ビスフェノール２５部を１５０℃で加熱溶解させた組成物３を、前記９５℃の反応浴に対し撹拌しながら徐々に投入して、その組成物３を２乃至３μｍ径の油滴状に分散させた。 2.0 parts of benzoyl leuco methylene blue as compound A, 200 parts of cetyl alcohol (alcohols with a melting point of 49.degree. C.) as compound B, and 25 parts of 4,4 '-(1-phenylethylidene) bisphenol as bisphenols at 150.degree. The composition 3 heated and dissolved was gradually introduced into the reaction bath at 95 ° C. with stirring to disperse the composition 3 into oil droplets of 2-3 μm diameter.
　次いで、１８０部のスミテックスレジンＭ－３を、前記９５℃の反応浴に対し撹拌しながら投入し、その反応浴のｐＨをシュウ酸により４．０乃至４．５に調整して５時間反応を行わせることにより、組成物３をメラミン樹脂で被覆した平均粒子径２．４μｍのマイクロカプセルが、そのマイクロカプセルを多量に含有する１０００ｇの水性スラリーの状態で得られた。 Next, 180 parts of Sumitex resin M-3 is added to the 95 ° C. reaction bath with stirring, and the pH of the reaction bath is adjusted to 4.0 to 4.5 with oxalic acid, and the reaction is carried out for 5 hours. As a result, microcapsules having an average particle diameter of 2.4 μm, in which the composition 3 was coated with a melamine resin, were obtained in the form of a 1000 g aqueous slurry containing a large amount of the microcapsules.
　得られたマイクロカプセル及びスラリーは、紫外線照射前は実質上無色で、所定量の紫外線照射により青色に発色し、その発色は、紫外線照射終了後も青色が消色しない不可逆的なものであった。 The obtained microcapsules and the slurry were substantially colorless before ultraviolet irradiation, and developed a blue color by irradiation with a predetermined amount of ultraviolet light, and the color development was irreversible such that the blue color did not disappear even after the completion of ultraviolet irradiation. .
　（実施例６） (Example 6)
　化合物Ａとしてのベンゾイルロイコメチレンブルー０．５部と化合物Ｂとしてのポリエチレン樹脂（ＭＦＲ＝２０ｇ／１０分［１９０℃、２．１６ｋｇ］９９．５部を、成形用ホッパーを用いて混合した。 0.5 parts of benzoyl leuco methylene blue as the compound A and 99.5 parts of a polyethylene resin as the compound B (MFR = 20 g / 10 min [190 ° C., 2.16 kg]) were mixed using a molding hopper.
　その混合物を成形機に投入し、２００℃に加熱して溶融混練することにより、ベンゾイルロイコメチレンブルー（化合物Ａ）をポリエチレン樹脂（化合物Ｂ）に対し分子状に配向させ、その混合物を冷却させた上でペレッターカッターを用いて直径１ｍｍ、長さ１０ｍｍのペレット状をなすポリエチレン樹脂成形物用のマスターバッチを得た。 The mixture was charged into a molding machine, heated to 200 ° C., and melt-kneaded to orient benzoyl leuco methylene blue (compound A) molecularly to the polyethylene resin (compound B), and to cool the mixture. In the above, using a pelleter cutter, a master batch for polyethylene resin moldings in the form of pellets 1 mm in diameter and 10 mm in length was obtained.
　得られたマスターバッチは、紫外線照射前は実質上無色で、所定量の紫外線照射により青色に発色し、その発色は、紫外線照射終了後も青色が消色しない不可逆的なものであった。 The obtained masterbatch was substantially colorless before ultraviolet irradiation, and developed a blue color upon irradiation with a predetermined amount of ultraviolet light, and the color development was irreversible such that the blue color did not disappear even after the completion of ultraviolet irradiation.
　（実施例７） (Example 7)
　実施例３で得られたマイクロカプセルパウダー１８部、低密度ポリエチレン樹脂（ＭＦＲ＝４５ｇ／１０分［１９０℃、２．１６ｋｇ］）７３部、高級脂肪酸ポリイミド誘導体２部、ポリエチレンワックス（融点１１７乃至１２３℃）１０部、ステアリン酸マグネシウム２部を成形用ホッパーで混合した後、ペレッター成形機を用いて１８０℃で溶融混練し、次いで冷却した後、ペレッターカッターを用いて直径１ｍｍ、長さ１０ｍｍのマスターバッチペレットを１０５部得た。 18 parts of the microcapsule powder obtained in Example 3, 73 parts of low density polyethylene resin (MFR = 45 g / 10 min [190 ° C., 2.16 kg]), 2 parts of a higher fatty acid polyimide derivative, polyethylene wax (melting point 117 to 123 C) 10 parts of magnesium stearate and 2 parts of magnesium stearate are mixed in a molding hopper, melt-kneaded at 180 ° C. using a pelleter molding machine, and then cooled, and then 1 mm in diameter and 10 mm in length using a pelleter cutter 105 parts of masterbatch pellets were obtained.
　（実施例８） (Example 8)
　実施例２で得られたマイクロカプセルスラリー３０部をバインダー５０Ｓ（水性スクリーン印刷用バインダーの商品名；株式会社松井色素化学工業所製）７０部に配合した印刷インキを、花柄の１００メッシュスクリーン版を使用して、和紙上にスクリーンプリントした。 100 mesh screen version of floral pattern printing ink containing 30 parts of microcapsule slurry obtained in Example 2 in 70 parts of binder 50S (trade name of binder for aqueous screen printing; manufactured by Matsui Dyeing & Chemical Co., Ltd.) Screen-printed on Japanese paper using
　得られた和紙は、紫外線照射前は実質上無色で、所定量の紫外線照射により青色の花柄が現れ、その青色花柄の発色は、紫外線照射終了後も消色しない不可逆的なものであった。 The obtained Japanese paper is substantially colorless before ultraviolet irradiation, and a blue flower pattern appears by irradiation with a predetermined amount of ultraviolet light, and the color development of the blue flower pattern is irreversible which does not disappear even after the completion of ultraviolet irradiation. The
　（実施例９） (Example 9)
　実施例２で得られたマイクロカプセルスラリー３０部をバインダー５０Ｓ（水性スクリーン印刷用バインダーの商品名；株式会社松井色素化学工業所製）７０部を配合した印刷インキを、全面ベタ柄の１００メッシュスクリーン版を使用して、和紙上にスクリーンプリントした。 Printing ink prepared by blending 30 parts of the microcapsule slurry obtained in Example 2 with 70 parts of binder 50S (trade name of binder for aqueous screen printing; manufactured by Matsui Dyeing & Chemical Co., Ltd.) It was screen printed on Japanese paper using a plate.
　得られた和紙は、紫外線照射前は実質上無色で、花柄の黒色マスキングフィルムを重ねて所定量の紫外線を照射することにより青色の花柄が現れ、その青色花柄の発色は、紫外線照射終了後も消色しない不可逆的なものであった。 The Japanese paper obtained is substantially colorless before ultraviolet irradiation, and a blue flower pattern appears by overlapping a black masking film of flower pattern and irradiating a predetermined amount of ultraviolet light, and the color development of the blue flower pattern is ultraviolet irradiation It was irreversible which did not fade even after the end.
　（実施例１０） (Example 10)
　実施例２で得られたマイクロカプセルスラリー３０部をバインダー５０Ｓ（水性スクリーン印刷用バインダーの商品名；株式会社松井色素化学工業所製）７０部に配合した印刷インキを、全面ベタ柄の１００メッシュスクリーン版を使用して、和紙上にスクリーンプリントした。 100 mesh screen of the whole surface solid pattern printing ink containing 30 parts of microcapsule slurry obtained in Example 2 in 70 parts of binder 50S (trade name of binder for aqueous screen printing; manufactured by Matsui Dyeing & Chemical Co., Ltd.) It was screen printed on Japanese paper using a plate.
　得られた和紙は、紫外線照射前は実質上無色で、コンピュータ制御により紫外線レーザーマーカーで花柄を描くように紫外線を照射することにより青色の花柄が現れ、その青色花柄の発色は、紫外線照射終了後も消色しない不可逆的なものであった。 The Japanese paper obtained is substantially colorless before ultraviolet irradiation, and a blue flower pattern appears by irradiating ultraviolet light so as to draw a flower pattern with an ultraviolet laser marker by computer control, and the color of the blue flower pattern is It was irreversible which did not lose color even after the end of irradiation.
　（実施例１１） (Example 11)
　実施例７で得られたマスターバッチペレット１０部と低密度ポリエチレン樹脂（ＭＦＲ＝２０ｇ／１０分［１９０℃、２．１６ｋｇ］）９０部を成形機用ホッパー内で混合したものを、マグカップ成形型をセットしたインジェクション成形機を用いて１８０℃で射出成型することにより、成形体Ａを得た。 A mixture of 10 parts of the masterbatch pellet obtained in Example 7 and 90 parts of low density polyethylene resin (MFR = 20 g / 10 min [190 ° C., 2.16 kg]) in a hopper for a molding machine is a mug-forming mold The molded object A was obtained by injection-molding at 180 degreeC using the injection molding machine which set (1).
　得られた成形体Ａは、紫外線照射前は実質上無色で、花柄のアルミニウム製マスキング材で覆って紫外線を照射することにより青色の花柄が現れ、その青色花柄の発色は、紫外線照射終了後も消色しない不可逆的なものであった。而も、成形体Ａの表面のみならず内方部まで青色が発色しているため、成形体Ａの表面を擦過しても青色の花柄は消えないものであった。 The obtained molded product A is substantially colorless before irradiation with ultraviolet light, and is covered with an aluminum masking material for flower pattern and irradiated with ultraviolet light to reveal a blue flower pattern, and the color of the blue flower pattern is irradiated with ultraviolet light. It was irreversible which did not fade even after the end. Also in the case of the rattan, the blue color developed not only on the surface of the molded product A but also on the inward part, so that the blue flower pattern did not disappear even if the surface of the molded product A was rubbed.
　（実施例１２） (Example 12)
　実施例７で得られたマスターバッチペレット１０部と低密度ポリエチレン樹脂（ＭＦＲ＝２０ｇ／１０分［１９０℃、２．１６ｋｇ］）９０部を成形機用ホッパー内で混合したものを、マグカップ成形型をセットしたインジェクション成形機を用いて１８０℃で射出成型することにより、成形体Ａを得た。 A mixture of 10 parts of the masterbatch pellet obtained in Example 7 and 90 parts of low density polyethylene resin (MFR = 20 g / 10 min [190 ° C., 2.16 kg]) in a hopper for a molding machine is a mug-forming mold The molded object A was obtained by injection-molding at 180 degreeC using the injection molding machine which set (1).
　得られた成形体Ａは、紫外線照射前は実質上無色で、コンピュータ制御により紫外線レーザーマーカーで花柄を描くように紫外線を照射することにより青色の花柄が現れ、その青色花柄の発色は、紫外線照射終了後も消色しない不可逆的なものであった。而も、成形体Ａの表面のみならず内方部まで青色が発色しているため、成形体Ａの表面を擦過しても青色の花柄は消えないものであった。 The obtained molded product A is substantially colorless before ultraviolet irradiation, and a blue flower pattern appears by irradiating ultraviolet light so as to draw a flower pattern with an ultraviolet laser marker by computer control, and the color of the blue flower pattern is After the completion of the ultraviolet irradiation, the color was irreversible. Also in the case of the rattan, the blue color developed not only on the surface of the molded product A but also on the inward part, so that the blue flower pattern did not disappear even if the surface of the molded product A was rubbed.
　（実施例１３） (Example 13)
　実施例３で得られたマイクロカプセルパウダー１９部、４０％バイロン３００溶液（バイロン３００［飽和ポリエステル樹脂の商品名；株式会社東洋紡製］をＰＧＭＡｃ（エステル系溶剤の商品名；株式会社クラレ製）に溶解させたもの）６５部、酢酸エチル１５部、及びＴＳＥ－３５０（シリコン系消泡剤の商品名；株式会社東芝シリコン製）１部からなる印刷用インキを、全面ベタ柄の１５０メッシュスクリーン版を使用して、ポリエステルフィルム上にプリントした。 19 parts of the microcapsule powder obtained in Example 3 and 40% Byron 300 solution (Byron 300 [trade name of a saturated polyester resin; manufactured by Toyobo Co., Ltd.]) to PGMAc (trade name of an ester solvent; manufactured by Kuraray Co., Ltd.) 150 parts of a printing ink consisting of 65 parts of dissolved, 15 parts of ethyl acetate, and 1 part of TSE-350 (trade name of silicone antifoamer; manufactured by Toshiba Silicon Co., Ltd.), all over a solid pattern, 150 mesh screen Printed on polyester film.
　得られたポリエステルフィルムは、紫外線照射前は実質上無色で、コンピュータ制御により紫外線レーザーマーカーで花柄を描くように紫外線を照射することにより青色の花柄が現れ、その青色花柄の発色は、紫外線照射終了後も消色しない不可逆的なものであった。 The obtained polyester film is substantially colorless before irradiation with ultraviolet light, and a blue flower pattern appears by irradiating ultraviolet light so as to draw a flower pattern with an ultraviolet laser marker by computer control, and the color of the blue flower pattern is It was irreversible which did not lose color even after the end of ultraviolet irradiation.
　（実施例１４） (Example 14)
　２００部の組成物１に対しＨＤＩ（イソシアネートの商品名：東ソー株式会社製）５０部を加えて加熱、撹拌して分散液を得た。 50 parts of HDI (trade name of isocyanate: manufactured by Tosoh Corp.) was added to 200 parts of Composition 1, heated and stirred to obtain a dispersion.
　分散安定剤としてコロイド状リン酸三カルシウム１０部とドデシルベンゼンスルホン酸ナトリウム０．２部を含む水溶液２０００部を６０℃に加熱したものに前記分散液を加え、それを前記水溶液中に２乃至３μｍ径となるよう分散させた。 The dispersion is added to an aqueous solution containing 2000 parts of an aqueous solution containing 10 parts of colloidal tricalcium phosphate and 0.2 parts of sodium dodecylbenzenesulfonate as a dispersion stabilizer, and the dispersion is added to the aqueous solution in an amount of 2 to 3 μm It was dispersed to be the diameter.
　このようにして得られた分散液にキシリレンジアミン１０部を滴下し、６０℃で３時間反応させることにより、組成物１をイソシアネート樹脂で被覆した平均粒子径２．６μｍのマイクロカプセルが、そのマイクロカプセルを多量に含有する１０００ｇの水性スラリーの状態で得られた。 10 parts of xylylenediamine is added dropwise to the dispersion thus obtained, and the mixture is reacted at 60 ° C. for 3 hours, whereby microcapsules having an average particle diameter of 2.6 μm, in which Composition 1 is coated with an isocyanate resin, It was obtained in the form of a 1000 g aqueous slurry containing a large amount of microcapsules.
　得られたマイクロカプセル及びスラリーは、紫外線照射前は実質上無色で、所定量の紫外線照射により青紫色に発色し、その発色は、紫外線照射終了後も青紫色が消色しない不可逆的なものであった。 The obtained microcapsules and slurry are substantially colorless before ultraviolet irradiation, and develop a blue-purple color by a predetermined amount of ultraviolet irradiation, and the color development is an irreversible one that the blue-purple color does not disappear even after the completion of the ultraviolet irradiation. there were.
　（比較例１） (Comparative example 1)
　化合物Ａとしてのベンゾイルロイコメチレンブルー１０部を三本ロールミル機を用いてバインダー５０Ｓ（水性スクリーン印刷用バインダーの商品名；株式会社松井色素化学工業所製）９０部中に分散した印刷インキを、花柄の１００メッシュスクリーン版を使用して、和紙上にスクリーンプリントした。 Flower pattern of printing ink in which 10 parts of benzoyl leuco methylene blue as compound A are dispersed in 90 parts of binder 50S (trade name of binder for aqueous screen printing; manufactured by Matsui Dye Chemicals Co., Ltd.) using a three roll mill machine Screen-printed on Japanese paper using 100 mesh screen version of.
　得られた和紙は、紫外線照射前は実質上無色で、紫外線を照射してもほとんど発色することはなかった。 The resulting Japanese paper was substantially colorless before ultraviolet irradiation and hardly developed even when irradiated with ultraviolet light.
　（紫外線発色性比較） (UV coloration comparison)
　実施例８で得られた和紙、実施例１１で得られた成形体Ａ、及び、比較例１で得られた和紙について、紫外線発色性を測定した結果を示す。 About the Japanese paper obtained in Example 8, the molded object A obtained in Example 11, and the Japanese paper obtained in Comparative Example 1, the result of having measured ultraviolet coloring property is shown.
　なお、紫外線光源として、ブラックライトは１５Ｗでメインピークが３５２ｎｍのものを用い、メタルハライドランプは１２０ｗでメインピークが２５０乃至４５０ｎｍのものを用いた。また、色差（ΔＥ）はＤａｔａｃｏｌｏｒ社製のＣＨＥＣＫ II ＰＬＵＳにて測定し、紫外線積算光量は株式会社トプコン製のＵＶＲ－３６にて測定した。 As an ultraviolet light source, a black light of 15 W and a main peak of 352 nm was used, and a metal halide lamp of 120 w and a main peak of 250 to 450 nm was used. Further, the color difference (ΔE) was measured by CHECK II PLUS manufactured by Datacolor, and the integrated ultraviolet light quantity was measured by UVR-36 manufactured by Topcon Corporation.
　１．発色濃度の比較（紫外線照射前と照射後の色差） 1. Comparison of color density (color difference before and after UV irradiation)
表１
Figure JPOXMLDOC01-appb-I000004
Table 1
Figure JPOXMLDOC01-appb-I000004
　２．初期安定性比較（紫外線受光前と受光後の色差）
　受光条件：日常の室内環境で放置した状態での紫外線受光 2. Initial stability comparison (color difference before and after receiving UV light)
Light reception condition: UV light reception in a state of being left in the daily indoor environment
表２
Figure JPOXMLDOC01-appb-I000005
Table 2
Figure JPOXMLDOC01-appb-I000005
　３．積算光量と発色濃度（紫外線照射前と照射後の色差）
　照射条件：ブラックライトにて紫外線照射 3. Integrated light quantity and coloring density (color difference between before and after UV irradiation)
Irradiation conditions: UV irradiation with black light
表３
Figure JPOXMLDOC01-appb-I000006
Table 3
Figure JPOXMLDOC01-appb-I000006
　照射条件：メタルハライドランプにて紫外線照射 Irradiation conditions: UV irradiation with metal halide lamp
表４
Figure JPOXMLDOC01-appb-I000007
Table 4
Figure JPOXMLDOC01-appb-I000007

Claims (14)

  1. 　式（Ｉ）で表わされる化合物Ａと、化合物Ａを溶解し得る化合物Ｂを含有してなる組成物であって、
    化合物Ａが化合物Ｂに溶解しており、紫外線が照射されることにより、前記化合物ＡからＸが脱離して不可逆発色する不可逆性紫外線発色組成物。
    Figure JPOXMLDOC01-appb-I000001
    ・・・（Ｉ）
    ［式（Ｉ）中、Ｒ１乃至Ｒ４はそれぞれ独立的に炭素数１乃至４の直鎖又は分岐鎖のアルキル基を示し、Ｑは酸素、窒素又は硫黄を示し、Ｘはベンゾイル基又はトルエンスルホニル基を示す。］     A composition comprising a compound A represented by the formula (I) and a compound B capable of dissolving the compound A,
    Irreversible ultraviolet coloring composition in which compound A is dissolved in compound B and X is detached from the compound A when irradiated with ultraviolet light to cause an irreversible color development.
    Figure JPOXMLDOC01-appb-I000001
    ... (I)
    [In formula (I), R 1 to R 4 each independently represent a linear or branched alkyl group having 1 to 4 carbon atoms, Q represents oxygen, nitrogen or sulfur, and X represents a benzoyl group or toluene] A sulfonyl group is shown. ]
  2. 　化合物Ｂがエステル類、アルコール類、ケトン類、エーテル類、ポリエチレン樹脂、ポリプロピレン樹脂から選ばれる少なくとも１種である請求項１記載の不可逆性紫外線発色組成物。 The irreversible ultraviolet coloring composition according to claim 1, wherein the compound B is at least one selected from esters, alcohols, ketones, ethers, polyethylene resin and polypropylene resin.
  3. 　重量比において化合物Ａに対し化合物Ｂが１乃至２０００である請求項１又は２に記載の不可逆性紫外線発色組成物。 The irreversible ultraviolet coloring composition according to claim 1 or 2, wherein the weight ratio of the compound B to the compound A is 1 to 2,000.
  4. 　ビスフェノール類を含有する請求項１乃至３の何れか１項に記載の不可逆性紫外線発色組成物。 The irreversible ultraviolet coloring composition according to any one of claims 1 to 3, which contains a bisphenol.
  5. 　光増感剤Ｄを含有する請求項１乃至４の何れか１項に記載の不可逆性紫外線発色組成物。 The irreversible ultraviolet coloring composition according to any one of claims 1 to 4, which contains a photosensitizer D.
  6. 　紫外線吸収剤Ｅを含有する請求項１乃至５の何れか１項に記載の不可逆性紫外線発色組成物。 The irreversible ultraviolet coloring composition according to any one of claims 1 to 5, which contains an ultraviolet absorber E.
  7. 　紫外線照射により上記化合物ＡからＸが脱離する前より組成物として着色しており、紫外線が照射されることにより、前記化合物ＡからＸが脱離して不可逆発色する請求項１乃至６の何れか１項に記載の不可逆性紫外線発色組成物。 The composition according to any one of claims 1 to 6, which is colored as a composition before X is desorbed from the compound A by ultraviolet irradiation, and X is desorbed from the compound A by irradiation with ultraviolet light. The irreversible ultraviolet coloring composition according to claim 1.
  8. 　マイクロカプセルに内包されてなる請求項１乃至７の何れか１項に記載の不可逆性紫外線発色組成物。 The irreversible ultraviolet coloring composition according to any one of claims 1 to 7, which is encapsulated in a microcapsule.
  9. 　マイクロカプセルの平均粒子径が０．５乃至１０μｍであり、２０μｍ未満の粒子を９０％以上含む請求項８記載の不可逆性紫外線発色組成物。 9. The irreversible ultraviolet coloring composition according to claim 8, wherein the microcapsules have an average particle size of 0.5 to 10 μm and 90% or more of particles smaller than 20 μm.
  10. 　マイクロカプセルの壁膜がメラミン樹脂又はイソシアネート樹脂からなる請求項８又は９記載の不可逆性紫外線発色組成物。 The irreversible ultraviolet coloring composition according to claim 8 or 9, wherein the wall film of the microcapsule comprises a melamine resin or an isocyanate resin.
  11. 　請求項１乃至１０の何れか１項に記載の不可逆性紫外線発色組成物を含有する着色用材料。 A coloring material comprising the irreversible ultraviolet coloring composition according to any one of claims 1 to 10.
  12. 　請求項１乃至１０の何れか１項に記載の不可逆性紫外線発色組成物を部分又は全体である所要箇所に含有し、前記所要箇所における所望位置に紫外線を照射してその位置における化合物ＡからＸを脱離させて不可逆発色させることにより所望の着色記録を行うための紫外線照射記録用材料。 The irreversible ultraviolet coloring composition according to any one of claims 1 to 10 is contained in a required part which is a part or the whole, and the desired position in the required part is irradiated with ultraviolet light to obtain compounds A to X at that position. A UV irradiation recording material for performing desired color recording by causing desorption and irreversible color development.
  13. 　請求項１乃至１０の何れか１項に記載の不可逆性紫外線発色組成物を部分又は全体である所要箇所に含有する材料に対し、前記所要箇所における所望位置に紫外線を照射してその位置における化合物ＡからＸを脱離させて不可逆発色させることにより所望の着色記録を行う記録方法。 A compound containing the irreversible ultraviolet coloring composition according to any one of claims 1 to 10 by irradiating ultraviolet light to a desired position at the required position with respect to a material containing the irreversible ultraviolet coloring composition according to any one of the parts or the whole A recording method in which desired color recording is performed by causing X to be released from A and causing irreversible color development.
  14. 　請求項１乃至１０の何れか１項に記載の不可逆性紫外線発色組成物において上記化合物ＡからＸが脱離して不可逆発色した発色組成物。 The irreversible ultraviolet coloring composition according to any one of claims 1 to 10, wherein X is desorbed from said compound A to cause irreversible coloring.
PCT/JP2018/037767 2017-10-12 2018-10-10 Irreversible ultraviolet colour developing composition, and technology related thereto WO2019074008A1 (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2017-198926 2017-10-12
JP2017198926A JP2021015131A (en) 2017-10-12 2017-10-12 Irreversible ultraviolet color developing composition and related technique

Publications (1)

Publication Number Publication Date
WO2019074008A1 true WO2019074008A1 (en) 2019-04-18

Family

ID=66101364

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP2018/037767 WO2019074008A1 (en) 2017-10-12 2018-10-10 Irreversible ultraviolet colour developing composition, and technology related thereto

Country Status (2)

Country Link
JP (1) JP2021015131A (en)
WO (1) WO2019074008A1 (en)

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5292610A (en) * 1991-03-21 1994-03-08 Agfa Gevaert Ag Microcapsules and their use
JPH0734447U (en) * 1993-12-07 1995-06-23 株式会社松井色素化学工業所 Photosensitive sheet
JP2007532707A (en) * 2004-04-07 2007-11-15 チバ　スペシャルティ　ケミカルズ　ホールディング　インコーポレーテッド Method for coloring a coating composition

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5292610A (en) * 1991-03-21 1994-03-08 Agfa Gevaert Ag Microcapsules and their use
JPH0734447U (en) * 1993-12-07 1995-06-23 株式会社松井色素化学工業所 Photosensitive sheet
JP2007532707A (en) * 2004-04-07 2007-11-15 チバ　スペシャルティ　ケミカルズ　ホールディング　インコーポレーテッド Method for coloring a coating composition

Also Published As

Publication number Publication date
JP2021015131A (en) 2021-02-12

Similar Documents

Publication Publication Date Title
US6048387A (en) Reversible thermochromic composition
JP4568027B2 (en) Photochromic material
JP3306609B2 (en) Thermochromic color memory composition
JP5833457B2 (en) Temperature-sensitive discoloration composition
JP3396787B2 (en) Thermochromic color memory microcapsule pigment
JPH0733997A (en) Thermochromic color-memorizing microencapsulated pigment
TW200906995A (en) Heat-sensitive coating compositions based on resorcinyl triazine derivatives
JP5595652B2 (en) Thermochromic composition and thermochromic microcapsule
CN105082815A (en) Thermosensitive recording material and preparation method thereof
WO2014129642A1 (en) Uv ray-sensitive sheet, production method therefor, and uv ray sensing method
US5879443A (en) Temperature-sensitive color-memorizing microencapsulated pigment
JP5464905B2 (en) Photochromic material and photochromic laminate using the same
JP3833563B2 (en) Thermosensitive color-changing composition with excellent light fastness
JPH04201483A (en) Diazo thermal recording material
JP2561470B2 (en) Temperature-dependent photochromic composition
JP4568042B2 (en) Photochromic liquid composition
WO2019074008A1 (en) Irreversible ultraviolet colour developing composition, and technology related thereto
JP6420059B2 (en) Water-based ink composition for writing instruments
JP2023067899A (en) Method of using photochromic toys
JPH0740660A (en) Reversible, color-variable, temperature-sensitive recording composition
JPH1036725A (en) Microcapsule pigment having color memory of temperature-sensitive change in color
JPH07186540A (en) Reversible thermal discoloring composition
JP3303199B2 (en) Reversible thermochromic microcapsule pigment
JP2005220201A (en) Lightfast temperature-sensitive discolorable composition
JP2006317541A (en) Photochromic print

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 18866341

Country of ref document: EP

Kind code of ref document: A1

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 18866341

Country of ref document: EP

Kind code of ref document: A1

NENP Non-entry into the national phase

Ref country code: JP