WO2013061753A1 - 色素、それを用いたマイクロカプセル顔料及び筆記具用インク組成物 - Google Patents
色素、それを用いたマイクロカプセル顔料及び筆記具用インク組成物 Download PDFInfo
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- WO2013061753A1 WO2013061753A1 PCT/JP2012/075914 JP2012075914W WO2013061753A1 WO 2013061753 A1 WO2013061753 A1 WO 2013061753A1 JP 2012075914 W JP2012075914 W JP 2012075914W WO 2013061753 A1 WO2013061753 A1 WO 2013061753A1
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- microcapsule pigment
- dye
- ink composition
- color
- bisphenol
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Classifications
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
- C09B11/00—Diaryl- or thriarylmethane dyes
- C09B11/04—Diaryl- or thriarylmethane dyes derived from triarylmethanes, i.e. central C-atom is substituted by amino, cyano, alkyl
- C09B11/10—Amino derivatives of triarylmethanes
- C09B11/24—Phthaleins containing amino groups ; Phthalanes; Fluoranes; Phthalides; Rhodamine dyes; Phthaleins having heterocyclic aryl rings; Lactone or lactame forms of triarylmethane dyes
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
- C09B67/00—Influencing the physical, e.g. the dyeing or printing properties of dyestuffs without chemical reactions, e.g. by treating with solvents grinding or grinding assistants, coating of pigments or dyes; Process features in the making of dyestuff preparations; Dyestuff preparations of a special physical nature, e.g. tablets, films
- C09B67/0001—Post-treatment of organic pigments or dyes
- C09B67/0004—Coated particulate pigments or dyes
- C09B67/0008—Coated particulate pigments or dyes with organic coatings
- C09B67/0013—Coated particulate pigments or dyes with organic coatings with polymeric coatings
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
- C09B67/00—Influencing the physical, e.g. the dyeing or printing properties of dyestuffs without chemical reactions, e.g. by treating with solvents grinding or grinding assistants, coating of pigments or dyes; Process features in the making of dyestuff preparations; Dyestuff preparations of a special physical nature, e.g. tablets, films
- C09B67/0097—Dye preparations of special physical nature; Tablets, films, extrusion, microcapsules, sheets, pads, bags with dyes
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D11/00—Inks
- C09D11/16—Writing inks
- C09D11/17—Writing inks characterised by colouring agents
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K9/00—Tenebrescent materials, i.e. materials for which the range of wavelengths for energy absorption is changed as a result of excitation by some form of energy
- C09K9/02—Organic tenebrescent materials
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
- C09K2211/10—Non-macromolecular compounds
- C09K2211/1018—Heterocyclic compounds
- C09K2211/1025—Heterocyclic compounds characterised by ligands
- C09K2211/1088—Heterocyclic compounds characterised by ligands containing oxygen as the only heteroatom
Definitions
- the present invention relates to a dye, a microcapsule pigment using the same, and an ink composition for a writing instrument. More specifically, the present invention uses a dye composed of a leuco dye excellent in color density and light resistance, and the development and decoloring mechanism of the dye.
- the present invention relates to a thermochromic microcapsule pigment and an ink composition for a writing instrument containing the microcapsule face.
- an ink composition for a writing instrument using a thermochromic colorant utilizing the development and decoloring mechanism of a leuco dye usually uses a pigment obtained by microencapsulating the dye.
- thermochromic microcapsule pigment encapsulating a reaction medium to be generated is known (for example, see Patent Document 1).
- azaphthalides are listed as specific dyes (compounds).
- azaphthalides are not yet sufficient in color density and light resistance, and microcapsule pigments and writing instrument inks using the azaphthalides have problems such as insufficient line density or the fact that the line may fade over time. is there.
- the present invention has been made in view of the above-mentioned problems of the prior art and the current state of the art, and is intended to solve this problem by utilizing a dye composed of a leuco dye excellent in color density and light resistance, and the color development and decoloring mechanism of this dye. It is an object of the present invention to provide a thermochromic microcapsule pigment excellent in color development / decoloring property and an ink composition for a writing instrument containing the microcapsule pigment.
- the present inventor has used the specific leuco dye and the microcapsule pigment using the dye to obtain the target dye and the microcapsule pigment using the dye.
- the inventors have found that an ink composition for writing instruments can be obtained, and have completed the present invention.
- [X and Y in the above formula (I) represent a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or a halogen atom, and these may be the same or different. However, the case where X and Y are both hydrogen atoms is excluded.
- a microcapsule pigment comprising at least the dye (1) or (2), a color developer, and a color change temperature adjusting agent.
- An ink composition for a writing instrument comprising the microcapsule pigment according to (3) above.
- the dye of the present invention is characterized by comprising a leuco dye represented by the following formula (I).
- X and Y in the above formula (I) represent a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or a halogen atom, and these may be the same or different. However, the case where X and Y are both hydrogen atoms is excluded.
- the dye represented by the above formula (I) used in the present invention is a blue leuco dye that is excellent in color density and light resistance and has a clear blue color tone.
- the blue leuco dye azaphthalides exemplified in Patent Document 1 are known.
- the color density and light resistance are further excellent. , It will be a clear blue.
- X and Y are hydrogen atoms, methyl groups, ethyl groups, n-propyl groups, isopropyl groups, n-butyl groups, sec-butyl groups, isobutyl groups, tert-butyl groups, etc.
- an alkyl group having 1 to 4 carbon atoms or a fluorine atom (—F), a chlorine atom (—Cl), a bromine atom (—Br), an iodine atom (—I), etc., which are the same as each other. It may or may not be. However, the case where X and Y are both hydrogen atoms is excluded.
- leuco dye represented by the above formula (I) include, for example, methyl-3 ′, 6′-bisdiphenylaminofluorane, ethyl-3 ′, 6′-bisdiphenylaminofluorane, and chloro-3 ′.
- X and Y are a methyl group (—CH 3 ) or a chlorine atom (—Cl).
- a chlorine atom is more desirable than a methyl group, and it is particularly desirable that both X and Y are chlorine atoms.
- each leuco dye represented by the above formula (I) is carried out by reacting a triarylamine derivative obtained by a commercially available or general-purpose synthesis means with a phthalic anhydride derivative in the presence of an acid catalyst by heating.
- a leuco dye excellent in color density and light resistance represented by the above formula (I) can be easily obtained.
- the microcapsule pigment of the present invention includes a thermochromic composition composed of at least a dye represented by the above formula (I), a color developer, and a color change temperature adjusting agent.
- the developer to be used is a component having the ability to develop a color represented by the formula (I).
- conventionally known developers can be used, and examples thereof include inorganic acids, aromatic carboxylic acids and anhydrides or metal salts thereof, organic sulfonic acids, other organic acids, and phenolic compounds. .
- it is a bisphenol derivative, and what is shown by the compound of following formula (II) is mentioned.
- R1 in the above formula (II) represents a hydrogen atom or an alkyl group having 1 to 2 carbon atoms
- R2 represents a linear or branched alkyl group having 4 to 10 carbon atoms.
- sulfonylurea compounds can also be preferably used.
- Specific examples of the compound of the formula (II) include 4,4 ′-(2-ethylhexylidene) bisphenol, 4,4 ′-(2-ethylpentylidene) bisphenol, 4,4′-octyl.
- the amount used may be arbitrarily selected according to the desired color density, and is not particularly limited, but is usually 1 part by mass of the dye represented by the above formula (I). It is preferable to select within a range of about 0.1 to 100 parts by mass.
- the color change temperature adjusting agent used in the present invention is a substance that controls the color change temperature in the coloration of the dye represented by the formula (I) and the developer.
- Conventionally known color change temperature adjusting agents can be used. Specific examples include alcohols, esters, ketones, ethers, acid amides, azomethines, fatty acids, hydrocarbons and the like.
- it is an ester compound composed of a compound having a hydroxyl group in the chemical structure and a saturated fatty acid having 8 to 22 carbon atoms.
- it is composed of a bisphenol derivative and a saturated fatty acid having 8 to 22 carbon atoms.
- the ester compound include those represented by the following formula (III).
- R3 and R4 in the formula (III) represent a linear or branched alkyl group having 7 to 21 carbon atoms
- R5 and R6 represent a hydrogen atom, an alkyl group having 1 to 2 carbon atoms, or CF 3 . Show. ]
- the compound of the formula (III) include 4,4 ′-(hexafluoroisopropylidene) bisphenol dicaprate, 4,4 ′-(hexafluoroisopropylidene) bisphenol dilaurate, 4,4 ′-( Hexafluoroisopropylidene) bisphenol dimyristate, 4,4 '-(hexafluoroisopropylidene) bisphenol dipalmiate, 4,4'-(hexafluoroisopropylidene) bisphenol diundecanoate, 4,4 '-(hexa) Fluoroisopropylidene) bisphenol ditridecanoate, 4,4 '-(isopropylidene) bisphenol dicaprate, 4,4'-(isopropylidene) bisphenol dilaurate, 4,4 '-(isopropylidene) bisphenol dimyristate, 4 , '-(Isopropylidene) bisphenol
- the amount of the color change temperature adjusting agent used may be appropriately selected depending on the desired hysteresis width and color density at the time of color development, and is not particularly limited. It is preferably used within a range of about 1 to 1000 parts by mass. In addition, if it is in the range which does not impair the various characteristics of the composition of this invention, a conventionally well-known discoloration temperature regulator can also be used in combination.
- the microcapsule pigment used in the present invention is a thermochromic composition comprising at least a dye represented by the above formula (I), a color developer, and a color change temperature adjusting agent, and preferably has an average particle size of 0.3 to 1. It can be manufactured by microencapsulation so as to be 0 ⁇ m.
- the microencapsulation method include interfacial polymerization method, interfacial polycondensation method, in situ polymerization method, liquid curing coating method, phase separation method from aqueous solution, phase separation method from organic solvent, melt dispersion cooling method, gas dispersion method, Examples thereof include a medium suspension coating method and a spray drying method, which can be appropriately selected depending on the application.
- the dye represented by the above formula (I), the developer, and the color change temperature adjusting agent are heated and melted, and then charged into an emulsifier solution, and heated and stirred to disperse into oil droplets.
- a resin raw material is used, for example, amino resin solution, specifically, each solution such as methylol melamine aqueous solution, urea solution, benzoguanamine solution is gradually added, and subsequently reacted to prepare,
- the desired thermochromic microcapsule pigment can be produced by filtering the dispersion.
- the content of these dyes, developer, and color change temperature adjusting agent varies depending on the dye represented by the above formula (I), the color developer, the color change temperature adjusting agent, the microencapsulation method, and the like.
- the developer ratio is 0.1 to 100 and the color change temperature adjusting agent is 1 to 100.
- the capsule membrane agent is 0.1 to 1 in mass ratio with respect to the capsule contents.
- the color development temperature and decoloring temperature of blue are suitably controlled by suitably combining the types, amounts, and the like of the dye represented by the above formula (I), the developer, and the color change temperature adjusting agent. Can be set to
- the wall film is preferably formed of a urethane resin, an epoxy resin, or an amino resin from the viewpoint of further improving the line density, storage stability, and writing property.
- a urethane resin the compound of isocyanate and a polyol is mentioned, for example.
- an epoxy resin the compound of an epoxy resin and an amine is mentioned, for example.
- the amino resin is preferably formed of, for example, a melamine resin, a urea resin, a benzoguanamine resin, and more preferably formed of a melamine resin from the viewpoints of manufacturability, storage stability, and writing properties.
- the thickness of the wall film of the microcapsule pigment is appropriately determined according to the required strength of the wall film and the drawn line density.
- a suitable amino resin raw material melamine resin, urea resin, benzoguanamine resin, etc.
- a dispersant a protective colloid, etc. select.
- the average particle size of the microcapsule pigment used in the present invention is preferably 0.3 to 1 from the viewpoints of colorability, color developability, easy decolorization, stability, and suppression of adverse effects on writability.
- a thickness of 0.0 ⁇ m is desirable.
- the “average particle size” defined in the present invention is a value obtained by measuring the average particle size with a particle size distribution measuring device [particle size measuring instrument N4Plus (manufactured by COULTER)]. If the average particle diameter is less than 0.3 ⁇ m, sufficient line density cannot be obtained. On the other hand, if it exceeds 1.0 ⁇ m, the writability is deteriorated and the dispersion stability of the microcapsule pigment is decreased. Absent.
- the microcapsule pigment having the above average particle size range (0.3 to 1.0 ⁇ m) varies depending on the microencapsulation method.
- the microcapsule pigment is produced at the time of production. It can be prepared by suitably combining stirring conditions.
- the microcapsule pigment of the present invention configured as described above is excellent in color density and light resistance, is excellent in easy decoloring property and stability, and can be suitably used as a thermochromic pigment for writing instruments, which will be described later.
- a thermochromic pigment for writing instruments which will be described later.
- the solvent type is used as a pigment of an ink composition for a writing instrument that is aqueous or oily, the above effects can be exhibited without being affected by the solvent type.
- the ink composition for a writing instrument according to the present invention is characterized by containing the microcapsule pigment having the above-described structure, and is used as an ink composition for a writing instrument such as an aqueous or oil-based ballpoint pen or a marking pen. Can do.
- the content of the microcapsule pigment of the present invention is preferably 5 to 30% by mass (hereinafter simply referred to as “%”), more preferably 10 to 25%, based on the total amount of each aqueous or oily ink composition. Is desirable. When the content of the microcapsule pigment is less than 5%, coloring power and color developability are insufficient. On the other hand, when the content exceeds 30%, blurring tends to occur, which is not preferable.
- Water-based ink composition for writing instruments in the case of aqueous, in addition to the above microcapsule pigment, the balance is water (tap water, purified water, distilled water, ion-exchanged water, pure water, etc.), and other writing instruments.
- water-soluble organic solvents, thickeners, lubricants, rust preventives, antiseptics or antibacterial agents are appropriately used within the range not impairing the effects of the present invention. Can be contained.
- water-soluble organic solvents examples include glycols such as ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, polyethylene glycol, 3-butylene glycol, thiodiethylene glycol, and glycerin, ethylene glycol monomethyl ether, and diethylene glycol monomethyl. Ethers can be used alone or in combination.
- the thickener that can be used, for example, at least one selected from the group consisting of synthetic polymers, celluloses and polysaccharides is desirable. Specifically, gum arabic, gum tragacanth, guar gum, locust bean gum, alginic acid, carrageenan, gelatin, xanthan gum, welan gum, succinoglycan, diutane gum, dextran, methylcellulose, ethylcellulose, hydroxyethylcellulose, carboxymethylcellulose, starch glycolic acid and Its salt, propylene glycol alginate, polyvinyl alcohol, polyvinyl pyrrolidone, polyvinyl methyl ether, polyacrylic acid and its salt, carboxyvinyl polymer, polyethylene oxide, copolymer of vinyl acetate and polyvinyl pyrrolidone, cross-linked acrylic acid polymer and its Salt, non-crosslinked acrylic acid polymer and its salt, styrene acrylic acid copolymer and its salt, etc
- Lubricants include nonionics such as fatty acid esters of polyhydric alcohols, higher fatty acid esters of sugars, polyoxyalkylene higher fatty acid esters, and alkyl phosphates, which are also used in pigment surface treatment agents, and alkyl sulfonic acids of higher fatty acid amides. Examples thereof include salts, anionic compounds such as alkyl allyl sulfonates, polyalkylene glycol derivatives, fluorosurfactants, and polyether-modified silicones.
- benzotriazole As rust preventives, benzotriazole, tolyltriazole, dicyclohexylammonium nitrite, saponins, etc., as preservatives or fungicides, phenol, sodium omadin, sodium benzoate, benzimidazole compounds, etc. Can be mentioned.
- this water-based ink composition for writing instruments, a conventionally known method can be employed. For example, in addition to the microcapsule pigment, a predetermined amount of each component in the aqueous composition is blended, and a homomixer, or It is obtained by stirring and mixing with a stirrer such as a disper. Further, if necessary, coarse particles in the ink composition may be removed by filtration or centrifugation.
- the oil composition contains the microcapsule pigment having the above-described configuration, and contains at least one selected from polypropylene glycol, polybutylene glycol, and polyoxypropylene diglyceryl ether as a main solvent. It is preferable. By selecting and using these solvents as the main solvent, the microcapsule pigment acts so as not to cause aggregation over time.
- Polypropylene glycol and polybutylene glycol can be used in various degrees of polymerization. From the viewpoint of further exerting the effects of the present invention, it is preferable to use a degree of polymerization (weight average) in the range of 400 to 700 for polypropylene glycol. Butylene glycol preferably has a degree of polymerization (weight average) in the range of 500 to 700.
- the polyoxypropylene diglyceryl ether [POP (n) diglyceryl ether] used in the present invention is obtained by addition polymerization of oxypropylene to the hydroxyl group of diglycerin.
- the number of moles (n) of oxypropylene in polyoxypropylene diglyceryl ether is preferably 4 to 25, more preferably, from the viewpoint of further exerting the effects of the present invention. 4-14.
- the content of these main solvents is preferably 50 to 100%, more preferably 80 to 100%, based on the total amount of the solvent in the ink composition.
- the content of the main solvent is 50% or more, the occurrence of aggregation over time can be suppressed as much as possible.
- the solvent which has a property compatible with the main solvent other than the said main solvent for example, solvents, such as glycerol, diglycerol, propylene glycol, can be contained suitably.
- oil-based ink composition for writing instruments in addition to the microcapsule pigment and the main solvent, the oil-based ink is adversely affected depending on the use for each writing instrument (for ballpoint pens, marking pens, etc.) and if necessary.
- a resin, a dispersant, a rust inhibitor, an antiseptic, a lubricant, and the like that can be compatible with each other can be contained.
- resins examples include ketone resins, styrene resins, styrene-acrylic resins, terpene phenol resins, rosin-modified maleic resins, rosin phenol resins, alkylphenol resins, phenol resins, styrene maleic resins, and rosin resins.
- resins typified by acrylic resins, urea aldehyde resins, maleic acid resins, cyclohexanone resins, polyvinyl butyral, polyvinyl pyrrolidone and the like.
- dispersant those that can disperse the microcapsule pigment from the resins listed above can be selected and used as long as the surfactants and oligomers meet the purpose. can do.
- Specific examples of the dispersant include synthetic resins such as polyvinyl alcohol, polyvinyl pyrrolidone, polyvinyl butyral, polyvinyl ether, styrene-maleic acid copolymer, ketone resin, hydroxyethyl cellulose and derivatives thereof, and styrene-acrylic acid copolymer. And PO / EO adducts and polyester amine oligomers.
- a rust preventive agent antiseptic
- preservative, and lubricant which were used by the above-mentioned aqueous solution can be used.
- the oil-based ink composition for a writing instrument for a writing instrument, a conventionally known method can be employed. For example, in addition to the microcapsule pigment, a predetermined amount of each component in the oiliness is blended, and a homomixer, or It is obtained by stirring and mixing with a stirrer such as a disper. Further, if necessary, coarse particles in the ink composition may be removed by filtration or centrifugation.
- the ink composition for a writing instrument of the present invention configured as described above contains a microcapsule pigment containing at least a coloring matter, a color developer, and a color change temperature adjusting agent having excellent color density and light resistance represented by the above formula (I). Even when water-based or oil-based inks are formulated and written on paper or the like with a writing instrument such as a ballpoint pen or marking pen mounted with this ink, aggregation and discoloration of the microcapsule pigment over time does not occur, An ink composition for a writing instrument that can favorably discolor the handwriting is obtained.
- part as a blending unit means part by mass.
- Production Example 2 Production of dye represented by the above formula (I)
- Production Example 1 a mixture of 100 g (0.591 mol) of diphenylamine, 130.1 g (1.182 mol) of resorcin, and 6.9 g of 85% phosphoric acid was heated and stirred at 200 ° C. for 6 hours in a nitrogen atmosphere. After allowing to cool, the mixture was washed with hot water, and the residue was subjected to column chromatography to obtain 64.0 g of m-hydroxytriphenylamine.
- Production Example 3 Production of dye represented by the above formula (I)
- a mixture of 100 g (0.591 mol) of diphenylamine, 130.1 g (1.182 mol) of resorcin, and 6.9 g of 85% phosphoric acid was heated and stirred at 200 ° C. for 6 hours in a nitrogen atmosphere. After allowing to cool, the mixture was washed with hot water, and the residue was subjected to column chromatography to obtain 64.0 g of m-hydroxytriphenylamine.
- methyl vinyl ether / maleic anhydride copolymer resin (Gantretz AN-179: manufactured by ISP Co., Ltd.) was adjusted to pH 4 with NaOH. While gradually adding to 100 parts of the dissolved 90 ° C. aqueous solution, the mixture is heated and stirred to be dispersed in the form of oil droplets having a diameter of about 0.5 to 1.0 ⁇ m. Then, as a capsule film agent, melamine resin (SMITEX resin) M-3 (manufactured by Sumitomo Chemical Co., Ltd.) was gradually added and heated at 90 ° C. for 30 minutes to form microcapsules. The microcapsules of the reversible temperature-sensitive color-changing composition comprising a melamine resin as a film agent A dispersion was obtained. The hue was dark blue in the colored state and completely colorless without any residual color in the decolored state.
- SMITEX resin melamine resin
- thermosensitive color-changing composition (Microcapsule pigment: A-4) In the above formula A-1, except that 4,4′-isopropylidenebisphenol dimyristate is used instead of 4,4 ′-(hexafluoroisopropylidene) bisphenol dimyristate as the color change temperature adjusting agent, Other than that, a microcapsule dispersion of a reversible thermosensitive color-changing composition was obtained in the same manner as the formulation of A-1. The hue was dark blue in the colored state and completely colorless with no residual color in the decolored state.
- thermosensitive color-changing composition (Microcapsule pigment: A-7)
- a microcapsule dispersion of the reversible thermosensitive color-changing composition was obtained in the same manner as in the formulation of A-1 except that methylindol-3-yl) -4-azaphthalide was used. The hue was blue in the colored state and colorless in the decolored state.
- Example 1 to 10 and Comparative Examples 1 and 2 Ink formula
- Formulations shown in Table 2 below microcapsule pigments: A-1 to A-7, Examples 1 to 5 and Comparative Example 1 are water-based ink components, Examples 6 to 10 and Comparative Example 2 are oil-based inks. According to the component), each water-based and each oil-based water-based ink composition for ballpoint pens was prepared by a conventional method.
- Each microcapsule pigment A-1 to A-7 was taken out and used as a microcapsule pigment by filtering and drying each microcapsule dispersion.
- Water-based ballpoint pens and oil-based ballpoint pens were prepared using the ink compositions obtained above. Specifically, using an axis of a ballpoint pen [Mitsubishi Pencil Co., Ltd., trade name: Signo UM-100], an inner diameter of 3.8 mm, a length of 113 mm, a polypropylene ink containing tube, and a stainless tip (a cemented carbide ball, A refill having a ball diameter of 0.5 mm) and a joint connecting the receiving tube and the tip is filled with each of the above water-based and oil-based inks, and an ink follower mainly composed of mineral oil is loaded at the rear end of the ink. An oil-based ballpoint pen was produced. Using the obtained ballpoint pens of Examples 1 to 10 and Comparative Examples 1 and 2, the light resistance and the line density were evaluated by the following evaluation methods. These results are shown in Table 2 below.
- Light resistance evaluation method The pigment concentration was adjusted to 15% by mass while adding the melamine / formaldehyde condensate to the microcapsule pigment dispersion.
- the obtained dispersion was developed on peach-kent paper using an eccentric applicator (10MIL / UESHIMA SEISAKUSHO).
- Light resistance was evaluated according to the following criteria. This was irradiated with a xenon fade meter X25F (FLR40SW / M / 36, manufactured by Suga Test Instruments Co., Ltd.) for 30 and 50 hours, and a color computer (Suga Test Instruments Co., Ltd. SC-P) for L values (lightness) before and after irradiation.
- the ink compositions for writing instruments of Examples 1 to 10 according to the present invention are the ink compositions for writing instruments of Comparative Examples 1 and 2 that are outside the scope of the present invention.
- the film had excellent light resistance and satisfactory line density.
- 3- (4-diethylamino-2-ethoxyphenyl) -3- (1-ethyl-2-methylindol-3-yl) -4-azaphthalide was used as the leuco dye of Comparative Examples 1 and 2.
- a pigment suitable for a writing instrument such as a water-based or oil-based ballpoint pen or a marking pen, a microcapsule pigment using the same, and an ink composition for a writing instrument are obtained.
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Abstract
Description
(1) 下記式(I)で示されるロイコ色素からなることを特徴とする色素。
(2) 上記式(I)中のX,Yの少なくとも一方がメチル基又は塩素原子であることを特徴とする上記(1)記載の色素。
(3) 上記(1)又は(2)の色素、顕色剤及び変色温度調整剤を少なくとも含むことを特徴とするマイクロカプセル顔料。
(4) 上記(3)に記載のマイクロカプセル顔料を含有することを特徴とする筆記具用インク組成物。
〔色素〕
本発明の色素は、下記式(I)で示されるロイコ色素からなることを特徴とするものである。
青色のロイコ色素としては、特許文献1で例示したアザフタリド類などが知られているが、本発明では、上記式(I)で示される色素を用いることで、更に、発色濃度及び耐光性に優れ、鮮明な青色となるものである。
上記式(I)中において、X、Yは、水素原子、または、メチル基、エチル基、n-プロピル基、イソプロピル基、n-ブチル基、sec-ブチル基、イソブチル基、tert-ブチル基などからなる炭素数1~4のアルキル基、若しくは、フッ素原子(-F)、塩素原子(-Cl)、臭素原子(-Br)、ヨウ素原子(-I)などが挙げられ、これらは互いに同一であっても異なっていてもよい。ただし、X,Yがともに水素原子である場合を除くものである。
次に、本発明のマイクロカプセル顔料は、上記式(I)で示される色素、顕色剤、変色温度調整剤から少なくとも構成される熱変色性組成物を内包させたものである。
用いる顕色剤は、上記式(I)で示される色素を発色させる能力を有する成分となるものである。用いられる顕色剤は、従来公知のものが使用可能であり、例えば、無機酸、芳香族カルボン酸及びその無水物又は金属塩類、有機スルホン酸、その他の有機酸及びフェノール性化合物等が挙げられる。
好ましくは、ビスフェノール誘導体であり、下記式(II)の化合物で示されるものが挙げられる。
上記以外にも、スルホニルウレア化合物も好ましく用いることができる。
本発明に用いる変色温度調整剤は、前記式(I)で示される色素と顕色剤の呈色において変色温度をコントロールする物質である。
用いることができる変色温度調整剤は、従来公知のものが使用可能である。具体的には、アルコール類、エステル類、ケトン類、エーテル類、酸アミド類、アゾメチン類、脂肪酸類、炭化水素類などが挙げられる。
好ましくは、化学構造中に水酸基を有する化合物と、炭素数8~22の飽和脂肪酸とから構成されるエステル化合物であり、例えば、ビスフェノール誘導体と、炭素数8~22の飽和脂肪酸とから構成されるエステル化合物であり、下記式(III)で示されるものが挙げられる。
なお、本発明の組成物の諸特性を損なわない範囲内であれば、従来公知の変色温度調整剤を組み合わせて用いることもできる。
本発明に用いるマイクロカプセル顔料は、少なくとも上記式(I)で示される色素、顕色剤、変色温度調整剤からなる熱変色性組成物を、好ましくは、平均粒子径が0.3~1.0μmとなるように、マイクロカプセル化することにより製造することができる。
マイクロカプセル化法としては、例えば、界面重合法、界面重縮合法、in situ重合法、液中硬化被覆法、水溶液からの相分離法、有機溶媒からの相分離法、融解分散冷却法、気中懸濁被覆法、スプレードライニング法などを挙げることができ、用途に応じて適宜選択することができる。
本発明のマイクロカプセル顔料では、上記式(I)で示される色素、顕色剤及び変色温度調整剤の種類、量などを好適に組み合わせることにより、青色の発色温度、消色温度を好適な温度に設定することができる。
マイクロカプセル顔料の壁膜の厚さは、必要とする壁膜の強度や描線濃度に応じて適宜決められる。
なお、壁膜がアミノ樹脂で形成するためには、各マイクロカプセル化法を用いる際に、好適なアミノ樹脂原料(メラミン樹脂、尿素樹脂、ベンゾグアナミン樹脂等)、並びに、分散剤、保護コロイドなどを選択する。
この平均粒子径が0.3μm未満であると、十分な描線濃度が得られず、一方、1.0μmを越えると、筆記性の劣化やマイクロカプセル顔料の分散安定性の低下が発生し、好ましくない。
なお、上記平均粒子径の範囲(0.3~1.0μm)となるマイクロカプセル顔料は、マイクロカプセル化法により変動するが、水溶液からの相分離法などでは、マイクロカプセル顔料を製造する際の攪拌条件を好適に組み合わせることにより調製することができる。
本発明の筆記具用インク組成物は、上記構成のマイクロカプセル顔料を含有することを特徴とするものであり、水性、または、油性のボールペン用、マーキングペン用等の筆記具用インク組成物として用いることをできる。
本発明のマイクロカプセル顔料の含有量は、各水性又は油性のインク組成物全量に対して、好ましくは、5~30質量%(以下、単に「%」という)、更に好ましくは、10~25%とすることが望ましい。
このマイクロカプセル顔料の含有量が5%未満であると、着色力、発色性が不十分となり、一方、30%を超えると、カスレが生じやすくなり、好ましくない。
本発明の筆記具用インク組成物において、水性では、上記マイクロカプセル顔料の他、残部として溶媒である水(水道水、精製水、蒸留水、イオン交換水、純水等)の他、各筆記具用(ボールペン用、マーキングペン用等)の用途に応じて、本発明の効果を損なわない範囲で、水溶性有機溶剤、増粘剤、潤滑剤、防錆剤、防腐剤もしくは防菌剤などを適宜含有することができる。
本発明の筆記具用インク組成物において、油性では、上記構成のマイクロカプセル顔料を含有すると共に、主溶剤として、ポリプロピレングリコール、ポリブチレングリコール、ポリオキシプロピレンジグリセリルエーテルから選ばれる少なくとも一つとを含有することが好ましい。これらの溶剤を主溶剤として選択、使用することで、上記マイクロカプセル顔料の経時的な凝集を発生しないように作用するものである。
また、本発明で用いるポリオキシプロピレンジグリセリルエーテル〔POP(n)ジグリセリルエーテル〕はジグリセリンの水酸基にオキシプロピレンが付加重合したものである。本発明においてポリオキシプロピレンジグリセリルエーテル〔POP(n)ジグリセリルエーテル〕におけるオキシプロピレンの付加モル数(n)は、本発明の効果を更に発揮せしめる点から、4~25が好ましく、更に好ましくは4~14である。
用いることができる樹脂としては、例えば、ケトン樹脂、スチレン樹脂、スチレン-アクリル樹脂、テルペンフェノール樹脂、ロジン変性マレイン酸樹脂、ロジンフェノール樹脂、アルキルフェノール樹脂、フェノール系樹脂、スチレンマレイン酸樹脂、ロジン系樹脂、アクリル系樹脂、尿素アルデヒド系樹脂、マレイン酸系樹脂、シクロヘキサノン系樹脂、ポリビニルブチラール、ポリビニルピロリドン等に代表される樹脂が挙げられる。
具体的な分散剤としては、例えば、ポリビニルアルコール、ポリビニルピロリドン、ポリビニルブチラール、ポリビニルエーテル、スチレン-マレイン酸共重合体、ケトン樹脂、ヒドロキシエチルセルロースやその誘導体、スチレン-アクリル酸共重合体等の合成樹脂やPO・EO付加物やポリエステルのアミン系オリゴマー等が挙げることができる。
また、防錆剤、防腐剤、潤滑剤としては、上述の水性で用いた各種の防錆剤、防腐剤、潤滑剤を用いることができる。
ジフェニルアミン100g(0.591モル)、レゾルシン130.1g(1.182モル)及び85%リン酸6.9gの混合物を窒素雰囲気下で200度に6時間、加熱攪拌した。放冷後、熱水で洗浄した後、残渣をカラムクロマトグラフィーにかけ、m-ヒドロキシトリフェニルアミン64.0gを得た。
次いで、m-ヒドロキシトリフェニルアミン42.3g(0.162モル)、4-メチル無水フタル酸23g(0.142モル)、無水塩化亜鉛15.8g(0.116モル)及びクロロベンゼン110gの混合物を100℃で5時間、加熱攪拌した。放冷後、水酸化ナトリウムを加え、トルエンで抽出した。抽出液からトルエンを減圧留去し、残渣をアセトン/メタノールから再結晶して、メチル-3’,6’-ビスジフェニルアミノフルオラン21gを得た。
上記製造例1において、ジフェニルアミン100g(0.591モル)、レゾルシン130.1g(1.182モル)及び85%リン酸6.9gの混合物を窒素雰囲気下で200度に6時間、加熱攪拌した。放冷後、熱水で洗浄した後、残渣をカラムクロマトグラフィーにかけ、m-ヒドロキシトリフェニルアミン64.0gを得た。
次いで、m-ヒドロキシトリフェニルアミン42.3g(0.162モル)、4-クロロ無水フタル酸26g(0.142モル)、無水塩化亜鉛15.8g(0.116モル)及びクロロベンゼン110gの混合物を100℃で5時間、加熱攪拌した。放冷後、水酸化ナトリウムを加え、トルエンで抽出した。抽出液からトルエンを減圧留去し、残渣をアセトン/メタノールから再結晶して、クロロ-3’,6’-ビスジフェニルアミノフルオラン21gを得た。
上記製造例1において、ジフェニルアミン100g(0.591モル)、レゾルシン130.1g(1.182モル)及び85%リン酸6.9gの混合物を窒素雰囲気下で200度に6時間、加熱攪拌した。放冷後、熱水で洗浄した後、残渣をカラムクロマトグラフィーにかけ、m-ヒドロキシトリフェニルアミン64.0gを得た。
次いで、m-ヒドロキシトリフェニルアミン42.3g(0.162モル)、3,4-ジクロロ無水フタル酸31g(0.142モル)、無水塩化亜鉛15.8g(0.116モル)及びクロロベンゼン110gの混合物を100℃で5時間、加熱攪拌した。放冷後、水酸化ナトリウムを加え、トルエンで抽出した。抽出液からトルエンを減圧留去し、残渣をアセトン/メタノールから再結晶して、3,4-ジクロロ-3’,6’-ビスジフェニルアミノフルオラン22gを得た。
(マイクロカプセル顔料:A-1~A-3)
ロイコ色素として、製造例1~3で得た各色素(下記表1)にそれぞれ示される色素1部、顕色剤として、4,4′-(2-エチルヘキシリデン)ビスフェノール2部、及び変色性温度調整剤として、4,4′-(ヘキサフルオロイソプロピリデン)ビスフェノールジミリステート24部を100℃に加熱溶融して、均質な組成物27部を得た。
上記で得た組成物27部の均一な熱溶液を、保護コロイド剤として、メチルビニルエーテル・無水マレイン酸共重合樹脂〔ガンツレッツAN-179:ISP(株)社製〕40部をNaOHにてpH4に溶解させた90℃の水溶液100部中に徐々に添加しながら、加熱攪拌して直径約0.5~1.0μmの油滴状に分散させ、次いでカプセル膜剤として、メラミン樹脂(スミテックスレジンM-3、(株)住友化学製)20部を徐々に添加し、90℃で30分間加熱してマイクロカプセル化を行い、膜剤がメラミン樹脂からなる可逆感温変色性組成物のマイクロカプセル分散液を得た。色相は、発色状態においては濃厚な青色を呈し、消色状態においては残色がなく完全に無色となるものであった。
上記A-1の処方において、変色温度調整剤として、4,4′-(ヘキサフルオロイソプロピリデン)ビスフェノールジミリステートに代えて、4,4′-イソプロピリデンビスフェノールジミリステートを用いることを除き、他は上記A-1の処方と同様にして、可逆感温変色性組成物のマイクロカプセル分散液を得た。色相は、発色状態においては濃厚な青色を呈し、消色状態においては残色がなく完全に無色となるものであった。
上記A-2の処方において、顕色剤として、4,4′-(2-エチルヘキシリデン)ビスフェノールに代えて、4,4′-(1,3-ジメチルブチリデン)ビスフェノールを用い、変色温度調整剤として、4,4′-(イソプロピリデン)ビスフェノールジミリステートに代えて、4,4′-エチリデンビスフェノールジラウレートを用いることを除き、他は上記A-2の処方と同様にして、可逆感温変色性組成物のマイクロカプセル分散液を得た。色相は、発色状態においては濃厚な青色を呈し、消色状態においては残色がなく完全に無色となるものであった。
上記A-3の処方において、変色温度調整剤として、4,4′-(ヘキサフルオロイソプロピリデン)ビスフェノールジミリステートに代えて、4,4′-エチリデンビスフェノールジラウレートを用いることを除き、他は上記A-3の処方と同様にして、可逆感温変色性組成物のマイクロカプセル分散液を得た。色相は、発色状態においては濃厚な青色を呈し、消色状態においては残色がなく完全に無色となるものであった。
上記A-1の処方において、ロイコ色素としてメチル-3’,6’-ビスジフェニルアミノフルオランに代えて、3-(4-ジエチルアミノ-2-エトキシフェニル)-3-(1-エチル-2-メチルインドール-3-イル)-4-アザフタリドを用いることを除き、他は上記A-1の処方と同様にして、可逆感温変色性組成物のマイクロカプセル分散液を得た。色相は、発色状態においては青色を呈し、消色状態においては無色となるものであった。
(インクの処方)
下記表2に示す配合処方(マイクロカプセル顔料:A-1~A-7、実施例1~5及び比較例1では水性インクの各成分、実施例6~10及び比較例2では油性インクの各成分)にしたがって、常法により各水性、各油性のボールペン用水性インク組成物を調製した。なお、各マイクロカプセル顔料A-1~A-7は、各マイクロカプセル分散液を濾過し、乾燥することによりマイクロカプセル顔料として取り出し使用した。
上記で得られた各インク組成物を用いて水性ボールペン、油性ボールペンを作製した。具体的には、ボールペン〔三菱鉛筆株式会社製、商品名:シグノUM-100〕の軸を使用し、内径3.8mm、長さ113mmポリプロピレン製インク収容管とステンレス製チップ(超硬合金ボール、ボール径0.5mm)及び該収容管と該チップを連結する継手からなるリフィールに上記各水性、油性インクを充填し、インク後端に鉱油を主成分とするインク追従体を装填し、水性ボールペン、油性ボールペンを作製した。
得られた実施例1~10及び比較例1~2の各ボールペンを用いて、下記評価方法で耐光性、描線濃度の評価を行った。
これらの結果を下記表2に示す。
上記マイクロカプセル顔料の分散液にメラミン・ホルムアルデヒド縮合物を添加しながら顔料濃度15質量%に調整した。得られた分散液について、偏心アプリケーター(10MIL/UESHIMA SEISAKUSHO社製)を用いてピーチケント紙に展色した。下記の基準で耐光性を評価した。これについて、キセノンフェードメーターX25F(FLR40SW/M/36、スガ試験機株式会社製)にて30および50時間照射し、照射前後のL値(明度)についてカラーコンピューター(スガ試験機株式会社SC-P)にて測定し、照射後のL値/照射前のL値にて評価を行った。なお、測定条件は、正反射光:除く、光源視野:D65/10、にて行った。
評価基準:
○:1.0~1.1
△:1.1超~1.2未満
×:1.2超
各ペン体をISO規格に準拠した筆記用紙に、フリーハンドで螺旋筆記後、目視により描線濃度を下記の基準で評価した。
評価基準:
○:発色状態は濃い青色。
△:発色状態で若干濃度が薄い。
×:発色状態で濃度が薄い。
これに対して、比較例1及び2のロイコ色素として3-(4-ジエチルアミノ-2-エトキシフェニル)-3-(1-エチル-2-メチルインドール-3-イル)-4-アザフタリドを用いたマイクロカプセル顔料を含有する各インク組成物では、満足のいく十分な耐光性、描線濃度が得られないものであった。
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WO2021085457A1 (ja) * | 2019-10-30 | 2021-05-06 | 株式会社パイロットコーポレーション | 油性ボールペン用インキ組成物およびそれを用いた油性ボールペン |
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US8883049B2 (en) * | 2013-03-15 | 2014-11-11 | Chromatic Technologies, Inc. | Small scale microencapsulated pigments and uses thereof |
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EP2772517A1 (en) | 2014-09-03 |
ES2699802T3 (es) | 2019-02-12 |
JP5595449B2 (ja) | 2014-09-24 |
EP2772517B1 (en) | 2018-09-12 |
TWI572679B (zh) | 2017-03-01 |
KR102009538B1 (ko) | 2019-08-09 |
CN103890101A (zh) | 2014-06-25 |
US20140299015A1 (en) | 2014-10-09 |
CA2853499A1 (en) | 2013-05-02 |
US9315672B2 (en) | 2016-04-19 |
TW201321451A (zh) | 2013-06-01 |
JP2013108054A (ja) | 2013-06-06 |
CA2853499C (en) | 2020-02-04 |
CN103890101B (zh) | 2016-06-22 |
KR20140091539A (ko) | 2014-07-21 |
EP2772517A4 (en) | 2015-07-22 |
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