WO2019189364A1 - Applicator - Google Patents

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Publication number
WO2019189364A1
WO2019189364A1 PCT/JP2019/013200 JP2019013200W WO2019189364A1 WO 2019189364 A1 WO2019189364 A1 WO 2019189364A1 JP 2019013200 W JP2019013200 W JP 2019013200W WO 2019189364 A1 WO2019189364 A1 WO 2019189364A1
Authority
WO
WIPO (PCT)
Prior art keywords
average particle
particle size
resin particles
wax
yellow
Prior art date
Application number
PCT/JP2019/013200
Other languages
French (fr)
Japanese (ja)
Inventor
清水　英明
小林　巧
大貫　幸子
惠子 伊澤
Original Assignee
ぺんてる株式会社
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 ぺんてる株式会社 filed Critical ぺんてる株式会社
Priority to CN201980005762.1A priority Critical patent/CN111356595A/en
Priority to JP2020509196A priority patent/JP7205534B2/en
Publication of WO2019189364A1 publication Critical patent/WO2019189364A1/en

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Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B43—WRITING OR DRAWING IMPLEMENTS; BUREAU ACCESSORIES
    • B43K—IMPLEMENTS FOR WRITING OR DRAWING
    • B43K1/00—Nibs; Writing-points
    • B43K1/12—Writing-points comprising fibres; Felt pads
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B43—WRITING OR DRAWING IMPLEMENTS; BUREAU ACCESSORIES
    • B43K—IMPLEMENTS FOR WRITING OR DRAWING
    • B43K8/00—Pens with writing-points other than nibs or balls
    • B43K8/02—Pens with writing-points other than nibs or balls with writing-points comprising fibres, felt, or similar porous or capillary material
    • 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
    • C09D11/02—Printing inks
    • C09D11/03—Printing inks characterised by features other than the chemical nature of the binder

Definitions

  • the present invention relates to an applicator provided with water-based ink.
  • an ink composition using colored resin particles and wax particles is mainly used for an ink jet including a pigment coated with a water-insoluble polymer and at least two kinds of waxes having different average particle diameters.
  • An ink composition is disclosed.
  • the applicator includes an aqueous solution containing at least colored resin particles and wax particles having an average particle size of 5% to 95% with respect to the average particle size of the colored resin particles.
  • a fiber bundling body is provided as the ink and application destination.
  • the colored resin particles may have an average particle size of 0.01 ⁇ m or more and 1 ⁇ m or less, and the wax particles may have an average particle size of 0.005 ⁇ m or more.
  • the addition amount of the colored resin particles in the water-based ink is x wt% and the addition amount of the wax particles is y wt%
  • (Formula 1) ⁇ 0.12x + 23.0 ⁇ y> ⁇ 0.12x + 6.8 may be satisfied
  • x may be 0.5 wt% or more and 56.0 wt% or less
  • y may be 0.1 wt% or more.
  • the fiber bundle at the application destination may be composed of at least fibers having a thickness of 0.5 to 50 denier and a porosity of 20 to 80%.
  • the applicator forms a complicated curved path because the average particle diameter of the wax particles with high lubricity is 5% or more and 95% or less with respect to the average particle diameter of the colored resin particles.
  • Preferentially discharged from the tip of the fiber bundling body as the application destination in the porous state prior to the colored resin particles having a larger diameter than this, it penetrates between the paper fibers to narrow the gap between the fibers, and coloring It is presumed that excessive penetration of the resin particles into the paper is suppressed, and the back-through can be suppressed.
  • the average particle diameter of the colored resin particles is 0.01 ⁇ m or more and 1 ⁇ m or less, obstacles to the movement of the particles such as collision with paper fibers and detouring are greatly reduced, and the colored resin particles are immediately formed immediately after application.
  • the quick-drying effect of the coating mark that hardly penetrates between the paper fibers and remains on the paper surface, and the average particle diameter of the wax particles that move between the paper fibers prior to the colored resin particles is In addition to being 5% or more and 95% or less with respect to the average particle size, the average particle size of the wax particles is 0.005 ⁇ m or more, whereby the colored resin particles reach the back surface of the paper. It is possible to reliably achieve both the suppressed strikethrough suppression effect.
  • the component containing wax particles having a relatively small average particle diameter in the water-based ink tends to penetrate the paper prior to the component containing the colored resin particles in the water-based ink.
  • the wax particles and the colored resin particles are both less hydrophilic than the fibers constituting the paper (for example, cellulose fibers), and the movement of the wax particles and the colored resin particles when the aqueous ink penetrates into the paper.
  • the speed is slower than water. For this reason, as it proceeds to the inside of the paper, water as a liquid medium decreases, wax particles or colored resin particles approximate close-packed packing, attracting force between aggregates, and apparently bulky. It becomes difficult to move in the paper fiber.
  • an aggregated structure is formed as the colored resin particles progress to the inside, and the aggregated structure of the wax particles already formed overlaps with the aggregated structure of the colored resin particles, so that the colored resin particles are removed from the back side of the paper. Can be suppressed.
  • the addition amount of the colored resin particles is x wt% and the addition amount of the wax particles is y wt%
  • the relationship between the addition amounts of the respective particles is (Formula 1) ⁇ 0.12x + 23.0 ⁇ y> ⁇
  • x is 0.5 wt% or more and 56.0 wt% or less
  • y is 0.1 wt% or more, prior to the penetration of the aqueous ink component containing the colored resin particles It becomes possible to appropriately form the aggregate structure of the wax particles, effectively overlapping the aggregate structure of the wax particles and the aggregate structure of the colored resin particles, and further suppressing the colored resin particles from coming out from the back side of the paper. be able to.
  • the coated fiber bundle is at least composed of fibers having a thickness of 0.5 denier or more and 50 denier or less, and the porosity is 20% or more and 80% or less. It is presumed that the balance with which the highly-lubricated wax particles having an average particle diameter of 5% to 95% with respect to the average particle diameter of the resin particles are discharged is suitable, and the back-through is further suppressed. It becomes.
  • An applicator includes a water-based ink containing at least colored resin particles and wax particles having an average particle size of 5% to 95% with respect to the average particle size of the colored resin particles;
  • a fiber bundle As a fiber bundle.
  • the fiber bundle used as an application destination refers to a bundle of fibers gathered in a bundle, and refers to a synthetic fiber core or a felt core.
  • the synthetic fiber core is made of acrylic, polyester, nylon, melamine, polyurethane, polyacetal alone or in combination of two or more, thermoformed, impregnated with resin, dried and cured, and then cut to an appropriate length. You can select the one that has been heated and then polished and shaped into the shape of the nib, etc.
  • the felt core is mainly made of animal fibers such as wool (wool) or monofilaments such as contracted synthetic fibers.
  • a felt fabric is impregnated with resin, dried and cured, press-molded, cut into strips, punched into the shape of a nib, and fibers such as acrylic and polyester.
  • a material obtained by press-molding a dough, cutting it into a strip, and punching it into the shape of a nib can be appropriately selected. In consideration of durability such as wear of the coating destination, it is preferable to use a synthetic fiber core.
  • the fiber thickness of the fiber bundle at the application destination is appropriately adjusted so that a difference in movement between the colored resin particles and the wax particles is likely to occur, and is preferably from 0.5 to 50 denier, preferably from 1 to 30 denier. More preferably, the porosity of the fiber bundle at the application destination is 1 denier or more and 5 denier or less, so that the difference in movement between the colored resin particles and the wax particles is likely to occur as with the fiber thickness of the fiber bundle. 20% or more and 80% or less is preferable, 40% or more and 70% or less is more preferable, and 50% or more and 70% or less is suitable for the balance in which the colored resin particles and the wax particles are discharged. Therefore, it is easy to be in a state close to the closest packing, and the effect of suppressing the back-through is more easily exhibited, which is preferable.
  • the colored resin particles contained in the water-based ink used in the applicator can be obtained by dyeing commercially available resin particles with dyes, using commercially available colored resin particles, dissolving dyes in resin monomer components, or dispersing pigments. And then emulsion polymerization or adding a pigment or dye to a solution obtained by dissolving a water-insoluble resin in a water-soluble organic solvent, adding water, kneading, and dispersing to form an O / W type dispersion. Colored resin particles having an arbitrary particle diameter can be obtained by adjusting and removing the organic solvent from the obtained dispersion.
  • the types of resin constituting the colored resin particles contained in the water-based ink used in the applicator include silicone / acrylic, benzoguanamine / formaldehyde condensate, benzoguanamine / melamine / formaldehyde condensate, melamine / formaldehyde condensate, acrylic and acrylic. ⁇ Styrene, polymethyl methacrylate, polybutyl methacrylate, polystyrene, styrene / acrylonitrile, polyester elastomer, polyphenylene sulfide resin, polybutylene terephthalate resin, polyethersulfone resin, polyamideimide resin, poly vinylidene fluoride resin, epoxy resin, poly Examples thereof include lactic acid resin, ethyl cellulose resin, nylon 12, and nylon 6.
  • the average particle diameter of the colored resin particles contained in the water-based ink used in the applicator is preferably 0.01 ⁇ m or more and 10 ⁇ m or less in consideration of suppression of showthrough.
  • the average particle diameter of the colored resin particles is 0.01 ⁇ m or more and 1 ⁇ m or less, there are few obstacles to the movement of the particles such as collision and detouring of the colored resin particles with the paper fibers, and the surface of the paper to be coated is reduced. It is inferred that the colored resin particles are less likely to remain, and the dried state of the applied trace can be obtained quickly.
  • the average particle size of the colored resin particles is measured by a laser diffraction / scattering particle size distribution measuring device (for example, Shimadzu Corporation; SALD-7100), a dynamic light scattering particle size distribution measuring device (for example, Otsuka). It is measured using ELSZ-2000S (manufactured by Electronics Co., Ltd.), Coulter counter (for example, Multisizer 4e, manufactured by Beckman Coulter, Inc.) and the like as appropriate depending on the range of the particle diameter.
  • a value obtained by calculating the average particle diameter (median diameter) on a volume basis based on a numerical value obtained from an apparatus appropriately selected according to the range of the particle diameter is adopted.
  • resin particles constituting the colored resin particles contained in the water-based ink used in the above applicator include silicone-acryl, Soliostar RA A type (average particle diameter: 3.5 ⁇ m), and B type (average) Particle size 3.5 ⁇ m), C type (average particle size 4.8 ⁇ m), D type (average particle size 5 ⁇ m), E type (average particle size 5 ⁇ m), same type (average particle size 6 ⁇ m) (above, As a benzoguanamine / formaldehyde condensate, Eposter MS (average particle size 2 ⁇ m), M05 (average particle size 5 ⁇ m), L15 (average particle size 9 ⁇ m) (above, manufactured by Nippon Shokubai Co., Ltd.) ), Eposter M30 (average particle size 3 ⁇ m) (above, Nippon Shokubai Co., Ltd.) as a benzoguanamine-melamine-formaldehyde condensate As a melamine-formaldehyde
  • the colored resin particles contained in the water-based ink used in the applicator include polystyrene as K005D (average particle size 0.05 ⁇ m), K007D (average particle size 0.06 ⁇ m), K010D (average particle size 0).
  • K015D average particle size 0.2 ⁇ m
  • K020D average particle size 0.2 ⁇ m
  • K025D average particle size 0.3 ⁇ m
  • K030D average particle size 0.3 ⁇ m
  • K035D average particle size 0) 0.4 ⁇ m
  • K040D average particle size 0.4 ⁇ m
  • K045D average particle size 0.5 ⁇ m
  • K050D average particle size 0.5 ⁇ m
  • K070D average particle size 0.7 ⁇ m
  • K080D average particle size 0) .8 ⁇ m
  • K100D average particle size 1 ⁇ m
  • L200D average particle size 2 ⁇ m
  • L300D average particle size 3 ⁇ m
  • FK 05 average particle size 0.05 ⁇ m
  • F-K007 average particle size 0.06 ⁇ m
  • F-K010 average particle size 0.1 ⁇ m
  • F-K015 average particle size 0.2 ⁇ m
  • F-K020 Average
  • the NKW-7500E series includes 7502E, 7517E, 7577E. 7518E, A-300E series, A-303E, A-301E, A-304E, A-305E, A-302E, A-308E, A-367E, A-347E, A-307E (above, average particle size of 0.4 ⁇ m or less) (above, manufactured by Nippon Fluorescent Chemical Co., Ltd.), Sinrohi Color SF-3022N, 3014N, 3015N, 3017N, 3037N, 3037N, 3038N 5012, 5013, 5014, 5015, 5017, 5027, No. 037, No. 5018 (above, average particle size 0.1 ⁇ m), No. 8012, No.
  • colored resin particles obtained by dyeing resin particles with a basic dye can also be used. Specific examples thereof include C.I. I. Basic Red 1: 1 and C.I. I. Basic violet 11: 1 and C.I. I. Colored styrene / acrylonitrile resin particles (average particle size 0.1 ⁇ m) dyed with Basic Violet 15, C.I. I. Colored styrene-acrylonitrile resin particles (average particle size 0.1 ⁇ m) dyed with basic violet 11: 1, C.I. I. Basic Red 1: 1 and C.I. I. Yellow 28 and C.I. I. Basic Yellow 40 and C.I. I. Basic violet 11: 1 and C.I. I.
  • Colored styrene / acrylonitrile resin particles (average particle size 0.1 ⁇ m) dyed with Basic Violet 15, C.I. I. Basic Red 1: 1 and C.I. I. Basic Yellow 28 and C.I. I. Basic Yellow 40 and C.I. I. Colored styrene-acrylonitrile resin particles (average particle size 0.1 ⁇ m) dyed with basic violet 11: 1, C.I. I. Basic Red 1: 1 and C.I. I. Basic Yellow 28 and C.I. I. Colored styrene / acrylonitrile resin particles (average particle diameter 0.1 ⁇ m) dyed with Basic Yellow 40, C.I. I. Basic Blue 3 and C.I. I.
  • Colored styrene / acrylonitrile resin particles (average particle diameter 0.1 ⁇ m) dyed with Basic Yellow 40, C.I. I. Basic Blue 3 and C.I. I. Colored styrene / acrylonitrile resin particles (average particle diameter 0.1 ⁇ m) dyed with Basic Yellow 40, C.I. I. Colored styrene / acrylonitrile resin particles (average particle size 0.1 ⁇ m) dyed with Basic Blue 3, C.I. I. Basic Blue 7 and C.I. I. Colored styrene / acrylonitrile resin particles (average particle size 0.1 ⁇ m) dyed with Basic Violet 15, C.I. I. Basic Yellow 28 and C.I. I. Basic Yellow 40 and C.I. I. Examples thereof include colored styrene / acrylonitrile resin particles (average particle size 0.1 ⁇ m) dyed with Basic Violet 1.
  • the content of these colored resin particles is preferably 0.5% by weight or more and 56.0% by weight or less, more preferably 1.0% by weight or more and 40.0% by weight or less based on the total amount of the ink composition. Preferably they are 3.0 weight% or more and 30.0 weight% or less. If it is less than 0.5% by weight, the color of the handwriting is insufficient, and if it exceeds 56.0% by weight, the pen-tip drying resistance may be adversely affected.
  • the wax particles contained in the water-based ink used in the applicator are particles obtained from solid wax that can be used as a lubricant, mainly in an environment of 25 ° C.
  • the wax particles have an average particle diameter of 5% or more and 95% or less with respect to the colored resin particles, and therefore, it is possible to suppress the penetration of the colored resin particles from the back side of the paper as much as possible. Further, when the average particle diameter is 33% or more and 67% or less of the average particle diameter with respect to the colored resin particles, the packing density of the aggregate structure of the wax particles and the aggregate structure of the colored resin particles is further increased. This is preferable because it becomes larger and the colored resin particles can be further prevented from coming off from the back side of the paper.
  • the average particle size of the wax particles is measured by a laser diffraction / scattering particle size distribution measuring device (for example, manufactured by Shimadzu Corp .; SALD-7100) and a dynamic light scattering particle size distribution measuring device in the same manner as the colored resin particles.
  • a laser diffraction / scattering particle size distribution measuring device for example, manufactured by Shimadzu Corp .; SALD-7100
  • a dynamic light scattering particle size distribution measuring device in the same manner as the colored resin particles.
  • Coulter counter for example, Multisizer 4e manufactured by Beckman Coulter Co., Ltd.
  • the average particle diameter a value obtained by calculating the average particle diameter (median diameter) on a volume basis based on a numerical value obtained from an apparatus appropriately selected according to the range of the particle diameter is adopted.
  • wax that can be used for the wax particles examples include petroleum wax such as paraffin wax, microcrystalline wax, and petrolatum.
  • plant waxes examples include carnauba wax, candelilla wax, rice wax, and wood wax.
  • animal waxes examples include lanolin and beeswax.
  • synthetic hydrocarbon wax examples include polyethylene wax, oxidized polyethylene wax, Fischer-Tropsch wax, and derivatives thereof. These waxes may be used alone or in combination of two or more.
  • the fiber bundling body, excellent mobility inside the paper, and the movement speed difference with the colored resin particles is further widened, so that the wax particles cause excessive penetration of the colored resin particles into the paper.
  • the use of oxidized polyethylene wax particles is more preferred because it can be further suppressed.
  • wax particles In the water-based ink used for the applicator, commercially available wax particles may be used as the wax particles, or a wax obtained by emulsifying and dispersing the wax in a liquid medium such as water may be used.
  • SELOSOL R-582 Average particle size 0.21 ⁇ m
  • R-585 average particle size 0.22 ⁇ m
  • R-586 average particle size 0.21 ⁇ m
  • SELOSOL 524 average particle size 0. 0
  • the content of these wax particles is preferably 0.1% by weight or more and 50.0% by weight or less, more preferably 0.5% by weight or more and 23.0% by weight or less based on the total amount of the ink composition. Preferably they are 1.0 weight% or more and 15.0 weight% or less. If it is less than 0.1% by weight, there is a risk that the showthrough suppression may be insufficient, and if it exceeds 50.0% by weight, the solid content in the water-based ink may become too high, which may adversely affect the nib drying resistance. is there.
  • wax particles depending on the difference in temperature, such as mechanical emulsification method, phase inversion emulsification method, liquid crystal emulsification method, D phase emulsification method, etc., mechanical milling method such as jet mill, etc. It may be prepared using a precipitation method due to differences in solubility, etc., but by minimizing the surface area of the wax particles, it is easy to move the complicated curved path formed in the fiber bundle or inside the paper, It is preferable to prepare wax particles by an emulsification method.
  • the ratio of the addition amount of each particle is (Formula 1) ⁇ 0.12x + 23.0 ⁇ y> ⁇ 0.12x + 6.8 Satisfy the relationship.
  • the component containing wax particles having a relatively small average particle diameter in the aqueous ink tends to penetrate into the paper prior to the component containing the colored resin particles in the aqueous ink.
  • the wax particles and the colored resin particles are both less hydrophilic than the fibers constituting the paper (for example, cellulose fibers), and the movement of the wax particles and the colored resin particles when the aqueous ink penetrates into the paper.
  • the speed is slower than water.
  • wax particles or colored resin particles approximate close-packed packing, attracting force between aggregates, and apparently bulky. It becomes difficult to move in the paper fiber.
  • an aggregated structure is formed as the colored resin particles progress to the inside, and the aggregated structure of the wax particles already formed overlaps with the aggregated structure of the colored resin particles, so that the colored resin particles are removed from the back side of the paper. Can be suppressed.
  • the relationship between the amount of colored resin particles added and the amount of wax particles added is (Formula 2) ⁇ 0.12x + 15.0 ⁇ y> ⁇ 0.12x + 8.0
  • the aggregated structure of the colored resin particles overlaps with the aggregated structure of the wax particles more closely, and the distance between the wax particles and the colored resin particles is the shortest.
  • the mutual attractive force increases to the maximum, and it is presumed that the cohesive action between the structures works most strongly. Therefore, it is further preferable to further suppress the colored resin particles from coming out from the back side of the paper.
  • the amount of the colored resin particles is preferably 0.5% by weight or more and 56.0% by weight or less, more preferably 1.0% by weight or more and 40% by weight based on the total amount of the ink composition. 0.0% by weight or less, most preferably 3.0% by weight or more and 30.0% by weight or less, and the content of the wax particles is 0.1% by weight or more and 50.50% or less based on the total amount of the ink composition. It is preferably 0% by weight or less, more preferably 0.5% by weight or more and 23.0% by weight or less, and most preferably 1.0% by weight or more and 15.0% by weight or less.
  • the ratio y / x of the addition amount y of the wax particles to the addition amount x of the colored resin particles is 0.02 or more and 21 or less, more preferably 0.42 or more and 1.6 or less.
  • the balance of the particles ejected through a certain coating destination is optimal, and it is easy to form a close-packed state on the handwriting, so that a handwriting having both high color developability and a back-through suppression effect is formed.
  • water-based ink used for the applicator examples include tap water, ground water, ion exchange water, pure water, and ultrapure water, and can be used without any particular limitation. Among these, ion exchange water and pure water are preferable.
  • a water-soluble organic solvent can be used for the water-based ink used in the applicator.
  • This water-soluble organic solvent refers to an organic solvent capable of dissolving 10 g or more with respect to 100 g of water.
  • water-soluble organic solvents include polyhydric alcohols such as glycerin, diglycerin, triglycerin, tetraglycerin, hexylene glycol, thiodiethylene glycol, 1,2,6-hexanetriol, trimethylolpropane, ethylene glycol, propylene.
  • polyhydric alcohols such as glycerin, diglycerin, triglycerin, tetraglycerin, hexylene glycol, thiodiethylene glycol, 1,2,6-hexanetriol, trimethylolpropane, ethylene glycol, propylene.
  • Glycol diethylene glycol, triethylene glycol, tetraethylene glycol, pentaethylene glycol, dipropylene glycol, tripropylene glycol, 2-butene-1,4-diol, 2-ethyl-1,3-hexanediol, 2-methyl-2 , 4-pentanediol, 1,2-octanediol, 1,2-hexanediol, 1,2-pentanediol, 4-methyl-1,2-pentanediol, 1,3-butanediol, 2,3-butane Diol, 1,4-butanediol, 3-methyl-1,3-butanediol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1, 2,4-butanetriol and the like, and monovalent alcohols include those having 1 to 4 carbon atoms
  • the glycol ether includes ethylene glycol monomethyl. Ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, ethylene glycol ethyl methyl ether, ethylene glycol monomethyl ether acetate, diethylene glycol Monoethyl ether, diethylene glycol monoethyl ether, diethylene glycol mono-n-propyl ether, ethylene glycol mono-iso-propyl ether, diethylene glycol mono-iso-propyl ether, ethylene glycol mono-n-butyl ether, ethylene glycol mono-t-butyl ether , Diethylene glycol mono-t-butyl ether, 1-methyl-1-methoxybutanol, diethylene glycol dimethyl glycol, diethylene glycol ethyl methyl ether, diethylene glycol diethyl ether, triethylene glycol dimethyl ether, propylene
  • -2-pyrrolidone N-ethyl-2-pyrrolidone, N-propyl-2-pyrrolidone, N-butyl-2-pyrrolidone, N-cyclohexyl-2-pyrrolidone, sulfolane, ⁇ -buty Lactone, 1,3-dimethyl-2-imidazolidinone, ethylene carbonate, propylene carbonate, are like, as the other, formamide, acetamide, dimethyl sulfoxide, acetin, diacetin, triacetin, and the like.
  • water-soluble organic solvents it is preferable to use diethylene glycol, triethylene glycol, or sulfolane from the viewpoint of penetrability of handwriting into paper and improvement in resistance to drying of the nib, or from diethylene glycol or triethylene glycol alone, or Mixing two or more types and using sulfolane together allows the colored resin particles and wax particles to penetrate into the paper while satisfying the high resistance to pen tip dryness. It is possible to achieve both suppression and anti-pen-tip drying suppression effects.
  • the amount of these water-soluble organic solvents added is preferably 0.1% by weight or more and 50.0% by weight or less, and more preferably 5.0% by weight or more and 20.0% by weight or less based on the total amount of the water-based ink.
  • These water-soluble organic solvents may be used alone or in combination of two or more.
  • a dye, a pigment, or both may be used as long as they do not adversely affect the quick-drying and back-through.
  • a water-soluble dye can be used as the dye.
  • specific examples of water-soluble dyes include direct dyes, acid dyes, and basic dyes.
  • Specific examples of direct dyes include Japan Fast Black D Conch (CI Direct Black 17), Water Black 100L (19), Water Black L-200 (19), Direct Fast Black B (22) Direct Fast Black AB (32), Direct Deep Black EX (38), Direct Fast Black Conk (51), Kayala Spragley VGN (71), Kayalas Direct Brilliant Yellow G (CI Direct) Yellow 4), Direct Fast Yellow 5GL (same 26), Eisen Primula Yellow GCLH (same 44), Direct Fast Yellow R (same 50), Eisen Direct Fast Red FH (CI Direct Red 1), Nippon Fast Scare GSX (same 4), Direct Fast Scarlet 4BS (same 23), Eisen Direct Rhodulin BH (same 31), Direct Scarlet B (same 37), Kayak Direct Scarlet 3B (same 39), Eisen Primula Pink 2BLH (same as above) 75), Sum
  • Acid Blue Black 10B (CI Acid Black 1), Nigrosine (2), Suminol Milling Black 8BX (24), Kayanol Milling Black VLG (26), Suminol Fast Black BR Conch (31), Mitsui Nylon Black GL (52), Eisen Opal Black WH Extra Conque (52), Sumilan Black WA (52), Ranil Black BG Extra Conk (107), Kayanol Milling Black TLB (109), Suminol Milling Black B (109), Kayanol Milling Black TLR (110), Eisen Opal Black New Conk (119), Water Black 187-L (154), Kayaqua Acid Brillian Flavin FF (CI Acid Yellow 7: 1), Kayasil Yellow GG (17), Xylene Light Yellow 2G 140% (17), Suminol Leveling Yellow NR (19), Daiwa Tarrazine (23), Kaya Cutter Torrazine (same 23), Suminoll Fast Yellow R (same 25), Diacid Light Yellow 2GP (same
  • basic dyes include Eisen Katylon Yellow 3GLH (CI Basic Yellow 11), Eisen Katylon Brilliant Yellow 5GLH (same 13), Sumiacryl Yellow E-3RD (same 15), Maxilon Yellow 2RL (19), Astrazon Yellow 7GLL (21), Kayacrill Golden Yellow GL-ED (28), Bright Yellow 3G Conch (40), Astrazon Yellow 5GL (51), Eisen Catillon Orange GLH ( CI Basic Orange 21), Eisen Catiron Brown 3GLH (30), Rhodamine 6GCP (CI Basic Red 1), Rhodamine 590 Chloride (1: 1), Eisen Astrafloxin (12), Sumi Acrylic Brilliant Red E- B (same 15), Astrazone Red GTL (same 18), Eisen Cachiron Brilliant Pink BGH (same 27), Maxilon Red GRL (same 46), Eisen Methyl Violet (CI Basic Violet 1), Eisen Crystal Violet (3), Eisen Rhodamine B (10), Rhodamine A (11: 1), C.I.
  • pigments include carbon black such as farnest black, contact black, thermal black, acetylene black, black iron oxide, yellow iron oxide, red iron oxide, ultramarine blue, bitumen, cobalt blue, titanium yellow, turquoise, molybdate Orange, titanium oxide, gold powder, silver powder, copper powder, aluminum powder, brass powder, tin powder, mica pigment, C.I. I.
  • PIGMENT BLUE 2 15, 15: 1, 15: 2, 15: 3, 15: 4, 15: 5, 16, 16, 17, 22, 25, 60, 66, C. I. PIGMENT BROWN 25, 26, C.I. I. PIGMENT YELLOW 1, 3, 12, 13, 24, 93, 94, 95, 97, 99, 108, 109, 110, 117, 120, 139, 153, 166, 167, 173, C.I. I. PIGMENT GREEN 7, 10, 36, etc. These pigments may be used alone or in combination of two or more.
  • a pigment dispersion in which a pigment is dispersed in an aqueous medium can also be used.
  • the pigment dispersion inorganic pigments, organic pigments, fluorescent pigments and the like can be used. Specific examples include the Unisperse series, Green GS, Red 3RS-E2, Red C2B-Agro RS, Red C2B. -Agro Syngenta, Yellow 10GN-S2 (manufactured by BASF Japan Ltd.), etc.
  • Red FGR Red FGR
  • Red HF3S Red F5RK VP3204
  • Red P2GL Red F2B
  • Black T Yellow HR
  • Violet RL Blue B2G
  • Yellow GR 30 VP 5176 Trans Oxide Red B 30, Magenta E, Green GN, Black T 30, Transoxide Red B 31 VP 6045, Trans Oxide Yellow R 30, Yellow HR 30 VP 6022, Transoxide Yellow R 31 VP 6043 (above, manufactured by Clariant Japan Co., Ltd.), FASTOGEN series, etc.
  • Blue 4RO-2 Blue 5003, Blue AE-8, Blue AE-8K, Blue AR-7, Blue BRF, Blue CA5380, Blue FA5375, Blue FA5380, Blue LA5380, Blue LA PA5380, Blue RSK, Green 2YK, Green 5720, Green S, Green SF, Green SMF-2, Super agent R, Super Magenta RE-03, Super Magenta RE-05, Super Magenta RG, Super Magenta RH, Super Magenta RTS, Twenty-six Super RY, Twenty-six -0200, Super Red 254 226-5254, Super Red 400RG, Super Red 500RG, Super Red 7061B, Super Red 7064B, Super Red 7100Y, Super Red ATY-01, Super Red ATY-01, Super Red ATY-01, Super Red ATY-01, Super Red ATY-01, Super Red ATY-01, Super Red ATY-01, Super Red ATY-01, Super Red ATY-01, Super Red ATY-01, Super Red ATY-01, Super Red B conc, Super Red YE, Super Scal
  • the PERRINDO series includes: Maron 179 229-6424, Maron 179 229-6436, Maron 179 229-6438, Maron 179 229-6440, Maron 179 229-6454, Red 224 229-6429, Violet 229 -4050, etc., and as QUINDO series, Magenta 202 228-6843, Magenta 202 228-6853, Violet 19 228-1119, etc., SYMULER Brilliant Carmine 6B 226, SYMULER Brilliant Carmin 6B 233S, SYMULER Brilliant Carmin 6B 233S, SYMULER SYMULER Brillant Carmin 6B 246, SYMULER Brillant Carmine 6B 300, SYMULER Brillant Carmin 6B 303S, SYMULER Brillant Carmin 6B 306L rmine 6B 308, the same SYMULER Brilliant Carmine 6B 313S, the same SYMULER Brilliant Carmine 6B 350K, same SYMULER
  • the Rio Fast series includes Black Fx 8012, Black Fx 8 313, Black Fx 8169, Red Fx 8209, Red Fx 8172, Red S Fx 8315, Red S Fx 8316, Blue Fx 8170, Blue Fx 8170, Blue S Fx 8312, G
  • the EMF color series includes the Yellow 3G, Orange O, Red HFB, Red HR, Blue HG, and Violet HB (above, manufactured by Toyocolor Co., Ltd.), and Pollux Color
  • the series includes the same PC5T1020, the same black PC8T135, the same red IT1030 (manufactured by Sumika Color Co., Ltd.), and the Victoria series includes the same yellow G-11, the same yellow G-20, the same orange G-16.
  • pigment dispersions may be used alone or in combination of two or more. However, when colored resin particles are used as a colorant, those in which the resin particles are not dissolved in an organic solvent are used.
  • a dispersant can be used to stably disperse the pigment.
  • the dispersant those used as a dispersant for pigments such as a water-soluble resin or a water-soluble resin generally used in the past and an anionic or nonionic surfactant can be used.
  • the dispersant include polymer dispersants such as lignin sulfonate, natural polymers such as shellac, polyacrylate, styrene-acrylic acid copolymer salt, vinylnaphthalene-maleic acid copolymer.
  • anionic polymers such as ⁇ -naphthalenesulfonic acid formalin condensate, sodium salts and phosphates
  • nonionic polymers such as polyvinyl alcohol and polyethylene glycol.
  • surfactants include alkyl sulfates, polyoxyethylene alkyl ether sulfates, N-acyl amino acids and salts thereof, N-acyl methyl taurate, polyoxyethylene alkyl ether acetates, alkyl sulfocarboxylic acids.
  • Anionic surfactants such as salts, ⁇ -olefin sulfonates, alkyl phosphates, polyoxyethylene alkyl ether phosphates, polyoxyethylene alkyl ethers, sorbitan alkyl esters, polyoxyethylene sorbitan alkyl esters, etc.
  • Nonionic surfactants and the like.
  • the amount of these water-soluble resin and surfactant added is preferably 0.05% by weight or more and 20.0% by weight or less with respect to 10.0% by weight of the pigment.
  • These water-soluble resins and surfactants may be used alone or in combination of two or more.
  • a general method can be used to disperse the pigment.
  • a pigment, a solvent, and a dispersant are mixed and stirred uniformly with a propeller stirrer or the like, and then the pigment is dispersed with a disperser.
  • the disperser include a roll mill, a ball mill, a sand mill, a bead mill, a Henschel mixer, a homogenizer, a high-pressure homogenizer, and a kneader.
  • the type of the disperser to be used can be appropriately selected depending on the solvent amount of the water-based ink, the pigment concentration, and the like.
  • the generated heat of dispersion can be used as it is, stirred, heated, cooled, pressurized, decompressed, or stirred in an inert gas atmosphere. .
  • These mixing, dispersion, filtration, heating, cooling, pressurization, decompression, inert gas atmosphere, etc. may be performed alone or two or more processes may be performed simultaneously.
  • the viscosity of the water-based ink used for the applicator can be appropriately adjusted depending on the form of the applicator using a fiber bundle as an application destination such as a marking pen and a brush pen.
  • the viscosity of the water-based ink is 1.0 mPa ⁇ s or more and 50.50 or more at a measurement temperature of 25 ° C. and a shear rate of 76.6 s ⁇ 1 . It is preferably 0 mPa ⁇ s or less, more preferably 1.0 mPa ⁇ s or more and 20.0 mPa ⁇ s or less.
  • the aqueous ink is preferably 1.0 mPa ⁇ s or more and 100.0 mPa ⁇ s or less, more preferably 1.0 mPa ⁇ s or more and 60.0 mPa ⁇ s or less at a measurement temperature of 25 ° C. and a shear rate of 76.6 s ⁇ 1 .
  • a viscosity modifier can be used to adjust the viscosity.
  • the viscosity modifier include HPC-SL, HPC-L, HPC-M, HPC-H (above, hydroxypropylcellulose, Nippon Soda Co., Ltd.), Theola SC-900, Theola SC-900S, Theola RC591S, Theolas RC-N81, Theolas RC-N30, Theolas CL-611S, Theolas DX-2, Theolas DX-3, Theolas UF-F711, Theolas UF-F702, Theolas ST-100, Theolas ST-02, Theolas FD- 101, Theolas FD-301, Theolas FD-F20, Theolas fiber DF-17 (above, crystalline cellulose, manufactured by Asahi Kasei Co., Ltd.), Kelzan, Kelzan S
  • additives such as a humectant, a lubricant, an antiseptic, an antifungal agent, a rust preventive, and an antifoaming agent can be used in combination.
  • a humectant such as a humectant, a lubricant, an antiseptic, an antifungal agent, a rust preventive, and an antifoaming agent.
  • moisturizers, lubricants, preservatives, antifungal agents, rust preventives and antifoaming agents may be used alone or in combination of two or more.
  • humectant examples include glycerin, glucose, mannose, fructose, ribose, xylose, arabinose, galactose, aldonic acid, glucitol (sorbitol), maltose, cellobiose, lactose, sucrose, Examples include trehalose, maltotriose, hyaluronic acid, trimethylglycine, glycine, urea, hydroxyethylurea, 1,2-dimethylurea, ethyleneurea, dimethylolethyleneurea, thiourea, guanidine, sorbit, and sorbitan.
  • glycerin Since glycerin has a strong ability to wet the handwriting on the paper surface, it is preferable not to use it as much as possible.
  • glycine has the smallest molecular weight among amino acids and has few steric hindrances, making it difficult to increase the viscosity of water-based inks and causing the handwriting to interact with colored resin particles and wax particles. It is preferable to use it because it can improve penetration into paper and maintain resistance to drying of the nib.
  • the addition amount of these humectants is preferably 0.1% by weight or more and 20.0% by weight or less, and more preferably 0.5% by weight or more and 10.0% by weight or less with respect to the total amount of the water-based ink. These humectants may be used alone or in combination of two or more.
  • antiseptics and antifungal agents include sodium dehydroacetate, benzisothiazolin-3-one, sodium omadin, sodium benzoate, morpholine, morpholine derivatives, and the like.
  • a pH adjuster In order to adjust the pH of the water-based ink, a pH adjuster can be used.
  • pH adjusters include basic substances such as sodium hydroxide, lithium hydroxide, monoethanolamine, diethanolamine, triethanolamine, aminomethylpropanediol, oxyethylene alkylamine, polyoxyethylene alkylamine, and acetic acid.
  • Acidic substances such as hydrochloric acid, nitric acid and sulfuric acid.
  • pH adjusters may be used alone or in combination of two or more. It is preferable to use two or more kinds of pH adjusting agents in combination because it is possible to finely adjust the pH and to easily suppress pH change over time.
  • the above colored resin particles, wax particles, water and / or an organic solvent, a dispersant, a propeller, a homomixer, etc. are mixed and stirred sufficiently, and then other additives such as It is obtained by mixing a viscosity adjusting agent, a pH adjusting agent, a lubricant, etc., and further dissolving and mixing until uniform.
  • the generated heat of dispersion is used as it is, stirred, heated, cooled, pressurized, depressurized, or replaced with inert gas, and stirred. Can do. You may perform the removal of the foam by a defoamer, filtration of the coarse thing by a filter, etc. as needed.
  • an aging step may be performed after adjusting the water-based ink in order to make the dispersibility of the polysaccharide sufficient.
  • These various mixing steps, dispersion steps, filtration steps, heating steps and / or cooling steps, pressurization and / or depressurization steps, and inert gas replacement steps may each be carried out independently, or two or more steps. May be performed in parallel.
  • water-based inks used in Examples 1 to 56 and Comparative Examples 1 to 11 were prepared by stirring with a propeller. As a production procedure, water and a water-soluble organic solvent were put into a container, stirred with a propeller for 5 minutes, other additives were added, and stirred with a propeller for 30 minutes to obtain a water-based ink.
  • Colored resin particles not commercially available can be obtained by emulsion polymerization of styrene / acrylonitrile monomers colored with dyes in water while adjusting the amount of propylene glycol, which is a water-soluble organic solvent, or modified alcohols, which are dyes that are organic solvents. And dissolved in acetone and mixed with acrylic resin particles and stirred, and then the organic solvent was evaporated.
  • propylene glycol which is a water-soluble organic solvent, or modified alcohols, which are dyes that are organic solvents.
  • the colored resin particles encapsulating the pigment are methacrylic acid, styrene, polyethylene (15) glycol monomethacrylate, polyethylene (5) glycol / polypropylene (7) glycol monomethacrylate, and styrene macromonomer as a monomer mixture, and methyl ethyl ketone and 2,2′- Create a polymer solution by polymerizing with azobisisobutyronitrile, octyl mercaptan and monomer mixture, add pigment while adding water while kneading with a disperser, remove methyl ethyl ketone under reduced pressure, remove moisture appropriately.
  • colored resin particles encapsulating the pigment were obtained.
  • Wax particles are obtained by emulsifying with sodium alkylbenzene sulfonate in water at a melting point or higher and then cooling, or by phase inversion emulsification with a water-soluble organic solvent that dissolves wax and polyoxyethylene sorbitan monooleate. I got it.
  • the average particle diameter was measured using a laser type particle size distribution analyzer SALD-7100 (manufactured by Shimadzu Corporation), and the average particle diameter (median diameter) was calculated on the basis of the obtained numerical value. Value.
  • SALD-7100 manufactured by Shimadzu Corporation
  • the ratio (wt%) of each particle in the ink is the ratio of the solid content of each dispersion.
  • the value calculated by multiplying the added amount of the liquid with respect to the ink by rounding off the second decimal place to the first decimal place is the blending ratio of the colored resin particles or the wax particles themselves with respect to the total amount of ink.
  • Colored resin particle dispersion (1) Pink resin particle dispersion (NKW3207E, colored styrene / acrylonitrile resin particles having an average particle size of 0.09 ⁇ m, solid content of 37.5% by weight, manufactured by Nippon Fluorescence Co., Ltd.)
  • Colored resin particle dispersion (2) Concentrated liquid of yellow resin particle dispersion (NKW3205E, colored styrene / acrylonitrile resin particles having an average particle size of 0.08 ⁇ m, solid content of 37.5% by weight, manufactured by Nippon Fluorescence Co., Ltd.) (Solid content 50% by weight)
  • the water-based inks used in Examples 1 to 56 and Comparative Examples 1 to 9 were made of batting (material of batting: mixed fiber of polyester and polypropylene, porosity of batting: 81% ( ⁇ 2% ) With a water mark pen (Knock-type Handyline S, product code SXNS15, manufactured by Pentel Co., Ltd.) shaft, pen tip (material of the pen tip: polyester fiber, Attach the nib porosity: 60% (with a variation of ⁇ 2%) and the nib material fiber thickness: 3 denier, knock and store the nib in the barrel to seal it After that, it was allowed to stand for 2 hours, and the water-based ink was sufficiently infiltrated into the pen tip to obtain applicators of Examples 1 to 56 and Comparative Examples 1 to 9. Further, the water-based ink used in Comparative Examples 10 and 11 was sucked with a syringe (Hamilton Microsyringe 701, manufactured by GL Science Co., Ltd.), so that 0.1 ⁇ l could
  • Tables 1 to 7 show the drying time (unit: “second”).
  • Handwriting back-through confirmation test Five test applicators for each of the above examples and comparative examples (excluding comparative examples 10 and 11) were prepared for each example and comparative example, and the environment was at a temperature of 25 ° C. and a humidity of 65%. , The state of see-through when writing at a writing speed of 0.5 cm / sec on a notebook (TANOSEEE notebook semi-B5 OSF-5A (US tsubo 65 g / m 2 ), manufactured by Otsuka Shokai Co., Ltd.) Taken with a digital microscope VHX-5000 (manufactured by Keyence Corporation) at a magnification of 30x, and image editing software Adobe Photoshop CC (manufactured by Adobe Systems Inc.) has the same number of pixels as the handwriting on the writing surface.
  • TANOSEEE notebook semi-B5 OSF-5A US tsubo 65 g / m 2
  • image editing software Adobe Photoshop CC (manufactured by Adobe Systems Inc.) has the same
  • Pen tip dryness confirmation test Using the test applicators of the above Examples and Comparative Examples (excluding Comparative Examples 10 and 11), the pen tip is exposed in an environment of a temperature of 25 ° C. and a humidity of 20%. The paper was handwritten every 30 minutes, 45 minutes, 60 minutes, and 90 minutes, and the longest time that the handwriting was less than 5 cm was defined as the time when writing was possible. Tables 1 to 7 show the time available for writing (unit: “minute”).
  • the applicators of Examples 1 to 3 are provided with water-based ink containing at least colored resin particles and wax particles having an average particle diameter of 5% to 95% with respect to the colored resin particles, and a fiber bundle as an application destination. Since it is an applicator, it is ejected preferentially from the tip of the fiber bundle as a porous application destination forming a complicated curved path, and the paper is preceded by colored resin particles of larger diameter than this. By making the gap between the fibers narrow and suppressing the excessive penetration of the colored resin particles into the paper, it was possible to suppress the breakthrough.
  • the applicators of Examples 4 to 6 are colored resin particles having an average particle diameter of 0.01 ⁇ m or more and 1.0 ⁇ m or less and a colored resin having an average particle diameter of 0.005 ⁇ m or more as compared with the applicators of Examples 1 to 3.
  • a colored resin having an average particle diameter of 0.005 ⁇ m or more as compared with the applicators of Examples 1 to 3.
  • wax particles smaller than the particles quick drying could be imparted, and both quick drying and set-off could be achieved.
  • the amount of colored resin particles added was x wt%, and the amount of wax particles added was y wt%.
  • the applicators of Examples 55 to 58 satisfy the relationship of (Equation 2) ⁇ 0.12x + 15.0 ⁇ y> ⁇ 0.12x + 8.0, compared with the applicators of Examples 28 and 30 to 32, and x Is 0.5% by weight or more and 56.0% by weight or less, and y is 0.1% by weight or more. Further, comparing the applicators of Examples 23, 43 and 58, the relationship of (Equation 2) ⁇ 0.12x + 15.0 ⁇ y> ⁇ 0.12x + 8.0 is satisfied, and x is 0.5 wt% or more 56 0.0% by weight or less and y is 0.1% by weight or more, so that it was possible to further improve back-through suppression and resistance to drying of the nib.
  • the applicators of Examples 22 and 48 contain quick-drying and nib-resistant dryness by including at least one of diethylene glycol and triethylene glycol in the water-soluble organic solvent. The property could be further improved.
  • the applicators of Examples 16 and 52 contained at least one of diethylene glycol and triethylene glycol in the water-soluble organic solvent, and further combined with sulfolane. Dryness could be further improved.
  • the applicators of Examples 31 and 50 were able to further improve the nib drying resistance while maintaining quick-drying properties by containing glycine.
  • the expression indicating that things such as “identical”, “equal”, and “homogeneous” are in an equal state not only represents an exactly equal state, but also includes a tolerance or the same function. It also represents a state in which a difference exists.
  • the expression “comprising”, “including”, or “having” one constituent element is not an exclusive expression for excluding the existence of another constituent element.

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  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
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Abstract

An applicator is provided with: an aqueous ink that includes at least colored resin particles and wax particles having an average particle size of 5-95% with respect to the average particle size of the colored resin particles; and a fiber bundle as the application tip.

Description

塗布具Applicator
　本発明は、水性インキを備えた塗布具に関するものである。 The present invention relates to an applicator provided with water-based ink.
　特許文献１には、着色樹脂粒子とワックス粒子を用いているインキ組成物として、水不溶性ポリマーによって被覆された顔料と、平均粒子径の異なる少なくとも２種類のワックスとを含む、主としてインキジェットに用いるインキ組成物が開示されている。 In Patent Document 1, an ink composition using colored resin particles and wax particles is mainly used for an ink jet including a pigment coated with a water-insoluble polymer and at least two kinds of waxes having different average particle diameters. An ink composition is disclosed.
特開２００７－２７７２９０号公報JP 2007-277290 A
　特許文献１に記載の発明では、着色樹脂粒子とワックス粒子が均一に分散した状態で紙面に吐出されてしまうため、水性インキ中の着色成分が紙に素早く浸透し塗布面の裏側まで浸透してしまう、所謂裏抜けと呼ばれる現象が発生してしまう事があった。 In the invention described in Patent Document 1, since the colored resin particles and the wax particles are discharged onto the paper surface in a uniformly dispersed state, the coloring component in the water-based ink quickly penetrates the paper and penetrates to the back side of the coated surface. In other words, a phenomenon called so-called back-throwing may occur.
　本発明の幾つかの実施形態では、裏抜けを極力抑制可能な塗布具を提供することを目的とする。 In some embodiments of the present invention, it is an object to provide an applicator that can suppress strikethrough as much as possible.
　即ち、本発明の幾つかの実施形態に係る塗布具は、着色樹脂粒子と、この着色樹脂粒子の平均粒子径に対して平均粒子径が５％以上９５％以下のワックス粒子とを少なくとも含む水性インキと、塗布先として、繊維集束体を備える。
　一実施形態では、前記着色樹脂粒子の平均粒子径が０．０１μｍ以上１μｍ以下であり、前記ワックス粒子の平均粒子径が０．００５μｍ以上であってもよい。
　一実施形態では、前記水性インキの、前記着色樹脂粒子の添加量をｘ重量％、前記ワックス粒子の添加量をｙ重量％としたとき、（式１）－０．１２ｘ＋２３．０≧ｙ＞－０．１２ｘ＋６．８を満たし、ｘが０．５重量％以上５６．０重量％以下、ｙが０．１重量％以上であってもよい。
　一実施形態では、前記塗布先の繊維集束体が、太さが０．５デニール以上５０デニール以下の繊維から少なくとも構成され、空孔率が２０％以上８０％以下であってもよい。 That is, the applicator according to some embodiments of the present invention includes an aqueous solution containing at least colored resin particles and wax particles having an average particle size of 5% to 95% with respect to the average particle size of the colored resin particles. A fiber bundling body is provided as the ink and application destination.
In one embodiment, the colored resin particles may have an average particle size of 0.01 μm or more and 1 μm or less, and the wax particles may have an average particle size of 0.005 μm or more.
In one embodiment, when the addition amount of the colored resin particles in the water-based ink is x wt% and the addition amount of the wax particles is y wt%, (Formula 1) −0.12x + 23.0 ≧ y> − 0.12x + 6.8 may be satisfied, x may be 0.5 wt% or more and 56.0 wt% or less, and y may be 0.1 wt% or more.
In one embodiment, the fiber bundle at the application destination may be composed of at least fibers having a thickness of 0.5 to 50 denier and a porosity of 20 to 80%.
　幾つかの実施形態に係る塗布具は、潤滑性の高いワックス粒子の平均粒子径が、着色樹脂粒子の平均粒子径に対して５％以上９５％以下なので、複雑な曲路を形成している多孔状態の塗布先としての繊維集束体の先端から優先して吐出され、これよりも大径である着色樹脂粒子に先んじて紙の繊維間に浸透して繊維間の隙間を狭いものとし、着色樹脂粒子の紙への過度な浸透が抑制されるものと推察され、裏抜けが抑制できるものである。
　また、前記着色樹脂粒子の平均粒子径が０．０１μｍ以上１μｍ以下であることで、紙の繊維との衝突や迂回など粒子の移動の障害が大きく減少し、塗布直後、即座に着色樹脂粒子が紙の繊維間に浸入して紙の表面に残り難いという塗布跡の速乾性効果と、着色樹脂粒子に先んじて紙の繊維間に移動する前記ワックス粒子の平均粒子径が、前記着色樹脂粒子の平均粒子径に対して５％以上９５％以下であることに加えて、このワックス粒子の平均粒子径が０．００５μｍ以上であることによって、前記着色樹脂粒子が紙の裏面へまで到達することを抑制した裏抜け抑制効果とを両立することが確実にできるものである。
　また、前述のとおり、上記塗布具では、水性インキのうち平均粒子径が相対的に小さいワックス粒子を含む成分が、水性インキのうち着色樹脂粒子を含む成分に先行して紙に浸透する傾向がある。ここで、ワックス粒子および着色樹脂粒子は、何れも、紙を構成する繊維（例えば、セルロース繊維）に比べて親水性が低く、水性インキの紙への浸透に際して、ワックス粒子及び着色樹脂粒子の移動速度は水に比べて遅い。このため、紙の内部に進むに従って、液媒体としての水が少なくなり、ワックス粒子又は着色樹脂粒子が最密充填に近似していって、凝集体間の引力が働き、見かけ上嵩高くなって紙繊維内を移動しにくくなる。その結果、着色樹脂粒子が内部に進むにしたがって凝集構造を形成し、既に形成されたワックス粒子の凝集構造と着色樹脂粒子の凝集構造とが重なり、着色樹脂粒子が紙の裏側から抜けることを効果的に抑制することができる。特に、着色樹脂粒子の添加量をｘ重量％、ワックス粒子の添加量をｙ重量％としたとき、それぞれの粒子の添加量の関係が、（式１）－０．１２ｘ＋２３．０≧ｙ＞－０．１２ｘ＋６．８の関係を満たし、ｘが０．５重量％以上５６．０重量％以下、ｙが０．１重量％以上であるとき、着色樹脂粒子を含む水性インキ成分の浸透に先立ってワックス粒子の凝集構造を適切に形成することが可能となり、ワックス粒子の凝集構造と着色樹脂粒子の凝集構造とを効果的に重なり合わせて、着色樹脂粒子が紙の裏側から抜けることを一層抑制することができる。
　また、前記塗布先の繊維集束体が、太さが０．５デニール以上５０デニール以下の繊維から少なくとも構成され、空孔率が２０％以上８０％以下であることによって、着色樹脂粒子と、着色樹脂粒子の平均粒子径に対して５％以上９５％以下の平均粒子径である潤滑性の高いワックス粒子とが吐出されるバランスが好適となるものと推察され、より裏抜けが抑制されたものとなる。 The applicator according to some embodiments forms a complicated curved path because the average particle diameter of the wax particles with high lubricity is 5% or more and 95% or less with respect to the average particle diameter of the colored resin particles. Preferentially discharged from the tip of the fiber bundling body as the application destination in the porous state, prior to the colored resin particles having a larger diameter than this, it penetrates between the paper fibers to narrow the gap between the fibers, and coloring It is presumed that excessive penetration of the resin particles into the paper is suppressed, and the back-through can be suppressed.
Further, when the average particle diameter of the colored resin particles is 0.01 μm or more and 1 μm or less, obstacles to the movement of the particles such as collision with paper fibers and detouring are greatly reduced, and the colored resin particles are immediately formed immediately after application. The quick-drying effect of the coating mark that hardly penetrates between the paper fibers and remains on the paper surface, and the average particle diameter of the wax particles that move between the paper fibers prior to the colored resin particles is In addition to being 5% or more and 95% or less with respect to the average particle size, the average particle size of the wax particles is 0.005 μm or more, whereby the colored resin particles reach the back surface of the paper. It is possible to reliably achieve both the suppressed strikethrough suppression effect.
Further, as described above, in the applicator, the component containing wax particles having a relatively small average particle diameter in the water-based ink tends to penetrate the paper prior to the component containing the colored resin particles in the water-based ink. is there. Here, the wax particles and the colored resin particles are both less hydrophilic than the fibers constituting the paper (for example, cellulose fibers), and the movement of the wax particles and the colored resin particles when the aqueous ink penetrates into the paper. The speed is slower than water. For this reason, as it proceeds to the inside of the paper, water as a liquid medium decreases, wax particles or colored resin particles approximate close-packed packing, attracting force between aggregates, and apparently bulky. It becomes difficult to move in the paper fiber. As a result, an aggregated structure is formed as the colored resin particles progress to the inside, and the aggregated structure of the wax particles already formed overlaps with the aggregated structure of the colored resin particles, so that the colored resin particles are removed from the back side of the paper. Can be suppressed. In particular, when the addition amount of the colored resin particles is x wt% and the addition amount of the wax particles is y wt%, the relationship between the addition amounts of the respective particles is (Formula 1) −0.12x + 23.0 ≧ y> − When the relationship of 0.12x + 6.8 is satisfied, x is 0.5 wt% or more and 56.0 wt% or less, and y is 0.1 wt% or more, prior to the penetration of the aqueous ink component containing the colored resin particles It becomes possible to appropriately form the aggregate structure of the wax particles, effectively overlapping the aggregate structure of the wax particles and the aggregate structure of the colored resin particles, and further suppressing the colored resin particles from coming out from the back side of the paper. be able to.
Further, the coated fiber bundle is at least composed of fibers having a thickness of 0.5 denier or more and 50 denier or less, and the porosity is 20% or more and 80% or less. It is presumed that the balance with which the highly-lubricated wax particles having an average particle diameter of 5% to 95% with respect to the average particle diameter of the resin particles are discharged is suitable, and the back-through is further suppressed. It becomes.
　以下に本発明の実施形態について詳細に説明する。 Hereinafter, embodiments of the present invention will be described in detail.
　幾つかの実施形態に係る塗布具は、着色樹脂粒子と、この着色樹脂粒子の平均粒子径に対して平均粒子径が５％以上９５％以下のワックス粒子とを少なくとも含む水性インキと、塗布先として、繊維集束体を備える。
　ここで、塗布先として使用する繊維集束体とは、繊維を束状に集合させたものをいい、合成繊維芯やフェルト芯のことを指す。 An applicator according to some embodiments includes a water-based ink containing at least colored resin particles and wax particles having an average particle size of 5% to 95% with respect to the average particle size of the colored resin particles; As a fiber bundle.
Here, the fiber bundle used as an application destination refers to a bundle of fibers gathered in a bundle, and refers to a synthetic fiber core or a felt core.
　合成繊維芯は、アクリル、ポリエステル、ナイロン、メラミン、ポリウレタン、ポリアセタールを単独、あるいは２種以上混合し、熱成形を行い、樹脂を含浸させて乾燥・硬化をした後に適当な長さに切断して適宜加熱工程を行った後に研磨を行ってペン先の形に成形したものなどが適宜選択でき、フェルト芯は主にウール（羊毛）などの獣毛や縮巻状の合成繊維などの単繊維をフェルト生地状に加工したものに樹脂を含浸させて乾燥・硬化をした後にプレス成形を行い、短冊状にカットし、ペン先の形に打ち抜きを行ったものや、アクリル、ポリエステルなどの繊維をフェルト生地状にしたものにプレス成形を行い、短冊状にカットし、ペン先の形に打ち抜きを行ったものなどが適宜選択できる。
　塗付先の磨耗などの耐久性を考慮すると合成繊維芯を用いることが好ましい。 The synthetic fiber core is made of acrylic, polyester, nylon, melamine, polyurethane, polyacetal alone or in combination of two or more, thermoformed, impregnated with resin, dried and cured, and then cut to an appropriate length. You can select the one that has been heated and then polished and shaped into the shape of the nib, etc. The felt core is mainly made of animal fibers such as wool (wool) or monofilaments such as contracted synthetic fibers. A felt fabric is impregnated with resin, dried and cured, press-molded, cut into strips, punched into the shape of a nib, and fibers such as acrylic and polyester. A material obtained by press-molding a dough, cutting it into a strip, and punching it into the shape of a nib can be appropriately selected.
In consideration of durability such as wear of the coating destination, it is preferable to use a synthetic fiber core.
　塗付先の繊維集束体の繊維の太さは着色樹脂粒子とワックス粒子の移動差が生じやすくなるように適宜調整し、０．５デニール以上５０デニール以下が好ましく、１デニール以上３０デニール以下がより好ましく、１デニール以上５デニール以下で、且つ、塗付先の繊維集束体の空孔率は繊維集束体の繊維の太さ同様には着色樹脂粒子とワックス粒子の移動差が生じやすくなるように適宜調整し、２０％以上８０％以下が好ましく、４０％以上７０％以下がより好ましく、５０％以上７０％以下が、着色樹脂粒子とワックス粒子との吐出されるバランスが好適となり、筆跡内で最密充填に近い状態となり易く裏抜けの抑制効果がより発揮されやすく、好ましい。 The fiber thickness of the fiber bundle at the application destination is appropriately adjusted so that a difference in movement between the colored resin particles and the wax particles is likely to occur, and is preferably from 0.5 to 50 denier, preferably from 1 to 30 denier. More preferably, the porosity of the fiber bundle at the application destination is 1 denier or more and 5 denier or less, so that the difference in movement between the colored resin particles and the wax particles is likely to occur as with the fiber thickness of the fiber bundle. 20% or more and 80% or less is preferable, 40% or more and 70% or less is more preferable, and 50% or more and 70% or less is suitable for the balance in which the colored resin particles and the wax particles are discharged. Therefore, it is easy to be in a state close to the closest packing, and the effect of suppressing the back-through is more easily exhibited, which is preferable.
　上記塗布具において使用する水性インキに含有される着色樹脂粒子は、市販の樹脂粒子を染料で染色したり、市販の着色樹脂粒子を用いたり、樹脂モノマー成分に染料を溶解させたり顔料を分散させたりした後に乳化重合したり、水不溶性樹脂を水溶性有機溶剤に溶解させて得られた溶液に顔料や染料を添加し、水を添加して混練、分散処理によってＯ／Ｗ型の分散体を調整し、得られた分散体から有機溶剤を除去することによって任意の粒子径の着色樹脂粒子を得ることが出来る。 The colored resin particles contained in the water-based ink used in the applicator can be obtained by dyeing commercially available resin particles with dyes, using commercially available colored resin particles, dissolving dyes in resin monomer components, or dispersing pigments. And then emulsion polymerization or adding a pigment or dye to a solution obtained by dissolving a water-insoluble resin in a water-soluble organic solvent, adding water, kneading, and dispersing to form an O / W type dispersion. Colored resin particles having an arbitrary particle diameter can be obtained by adjusting and removing the organic solvent from the obtained dispersion.
　上記塗布具において使用する水性インキに含有される着色樹脂粒子を構成する樹脂の種類として、シリコーン・アクリル、ベンゾグアナミン・ホルムアルデヒド縮合物、ベンゾグアナミン・メラミン・ホルムアルデヒド縮合物、メラミン・ホルムアルデヒド縮合物、アクリル、アクリル・スチレン、ポリメタクリル酸メチル、ポリメタクリル酸ブチル、ポリスチレン、スチレン・アクリルニトリル、ポリエステルエラストマー、ポリフェニレンスルフィド樹脂、ポリブチレンテレフタレート樹脂、ポリエーテルスルホン樹脂、ポリアミドイミド樹脂、ポリフッ化ビリニデン樹脂、エポキシ樹脂、ポリ乳酸樹脂、エチルセルロース樹脂、ナイロン１２、ナイロン６などが挙げられる。 The types of resin constituting the colored resin particles contained in the water-based ink used in the applicator include silicone / acrylic, benzoguanamine / formaldehyde condensate, benzoguanamine / melamine / formaldehyde condensate, melamine / formaldehyde condensate, acrylic and acrylic.・ Styrene, polymethyl methacrylate, polybutyl methacrylate, polystyrene, styrene / acrylonitrile, polyester elastomer, polyphenylene sulfide resin, polybutylene terephthalate resin, polyethersulfone resin, polyamideimide resin, poly vinylidene fluoride resin, epoxy resin, poly Examples thereof include lactic acid resin, ethyl cellulose resin, nylon 12, and nylon 6.
　上記塗布具において使用する水性インキに含有される着色樹脂粒子の平均粒子径は裏抜けの抑制を考慮すると、０．０１μｍ以上１０μｍ以下であることが好ましい。着色樹脂粒子の平均粒子径が０．０１μｍ以上１μｍ以下であることで、着色樹脂粒子の紙の繊維との衝突や迂回など粒子の移動の障害が少なく、被塗付面である紙の表面に着色樹脂粒子が残りにくくなると推察され、塗付跡の乾燥状態が早く得られる。 The average particle diameter of the colored resin particles contained in the water-based ink used in the applicator is preferably 0.01 μm or more and 10 μm or less in consideration of suppression of showthrough. When the average particle diameter of the colored resin particles is 0.01 μm or more and 1 μm or less, there are few obstacles to the movement of the particles such as collision and detouring of the colored resin particles with the paper fibers, and the surface of the paper to be coated is reduced. It is inferred that the colored resin particles are less likely to remain, and the dried state of the applied trace can be obtained quickly.
　尚、着色樹脂粒子の平均粒子径の測定はレーザ回折／散乱式粒子径分布測定装置（例えば、（株）島津製作所製；ＳＡＬＤ－７１００）、動的光散乱式粒度分布測定装置（例えば、大塚電子（株）製、ＥＬＳＺ－２０００Ｓ）、コールターカウンター（例えば、ベックマン・コールター（株）製、Ｍｕｌｔｉｓｉｚｅｒ　４ｅ）等を粒子径の範囲に応じて適宜使用して測定される。また平均粒子径は、粒子径の範囲に応じて適宜選択した装置より得られた数値を基に平均粒子径（メジアン径）を体積基準で算出した値を採用する。 The average particle size of the colored resin particles is measured by a laser diffraction / scattering particle size distribution measuring device (for example, Shimadzu Corporation; SALD-7100), a dynamic light scattering particle size distribution measuring device (for example, Otsuka). It is measured using ELSZ-2000S (manufactured by Electronics Co., Ltd.), Coulter counter (for example, Multisizer 4e, manufactured by Beckman Coulter, Inc.) and the like as appropriate depending on the range of the particle diameter. As the average particle diameter, a value obtained by calculating the average particle diameter (median diameter) on a volume basis based on a numerical value obtained from an apparatus appropriately selected according to the range of the particle diameter is adopted.
　上記塗布具に使用する水性インキに含有される着色樹脂粒子を構成する樹脂粒子の具体例としては、シリコーン－アクリルとして、ソリオスターＲＡ　Ａタイプ（平均粒子径　３．５μｍ）、同Ｂタイプ（平均粒子径　３．５μｍ）、同Ｃタイプ（平均粒子径　４．８μｍ）、同Ｄタイプ（平均粒子径　５μｍ）、同Ｅタイプ（平均粒子径　５μｍ）、同タイプ（平均粒子径　６μｍ）（以上、（株）日本触媒製）、ベンゾグアナミン・ホルムアルデヒド縮合物として、エポスターＭＳ（平均粒子径　２μｍ）、同Ｍ０５（平均粒子径　５μｍ）、同Ｌ１５（平均粒子径　９μｍ）（以上、（株）日本触媒製）、ベンゾグアナミン－メラミン－ホルムアルデヒド縮合物として、エポスターＭ３０（平均粒子径　３μｍ）（以上、（株）日本触媒製）、メラミン－ホルムアルデヒド縮合物として、エポスターＳＳ（平均粒子径　０．１μｍ）、同Ｓ（平均粒子径　０．２μｍ）、同ＦＳ（平均粒子径　０．２μｍ）、同Ｓ６（平均粒子径　０．４μｍ）、同Ｓ１２（平均粒子径　１２μｍ）（以上、（株）日本触媒製）、アクリル系として、エポスターＭＡ１００２（平均粒子径　２μｍ）、同１００４（平均粒子径　４μｍ）、同１００６（平均粒子径　６μｍ）、同１０１０（平均粒子径　１０μｍ）（以上、（株）日本触媒製）、ＭＸ８０Ｈ３ｗＴ（平均粒子径　０．８μｍ）、同１５０（平均粒子径　１．５μｍ）、同１８０ＴＡ（平均粒子径　１．８μｍ）、同３００（平均粒子径　３μｍ）、同５００（平均粒子径　５μｍ）、同１０００（平均粒子径　１０μｍ）、同１５００Ｈ（平均粒子径　１５μｍ）、同２０００（平均粒子径　２０μｍ）、同３０００（平均粒子径　３０μｍ）（以上、総研化学（株）製）、アクリル－スチレン系として、エポスターＭＡ２００３（平均粒子径　３μｍ）（以上、（株）日本触媒製）、ポリメタクリル酸メチル系として、エポスターＭＸ０２０Ｗ（平均粒子径　０．０２０μｍ）、同０３０Ｗ（平均粒子径　０．０４０μｍ）、同０５０Ｗ（平均粒子径　０．０７０μｍ）、同１００Ｗ（平均粒子径　０．１５０μｍ）、同２００Ｗ（平均粒子径　０．３５０μｍ）、同３００Ｗ（平均粒子径　０．４５０μｍ）（以上、（株）日本触媒製）、テクポリマーＭＢＸＭＢＸ－５（平均粒子径　５μｍ）、同－８（平均粒子径　８μｍ）、同－１２（平均粒子径　１２μｍ）、同－２０（平均粒子径　２０μｍ）、同－３０（平均粒子径　３０μｍ）、同－４０（平均粒子径　４０μｍ）、同－５０（平均粒子径　５０μｍ）、テクポリマーＭＢ２０Ｘ－５（平均粒子径　５μｍ）、同－３０（平均粒子径　３０μｍ）、テクポリマーＭＢ３０Ｘ－５（平均粒子径　５μｍ）、同－８（平均粒子径　８μｍ）、同－２０（平均粒子径　２０μｍ）、テクポリマーＳＳＸ－１０１（平均粒子径　１μｍ）、同－１０２（平均粒子径　２μｍ）、同－１０３（平均粒子径　３μｍ）、同－１０４（平均粒子径　４μｍ）、同－１０５（平均粒子径　５μｍ）、同－１０８（平均粒子径　８μｍ）、同－１１０（平均粒子径　１０μｍ）、同－１１５（平均粒子径　１５μｍ）、同－１２０（平均粒子径　２０μｍ）、同－１２７（平均粒子径　２７μｍ）（以上、積水化成品工業（株）製）、テクポリマーＭＢＰ－８（平均粒子径　８μｍ）（以上、積水化成品工業（株）製）、ポリメタクリル酸ブチル系として、テクポリマーＢＭ３０Ｘ－５（平均粒子径　５μｍ）、同－８（平均粒子径　８μｍ）、同－１２（平均粒子径　１２μｍ）（以上、積水化成品工業（株）製）、ポリスチレン系として、テクポリマーＳＢＸ－４（平均粒子径　４μｍ）、同－６（平均粒子径　６μｍ）、同－８（平均粒子径　８μｍ）、同－１２（平均粒子径　１２μｍ）（以上、積水化成品工業（株）製）が挙げられる。 Specific examples of the resin particles constituting the colored resin particles contained in the water-based ink used in the above applicator include silicone-acryl, Soliostar RA A type (average particle diameter: 3.5 μm), and B type (average) Particle size 3.5 μm), C type (average particle size 4.8 μm), D type (average particle size 5 μm), E type (average particle size 5 μm), same type (average particle size 6 μm) (above, As a benzoguanamine / formaldehyde condensate, Eposter MS (average particle size 2 μm), M05 (average particle size 5 μm), L15 (average particle size 9 μm) (above, manufactured by Nippon Shokubai Co., Ltd.) ), Eposter M30 (average particle size 3 μm) (above, Nippon Shokubai Co., Ltd.) as a benzoguanamine-melamine-formaldehyde condensate As a melamine-formaldehyde condensate, Eposter SS (average particle size 0.1 μm), S (average particle size 0.2 μm), FS (average particle size 0.2 μm), S6 (average particle size 0.4 μm) ), S12 (average particle size: 12 μm) (made by Nippon Shokubai Co., Ltd.), acrylic, Epostor MA1002 (average particle size: 2 μm), 1004 (average particle size: 4 μm), 1006 (average particle size: 6 μm) ), 1010 (average particle size 10 μm) (manufactured by Nippon Shokubai Co., Ltd.), MX80H3wT (average particle size 0.8 μm), 150 (average particle size 1.5 μm), 180 TA (average particle size 1. 8 μm), 300 (average particle size 3 μm), 500 (average particle size 5 μm), 1000 (average particle size 10 μm), 1500 H (average) Particle size 15 μm), 2000 (average particle size 20 μm), 3000 (average particle size 30 μm) (above, manufactured by Soken Chemical Co., Ltd.), acrylic-styrene system, Eposta MA 2003 (average particle size 3 μm) (above, (Manufactured by Nippon Shokubai Co., Ltd.), polymethyl methacrylate, Eposter MX020W (average particle size 0.020 μm), 030 W (average particle size 0.040 μm), 050 W (average particle size 0.070 μm), 100 W (Average particle size 0.150 μm), 200 W (average particle size 0.350 μm), 300 W (average particle size 0.450 μm) (manufactured by Nippon Shokubai Co., Ltd.), Techpolymer MBXMBX-5 (average particle size) 5μm), -8 (average particle size 8μm), -12 (average particle size 12μm), -20 (average particle size) 20 μm), -30 (average particle size 30 μm), -40 (average particle size 40 μm), -50 (average particle size 50 μm), Techpolymer MB20X-5 (average particle size 5 μm), -30 (average) Particle diameter 30 μm), techpolymer MB30X-5 (average particle diameter 5 μm), -8 (average particle diameter 8 μm), -20 (average particle diameter 20 μm), techpolymer SSX-101 (average particle diameter 1 μm), the same -102 (average particle size 2 μm), -103 (average particle size 3 μm), -104 (average particle size 4 μm), -105 (average particle size 5 μm), -108 (average particle size 8 μm), same -110 (average particle size: 10 μm), -115 (average particle size: 15 μm), -120 (average particle size: 20 μm), -127 (average particle size: 27 μm) ( Above, Sekisui Plastics Co., Ltd.), Techpolymer MBP-8 (average particle size: 8 μm) (Sekisui Plastics Co., Ltd.), polybutyl methacrylate, Techpolymer BM30X-5 (Average Particle size 5μm), -8 (average particle size 8μm), -12 (average particle size 12μm) (above, manufactured by Sekisui Plastics Co., Ltd.), polystyrene, Techpolymer SBX-4 (average particle size) 4 μm), -6 (average particle size: 6 μm), -8 (average particle size: 8 μm), and -12 (average particle size: 12 μm) (above, manufactured by Sekisui Plastics Co., Ltd.).
　上記塗布具に使用する水性インキに含有される着色樹脂粒子の具体例としては、ポリスチレンとして、Ｋ００５Ｄ（平均粒子径　０．０５μｍ）、Ｋ００７Ｄ（平均粒子径　０．０６μｍ）、Ｋ０１０Ｄ（平均粒子径　０．１μｍ）、Ｋ０１５Ｄ（平均粒子径　０．２μｍ）、Ｋ０２０Ｄ（平均粒子径　０．２μｍ）、Ｋ０２５Ｄ（平均粒子径　０．３μｍ）、Ｋ０３０Ｄ（平均粒子径　０．３μｍ）、Ｋ０３５Ｄ（平均粒子径　０．４μｍ）、Ｋ０４０Ｄ（平均粒子径　０．４μｍ）、Ｋ０４５Ｄ（平均粒子径　０．５μｍ）、Ｋ０５０Ｄ（平均粒子径　０．５μｍ）、Ｋ０７０Ｄ（平均粒子径　０．７μｍ）、Ｋ０８０Ｄ（平均粒子径　０．８μｍ）、Ｋ１００Ｄ（平均粒子径　１μｍ）、Ｌ２００Ｄ（平均粒子径　２μｍ）、Ｌ３００Ｄ（平均粒子径　３μｍ）、Ｆ－Ｋ００５（平均粒子径　０．０５μｍ）、Ｆ－Ｋ００７（平均粒子径　０．０６μｍ）、Ｆ－Ｋ０１０（平均粒子径　０．１μｍ）、Ｆ－Ｋ０１５（平均粒子径　０．２μｍ）、Ｆ－Ｋ０２０（平均粒子径　０．２μｍ）、Ｆ－Ｋ０２５（平均粒子径　０．３μｍ）、Ｆ－Ｋ０３０（平均粒子径　０．３μｍ）、Ｆ－Ｋ０３５（平均粒子径　０．４μｍ）、Ｆ－Ｋ０４０（平均粒子径　０．４μｍ）、Ｆ－Ｋ０４５（平均粒子径　０．５μｍ）、Ｆ－Ｋ０５０（平均粒子径　０．５μｍ）、Ｆ－Ｋ０７０（平均粒子径　０．７μｍ）、Ｆ－Ｋ０８０（平均粒子径　０．８μｍ）、Ｆ－Ｋ１００（平均粒子径　１μｍ）、Ｆ－Ｌ２００（平均粒子径　２μｍ）、Ｆ－Ｌ３００（平均粒子径　３μｍ）（以上、コアフロント（株）製）、ポリメタクリル酸メチルとして、タフチックＡＲ６５０Ｓ（平均粒子径　１８μｍ）、同Ｍ（平均粒子径　３０μｍ）、同ＭＸ（平均粒子径　４０μｍ）、同ＭＺ（平均粒子径　６０μｍ）、同ＭＬ（平均粒子径　８０μｍ）、同Ｌ（平均粒子径　１００μｍ）、同ＬＸ（平均粒子径　１３０μｍ）、同ＬＬ（平均粒子径　１５０μｍ）（以上、東洋紡（株）製）、アクリルとして、アートパールＧＲシリーズ黒色（平均粒子径　３．８μｍ、６μｍ、１０μｍ、１５μｍ、２２μｍ、３２μｍ、９０μｍ、１２０μｍ）、同白色（平均粒子径　１５μｍ、２２μｍ、３２μｍ、９０μｍ、１２０μｍ）、同黄土色（平均粒子径　１２０μｍ）、同茶色（平均粒子径　１２０μｍ）、アートパールＧシリーズ黒色（平均粒子径　６μｍ、１５μｍ）（以上、根上工業（株）製）、ウレタンとして、アートパールＣシリーズ黒色（平均粒子径　６μｍ、１５μｍ、２２μｍ、３２μｍ）、同白色（平均粒子径　６μｍ、１５μｍ、２２μｍ、３２μｍ）、同緑色（平均粒子径　１５μｍ）、同黄色（平均粒子径　１５μｍ）、同青色（平均粒子径　１５μｍ）、同赤色（平均粒子径　１５μｍ）、アートパールＭＴシリーズ茶色（平均粒子径　１５μｍ）、同黄土色（平均粒子径　１５μｍ）、アートパールＨＩシリーズ黒色（平均粒子径　１５μｍ）、同白色（平均粒子径　１５μｍ）、アートパールＨＢシリーズ黒色（平均粒子径　８μｍ、１５μｍ）、アートパールＣＨシリーズ赤色（平均粒子径　６μｍ）、同青色（平均粒子径　６μｍ）（以上、根上工業（株）製）、スチレン・アクリルニトリルとして、ＮＫＷ３９０３Ｅ、同３９２６Ｅ、同３９０４Ｅ、同３９０５Ｅ、同３９０２Ｅ、同３９０８Ｅ、同３９３８Ｅ、同３９７７Ｅ、同３９４７Ｅ、同３９０７Ｅ、同３２０３Ｅ、同３２２６Ｅ、同３２０４Ｅ、同３２０５Ｅ、同３２１５Ｅ、同３２０２Ｅ、同３２０８Ｅ、同３２７７Ｅ、同３２０７Ｅ、同６０１３Ｅ、同６００４Ｅ、同６００５Ｅ、同６００２Ｅ、同６００８Ｅ、同６０３８Ｅ、同６０４７Ｅ、同６００７Ｅ（以上、平均粒子径　０．１μｍ以下）、同Ｃ２１０３Ｅ、同Ｃ２１０４Ｅ、同Ｃ２１０５Ｅ、同Ｃ２１０２Ｅ、同Ｃ２１０８Ｅ、同Ｃ２１６７Ｅ、同Ｃ２１４７Ｅ、同Ｃ２１１７Ｅ、同２１０３Ｅ、同２１０１Ｅ、同２１０４Ｅ、同２１０６Ｅ、同２１０５Ｅ、同２１０２Ｅ、同２１０８Ｅ、同２１６７Ｅ、同２１３７Ｅ、同２１２７Ｅ、同２１１７Ｅ、同２１０７Ｅ、同２１０９Ｅ、同７００２Ｅ、同７０１２Ｅ、同７０５２Ｅ、同７００３Ｅ、同７００４Ｅ、同７００５Ｅ、同７０２６Ｅ、同７０１７Ｅ、同７０４７Ｅ、同７０６７Ｅ、同７００８Ｅ、同７０３８Ｅなどが挙げられ、ＮＫＷ－７５００Ｅシリーズとして、同７５０２Ｅ、同７５１７Ｅ、同７５７７Ｅ、同７５１８Ｅ、Ａ－３００Ｅシリーズとして、同Ａ－３０３Ｅ、同Ａ－３０１Ｅ、同Ａ－３０４Ｅ、同Ａ－３０５Ｅ、同Ａ－３０２Ｅ、同Ａ－３０８Ｅ、同Ａ－３６７Ｅ、同Ａ－３４７Ｅ、同Ａ－３０７Ｅ（以上、平均粒子径　０．４μｍ以下）（以上、日本蛍光化学（株）製）、シンロイヒカラーＳＦ－３０２２Ｎ、同３０１４Ｎ、同３０１５Ｎ、同３０１７Ｎ、同３０３７Ｎ、同３０３８Ｎ、同５０１２、同５０１３、同５０１４、同５０１５、同５０１７、同５０２７、同５０３７、同５０１８（以上、平均粒子径　０．１μｍ）、同８０１２、同８０１４、同８０１５、同８０１７、同８０３７、同８０２８（以上、平均粒子径　０．４μｍ）、シンロイヒカラーＳＰ－１３、同１４、同１５、同１６、同１７、同２７、同３７、同４７（以上、平均粒子径　１．０μｍ前後）、シンロイヒカラーＳＷ－同１１１、同１１２、同１１３、同１１４、同１１５、同１１６、同１０７、同１１７、同１２７、同１３７、同１４７、同１２８（以上、平均粒子径　１．０μｍ以下）、ＦＷ－８５１２ＫＳ、同８５１４ＫＳ、同８５０５ＫＳ、同８５０６ＫＳ、同８５３７ＫＳ（以上、平均粒子径　３．５μｍ以上４．５μｍ以下）（以上、シンロイヒ（株）製）が挙げられる。
　また、樹脂粒子を塩基性染料で染着した着色樹脂粒子も使用できる。その具体例としては、Ｃ．Ｉ．ベーシックレッド１：１とＣ．Ｉ．ベーシックバイオレット１１：１とＣ．Ｉ．ベーシックバイオレット１５で染着した着色スチレン・アクリロニトリル樹脂粒子（平均粒子径　０．１μｍ）、Ｃ．Ｉ．ベーシックバイオレット１１：１で染着した着色スチレン・アクリロニトリル樹脂粒子（平均粒子径　０．１μｍ）、Ｃ．Ｉ．ベーシックレッド１：１とＣ．Ｉ．イエロー２８とＣ．Ｉ．ベーシックイエロー４０とＣ．Ｉ．ベーシックバイオレット１１：１とＣ．Ｉ．ベーシックバイオレット１５で染着した着色スチレン・アクリロニトリル樹脂粒子（平均粒子径　０．１μｍ）、Ｃ．Ｉ．ベーシックレッド１：１とＣ．Ｉ．ベーシックイエロー２８とＣ．Ｉ．ベーシックイエロー４０とＣ．Ｉ．ベーシックバイオレット１１：１で染着した着色スチレン・アクリロニトリル樹脂粒子（平均粒子径　０．１μｍ）、Ｃ．Ｉ．ベーシックレッド１：１とＣ．Ｉ．ベーシックイエロー２８とＣ．Ｉ．ベーシックイエロー４０で染着した着色スチレン・アクリロニトリル樹脂粒子（平均粒子径　０．１μｍ）、Ｃ．Ｉ．ベーシックブルー３とＣ．Ｉ．ベーシックイエロー４０で染着した着色スチレン・アクリロニトリル樹脂粒子（平均粒子径　０．１μｍ）、Ｃ．Ｉ．ベーシックブルー３とＣ．Ｉ．ベーシックイエロー４０で染着した着色スチレン・アクリロニトリル樹脂粒子（平均粒子径　０．１μｍ）、Ｃ．Ｉ．ベーシックブルー３で染着した着色スチレン・アクリロニトリル樹脂粒子（平均粒子径　０．１μｍ）、Ｃ．Ｉ．ベーシックブルー７とＣ．Ｉ．ベーシックバイオレット１５で染着した着色スチレン・アクリロニトリル樹脂粒子（平均粒子径　０．１μｍ）、Ｃ．Ｉ．ベーシックイエロー２８とＣ．Ｉ．ベーシックイエロー４０とＣ．Ｉ．ベーシックバイオレット１で染着した着色スチレン・アクリロニトリル樹脂粒子（平均粒子径　０．１μｍ）が挙げられる。 Specific examples of the colored resin particles contained in the water-based ink used in the applicator include polystyrene as K005D (average particle size 0.05 μm), K007D (average particle size 0.06 μm), K010D (average particle size 0). 0.1 μm), K015D (average particle size 0.2 μm), K020D (average particle size 0.2 μm), K025D (average particle size 0.3 μm), K030D (average particle size 0.3 μm), K035D (average particle size 0) 0.4 μm), K040D (average particle size 0.4 μm), K045D (average particle size 0.5 μm), K050D (average particle size 0.5 μm), K070D (average particle size 0.7 μm), K080D (average particle size 0) .8 μm), K100D (average particle size 1 μm), L200D (average particle size 2 μm), L300D (average particle size 3 μm), FK 05 (average particle size 0.05 μm), F-K007 (average particle size 0.06 μm), F-K010 (average particle size 0.1 μm), F-K015 (average particle size 0.2 μm), F-K020 ( Average particle size 0.2 μm), F-K025 (average particle size 0.3 μm), F-K030 (average particle size 0.3 μm), F-K035 (average particle size 0.4 μm), F-K040 (average particle) Diameter 0.4 μm), F-K045 (average particle size 0.5 μm), F-K050 (average particle size 0.5 μm), F-K070 (average particle size 0.7 μm), F-K080 (average particle size 0) .8 μm), F-K100 (average particle size 1 μm), FL-L200 (average particle size 2 μm), FL-300 (average particle size 3 μm) (above, manufactured by Corefront Co., Ltd.), polymethyl methacrylate, Tuftic A 650S (average particle size 18 μm), M (average particle size 30 μm), MX (average particle size 40 μm), MZ (average particle size 60 μm), ML (average particle size 80 μm), L (average particle size) 100 μm), the same LX (average particle size 130 μm), the same LL (average particle size 150 μm) (above, manufactured by Toyobo Co., Ltd.), acrylic, Art Pearl GR series black (average particle size 3.8 μm, 6 μm, 10 μm, 15 μm, 22 μm, 32 μm, 90 μm, 120 μm), the same white (average particle size 15 μm, 22 μm, 32 μm, 90 μm, 120 μm), the same ocher color (average particle size 120 μm), the same brown (average particle size 120 μm), Art Pearl G Series black (average particle size 6μm, 15μm) (Negami Kogyo Co., Ltd.), urethane, Art Pearl C Series Black ( Average particle size 6 μm, 15 μm, 22 μm, 32 μm), white (average particle size 6 μm, 15 μm, 22 μm, 32 μm), green (average particle size 15 μm), yellow (average particle size 15 μm), blue (average particle) Diameter 15 μm), red (average particle size 15 μm), art pearl MT series brown (average particle size 15 μm), ocher color (average particle size 15 μm), art pearl HI series black (average particle size 15 μm), white ( Average particle size 15 μm), Art Pearl HB series black (average particle size 8 μm, 15 μm), Art Pearl CH series red (average particle size 6 μm), Blue (average particle size 6 μm) (Negami Kogyo Co., Ltd.) Styrene / acrylonitrile, NKW 3903E, 3926E, 3904E, 3905E, 3902E, 3 08E, 3938E, 3976E, 3997E, 3947E, 3907E, 3307E, 3203E, 3226E, 3204E, 3205E, 3215E, 3202E, 3208E, 3277E, 3207E, 6013E, 6004E, 6005E, 6002E, 6008E, 6038E, 6038E, 6047E, 6007E (average particle size of 0.1 μm or less), C2103E, C2104E, C2105E, C2102E, C2108E, C2167E, C2147E, C2117E, 2103E, 2101E, 2104E, 2106E, 2106E, 2105E, 2102E, 2108E, 2167E, 2137E, 2127E, 2117E, 2107E, 2109E, 7002E, 70 12E, 7052E, 7003E, 7004E, 7004E, 7005E, 7026E, 7017E, 7047E, 7047E, 7067E, 7008E, 7038E, etc. The NKW-7500E series includes 7502E, 7517E, 7577E. 7518E, A-300E series, A-303E, A-301E, A-304E, A-305E, A-302E, A-308E, A-367E, A-347E, A-307E (above, average particle size of 0.4 μm or less) (above, manufactured by Nippon Fluorescent Chemical Co., Ltd.), Sinrohi Color SF-3022N, 3014N, 3015N, 3017N, 3037N, 3037N, 3038N 5012, 5013, 5014, 5015, 5017, 5027, No. 037, No. 5018 (above, average particle size 0.1 μm), No. 8012, No. 8014, No. 8015, No. 8017, No. 8037, No. 8028 (above, average particle size of 0.4 μm), Sinlohi color SP-13, 14, 15, 16, 17, 27, 37, 47 (above, average particle size around 1.0 μm), Sinroich color SW-111, 112, 113, 114, 115, 116, 107, 117, 127, 137, 147, 128 (above, average particle size 1.0 μm or less), FW-8512KS, 8514KS, 8505KS, 8506KS, 8537KS ( The average particle size is 3.5 μm or more and 4.5 μm or less) (manufactured by Sinloihi Co., Ltd.).
Further, colored resin particles obtained by dyeing resin particles with a basic dye can also be used. Specific examples thereof include C.I. I. Basic Red 1: 1 and C.I. I. Basic violet 11: 1 and C.I. I. Colored styrene / acrylonitrile resin particles (average particle size 0.1 μm) dyed with Basic Violet 15, C.I. I. Colored styrene-acrylonitrile resin particles (average particle size 0.1 μm) dyed with basic violet 11: 1, C.I. I. Basic Red 1: 1 and C.I. I. Yellow 28 and C.I. I. Basic Yellow 40 and C.I. I. Basic violet 11: 1 and C.I. I. Colored styrene / acrylonitrile resin particles (average particle size 0.1 μm) dyed with Basic Violet 15, C.I. I. Basic Red 1: 1 and C.I. I. Basic Yellow 28 and C.I. I. Basic Yellow 40 and C.I. I. Colored styrene-acrylonitrile resin particles (average particle size 0.1 μm) dyed with basic violet 11: 1, C.I. I. Basic Red 1: 1 and C.I. I. Basic Yellow 28 and C.I. I. Colored styrene / acrylonitrile resin particles (average particle diameter 0.1 μm) dyed with Basic Yellow 40, C.I. I. Basic Blue 3 and C.I. I. Colored styrene / acrylonitrile resin particles (average particle diameter 0.1 μm) dyed with Basic Yellow 40, C.I. I. Basic Blue 3 and C.I. I. Colored styrene / acrylonitrile resin particles (average particle diameter 0.1 μm) dyed with Basic Yellow 40, C.I. I. Colored styrene / acrylonitrile resin particles (average particle size 0.1 μm) dyed with Basic Blue 3, C.I. I. Basic Blue 7 and C.I. I. Colored styrene / acrylonitrile resin particles (average particle size 0.1 μm) dyed with Basic Violet 15, C.I. I. Basic Yellow 28 and C.I. I. Basic Yellow 40 and C.I. I. Examples thereof include colored styrene / acrylonitrile resin particles (average particle size 0.1 μm) dyed with Basic Violet 1.
　これら着色樹脂粒子の含有量は、インキ組成物全量に対し、０．５重量％以上５６．０重量％以下が好ましく、より好ましくは１．０重量％以上４０．０重量％以下であり、最も好ましくは３．０重量％以上３０．０重量％以下である。０．５重量％未満だと筆跡の発色が不十分で、５６．０重量％を越えると耐ペン先乾燥性に悪影響を与える恐れがある。 The content of these colored resin particles is preferably 0.5% by weight or more and 56.0% by weight or less, more preferably 1.0% by weight or more and 40.0% by weight or less based on the total amount of the ink composition. Preferably they are 3.0 weight% or more and 30.0 weight% or less. If it is less than 0.5% by weight, the color of the handwriting is insufficient, and if it exceeds 56.0% by weight, the pen-tip drying resistance may be adversely affected.
　上記塗布具において使用する水性インキに含有されるワックス粒子とは滑剤として使用可能な、主に２５℃の環境下において固体のワックスから得られる粒子である。 The wax particles contained in the water-based ink used in the applicator are particles obtained from solid wax that can be used as a lubricant, mainly in an environment of 25 ° C.
　上述の実施形態によれば、ワックス粒子は、着色樹脂粒子に対して平均粒子径が５％以上９５％以下であるので、着色樹脂粒子が紙の裏側から抜ける裏抜けが極力抑制できる。
　更に、着色樹脂粒子に対して平均粒子径が平均粒子径の３３％以上６７％以下の粒子径である場合には、ワックス粒子の凝集構造と、着色樹脂粒子の凝集構造との充填密度が一層大きくなり、着色樹脂粒子が紙の裏側から抜けることをより一層抑制できるため好ましい。 According to the above-described embodiment, the wax particles have an average particle diameter of 5% or more and 95% or less with respect to the colored resin particles, and therefore, it is possible to suppress the penetration of the colored resin particles from the back side of the paper as much as possible.
Further, when the average particle diameter is 33% or more and 67% or less of the average particle diameter with respect to the colored resin particles, the packing density of the aggregate structure of the wax particles and the aggregate structure of the colored resin particles is further increased. This is preferable because it becomes larger and the colored resin particles can be further prevented from coming off from the back side of the paper.
　尚、ワックス粒子の平均粒子径の測定は着色樹脂粒子同様にレーザ回折／散乱式粒子径分布測定装置（例えば、（株）島津製作所製；ＳＡＬＤ－７１００）、動的光散乱式粒度分布測定装置（例えば、大塚電子（株）製、ＥＬＳＺ－２０００Ｓ）、コールターカウンター（例えば、ベックマン・コールター（株）製、Ｍｕｌｔｉｓｉｚｅｒ　４ｅ）等を粒子径の範囲に応じて適宜使用して測定される。また平均粒子径は、粒子径の範囲に応じて適宜選択した装置より得られた数値を基に平均粒子径（メジアン径）を体積基準で算出した値を採用する。 The average particle size of the wax particles is measured by a laser diffraction / scattering particle size distribution measuring device (for example, manufactured by Shimadzu Corp .; SALD-7100) and a dynamic light scattering particle size distribution measuring device in the same manner as the colored resin particles. (For example, ELSZ-2000S manufactured by Otsuka Electronics Co., Ltd.), Coulter counter (for example, Multisizer 4e manufactured by Beckman Coulter Co., Ltd.) and the like are appropriately used according to the range of the particle diameter. As the average particle diameter, a value obtained by calculating the average particle diameter (median diameter) on a volume basis based on a numerical value obtained from an apparatus appropriately selected according to the range of the particle diameter is adopted.
　ワックス粒子に使用できるワックスとして、例えば、石油系ワックスとしては、パラフィンワックス、マイクロクリスタリンワックス、ペトロラタムなどが挙げられる。また、植物系ワックスとしては、カルナバワックス、キャンデリラワックス、ライスワックス、木ロウなどが挙げられる。また、動物系ワックスとしては、ラノリン、みつろうなどが挙げられる。
　合成炭化水素系ワックスとしては、ポリエチレンワックス、酸化ポリエチレンワックス、フィッシャー・トロプシュワックス、これらの誘導体などが挙げられる。これらのワックスは、単独、あるいは２種以上混合して使用しても良い。 Examples of the wax that can be used for the wax particles include petroleum wax such as paraffin wax, microcrystalline wax, and petrolatum. Examples of plant waxes include carnauba wax, candelilla wax, rice wax, and wood wax. Examples of animal waxes include lanolin and beeswax.
Examples of the synthetic hydrocarbon wax include polyethylene wax, oxidized polyethylene wax, Fischer-Tropsch wax, and derivatives thereof. These waxes may be used alone or in combination of two or more.
　ワックス粒子として酸化ポリエチレンワックス粒子を用いると繊維集束体、紙内部での移動性に優れ、着色樹脂粒子との移動速度差がより広がることでワックス粒子によって着色樹脂粒子の紙への過度な浸透を一層抑制できるため、酸化ポリエチレンワックス粒子の使用がより好ましい。 When polyethylene oxide wax particles are used as wax particles, the fiber bundling body, excellent mobility inside the paper, and the movement speed difference with the colored resin particles is further widened, so that the wax particles cause excessive penetration of the colored resin particles into the paper. The use of oxidized polyethylene wax particles is more preferred because it can be further suppressed.
　上記塗布具に使用する水性インキにおいて、ワックス粒子は市販のワックス粒子を用いても良いし、ワックスを水などの液媒体中で乳化分散などによって得られたものを用いても良い。
　ワックス粒子の具体例として、パラフィンワックス粒子として、ＳＥＬＯＳＯＬ　Ｒ－５８２（平均粒子径　０．２１μｍ）、同Ｒ－５８５（平均粒子径　０．２２μｍ）、同Ｒ－５８６（平均粒子径　０．２１μｍ）（以上、中京油脂（株）製）、変性パラフィンワックス粒子として、ＡＱＵＡＣＥＲ５３７（平均粒子径　０．０５μｍ）（以上、ビックケミー・ジャパン（株）製）、カルナバワックス粒子として、ＳＥＬＯＳＯＬ５２４（平均粒子径　０．０７μｍ）（以上、ビックケミー・ジャパン（株）製）、変性ポリエチレンワックス粒子として、ＣＥＲＡＦＬＯＵＲ９２５（平均粒子径　６μｍ）、同９２９（平均粒子径　８μｍ）、同９５０（平均粒子径　９μｍ）、同９８８（平均粒子径　６μｍ）、ＡＱＵＡＣＥＲ５３１（平均粒子径　０．１５μｍ）、同（μｍ）、同９９８（平均粒子径　５μｍ）（以上、ビックケミー・ジャパン（株）製）、ポリエチレンワックス粒子として、ＣＥＲＡＦＬＯＵＲ９９１（平均粒子径　５μｍ）、同９９６（平均粒子径　６μｍ）（以上、ビックケミー・ジャパン（株）製）、アマイドワックス粒子として、ＣＥＲＡＦＬＯＵＲ９９４（平均粒子径　５μｍ）（以上、ビックケミー・ジャパン（株）製）、酸化ポリエチレンワックス粒子として、ＡＱＵＡＣＥＲ５０７（平均粒子径　０．０４μｍ）、同５１５（平均粒子径　０．０４μｍ）（以上、ビックケミー・ジャパン（株）製）、ＨＹＴＥＣ　Ｅ－６５００（平均粒子径　０．０６μｍ）、同－９０１５（平均粒子径　０．０５μｍ）、同－６４００（平均粒子径　０．０５５μｍ）、同－８２３７（平均粒子径　０．０８μｍ）、同－５４０３Ｐ（平均粒子径　０．０５μｍ）、同－１０００（平均粒子径　０．１４μｍ）、同－４Ａ（平均粒子径　０．０６μｍ）（以上、東邦化学工業（株）製）、カルボキシル基含有エチレン系共重合体ワックス粒子として、ＨＹＴＥＣ　Ｓ－３１２１（平均粒子径　０．０３５μｍ）、同－３８００（平均粒子径　０．１μｍ）、同－９２４２（平均粒子径　０．０４μｍ）、同－９２００（平均粒子径　０．０４μｍ）、同－８５１２（平均粒子径　０．０８μｍ）、同－３１４８Ｋ（平均粒子径　０．０４５μｍ）（以上、東邦化学工業（株）製）、マイクロクリスタリンワックス粒子として、Ｍｉｃｈｅｍ　Ｌｕｂｅ　１２４（平均粒子径　０．０５μｍ）、ＰｒｏＨｅｒｅ　Ｌ９０１０９（平均粒子径　０．０５μｍ）（以上、Ｍｉｃｈｅｌｍａｎ，　Ｉｎｃ．製）が挙げられる。
　これらのワックス粒子の含有量は、インキ組成物全量に対し、０．１重量％以上５０．０重量％以下が好ましく、より好ましくは０．５重量％以上２３．０重量％以下であり、最も好ましくは１．０重量％以上１５．０重量％以下である。０．１重量％未満だと裏抜け抑制が不十分の恐れがあり、５０．０重量％を越えると水性インキ中での固形分が高くなりすぎて耐ペン先乾燥性に悪影響を与える恐れがある。 In the water-based ink used for the applicator, commercially available wax particles may be used as the wax particles, or a wax obtained by emulsifying and dispersing the wax in a liquid medium such as water may be used.
As specific examples of wax particles, SELOSOL R-582 (average particle size 0.21 μm), R-585 (average particle size 0.22 μm), and R-586 (average particle size 0.21 μm) are used as paraffin wax particles. (Above, manufactured by Chukyo Yushi Co., Ltd.), AQUACER 537 (average particle size 0.05 μm) (above, manufactured by Big Chemie Japan Co., Ltd.) as modified paraffin wax particles, SELOSOL 524 (average particle size 0. 0) as carnauba wax particles. 07 μm) (above, manufactured by Big Chemie Japan Co., Ltd.), modified polyethylene wax particles, CERAFLOUR 925 (average particle size 6 μm), 929 (average particle size 8 μm), 950 (average particle size 9 μm), 988 (average) Particle diameter 6 μm), AQUACER 531 (average particle diameter 0.1) (μm), the same (μm), the same 998 (average particle size 5 μm) (manufactured by Big Chemie Japan Co., Ltd.), polyethylene wax particles, CERAFLOUR991 (average particle size 5 μm), 996 (average particle size 6 μm) ( Above, manufactured by Big Chemie Japan Co., Ltd.), CERAFLOUR 994 (average particle size of 5 μm) as amide wax particles (above, manufactured by Big Chemie Japan Co., Ltd.), and AQUACER 507 (average particle size of 0.04 μm) as oxidized polyethylene wax particles 515 (average particle size 0.04 μm) (above, manufactured by Big Chemie Japan Co., Ltd.), HYTEC E-6500 (average particle size 0.06 μm), -9015 (average particle size 0.05 μm), 6400 (average particle size 0.055 μm), -8237 (average particle size) 0.08 μm), -5403P (average particle size 0.05 μm), -1000 (average particle size 0.14 μm), -4A (average particle size 0.06 μm) (above, manufactured by Toho Chemical Co., Ltd.) ), Carboxyl group-containing ethylene copolymer wax particles as HYTEC S-3121 (average particle size 0.035 μm), −3800 (average particle size 0.1 μm), and −9242 (average particle size 0.04 μm) -9200 (average particle size 0.04 μm), -8512 (average particle size 0.08 μm), -3148 K (average particle size 0.045 μm) (above, manufactured by Toho Chemical Co., Ltd.), microcrystalline As wax particles, Michem Lube 124 (average particle size 0.05 μm), ProHere L90109 (average particle size 0.05 μm) (above, Mi helman, Inc. Manufactured).
The content of these wax particles is preferably 0.1% by weight or more and 50.0% by weight or less, more preferably 0.5% by weight or more and 23.0% by weight or less based on the total amount of the ink composition. Preferably they are 1.0 weight% or more and 15.0 weight% or less. If it is less than 0.1% by weight, there is a risk that the showthrough suppression may be insufficient, and if it exceeds 50.0% by weight, the solid content in the water-based ink may become too high, which may adversely affect the nib drying resistance. is there.
　ワックス粒子を作製する場合、目的の粒子径に適した機械的乳化法、転相乳化法、液晶乳化法、Ｄ相乳化法などの乳化方法やジェットミルなどの機械的粉砕方法や温度の違いによる溶解度の差などによる析出方法を用いて作製すればよいが、ワックス粒子の表面積を最小限にすることで、繊維集束体中や紙内部で形成している複雑な曲路を移動しやすいため、乳化方法によってワックス粒子を作製する事が好ましい。 When producing wax particles, depending on the difference in temperature, such as mechanical emulsification method, phase inversion emulsification method, liquid crystal emulsification method, D phase emulsification method, etc., mechanical milling method such as jet mill, etc. It may be prepared using a precipitation method due to differences in solubility, etc., but by minimizing the surface area of the wax particles, it is easy to move the complicated curved path formed in the fiber bundle or inside the paper, It is preferable to prepare wax particles by an emulsification method.
　幾つかの実施形態では、着色樹脂粒子の添加量をｘ重量％、ワックス粒子の添加量をｙ重量％としたとき、それぞれの粒子の添加量の割合が、
（式１）－０．１２ｘ＋２３．０≧ｙ＞－０．１２ｘ＋６．８
の関係を満たす。
　上記塗布具では、水性インキのうち平均粒子径が相対的に小さいワックス粒子を含む成分が、水性インキのうち着色樹脂粒子を含む成分に先行して紙に浸透する傾向がある。ここで、ワックス粒子および着色樹脂粒子は、何れも、紙を構成する繊維（例えば、セルロース繊維）に比べて親水性が低く、水性インキの紙への浸透に際して、ワックス粒子及び着色樹脂粒子の移動速度は水に比べて遅い。このため、紙の内部に進むに従って、液媒体としての水が少なくなり、ワックス粒子又は着色樹脂粒子が最密充填に近似していって、凝集体間の引力が働き、見かけ上嵩高くなって紙繊維内を移動しにくくなる。その結果、着色樹脂粒子が内部に進むにしたがって凝集構造を形成し、既に形成されたワックス粒子の凝集構造と着色樹脂粒子の凝集構造とが重なり、着色樹脂粒子が紙の裏側から抜けることを効果的に抑制することができる。特に、上述の（式１）を満たす場合、着色樹脂粒子を含む水性インキ成分の浸透に先立ってワックス粒子の凝集構造を適切に形成することが可能となり、ワックス粒子の凝集構造と着色樹脂粒子の凝集構造とを効果的に重なり合わせて、着色樹脂粒子が紙の裏側から抜けることを一層抑制することが可能である。
　なお、ｘが３．０重量％以上３０．０重量％以下、ｙが１．０重量％以上１５．０重量％以下であると更に好ましい。
　ｙが（式１）の範囲を越えるとペン先において粒子の目詰まりが発生しやすく、耐ペン先乾燥性を向上する添加剤を用いても耐ペン先乾燥性が向上しない恐れがあり、ｙが（式１）の範囲を越えないことが好ましい。 In some embodiments, when the addition amount of the colored resin particles is x wt% and the addition amount of the wax particles is y wt%, the ratio of the addition amount of each particle is
(Formula 1) −0.12x + 23.0 ≧ y> −0.12x + 6.8
Satisfy the relationship.
In the above applicator, the component containing wax particles having a relatively small average particle diameter in the aqueous ink tends to penetrate into the paper prior to the component containing the colored resin particles in the aqueous ink. Here, the wax particles and the colored resin particles are both less hydrophilic than the fibers constituting the paper (for example, cellulose fibers), and the movement of the wax particles and the colored resin particles when the aqueous ink penetrates into the paper. The speed is slower than water. For this reason, as it proceeds to the inside of the paper, water as a liquid medium decreases, wax particles or colored resin particles approximate close-packed packing, attracting force between aggregates, and apparently bulky. It becomes difficult to move in the paper fiber. As a result, an aggregated structure is formed as the colored resin particles progress to the inside, and the aggregated structure of the wax particles already formed overlaps with the aggregated structure of the colored resin particles, so that the colored resin particles are removed from the back side of the paper. Can be suppressed. In particular, when satisfying the above (Equation 1), it becomes possible to appropriately form the aggregate structure of the wax particles prior to the penetration of the water-based ink component containing the colored resin particles. It is possible to effectively overlap the aggregated structure and further suppress the colored resin particles from coming out from the back side of the paper.
It is more preferable that x is 3.0 wt% or more and 30.0 wt% or less, and y is 1.0 wt% or more and 15.0 wt% or less.
If y exceeds the range of (Formula 1), clogging of particles is likely to occur in the nib, and there is a possibility that the nib drying resistance may not be improved even if an additive that improves the nib drying resistance is used. Preferably does not exceed the range of (Formula 1).
　更に、着色樹脂粒子の添加量、ワックス粒子の添加量との関係が、
（式２）－０．１２ｘ＋１５．０≧ｙ＞－０．１２ｘ＋８．０
の関係を満たすとき、着色樹脂粒子とワックス粒子の割合になったときにワックス粒子の凝集構造に着色樹脂粒子の凝集構造の重なりが一層密になり、ワックス粒子と着色樹脂粒子との距離が最接近することでお互いの引力が最大限増大し、構造同士の凝集作用が最も強く働くと推察されるため、着色樹脂粒子が紙の裏側から抜けることをより一層抑制するため更に好ましい。
　ｙが（式２）の範囲を越えるとペン先において粒子の目詰まりの恐れがわずかにあり、耐ペン先乾燥性を向上する添加剤を用いても十分に耐ペン先乾燥性が発揮できない恐れがあるが、ｙが（式２）の関係を満たすことで耐ペン先乾燥性の向上が十分に発揮されるため好ましい。 Furthermore, the relationship between the amount of colored resin particles added and the amount of wax particles added is
(Formula 2) −0.12x + 15.0 ≧ y> −0.12x + 8.0
When the ratio of the colored resin particles to the wax particles is satisfied, the aggregated structure of the colored resin particles overlaps with the aggregated structure of the wax particles more closely, and the distance between the wax particles and the colored resin particles is the shortest. By approaching each other, the mutual attractive force increases to the maximum, and it is presumed that the cohesive action between the structures works most strongly. Therefore, it is further preferable to further suppress the colored resin particles from coming out from the back side of the paper.
If y exceeds the range of (Formula 2), there is a slight possibility of clogging of particles at the nib, and even if an additive that improves the nib drying resistance is used, the nib drying resistance may not be sufficiently exhibited. However, it is preferable that y satisfies the relationship of (Formula 2), since the improvement of the resistance to drying of the nib is sufficiently exhibited.
　上記塗布具に使用する水性インキにおいて、着色樹脂粒子の添加量が、インキ組成物全量に対し、０．５重量％以上５６．０重量％以下が好ましく、より好ましくは１．０重量％以上４０．０重量％以下であり、最も好ましくは３．０重量％以上３０．０重量％以下であり、且つ、ワックス粒子の含有量が、インキ組成物全量に対し、０．１重量％以上５０．０重量％以下が好ましく、より好ましくは０．５重量％以上２３．０重量％以下であり、最も好ましくは１．０重量％以上１５．０重量％以下である。更に、この着色樹脂粒子の添加量ｘに対するワックス粒子の添加量ｙの割合ｙ／ｘが０．０２以上２１以下、より好ましくは０．４２以上１．６以下であることによって、繊維集束体である塗布先を通過して吐出される粒子のバランスが最適となり、筆跡上で最密充填状態を形成しやすく、高い発色性と裏抜け抑制効果の両立された筆跡が形成される。 In the water-based ink used for the applicator, the amount of the colored resin particles is preferably 0.5% by weight or more and 56.0% by weight or less, more preferably 1.0% by weight or more and 40% by weight based on the total amount of the ink composition. 0.0% by weight or less, most preferably 3.0% by weight or more and 30.0% by weight or less, and the content of the wax particles is 0.1% by weight or more and 50.50% or less based on the total amount of the ink composition. It is preferably 0% by weight or less, more preferably 0.5% by weight or more and 23.0% by weight or less, and most preferably 1.0% by weight or more and 15.0% by weight or less. Further, the ratio y / x of the addition amount y of the wax particles to the addition amount x of the colored resin particles is 0.02 or more and 21 or less, more preferably 0.42 or more and 1.6 or less. The balance of the particles ejected through a certain coating destination is optimal, and it is easy to form a close-packed state on the handwriting, so that a handwriting having both high color developability and a back-through suppression effect is formed.
　上記塗布具に使用する水性インキにおいて、水としては、水道水、地下水、イオン交換水、純水、超純水などが挙げられ、特に限定されることなく使用できる。中でも、イオン交換水、純水が好ましい。 In the water-based ink used for the applicator, examples of water include tap water, ground water, ion exchange water, pure water, and ultrapure water, and can be used without any particular limitation. Among these, ion exchange water and pure water are preferable.
　上記塗布具に使用する水性インキに、水溶性有機溶剤を用いることができる。
　この水溶性有機溶剤とは、水１００ｇに対して１０ｇ以上溶解することのできる有機溶剤を指す。 A water-soluble organic solvent can be used for the water-based ink used in the applicator.
This water-soluble organic solvent refers to an organic solvent capable of dissolving 10 g or more with respect to 100 g of water.
　水溶性有機溶剤の具体例としては、多価アルコールとして、グリセリン、ジグリセリン、トリグリセリン、テトラグリセリン、ヘキシレングリコール、チオジエチレングリコール、１，２，６－ヘキサントリオール、トリメチロールプロパン、エチレングリコール、プロピレングリコール、ジエチレングリコール、トリエチレングリコール、テトラエチレングリコール、ペンタエチレングリコール、ジプロピレングリコール、トリプロピレングリコール、２－ブテン－１，４－ジオール、２－エチル－１，３－ヘキサンジオール、２－メチル－２，４－ペンタンジオール、１，２－オクタンジオール、１，２－ヘキサンジオール、１，２－ペンタンジオール、４－メチル－１，２－ペンタンジオール、１，３－ブタンジオール、２，３－ブタンジオール、１，４－ブタンジオール、３－メチル－１，３－ブタンジオール、１，３－プロパンジオール、１，４－ブタンジオール、１，５－ペンタンジオール、１，６－ヘキサンジオール、１，２，４－ブタントリオール、等が挙げられ、１価のアルコールとして、エタノール、メタノール、ブタノール、プロパノール、イソプロパノールなどの炭素数１～４のもの、などが挙げられ、グリコールエーテルとしては、エチレングリコールモノメチルエーテル、エチレングリコールモノエチルエーテル、エチレングリコールモノブチルエーテル、エチレングリコールジメチルエーテル、エチレングリコールジエチルエーテル、エチレングリコールエチルメチルエーテル、エチレングリコールモノメチルエーテルアセテート、ジエチレングリコールモノメチルエーテル、ジエチレングリコールモノエチルエーテル、ジエチレングリコールモノ－ｎ－プロピルエーテル、エチレングリコールモノ－ｉｓｏ－プロピルエーテル、ジエチレングリコールモノ－ｉｓｏ－プロピルエーテル、エチレングリコールモノ－ｎ－ブチルエーテル、エチレングリコールモノ－ｔ－ブチルエーテル、ジエチレングリコールモノ－ｔ－ブチルエーテル、１－メチル－１－メトキシブタノール、ジエチレングリコールジメチルグリコール、ジエチレングリコールエチルメチルエーテル、ジエチレングリコールジエチルエーテル、トリエチレングリコールジメチルエーテル、プロピレングリコールモノメチルエーテル、プロピレングリコールモノエチルエーテル、プロピレングリコールモノ－ｔ－ブチルエーテル、プロピレングリコールモノ－ｎ－プロピルエーテル、プロピレングリコールモノ－ｉｓｏ－プロピルエーテル、ジプロピレングリコールモノメチルエーテル、ジプロピレングリコールモノエチルエーテル、ジプロピレングリコールモノ－ｎ－プロピルエーテル、ジプロピレングリコールモノ－ｉｓｏ－プロピルエーテル、ジプロピレングリコールジメチルエーテル、などが挙げられ、環状構造を持つ水溶性有機溶剤としては、１，３－ジオキソラン、１，４－ジオキソラン、テトラヒドロフラン、２－メチルテトラヒドロフラン、２－ピロリドン、Ｎ－メチル－２－ピロリドン、Ｎ－エチル－２－ピロリドン、Ｎ－プロピル－２－ピロリドン、Ｎ－ブチル－２－ピロリドン、Ｎ－シクロヘキシル－２－ピロリドン、スルホラン、γ－ブチロラクトン、１，３－ジメチル－２－イミダゾリジノン、炭酸エチレン、炭酸プロピレン、などが挙げられ、その他としては、ホルムアミド、アセトアミド、ジメチルスルホキシド、アセチン、ジアセチン、トリアセチン、などが挙げられる。
　これらの水溶性有機溶剤の中でも、筆跡の紙への浸透性と耐ペン先乾燥性向上の観点から、ジエチレングリコール、トリエチレングリコール、スルホランを使用することが好ましく、ジエチレングリコール、トリエチレングリコールから単独、あるいは２種以上混合して使用し、更にスルホランを併用すると耐ペン先乾燥性を高い状態で満足しながら着色樹脂粒子とワックス粒子を紙内部へ浸透させることが出来るため、筆跡の速乾性と裏抜け抑制と耐ペン先乾燥抑制効果を両立することが可能になる。 Specific examples of water-soluble organic solvents include polyhydric alcohols such as glycerin, diglycerin, triglycerin, tetraglycerin, hexylene glycol, thiodiethylene glycol, 1,2,6-hexanetriol, trimethylolpropane, ethylene glycol, propylene. Glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, pentaethylene glycol, dipropylene glycol, tripropylene glycol, 2-butene-1,4-diol, 2-ethyl-1,3-hexanediol, 2-methyl-2 , 4-pentanediol, 1,2-octanediol, 1,2-hexanediol, 1,2-pentanediol, 4-methyl-1,2-pentanediol, 1,3-butanediol, 2,3-butane Diol, 1,4-butanediol, 3-methyl-1,3-butanediol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1, 2,4-butanetriol and the like, and monovalent alcohols include those having 1 to 4 carbon atoms such as ethanol, methanol, butanol, propanol, and isopropanol. The glycol ether includes ethylene glycol monomethyl. Ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, ethylene glycol ethyl methyl ether, ethylene glycol monomethyl ether acetate, diethylene glycol Monoethyl ether, diethylene glycol monoethyl ether, diethylene glycol mono-n-propyl ether, ethylene glycol mono-iso-propyl ether, diethylene glycol mono-iso-propyl ether, ethylene glycol mono-n-butyl ether, ethylene glycol mono-t-butyl ether , Diethylene glycol mono-t-butyl ether, 1-methyl-1-methoxybutanol, diethylene glycol dimethyl glycol, diethylene glycol ethyl methyl ether, diethylene glycol diethyl ether, triethylene glycol dimethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol mono- t-Butyl ether Propylene glycol mono-n-propyl ether, propylene glycol mono-iso-propyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol mono-n-propyl ether, dipropylene glycol mono-iso- Examples of water-soluble organic solvents having a cyclic structure include 1,3-dioxolane, 1,4-dioxolane, tetrahydrofuran, 2-methyltetrahydrofuran, 2-pyrrolidone, and N-methyl. -2-pyrrolidone, N-ethyl-2-pyrrolidone, N-propyl-2-pyrrolidone, N-butyl-2-pyrrolidone, N-cyclohexyl-2-pyrrolidone, sulfolane, γ-buty Lactone, 1,3-dimethyl-2-imidazolidinone, ethylene carbonate, propylene carbonate, are like, as the other, formamide, acetamide, dimethyl sulfoxide, acetin, diacetin, triacetin, and the like.
Among these water-soluble organic solvents, it is preferable to use diethylene glycol, triethylene glycol, or sulfolane from the viewpoint of penetrability of handwriting into paper and improvement in resistance to drying of the nib, or from diethylene glycol or triethylene glycol alone, or Mixing two or more types and using sulfolane together allows the colored resin particles and wax particles to penetrate into the paper while satisfying the high resistance to pen tip dryness. It is possible to achieve both suppression and anti-pen-tip drying suppression effects.
　これらの水溶性有機溶剤の添加量は、水性インキ全量に対し０．１重量％以上５０．０重量％以下が好ましく、５．０重量％以上２０．０重量％以下がより好ましい。これらの水溶性有機溶剤は、単独、あるいは２種以上混合して使用しても良い。 The amount of these water-soluble organic solvents added is preferably 0.1% by weight or more and 50.0% by weight or less, and more preferably 5.0% by weight or more and 20.0% by weight or less based on the total amount of the water-based ink. These water-soluble organic solvents may be used alone or in combination of two or more.
　上記塗布具に使用する水性インキにおいて、着色樹脂粒子以外の着色剤として、速乾性、裏抜けに悪影響を与えない範囲で染料、顔料及び、その両方を使用しても良い。 In the water-based ink used for the applicator, as a colorant other than the colored resin particles, a dye, a pigment, or both may be used as long as they do not adversely affect the quick-drying and back-through.
　染料は、水溶性染料が使用できる。水溶性染料の具体的としては、直接染料、酸性染料、塩基性染料などが挙げられる。直接染料の具体例としては、ジャパノールファストブラックＤコンク（Ｃ．Ｉ．ダイレクトブラック１７）、ウォーターブラック１００Ｌ（同１９）、ウォーターブラックＬ－２００（同１９）、ダイレクトファストブラックＢ（同２２）、ダイレクトファストブラックＡＢ（同３２）、ダイレクトディープブラックＥＸ（同３８）、ダイレクトファストブラックコンク（同５１）、カヤラススプラグレイＶＧＮ（同７１）、カヤラスダイレクトブリリアントエローＧ（Ｃ．Ｉ．ダイレクトエロー４）、ダイレクトファストエロー５ＧＬ（同２６）、アイゼンプリムラエローＧＣＬＨ（同４４）、ダイレクトファストエローＲ（同５０）、アイゼンダイレクトファストレッドＦＨ（Ｃ．Ｉ．ダイレクトレッド１）、ニッポンファストスカーレットＧＳＸ（同４）、ダイレクトファストスカーレット４ＢＳ（同２３）、アイゼンダイレクトローデュリンＢＨ（同３１）、ダイレクトスカーレットＢ（同３７）、カヤクダイレクトスカーレット３Ｂ（同３９）、アイゼンプリムラピンク２ＢＬＨ（同７５）、スミライトレッドＦ３Ｂ（同８０）、アイゼンプリムラレッド４ＢＨ（同８１）、カヤラススプラルビンＢＬ（同８３）、カヤラスライトレッドＦ５Ｇ（同２２５）、カヤラスライトレッドＦ５Ｂ（同２２６）、カヤラスライトローズＦＲ（同２２７）、ダイレクトスカイブルー６Ｂ（Ｃ．Ｉ．ダイレクトブルー１）、ダイレクトスカイブルー５Ｂ（同１５）、スミライトスプラブルーＢＲＲコンク（同７１）、ダイボーゲンターコイズブルーＳ（同８６）、ウォーターブルー＃３（同８６）、カヤラスターコイズブルーＧＬ（同８６）、カヤラススプラブルーＦＦ２ＧＬ（同１０６）、カヤラススプラターコイズブルーＦＢＬ（同１９９）などが挙げられる。
　酸性染料の具体例としては、アシッドブルーブラック１０Ｂ（Ｃ．Ｉ．アシッドブラック１）、ニグロシン（同２）、スミノールミリングブラック８ＢＸ（同２４）、カヤノールミリングブラックＶＬＧ（同２６）、スミノールファストブラックＢＲコンク（同３１）、ミツイナイロンブラックＧＬ（同５２）、アイゼンオパールブラックＷＨエクストラコンク（同５２）、スミランブラックＷＡ（同５２）、ラニルブラックＢＧエクストラコンク（同１０７）、カヤノールミリングブラックＴＬＢ（同１０９）、スミノールミリングブラックＢ（同１０９）、カヤノールミリングブラックＴＬＲ（同１１０）、アイゼンオパールブラックニューコンク（同１１９）、ウォーターブラック１８７－Ｌ（同１５４）、カヤクアシッドブリリアントフラビンＦＦ（Ｃ．Ｉ．アシッドエロー７：１）、カヤシルエローＧＧ（同１７）、キシレンライトエロー２Ｇ１４０％（同１７）、スミノールレベリングエローＮＲ（同１９）、ダイワタートラジン（同２３）、カヤクタートラジン（同２３）、スミノールファストエローＲ（同２５）、ダイアシッドライトエロー２ＧＰ（同２９）、スミノールミリングエローＯ（同３８）、スミノールミリングエローＭＲ（同４２）、ウォーターエロー＃６（同４２）、カヤノールエローＮＦＧ（同４９）、スミノールミリングエロー３Ｇ（同７２）、スミノールファストエローＧ（同６１）、スミノールミリングエローＧ（同７８）、カヤノールエローＮ５Ｇ（同１１０）、スミノールミリングエロー４Ｇ２００％（同１４１）、カヤノールエローＮＧ（同１３５）、カヤノールミリングエロー５ＧＷ（同１２７）、カヤノールミリングエロー６ＧＷ（同１４２）、スミトモファストスカーレットＡ（Ｃ．Ｉ．アシッドレッド８）、カヤクシルクスカーレット（同９）、ソーラールビンエクストラ（同１４）、ダイワニューコクシン（同１８）、アイゼンボンソーＲＨ（同２６）、ダイワ赤色２号（同２７）、スミノールレベリングブリリアントレッドＳ３Ｂ（同３５）、カヤシルルビノール３ＧＳ（同３７）、アイゼンエリスロシン（同５１）、カヤクアシッドローダミンＦＢ（同５２）、スミノールレベリングルビノール３ＧＰ（同５７）、ダイアシッドアリザリンルビノールＦ３Ｇ２００％（同８２）、アイゼンエオシンＧＨ（同８７）、ウォーターピンク＃２（同９２）、アイゼンアシッドフロキシンＰＢ（同９２）、ローズベンガル（同９４）、カヤノールミリングスカーレットＦＧＷ（同１１１）、カヤノールミリングルビン３ＢＷ（同１２９）、スミノオールミリングブリリアントレッド３ＢＮコンク（同１３１）、スミノールミリングブリリアントレッドＢＳ（同１３８）、アイゼンオパールピンクＢＨ（同１８６）、スミノールミリングブリリアントレッドＢコンク（同２４９）、カヤクアシッドブリリアントレッド３ＢＬ（同２５４）、カヤクアシッドブリリドブリリアントレッドＢＬ（同２６５）、カヤノールミリングレッドＧＷ（同２７６）、ミツイアシッドバイオレット６ＢＮ（Ｃ．Ｉ．アシッドバイオレット１５）、ミツイアシッドバイオレットＢＮ（同１７）、スミトモパテントピュアブルーＶＸ（Ｃ．Ｉ．アシッドブルー１）、ウォーターブルー＃１０６（同１）、パテントブルーＡＦ（同７）、ウォーターブルー＃９（同９）、ダイワ青色１号（同９）、スプラノールブルーＢ（同１５）、オリエントソルブルブルーＯＢＣ（同２２）、スミノールレベリングブルー４ＧＬ（同２３）、ミツイナイロンファストブルーＧ（同２５）、カヤシルブルーＡＧＧ（同４０）、カヤシルブルーＢＲ（同４１）、ミツイアリザリンサフィロールＳＥ（同４３）、スミノールレベリングスカイブルーＲエクストラコンク（同６２）、ミツイナイロンファストスカイブルーＢ（同７８）、スミトモブリリアントインドシアニン６Ｂｈ／ｃ（同８３）、サンドランシアニンＮ－６Ｂ３５０％（同９０）、ウォーターブルー＃１１５（同９０）、オリエントソルブルブルーＯＢＢ（同９３）、スミトモブリリアントブルー５Ｇ（同１０３）、カヤノールミリングウルトラスカイＳＥ（同１１２）、カヤノールミリングシアニン５Ｒ（同１１３）、アイゼンオパールブルー２ＧＬＨ（同１５８）、ダイワギニアグリーンＢ（Ｃ．Ｉ．アシッドグリーン３）、アシッドブリリアントミリンググリーンＢ（同９）、ダイワグリーン＃７０（同１６）、カヤノールシアニングリーンＧ（同２５）、スミノールミリンググリーンＧ（同２７）、などが挙げられる。
　塩基性染料の具体例としては、アイゼンカチロンイエロー３ＧＬＨ（Ｃ．Ｉ．ベーシックイエロー１１）、アイゼンカチロンブリリアントイエロー５ＧＬＨ（同１３）、スミアクリルイエローＥ－３ＲＤ（同１５）、マキシロンイエロー２ＲＬ（同１９）、アストラゾンイエロー７ＧＬＬ（同２１）、カヤクリルゴールデンイエローＧＬ－ＥＤ（同２８）、ブライトイエロー３Ｇコンク（同４０）、アストラゾンイエロー５ＧＬ（同５１）、アイゼンカチロンオレンジＧＬＨ（Ｃ．Ｉ．ベーシックオレンジ２１）、アイゼンカチロンブラウン３ＧＬＨ（同３０）、ローダミン６ＧＣＰ（Ｃ．Ｉ．ベーシックレッド１）、ローダミン５９０クロリド（同１：１）、アイゼンアストラフロキシン（同１２）、スミアクリルブリリアントレッドＥ－２Ｂ（同１５）、アストラゾンレッドＧＴＬ（同１８）、アイゼンカチロンブリリアントピンクＢＧＨ（同２７）、マキシロンレッドＧＲＬ（同４６）、アイゼンメチルバイオレット（Ｃ．Ｉ．ベーシックバイオレット１）、アイゼンクリスタルバイオレット（同３）、アイゼンローダミンＢ（同１０）、ローダミンＡ（同１１：１）、Ｃ．Ｉ．ベーシックバイオレット１５、アストラゾンブルーＧ（Ｃ．Ｉ．ベーシックブルー１）、アストラゾンブルーＢＧ（同３）、ビクトリアピュアブルーＢＯ（同７）、メチレンブルー（同９）、マキシロンブルーＧＲＬ（同４１）、アイゼンカチロンブルーＢＲＬＨ（同５４）、アイゼンダイヤモンドグリーンＧＨ（Ｃ．Ｉ．ベーシックグリーン１）、アイゼンマラカイトグリーン（同４）、ビスマルクブラウンＧ（Ｃ．Ｉ．ベーシックブラウン１）などが挙げられる。これらの染料は、単独、あるいは２種以上混合して使用しても良い。 A water-soluble dye can be used as the dye. Specific examples of water-soluble dyes include direct dyes, acid dyes, and basic dyes. Specific examples of direct dyes include Japan Fast Black D Conch (CI Direct Black 17), Water Black 100L (19), Water Black L-200 (19), Direct Fast Black B (22) Direct Fast Black AB (32), Direct Deep Black EX (38), Direct Fast Black Conk (51), Kayala Spragley VGN (71), Kayalas Direct Brilliant Yellow G (CI Direct) Yellow 4), Direct Fast Yellow 5GL (same 26), Eisen Primula Yellow GCLH (same 44), Direct Fast Yellow R (same 50), Eisen Direct Fast Red FH (CI Direct Red 1), Nippon Fast Scare GSX (same 4), Direct Fast Scarlet 4BS (same 23), Eisen Direct Rhodulin BH (same 31), Direct Scarlet B (same 37), Kayak Direct Scarlet 3B (same 39), Eisen Primula Pink 2BLH (same as above) 75), Sumilite Red F3B (80), Eisen Primula Red 4BH (81), Kayara Spral Bin BL (83), Kayara Light Red F5G (225), Kayara Light Red F5B (226) , Kayara Light Rose FR (227), Direct Sky Blue 6B (CI Direct Blue 1), Direct Sky Blue 5B (15), Sumilite Splash Blue BRR Conch (71), Dibogen Turquoise Blue S (86), Water Blue # (The 86), Kaya Las Turquoise GL (the 86), Kaya Las Supra Blue FF2GL (the 106), Kaya Las Supra Turquoise Blue FBL (the 199), and the like.
Specific examples of acid dyes include Acid Blue Black 10B (CI Acid Black 1), Nigrosine (2), Suminol Milling Black 8BX (24), Kayanol Milling Black VLG (26), Suminol Fast Black BR Conch (31), Mitsui Nylon Black GL (52), Eisen Opal Black WH Extra Conque (52), Sumilan Black WA (52), Ranil Black BG Extra Conk (107), Kayanol Milling Black TLB (109), Suminol Milling Black B (109), Kayanol Milling Black TLR (110), Eisen Opal Black New Conk (119), Water Black 187-L (154), Kayaqua Acid Brillian Flavin FF (CI Acid Yellow 7: 1), Kayasil Yellow GG (17), Xylene Light Yellow 2G 140% (17), Suminol Leveling Yellow NR (19), Daiwa Tarrazine (23), Kaya Cutter Torrazine (same 23), Suminoll Fast Yellow R (same 25), Diacid Light Yellow 2GP (same 29), Suminol Milling Yellow O (same 38), Suminol Milling Yellow MR (same 42), Water Yellow # 6 (42), Kayanol Yellow NFG (49), Suminol Milling Yellow 3G (72), Suminol Fast Yellow G (61), Suminol Milling Yellow G (78), Kayanol N5G (Same 110), Suminoll Milling Yellow 4G 200% (Same 141), Kayanor Yellow G (135), Kayanol Milling Yellow 5 GW (127), Kayanol Milling Yellow 6 GW (142), Sumitomo Fast Scarlet A (CI Acid Red 8), Kayak Silk Scarlet (9), Solar Rubin Extra (14), Daiwa New Coxin (18), Eisenbonso RH (26), Daiwa Red No. 2 (27), Suminol Leveling Brilliant Red S3B (35), Kayasil Rubinol 3GS ( 37), Eisen Erythrosine (51), Kayaqua Acid Rhodamine FB (52), Suminol Leveling Lubinol 3GP (57), Diacid Alizarin Rubinol F3G 200% (82), Eisen Eosin GH (87) , Water Pink # 2 (92), Aizen Acid Phloxine PB (92), Rose Bengal (94), Kayanol Milling Scarlet FGW (111), Kayanol Milling Rubin 3BW (129), Suminoall Milling Brilliant Red 3BN Conch (131), Suminol Milling Brilliant Red BS (138), Eisen Opal Pink BH (186), Suminoll Milling Brilliant Red B Conch (249), Kayaku Acid Brilliant Red 3BL (254), Kayaku Acid Brilliant Red BL (265) Kayanol Milling Red GW (276), Mitsui Acid Violet 6BN (C.I. I. Acid Violet 15), Mitsui Acid Violet BN (17), Sumitomo Patent Pure Blue VX (CI Acid Blue 1), Water Blue # 106 (1), Patent Blue AF (7), Water Blue # 9 (Same 9), Daiwa Blue No. 1 (same 9), Supranol Blue B (same 15), Orient Soluble Blue OBC (same 22), Suminol Leveling Blue 4GL (same 23), Mitsui Nylon Fast Blue G (same as above) 25), Kayasil Blue AGG (40), Kayasil Blue BR (41), Mitsui Alizarin Saphirol SE (43), Suminol Leveling Sky Blue R Extraconk (62), Mitsui Nylon Fast Sky Blue B (78) , Sumitomo Brilliant Indocyanine 6Bh / 83), Sandlancyanine N-6B 350% (90), Water Blue # 115 (90), Orient Soluble Blue OBB (93), Sumitomo Brilliant Blue 5G (103), Kayanol Milling Ultra Sky SE (112), Kyanol Milling Cyanine 5R (113), Eisen Opal Blue 2GLH (158), Daiwa Guinea Green B (CI Acid Green 3), Acid Brilliant Milling Green B (9), Daiwa Examples include Green # 70 (same 16), Cyanol Cyanine Green G (same 25), Suminol Milling Green G (same 27), and the like.
Specific examples of basic dyes include Eisen Katylon Yellow 3GLH (CI Basic Yellow 11), Eisen Katylon Brilliant Yellow 5GLH (same 13), Sumiacryl Yellow E-3RD (same 15), Maxilon Yellow 2RL (19), Astrazon Yellow 7GLL (21), Kayacrill Golden Yellow GL-ED (28), Bright Yellow 3G Conch (40), Astrazon Yellow 5GL (51), Eisen Catillon Orange GLH ( CI Basic Orange 21), Eisen Catiron Brown 3GLH (30), Rhodamine 6GCP (CI Basic Red 1), Rhodamine 590 Chloride (1: 1), Eisen Astrafloxin (12), Sumi Acrylic Brilliant Red E- B (same 15), Astrazone Red GTL (same 18), Eisen Cachiron Brilliant Pink BGH (same 27), Maxilon Red GRL (same 46), Eisen Methyl Violet (CI Basic Violet 1), Eisen Crystal Violet (3), Eisen Rhodamine B (10), Rhodamine A (11: 1), C.I. I. Basic Violet 15, Astrazone Blue G (CI Basic Blue 1), Astrazone Blue BG (3), Victoria Pure Blue BO (7), Methylene Blue (9), Maxilon Blue GRL (41) Eisen Cachilon Blue BRLH (54), Eisen Diamond Green GH (CI Basic Green 1), Eisen Malachite Green (4), Bismarck Brown G (CI Basic Brown 1), and the like. These dyes may be used alone or in combination of two or more.
　顔料の具体例としては、ファーネストブラック、コンタクトブラック、サーマルブラック、アセチレンブラックなどのカーボンブラック、黒色酸化鉄、黄色酸化鉄、赤色酸化鉄、群青、紺青、コバルトブルー、チタンイエロー、ターコイズ、モリブデートオレンジ、酸化チタン、金粉、銀粉、銅粉、アルミニウム粉、真鍮粉、錫粉、雲母系顔料、Ｃ．Ｉ．ＰＩＧＭＥＮＴ　ＲＥＤ　２、同３、同５、同１７、同２２、同３８、同４１、同４８：２、同４８：３、同４９、同５０：１、同５３：１、同５７：１、同５８：２、同６０、同６３：１、同６３：２、同６４：１、同８８、同１１２、同１２２、同１２３、同１４４、同１４６、同１４９、同１６６、同１６８、同１７０、同１７６、同１７７、同１７８、同１７９、同１８０、同１８５、同１９０、同１９４、同２０６、同２０７、同２０９、同２１６、同２４５、Ｃ．Ｉ．ＰＩＧＭＥＮＴ　ＯＲＡＮＧＥ　５、同１０、同１３、同１６、同３６、同４０、同４３、Ｃ．Ｉ．ＰＩＧＭＥＮＴ　ＶＩＯＬＥＴ　１９、同２３、同３１、同３３、同３６、同３８、同５０、Ｃ．Ｉ．ＰＩＧＭＥＮＴ　ＢＬＵＥ　２、同１５、同１５：１、同１５：２、同１５：３、同１５：４、同１５：５、同１６、同１７、同２２、同２５、同６０、同６６、Ｃ．Ｉ．ＰＩＧＭＥＮＴ　ＢＲＯＷＮ　２５、同２６、Ｃ．Ｉ．ＰＩＧＭＥＮＴ　ＹＥＬＬＯＷ　１、同３、同１２、同１３、同２４、同９３、同９４、同９５、同９７、同９９、同１０８、同１０９、同１１０、同１１７、同１２０、同１３９、同１５３、同１６６、同１６７、同１７３、Ｃ．Ｉ．ＰＩＧＭＥＮＴ　ＧＲＥＥＮ　７、同１０、同３６、などが挙げられる。これらの顔料は、単独、あるいは２種以上混合して使用しても良い。 Specific examples of pigments include carbon black such as farnest black, contact black, thermal black, acetylene black, black iron oxide, yellow iron oxide, red iron oxide, ultramarine blue, bitumen, cobalt blue, titanium yellow, turquoise, molybdate Orange, titanium oxide, gold powder, silver powder, copper powder, aluminum powder, brass powder, tin powder, mica pigment, C.I. I. PIGMENT RED 2, 3, 5, 17, 17, 38, 41, 48: 2, 48: 3, 49, 50: 1, 53: 1, 57: 1, 58: 2, 60, 63: 1, 63: 2, 64: 1, 88, 112, 122, 123, 144, 146, 149, 166, 168, 170, 176, 177, 178, 179, 180, 185, 190, 194, 206, 207, 209, 216, 245, C.I. I. PIGMENT ORANGE 5, 10, 13, 16, 36, 40, 43, C.I. I. PIGMENT VIOLET 19, 23, 31, 33, 36, 38, 50, C.I. I. PIGMENT BLUE 2, 15, 15: 1, 15: 2, 15: 3, 15: 4, 15: 5, 16, 16, 17, 22, 25, 60, 66, C. I. PIGMENT BROWN 25, 26, C.I. I. PIGMENT YELLOW 1, 3, 12, 13, 24, 93, 94, 95, 97, 99, 108, 109, 110, 117, 120, 139, 153, 166, 167, 173, C.I. I. PIGMENT GREEN 7, 10, 36, etc. These pigments may be used alone or in combination of two or more.
　また、顔料を水性媒体に分散した顔料分散体も用いることができる。顔料分散体としては、無機顔料、有機顔料、蛍光顔料などが使用でき、具体例としては、ｕｎｉｓｐｅｒｓｅシリーズとして、同Ｇｒｅｅｎ　Ｇ－Ｓ、同Ｒｅｄ　３ＲＳ－Ｅ２、同Ｒｅｄ　Ｃ２Ｂ－Ａｇｒｏ　ＲＳ、同Ｒｅｄ　Ｃ２Ｂ－Ａｇｒｏ　Ｓｙｎｇｅｎｔａ、同Ｙｅｌｌｏｗ　１０ＧＮ－Ｓ２（以上、ＢＡＳＦジャパン（株）製）などが挙げられ、Ｈｏｓｔａｆｉｎｅシリーズとして、同Ｒｅｄ　ＦＧＲ、同Ｒｅｄ　ＨＦ３Ｓ、同Ｒｅｄ　Ｆ５ＲＫ　ＶＰ３２０４、同Ｒｅｄ　Ｐ２ＧＬ、同Ｒｕｂｉｎｅ　Ｆ６Ｂ、同Ｂｌａｃｋ　Ｔ　３０、同Ｙｅｌｌｏｗ　ＨＲ、同Ｖｉｏｌｅｔ　ＲＬ、同Ｂｌｕｅ　Ｂ２Ｇ、同Ｙｅｌｌｏｗ　ＧＲ　３０　ＶＰ　５１７６、同Ｔｒａｎｓ　Ｏｘｉｄｅ　Ｒｅｄ　Ｂ　３０、同Ｍａｇｅｎｔａ　Ｅ、同Ｇｒｅｅｎ　ＧＮ、同Ｂｌａｃｋ　ＴＳ　３０、同Ｔｒａｎｓｏｘｉｄ　Ｒｅｄ　Ｂ　３１　ＶＰ　６０４５、同Ｔｒａｎｓ　Ｏｘｉｄｅ　Ｙｅｌｌｏｗ　Ｒ　３０、同Ｙｅｌｌｏｗ　ＨＲ　３０　ＶＰ　６０２２、同Ｔｒａｎｓｏｘｉｄｅ　Ｙｅｌｌｏｗ　Ｒ　３１　ＶＰ　６０４３（以上、クラリアントジャパン（株）製）などが挙げられ、ＦＡＳＴＯＧＥＮシリーズとして、同Ｂｌｕｅ　４ＲＯ－２、同Ｂｌｕｅ　５００３、同Ｂｌｕｅ　ＡＥ－８、同Ｂｌｕｅ　ＡＥ－８Ｋ、同Ｂｌｕｅ　ＡＲ－７、同Ｂｌｕｅ　ＢＲＦ、同Ｂｌｕｅ　ＣＡ５３８０、同Ｂｌｕｅ　ＦＡ５３７５、同Ｂｌｕｅ　ＦＡ５３８０、同Ｂｌｕｅ　ＬＡ５３８０、同Ｂｌｕｅ　ＰＡ５３８０、同Ｂｌｕｅ　ＲＳＫ、同Ｇｒｅｅｎ　２ＹＫ、同Ｇｒｅｅｎ　５７２０、同Ｇｒｅｅｎ　Ｓ、同Ｇｒｅｅｎ　ＳＦ、同Ｇｒｅｅｎ　ＳＭＦ－２、同Ｓｕｐｅｒ　Ｍａｇｅｎｔａ　Ｒ、同Ｓｕｐｅｒ　Ｍａｇｅｎｔａ　ＲＥ－０３、同Ｓｕｐｅｒ　Ｍａｇｅｎｔａ　ＲＥ－０５、同Ｓｕｐｅｒ　Ｍａｇｅｎｔａ　ＲＧ、同Ｓｕｐｅｒ　Ｍａｇｅｎｔａ　ＲＨ、同Ｓｕｐｅｒ　Ｍａｇｅｎｔａ　ＲＴＳ、同Ｓｕｐｅｒ　Ｍａｇｅｎｔａ　ＲＹ、同Ｓｕｐｅｒ　Ｒｅｄ　２０９　２２８－６７３６、同Ｓｕｐｅｒ　Ｒｅｄ　２５４　２２６－０２００、同Ｓｕｐｅｒ　Ｒｅｄ　２５４　２２６－５２５４、同Ｓｕｐｅｒ　Ｒｅｄ　４００ＲＧ、同Ｓｕｐｅｒ　Ｒｅｄ　５００ＲＧ、同Ｓｕｐｅｒ　Ｒｅｄ　７０６１Ｂ、同Ｓｕｐｅｒ　Ｒｅｄ　７０６４Ｂ、同Ｓｕｐｅｒ　Ｒｅｄ　７１００Ｙ、同Ｓｕｐｅｒ　Ｒｅｄ　ＡＴＹ－０１、同Ｓｕｐｅｒ　Ｒｅｄ　ＡＴＹ－ＴＲ、同Ｓｕｐｅｒ　Ｒｅｄ　Ｂ　ｃｏｎｃ、同Ｓｕｐｅｒ　Ｒｅｄ　ＹＥ、同Ｓｕｐｅｒ　Ｓｃａｒｌｅｔ　ＧＫ、同Ｓｕｐｅｒ　Ｖｉｏｌｅｔ　ＲＮ、同Ｓｕｐｅｒ　Ｖｉｏｌｅｔ　ＲＮＳ、同Ｓｕｐｅｒ　Ｖｉｏｌｅｔ　ＲＮ－ＳＵ－０２、同Ｓｕｐｅｒ　Ｖｉｏｌｅｔ　ＲＺＥ、同Ｓｕｐｅｒ　Ｖｉｏｌｅｔ　ＲＺＳなどが挙げられ、ＰＡＬＯＭＡＲシリーズとして、同Ｔｕｒｑｕｏｉｓｅ　２６４－４９００などが挙げられ、ＰＥＲＲＩＮＤＯシリーズとして、同Ｍａｒｏｏｎ　１７９　２２９－６４２４、同Ｍａｒｏｏｎ　１７９　２２９－６４３６、同Ｍａｒｏｏｎ　１７９　２２９－６４３８、同Ｍａｒｏｏｎ　１７９　２２９－６４４０、同Ｍａｒｏｏｎ　１７９　２２９－６４５４、同Ｒｅｄ　２２４　２２９－６４２０、同Ｖｉｏｌｅｔ　２９　２２９－４０５０などが挙げられ、ＱＵＩＮＤＯシリーズとして、同Ｍａｇｅｎｔａ　２０２　２２８－６８４３、同Ｍａｇｅｎｔａ　２０２　２２８－６８５３、同Ｖｉｏｌｅｔ　１９　２２８－１１１９などが挙げられ、ＳＹＭＵＬＥＲシリーズとして、同ＳＹＭＵＬＥＲ　Ｂｒｉｌｌｉａｎｔ　Ｃａｒｍｉｎｅ　６Ｂ　２２６、同ＳＹＭＵＬＥＲ　Ｂｒｉｌｌｉａｎｔ　Ｃａｒｍｉｎｅ　６Ｂ　２３３Ｓ、同ＳＹＭＵＬＥＲ　Ｂｒｉｌｌｉａｎｔ　Ｃａｒｍｉｎｅ　６Ｂ　２３６Ｓ、同ＳＹＭＵＬＥＲ　Ｂｒｉｌｌｉａｎｔ　Ｃａｒｍｉｎｅ　６Ｂ　２４３、同ＳＹＭＵＬＥＲ　Ｂｒｉｌｌｉａｎｔ　Ｃａｒｍｉｎｅ　６Ｂ　２４６、同ＳＹＭＵＬＥＲ　Ｂｒｉｌｌｉａｎｔ　Ｃａｒｍｉｎｅ　６Ｂ　３００、同ＳＹＭＵＬＥＲ　Ｂｒｉｌｌｉａｎｔ　Ｃａｒｍｉｎｅ　６Ｂ　３０３Ｓ、同ＳＹＭＵＬＥＲ　Ｂｒｉｌｌｉａｎｔ　Ｃａｒｍｉｎｅ　６Ｂ　３０６、同ＳＹＭＵＬＥＲ　Ｂｒｉｌｌｉａｎｔ　Ｃａｒｍｉｎｅ　６Ｂ　３０８、同ＳＹＭＵＬＥＲ　Ｂｒｉｌｌｉａｎｔ　Ｃａｒｍｉｎｅ　６Ｂ　３１３Ｓ、同ＳＹＭＵＬＥＲ　Ｂｒｉｌｌｉａｎｔ　Ｃａｒｍｉｎｅ　６Ｂ　３５０Ｋ、同ＳＹＭＵＬＥＲ　Ｂｒｉｌｌｉａｎｔ　Ｃａｒｍｉｎｅ　６Ｂ　３９２、同ＳＹＭＵＬＥＲ　Ｂｒｉｌｌｉａｎｔ　Ｃａｒｍｉｎｅ　６Ｂ　３９３、同ＳＹＭＵＬＥＲ　Ｂｒｉｌｌｉａｎｔ　Ｃａｒｍｉｎｅ　６Ｂ　３９７、同ＳＹＭＵＬＥＲ　Ｂｒｉｌｌｉａｎｔ　Ｃａｒｍｉｎｅ　６Ｂ　４００Ｓ、同ＳＹＭＵＬＥＲ　Ｂｒｉｌｌｉａｎｔ　Ｃａｒｍｉｎｅ　６Ｂ　４０１、同ＳＹＭＵＬＥＲ　Ｂｒｉｌｌｉａｎｔ　Ｃａｒｍｉｎｅ　６Ｂ　４１２Ｗ、同ＳＹＭＵＬＥＲ　Ｂｒｉｌｌｉａｎｔ　Ｃａｒｍｉｎｅ　６Ｂ　４１３Ｗ、同ＳＹＭＵＬＥＲ　Ｆａｓｔ　Ｏｒａｎｇｅ　Ｇ、同ＳＹＭＵＬＥＲ　Ｆａｓｔ　Ｏｒａｎｇｅ　Ｋ、同ＳＹＭＵＬＥＲ　Ｆａｓｔ　Ｏｒａｎｇｅ　Ｖ、同ＳＹＭＵＬＥＲ　Ｆａｓｔ　Ｒｅｄ　４１３４Ａ、同ＳＹＭＵＬＥＲ　Ｆａｓｔ　Ｒｅｄ　４１３４Ｓ、同ＳＹＭＵＬＥＲ　Ｆａｓｔ　Ｒｅｄ　４５８０、同ＳＹＭＵＬＥＲ　Ｆａｓｔ　Ｒｅｄ　４５８６、同ＳＹＭＵＬＥＲ　Ｆａｓｔ　Ｒｅｄ　４６０１、同ＳＹＭＵＬＥＲ　Ｆａｓｔ　Ｒｅｄ　４６０８、同ＳＹＭＵＬＥＲ　Ｆａｓｔ　Ｒｅｄ　４６１０、同ＳＹＭＵＬＥＲ　Ｆａｓｔ　Ｒｅｄ　ＢＲ　４５９８、同ＳＹＭＵＬＥＲ　Ｆａｓｔ　Ｙｅｌｌｏｗ　４０５９Ｇ、同ＳＹＭＵＬＥＲ　Ｆａｓｔ　Ｙｅｌｌｏｗ　４０９０Ｇ、同ＳＹＭＵＬＥＲ　Ｆａｓｔ　Ｙｅｌｌｏｗ　４１９２、同ＳＹＭＵＬＥＲ　Ｆａｓｔ　Ｙｅｌｌｏｗ　４ＧＯ、同ＳＹＭＵＬＥＲ　Ｆａｓｔ　Ｙｅｌｌｏｗ　５ＧＦ、同ＳＹＭＵＬＥＲ　Ｆａｓｔ　Ｙｅｌｌｏｗ　８ＧＦ、同ＳＹＭＵＬＥＲ　Ｆａｓｔ　Ｙｅｌｌｏｗ　８ＧＴＦ、同ＳＹＭＵＬＥＲ　Ｆａｓｔ　Ｙｅｌｌｏｗ　ＢＹ　２０００ＧＴ、同ＳＹＭＵＬＥＲ　Ｆａｓｔ　Ｙｅｌｌｏｗ　ＧＦｃｏｎｃ、同ＳＹＭＵＬＥＲ　Ｆａｓｔ　Ｙｅｌｌｏｗ　ＧＦｃｏｎｃＰ、同ＳＹＭＵＬＥＲ　Ｆａｓｔ　Ｙｅｌｌｏｗ　ＧＲＦ、同ＳＹＭＵＬＥＲ　Ｆａｓｔ　Ｙｅｌｌｏｗ　ＮＩＦ、同ＳＹＭＵＬＥＲ　Ｌａｋｅ　Ｒｅｄ　Ｃｃｏｎｃ２１０、同ＳＹＭＵＬＥＲ　Ｒｅｄ　２ＢＹ、同ＳＹＭＵＬＥＲ　Ｒｅｄ　３０１３、同ＳＹＭＵＬＥＲ　Ｒｅｄ　３０１３Ｐ、同ＳＹＭＵＬＥＲ　Ｒｅｄ　３０１４、同ＳＹＭＵＬＥＲ　Ｒｅｄ　３０７０、同ＳＹＭＵＬＥＲ　Ｒｅｄ　３０７５、同ＳＹＭＵＬＥＲ　Ｒｅｄ　３１１１、同ＳＹＭＵＬＥＲ　Ｒｅｄ　３１２３、同ＳＹＭＵＬＥＲ　Ｒｅｄ　ＮＲＹなどが挙げられ、ＲＹＵＤＹＥ－Ｗシリーズとして、同ＹＥＬＬＯＷ　ＫＧＲ、同ＹＥＬＬＯＷ　ＦＲＴ－Ｋ、同ＯＲＡＮＧＥ　ＦＫＳ、同ＳＣＡＲＬＥＴ　Ｆ３Ｇ、同ＲＥＤ　ＦＢＹ、同ＶＩＯＬＥＴ　ＦＦＢＮ、同ＢＬＵＥ　ＧＬＫ、同ＧＲＥＥＮ　ＦＢＴ、同ＢＲＯＷＮ　ＦＦＭ、同ＢＬＡＣＫ　ＲＣ、同ＹＥＬＬＯＷ　ＦＦ７Ｇ、同ＹＥＬＬＯＷ　ＦＦ３Ｒ、同ＯＲＡＮＧＥ　ＦＦ２Ｒ、同ＲＥＤ　ＦＦＧＲ、同ＶＩＯＬＥＴ　ＦＦＢＮ、同ＢＬＵＥ　ＧＬＫ、同ＧＲＥＥＮ　ＦＢＴ、同ＢＲＯＷＮ　ＦＦＲ、同ＢＬＡＣＫ　ＲＣ、同ＹＥＬＬＯＷ　ＫＧ、同ＧＯＬＤ　ＹＥＬＬＯＷ　ＦＦＲ、同ＯＲＡＮＧＥ　ＦＫＶ、同ＳＣＡＲＬＥＴ　Ｆ３Ｇ、同ＲＥＤ　ＧＣＬ、同ＶＩＯＬＥＴ　ＦＮ、同ＢＬＵＥ　ＲＣ、同ＧＲＥＥＮ　Ｓ　ＣＯＮＣ、同ＢＲＯＷＮ　ＧＤＲ、同ＢＬＡＣＫ　ＷＴ、同ＹＥＬＬＯＷ　ＦＦ４Ｇ、同ＹＥＬＬＯＷ　ＦＦＲＧ、同ＯＲＡＮＧＥ　ＦＦＹＲ、同ＲＥＤ　ＦＦ２Ｇ、同ＶＩＯＬＥＴ　ＦＮ、同ＢＬＵＥ　ＲＣ、同ＧＲＥＥＮ　Ｓ　ＣＯＮＣ、同ＢＲＯＷＮ　ＦＦＲ、同ＢＬＡＣＫ　ＷＴ（以上、ＤＩＣ（株）製）などが挙げられ、Ｆｕｊｉ　ＳＰシリーズとして、同Ｂｌａｃｋ　８０３１、同Ｂｌａｃｋ　８０４１、同Ｂｌａｃｋ　８１１９、同Ｂｌａｃｋ　８１６７、同Ｂｌａｃｋ　８２７６、同Ｂｌａｃｋ　８３８１、同Ｂｌａｃｋ　８４０６、同Ｒｅｄ　５０９６、同Ｒｅｄ　５１１１、同Ｒｅｄ　５１９３、同Ｒｅｄ　５２２０、同Ｂｏｒｄｅａｕｘ　５５００、同Ｂｌｕｅ　６０６２、同Ｂｌｕｅ　６４７４、同Ｂｌｕｅ　６１３３、同Ｂｌｕｅ　６１３４、同Ｂｌｕｅ　６４０１、同Ｂｌｕｅ　６５５５、同Ｂｌｕｅ　６４７４、同Ｇｒｅｅｎ　７０５１、同Ｙｅｌｌｏｗ　４０６０、同Ｙｅｌｌｏｗ　４３６０、同Ｙｅｌｌｏｗ　４１７８、同Ｖｉｏｌｅｔ　９０１１、同Ｖｉｏｌｅｔ　９６０２、同ＦｕｊｉＳＰ　Ｐｉｎｋ　９５２４、同Ｐｉｎｋ　９５２７、同Ｏｒａｎｇｅ　５３４、同Ｐｉｎｋ　６３６、同Ｐｉｎｋ　９４２９、同Ｂｒｏｗｎ　３０７４、同ＲＥＤ　５５４３、同ＲＥＤ　５６５７、同ＲＥＤ　５６５３、同ＲＥＤ　５５４４（以上、冨士色素（株）製）などが挙げられ、Ｅｍａｃｏｌシリーズとして、同Ｂｌａｃｋ　ＣＮ、同Ｂｌｕｅ　ＦＢＢ、同Ｂｌｕｅ　ＦＢ、同Ｂｌｕｅ　ＫＲ、同Ｇｒｅｅｎ　ＬＸＢ、同Ｖｉｏｌｅｔ　ＢＬ、同Ｂｒｏｗｎ３１０１、同Ｃａｒｍｍｉｎｅ　ＦＢ、同ＲｅｄＢＳ、同Ｏｒａｎｇｅ　Ｒ、同Ｙｅｌｌｏｗ　ＦＤ、同Ｙｅｌｌｏｗ　ＩＲＮ、同Ｙｅｌｌｏｗ　３６０１、同Ｙｅｌｌｏｗ　ＦＧＮ、同Ｙｅｌｌｏｗ　ＧＮ、同Ｙｅｌｌｏｗ　ＧＧ、同Ｙｅｌｌｏｗ　Ｆ５Ｇ、同Ｙｅｌｌｏｗ　Ｆ７Ｇ、同Ｙｅｌｌｏｗ　１０ＧＮ、同Ｙｅｌｌｏｗ　１０Ｇなどが挙げられ、Ｓａｎｄｙｅシリーズとして、同Ｓｕｐｅｒ　Ｂｌａｃｋ　Ｋ、同Ｓｕｐｅｒ　Ｂｌａｃｋ　Ｃ、同Ｓｕｐｅｒ　Ｇｒｅｙ　Ｂ、同Ｓｕｐｅｒ　Ｂｒｏｗｎ　ＳＢ、同Ｓｕｐｅｒ　Ｂｒｏｗｎ　ＦＲＬ、同Ｓｕｐｅｒ　Ｂｒｏｗｎ　ＲＲ、同Ｓｕｐｅｒ　Ｇｒｅｅｎ　Ｌ５Ｇ、同Ｓｕｐｅｒ　Ｇｒｅｅｎ　ＧＸＢ、同Ｓｕｐｅｒ　Ｎａｖｙ　Ｂｌｕｅ　ＨＲＬ、同Ｙｅｌｌｏｗ　Ｓｕｐｅｒ　Ｎａｖｙ　Ｂｌｕｅ　ＧＬＬ、同Ｙｅｌｌｏｗ　Ｓｕｐｅｒ　Ｎａｖｙ　Ｂｌｕｅ　ＨＢ、同Ｙｅｌｌｏｗ　Ｓｕｐｅｒ　Ｎａｖｙ　Ｂｌｕｅ　ＦＢＬ－Ｈ、同Ｙｅｌｌｏｗ　Ｓｕｐｅｒ　Ｎａｖｙ　Ｂｌｕｅ　ＦＢＬ－１６０、同Ｙｅｌｌｏｗ　Ｓｕｐｅｒ　Ｎａｖｙ　Ｂｌｕｅ　ＦＢＢ、同Ｓｕｐｅｒ　Ｖｉｏｌｅｔ　ＢＬ　Ｈ／Ｃ、同Ｓｕｐｅｒ　Ｖｉｏｌｅｔ　ＢＬ、同Ｓｕｐｅｒ　Ｂｏｒｄｅａｕｘ　ＦＲ、同Ｓｕｐｅｒ　Ｐｉｎｋ　ＦＢＬ、同Ｓｕｐｅｒ　Ｐｉｎｋ　Ｆ５Ｂ、同Ｓｕｐｅｒ　Ｒｕｂｉｎｅ　ＦＲ、同Ｓｕｐｅｒ　Ｃａｒｍｍｉｎｅ　ＦＢ、同Ｓｕｐｅｒ　Ｒｅｄ　ＦＦＧ、同Ｓｕｐｅｒ　Ｒｅｄ　ＲＲ、同Ｓｕｐｅｒ　Ｒｅｄ　ＢＳ、同Ｓｕｐｅｒ　Ｒｅｄ　１３１５、同Ｓｕｐｅｒ　Ｏｒａｎｇｅ　ＦＬ、同Ｓｕｐｅｒ　Ｏｒａｎｇｅ　Ｒ、同Ｓｕｐｅｒ　Ｏｒａｎｇｅ　ＢＯ、同Ｇｏｌｄ　Ｙｅｌｌｏｗ　５ＧＲ、同Ｇｏｌｄ　Ｙｅｌｌｏｗ　Ｒ、同Ｇｏｌｄ　Ｙｅｌｌｏｗ　３Ｒ、同Ｙｅｌｌｏｗ　ＧＧ、同Ｙｅｌｌｏｗ　Ｆ３Ｒ、同Ｙｅｌｌｏｗ　ＩＲＣ、同Ｙｅｌｌｏｗ　ＦＧＮ、同Ｙｅｌｌｏｗ　ＧＮ、同Ｙｅｌｌｏｗ　ＧＲＳ、同Ｙｅｌｌｏｗ　ＧＳＲ－１３０、同Ｙｅｌｌｏｗ　ＧＳＮ－１３０、同Ｙｅｌｌｏｗ　ＧＳＮ、同Ｙｅｌｌｏｗ　１０ＧＮ（以上、山陽色素（株）製）などが挙げられ、ＭＩＣＲＯＰＩＧＭＯシリーズとして、同ＡＭＢＥ－４、同ＡＭＢＥ－８、同ＡＭＢＫ－２、同ＡＭＢＫ－８、同ＡＭＧＮ－２、同ＡＭＧＮ－６、同ＡＭＧＮ－８、同ＡＭＶＴ－２、同ＡＭＲＤ－２、同ＡＭＲＤ－８、同ＡＭＯＥ－６、同ＷＭＢＥ－５、同ＷＭＢＫ－５、同ＷＭＧＮ－６、同ＷＭＲＤ－５、同ＷＭＲＤ－８、同ＷＭＶＴ－５、同ＷＭＷＥ－１、同ＷＭＹＷ－５、同ＷＭＹＷ－６などが挙げられ、ＢＯＮＪＥＴシリーズとして、同ＢＬＡＣＫ　ＣＷ－１、同ＢＬＡＣＫ　ＣＷ－１Ｓ、同ＢＬＡＣＫ　ＣＷ－２、同ＢＬＡＣＫ　Ｍ－８００（以上、オリヱント化学工業（株）製）などが挙げられ、Ｒｉｏ　Ｆａｓｔシリーズとして、同Ｂｌａｃｋ　Ｆｘ　８０１２、同Ｂｌａｃｋ　Ｆｘ　８
３１３、同Ｂｌａｃｋ　Ｆｘ　８１６９、同Ｒｅｄ　Ｆｘ　８２０９、同Ｒｅｄ　Ｆｘ　８１７２、同Ｒｅｄ　Ｓ　Ｆｘ　８３１５、同Ｒｅｄ　Ｓ　Ｆｘ　８３１６、同Ｂｌｕｅ　Ｆｘ　８１７０、同Ｂｌｕｅ　Ｆｘ　８１７０、同Ｂｌｕｅ　Ｓ　Ｆｘ　８３１２、同Ｇｒｅｅｎ　Ｓ　Ｆｘ　８３１４などが挙げられ、ＥＭＦカラーシリーズとして、同イエロー３Ｇ、同オレンジＯ、同レッドＨＦＢ、同レッドＨＲ、同ブルーＨＧ、同バイオレットＨＢ（以上、トーヨーカラー（株）製）などが挙げられ、ポルックスカラーシリーズとして、同ＰＣ５Ｔ１０２０、同ブラックＰＣ８Ｔ１３５、同レッドＩＴ１０３０（以上、住化カラー（株）製）などが挙げられ、ビクトリアシリーズとして、同イエロー　Ｇ－１１、同イエロー　Ｇ－２０、同オレンジ　Ｇ－１６、同オレンジ　Ｇ－２１、同レッド　Ｇ－１９、同レッド　Ｇ－２２、同ピンク　Ｇ－１７、同ピンク　Ｇ－２３、同グリーン　Ｇ－１８、同グリーン　Ｇ－２４、同ブルー　Ｇ－１５、同ブルー　Ｇ－２５（以上、御国色素（株）製）などが挙げられる。
　これらの顔料分散体は、単独、あるいは２種以上混合して使用しても良い。ただし、着色された樹脂粒子を着色剤として用いる場合は、樹脂粒子が有機溶剤に溶解しないものを用いる。 A pigment dispersion in which a pigment is dispersed in an aqueous medium can also be used. As the pigment dispersion, inorganic pigments, organic pigments, fluorescent pigments and the like can be used. Specific examples include the Unisperse series, Green GS, Red 3RS-E2, Red C2B-Agro RS, Red C2B. -Agro Syngenta, Yellow 10GN-S2 (manufactured by BASF Japan Ltd.), etc. As the Hostafine series, Red FGR, Red HF3S, Red F5RK VP3204, Red P2GL, Red F2B, Black T 30, Yellow HR, Violet RL, Blue B2G, Yellow GR 30 VP 5176, Trans Oxide Red B 30, Magenta E, Green GN, Black T 30, Transoxide Red B 31 VP 6045, Trans Oxide Yellow R 30, Yellow HR 30 VP 6022, Transoxide Yellow R 31 VP 6043 (above, manufactured by Clariant Japan Co., Ltd.), FASTOGEN series, etc. Blue 4RO-2, Blue 5003, Blue AE-8, Blue AE-8K, Blue AR-7, Blue BRF, Blue CA5380, Blue FA5375, Blue FA5380, Blue LA5380, Blue LA PA5380, Blue RSK, Green 2YK, Green 5720, Green S, Green SF, Green SMF-2, Super agent R, Super Magenta RE-03, Super Magenta RE-05, Super Magenta RG, Super Magenta RH, Super Magenta RTS, Twenty-six Super RY, Twenty-six -0200, Super Red 254 226-5254, Super Red 400RG, Super Red 500RG, Super Red 7061B, Super Red 7064B, Super Red 7100Y, Super Red ATY-01, Super Red ATY-01, Super Red ATY-01, Super Red ATY-01, Super Red ATY-01, Super Red ATY-01 Super Red B conc, Super Red YE, Super Scal et GK, Super Violet RN, Super Violet RNS, Super Violet RN-SU-02, Super Violet RZE, Super Violet RZS, etc., PALOMAR Series, Tur4-Cue4, etc. The PERRINDO series includes: Maron 179 229-6424, Maron 179 229-6436, Maron 179 229-6438, Maron 179 229-6440, Maron 179 229-6454, Red 224 229-6429, Violet 229 -4050, etc., and as QUINDO series, Magenta 202 228-6843, Magenta 202 228-6853, Violet 19 228-1119, etc., SYMULER Brilliant Carmine 6B 226, SYMULER Brilliant Carmin 6B 233S, SYMULER Brilliant Carmin 6B 233S, SYMULER SYMULER Brillant Carmin 6B 246, SYMULER Brillant Carmine 6B 300, SYMULER Brillant Carmin 6B 303S, SYMULER Brillant Carmin 6B 306L rmine 6B 308, the same SYMULER Brilliant Carmine 6B 313S, the same SYMULER Brilliant Carmine 6B 350K, same SYMULER Brilliant Carmine 6B 392, the same SYMULER Brilliant Carmine 6B 393, the same SYMULER Brilliant Carmine 6B 397, the same SYMULER Brilliant Carmine 6B 400S, the same SYMULER Brilliant Carmine 6B 401, SYMULER Brilliant Carmine 6B 412W, SYMULER Brilliant Carmine 6B 413W, SYMULER Fast Orange G, SYMULER Fast Range K, SYMULER Fast Orange V, SYMULER Fast Red 4134A, SYMULER Fast Red 4134S, SYMULER Fast Red 4580, SYMULER Fast Red 4580, SYMUER Fast Red 4580, SYMULER Fast Red 4580, SYMULER Fast Red 4580, SYMULER Fast Red 4580 SYMULER Fast Yellow Yellow 4909G, SYMULER Fast Yellow 4990G, SYMULER Fast Yellow 4940, SYMULER Fast Yellow Yellow 4192G, SYMULER Fast Yellow Yellow 4192G, SYMULER Fast Yellow Yellow 4192G, SYMULER Fast Yellow Yellow 4192G, SYMULER Fast Yellow Yellow 4192G Yellow 8GF, same SYMULER Fast Yellow 8GTF, same SYMULER Fast Yellow BY 2000GT, the SYMULER Fast Yellow GFconc, same SYMULER Fast Yellow GFconcP, same SYMULER Fast Yellow GRF, the SYMULER Fast Yellow NIF, the SYMULER Lake Red Cconc210, same SYMULER Red 2BY SYMULER Red 3013, SYMULER Red 3013P, SYMULER Red 3014, SYMULER Red 3070, SYMULER Red 3075, SYMULER Red 3111, SYMULER Red 3LER, SYMULER Red 3013 Y, etc., as RYUDYE-W series, YELLOW KGR, YELLOW FRT-K, ORANGE FKS, SCARET F3G, RED FBY, VIOLET FFBN, BLUE GLK, GREEN FBT, BRO BLACK RC, YELLOW FF7G, YELLOW FF3R, ORANGE FF2R, RED FFGR, VIOLET FFBN, BLUE GLK, GREEN FBT, BROWN FFR, BLACK RC, YELLOW KG, GEL ORANGE FKV, SCARLET F3G, RED GCL, VOOLET FN, BLUE RC, GREEN S CONC, BROWN GDR, LACK WT, YELLOW FF4G, YELLOW FFRG, ORANGE FFYR, RED FF2G, VIOLET FN, BLUE RC, GREEN S CONC, BROWN FFR, BLACK WT (above, manufactured by DIC Corporation), etc. As the Fuji SP series, the same Black 8031, the same Black 8041, the same Black 8119, the same Black 8167, the same Black 8276, the same Black 8381, the same Black 8406, the same Red 5096, the same Red 5111, the same Red 5193, and the same Red. 5220, Bordeaux 5500, Blue 6062, Blue 6474, Blue 6133, Blue 6133, Blue 6134, Blue 6401, Blue 6555, Blue 6555, B Lue 6474, Green 7051, Yellow 4060, Yellow 4360, Yellow 4178, Yellow 4178, Violet 9011, Violet 9602, FujiSP Pink 9524, Pink 9527, Orange 534, Orange 634, Bink 636, Pink 636, Pink 636 3074, the same RED 5543, the same RED 5657, the same RED 5653, the same RED 5544 (manufactured by Fuji Dye Co., Ltd.) and the like, and the Emacol series includes the Black CN, the Blue FBB, the Blue FB, and the Blue. KR, Green LXB, Violet BL, Brown 3101, Carmine FB, RedBS, Orange R, Yellow FD, Yell w IRN, Yellow 3601, Yellow FGN, Yellow GN, Yellow GG, Yellow F5G, Yellow F7G, Yellow 10GN, Yellow 10G, etc. Sandy series, Super Black K, Black C, Super Gray B, Super Brown SB, Super Brown FRL, Super Brown RR, Super Brown RR, Super Green L5G, Super Green GX, Super Super GX. Blue HB, Yellow Super Navy Blue FBL-H, Ye low Super Nav Blue FBL-160, Yellow Super Nav Blue FBB, Super Violet BL H / C, Super Violet BL, Super Bude Super F, Flu-Sup Carmine FB, Super Red FFG, Super Red RR, Super Red BS, Super Red 1315, Super Orange FL, Super Orange R, Super Orange BO, Gold 5G, Gold 5 Yellow 3R, Yellow GG, Yellow F3R, Yellow F3R Yellow IRC, Yellow FGN, Yellow GN, Yellow GRS, Yellow GSR-130, Yellow GSN-130, Yellow GSN, Yellow 10GN (Sanyo Dye Co., Ltd.) As series, AMBE-4, AMBE-8, AMBK-2, AMBK-8, AMGN-2, AMGN-6, AMGN-8, AMVT-2, AMRD-2, AMRD -8, AMOE-6, WMBE-5, WMBK-5, WMGN-6, WMRD-5, WMRD-8, WMVT-5, WMWE-1, WMYW-5, WMYW -6 etc., as the BONJET series, the BLACK CW-1, the BLACK CW-1S, BLACK CW-2, BLACK M-800 (manufactured by Orient Chemical Industry Co., Ltd.), and the like. The Rio Fast series includes Black Fx 8012, Black Fx 8
313, Black Fx 8169, Red Fx 8209, Red Fx 8172, Red S Fx 8315, Red S Fx 8316, Blue Fx 8170, Blue Fx 8170, Blue S Fx 8312, G The EMF color series includes the Yellow 3G, Orange O, Red HFB, Red HR, Blue HG, and Violet HB (above, manufactured by Toyocolor Co., Ltd.), and Pollux Color The series includes the same PC5T1020, the same black PC8T135, the same red IT1030 (manufactured by Sumika Color Co., Ltd.), and the Victoria series includes the same yellow G-11, the same yellow G-20, the same orange G-16. The same orange -21, Red G-19, Red G-22, Pink G-17, Pink G-23, Green G-18, Green G-24, Blue G-15, Blue G-25 (Above, made by Gokoku Color Co., Ltd.).
These pigment dispersions may be used alone or in combination of two or more. However, when colored resin particles are used as a colorant, those in which the resin particles are not dissolved in an organic solvent are used.
　着色剤に顔料や油性染料を用いることで、筆跡の耐水性を備えるものとすることもでき、顔料のみを用いることで筆跡の耐光性を備えるものとすることができる。 It is possible to provide water resistance of handwriting by using a pigment or oil-based dye as a colorant, and it is possible to provide light resistance of handwriting by using only a pigment.
　着色剤に顔料を用いた場合は、顔料を安定に分散させるために分散剤を使用することもできる。分散剤として、従来一般に用いられている水溶性樹脂もしくは水可溶性樹脂や、アニオン系もしくはノニオン系の界面活性剤などの、顔料の分散剤として用いられるものを用いることができる。分散剤の具体例としては、高分子分散剤として、リグニンスルホン酸塩、セラックなどの天然高分子、ポリアクリル酸塩、スチレン－アクリル酸共重合物の塩、ビニルナフタレン－マレイン酸共重合物の塩、β－ナフタレンスルホン酸ホルマリン縮合物のナトリウム塩、リン酸塩、などの陰イオン性高分子やポリビニルアルコール、ポリエチレングリコールなどの非イオン性高分子などが挙げられる。また、界面活性剤の具体例としては、アルキル硫酸塩、ポリオキシエチレンアルキルエーテル硫酸塩、Ｎ－アシルアミノ酸およびその塩、Ｎ－アシルメチルタウリン塩、ポリオキシエチレンアルキルエーテル酢酸塩、アルキルスルホカルボン酸塩、α－オレフィンスルホン酸塩、アルキルリン酸塩、ポリオキシエチレンアルキルエーテルリン酸塩などの陰イオン界面活性剤、ポリオキシエチレンアルキルエーテル類、ソルビタンアルキルエステル類、ポリオキシエチレンソルビタンアルキルエステル類などの非イオン性界面活性剤、などが挙げられる。これらの水可溶性樹脂および界面活性剤の添加量は顔料１０．０重量％に対し、０．０５重量％以上２０．０重量％以下が好ましい。これらの水可溶性樹脂および界面活性剤は、単独、あるいは２種以上混合して使用しても良い。 When a pigment is used as the colorant, a dispersant can be used to stably disperse the pigment. As the dispersant, those used as a dispersant for pigments such as a water-soluble resin or a water-soluble resin generally used in the past and an anionic or nonionic surfactant can be used. Specific examples of the dispersant include polymer dispersants such as lignin sulfonate, natural polymers such as shellac, polyacrylate, styrene-acrylic acid copolymer salt, vinylnaphthalene-maleic acid copolymer. Salts, anionic polymers such as β-naphthalenesulfonic acid formalin condensate, sodium salts and phosphates, and nonionic polymers such as polyvinyl alcohol and polyethylene glycol. Specific examples of surfactants include alkyl sulfates, polyoxyethylene alkyl ether sulfates, N-acyl amino acids and salts thereof, N-acyl methyl taurate, polyoxyethylene alkyl ether acetates, alkyl sulfocarboxylic acids. Anionic surfactants such as salts, α-olefin sulfonates, alkyl phosphates, polyoxyethylene alkyl ether phosphates, polyoxyethylene alkyl ethers, sorbitan alkyl esters, polyoxyethylene sorbitan alkyl esters, etc. Nonionic surfactants, and the like. The amount of these water-soluble resin and surfactant added is preferably 0.05% by weight or more and 20.0% by weight or less with respect to 10.0% by weight of the pigment. These water-soluble resins and surfactants may be used alone or in combination of two or more.
　上記塗布具に使用する水性インキにおいて、顔料を分散するには一般的な方法が使用可能である。
　例えば、顔料と、溶媒と、分散剤とを混合し、プロペラ撹拌機等で均一に撹拌した後、分散機で顔料を分散する。分散機の具体例としては、ロールミル、ボールミル、サンドミル、ビーズミル、ヘンシェルミキサー、ホモジナイザー、高圧ホモジナイザー、ニーダーなどが挙げられる。使用する分散機の種類は、水性インキの溶媒量や、顔料濃度などによって適宜選択できる。
　また、これらの分散する工程において、発生した分散熱をそのまま利用して撹拌したり、熱をかけたり、冷却したり、加圧したり、減圧したり、不活性ガス雰囲気中で撹拌することができる。脱泡機による泡の除去やろ過機による粗大物のろ過等を必要に応じて行っても良い。更に、多糖類の分散性を十分にするために水性インキ調整後に加熱処理工程及び／又は冷却処理工程を行っても良い。
　これらの混合、分散、ろ過、加熱、冷却、加圧、減圧、不活性ガス雰囲気とすることなどは、それぞれ単独で行ってもよく、あるいは、２種以上の工程を同時に行ってもよい。 In the water-based ink used for the applicator, a general method can be used to disperse the pigment.
For example, a pigment, a solvent, and a dispersant are mixed and stirred uniformly with a propeller stirrer or the like, and then the pigment is dispersed with a disperser. Specific examples of the disperser include a roll mill, a ball mill, a sand mill, a bead mill, a Henschel mixer, a homogenizer, a high-pressure homogenizer, and a kneader. The type of the disperser to be used can be appropriately selected depending on the solvent amount of the water-based ink, the pigment concentration, and the like.
In these dispersing steps, the generated heat of dispersion can be used as it is, stirred, heated, cooled, pressurized, decompressed, or stirred in an inert gas atmosphere. . You may perform the removal of the foam by a defoamer, filtration of the coarse thing by a filter, etc. as needed. Furthermore, in order to make the dispersibility of polysaccharide sufficient, you may perform a heat processing process and / or a cooling process process after water-based ink adjustment.
These mixing, dispersion, filtration, heating, cooling, pressurization, decompression, inert gas atmosphere, etc. may be performed alone or two or more processes may be performed simultaneously.
　上記塗布具に使用する水性インキの粘度は、マーキングペン、筆ペンなどの塗布先として繊維集束体を用いる塗布具の形態によって適宜調整することができる。 The viscosity of the water-based ink used for the applicator can be appropriately adjusted depending on the form of the applicator using a fiber bundle as an application destination such as a marking pen and a brush pen.
　上記塗布具に使用する水性インキにおいて、インキ吸蔵体にインキを充填して使用する形態では、水性インキの粘度が測定温度２５℃、剪断速度７６．６ｓ－１において１．０ｍＰａ・ｓ以上５０．０ｍＰａ・ｓ以下であることが好ましく、１．０ｍＰａ・ｓ以上２０．０ｍＰａ・ｓ以下がより好ましく、インキ吸蔵体を用いることなく、インキを塗布具に充填して使用する形態では、水性インキの粘度が測定温度２５℃、剪断速度７６．６ｓ－１において１．０ｍＰａ・ｓ以上１００．０ｍＰａ・ｓ以下であることが好ましく、１．０ｍＰａ・ｓ以上６０．０ｍＰａ・ｓ以下がより好ましい。 In the water-based ink used for the applicator, when the ink occlusion body is filled with ink, the viscosity of the water-based ink is 1.0 mPa · s or more and 50.50 or more at a measurement temperature of 25 ° C. and a shear rate of 76.6 s −1 . It is preferably 0 mPa · s or less, more preferably 1.0 mPa · s or more and 20.0 mPa · s or less. In the form in which the ink is filled in the applicator without using the ink occlusion body, the aqueous ink The viscosity is preferably 1.0 mPa · s or more and 100.0 mPa · s or less, more preferably 1.0 mPa · s or more and 60.0 mPa · s or less at a measurement temperature of 25 ° C. and a shear rate of 76.6 s −1 .
　上記塗布具に使用する水性インキにおいて、粘度を調整するために粘度調整剤を用いることができる。粘度調整剤の具体例としては、ＨＰＣ－ＳＬ、ＨＰＣ－Ｌ、ＨＰＣ－Ｍ、ＨＰＣ－Ｈ（以上、ヒドロキシプロピルセルロース、日本曹達（株）製）、セオラスＳＣ－９００、セオラスＳＣ－９００Ｓ、セオラスＲＣ５９１Ｓ、セオラスＲＣ－Ｎ８１、セオラスＲＣ－Ｎ３０、セオラスＣＬ－６１１Ｓ、セオラスＤＸ－２、セオラスＤＸ－３，セオラスＵＦ－Ｆ７１１、セオラスＵＦ－Ｆ７０２、セオラスＳＴ－１００、セオラスＳＴ－０２、セオラスＦＤ－１０１，セオラスＦＤ－３０１、セオラスＦＤ－Ｆ２０、セオラスファイバーＤＦ－１７（以上、結晶セルロース、旭化成（株）製）などのセルロース類、ケルザン、ケルザンＳ、ケルザンＴ、ケルザンＳＴ、ケルザンＡＳＸ、ケルザンＡＲ、ケルザンＨＰ、ケルザンＧ、ケトロールＣＧ、ケトロールＣＧ－Ｔ、ケトロールＣＧ－ＳＦＴ（以上、三晶（株）製）、サンエース、サンエースＳ、サンエースＣ、サンエースＣ－Ｓ、サンエースＢ－Ｓ、サンエースＮＦ、サンエースＧ、サンエースＥ－Ｓ、サンエースＮＸＧ－Ｓ、サンエースＮＸＧ－Ｃ、ビストップＤ－３０００－ＤＦ、ビストップＤ－３０００－ＤＦ－Ｃ（以上、三栄源エフ・エス・アイ（株）製）、コージン、コージンＦ、コージンＴ、コージンＫ（以上、（株）興人製）などのキサンタンガム、レオザン（サクシノグルカン、三晶（株）製）、Ｋ１Ａ９６、ＢＧ３８１０（以上、三晶（株）製）などのウェランガム、Ｋ１Ａ１１２、Ｋ７Ｃ２４３３（以上、三晶（株）製）などのラムザンガム、ジャガー８１１１、同８６００、同ＨＰ－８、同ＨＰ－６０、ＣＰ－１３（以上、三晶（株）製）などのグァーガム類、プルラン（水溶性多糖類、（株）林原商事製）、レオジック２５０Ｈ（日本純薬（株）製）、ジュンロンＰＷ１１１（日本純薬（株）製）、Ｕジェリ・ＣＰ（昭和電工（株）製）などの架橋型アクリル酸樹脂、カーボポール９３４、カーボポール９４０、カーボポール９４１、カーボポール９８０、カーボポール９８１、カーボポール１３４２、カーボポール１３８２、カーボポール２９８４、カーボポール５９８４、カーボポールＥＴＤ２０２０、カーボポールＥＴＤ２０５０、ＥＺ－１、ペミュレンＴＲ－１、ペミュレンＴＲ－２（ルーブリゾール社製、アメリカ合衆国）などのアクリル酸メタクリル酸アルキル共重合体、ＧＸ－２０５、ＮＡ－０１０（昭和電工（株）製）などのＮ－ビニルアセトアミド重合架橋物、などが挙げられる。
　これらの粘度調整剤は、単独、あるいは２種以上混合して使用しても良い。 In the water-based ink used for the applicator, a viscosity modifier can be used to adjust the viscosity. Specific examples of the viscosity modifier include HPC-SL, HPC-L, HPC-M, HPC-H (above, hydroxypropylcellulose, Nippon Soda Co., Ltd.), Theola SC-900, Theola SC-900S, Theola RC591S, Theolas RC-N81, Theolas RC-N30, Theolas CL-611S, Theolas DX-2, Theolas DX-3, Theolas UF-F711, Theolas UF-F702, Theolas ST-100, Theolas ST-02, Theolas FD- 101, Theolas FD-301, Theolas FD-F20, Theolas fiber DF-17 (above, crystalline cellulose, manufactured by Asahi Kasei Co., Ltd.), Kelzan, Kelzan S, Kelzan T, Kelzan ST, Kelzan ASX, Kelzan AR , Kelzan HP, Kelzan G, Ketrol C , Ketorol CG-T, Ketorol CG-SFT (manufactured by Sanki Co., Ltd.), SAN ACE, SAN ACE S, SAN ACE C, SAN ACE CS, SAN ACE BS, SAN ACE NF, SAN ACE G, SAN ACE ES, San Ace NXG-S, San Ace NXG-C, Bistop D-3000-DF, Bistop D-3000-DF-C (above, manufactured by Saneigen FSI Co., Ltd.), Kojin, Kojin F, Kojin T Xanthan gum such as Kojin K (manufactured by Kojin Co., Ltd.), Leozan (succinoglucan, Sanki Co., Ltd.), K1A96, BG3810 (manufactured by Sanki Co., Ltd.), Welan gum, K1A112, Ramzan gum such as K7C2433 (manufactured by Sanki Co., Ltd.), Jaguar 8111, 8600, HP-8, HP-60, Guar gums such as P-13 (manufactured by Sanki Co., Ltd.), pullulan (water-soluble polysaccharides, Hayashibara Shoji Co., Ltd.), Rheozic 250H (manufactured by Nippon Seiyaku Co., Ltd.), Junron PW111 (Nippon Jun) Yakugyo Co., Ltd.), U Jeri CP (Showa Denko Co., Ltd.) and other cross-linked acrylic resins, Carbopol 934, Carbopol 940, Carbopol 941, Carbopol 980, Carbopol 981, Carbopol 1342 , Alkyl methacrylates such as Carbopol 1382, Carbopol 2984, Carbopol 5984, Carbopol ETD2020, Carbopol ETD2050, EZ-1, Pemulen TR-1, and Pemulen TR-2 (made by Lubrizol, USA) Polymer, GX-205, NA-010 (manufactured by Showa Denko KK), etc. N-vinylacetamide polymerization cross-linked product and the like.
These viscosity modifiers may be used alone or in admixture of two or more.
　上記成分の他に必要に応じて、保湿剤、潤滑剤、防腐剤、防黴剤、防錆剤、消泡剤、などの添加剤を併用して用いることができる。
　これらの、保湿剤、潤滑剤、防腐剤、防黴剤、防錆剤、消泡剤は、単独、あるいは２種以上混合して使用しても良い。 In addition to the above components, additives such as a humectant, a lubricant, an antiseptic, an antifungal agent, a rust preventive, and an antifoaming agent can be used in combination.
These moisturizers, lubricants, preservatives, antifungal agents, rust preventives and antifoaming agents may be used alone or in combination of two or more.
　上記塗布具に使用する水性インキにおいて、保湿剤の具体例としては、グリセリン、グルコース、マンノース、フルクトース、リボース、キシロース、アラビノース、ガラクトース、アルドン酸、グルシトール（ソルビット）、マルトース、セロビオース、ラクトース、スクロース、トレハロース、マルトトリオース、ヒアルロン酸、トリメチルグリシン、グリシン、尿素、ヒドロキシエチル尿素、１，２－ジメチル尿素、エチレン尿素、ジメチロールエチレン尿素、チオ尿素、グアニジン、ソルビット、ソルビタンが挙げられる。
　グリセリンは紙面上の筆跡を湿潤させる力が強いため極力使用しないことが好ましい。
　保湿剤の中でもグリシンはアミノ酸の中でも最も分子量が小さく、立体障害が少ないことなどの理由から、水性インキの粘度を増粘させにくく、着色樹脂粒子とワックス粒子との相互作用を起こすことによって筆跡の紙への浸透を向上させると共に耐ペン先乾燥性を維持することができるため使用することが好ましい。 In the water-based ink used for the applicator, specific examples of the humectant include glycerin, glucose, mannose, fructose, ribose, xylose, arabinose, galactose, aldonic acid, glucitol (sorbitol), maltose, cellobiose, lactose, sucrose, Examples include trehalose, maltotriose, hyaluronic acid, trimethylglycine, glycine, urea, hydroxyethylurea, 1,2-dimethylurea, ethyleneurea, dimethylolethyleneurea, thiourea, guanidine, sorbit, and sorbitan.
Since glycerin has a strong ability to wet the handwriting on the paper surface, it is preferable not to use it as much as possible.
Among moisturizers, glycine has the smallest molecular weight among amino acids and has few steric hindrances, making it difficult to increase the viscosity of water-based inks and causing the handwriting to interact with colored resin particles and wax particles. It is preferable to use it because it can improve penetration into paper and maintain resistance to drying of the nib.
　これらの保湿剤の添加量は、水性インキ全量に対し０．１重量％以上２０．０重量％以下が好ましく、０．５重量％以上１０．０重量％以下がより好ましい。これらの保湿剤は、単独、あるいは２種以上混合して使用しても良い。 The addition amount of these humectants is preferably 0.1% by weight or more and 20.0% by weight or less, and more preferably 0.5% by weight or more and 10.0% by weight or less with respect to the total amount of the water-based ink. These humectants may be used alone or in combination of two or more.
　防腐剤、防黴剤の具体例としては、デヒドロ酢酸ナトリウム、ベンゾイソチアゾリン－３－オン、オマジンナトリウム、安息香酸ナトリウム、モルホリン、モルホリン誘導体、などが挙げられる。 Specific examples of antiseptics and antifungal agents include sodium dehydroacetate, benzisothiazolin-3-one, sodium omadin, sodium benzoate, morpholine, morpholine derivatives, and the like.
　水性インキのｐＨを調整するために、ｐＨ調整剤を用いることができる。ｐＨ調整剤の具体例としては、水酸化ナトリウム、水酸化リチウム、モノエタノールアミン、ジエタノールアミン、トリエタノールアミン、アミノメチルプロパンジオール、オキシエチレンアルキルアミン、ポリオキシエチレンアルキルアミンなどの塩基性物質や、酢酸、塩酸、硝酸、硫酸、などの酸性物質が挙げられる。これらのｐＨ調整剤は、単独、あるいは２種以上混合して使用しても良い。２種類以上のｐＨ調整剤を併用することで、ｐＨの微調整が可能となったり、経時におけるｐＨ変化を抑制しやすくなるため好ましい。 In order to adjust the pH of the water-based ink, a pH adjuster can be used. Specific examples of pH adjusters include basic substances such as sodium hydroxide, lithium hydroxide, monoethanolamine, diethanolamine, triethanolamine, aminomethylpropanediol, oxyethylene alkylamine, polyoxyethylene alkylamine, and acetic acid. , Acidic substances such as hydrochloric acid, nitric acid and sulfuric acid. These pH adjusters may be used alone or in combination of two or more. It is preferable to use two or more kinds of pH adjusting agents in combination because it is possible to finely adjust the pH and to easily suppress pH change over time.
　水性インキを製造するには、上記の着色樹脂粒子と、ワックス粒子と水及び／又は有機溶剤と、分散剤と、プロペラやホモミキサー等にて充分に混合攪拌した後、他の添加剤、例えば粘度調整剤や、ｐＨ調整剤、潤滑剤等を混合し、更に均一になるまで溶解、混合することで得られる。
　また、これらの調製工程において、発生した分散熱をそのまま利用して撹拌したり、熱をかけたり、冷却したり、加圧したり、減圧したり、不活性ガス置換したりして、撹拌することができる。脱泡機による泡の除去やろ過機による粗大物のろ過等を必要に応じて行っても良い。更に、多糖類の分散性を十分にするために水性インキ調整後にエージング工程を行っても良い。
　これらの種々の混合工程、分散工程、ろ過工程、加熱工程および／又は冷却工程、加圧及び又は減圧工程、不活性ガス置換工程は、それぞれ単独で行ってもよく、あるいは、２種以上の工程を並行して行ってもよい。 To produce a water-based ink, the above colored resin particles, wax particles, water and / or an organic solvent, a dispersant, a propeller, a homomixer, etc. are mixed and stirred sufficiently, and then other additives such as It is obtained by mixing a viscosity adjusting agent, a pH adjusting agent, a lubricant, etc., and further dissolving and mixing until uniform.
Also, in these preparation steps, the generated heat of dispersion is used as it is, stirred, heated, cooled, pressurized, depressurized, or replaced with inert gas, and stirred. Can do. You may perform the removal of the foam by a defoamer, filtration of the coarse thing by a filter, etc. as needed. Further, an aging step may be performed after adjusting the water-based ink in order to make the dispersibility of the polysaccharide sufficient.
These various mixing steps, dispersion steps, filtration steps, heating steps and / or cooling steps, pressurization and / or depressurization steps, and inert gas replacement steps may each be carried out independently, or two or more steps. May be performed in parallel.
　以下、実施例により本発明を更に具体的に説明するが、本発明は、これらの実施例によって限定されるものではない。 Hereinafter, the present invention will be described more specifically with reference to examples. However, the present invention is not limited to these examples.
　実施例、比較例に記載の材料の添加量は重量％で表す。
　表１～７に示すとおり、実施例１～５６、比較例１～１１に使用した水性インキを、プロペラを用いて攪拌し作製した。作製手順としては、水と水溶性有機溶剤を容器に投入してプロペラで５分攪拌し、その他の添加剤を添加し、プロペラで３０分攪拌して水性インキを得た。
　市販されていない着色樹脂粒子は染料で着色したスチレン・アクリロニトリルモノマーを水溶性有機溶剤であるプロピレングリコールの添加量を調整しながら水中で乳化重合することで得たり、染料を有機溶剤である変性アルコールとアセトンに溶解させアクリル樹脂粒子と混合、攪拌させた後に有機溶剤を蒸発させて得た。
　顔料を内包した着色樹脂粒子はメタクリル酸、スチレン、ポリエチレン（１５）グリコールモノメタクリレート、ポリエチレン（５）グリコール・ポリプロピレン（７）グリコールモノメタクリレート、スチレンマクロモノマーをモノマー混合物とし、メチルエチルケトンと２，２‘－アゾビスイソブチロニトリルとオクチルメルカプタンとモノマー混合物を用いて重合することでポリマー溶液を作成し、顔料を加え分散機で混練しながら水を加え、減圧下でメチルエチルケトンを除去、水分を適宜除去して顔料を内包した着色樹脂粒子を得た。
　ワックス粒子は、融点以上で水中にてアルキルベンゼンスルホン酸ナトリウムを用いて乳化させた後冷却することで得たり、ワックスを溶解する水溶性有機溶剤とポリオキシエチレンソルビタンモノオレートを用いて転相乳化することで得た。
　また、平均粒子径は、レーザ式粒度分布測定機ＳＡＬＤ－７１００（（株）島津製作所製）を用いて測定し、得られた数値を基に平均粒子径（メジアン径）を体積基準で算出した値である。
　また、着色樹脂粒子とワックス粒子の平均粒子径の大きさを比較する場合は下記の通り計算を行った。（着色樹脂粒子の平均粒子径）／（ワックス粒子の平均粒子径）の値を％表記にした時の値の小数点第１を四捨五入して整数の値に丸めた値を用いて比較した。
　着色樹脂粒子及びワックス粒子をインキに配合するに当り、それぞれの分散液を使用する場合には、各粒子のインキ中における割合（重量％）は、各分散液の固形分の割合を、各分散液のインキに対する添加量に乗じて計算される値の小数点第２位を四捨五入して小数点第１位の値に丸めた値が、インキ全量に対する着色樹脂粒子又はワックス粒子そのものの配合割合である。 The addition amount of the material described in Examples and Comparative Examples is expressed in wt%.
As shown in Tables 1 to 7, water-based inks used in Examples 1 to 56 and Comparative Examples 1 to 11 were prepared by stirring with a propeller. As a production procedure, water and a water-soluble organic solvent were put into a container, stirred with a propeller for 5 minutes, other additives were added, and stirred with a propeller for 30 minutes to obtain a water-based ink.
Colored resin particles not commercially available can be obtained by emulsion polymerization of styrene / acrylonitrile monomers colored with dyes in water while adjusting the amount of propylene glycol, which is a water-soluble organic solvent, or modified alcohols, which are dyes that are organic solvents. And dissolved in acetone and mixed with acrylic resin particles and stirred, and then the organic solvent was evaporated.
The colored resin particles encapsulating the pigment are methacrylic acid, styrene, polyethylene (15) glycol monomethacrylate, polyethylene (5) glycol / polypropylene (7) glycol monomethacrylate, and styrene macromonomer as a monomer mixture, and methyl ethyl ketone and 2,2′- Create a polymer solution by polymerizing with azobisisobutyronitrile, octyl mercaptan and monomer mixture, add pigment while adding water while kneading with a disperser, remove methyl ethyl ketone under reduced pressure, remove moisture appropriately. Thus, colored resin particles encapsulating the pigment were obtained.
Wax particles are obtained by emulsifying with sodium alkylbenzene sulfonate in water at a melting point or higher and then cooling, or by phase inversion emulsification with a water-soluble organic solvent that dissolves wax and polyoxyethylene sorbitan monooleate. I got it.
The average particle diameter was measured using a laser type particle size distribution analyzer SALD-7100 (manufactured by Shimadzu Corporation), and the average particle diameter (median diameter) was calculated on the basis of the obtained numerical value. Value.
Moreover, when comparing the magnitude | size of the average particle diameter of a colored resin particle and a wax particle, it computed as follows. Comparison was made using a value obtained by rounding off the first decimal point of the value when the value of (average particle diameter of colored resin particles) / (average particle diameter of wax particles) was expressed in%, and rounding to an integer value.
When blending colored resin particles and wax particles in the ink, when using the respective dispersions, the ratio (wt%) of each particle in the ink is the ratio of the solid content of each dispersion. The value calculated by multiplying the added amount of the liquid with respect to the ink by rounding off the second decimal place to the first decimal place is the blending ratio of the colored resin particles or the wax particles themselves with respect to the total amount of ink.
Figure JPOXMLDOC01-appb-T000001
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Figure JPOXMLDOC01-appb-T000002
Figure JPOXMLDOC01-appb-T000002
Figure JPOXMLDOC01-appb-T000003
Figure JPOXMLDOC01-appb-T000003
Figure JPOXMLDOC01-appb-T000004
Figure JPOXMLDOC01-appb-T000004
Figure JPOXMLDOC01-appb-T000005
Figure JPOXMLDOC01-appb-T000005
Figure JPOXMLDOC01-appb-T000006
Figure JPOXMLDOC01-appb-T000006
Figure JPOXMLDOC01-appb-T000007
Figure JPOXMLDOC01-appb-T000007
　表１～７に示す各組成物の材料としては、具体的には下記のものを使用した。
着色樹脂粒子分散液（１）：桃色樹脂粒子分散液（ＮＫＷ３２０７Ｅ、平均粒子径　０．０９μｍの着色スチレン・アクリロニトリル樹脂粒子、固形分３７．５重量％、日本蛍光（株）製）
着色樹脂粒子分散液（２）：黄色樹脂粒子分散液（ＮＫＷ３２０５Ｅ、平均粒子径　０．０８μｍの着色スチレン・アクリロニトリル樹脂粒子、固形分３７．５重量％、日本蛍光（株）製）の濃縮液（固形分５０重量％）
着色樹脂粒子分散液（３）：紫色樹脂粒子分散液（ＳＦ－３０３７Ｎ、平均粒子径　０．０７μｍの着色スチレン・アクリロニトリル樹脂粒子、固形分４０重量％、シンロイヒ（株）製）
着色樹脂粒子分散液（４）：茶色樹脂粒子分散液（ＮＫＷ３２２６Ｅ、平均粒子径　０．１μｍの着色スチレン・アクリロニトリル樹脂粒子、固形分３７．５重量％、日本蛍光（株）製）
着色樹脂粒子分散液（５）：青色樹脂粒子分散液（平均粒子径　０．０１μｍの着色スチレン・アクリロニトリル樹脂粒子をＣ．Ｉ．ベーシックブルー３にて着色、固形分２０重量％）
着色樹脂粒子分散液（６）：赤色樹脂粒子（平均粒子径　１．０μｍのＣ．Ｉ．ピグメントレッド３内包スチレン樹脂粒子、固形分２０重量％）
着色樹脂粒子（１）：桃色樹脂粒子（ＭＰ－１０００、平均粒子径　０．４μｍのアクリル樹脂粒子、総研化学（株）製をＣ．Ｉ．ベーシックレッド１：１にて染着したもの）
着色樹脂粒子（２）：桃色樹脂粒子（ＭＸ－１０００、平均粒子径　１０μｍのアクリル樹脂粒子、総研化学（株）製をＣ．Ｉ．ベーシックレッド１：１にて染着したもの）
着色樹脂粒子（３）：桃色樹脂粒子（ＭＸ－５００、平均粒子径　５μｍのアクリル樹脂粒子、総研化学（株）製をＣ．Ｉ．ベーシックレッド１：１にて染着したもの）
着色樹脂粒子（４）：桃色樹脂粒子（ＳＸ－１３０Ｈ、平均粒子径　１．３μｍのアクリル樹脂粒子、総研化学（株）製をＣ．Ｉ．ベーシックレッド１：１にて染着したもの）
着色樹脂粒子（５）：蛍光橙色樹脂粒子（平均粒子径　３μｍ、着色アクリル樹脂粒子）顔料分散液（１）：黒色顔料分散液（平均粒子径　０．０９μｍのＣ．Ｉ．ピグメントブラック７分散液、固形分１５重量％）
顔料分散液（２）：赤色顔料分散液（平均粒子径　０．４０μｍのＣ．Ｉ．ピグメントレッド４分散液、固形分２５重量％）
染料（１）：黒色染料（ＷＡＴＥＲ　ＢＬＡＣＫ　３１、オリヱント化学工業（株）製）着色ワックス粒子分散液（１）：シアン顔料で着色したワックス粒子分散液（平均粒子径　０．１８μｍ、固形分１９．９重量％）
ワックス粒子分散液（１）：酸化ポリエチレンワックス粒子分散液（平均粒子径　０．０３μｍの酸化ポリエチレンワックス粒子分散液、固形分２０重量％）
ワックス粒子分散液（２）：ＡＱＵＡＣＥＲ　５０７（平均粒子径　０．０４μｍの酸化高密度ポリエチレンワックス粒子分散液、固形分３５重量％、ビックケミー・ジャパン（株）製）
ワックス粒子分散液（３）：ＡＱＵＡＣＥＲ　５１５（平均粒子径　０．０４μｍの酸化高密度ポリエチレンワックス粒子分散液、固形分３５重量％、ビックケミー・ジャパン（株）製）
ワックス粒子分散液（４）：ＨＹＴＥＣ　Ｅ－８２３７（平均粒子径　０．０８μｍの酸化ポリエチレンワックス粒子分散液、固形分３５重量％、東邦化学工業（株）製）
ワックス粒子分散液（５）：ＨＹＴＥＣ　Ｅ－４Ａ（平均粒子径　０．０６μｍの酸化ポリエチレンワックス粒子分散液、固形分３５重量％、東邦化学工業（株）製）
ワックス粒子分散液（６）：酸化ポリエチレンワックス粒子分散液（平均粒子径　０．００５μｍの酸化ポリエチレンワックス粒子分散液、固形分２０重量％）
ワックス粒子分散液（７）：Ｊｏｎｃｒｙｌ　Ｗａｘ　２６（平均粒子径　０．０７μｍの酸化ポリエチレンワックス粒子分散液、固形分２５重量％、ＢＡＳＦジャパン（株）製）
ワックス粒子分散液（８）：ＨＹＴＥＣ　Ｅ－１０００（平均粒子径　０．１４μｍの酸化ポリエチレンワックス粒子分散液、固形分３５重量％、東邦化学工業（株）製）
ワックス粒子分散液（９）：カルナバワックス粒子分散液（平均粒子径　０．０５μｍのカルナバワックス粒子分散液、固形分１０重量％）
ワックス粒子分散液（１０）：カルナバワックス粒子分散液（平均粒子径　０．００５μｍのカルナバワックス粒子分散液、固形分１０重量％）
ワックス粒子分散液（１１）：ＨＹＴＥＣ　Ｐ－９０１８（平均粒子径　０．０６μｍの酸化ポリプロピレンワックス粒子分散液、固形分３５重量％、東邦化学工業（株）製）
ワックス粒子分散液（１２）：Ｍｉｃｈｅｍ　Ｌｕｂｅ　１２４（平均粒子径　０．０５μｍのマイクロクリスタリンワックス粒子分散液、固形分４２重量％）
ワックス粒子分散液（１３）：マイクロクリスタリンワックス粒子分散液（平均粒子径　０．００７μｍのマイクロクリスタリンワックス粒子分散液、固形分２０重量％）
ワックス粒子分散液（１４）：パラフィンワックス粒子分散液（平均粒子径　０．０５μｍのパラフィンワックス粒子分散液、固形分１０重量％）
ワックス粒子分散液（１５）：パラフィンワックス粒子分散液（平均粒子径　０．０８μｍのパラフィンワックス粒子分散液、固形分１０重量％）
ワックス粒子分散液（１６）：カルナバワックス粒子分散液（平均粒子径　０．２５μｍのカルナバワックス粒子分散液、固形分４０重量％）
ワックス粒子分散液（１７）：カルナバワックス粒子分散液（平均粒子径　０．４μｍのカルナバワックス粒子分散液、固形分４０重量％）
ワックス粒子分散液（１８）：カルナバワックス粒子分散液（平均粒子径　３μｍのカルナバワックス粒子分散液、固形分４０重量％）
ワックス粒子分散液（１９）：カルナバワックス粒子分散液（平均粒子径　９．５μｍのカルナバワックス粒子分散液、固形分４０重量％）
樹脂エマルション（１）：Ｊｏｎｃｒｙｌ　５３７（平均粒子径　０．０７μｍのスチレン・アクリルエマルション、固形分４６重量％、ＢＡＳＦジャパン（株）製）
ラテックス粒子分散液（１）：ナルスター　ＳＲ－１００（平均粒子径　０．１８μｍのカルボキシ変性スチレンブタジエンゴム粒子を含むラテックス粒子分散液、固形分５１重量％、日本エイアンドエル（株）製）
ラテックス粒子分散液（２）：Ｎｉｐｏｌ　１５７１ＣＬ（平均粒子径　０．１０μｍのアクリロニトリルブタジエンゴム粒子を含むラテックス粒子分散液、固形分３８重量％、日本ゼオン（株）製）
樹脂粒子（１）：ケミスノー　ＭＰ－１０００（平均粒子径　０．４μｍのアクリル樹脂粒子、総研化学（株）製）
水溶性有機溶剤（１）：エチレングリコール
水溶性有機溶剤（２）：グリセリン
水溶性有機溶剤（３）：γ－ブチロラクトン
水溶性有機溶剤（４）：ヘキシレングリコール
水溶性有機溶剤（５）：エチレングリコールモノイソプロピルエーテル
水溶性有機溶剤（６）：ジエチレングリコールモノイソプロピルエーテル
水溶性有機溶剤（７）：ジエチレングリコールジエチルエーテル
水溶性有機溶剤（８）：Ｎ，Ｎ－ジメチルホルムアミド
水溶性有機溶剤（９）：トリエチレングリコールモノヘキシルエーテル
水溶性有機溶剤（１０）：１，２－ペンタンジオール
水溶性有機溶剤（１１）：１，２－ブタンジオール
水溶性有機溶剤（１２）：１，２－ヘキサンジオール
水溶性有機溶剤（１３）：ジエチレングリコール
水溶性有機溶剤（１４）：トリエチレングリコール
水溶性有機溶剤（１５）：スルホラン
保湿剤（１）：トリメチルグリシン（東京化成工業（株）製）
保湿剤（２）：ペンタエリスリトール
保湿剤（３）：グリシン（磐田化学工業（株）製）
活性剤（１）：ＢＹＫ－３４８（ポリエーテル変性シロキサン、ビックケミー・ジャパン（株）製）
活性剤（２）：サーフィノール　ＤＦ１１０Ｄ（アセチレングリコール系活性剤、日信化学工業（株）製）
活性剤（３）：サーフロンＳ１１１Ｎ（フッ素系界面活性剤、ＡＧＣセイケミカル（株）製）
活性剤（４）：ノイゲンＸＬ８０（ポリオキシエチレンアルキレン分鎖デシルエーテル、第一工業製薬（株）製）
ｐＨ調整剤（１）：トリエタノールアミン
防腐剤（１）：ＰＲＯＸＥＬ　ＧＸＬ（Ｓ）（ベンズイソチアゾリン－３－オン、ロンザジャパン（株）製） Specifically, the following materials were used as materials for the compositions shown in Tables 1 to 7.
Colored resin particle dispersion (1): Pink resin particle dispersion (NKW3207E, colored styrene / acrylonitrile resin particles having an average particle size of 0.09 μm, solid content of 37.5% by weight, manufactured by Nippon Fluorescence Co., Ltd.)
Colored resin particle dispersion (2): Concentrated liquid of yellow resin particle dispersion (NKW3205E, colored styrene / acrylonitrile resin particles having an average particle size of 0.08 μm, solid content of 37.5% by weight, manufactured by Nippon Fluorescence Co., Ltd.) (Solid content 50% by weight)
Colored resin particle dispersion (3): Purple resin particle dispersion (SF-3037N, colored styrene / acrylonitrile resin particles having an average particle size of 0.07 μm, solid content of 40% by weight, manufactured by Sinloihi Co., Ltd.)
Colored resin particle dispersion (4): Brown resin particle dispersion (NKW3226E, colored styrene / acrylonitrile resin particles having an average particle size of 0.1 μm, solid content of 37.5% by weight, manufactured by Nippon Fluorescence Co., Ltd.)
Colored resin particle dispersion (5): Blue resin particle dispersion (colored styrene / acrylonitrile resin particles having an average particle diameter of 0.01 μm are colored with CI Basic Blue 3, solid content 20% by weight)
Colored resin particle dispersion (6): Red resin particles (CI pigment red 3 encapsulated styrene resin particles having an average particle size of 1.0 μm, solid content 20% by weight)
Colored resin particles (1): Pink resin particles (MP-1000, acrylic resin particles having an average particle size of 0.4 μm, manufactured by Soken Chemical Co., Ltd., dyed with CI Basic Red 1: 1)
Colored resin particles (2): Pink resin particles (MX-1000, acrylic resin particles having an average particle size of 10 μm, dyed by CI Basic Red 1: 1 manufactured by Soken Chemical Co., Ltd.)
Colored resin particles (3): Pink resin particles (MX-500, acrylic resin particles having an average particle diameter of 5 μm, dyed by CI Basic Red 1: 1 manufactured by Soken Chemical Co., Ltd.)
Colored resin particles (4): Pink resin particles (SX-130H, acrylic resin particles having an average particle size of 1.3 μm, manufactured by Soken Chemical Co., Ltd., dyed with CI Basic Red 1: 1)
Colored resin particles (5): Fluorescent orange resin particles (average particle size 3 μm, colored acrylic resin particles) Pigment dispersion (1): Black pigment dispersion (CI pigment black 7 dispersion having an average particle size of 0.09 μm) , 15 wt% solids)
Pigment dispersion (2): Red pigment dispersion (CI pigment red 4 dispersion having an average particle size of 0.40 μm, solid content of 25% by weight)
Dye (1): Black dye (WATER BLACK 31, manufactured by Orient Chemical Co., Ltd.) Colored wax particle dispersion (1): Wax particle dispersion colored with a cyan pigment (average particle size 0.18 μm, solid content 19. 9% by weight)
Wax particle dispersion (1): Oxidized polyethylene wax particle dispersion (Oxidized polyethylene wax particle dispersion with an average particle size of 0.03 μm, solid content 20% by weight)
Wax particle dispersion (2): AQUACER 507 (Oxidized high-density polyethylene wax particle dispersion with an average particle size of 0.04 μm, solid content of 35% by weight, manufactured by Big Chemie Japan Co., Ltd.)
Wax particle dispersion (3): AQUACER 515 (oxidized high-density polyethylene wax particle dispersion with an average particle size of 0.04 μm, solid content of 35% by weight, manufactured by Big Chemie Japan Co., Ltd.)
Wax particle dispersion (4): HYTEC E-8237 (Oxidized polyethylene wax particle dispersion with an average particle size of 0.08 μm, solid content 35% by weight, manufactured by Toho Chemical Industry Co., Ltd.)
Wax particle dispersion (5): HYTEC E-4A (Oxidized polyethylene wax particle dispersion having an average particle size of 0.06 μm, solid content of 35% by weight, manufactured by Toho Chemical Industry Co., Ltd.)
Wax particle dispersion (6): Oxidized polyethylene wax particle dispersion (Oxidized polyethylene wax particle dispersion having an average particle size of 0.005 μm, solid content of 20% by weight)
Wax particle dispersion (7): Joncryl Wax 26 (Oxidized polyethylene wax particle dispersion having an average particle size of 0.07 μm, solid content 25% by weight, manufactured by BASF Japan Ltd.)
Wax particle dispersion (8): HYTEC E-1000 (Oxidized polyethylene wax particle dispersion having an average particle size of 0.14 μm, solid content of 35% by weight, manufactured by Toho Chemical Industry Co., Ltd.)
Wax particle dispersion (9): Carnauba wax particle dispersion (carnauba wax particle dispersion having an average particle size of 0.05 μm, solid content of 10% by weight)
Wax particle dispersion (10): Carnauba wax particle dispersion (carnauba wax particle dispersion with an average particle size of 0.005 μm, solid content of 10% by weight)
Wax particle dispersion (11): HYTEC P-9018 (Oxidized polypropylene wax particle dispersion having an average particle size of 0.06 μm, solid content of 35% by weight, manufactured by Toho Chemical Industry Co., Ltd.)
Wax particle dispersion (12): Michem Lube 124 (microcrystalline wax particle dispersion with an average particle size of 0.05 μm, solid content of 42% by weight)
Wax particle dispersion (13): Microcrystalline wax particle dispersion (microcrystalline wax particle dispersion having an average particle size of 0.007 μm, solid content of 20% by weight)
Wax particle dispersion (14): Paraffin wax particle dispersion (paraffin wax particle dispersion having an average particle size of 0.05 μm, solid content of 10% by weight)
Wax particle dispersion (15): Paraffin wax particle dispersion (paraffin wax particle dispersion having an average particle size of 0.08 μm, solid content of 10% by weight)
Wax particle dispersion (16): Carnauba wax particle dispersion (carnauba wax particle dispersion having an average particle size of 0.25 μm, solid content of 40% by weight)
Wax particle dispersion (17): Carnauba wax particle dispersion (carnauba wax particle dispersion with an average particle size of 0.4 μm, solid content of 40% by weight)
Wax particle dispersion (18): Carnauba wax particle dispersion (carnauba wax particle dispersion having an average particle size of 3 μm, solid content of 40% by weight)
Wax particle dispersion (19): Carnauba wax particle dispersion (carnauba wax particle dispersion with an average particle size of 9.5 μm, solid content of 40% by weight)
Resin emulsion (1): Joncryl 537 (styrene acrylic emulsion having an average particle size of 0.07 μm, solid content 46% by weight, manufactured by BASF Japan Ltd.)
Latex particle dispersion (1): Nalstar SR-100 (latex particle dispersion containing carboxy-modified styrene butadiene rubber particles having an average particle size of 0.18 μm, solid content 51% by weight, manufactured by Nippon A & L Co., Ltd.)
Latex particle dispersion liquid (2): Nipol 1571CL (latex particle dispersion liquid containing acrylonitrile butadiene rubber particles having an average particle diameter of 0.10 μm, solid content 38% by weight, manufactured by Nippon Zeon Co., Ltd.)
Resin particles (1): Chemisnow MP-1000 (acrylic resin particles having an average particle size of 0.4 μm, manufactured by Soken Chemical Co., Ltd.)
Water-soluble organic solvent (1): Ethylene glycol water-soluble organic solvent (2): Glycerin water-soluble organic solvent (3): γ-butyrolactone water-soluble organic solvent (4): Hexylene glycol water-soluble organic solvent (5): Ethylene Glycol monoisopropyl ether water-soluble organic solvent (6): Diethylene glycol monoisopropyl ether water-soluble organic solvent (7): Diethylene glycol diethyl ether water-soluble organic solvent (8): N, N-dimethylformamide water-soluble organic solvent (9): Tri Ethylene glycol monohexyl ether water-soluble organic solvent (10): 1,2-pentanediol water-soluble organic solvent (11): 1,2-butanediol water-soluble organic solvent (12): 1,2-hexanediol water-soluble organic solvent Solvent (13): Diethylene glycol water-soluble organic solvent (14): Triethylene glycol-soluble organic solvent (15): sulfolane humectant (1): trimethyl glycine (Tokyo Kasei Kogyo Co., Ltd.)
Moisturizer (2): Pentaerythritol moisturizer (3): Glycine (manufactured by Iwata Chemical Industry Co., Ltd.)
Activator (1): BYK-348 (polyether-modified siloxane, manufactured by Big Chemie Japan Co., Ltd.)
Activator (2): Surfynol DF110D (acetylene glycol-based activator, manufactured by Nissin Chemical Industry Co., Ltd.)
Activator (3): Surflon S111N (Fluorosurfactant, manufactured by AGC Sey Chemical Co., Ltd.)
Activator (4): Neugen XL80 (polyoxyethylene alkylene branched decyl ether, manufactured by Daiichi Kogyo Seiyaku Co., Ltd.)
pH adjuster (1): Triethanolamine preservative (1): PROXEL GXL (S) (benzisothiazolin-3-one, manufactured by Lonza Japan Co., Ltd.)
　試験用塗布具の作製
　実施例１～５６、比較例１～９にて使用した水性インキを、中綿（中綿の材質：ポリエステルとポリプロピレン混合繊維、中綿の空孔率：８１％（±２％のばらつきを有する））に１．２５ｍｌ充填したものを、水性マーキングペン（ノック式ハンディラインＳ、製品符号ＳＸＮＳ１５、ぺんてる（株）製）軸にセットし、ペン先（ペン先の材質：ポリエステル繊維、ペン先の空孔率：６０％（±２％のばらつきを有する）、ペン先の材質の繊維の太さ：３デニール）を取り付け、ノックをしてペン先を軸筒内に収納して密閉状態とし、その後２時間静置してペン先まで水性インキを十分に浸透させ、実施例１～５６、比較例１～９の塗布具を得た。また、比較例１０、１１にて使用した水性インキをシリンジ（ハミルトンマイクロシリンジ７０１、ジーエルサイエンス（株）製）で吸引し、０．１μｌ吐出出来る状態にした。 Preparation of test applicator The water-based inks used in Examples 1 to 56 and Comparative Examples 1 to 9 were made of batting (material of batting: mixed fiber of polyester and polypropylene, porosity of batting: 81% (± 2% ) With a water mark pen (Knock-type Handyline S, product code SXNS15, manufactured by Pentel Co., Ltd.) shaft, pen tip (material of the pen tip: polyester fiber, Attach the nib porosity: 60% (with a variation of ± 2%) and the nib material fiber thickness: 3 denier, knock and store the nib in the barrel to seal it After that, it was allowed to stand for 2 hours, and the water-based ink was sufficiently infiltrated into the pen tip to obtain applicators of Examples 1 to 56 and Comparative Examples 1 to 9. Further, the water-based ink used in Comparative Examples 10 and 11 was sucked with a syringe (Hamilton Microsyringe 701, manufactured by GL Science Co., Ltd.), so that 0.1 μl could be discharged.
　筆跡乾燥確認試験
　上記の各実施例、比較例（比較例１０、１１を除く）の試験用塗布具を、各実施例、比較例あたり３本ずつ用意し、温度２５℃、湿度６５％の環境下にて、筆記用紙（アルティマグロス７０（米坪８０ｇ／ｍ２）、日本製紙（株）製）に手書きで３０ｃｍの直線を筆記した後、筆記用紙紙面上の跡を指で横断するように１回擦ることを１秒ごとに繰り返し、筆跡が伸びなくなる時間を乾燥時間とした。比較例１０、１１の試験用塗布具を用いて、温度２５℃、湿度６５％の環境下にて、筆記用紙に０．１μｌ滴下した後、インキの滴下した面上を指で擦ることを１秒ごとに繰り返し、インキの滴下した面が伸びて周囲の筆記用紙に転写されなくなる時間を乾燥時間とした。
　表１～７には、乾燥時間を記載した（単位「秒」）。 Handwriting Drying Confirmation Test Three test applicators for each of the above Examples and Comparative Examples (excluding Comparative Examples 10 and 11) were prepared for each Example and Comparative Example, and the environment was at a temperature of 25 ° C. and a humidity of 65%. Below, write a 30cm straight line on writing paper (Artimagros 70 (80g / m 2 US tsubo), manufactured by Nippon Paper Industries Co., Ltd.) and then cross the trace on the writing paper with your finger. Rubbing once was repeated every second, and the time during which the handwriting did not extend was defined as the drying time. Using the test applicator of Comparative Examples 10 and 11, 0.1 μl was dropped on writing paper in an environment of a temperature of 25 ° C. and a humidity of 65%, and then the surface on which the ink was dropped was rubbed with a finger. Repeated every second, the time when the surface on which the ink was dropped extended and was not transferred to the surrounding writing paper was defined as the drying time.
Tables 1 to 7 show the drying time (unit: “second”).
　筆跡裏抜け確認試験
　上記の各実施例、比較例（比較例１０、１１を除く）の試験用塗布具を各実施例、比較例あたり５本ずつ用意し、温度２５℃湿度６５％の環境下にて、ノート（ＴＡＮＯＳＥＥ　ノートブック　セミＢ５　ＯＳＦ－５Ａ（米坪６５ｇ／ｍ２）、（株）大塚商会製）に手書きで０．５ｃｍ／秒の筆記速度で筆記した際の裏抜けの様子をデジタルマイクロスコープＶＨＸ－５０００（（株）キーエンス製）にて３０倍にて撮影し、画像編集ソフトＡｄｏｂｅ　Ｐｈｏｔｏｓｈｏｐ　ＣＣ（アドビシステムズ（株）製）によって筆跡全体のピクセル数と、筆記面の筆跡と同じ色としてソフトウェア上で認識される筆記面裏側の筆跡部分を裏抜け部分として裏抜け部分のピクセル数を計測し、筆跡全体に対する裏抜け部分の割合を求めた。比較例１０、１１の試験用塗布具を用いて、温度２５℃、湿度６５％の環境下にて、ノートに０．１μｌ滴下した際の裏抜けの様子をデジタルマイクロスコープにて撮影し、画像編集ソフトによって塗付面全体のピクセル数と、塗付面と同じ色としてソフトウェア上で認識される塗布面裏側を裏抜け部分として裏抜け部分のピクセル数を計測し、塗布面全体に対する裏抜け部分の割合を求めた。表１～７には、裏抜けの割合を記載した（単位「％」）。 Handwriting back-through confirmation test Five test applicators for each of the above examples and comparative examples (excluding comparative examples 10 and 11) were prepared for each example and comparative example, and the environment was at a temperature of 25 ° C. and a humidity of 65%. , The state of see-through when writing at a writing speed of 0.5 cm / sec on a notebook (TANOSEEE notebook semi-B5 OSF-5A (US tsubo 65 g / m 2 ), manufactured by Otsuka Shokai Co., Ltd.) Taken with a digital microscope VHX-5000 (manufactured by Keyence Corporation) at a magnification of 30x, and image editing software Adobe Photoshop CC (manufactured by Adobe Systems Inc.) has the same number of pixels as the handwriting on the writing surface. Measure the number of pixels in the back-through part using the hand-written part on the back side of the writing surface recognized as software as the back-through part, and obtain the ratio of the back-through part to the whole handwriting. . Using the test applicator of Comparative Examples 10 and 11, the state of back-throwing when 0.1 μl was dropped on a notebook in an environment of a temperature of 25 ° C. and a humidity of 65% was photographed with a digital microscope. The number of pixels on the entire coated surface is measured by the editing software, and the number of pixels on the back surface of the coated surface that is recognized on the software as the same color as the painted surface is measured. The ratio was calculated. Tables 1 to 7 show the percentage of strikethrough (unit: “%”).
　耐ペン先乾燥性確認試験
　上記の各実施例、比較例（比較例１０、１１を除く）の試験用塗布具を用いて、温度２５℃湿度２０％の環境下で、ペン先を露出した状態で横向きで放置して、３０分後、４５分後、６０分後、９０分後ごとに手書きで筆記し、筆跡のカスレが５ｃｍ以下であった最長の時間を筆記可能な時間とした。表１～７には、筆記可能な時間を記載した（単位「分」）。 Pen tip dryness confirmation test Using the test applicators of the above Examples and Comparative Examples (excluding Comparative Examples 10 and 11), the pen tip is exposed in an environment of a temperature of 25 ° C. and a humidity of 20%. The paper was handwritten every 30 minutes, 45 minutes, 60 minutes, and 90 minutes, and the longest time that the handwriting was less than 5 cm was defined as the time when writing was possible. Tables 1 to 7 show the time available for writing (unit: “minute”).
　結果を表１～７に示す。 Results are shown in Tables 1-7.
　実施例１～３の塗布具は、着色樹脂粒子と着色樹脂粒子に対して平均粒子径が５％以上９５％以下のワックス粒子とを少なくとも含む水性インキと、塗布先として、繊維集束体を備える塗布具であることから、複雑な曲路を形成している多孔状態の塗布先としての繊維集束体の先端から優先して吐出され、これよりも大径粒子の着色樹脂粒子に先んじて紙の繊維間の隙間を狭いものとし、着色樹脂粒子の紙への過度な浸透が抑制されることで、裏抜けが抑制できた。
　実施例４～６の塗布具は、実施例１～３の塗布具と比較して平均粒子径が０．０１μｍ以上１．０μｍ以下の着色樹脂粒子と平均粒子径が０．００５μｍ以上で着色樹脂粒子よりも小さいワックス粒子であることで、速乾性を付与でき、速乾性と裏移りの両立を達成することができた。
　実施例２４～２７、２９の塗布具と、実施例７～８、１３の塗布具を比較して、着色樹脂粒子の添加量をｘ重量％、前記ワックス粒子の添加量をｙ重量％としたとき、（式１）－０．１２ｘ＋２３．０≧ｙ＞－０．１２ｘ＋６．８の関係を満たし、ｘが０．５重量％以上５６．０重量％以下、ｙが０．１重量％以上であるので、裏抜け抑制と耐ペン先乾燥性を両立できた。
　また、実施例３６，３７、３９～４１の塗布具は実施例１７～２０の塗布具と比較して、着色樹脂粒子の添加量をｘ重量％、前記ワックス粒子の添加量をｙ重量％としたとき、（式１）－０．１２ｘ＋２３．０≧ｙ＞－０．１２ｘ＋６．８の関係を満たし、ｘが０．５重量％以上５６．０重量％以下、ｙが０．１重量％以上であるので、裏抜け抑制と耐ペン先乾燥性を両立できた。
　実施例１０および４５の塗布具は、実施例９および４４の塗布具と比較して、ワックス粒子が酸化ポリエチレンワックス粒子であることで裏抜け抑制効果が一層向上することができた。
　実施例４９および５４の塗布具は、実施例４６および５３の塗布具と比較して、着色樹脂粒子と着色樹脂粒子に対して平均粒子径が３３％以上６７％以下であることで裏抜け抑制効果が一層向上することができた。
　実施例５５～５８の塗布具は、実施例２８、３０～３２の塗布具と比較して、（式２）－０．１２ｘ＋１５．０≧ｙ＞－０．１２ｘ＋８．０の関係を満たし、ｘが０．５重量％以上５６．０重量％以下、ｙが０．１重量％以上であるので、裏抜け抑制と耐ペン先乾燥性を一層向上できた。
　また、実施例２３および４３および５８の塗布具を比較して、（式２）－０．１２ｘ＋１５．０≧ｙ＞－０．１２ｘ＋８．０の関係を満たし、ｘが０．５重量％以上５６．０重量％以下、ｙが０．１重量％以上であるので、裏抜け抑制と耐ペン先乾燥性を一層向上できた。
　実施例２２および４８の塗布具は、実施例２１および４７の塗布具と比較して、水溶性有機溶剤にジエチレングリコール、トリエチレングリコールの内少なくとも１つ以上含むことで、速乾性と耐ペン先乾燥性を一層向上することができた。
　実施例１６および５２の塗布具は、実施例１５および５１の塗布具と比較して、水溶性有機溶剤にジエチレングリコール、トリエチレングリコールの内少なくとも１つ以上含み、更にスルホランを併用することで、速乾性を一層向上することができた。
　実施例３１および５０の塗布具は、実施例３０および４９の塗布具と比較してグリシンを含むことで、速乾性を維持したまま、耐ペン先乾燥性を一層向上することができた。 The applicators of Examples 1 to 3 are provided with water-based ink containing at least colored resin particles and wax particles having an average particle diameter of 5% to 95% with respect to the colored resin particles, and a fiber bundle as an application destination. Since it is an applicator, it is ejected preferentially from the tip of the fiber bundle as a porous application destination forming a complicated curved path, and the paper is preceded by colored resin particles of larger diameter than this. By making the gap between the fibers narrow and suppressing the excessive penetration of the colored resin particles into the paper, it was possible to suppress the breakthrough.
The applicators of Examples 4 to 6 are colored resin particles having an average particle diameter of 0.01 μm or more and 1.0 μm or less and a colored resin having an average particle diameter of 0.005 μm or more as compared with the applicators of Examples 1 to 3. By using wax particles smaller than the particles, quick drying could be imparted, and both quick drying and set-off could be achieved.
By comparing the applicators of Examples 24 to 27 and 29 with the applicators of Examples 7 to 8 and 13, the amount of colored resin particles added was x wt%, and the amount of wax particles added was y wt%. When (Formula 1) −0.12x + 23.0 ≧ y> −0.12x + 6.8 is satisfied, x is 0.5 wt% or more and 56.0 wt% or less, and y is 0.1 wt% or more. As a result, it was possible to achieve both strikethrough suppression and resistance to pen tip drying.
Further, in the applicators of Examples 36, 37, and 39 to 41, the amount of the colored resin particles added was x wt%, and the amount of the wax particles added was y wt% compared to the applicators of Examples 17 to 20. When satisfying the relationship of (formula 1) −0.12x + 23.0 ≧ y> −0.12x + 6.8, x is 0.5 wt% or more and 56.0 wt% or less, and y is 0.1 wt% or more. As a result, it was possible to achieve both suppression of back-through and resistance to drying of the nib.
Compared with the applicator of Examples 9 and 44, the applicator of Examples 10 and 45 was able to further improve the effect of suppressing the breakthrough when the wax particles were oxidized polyethylene wax particles.
Compared to the applicators of Examples 46 and 53, the applicators of Examples 49 and 54 have an average particle diameter of 33% or more and 67% or less with respect to the colored resin particles and the colored resin particles. The effect could be further improved.
The applicators of Examples 55 to 58 satisfy the relationship of (Equation 2) −0.12x + 15.0 ≧ y> −0.12x + 8.0, compared with the applicators of Examples 28 and 30 to 32, and x Is 0.5% by weight or more and 56.0% by weight or less, and y is 0.1% by weight or more.
Further, comparing the applicators of Examples 23, 43 and 58, the relationship of (Equation 2) −0.12x + 15.0 ≧ y> −0.12x + 8.0 is satisfied, and x is 0.5 wt% or more 56 0.0% by weight or less and y is 0.1% by weight or more, so that it was possible to further improve back-through suppression and resistance to drying of the nib.
Compared with the applicators of Examples 21 and 47, the applicators of Examples 22 and 48 contain quick-drying and nib-resistant dryness by including at least one of diethylene glycol and triethylene glycol in the water-soluble organic solvent. The property could be further improved.
Compared to the applicators of Examples 15 and 51, the applicators of Examples 16 and 52 contained at least one of diethylene glycol and triethylene glycol in the water-soluble organic solvent, and further combined with sulfolane. Dryness could be further improved.
Compared with the applicators of Examples 30 and 49, the applicators of Examples 31 and 50 were able to further improve the nib drying resistance while maintaining quick-drying properties by containing glycine.
　これに対して、比較例１の塗布具は特許文献１に記載の発明であるが、速乾性を担保しようとした結果、ワックス粒子が含まれていないため裏抜けを担保する事ができなくなってしまった。
　比較例２、３、４の塗布具は着色剤が一般顔料であったり、染料であったりすることからノートのような薄い紙では筆跡の裏抜け抑制が十分満足できるものではなかった。
　比較例５の塗布具は着色剤としてワックスに着色剤を含有した粒子を用いているが、着色剤樹脂粒子とワックス粒子を併用していないので裏抜け抑制効果を満足できていない。
　比較例６の塗布具はワックス粒子の平均粒子径が着色樹脂粒子よりも大きいため、着色樹脂粒子が紙内部に先に浸透してしまうため裏移り抑制効果を満足できていない。
　比較例７～９の塗布具はワックス粒子以外の粒子を用いているが、ノートのような薄い紙に筆記すると裏移り抑制効果を発揮することができなかった。
　比較例１０、１１の塗布具は繊維集束体以外の方法で塗布しているため、紙面に水性インキを塗付した際に着色樹脂粒子とワックス粒子の移動速度の差が生じることがないため、着色樹脂粒子とワックス粒子が均等に紙面に塗付されるため着色樹脂粒子が紙に浸透しやすく裏抜けが発生しやすくなってしまった。 On the other hand, although the applicator of Comparative Example 1 is the invention described in Patent Document 1, as a result of trying to ensure quick drying, it is impossible to ensure the strikethrough because wax particles are not included. Oops.
In the applicators of Comparative Examples 2, 3, and 4, since the colorant is a general pigment or a dye, the thin paper such as a notebook is not sufficiently satisfactory in suppressing the penetrating of the handwriting.
The applicator of Comparative Example 5 uses particles containing a colorant in a wax as a colorant, but does not satisfy the effect of suppressing the strikethrough because the colorant resin particles and the wax particles are not used in combination.
In the applicator of Comparative Example 6, since the average particle size of the wax particles is larger than that of the colored resin particles, the colored resin particles penetrate into the paper first, so that the effect of preventing the set-off is not satisfied.
The applicators of Comparative Examples 7 to 9 used particles other than wax particles, but when they were written on a thin paper such as a notebook, the effect of preventing the set-off could not be exhibited.
Since the applicators of Comparative Examples 10 and 11 are applied by a method other than the fiber bundle, there is no difference in moving speed between the colored resin particles and the wax particles when water-based ink is applied to the paper surface. Since the colored resin particles and the wax particles are evenly applied to the paper surface, the colored resin particles easily penetrate into the paper and the back-through easily occurs.
　以上、本発明の実施形態について説明したが、本発明は上述した実施形態に限定されることはなく、上述した実施形態に変形を加えた形態や、これらの形態を適宜組み合わせた形態も含む。 As mentioned above, although embodiment of this invention was described, this invention is not limited to embodiment mentioned above, The form which added the deformation | transformation to embodiment mentioned above, and the form which combined these forms suitably are included.
　本明細書において、「同一」、「等しい」及び「均質」等の物事が等しい状態であることを表す表現は、厳密に等しい状態を表すのみならず、公差、若しくは、同じ機能が得られる程度の差が存在している状態も表すものとする。
　また、本明細書において、一の構成要素を「備える」、「含む」、又は、「有する」という表現は、他の構成要素の存在を除外する排他的な表現ではない。 In this specification, the expression indicating that things such as “identical”, “equal”, and “homogeneous” are in an equal state not only represents an exactly equal state, but also includes a tolerance or the same function. It also represents a state in which a difference exists.
In this specification, the expression “comprising”, “including”, or “having” one constituent element is not an exclusive expression for excluding the existence of another constituent element.

Claims (4)

  1. 着色樹脂粒子と、着色樹脂粒子の平均粒子径に対して平均粒子径が５％以上９５％以下のワックス粒子とを少なくとも含む水性インキと、塗布先として繊維集束体を備える塗布具。 An applicator comprising a water-based ink containing at least colored resin particles, wax particles having an average particle size of 5% or more and 95% or less with respect to the average particle size of the colored resin particles, and a fiber bundle as an application destination.
  2. 前記着色樹脂粒子の平均粒子径が０．０１μｍ以上１μｍ以下であり、前記ワックス粒子の平均粒子径が０．００５μｍ以上である請求項１に記載の塗布具。 The applicator according to claim 1, wherein an average particle diameter of the colored resin particles is 0.01 µm or more and 1 µm or less, and an average particle diameter of the wax particles is 0.005 µm or more.
  3. 前記着色樹脂粒子の添加量をｘ重量％、前記ワックス粒子の添加量をｙ重量％としたとき、（式１）－０．１２ｘ＋２３．０≧ｙ＞－０．１２ｘ＋６．８を満たし、ｘが０．５重量％以上５６．０重量％以下、ｙが０．１重量％以上である請求項１又は請求項２に記載の塗布具。 When the addition amount of the colored resin particles is x wt% and the addition amount of the wax particles is y wt%, (Equation 1) −0.12x + 23.0 ≧ y> −0.12x + 6.8 is satisfied, and x is The applicator according to claim 1 or 2, wherein 0.5 wt% or more and 56.0 wt% or less, and y is 0.1 wt% or more.
  4. 前記繊維集束体が、太さが０．５デニール以上５０デニール以下の繊維から少なくとも構成され、空孔率が２０％以上８０％以下である請求項１ないし請求項３のいずれかに記載の塗布具。 The coating according to any one of claims 1 to 3, wherein the fiber bundle is at least composed of fibers having a thickness of 0.5 denier or more and 50 denier or less, and a porosity is 20% or more and 80% or less. Ingredients.
PCT/JP2019/013200 2018-03-28 2019-03-27 Applicator WO2019189364A1 (en)

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EP4424785A1 (en) 2023-03-01 2024-09-04 Mitsubishi Pencil Company, Limited Writing instrument

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