JP6189103B2 - Marking pen - Google Patents

Description

  The present invention relates to a water-based ink composition using a pigment as a colorant and a marking pen incorporating the same.

  Conventionally, in a water-based ink composition using a pigment as a colorant, the dispersion state of the pigment is maintained by increasing the ink viscosity or adding a pigment dispersant in order to suppress the aggregation and precipitation of the pigment. Attempts have been made (see, for example, Patent Documents 1 and 2). In particular, among the above pigments, those having a large particle diameter exceeding 0.1 μm have extremely poor dispersion stability in water-based inks, so that a dispersion effect is imparted by adding a general-purpose pigment dispersant or adjusting the viscosity. Even in this case, aggregation and sedimentation may occur over time, resulting in poor writing.

  In contrast, in ballpoint pens, by imparting shear thinning to the ink, it is possible to maintain pigment dispersion in a high-viscosity state when not writing, and to lower the viscosity of the ink that is ejected using the rotation of the ball during writing. Therefore, the aggregation and sedimentation of the pigment can be effectively suppressed. However, since the ink cannot be applied to the marking pen, it is difficult to suppress the aggregation and sedimentation of the pigment over time.

JP 2004-231943 A JP 2004-18675 A

  Even when a water-based ink using a pigment as a colorant is applied to a marking pen, the present invention can stably maintain a dispersed state in the ink for a long period of time without causing blurring in handwriting. The present invention provides a marking pen incorporating a water-based ink composition for a marking pen that can continuously exhibit good writing performance.

The present invention requires a marking pen containing water, a pigment, fermented cellulose, and a water-based ink composition containing carboxymethylcellulose or a salt thereof that crosslinks the pigment and fermented cellulose.
Furthermore, it is a requirement that the pigment is in the range of an average particle size of 0.1 to 30 μm.
Furthermore, it is a requirement that a nib made of a fiber bundle is provided.

  The marking pen of the present invention can stably maintain the dispersion state in the ink for a long period of time even when a pigment is used as a colorant, and it can be written well without causing handwriting or poor writing. A marking pen capable of continuously exhibiting performance can be formed.

The water-based ink composition incorporated in the marking pen of the present invention contains a pigment and fermented cellulose in a cross-linked state in an aqueous medium using a cross-linking agent.
The fermented cellulose is obtained by aeration and agitation culture of subspecies of acetic acid bacteria in an appropriate medium, and separating and recovering the cellulose fibers produced outside the cells, forming a very fine three-dimensional network structure in an aqueous medium It is a fibrous material. Therefore, when added to water-based ink, a three-dimensional network structure is formed without increasing the ink viscosity. In the present invention, by using a cross-linking agent and fermented cellulose in combination, the dispersibility of the pigment is imparted using the fermented cellulose network, and the dispersed material and the simple substance of the fermented cellulose and the pigment are appropriately combined with the cross-linking agent. A bridge is used to maintain even dispersion throughout the ink. Therefore, even for marking pen applications, the dispersion state of the pigment can be maintained for a long time without increasing the ink viscosity, so that good writing can be performed for a long time without causing shading or blurring of handwriting. It will be something.

  The said fermented cellulose is added in 0.005-1.0 mass% with respect to the ink composition whole quantity, Preferably it is 0.01-0.5 mass%. Below this range, the pigment dispersion retention is not sufficient, and even if this range is exceeded, no further improvement in performance can be obtained.

The cross-linking agent ties together the fermented cellulose and the pigment or the network structure of each fermented cellulose to form a composite, and further refines the network structure of the fermented cellulose. Therefore, it is possible to ensure a state in which the pigment is more excellent in dispersion stability.
The cross-linking agent is not particularly limited as long as it has sufficient solubility in water or a water-soluble organic solvent in the ink, but a water-soluble polymer is particularly suitable. . Specific examples include synthetic polymers such as polyvinyl pyrrolidone and polyethylene glycol, and cellulose derivatives. Examples of the cellulose derivative include carboxymethylcellulose or a salt thereof, methylcellulose, ethylcellulose, hydroxyethylcellulose, hydroxypropylcellulose, hydroxypropylmethylcellulose, hydroxypropylethylcellulose, cellulose acetate and the like having a structure different from that of fermented cellulose. In particular, it is preferable to use carboxymethylcellulose or a salt thereof because it is easily entangled with fermented cellulose and can stably maintain a composite state for a long period of time. Furthermore, there are polyacrylic acid, acrylic acid copolymer, maleic acid resin, etc. Specifically, a resin such as acrylic resin, styrene acrylic resin, styrene maleic acid resin, etc. made into a salt form and made water-soluble. Can be used. The alkali metal forming the salt is typically sodium or potassium, and the amine is an aliphatic primary to tertiary amine such as mono-, di-, or tri-methylamine, mono-, di- or Representative examples include alcohol amines such as tri-propanolamine, methylethanolamine, methylpropanolamine, and dimethylethanolamine, ammonia, morpholine, N-methylphorin, and the like.
These crosslinking agents may be used alone or in combination of two or more.
The content of the crosslinking agent is 0.005 to 5.0% by mass, preferably 0.01 to 3.0% by mass, based on the total amount of the ink composition. Below this range, it is insufficient for improving the dispersion effect, and even if this range is exceeded, further performance improvement cannot be obtained.

Furthermore, in combination with the fermented cellulose, natural polymers such as xanthan gum and guar gum (ultrapolymer with a large molecular weight) and their derivatives are added to improve the dispersion state (diffusibility) of fermented cellulose and pigment in water. Can hold. Therefore, it is possible to secure a more stable dispersion state of the pigment.
The natural polymer is 0.001 to 0.5% by weight, preferably 0.05 to 0.1% by weight, based on the total amount of the ink composition.

Examples of the pigment include inorganic pigments such as carbon black and ultramarine blue, and organic pigments such as copper phthalocyanine blue and benzidine yellow, as well as water-dispersed pigments that are finely and stably dispersed in an aqueous medium in advance using a surfactant or the like. For example, C.I. I. Pigment Blue 15: 3B [Product Name: S.P. S. Blue GLL, pigment content 22%, manufactured by Sanyo Color Co., Ltd.], C.I. I. Pigment Red 146 [Product Name: S.P. S. Pink FBL, pigment content 21.5%, manufactured by Sanyo Dye Co., Ltd.], C.I. I. Pigment Yellow 81 [Product name: TC Yellow FG, pigment content about 30%, manufactured by Dainichi Seika Kogyo Co., Ltd.], C.I. I. Pigment Red220 / 166 [Product name: TC Red FG, pigment content: about 35%, manufactured by Dainichi Seika Kogyo Co., Ltd.].
As the fluorescent pigment, a fluorescent pigment in the form of fine particles of a synthetic resin in which various fluorescent dyes are formed into a solid solution in a resin matrix can be used.
In addition, the surface of a core substance selected from white pigments such as titanium oxide, phosphorescent pigments, metal powder pigments such as aluminum and bronze powder, natural mica, synthetic mica, alumina, and glass pieces is coated with a metal oxide such as titanium dioxide. Pearl pigments, cholesteric liquid crystal type bright pigments, and the like can also be used. Furthermore, the capsule pigment etc. which directly or microencapsulated the thermochromic composition, the photochromic composition, the fragrance | flavor etc. can be illustrated.

The thermochromic composition includes (a) an electron-donating color-forming organic compound, (b) an electron-accepting compound, and (c) a reversible thermochromic composition comprising a reaction medium that determines the temperature at which the color reaction occurs. The composition is suitable and is encapsulated in microcapsules and applied as a reversible thermochromic microcapsule pigment.
Examples of the reversible thermochromic composition include those described in Japanese Patent Publication No. 51-44706, Japanese Patent Publication No. 51-44707, Japanese Patent Publication No. 1-29398, etc., at a predetermined temperature (discoloration point). Discolored before and after, decolored state in the temperature range above the high temperature side discoloration point, color development state in the temperature range below the low temperature side discoloration point, only one specific state exists in the normal temperature range among the two states, The other state is maintained as long as the heat or cold required to develop the state is applied, but when the heat or cold is no longer applied, the hysteresis width returns to the state exhibited in the normal temperature range. A heat decolorable microcapsule pigment in which a reversible thermochromic composition having relatively small characteristics (ΔH = 1 to 7 ° C.) is encapsulated in a microcapsule can be applied.
Furthermore, comparatively large hysteresis characteristics (ΔH = 8 to 50) described in JP-B-4-17154, JP-A-7-179777, JP-A-7-33997, JP-A-8-39936, and the like. ° C), and exhibit large hysteresis characteristics described in JP-A-2006-137886, JP-A-2006-188660, JP-A-2008-45062, JP-A-2008-280523, In other words, the shape of the curve plotting the change in color density due to temperature change differs greatly between when the temperature is raised from the lower temperature side than the color change temperature range and when the temperature is lowered from the higher temperature side than the color change temperature range. The color changes following the path, and the color development state in the low temperature range below the complete color development temperature, or the color erase state in the high temperature range above the complete color erase temperature is in the specific temperature range. Microcapsule pigment was contained a reversible thermochromic composition heated decolorizable having chroma memory property can be applied.
Specifically, as the reversible thermochromic composition having color memory, a complete color development temperature can be obtained only in a freezing room, a cold district, etc., that is, −50 to 0 ° C., preferably −40 to − 5 ° C., more preferably −30 to −10 ° C., and complete decoloring temperature obtained from a frictional heat generated by a friction body, a heating body such as a hair dryer, that is, 50 to 95 ° C., preferably 50 to 90 ° C. More preferably, by specifying the range of 60 to 80 ° C. and specifying the ΔH value of 40 to 100 ° C., it is possible to effectively function to maintain the color exhibited in the normal state (daily life temperature range).

  Among the pigments, those having an average particle diameter of 0.1 μm or more have particularly poor dispersion stability, and therefore the constitution of the present invention is more useful. Specifically, those having an average particle size of 0.1 to 30 μm, preferably 0.1 to 20 μm are suitable because they can express a clear hue without hindering ink dischargeability (laser diffraction method, volume). By standards).

Furthermore, if necessary, a dye that can be dissolved in an aqueous medium may be used in combination.
As the dye, an acid dye, a basic dye, a direct dye, or the like can be used. As the acid dye, neucoccin (CI. 16255), tartrazine (CI. 19140), acid blue black 10B (C.I. 20470), Guinea Green (C.I. 42085), Brilliant Blue FCF (C.I. 42090), Acid Violet 6B (C.I. 42640), Soluble Blue (C.I. 42755) ), Naphthalene green (C.I. 44025), eosin (C.I. 45380), phloxine (C.I. 45410), erythrosin (C.I. 45430), nigrosine (C.I. 50420), acid flavin (C.I. 56205) or the like is used.
Examples of basic dyes include chrysoidine (C.I. 11270), methyl violet FN (C.I. 42535), crystal violet (C.I. 42555), malachite green (C.I. 42000), Victoria blue FB ( CI 44045), rhodamine B (C.I. 45170), acridine orange NS (C.I. 46005), methylene blue B (C.I. 52015) and the like are used.
As direct dyes, Congo Red (C.I. 22120), Direct Sky Blue 5B (C.I. 24400), Violet BB (C.I. 27905), Direct Deep Black EX (C.I. 30235), Kaya Las Black G Conch (C.I. 35225), Direct Fast Black G (C.I. 35255), Phthalocyanine Blue (C.I. 74180) and the like are used.

  The colorant containing the pigment can be used singly or in combination of two or more, and is used in the ink composition in the range of 1 to 35% by mass, preferably 2 to 30% by mass.

Furthermore, a pigment dispersant can also be used. The pigment dispersant is for adsorbing on the surface of the pigment particles and dispersing the pigment in water, and a water-soluble resin, a surfactant, or the like can be applied. Examples of water-soluble resins include water-soluble acrylic resins, cross-linked water-soluble acrylic resins, water-soluble maleic acid resins, water-soluble styrene resins, water-soluble styrene acrylic resins, water-soluble styrene maleic acid resins, polyvinyl pyrrolidone, and polyvinyl alcohol. And water-soluble urethane resins. The surfactant is selected from any of anionic, cationic, nonionic and amphoteric surfactants.
These pigment dispersants are applied in a range of 0.05 to 2% by mass, preferably in a range of 0.2 to 0.5% by mass with respect to 1% by mass of the pigment. If the amount used is small, further dispersion stability of the pigment cannot be obtained, and if it is large, the viscosity becomes high and the ink ejection property is deteriorated.

In addition, a conventional general-purpose water-soluble organic solvent compatible with water can be used, for example, ethanol, propanol, butanol, glycerin, sorbitol, triethanolamine, diethanolamine, monoethanolamine, ethylene glycol, diethylene glycol, thiodiethylene glycol. , Hexylene glycol, 1,3-butanediol, neoprene glycol, polyethylene glycol, propylene glycol, butylene glycol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, ethylene glycol monomethyl ether acetate, Propylene glycol monomethyl ether, propylene glycol Monoethyl ether, 2-pyrrolidone, N- methyl-2-pyrrolidone.
In addition, the said water-soluble organic solvent can also use 1 type, or 2 or more types together, It is 2-60 mass% in an ink composition, Preferably it is used in 5-35 mass%.

In addition, if necessary, pH adjusters such as inorganic salts such as sodium carbonate, sodium phosphate and sodium acetate, organic basic compounds such as water-soluble amine compounds, rust preventives such as benzotriazole, tolyltriazole and saponin , Carboxylic acid, sodium salt of 1,2-benzthiazolin-3-one, sodium benzoate, sodium dehydroacetate, potassium sorbate, propyl paraoxybenzoate, 2,3,5,6-tetrachloro-4- (methylsulfonyl) Preservatives or antifungal agents such as pyridine, urea, sorbit, mannitol, sucrose, glucose, reduced starch hydrolyzate, wetting agents such as sodium pyrophosphate, antifoaming agents, antioxidants, and ink penetration You may use the fluorine-type surfactant and nonionic surfactant to make.
Further, a lubricant can be added, such as metal soap, polyalkylene glycol fatty acid ester, ethylene oxide addition type cationic surfactant, phosphate ester type surfactant, N-acyl amino acid type surfactant, dicarboxylic acid type surfactant. , Β-alanine type surfactant, 2,5-dimercapto-1,3,4-thiadiazole and its salts and oligomers, 3-amino-5-mercapto-1,2,4-triazole, thiocarbamate, dimethyl A dithiocarbamate, α-lipoic acid, a condensate of N-acyl-L-glutamic acid and L-lysine, a salt thereof, or the like is used.
Further, oligomers of N-vinyl-2-pyrrolidone, oligomers of N-vinyl-2-piperidone, N-vinyl-2-pyrrolidone, N-cyclohexyl-2-pyrrolidone, ε-caprolactam, N-vinyl-ε-caprolactam By adding a thickening inhibitor such as an oligomer, it is possible to enhance the function in the intruding form.

  In addition, one or two or more water-soluble resins such as alkyd resin, acrylic resin, styrene maleic acid copolymer, cellulose derivative, polyvinyl pyrrolidone, polyvinyl alcohol, dextrin may be added in a category that does not hinder drying resistance, urea, One or more wetting agents such as nonionic surfactants, sorbitol, mannitol, sucrose, glucose, reduced starch hydrolyzate and sodium pyrophosphate can be added.

Furthermore, if necessary, a general-purpose shear thinning agent can be used to adjust the ink viscosity.
As the shear thinning agent, a substance that is soluble or dispersible in water is effective, and xanthan gum, welan gum, zetasy gum, dieutan gum, macrohomopsis gum, and a constituent monosaccharide is an organic acid-modified heterogeneous of glucose and galactose. Succinoglycan, which is a polysaccharide (average molecular weight: about 100 to 8 million), guar gum, locust bean gum and its derivatives, hydroxyethyl cellulose, alkyl alginate, alkyl ester of methacrylic acid, molecular weight 100,000 to 150,000 Polymers, glucomannan, carbohydrates having gelling ability extracted from seaweed such as agar and carrageenan, cross-linked poly N-vinyl-carboxylic acid amide, benzylidene sorbitol and benzylidene xylitol or their derivatives, cross-linkable acrylic acid Coalescence Inorganic fine particles, nonionic surfactants having an HLB value of 8 to 12, can be exemplified metal salts and amine salts of dialkyl sulfosuccinate. Furthermore, N-alkyl-2-pyrrolidone and an anionic surfactant may be used in combination in the ink composition.
The shear thinning agent can be used in the range of 0.1 to 20% by mass in the ink composition.

  The water-based ink composition of the present invention is practically used by filling a marking pen with a marking pen tip attached to a writing tip. The marking pen and the ballpoint pen have a cap type with a cap that covers the pen tip, a knock type, a rotary type, a slide type, etc. It may be.

The structure and shape of the marking pen itself are not particularly limited. For example, the tip of a marking pen (cannonball type, chisel type, brush pen type, etc.) such as a fiber tip, a felt tip, a plastic tip, etc. The ink occlusion body consisting of fiber bundles housed in the shaft cylinder is impregnated with ink, and the ink is supplied to the tip of the writing. A structure that supplies a predetermined amount of ink to the writing tip by interposing an ink flow rate adjusting member consisting of a member and a fiber bundle, storing ink directly inside the shaft cylinder, and applying a predetermined amount of ink to the writing tip by a valve mechanism A marking pen having a structure to be supplied may be mentioned.
Further, in addition to a single nib, a double-headed form in which nibs having different thicknesses and shapes are provided at both ends of the shaft cylinder may be used. In the double-headed form, one end may be a ballpoint pen.

  In particular, a fiber tip or felt tip made of a fiber converging body as a nib is more advantageous in terms of stability because a bridging pigment can be more stably held between fibers in the nib. A thing using an ink occlusion body made of a fiber bundle is also particularly useful for the same reason.

  Although the ink composition of an Example and a comparative example is shown in the following tables, this invention is not limited to these Examples. In addition, the numerical value of the composition in a table | surface shows a mass part. Moreover, each particle size used the laser type particle size distribution measuring machine LA-300 by Horiba, Ltd., and the median diameter was made into the average particle size.

The contents of the raw materials in the table will be described along the note numbers.
(1) Product name: WXM630 (particle size: 11-12 μm), manufactured by Toyo Aluminum Co., Ltd.
(2) Product name: EMR-D5660 (particle size: 11-12 μm), manufactured by Toyo Aluminum Co., Ltd.
(3) 4- (2,6-bis (2-ethoxyphenyl) -4-pyridinyl] -N, N-dimethylbenzenamine as component (a), 2,2-bis (4 ′) as component (b) -Hydroxyphenyl) -hexafluoropropane, a microcapsule pigment encapsulating a reversible thermochromic composition having color memory composed of 4-benzyloxyphenylethyl caprate as (c) component (cooled to -20 ° C or lower in advance) The microcapsule pigment is colored yellow). Average particle size: 2.5 μm, complete color erasing temperature: 61 ° C., complete color development temperature: −20 ° C., the color changes from yellow to colorless with temperature change.
(4) Product name: JR707 manufactured by Teika Co., Ltd. (particle size: 0.1-0.3 μm)
(5) Sanyo Dye Co., Ltd., trade name: Sundai Super Black (particle size: 0.1-0.2 μm)
(6) Anionic surfactant, manufactured by Daiichi Kogyo Seiyaku Co., Ltd., trade name: Rapisol A30
(7) Polymer active agent, manufactured by Lubrizol Corporation, trade name: Solsperse 43000
(8) Arch Chemicals Japan, trade name: Proxel XL-2

Preparation of ink Each raw material other than thickening components (fermented cellulose, carboxymethyl cellulose, xanthan gum, guar gum) was mixed in the blending amounts of the above Examples and Comparative Examples, and the mixture was stirred and mixed at 1000 rpm (20 ° C.) for 10 minutes, and then separately prepared. For the marking pen, add fermented cellulose, carboxymethylcellulose, xanthan gum and guar gum to water and stir and mix at 4000 rpm (20 ° C. for 1 hour), and stir and disperse at 2000 rpm for 10 minutes. A water-based ink composition was obtained.

Preparation of marking pens Each ink composition obtained is filled into an ink storage body in a shaft cylinder, and a tip is provided for a sample by providing an acrylic fiber bundle that is connected to the ink storage body with a resin at the tip. A marking pen was obtained.

The following tests were performed using each marking pen.
Written test For each sample marking pen that was confirmed to be writable, immediately after preparation (initial stage) and after being left in a 20 ° C environment for 60 days in the pen tip downward state (after time), the old JIS P3201 writing paper A The state of the handwriting when the hand-written spiral circle was continuously written was visually confirmed.
The results of the test are shown in the following table.

The evaluation of the test results is as follows.
Written test / initial ○: Good handwriting was obtained.
X: The ink viscosity was high and blurring and line jumping were observed in the handwriting.
-After time ○: Good handwriting was obtained.
Δ: Although writing is possible, many blurring and line jumps are seen in the handwriting from the start of writing, or a shading difference is seen in the handwriting.
X: A coloring component is not discharged or writing is impossible.

Claims (3)

A marking pen comprising water, a pigment, fermented cellulose, and a water-based ink composition containing carboxymethyl cellulose or a salt thereof for crosslinking the pigment and fermented cellulose.   The marking pen according to claim 1, wherein the pigment has an average particle size in the range of 0.1 to 30 µm. The marking pen according to claim 1, further comprising a pen tip made of a fiber bundling body.