JP2019206118A - Water based ball point pen refill - Google Patents

Abstract

To provide a water based ball point pen refill which can produce multicolored handwriting such that the handwriting colors form multi-colored marble patterns or change during writing, and realize good dry-up property and storage stability.SOLUTION: A water based ball point pen refill has an ink storage part in which two or more kinds of water-based ink of different color tones are stored inhomogeneously; and the two or more kinds of water-based ink of the water based ball point pen refill respectively include color agents, water-soluble organic solvent and resin particles.SELECTED DRAWING: Figure 1

Description

  The present invention relates to a refill for an aqueous ballpoint pen.

  Water-based ballpoint pens that can form multicolored handwritings that form a marble pattern having a plurality of handwriting colors or change the handwriting color during writing are known. In order to make it possible to form such a handwriting, a plurality of water-based inks having different color tones are usually filled in the ink container without being mixed in the ink container.

  As a water-based ink used in the water-based ballpoint pen, for example, a water-based ink containing titanium oxide, aluminum powder, or a pearl pigment is known (see Patent Document 1 below).

JP 2000-25380 A

  By using a water-based ink blended with titanium oxide, aluminum powder or pearl pigment, it becomes possible to form the above-mentioned multicolored handwriting. It has been found that there is room for further improvement in terms of storage stability.

  The present invention has been made in view of the above circumstances, and forms a multicolored handwriting in which the color of the handwriting forms a multi-colored marble pattern or the color of the handwriting changes during writing. It is an object of the present invention to provide an aqueous ballpoint pen refill that can achieve good dry-up properties and storage stability.

  The present invention is a water-based ballpoint pen refill comprising an ink containing portion in which two or more types of water-based inks having different colors are stored non-uniformly, each of the two or more types of water-based inks comprising a colorant, a water-soluble organic solvent, and An aqueous ballpoint pen refill comprising resin particles is provided.

  By using the refill for a ballpoint pen according to the present invention, it is possible to achieve good dry-up properties and storage stability while enabling the formation of multicolored handwriting. Here, “non-uniform” means that the water-based ink is not uniform in color tone, in other words, has a distribution in the ink containing portion.

  As the water-based ink, for example, one having a viscosity of 3000 to 6000 mPa · s can be adopted. By using such water-based ink, it becomes possible to more effectively suppress sedimentation of pigments and resin particles over time, and ink followability can be obtained, so that further storage stability can be achieved. it can.

  The colorant may be a fluorescent pigment. By using the fluorescent pigment as the colorant, the decorative effect on the appearance of the handwriting can be improved, and the aesthetic effect of the ink containing portion containing the aqueous ink containing the fluorescent pigment can also be obtained.

  According to the present invention, it is possible to form a multicolored handwriting that forms a multi-colored marble pattern, or the handwriting color changes during writing, and is good It is possible to provide an aqueous ballpoint pen refill that can achieve excellent dry-up property and storage stability.

It is a schematic sectional drawing which shows the refill for water based ball-point pens concerning this embodiment.

  The refill for a water-based ballpoint pen according to the present embodiment includes an ink storage unit in which two or more types of water-based inks having different color tones are stored non-uniformly. Each of the water-based inks contains a colorant, a water-soluble organic solvent, resin particles, and water. Such a water-based ballpoint pen refill makes it possible to form a multicolored handwriting in which the handwriting color forms a multi-colored marble pattern or the handwriting color changes during writing. In addition, good dry-up property and storage stability can be achieved.

  The present inventors infer the reason why the above-described effects, particularly good dry-up property and storage stability, are achieved by using the aqueous ballpoint pen refill according to the present embodiment as follows. That is, the titanium oxide, aluminum powder or pearl pigment contained in the conventional water-based ink has a large specific gravity, and the uniformity of the ink is lowered by long-term storage, so that the dry-up property and the storage stability are lowered. On the other hand, the water-based ink used in the refill for the water-based ballpoint pen according to the present embodiment is less likely to deteriorate the uniformity of the ink even when stored for a long period of time by blending resin particles. And storage stability are considered to have been achieved.

  Hereinafter, preferred embodiments of the present invention will be described in detail with reference to the drawings as necessary.

  FIG. 1 is a schematic sectional view showing a refill for an aqueous ballpoint pen according to the present embodiment. As shown in FIG. 1, the water-based ballpoint pen refill 1 according to the present embodiment includes a hollow cylindrical ink containing portion 11, a ballpoint pen tip 12, a joint member 13 that connects the ink containing portion 11 and the ballpoint pen tip 12, and These are filled with water-based ink 14 inside. In the ink containing portion 11, two or more (for example, three, four, five, etc.) water-based inks 14 having different color tones are accommodated unevenly. In FIG. The inks 14a, 14b, and 14c are filled so as to form a spiral pattern without being mixed with each other in the ink containing portion 11. Further, a backflow preventer 15 is accommodated in a state adjacent to the water-based ink 14 on the side opposite to the contact member 13 of the water-based ink 14 in the ink storage unit 11. The ball-point pen tip 12 includes a ball holder 16 and a ball 17 that is rotatably held by the ball holder 16. Further, although not shown, a tail plug that prevents leakage of the water-based ink 14 and the backflow preventer 15 may be provided at the end of the ink containing portion 11 opposite to the joint member 13.

  The ink containing portion 11 can use a resin made of polypropylene, polyethylene, polyethylene terephthalate, nylon, polyacetal, polycarbonate, or the like as an ink containing member. The shape of the ink containing portion 11 is not particularly limited as long as it is a hollow cylindrical shape, and may be a cylindrical shape, for example.

  As the ball holder 16 and the ball 17 in the ballpoint pen tip 12, those used in a normal ballpoint pen can be used as appropriate. Moreover, the diameter of the ball | bowl 17 may be 0.3-1.2 mm, for example.

  As the joint member 13, for example, a member made of polypropylene, polyethylene, polyethylene terephthalate, nylon, polyacetal, polycarbonate, or the like can be used.

  The backflow preventer 15 has a function of preventing the water-based ink from flowing out (prevention of outflow), a function of preventing the water-based ink from drying up (sealing performance), and the like, and the backflow preventer having such a function is used without particular limitation. be able to. Such a backflow preventer 15 includes, for example, a base oil and a thickener. Examples of the base oil include mineral oil, polybutene, silicone oil, glycerin, polyalkylene glycol and the like. Examples of thickeners include metal soap thickeners, organic thickeners, and inorganic thickeners.

  Each of the water-based inks 14 includes a colorant, a water-soluble organic solvent, resin particles, and water. Here, the water-based ink having a different color tone may be a water-based ink obtained by variously changing the type, combination, content, and the like of the colorant among the above components. For example, when the water-based ink 14 includes three types of water-based inks having different color tones, the first water-based ink includes a first colorant, and the second water-based ink is a second different from the first colorant. The third water-based ink may contain a third colorant different from the first and second colorants.

  Examples of the colorant include dyes and pigments. The dye is preferably a water-soluble dye, and examples thereof include a direct dye, an acid dye, and a basic dye. The pigment is preferably a water-dispersible pigment, and examples thereof include organic pigments and inorganic pigments. You may use a coloring agent individually by 1 type or in combination of 2 or more types.

  Examples of direct dyes include color index (hereinafter referred to as CI) Direct Black 17, 19, 38, 154, C.I. I. Direct Yellow 1, 4, 12, 29, C.I. I. Direct Orange 6, 8, 26, 29, C.I. I. Direct Red 1, 2, 4, 13, C.I. I. Direct Blue 2, 6, 15, 15, 78, and the like.

  Examples of acid dyes include C.I. I. Acid Black 2, 31 and C.I. I. Acid Yellow 3, 17, 23, 73, C.I. I. Acid Orange 10, C.I. I. Acid Red 13, 14, 18, 27, 52, 73, 87, 92, C.I. I. Acid Blue 5, 9, 74, 90 and the like.

  Examples of basic dyes include C.I. I. Basic Yellow 2, 3 and C.I. I. Basic Red 1, 2, 8, 8, C.I. I. Basic Violet 1, 3, 10, C.I. I. Basic Blue 5, 9, 26 and the like.

  The water-dispersible pigment is not particularly limited as long as it is dispersible in an aqueous medium, and examples thereof include inorganic pigments such as carbon black and metal powder, organic pigments such as azo-based, phthalocyanine-based, and quinacdrine-based, fluorescent pigments, and the like. It is done.

  The content of the colorant is preferably 5 to 40% by mass, more preferably 20 to 30% by mass, based on the amount of each aqueous ink containing the colorant.

  Water-soluble organic solvents include ethylene glycol, diethylene glycol, triethylene glycol, polyethylene glycol, propylene glycol, ethylene glycol monomethyl ether, glycerin, pyrrolidone, urea, thiourea, ethylene urea, sorbit, mannitol, sucrose, glucose, reduced Examples include starch hydrolysates and sodium pyrophosphate. The content of the water-soluble organic solvent is preferably 1 to 30% by mass and more preferably 5 to 20% by mass based on the amount of each water-based ink containing the water-soluble organic solvent.

  As the resin particles, for example, resin fine particles having an average particle diameter of 0.1 to 2 μm, preferably 0.5 to 1.5 μm can be used. If the average particle size is 0.1 μm or more, the temporal stability of the ink is further improved. If the average particle size is 2 μm or less, the dry-up performance is further improved, and ink can be discharged more stably. The average particle size of the resin particles can be measured by a laser diffraction particle size distribution measurement method on a volume basis.

  From the viewpoint of more effectively improving storage stability, the specific gravity of the 30% by mass aqueous dispersion of resin particles is preferably 1.40 or less. On the other hand, the lower limit of the specific gravity of the 30% by mass aqueous dispersion of resin particles is not particularly limited, but is, for example, 1.0 or more.

  Examples of the resin particles include acrylic resin particles, acrylic resin particles, urethane resin particles, epoxy resin particles, vinyl acetate resin particles, vinyl chloride resin particles, polyester resin particles, polyolefin resin particles, Examples include melamine resin particles, benzoguanamine resin particles, phenol resin particles, and silicone resin particles.

  The content of the resin particles is preferably 0.5 to 15% by mass, more preferably 3 to 10% by mass based on the amount of each aqueous ink containing the resin particles. If the content of the resin particles is within the above range, multicolored handwriting can be expressed and maintained more effectively, and writing characteristics such as ink followability can be improved.

  The water-based ink according to this embodiment may contain water as an aqueous solution or an aqueous dispersion of the above-described components or separately from the above-described components.

  The water-based ink according to this embodiment may contain additives such as preservatives, rust preventives, lubricants, thickeners and the like in addition to the components described above.

  Examples of preservatives include carboxylic acid, sodium salt of 1,2-benzisothiazolin-3-one, sodium benzoate, sodium dehydroacetate, nitrogen-containing sulfur compounds, potassium sorbate, propyl paraoxybenzoate, 2,3,5, Examples include 6-tetrachloro-4- (methylsulfonyl) pyridine. These can be used individually by 1 type or in combination of 2 or more types. The content of the preservative may be 0.1 to 5% by mass or 0.1 to 1% by mass based on the amount of each aqueous ink containing the preservative.

  Examples of rust inhibitors include benzotriazole or derivatives thereof, tolyltriazole, dicyclohexylammonium nitrite, diisopropylammonium nitrite, sodium thiosulfate, ethylenediaminetetraacetate, octyl phosphate, imidazole, benzimidazole, saponin, dialkylthiourea, etc. Is mentioned. These can be used individually by 1 type or in combination of 2 or more types. The content of the rust inhibitor may be 0.3 to 5 mass% or 0.5 to 3 mass% based on the amount of each water-based ink containing the rust inhibitor.

  Lubricants include higher fatty acids such as oleic acid, nonionic surfactants having a long chain alkyl group, polyether-modified silicone oil, thiophosphite tri (alkoxycarbonylmethyl ester), thiophosphite tri (alkoxycarbonyl) Thiophosphorous triesters such as ethyl ester), or metal salts, ammonium salts, amine salts, alkanolamine salts thereof, and the like. These can be used individually by 1 type or in combination of 2 or more types. The content of the lubricant may be 0.1 to 5% by mass or 0.3 to 3% by mass based on the amount of each water-based ink containing the lubricant.

  As the thickener, natural-xanthan gum, guar gum, locust bean gum, carrageenan, gum arabic, tragacanth gum, alginic acid, gelatin, agar, casein, psyllium sheet gum, tamarind sheet gum, synthetic system-methylcellulose, ethylcellulose, hydroxyethylcellulose, Examples thereof include carboxymethyl cellulose, sodium carboxymethyl cellulose, sodium alginate, polyvinyl pyrrolidone, polyvinyl alcohol, polyvinyl methyl ether, sodium polyacrylate, carboxyvinyl polymer and the like. These can be used individually by 1 type or in combination of 2 or more types. The content of the thickening agent may be 0.1 to 3% by mass or 0.2 to 1% by mass based on the amount of each aqueous ink containing the thickening agent.

  The water-based ink according to the present embodiment preferably has a viscosity of 3000 to 6000 mPa · s, and is 3500 to 5000 mPa · s, measured at 25 ° C. and 0.1 rpm using an E-type viscometer. More preferably. By using such water-based ink, it becomes possible to more effectively suppress sedimentation of pigments and resin particles over time, and ink followability can be obtained, so that further storage stability can be achieved. it can.

  The water-based ink according to this embodiment can be obtained by mixing the above-described raw materials using, for example, a stirrer such as a dissolver, a Henschel mixer, or a homomixer. The stirring conditions of the stirrer are not particularly limited. For example, by using a dissolver stirrer and stirring at a rotation speed of 5000 to 12000 rpm for 60 to 120 minutes, a water-based ink in which each component is uniformly dispersed can be obtained.

  An aqueous ball-point pen can be manufactured by the manufacturing method of a normal ball-point pen etc. using the refill 1 for water-based ball-point pens concerning this embodiment mentioned above.

  As mentioned above, although the refill for water-based ball-point pens concerning this embodiment was explained, the present invention is not limited to the above-mentioned embodiment. For example, in the above-described embodiment, an example in which three types of water-based inks 14a, 14b, and 14c having different color tones are filled in the ink storage unit 11 so as to form a spiral pattern without being mixed with each other is shown. However, for example, the water-based inks 14a, 14b, and 14c may be filled so as to form a layer in the vertical direction or the horizontal direction without being mixed with each other in the ink containing portion 11, or in a marble shape. It may be filled to form a pattern.

  EXAMPLES Hereinafter, although an Example and a comparative example are given and this invention is demonstrated concretely, this invention is not limited to a following example.

[Preparation of water-based ink]
Water-based inks having the compositions shown in Table 1 and Table 2 were prepared using the components shown below. The viscosity of each obtained water-based ink was measured using an E-type viscometer under the conditions of 25 ° C., cone radius 24 mm, cone angle 0.8 °, and 0.1 rpm. Tables 1 and 2 show the composition (unit: mass%) and viscosity (unit: mPa · s) of each water-based ink.

(Coloring agent)
A1: Fluorescent yellow pigment (trade name “Lumicol NKW-7005E” manufactured by Nippon Fluorescent Chemical Co., Ltd.)
A2: Fluorescent red pigment (trade name “Lumicol NKW-7003E” manufactured by Nippon Fluorescent Chemical Co., Ltd.)
A3: Fluorescent light blue pigment (trade name “Lumicol NKW-7008E” manufactured by Nippon Fluorochemicals, Inc.)

(Water-soluble organic solvent)
B: Glycerin

(Resin particles)
C1: Acrylic acid resin particles (manufactured by Nippon Zeon Co., Ltd., trade name “Nipol MH5055”; average particle size: 500 nm, solid content: 30 mass%, specific gravity of 30 mass% aqueous dispersion: 1.30)
C2: Melamine resin particles (manufactured by Nippon Shokubai Co., Ltd., trade name “Eposter S12”; average particle size: 1.2 μm, solid content: 100 mass%, specific gravity of 30 mass% aqueous dispersion: 1.40)

(Preservative)
D: Nitrogen-containing sulfur compound (manufactured by Nippon Enviro Chemicals Co., Ltd., trade name “Slout 99N”)

(Rust inhibitor)
E: Benzotriazole

(lubricant)
F: Made by NOF Corporation, trade name "Naymin L-202"

(Thickener)
G: Xanthan gum

(Other ingredients)
H1: Pearl pigment (manufactured by Merck Japan Ltd., trade name “Iriodin 111”; average particle diameter: 1 to 15 μm, solid content: 100 mass%, specific gravity of 30 mass% aqueous dispersion: 1.59)
H2: Aluminum paste (made by Showa Aluminum Powder Co., Ltd., trade name “SAP 5502SW”; average particle size: 15 μm, solid content: 64-68% by mass, specific gravity of 30% by mass aqueous dispersion: 1.53)

[Preparation of ballpoint pen refill]
Example 1
A ballpoint pen refill was prepared by filling the ink containing portion with the water-based ink 1-1, 1-2, and 1-3 obtained above so as to form a marble pattern in the ink containing portion 11.

(Example 2)
A ballpoint pen refill was prepared in the same manner as in Example 1 except that the water-based ink was replaced with 2-1, 2-2 and 2-3.

(Example 3)
A ballpoint pen refill was prepared in the same manner as in Example 1 except that the water-based ink was replaced with 3-1, 3-2 and 3-3.

Example 4
A ballpoint pen refill was prepared in the same manner as in Example 1 except that the water-based ink was replaced with 4-1, 4-2, and 4-3.

(Comparative Example 1)
A ballpoint pen refill was prepared in the same manner as in Example 1 except that the water-based ink was replaced with 5-1, 5-2 and 5-3.

(Comparative Example 2)
A ballpoint pen refill was prepared in the same manner as in Example 1 except that the water-based ink was replaced with 6-1, 6-2 and 6-3.

[Evaluation of ballpoint pen refill]
The following evaluation was performed with respect to the refill for ball-point pens produced in Examples 1-4 and Comparative Examples 1-2.

(Dry-up property)
Each ballpoint pen refill was stored at 25 ° C. for 3 months. Characters and loops were written on the report paper using the ball pen refill after storage, and the state of the handwriting was visually observed. Based on the observation results, the dry-up property was evaluated according to the following criteria. The results are shown in Table 3.
A: Characters and loops can be written with no problem, and there is no abnormality such as rubbing on the writing line.
B: Characters and loops can be written, but rubbing or the like is observed on the writing line.
C: Characters and loops cannot be written.

(Storage stability)
The balls in the ballpoint pen tip of each ballpoint pen refill were protected with resin balls and stored at a temperature of 50 ° C. for 2 months. Characters and loops were written on the report paper using the ball pen refill after storage, and the state of the handwriting was visually observed. Based on the observation results, the storage stability was evaluated according to the following criteria. The results are shown in Table 3.
A: Characters and loops can be written with no problem, and there is no abnormality such as rubbing on the writing line.
B: Characters and loops can be written, but rubbing or the like is observed on the writing line.
C: Characters and loops cannot be written.

(Writing characteristics)
When the loop was written using the refill for ball-point pens produced in Examples 1 to 4 and the handwriting was confirmed, it was confirmed that the color of the handwriting formed a multi-colored marble pattern.

  DESCRIPTION OF SYMBOLS 1 ... Refill for water-based ball-point pen, 11 ... Ink storage part, 12 ... Ball-point pen tip, 13 ... Joint member, 14 ... Water-based ink, 15 ... Backflow prevention body, 16 ... Ball holder, 17 ... Ball

Claims (3)

A refill for a water-based ballpoint pen comprising an ink storage portion in which two or more types of water-based inks having different color tones are stored non-uniformly,
The aqueous ballpoint pen refill, wherein each of the two or more water-based inks contains a colorant, a water-soluble organic solvent, and resin particles.   The aqueous ballpoint pen refill according to claim 1, wherein the two or more types of water-based inks each have a viscosity of 3000 to 6000 mPa · s.   The aqueous ballpoint pen refill according to claim 1 or 2, wherein the colorant is a fluorescent pigment.

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