JP2001342393A - Aqueous ink composition for writing utensil - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an aqueous ink composition for writing utensils which scarcely causes blotting of a writing, and has a persistent scent by containing a perfume stably dispersed in the aqueous medium. SOLUTION: The ink composition contains at least one compound comprising a polyoxyethylene cholesteryl ether, and it also contains a coloring agent, a perfume and water.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a water-based ink composition for a writing instrument, which has a feature of emitting a scent at the time of writing and leaving a faint scent even in a trace of a drawing line.

[0002]

2. Description of the Related Art Generally, a fragrance is oil-soluble, and an emulsifier or a dispersant that serves as a protective colloid is required for emulsification and dispersion in water. Although a water-soluble resin or a surfactant is used as the protective colloid, for most water-soluble resins, the viscosity of the liquid increases when a resin amount sufficient to disperse a necessary and sufficient fragrance increases the suitability as a writing implement ink. Will be lacking.

On the other hand, an emulsified liquid prepared by using a surfactant in an amount sufficient to emulsify a fragrance in a stable state causes a significant decrease in surface tension and makes practical handwriting such as handwriting bleed easily. There are issues. In addition, if the fragrance is simply emulsified or dispersed by the above-described method, a fragrance is emitted immediately after writing, but the fragrance is immediately lost and cannot be retained for a long time (there is no sustainability).

[0004] On the other hand, conventionally, as a writing instrument ink composition containing a fragrance that emits an fragrance at the time of writing, for example, a fragrance having compatibility with the ink in a ballpoint pen ink composed of dyes, resins and organic solvents. A ballpoint pen ink (JP-A-56-81377), a fragrance-containing water-based ink containing a fragrance, maltosyl cyclodextrin (MCD), a colorant and water (JP-A-63-1981). No. 223078),
A water-based ink composition for a writing implement comprising a colorant, a fragrance, a partially sulfonated polyester resin and water
No. 283645) is known.

[0005] However, Japanese Patent Application Laid-Open No.
In the ink composition of JP-A No. 7, there is a problem that even when a compatible fragrance is added, the paper surface is blurred at the time of writing. In the ink composition of JP-A-63-223078, Since the perfume is included in the MCD and the inclusion compound is added to the water-based ink, the water-based ink tends to separate the perfume with the passage of time, particularly at a high temperature, and the dispersibility of the perfume In addition, there is a problem in the persistence of the scent, and further, in the ink composition of JP-A-8-283645, although scent is emitted immediately after writing,
Thereafter, the scent is lost, and there is a problem that the scent cannot be maintained for a long time (it is not persistent).

[0006]

SUMMARY OF THE INVENTION The present invention has been made in view of the above-mentioned problems of the prior art, and aims to solve the problem.
It is an object of the present invention to provide a water-based ink composition for writing implements, in which handwriting is less likely to bleed, fragrance is persistent, and a fragrance is dispersed and maintained in a stable state in an aqueous medium.

[0007]

Means for Solving the Problems As a result of intensive studies on the above-mentioned problems of the prior art, the present inventors have found that a specific ink component is contained in a water-based ink composition for writing implements containing a coloring agent and a fragrance. Thus, the present invention succeeded in obtaining the aqueous ink composition for writing implements, and completed the present invention. That is, the aqueous ink composition for a writing instrument of the present invention is characterized in that it contains a compound composed of polyoxyethylene cholesteryl ether and also contains a colorant, a fragrance and water.

[0008]

Embodiments of the present invention will be described below in detail. The aqueous ink composition for a writing instrument of the present invention,
It comprises a compound comprising polyoxyethylene cholesteryl ether and a coloring agent, a fragrance and water.

The compound comprising polyoxyethylene cholesteryl ether used in the present invention is used for the purpose of suppressing bleeding, improving the persistence of fragrance, and suppressing separation of fragrance. A compound comprising polyoxyethylene cholesteryl ether can be obtained by addition polymerization of phytosterol which is widely present in vegetable fats and oils and cholesterol which is present in animal fats and oils, with ethylene oxide. Preferred addition mole number of ethylene oxide is preferably 3 moles to 50 moles, and the higher the mole number, the higher the HLB and the higher the hydration tendency. Depending on the type of fragrance, one or two or more types may be used. You can select and use. Specific examples of commercially available products include BPS-5, a type obtained by adding ethylene oxide to vegetable oil phytosterol,
BPS-10, BPS-20, BPS-30, BPSH
-25 (manufactured by Nikko Chemicals), and DHC-30 (manufactured by Nikko Chemicals) and Emarex CS as a type obtained by adding ethylene oxide to animal fat and oil cholesterol.
-5, Emarex CS-10, Emarex CS-1
5, Emarex CS-24, Emarex CS-30
(Made by Nippon Emulsion).

In the present invention, the total content of one or a mixture of two or more of the above polyoxyethylene cholesteryl ether compounds is 0.1% with respect to the total amount of the ink composition.
-15% by weight, preferably 0.5-7% by weight. The content of these polyoxyethylene cholesteryl ether compounds is 0.1% by weight based on the total weight of the ink composition.
When the amount is less than the above, the effect of suppressing bleeding, the effect of improving the persistence of the fragrance, and the effect of suppressing the dispersion of the fragrance are inferior, and the effect of the present invention cannot be exerted. When it is used for a ball-point pen, the amount of ink flowing out from the tip of the chip decreases, which is not preferable.

The coloring agent used in the present invention includes, for example, pigments and water-soluble dyes. The pigment is not particularly limited, and includes at least one selected from inorganic and organic pigments conventionally used in aqueous ink compositions, titanium oxide, and pseudo pigments obtained by coloring a resin emulsion with a dye. As the inorganic pigment, for example,
Examples include carbon black and metal powder. As organic pigments, for example, azo lakes, insoluble azo pigments, chelate azo pigments, phthalocyanine pigments, perylene and perinone pigments, anthraquinone pigments, quinacridone pigments,
Dye lakes, nitro pigments, nitroso pigments and the like.

More specifically, carbon black, titanium black, zinc white, red iron oxide, chromium oxide, titanium mica,
Iron black, cobalt blue, iron oxide yellow, pyridian, zinc sulfide, lithopone, cadmium yellow, vermilion, cadmium red, graphite, molybdenum orange, zinc chromate,
Strontium chromate, white carbon, clay, talc, ultramarine, sedimentable barium sulfate, barite powder,
Calcium carbonate, lead white, navy blue, manganese violet,
Inorganic powders such as aluminum powder and brass powder; I. Pigment Blue 1, C.I. I. Pigment Blue 15, C.I.
I. Pigment Blue 17, C.I. I. Pigment Blue 27, C.I. I. Pigment Red 5, C.I. I. Pigment Red 22, C.I. I. Pigment Red 38, C.I.
I. Pigment Red 48, C.I. I. Pigment Red 49, C.I. I. Pigment Red 53, C.I. I. Pigment Red 57, C.I. I. Pigment Red 81, C.I.
I. Pigment Red 104, C.I. I. Pigment Red 146, C.I. I. Pigment Red 245, C.I. I.
Pigment Yellow 1, C.I. I. Pigment Yellow 3, C.I. I. Pigment Yellow 12, C.I. I. Pigment Yellow 13, C.I. I. Pigment Yellow 14,
C. I. Pigment Yellow 17, C.I. I. Pigment Yellow 34, C.I. I. Pigment yellow 55, C.I.
I. Pigment yellow 74, C.I. I. Pigment yellow 83, C.I. I. Pigment Yellow 95, C.I. I.
Pigment yellow 166, C.I. I. Pigment yellow 167, C.I. I. Pigment Orange 5, C.I. I. Pigment Orange 13, C.I. I. Pigment Orange 1
6, C.I. I. Pigment Violet 1, C.I. I. Pigment Violet 3, C.I. I. Pigment Violet 19, C.I. I. Pigment Violet 23, C.I.
I. Pigment Violet 50, C.I. I. Pigment Green 7 and the like. Examples of pseudo pigments obtained by coloring a resin emulsion with a dye include those obtained by coloring a resin made of a copolymer such as acrylonitrile, styrene, methyl methacrylate, or the like with a dye.

Further, as the water-soluble dye, any of direct dyes, acid dyes, food dyes and basic dyes can be used. Examples of the direct dye include C.I. I. Direct Black 17, 19, 22, 22, 32, 5
1, and 71, C.I. I. Direct Yellow 4, 26, 44, 50, C.I. I. Direct Red 1, Same 4, Same 23, Same 31, Same 37, Same 39, Same 75, Same 80, Same 8
1, 83, 225, 226, 227, C.I. I.
Direct Blue 1, 15, 15, 71, 86, 10
6, 119 and the like. Examples of the acid dye include C.I. I. Acid Black 1, 2, 24, 26, 31, 52, 107, 109, 11
0, 119, 154, C.I. I. Acid Yellow 7,
17, 17, 23, 25, 29, 38, 42, 49, 61, 72, 78, 110, 141, 127, 135, 142, C.I. I. Acid Red 8, 9, 14, 18, 18, 26, 2
7, 35, 37, 51, 52, 57, 8
2, 87, 92, 94, 115, 129, 131, 138, 186, 249, 254, 265, 276, C.I. I. Acid Violet 1
5, ditto 17, C.I. I. Acid Blue 1, 7, 7,
15, 15, 23, 25, 40, 41, 43, 62, 78, 83, 90, 93, 1
03, 112, 113, 158, C.I. I. Acid Green 3, 9, 16, 16, 25, and 27. Most of the food dyes are included in direct dyes or acid dyes, but examples of those not included include C.I. I. Food Yellow 3. Examples of the basic dye include C.I. I. Basic Yellow 1, 2, 21 and C.I. I. Basic Orange 2, 14,
32, C.I. I. Basic Red 1, 2, 9, 14, C.I. I. Basic Violet 1, 3 and 7, C.I. I. Basic Green 4, C.I. I. Basic Brown 12, C.I. I. Basic Black 2, 8
And the like. These colorants may be used alone or in combination of two or more. The content of these coloring agents is 0.5 to 40% by weight, preferably 1 to 40% by weight based on the total amount of the ink composition.
It is desirably about 30% by weight.

Examples of the fragrance used in the present invention include the following 1) to 6), and these may be used alone or in combination of two or more. 1) Essential oils such as grapefruit oil, orange oil, lemon oil, lime oil, ylang-ylang oil, chamomile oil, jasmine oil, hiba oil, peppermint oil, lavender oil, rosemary oil and the like. 2) Terpenes such as α-pinene, β-pinene and limonene. 3) Alcohols such as linalool, 1-menthol, geraniol, borneol, labazurol, hexyl alcohol, phenylethyl alcohol (rose P), furfuryl alcohol, cycloten, maltol, eugenol, α-phenylethanol and the like. 4) Aldehydes such as heptanal, octanal, dodecanal, tetradecanal, hexadecanal, citral, liral, benzaldehyde, cyclamenaldehyde and vanillin. 5) Esters such as ethyl acetate (ethyl acetate), propyl acetate (propyl acetate), amyl acetate, linalyl acetate, benzyl acetate (benzyl acetate), dimethyl benzylcarbinyl acetate, and benzyl propionate. 6) Aromatic compounds such as nootkatone, ethyl pyrazine, lemon terpenes, orange terpenes, crocodile, ethyl crocodile, furfuryl mercaptan, bonene and heliol.

In the present invention, a compounded fragrance which suitably combines the above fragrances, such as a banana fragrance, a blueberry fragrance, a vanilla fragrance, a mint fragrance, an apple fragrance, a peach fragrance, a melon fragrance, a pineapple fragrance, a grape fragrance,
Various blended flavors such as lilac flavor and jasmine flavor can also be formulated and used. For example, as a banana flavor, vanillin, ethyl vanillin, n-hexanal, isoamyl alcohol, trans-2-hexenal, n
-Butanol, isoamyl acetate, butyl acetate, isobutyl acetate, diacetyl, ethyl acetate, hexyl acetate, isoamyl butyrate, isoamyl isovalerate, cis-3-hexenol, cis-3-hexenyl acetate, acetic acid, isoeugenol,
Ethyl butyrate, a solvent and the like can be suitably blended to form a banana flavor, and pineapple flavors include benzyl acetate, orange oil 3-fold, vanillin,
Pineapple flavor can be prepared by suitably blending isoamyl acetate, isoamyl butyrate, ethyl acetate, ethyl heptanoate, ethyl hexanoate, ethyl butyrate, allyl hexanoate and the like. In addition, various prescription flavors that are commercially available,
For example, vanilla flavor [Vanilla BVK-3359 (manufactured by Takasago International Corporation)], mint flavor [mint THP-81]
48 (manufactured by Hasegawa Inc.), banana flavor [banana T-
1510 (manufactured by Yamamoto Inc.)] and blueberry flavor (Blueberry V-647 (manufactured by Yamamoto Inc.)) can also be used.

The content of these fragrances is 0.01 to 10% by weight, preferably 0.1 to 10% by weight, based on the total weight of the ink composition.
It is used in the range of ６6% by weight. When the content of these fragrances is less than 0.01% by weight, the persistence of the scent is inferior, and the scent can hardly be felt.
If the content exceeds% by weight, the stability over time is adversely affected, which is not preferable. In the present invention, the fragrance is used in the above content range (0.01 to 10% by weight).
Preferably, the fragrance is added in a weight ratio of 70 to at least one (one or a mixture of two or more) selected from the above compounds composed of polyoxyethylene cholesteryl ether.
%, More preferably 60% or less. By setting the weight ratio, it is possible to exhibit a further effect of suppressing bleeding, an effect of improving the persistence of fragrance, and an effect of suppressing separation of fragrance.

In the present invention, preferably, when the sedimentation of the pigment is remarkable, it is desirable to add a viscosity modifier from the viewpoint of preventing sedimentation. Examples of the viscosity modifier used include at least one selected from synthetic polymers, natural gums, celluloses, and polysaccharides. As synthetic polymers, for example, polyacrylic acid and its cross-linked copolymer,
Polyvinyl alcohol, polyvinylpyrrolidone and derivatives thereof, polyvinyl methyl ether and derivatives thereof, and the like. Examples of natural gums and polysaccharides include tragacanth gum, guar gum, locust bean gum,
Examples of celluloses such as xanthan gum include methyl cellulose, ethyl cellulose, hydroxyethyl cellulose, carboxymethyl cellulose and the like.
Specifically, “Junron PW-11” manufactured by Nippon Junyaku Co., Ltd.
1), “Hibiswako 104” manufactured by Wako Pure Chemical Industries, Ltd., “KELZAN”, “KELZANAR” manufactured by Sanseki Co., Ltd.,
“K1A96”, “K1A112”, “Leosan”,
“K7C233”, “JAGUAR HP-8”, “JAGUAR HP-6” manufactured by Rhone Poulin Japan KK
0 ”,“ RHODOPOL23 ”,“ RHODOPOL ”
50MC ", Dainippon Pharmaceutical Co., Ltd." Echo Gum GM "
And other commercially available products. The content of these viscosity modifiers is preferably 0.1 to 1.5% by weight based on the total amount of the ink composition. The content differs depending on the type of the viscosity modifier, and is preferably 0.1 to 1.5% by weight for a synthetic polymer, and 0.1 to 0.8% by weight for a natural polysaccharide. If the content of these viscosity modifiers is less than 0.1% by weight, no further effect of containing the viscosity modifiers can be exerted. And the poor writing performance due to poor ink followability tends to occur.

The ink composition of the present invention may further contain, if necessary, other components (optional components) used in the ink composition for a writing instrument as long as the effects of the present invention are not impaired. . Other components that can be used include, for example, water-soluble polyhydric alcohols such as ethylene glycol, propylene glycol, and glycerin, ethylene glycol monomethyl ether (methylcellosolve), and ethylene glycol monoethylether (ethylcellosolve). Aqueous media such as cellsolves, carbitols such as diethylene glycol monomethyl ether (methyl carbitol) and diethylene glycol monoethyl ether (ethyl carbitol), and glycol ether esters such as ethylene glycol monoethyl ether acetate, ammonia, urea, mono Alkali metal salts of carbonic acid and phosphoric acid such as ethanolamine, diethanolamine, triethanolamine, sodium tripolyphosphate and sodium carbonate, and sodium hydroxide pH adjusting agents of alkali metal hydroxides such helium, phenol, sodium omadine, sodium pentachlorophenol, 1,2-benzisothiazolin-3-one,
Antiseptic or fungicidal agents such as 2,3,5,6-tetrachloro-4 (methylsulfonyl) pyridine, benzoic acid such as sodium benzoate, sorbic acid, alkali metal salts of dehydroacetic acid, benzimidazole compounds and the like, benzotriazole Rust inhibitors such as dicyclohexylammonium nitrite, diisopropylammonium nitrite, tolyltriazole, anionic surfactants such as carboxylic acids and sulfonic acids, cationic surfactants such as ammonium salts and amines, and other amphoteric surfactants A lubricant, a wetting agent, a defoaming agent, etc. comprising a nonionic surfactant or a nonionic surfactant can be appropriately selected and used. Further, examples of the water used in the present invention include purified water, ion-exchanged water, and the like, and the content thereof is the remaining amount (remaining part) of the total content of the above components.

The aqueous ink composition for a writing instrument of the present invention can be suitably used for ballpoint pens, brush pens, felt-tip pens, markers and the like. In the aqueous ink composition for a writing instrument of the present invention configured as described above, in order to solve the above-described conventional problems when a fragrance is used, a coloring agent, a fragrance and water are contained, and the bleeding inhibitor is used. Function of,
For the first time, by containing at least one compound consisting of polyoxyethylene cholesteryl ether having a function as a fragrance persistence improver and a function of suppressing separation of fragrance, handwriting is less likely to bleed and fragrance is persistent, The peculiar effect is exhibited such that the fragrance is dispersed and maintained in a stable state in the aqueous medium (these points will be described in detail in Examples and the like which will be described later).

[0020]

EXAMPLES The present invention will be described in detail below with reference to Examples and Comparative Examples, but it goes without saying that the present invention is not limited to the following Examples.

Examples 1 to 10 and Comparative Examples 1 to 3 Water-based ink compositions for writing implements were prepared according to the composition shown in Table 1 below. The obtained Examples 1 to 10 and Comparative Examples 1 to
For the aqueous ink composition of No. 3, according to the following evaluation method,
The bleeding property, fragrance, separation of fragrance, aggregation of pigment and writing taste of the ink were evaluated. In addition, the bleeding property, the aromaticity, and the writing taste of the ink were evaluated by preparing a ball-point pen for evaluation. The results are shown in Table 1 below.

(Preparation of Ballpoint Pen for Evaluation) Each ink was filled into a polypropylene ink storage tube having an inner diameter of 4.0 mm and a length of 115 mm without a relay core and a refill consisting of a stainless steel tip having a ball diameter of 0.7 mm. And
An evaluation ballpoint pen body (UM-100 manufactured by Mitsubishi Pencil) was produced.

(Evaluation method of bleeding property) A ballpoint pen was used to write on the paper surface (high quality paper), and the sensory evaluation was performed according to the following evaluation criteria. Evaluation criteria: ：: clear handwriting without bleeding. Δ: Blurred and unclear handwriting. ×: Handwriting very unclear due to bleeding.

(Evaluation method of fragrance) A ballpoint pen was used to write on the paper surface (high quality paper), and the sensory evaluation was performed according to the following evaluation criteria. Evaluation criteria: ○: Smell at the time of writing, handwriting still smells after 5 hours. X: Smell at the time of handwriting, and the handwriting does not smell after 5 hours.

(Evaluation Method for Perfume Separation) Each ink was sealed in a container, left in a thermostat at 50 ° C. for 7 days, allowed to cool, and the state of the liquid was evaluated according to the following evaluation criteria. Evaluation criteria: ：: No change from before test. ×: fragrance separated.

(Evaluation Method of Pigment Aggregation) Each ink was sealed in a container, allowed to stand at room temperature for one week, passed through a 100 μm sieve, and evaluated according to the following evaluation criteria. The evaluation of the aggregation of the pigment is to evaluate the dispersion stability of the pigment. Evaluation criteria: ：: no residue. ×: Ink is difficult to pass through the sieve or there is a residue.

(Evaluation Method of Writing Taste) Writing was performed on a paper surface (high quality paper) using a ballpoint pen, and writing taste was evaluated according to the following evaluation criteria. Evaluation criteria: A: Very smooth writing feeling. ：: Smooth writing feeling. Δ: Writing feeling slightly lacking in smoothness. X: An unpleasant sensation at the time of use, such as a very heavy writing feeling or catching (a level that cannot be used).

[0028]

[Table 1]

The remarks (1) to (13) in Table 1 are as follows. (1) Phthalocyanine blue (Chromofine manufactured by Dainichi Seika)
Blue4965) (2) Lactimine color (Golden Yellow F manufactured by Dainichi Seika)
L2R Conc) (3) Thai Pure R-900 (manufactured by Dupont) (4) Iliodin 303 Royal Gold (manufactured by Merck Japan) (5) Potassium oleate (6) KELZAN (manufactured by Sansei) (7) Fit 10 mol EO adduct of sterol: BPS-
10 (manufactured by Nikko Chemicals) (8) EO 5 mol adduct of cholesterol: CS-5 (manufactured by Nippon Emulsion Co.) (9) EO 20 mol adduct of cholesterol: CS-20
(Manufactured by Nippon Emulsion) (10) Banana T-1510 (manufactured by Yamamoto Inc.) (11) Blueberry V-647 (manufactured by Yamamoto Inc.) (12) Vanilla BVK-3359 (manufactured by Takasago Inc.) (13) Mint THP-8148 (manufactured by Hasegawa Inc.)

(Consideration of Table 1) As is apparent from the results of Table 1, the ink bleeding of Examples 1 to 10 falling within the scope of the present invention was higher than Comparative Examples 1 to 3 falling outside the scope of the invention. No fragrance, no separation of perfume, no aggregation of pigments, and a very smooth writing feel was obtained. On the other hand, Comparative Examples 1 to 3 are polyoxyethylene cholesteryl ethers having a function as a bleeding inhibitor which is an essential component in the present invention, a function as a fragrance persistence improver, and a function as a fragrance separation inhibitor. In these cases, it was found that all of the evaluation items such as ink bleeding property, fragrance, separation of fragrance, aggregation of pigment, and writing taste could not be satisfied.

[0031]

According to the present invention, there is provided a water-based ink composition for writing implements, in which handwriting hardly bleeds, scent persistence, and a fragrance dispersed and maintained in a stable state in an aqueous medium.

Continued on the front page F-term (reference) 4J039 AB04 AE07 AF07 BA04 BA06 BA13 BA16 BA23 BA30 BA31 BA32 BA34 BA35 BA36 BA37 BC02 BC07 BC12 BC13 BC16 BC17 BC20 BC39 BC60 BE01 BE03 BE04 BE05 BE06 BE21 BE22 CA06 EA15 EA16 EA17 EA21 EA21 EA44 GA27

Claims (1)

[Claims] 1. A water-based ink composition for a writing implement, comprising a compound comprising polyoxyethylene cholesteryl ether and a colorant, a fragrance and water.