JP2003306630A - Water-base ink composition for writing utensil - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a water-base ink composition for writing utensils suppressing the deterioration rate of a handwriting with light of sunshine, etc., and having excellent solubility in aqueous media without forming residues. <P>SOLUTION: The water-base ink composition for the writing utensils comprises at least a colorant and water. In the water-base ink composition, 0.1-10 wt.% of an α-glucosylhesperidin represented by general formula (1) (wherein, R is a glucose residue; and n is 1-10 and the number of glucose residues at the α-position) is contained in the ink composition. <P>COPYRIGHT: (C)2004,JPO

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a water-based ink composition for writing instruments. More specifically, it relates to a water-based ink composition for a writing instrument having excellent light resistance.

[0002]

2. Description of the Related Art Conventionally, various colorants have been used in water-based ink compositions for writing instruments, but particularly in acid dyes, basic dyes, fluorescent dyes, fluorescent pigments, natural pigments, etc.
There are many things whose color tone fades or discolors due to light. In order to solve the above problems, it is disclosed that a benzophenone-based, salicylic acid-based, benzotriazole-based, and cyanoacrylate-based UV absorber is added. For example, 2- (2'-hydroxy-3'-t-butyl-5'-methylphenyl) -5 is used as an ultraviolet absorber in an ink composition containing a fluorescent dye or a fluorescent pigment.
-Chlorobenzotriazole, 2- (2'-hydroxy-5'-methylphenyl) benzotriazole, and 2-hydroxybenzophenone p-aminobenzoic acid have been exemplified (JP-A-9-279080). . However, these ultraviolet absorbers have very poor solubility in an aqueous medium, and when used in an aqueous ink, only a small amount can be added, so that it is difficult to obtain a sufficient light resistance improving effect.

[0003]

DISCLOSURE OF THE INVENTION The present invention relates to an aqueous ink using a dye or a pigment as a colorant, which has an excellent solubility in an aqueous medium and an ultraviolet absorber capable of imparting sufficient light resistance. It is intended to provide an aqueous ink composition for a writing instrument containing the same.

[0004]

The present invention provides an aqueous ink composition containing at least a colorant and water,
It is required to contain α-glucosyl hesperidin represented by the general formula (1). Further, it is required that the ink composition contains 0.1 to 10% by weight of the α-glucosyl hesperidin.

The α-glucosyl hesperidin is a compound represented by the general formula (1), has a high solubility in an aqueous medium, and when contained in the ink, it can prevent fading of handwriting due to sunlight. . In the general formula (1), R is a glucose residue, and the integer n is 1 to 1
0 is the number of glucose residues in the α-position. If n is 0,
That is, since hesperidin has low solubility in an aqueous medium, when it is added in a necessary amount, hesperidin cannot be completely dissolved and precipitates. When n exceeds 10, the solubility in an aqueous medium becomes low, and it may not be completely dissolved and precipitate.

The α-glucosyl hesperidin may be produced by any method as long as it has a structure represented by the general formula (1), and one kind or two or more kinds may be appropriately mixed and used. It is used in the ink composition in an amount of 0.1 to 10% by weight, preferably 1 to 5% by weight.
If it is less than 0.1% by weight, sufficient light resistance cannot be imparted, and if it exceeds 10% by weight, the solubility of other compositions is lowered and the ink performance is lowered.

As the colorant, dyes, pigments and natural dyes which can be dissolved or dispersed in an aqueous medium can all be used, and specific examples thereof are shown below. As the dye,
Acid dyes, basic dyes, direct dyes and the like can be used. As an acid dye, neucoccin (C.I.
6255), tartrazine (CI.19140), acid blue black 10B (CI.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.
I. 44025), eosin (C.I. 45380),
Phloxine (CI.45410), Erythrosin (CI.45430), Nigrosine (CI.504)
20), acid flavin (CI.56205) and the like are used.

As the basic dye, chrysoidine (C.I.
I. 11270), methyl violet FN (C.I.
42535), crystal violet (C.I. 42)
555), malachite green (C.I. 4200)
0), Victoria Blue FB (C.I. 44045),
Rhodamine B (CI.45170), Acridine Orange NS (CI.46005), Methylene Blue B
(C.I.52015) and the like are used.

As a direct dye, Congo red (C.
I. 22120), Direct Sky Blue 5B (C.
I. 24400), violet BB (C.I.279)
05), Direct Deep Black EX (C.I.3)
0235), Kayarasu Black G Conc (C.I. 35)
225), Direct Fast Black G (C.I.3)
5255), phthalocyanine blue (C.I. 7418)
0) and the like are used.

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 a surfactant and a water-soluble resin that are finely and stably dispersed in an aqueous medium. Dispersed water-dispersed pigment products and colored resin pigments are used. For example, as water-dispersed pigments using a surfactant, C.I. I. Pigment Blue 15: 3B [Product name: Sandy Super Blue GLL, pigment content 24%, Sanyo Dye Co., Ltd.] C.I. I. Pigment Red 146 [Product Name: Sa
ndye SuperPink 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 Dainichiseika Kogyo Co., Ltd.] C.I. I. Pigment Red 220/166 [Product name: TC Red FG, pigment content about 35%, manufactured by Dainichiseika Kogyo KK] and the like. Further, as the water-dispersed pigment using the water-soluble resin, C.I. I. Pigment Black 7 [Product Name: WA
color Black A250, pigment content 15%,
Dainichi Seika Kogyo Co., Ltd.] C.I. I. Pigment Green 7 [Product Name: WA
-S color Green, pigment content 8%, manufactured by Dainichiseika Kogyo Co., Ltd.] C.I. I. Pigment Violet 23 [Product Name:
Micro Pigmo WMVT-5, pigment content 20%, manufactured by Orient Chemical Industry Co., Ltd.] C.I. I. Pigment Yellow 83 [Product Name:
Emmacor NS Yellow 4618, pigment content about 30%, manufactured by Sanyo Dye Co., Ltd.] and the like. For the colored resin pigment, a fluorescent pigment in the form of fine particles of a synthetic resin obtained by solid-solutioning various fluorescent dyes in a resin matrix can be used as the fluorescent pigment, and as the coloring pigment, various basic dyes can be used as a solid solution in the resin matrix. Synthetic resin fine particle color pigments can be used. Other examples include metallic luster pigments, white pigments such as titanium dioxide, silica and calcium carbonate, phosphorescent pigments, capsule pigments containing a thermochromic composition, fragrances or capsule pigments containing a fragrance. Examples of the metallic luster pigment include metallic luster pigments such as aluminum and brass, natural mica as a core substance, synthetic mica, glass pieces,
Alumina, a metallic luster pigment (pearl pigment) in which the surface of a transparent film piece is coated with a metal oxide such as titanium oxide, a metallic luster pigment in which a metal vapor deposition film is formed on a transparent or colored transparent film, and a plurality of transparent resin layers are laminated. Illustrative are lustrous metal luster pigments obtained by finely cutting the above iris film. Further, when a metallic luster pigment such as aluminum or brass is used, a pigment obtained by coating the surface of the metallic luster pigment with a transparent resin or a colored transparent resin is preferably used and is excellent in stability in the ink composition. Specific examples of the metallic luster pigment coated with the transparent resin or the above include flat metal powder coated on both sides with a transparent or colored transparent resin film.

Examples of the natural pigment include turmeric pigment, gardenia yellow pigment, beta-carotene, red pearl pigment, capsicum pigment, annatto pigment, red pigment, beet red and chlorophyll.

The colorants may be used alone or in admixture of two or more, and are used in the ink composition in an amount of 1 to 25% by weight, preferably 2 to 15% by weight.

In addition, if necessary, a shear thinning agent,
A water-soluble organic solvent, a water-soluble resin, a pH adjuster, a rust preventive, an antiseptic or a fungicide, a wetting agent, a lubricant and the like can be added. As the shear thinning agent, a substance that is soluble or dispersible in water is effective, xanthan gum, welan gum, succinoglycan, which is a constituent monosaccharide of glucose and galactose, which is an organic acid-modified heteropolysaccharide,
Guar gum, locust bean gum and its derivatives, hydroxylethyl cellulose, alginic acid alkyl esters, polymers having a molecular weight of 100,000 to 150,000 and containing alkyl ester of methacrylic acid as a main component, glycomannan, gel extracted from seaweed of agar and carrageenan. Thickening polysaccharides, benzylidene sorbitol, benzylidene xylitol and their derivatives, crosslinkable acrylic acid polymers, inorganic fine particles, polyglycerin fatty acid ester, polyoxyethylene sorbitan fatty acid ester, polyethylene glycol fatty acid ester, polyoxyethylene castor Oil, polyoxyethylene lanolin, lanolin alcohol, beeswax derivative, polyoxyethylene alkyl ether, polyoxypropylene alkyl ether, polyoxyethylene Alkyl phenyl ethers, fatty acid having an HLB value of such amide 8-12 of a nonionic surface active agent can be exemplified salts such dialkyl or dialkenyl sulfosuccinic acids, can be mixed and used either singly or in combination.

As the water-soluble organic solvent, one or more conventional water-soluble general-purpose solvents can be used in combination, and specifically, ethanol, propanol, butanol, glycerin, sorbitol can be used. , Triethanolamine, diethanolamine, monoethanolamine, ethylene glycol, diethylene glycol, thiodiethylene 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 Examples include monomethyl ether acetate, sulfolane, 2-pyrrolidone, N-methyl-2-pyrrolidone and the like.

As the water-soluble resin, one or more kinds of alkyd resin, acrylic resin, styrene-maleic acid copolymer, cellulose derivative, polyvinylpyrrolidone, polyvinyl alcohol, dextrin, etc. may be used to fix the paper to the paper or to impart viscosity. Can be used for

Examples of the pH adjusting agent include inorganic salts such as sodium carbonate, sodium phosphate and sodium acetate, and organic basic compounds such as water-soluble amine compounds. Examples of the rust inhibitor include benzotriazole and its derivative, tolyltriazole, dicyclohexylammonium nitrite, diisopropylammonium nitrite, sodium thiosulfate, ethylenediaminetetraacetic acid salt, saponin, dialkylthiourea and the like.
Examples of the preservative or antifungal agent include 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) pyridine and the like can be mentioned. Examples of the wetting agent include urea, nonionic surfactants, sorbit, mannitol, sucrose, glucose, reduced starch hydrolyzate, sodium pyrophosphate and the like. Examples of the lubricant include metal soap, polyalkylene glycol, fatty acid ester, ethylene oxide addition type cationic activator, phosphoric acid activator, thiocarbamate and dimethyldithiocarbamate.

[0017]

BEST MODE FOR CARRYING OUT THE INVENTION The aqueous ink composition for a writing instrument of the present invention comprises a colorant and α-glucosyl hesperidin added to an aqueous medium, and when the additive is blended, the additive is appropriately added. It is prepared by heating, stirring if necessary, dissolving or dispersing, and a ballpoint pen, felt-tip pen,
It is used by filling writing instruments in the form of felt pens, fountain pens, brush pens, etc.

[0018]

EXAMPLES The formulations of the aqueous ink compositions for writing instruments prepared in Examples 1 to 7 and Comparative Examples 1 to 9 are shown below. still,
Numerical values indicate parts by weight.

Example 1 Pink fluorescent pigment 40.0 [trade name: SF5017 pink, manufactured by Shin Roihi Co., Ltd.] Glycerin 10.0 1,2-benzisothiazolin-3-one 0.1 [trade name: Proxel XL-2 , Manufactured by Zeneca Co., Ltd.] α-Glucosyl hesperidin 1.0 [Product name: αG hesperidin PA, manufactured by Toyo Seika Sugar Co., Ltd.] Water 48.9 Total 100.0 The above compositions are mixed and allowed to stand at room temperature with a three-one motor. 1
A water-based ink for writing instruments was obtained by stirring for 0 minutes.

Example 2 Yellow fluorescent pigment 40.0 [Brand name: SF5015 Yellow, manufactured by Shin Loihi Co., Ltd.] Glycerin 10.0 1,2-benzisothiazolin-3-one 0.1 [Brand name: Proxel XL-2 , Manufactured by Zeneca Co., Ltd.] α-Glucosyl hesperidin 3.0 [Product name: αG Hesperidin PA, manufactured by Toyo Seika Sugar Co., Ltd.] Water 46.9 Total 100.0 The above compositions are mixed, and at room temperature with a three-one motor. 1
A water-based ink for writing instruments was obtained by stirring for 0 minutes.

Example 3 Yellow fluorescent dye 10.0 [trade name: S.I. W. T Yellow2, manufactured by Hodogaya Chemical Co., Ltd.] Red fluorescent dye 1.0 [Brand name: Vanisole Red 485, manufactured by BASF] Pink fluorescent dye 0.6 [Brand name: Rhodamine B, manufactured by BASF] Poly (oxy Ethylene) oleyl ether 3.8 [Brand name: Emlan OG, manufactured by BASF] Diethylene glycol 10.0 2-Pyrrolidone 10.0 α-Glucosyl hesperidin 5.0 [Brand name: αG hesperidin PA, manufactured by Toyo Seika Sugar Co., Ltd.] Water 59.6 Total 100.0 Mix the above composition and mix with a three-one motor at room temperature for 1 hour.
A water-based ink for writing instruments was obtained by stirring for 0 minutes.

Example 4 Orange Dye 5.0 [Brand name: Water Orange 18, manufactured by Orient Chemical Industry Co., Ltd.] Diethylene glycol 10.0 Ethylene glycol 10.0 Triethanolamine 1.0 1,2-benzisothiazoline-3 -ON 0.5 [Brand name: Proxel XL-2, manufactured by Zeneca Co., Ltd.] α-Glucosyl hesperidin 2.0 [Brand name: αG Hesperidin PA, manufactured by Toyo Pure Sugar Co., Ltd.] Water 71.5 Total 100.0 A water-based ink for a writing instrument was obtained by mixing the above-mentioned compositions and stirring with a three-one motor for 10 minutes while heating at 40 to 50 ° C.

Example 5 Red Acid Dye 5.0 (CI Acid Red 92, CI 45410) [Brand name: Phloxine, manufactured by Eisen Co., Ltd.] Diethylene glycol 10.0 Ethylene glycol 10.0 Triethanolamine 1.0 1,2-benzisothiazolin-3-one 0.5 [trade name: Proxel XL-2, manufactured by Zeneca Corporation] α-glucosyl hesperidin 2.0 [trade name: αG hesperidin PA, Toyo Sugar Refining Co., Ltd. )] Water 71.5 Total 100.0 The above composition was mixed and stirred with a three-one motor for 10 minutes while heating at 40 to 50 ° C. to obtain a water-based ink for writing instruments.

Example 6 Yellow Acid Dye 5.0 [Brand name: Acid Yellow PY, manufactured by Sumitomo Chemical Co., Ltd.] Diethylene glycol 10.0 Ethylene glycol 10.0 Triethanolamine 1.0 1,2-benzisothiazoline-3 -ON 0.5 [Brand name: Proxel XL-2, manufactured by Zeneca Co., Ltd.] α-Glucosyl hesperidin 3.0 [Brand name: αG Hesperidin PA, manufactured by Toyo Pure Sugar Co., Ltd.] Water 70.5 Total 100.0 A water-based ink for a writing instrument was obtained by mixing the above-mentioned compositions and stirring with a three-one motor for 10 minutes while heating at 40 to 50 ° C.

Example 7 Basic dye 5.0 [Brand name: Methyl violet pure special, Hodogaya Chemical Co., Ltd.] Diethylene glycol 10.0 Ethylene glycol 10.0 α-Glucosyl hesperidin 5.0 [Brand name: αG Hesperidin PA, manufactured by Toyo Seito Sugar Co., Ltd.] Water 70.0 Total 100.0 The above composition is mixed and stirred at a three-one motor for 10 minutes while heating at 40 to 50 ° C to obtain a water-based ink for writing instruments. Was given.

Comparative Example 1 A water-based ink for writing instruments was obtained in the same manner as in Example 1, except that α-glucosyl hesperidin was removed and water was used instead.

Comparative Example 2 A water-based ink for writing instruments was obtained in the same manner as in Example 2 except that α-glucosyl hesperidin was removed and water was used instead.

Comparative Example 3 A water-based ink for writing instruments was obtained in the same manner as in Example 3, except that α-glucosyl hesperidin was removed and water was used instead.

Comparative Example 4 A water-based ink for writing instruments was obtained in the same manner as in Example 4 except that α-glucosyl hesperidin was removed and water was used instead.

Comparative Example 5 A water-based ink for writing instruments was obtained in the same manner as in Example 5 except that α-glucosyl hesperidin was removed and water was used instead.

Comparative Example 6 A water-based ink for writing instruments was obtained in the same manner as in Example 6 except that α-glucosyl hesperidin was removed and water was used instead.

Comparative Example 7 A water-based ink for writing instruments was obtained in the same manner as in Example 7 except that α-glucosyl hesperidin was removed and water was used instead.

Comparative Example 8 A water-based ink for writing instruments was obtained in the same manner as in Example 5, except that α-glucosyl hesperidin was removed and 2-hydroxy-4-methoxybenzophenone was used instead.

Comparative Example 9 An aqueous solution for a writing instrument was prepared in the same manner as in Example 5 except that α-glucosyl hesperidin was removed and 2- (2'-hydroxy-5-methylphenyl) benzotriazole was used instead. I got ink.

After confirming the solubility of the water-based inks prepared in Examples 1 to 7 and Comparative Examples 1 to 9, 2.0 g of the water-based ink was added to a commercially available writing instrument [product number: SGR-8SL,
[Manufactured by Pilot Co., Ltd.] and the light resistance test was performed on the written handwriting. The test results are shown in Table 1.

(1) Solubility test 50 g of the above water-based ink was applied to a filter paper [N manufactured by Advantech, N
o. 2 (diameter 20 mm)], and the insoluble residue remaining on the filter paper after filtration was visually confirmed. ◯: No residual insoluble matter Δ: Small amount of residual insoluble matter X: Large amount of residual insoluble matter (2) Light resistance test The water-based ink subjected to the solubility test was poured into a writing instrument to write on a writing paper A ( Three 5 cm lines were written on JISP3201) to prepare a test piece. The test piece was irradiated with a fade meter (manufactured by Suga Test Instruments Co., Ltd., applying long life carbon arc) for 3 hours and 5 hours, and the unwritten and the handwriting were compared. Incidentally, in Comparative Examples 8 and 9, the generation of residues was confirmed in the solubility test, and thus the light resistance test was not performed. ◎: Good ○: Slightly deteriorated △: Greatly deteriorated ×: Discoloration deterioration

[0037]

[Table 1]

[0038]

INDUSTRIAL APPLICABILITY The present invention uses an α-glucosyl hesperidin represented by the general formula (1) in a water-based ink composition for a writing instrument, without causing a residue.
It is possible to provide a water-based ink composition for a writing instrument that exhibits excellent solubility and can suppress deterioration of handwriting due to light.

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Claims (2)

[Claims] 1. A water-based ink composition containing at least a colorant and water, which contains α-glucosyl hesperidin represented by the following general formula (1). . [Chemical 1] (However, R is a glucose residue and n is the number of glucose residues at the α-position of 1 to 10.) 2. The water-based ink composition for a writing instrument according to claim 1, wherein the ink composition contains 0.1 to 10% by weight of the α-glucosyl hesperidin.