KR101879600B1

KR101879600B1 - Eco-friendly water-removable aqueous ink composition and marking pen using the same

Info

Publication number: KR101879600B1
Application number: KR1020160019111A
Authority: KR
Inventors: 신선화; 이병선; 이병철
Original assignee: 이병선
Priority date: 2016-02-18
Filing date: 2016-02-18
Publication date: 2018-07-18
Also published as: KR20160026941A

Abstract

According to the present invention, by adding a polyoxyethylene alkyl ether-based dispersing and leveling agent to an aqueous ink composition containing a water-soluble dye, a water-soluble resin and water to lower the dynamic surface tension, it is possible to maintain the uniformity There is provided a hydrogen-over-water-based ink composition excellent in writing performance and excellent in decolorization ability to be cleaned and removed promptly with water without leaving traces or debris.

Description

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a water-

The present invention relates to a water-based ink composition which is eco-friendly and is erased in water. More particularly, the present invention relates to a water-based ink composition which is capable of maintaining uniformity without breaking a writing line and being capable of being cleaned and cleaned with water without leaving any marks or residues. And more particularly to an environmentally friendly hydrogen-over-water-based ink composition having an effect.

Various ink compositions have been known in which handwriting is removed from a writing surface by gently wiping a writing handwritten on a non-penetrating writing surface such as glass, acrylic plate, or blackboard with a soft cloth.

As a hydrogen-diffusing ink composition, a releasing agent composed of an emulsion of an oily substance which is hardly volatile at room temperature, such as a higher fatty acid ester or the like, in order to peel the ink composition containing water as a solvent, a pigment as a coloring agent and a resin, (Refer to Japanese Patent Application Laid-Open No. 1-252681).

As another example of the hydrogen-diffusing ink, an ink composed of a microcapsule pigment or colored resin particles having a predetermined average particle diameter as a coloring agent together with water and a water-soluble resin is wiped with a cloth dipped in water to remove the handwriting on the writing surface (See, for example, Japanese Patent Application Laid-Open No. 2000-34436).

Further, a hydrogenated aqueous colorant composition composed of a water-soluble dye instead of the microcapsule pigment or colored resin particles as a colorant has also been proposed (Japanese Patent Application Laid-Open No. 2002-129085).

However, in the conventional hydrogenated aqueous coloring composition proposed in the above documents, when water is used as a substrate, a problem occurs that handwriting is interrupted on the handwriting surface when handwriting is performed on a non-penetrating handwriting surface, It has been proposed to include a large amount of organic solvent or add a small amount of a dispersing leveling agent (leveling agent). The dispersion leveling agent is intended to enhance the saturation of the color after writing, and in particular, when the writing is performed on a smooth surface material such as a white board, the ink is not evenly distributed due to the surface tension, thereby preventing the uniform color and saturation from being expressed .

For example, Korean Patent Laid-Open Publication No. 10-2004-0065803 discloses a method of producing a coloring effect that is clean and quickly erased with water without leaving any traces or residue, and a retarding effect for stimulating the curiosity and curiosity of children and children Wherein the hydrogen-gaseous ink composition comprises a dye, a surfactant, a water-soluble organic solvent, and the like, wherein oleic acid, polyethylene glycol, stearic acid, polyoxyalkylene triesterinated phenol, and polyoxy And a mixture containing an ethylene-polyoxypropylene block copolymer as a dispersion leveling agent in an amount of 0.5 to 1% by weight.

However, the conventional hydrogenated aqueous coloring composition or the above-mentioned ink compositions are still insufficient in handwriting property and discoloration property, and it is not easy to handwriting on the impermeable handwriting surface without interrupting the handwriting. It is not easy to erase from the writing surface by wiping with a tissue or the like.

Under such circumstances, there has been a need to develop a new hydrogen-rich ink composition that is excellent in writing and coloring properties.

1. Japanese Patent Application Laid-Open No. 1-252681 2. Japanese Patent Application Laid-Open No. 2000-34436 3. Japanese Patent Application Laid-Open No. 2002-129085 4. Korean Patent Publication No. 10-2004-0065803

In order to solve the problems of the conventional hydrogen-over-water-based ink composition which is poor in handwriting property and discoloration property, the present inventors have studied with varying constituents and solvents.

The present inventors have found that by adding a specific alcohol alkoxylate- or polyoxyethylene alkyl ether-based surfactant as a dispersing leveling agent to an aqueous ink composition comprising a water-soluble dye, a water-soluble resin and water, Which is capable of maintaining uniformity without being scratched, and capable of maintaining uniformity, and which is excellent in decolorability, which can be cleaned and removed promptly with water without leaving any marks or residue, can be provided.

The hydrogenated aqueous ink composition according to the present invention is excellent in handwriting property capable of maintaining uniformity without breaking the writing line, and excellent in decolorization property, which can be cleaned quickly with water without leaving any traces or residue.

A first object of the present invention is to provide a hydrogenated aqueous ink composition containing a polyoxyethylene alkyl ether represented by the following formula (1) as a water-soluble dye, (b) a water-soluble resin, (c) water as a solvent, and &Lt; / RTI >

Wherein x and y are each selected from 1 to 40, preferably from 3 to 30, more preferably from 6 to 20, and m and n are each from 1 to 12, preferably from 3 to 10, Is selected from 5 to 8, and m + n is selected from 4 to 15, preferably from 7 to 13, more preferably from 9 to 11.)

According to one embodiment of the present invention, the above-mentioned water-soluble dyes can be selected from water-soluble food dyes, and the above-mentioned water-soluble resins can be selected from polyvinylpyrrolidone or polyvinyl alcohol.

In the composition of the present invention, the above-mentioned water-soluble dye may be selected from the range of 0.1 to 15% by weight, preferably 0.5 to 10% by weight, more preferably 1 to 7% by weight, To 20% by weight, preferably 2 to 15% by weight, and more preferably 3 to 12% by weight. The above-mentioned dispersant leveling agent may be selected from the range of 0.1 to 10% by weight, preferably 0.3 to 3% By weight, more preferably 0.5 to 2% by weight.

According to a preferred embodiment, the hydrogen-overwater ink composition of the present invention comprises 0.1 to 15% by weight of a water-soluble dye, 1 to 20% by weight of a water-soluble resin, 0.1 to 10% by weight of a dispersion leveling agent, ) Water. &Lt; / RTI >

In the marking pen ink composition according to the present invention, water is used as a solvent. The amount of water in the ink composition is generally in the range of 60 to 90% by weight, preferably 70 to 90% by weight.

In the present invention, "water-soluble" means that the dye or resin used can be completely dissolved in water of the above-mentioned composition ratio (for example, 60 to 90% by weight) without water scarcely.

In the present invention, acid dyes, basic dyes or direct dyes may be used as colorants or dyes usable.

Examples of specific water-soluble dyes include Water Yellow 1 (CI Acid Yellow 23), Water Red 1 (CI Acid Red 18), Water Red 3 (CI Acid Red 73), Water Violet 7 (CI Acid Violet 17) 3 (CI Direct Blue 87), Water Blue 9 (CI Acid Blue 9), Water Black 191-L (CI Direct Black 19), Water Black R-510 (CI Acid Black 2) ; Rhodamine 6GCP (CI Basic Red 1) (manufactured by Sumitomo Chemical Co., Ltd.); Mention may be made of Methyl Violet (CI Basic Violet 1), Rhodamine B (CI Basic Violet 10), Victoria Blue (CI Basic Blue 26), Malachite Green (CI Basic Green 4) .

Examples of preferable water-soluble dyes include water-soluble dyes used as food coloring matter, specifically, Food Red No. 1, Food Red No. 3, Food Red No. 102, Food Red No. 104, Food Red No. 105, Red No. 106, Food Yellow No. 4, Food Yellow No. 5, Food Green No. 3, Food Blue No. 1, Food Blue No. 2 can be mentioned.

In the hydrogenated aqueous ink composition according to the present invention, such a water-soluble dye is used in an amount of 0.1 to 15% by weight, preferably 0.5 to 10% by weight, more preferably 1 to 7% by weight, based on the total weight of the ink composition Can be used in selected amounts.

In the present invention, the water-soluble resin improves the color developability of handwriting when writing on a non-impermeable writing surface, and improves the fixing property of the handwriting on the writing surface. The water- And is used to impart hydrogen gaugeability. Examples of such a water-soluble resin include, but are not limited to, gum arabic, traganth gum, xanthan gum, dextrin, gelatin, casein, alginic acid, methylcellulose, ethylcellulose, carboxymethylcellulose, hydroxyethylcellulose, polyvinylpyrrolidone, , Sodium polyacrylate, polyethylene oxide and the like can be mentioned, but from the viewpoint of safety, polyvinylpyrrolidone or polyvinyl alcohol can be preferably mentioned.

The polyvinylpyrrolidone which can be used as a water-soluble resin in the present invention can be exemplified by a polymer compound obtained by polymerizing N-vinyl-2-pyrrolidone, and can be classified by a characteristic value related to molecular weight called K value have. The K value is preferably 15 to 85, more preferably 15 to 30. When the K value is within the above range, the ink leaks from the marking pen tends to be good. Further, polyvinylpyrrolidone is soluble in alcohols, and it is possible to increase quick-drying property by adding alcohol to the ink.

The polyvinyl alcohol which can be used as a water-soluble resin in the present invention is exemplified by a water-soluble polymer obtained by saponifying a polyacetic acid vinyl acetate group to an alcohol group, and is classified by the degree of polymerization and the saponification degree of the acetic acid group.

The degree of polymerization of the polyvinyl alcohol may be selected from 200 to 1000, preferably 200 to 500, and more preferably 200 to 400. When the degree of polymerization is within the above range, the outflowability of the ink from the marking pen tends to be good.

The degree of saponification of the acetic acid group of the polyvinyl alcohol is preferably 78.5 to 99.0 mol%, more preferably 78.5 to 89.0 mol%. When the degree of saponification is within the above range, the solubility in the hydrogen-based aqueous ink composition and the hydrogen curing property of the writing wire tend to be better.

In the ink composition according to the present invention, the content of such a water-soluble resin may be generally selected in the range of 1 to 20% by weight, preferably 2 to 15% by weight, more preferably 3 to 12% by weight. When the content of the water-soluble resin in the ink composition is too small, not only the coloring property of the handwriting and the fixability are bad, but also the hydrogen-solubility of handwriting written on the impermeable surface is deteriorated. However, when the content of the water-soluble resin in the ink composition is too large, the viscosity of the obtained ink composition becomes excessively high, so that the outflow of the ink composition from the pen tip becomes poor when the marking pen is charged, for example.

According to the present invention, a polyoxyethylene alkyl ether-based compound represented by the general formula (1) can be used as a leveling agent or a dispersing leveling agent in order to reduce the dynamic surface tension of the ink composition and improve the wettability to the impermeable writing surface. In the polyoxyethylene alkyl ether compounds of formula (I), the alkyl moiety is derived from a secondary alcohol having 5 to 15 carbon atoms, preferably 7 to 13, more preferably 9 to 11 carbon atoms, The ethylene moiety may be derived from a polyoxyethylene-polyoxypropylene block copolymer or a polyoxypropylene-polyoxyethylene block copolymer. The polymerization degree of the polyoxyethylene moiety is not particularly limited, but in the formula (1), x + y may be selected from 4 to 60, preferably from 6 to 60, more preferably from 8 to 50.

Some of the polyoxyethylene alkyl ether-based dispersing and leveling agents of the above-mentioned formula (1) are commercially available as alcohol alkoxylate surfactants, and examples thereof include EP-5035, EP-7045 (manufactured by Nihon Shokubai Co., Ltd.), DYNWET 800 Ltd.), and the like.

The hydrogen-permanging ink composition according to the present invention contains a polyoxyethylene alkyl ether compound as a leveling agent, so that when the ink is written on an impermeable writing surface, the handwriting is not interrupted on the writing surface.

In the hydrogen-rich ink composition according to the present invention, the content of the polyoxyethylene alkyl ether leveling agent is generally 0.1 to 10% by weight, preferably 0.3 to 3% by weight, more preferably 0.5 By weight to 2% by weight. When the content of the polyoxyethylene alkyl ether leveling agent is less than 0.1% by weight, the handwriting is still interrupted when written on a non-permeable writing surface. When the content is more than 10% by weight, Is difficult to dry, and the manufacturing cost of the ink composition also increases.

The hydrogenated ink composition according to the present invention may contain an appropriate amount of a wetting agent such as ethylene glycol or glycerin, a pH adjuster, an antiseptic, an antiseizing agent, etc., which is generally compounded in an aqueous ink composition, if necessary. Although the hydrogen-diffusing ink composition according to the present invention uses water as a basic solvent, it is also possible to use a low-alcohol such as ethanol, propanol, and butanol or a water-soluble organic solvent that can be selected from acetone, methyl ethyl ketone, For example up to 10% by weight, preferably up to 5% by weight.

The method for producing the hydrogen-rich ink composition according to the present invention is not particularly limited and can be suitably carried out according to methods known in the art. For example, it can be prepared by adding a water-soluble dye, a water-soluble resin and a dispersing leveling agent to water at room temperature and uniformly mixing with stirring.

The hydrogenated ink composition according to the present invention can be used without particular limitation in an aqueous writing instrument, and can be suitably used particularly for marking pens. The marking pen means a felt pen or a free ink type marking pen. The felt pen has ink storing means made of a fiber bundle, a sintered body, or a plastic pen and having a central portion made of a felt or a fiber bundle in the body and impregnated with ink. The ink storing means uses a capillary phenomenon Refers to a writing instrument capable of supplying ink to enable writing, and may be referred to as a center-marking marking pen in some cases. The free ink type marking pen means a marking pen of a non-centering type in which ink is directly stored directly in the cylindrical body and the stored ink is supplied to the pen tip. The hydrogenated ink composition according to the present invention can be suitably used for any of these marking pens.

The hydrogen-based ink according to the present invention is an eco-friendly product that minimizes the generation of environmental hormone which is a disadvantage of the ink used in the conventional marking pen. It is an environmentally friendly product that not only impermeable writing surface such as a white board, but also permeable writing surface such as paper or fabric Even when applied, there is an advantage that it can be simply erased with water.

Hereinafter, the present invention will be described in more detail based on examples, but the present invention is not limited thereto.

The ingredients used in the examples and comparative examples are as follows:

- Food Yellow No. 4: C.I. Acid Yellow 23 (manufactured by Daiwa Hoso),

- edible red No. 102: C.I. Acid Red 18 (manufactured by Daiwa Kasei),

- Edible Blue No. 1: C.I. Acid Blue 9 (manufactured by Daiwa Kasei),

-Polyoxyethylene alkyl ether leveling agents: EP-5035, EP-7045 (manufactured by Nippon Shokubai Co., Ltd.), DYNWET 800 (manufactured by BYK)

- silicone surfactant: BYK-348 (BYK),

- Fluorine-based surfactant: Suflon S-211 (manufactured by Seiyaku Chemical Co., Ltd.)

-Acetylene glycol surfactant: Sufynol 465 (manufactured by Air Products),

PVP K-30 (trade name, manufactured by ISP Inc., weight average molecular weight: 40000 to 80000 (catalog value)), polyvinyl pyrrolidone resin: PVP K-15 (weight average molecular weight 6000 to 15000

- Polyvinyl alcohol resin: PVA 405 (manufactured by Kuraray Co., Ltd., polymerization degree: 500, degree of saponification: 80.0 to 83.0 mol% (catalog value)),

- Urethane resin emulsion: W5025 (manufactured by Mitsui Takeda)

When the hydrogenated aqueous ink compositions obtained in the above Examples and Comparative Examples were filled in a central knowledge marking pen having a pen tip composed of fiber bundles and written on a polypropylene resin sheet, the degree of blurring of the handwriting on the writing surface, And the hydrogen gauge was evaluated on the basis of the following criteria.

Examples 1 to 7

Each component was uniformly mixed according to the ratio (weight%) described in Table 1 to prepare the hydrogenated aqueous ink composition according to the present invention.

Comparative Examples 1 to 12

Each of the components was uniformly mixed according to the ratio (weight%) shown in Table 2 to prepare a comparative hydrogenated aqueous ink composition.

Test Example 1: Fast and Color Development

Using a marking pen filled with the ink composition prepared in the above Examples and Comparative Examples, ten straight lines of 30 cm were continuously written on a polypropylene resin sheet at a speed of about 30 cm / sec. .

When the handwriting is not blurred at all, it is indicated by o, when the handwriting is slightly blurred, and when the handwriting is markedly blurred by x.

When the color of the handwriting was good, it was indicated by o, and when the handwriting color was bad, it was indicated by x.

The results of the above tests are shown in Tables 1 and 2, respectively.

Test Example 2: Hydrogen gauging

In the test example 1, a handwriting line written on a writing surface made of a polypropylene resin sheet was allowed to stand for 10 minutes, and then handwriting was respectively wiped with a wetted tissue with water. When the handwriting is erased, it is indicated by o, when the handwriting is partially left, and when all the handwriting is left is indicated by x.

The results of the above tests are shown in Tables 1 and 2, respectively.

Test Example 3: Long-term Hydrogenation

In the test example 1, a handwriting line written on a writing surface made of a polypropylene resin sheet was allowed to stand for 24 hours, and then handwriting was wiped with a tissue soaked with water. The hydrogen-germanium ink according to the present invention was also completely erased after 24 hours, indicating excellent long-term hydrogenation.

Ink composition composition (% by weight) Example One 2 3 4 5 6 7 Water-soluble dye Food Yellow No. 4 3.0 2.3 3.0 1.5 Edible red No. 102 4.8 4.8 4.8 Edible blue No. 1 2.0 Water-soluble resin PVP K15 10.0 10.0 10.0 PVP K30 5.0 5.0 PVA 405 10.0 10.0 Leveling agent EP5035 1.0 1.0 EP7045 1.0 1.0 DYNWET 800 1.0 1.0 1.0 antiseptic Sodium benzoate 1.0 1.0 1.0 1.0 1.0 1.0 1.0 Potassium sorbate 0.5 0.5 0.5 0.5 0.5 0.5 0.5 solvent Distilled water 84.5 82.7 85.2 89.5 87.7 84 82.7 Ink composition characteristics One 2 3 4 5 6 7 Quick-handedness of handwriting ○ ○ ○ ○ ○ ○ ○ Color of handwriting ○ ○ ○ ○ ○ ○ ○ Handwriting hydrogen giant ○ ○ ○ ○ ○ ○ ○

Ink composition composition (% by weight) Comparative Example One 2 3 4 5 6 7 8 9 10 11 12 Water-soluble dye Edible
Yellow No. 4 Edible
Red No. 102 4.8
4.8
4.8
4.8
4.8
4.8
4.8
4.8
4.8
4.8
4.8
4.8
Edible
Blue No. 1 Water-soluble resin PVP K15 10.0 10.0 10.0 10.0 PVP K30 5.0 5.0 5.0 PVA 405 10.0 10.0 10.0 W5025 60 Leveling agent Suflon S211 1.0 1.0 1.0 Surfynol 465 1.0 1.0 1.0 BYK348 1.0 1.0 1.0 EP5035 1.0 1.0 antiseptic Benzoic acid
salt 1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
Sorbic acid
potassium 0.5
0.5
0.5
0.5
0.5
0.5
0.5
0.5
0.5
0.5
0.5
0.5
solvent Distilled water 82.7
82.7
82.7
87.7
87.7
87.7
82.7
82.7
82.7
83.7
92.7
32.7
Ink composition characteristics One 2 3 4 5 6 7 8 9 10 11 12 Quick-handedness of handwriting × △ × × △ × × △ × × ○ ○ Color of handwriting ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ × ○ Handwriting hydrogen giant ○ ○ ○ ○ ○ ○ ○ ○ ○ △ × ×

As shown in Table 1, the hydrogen-rich ink compositions of Examples 1 to 7 including the polyoxyethylene alkyl ether dispersion leveling agent can be written on the impermeable writing surface without blurring of handwriting, and further, As well as excellent color development.

The results of Table 2 show that the ink compositions of Comparative Examples 1 to 10 use different types of dispersing leveling agents without using the polyoxyethylene alkylether dispersing leveling agent according to the present invention and thus lack the effect of lowering the dynamic surface tension Therefore, when handwriting on the writing surface, the handwriting was somewhat or significantly blurred.

Since the ink composition of Comparative Example 10 contains no dispersing leveling agent (leveling agent), when the writing surface was written on the writing surface, the writing was remarkably blurred.

The ink composition of Comparative Example 11 contained the polyoxyethylene alkyl ether dispersion leveling agent according to the present invention, but did not contain a water-soluble resin, resulting in poor not only the color rendering property of the handwriting but also the hydrogen germination of the handwriting.

The ink composition of Comparative Example 12 contained the polyoxyethylene alkyl ether dispersion leveling agent according to the present invention, but contained an emulsion instead of the water-soluble resin, and the result was that the handwriting was not erased at all in water.

Therefore, it is intended that the present invention cover the modifications and variations of this invention provided they come within the scope of the appended claims and their equivalents. * * * * * Recently Added Patents .

Claims

A hydrogenated aqueous ink composition comprising (a) a water-soluble dye, (b) a water-soluble resin, (c) water as a solvent, and (d) a polyoxyethylene alkyl ether represented by the following formula (1) as a dispersion leveling agent.
[Chemical Formula 1]

(Wherein x and y are each selected from 1 to 40, m and n are each selected from 1 to 12, and m + n is selected from 5 to 15.)

The hydrogen-based aqueous ink composition according to claim 1, wherein the water-soluble dye is a food dye.

The hydrogenated aqueous ink composition according to claim 1, wherein the water-soluble resin is polyvinylpyrrolidone or polyvinyl alcohol.

The hydrogen-based aqueous ink composition according to claim 1, wherein the water-soluble dye is contained in an amount of 0.1 to 15% by weight, and the water-soluble resin is contained in an amount of 1 to 20% by weight.

The hydrogen-based aqueous ink composition according to claim 1, wherein the dispersing leveling agent is contained in an amount of 0.1 to 10% by weight based on the whole composition.

The method according to claim 1, further comprising the step of: (a) adding a water-soluble dye in an amount of 0.1 to 15% by weight, (b) 1 to 20% by weight of a water-soluble resin, (c) Aqueous ink composition.

An aqueous marking pen comprising the hydrogenated aqueous ink composition according to claim 1.