JP2003313484A - Aqueous ink for writing board - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an aqueous ink for a writing board that can be written on an impermeable writing surface and give handwriting readily erasable with a wet wiping material such as a wet dustcloth, wet tissue paper, a wet blackboard eraser and yet does not vanish even in the case of getting wet in the rain when used outdoors. <P>SOLUTION: The aqueous ink for a writing board comprises, at least, 5-30 wt.% of an organic or inorganic pigment, 0.1-15 wt.% of an extender pigment such as aluminum silicate, calcium carbonate and the like, 2-7 wt.%, in terms of solid content, of a water-soluble salt of a polyacrylic acid such as sodium polyacrylate, ammonium polyacrylate and the like, 0.05-3 wt.% of one selected from among a partially saponified polyvinyl alcohol having a polymerization degree of about 300 to 700 and a saponification degree of about 85-90 mole%, hydroxyethyl cellulose and hydroxypropyl cellulose, 1-9 wt.% of polyethylene glycol having a molecular weight of about 600 to 6,000, 0.02-0.5 wt.% of an aliphatic carboxylate and water. <P>COPYRIGHT: (C)2004,JPO

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 for writing boards, and more particularly to a writing surface such as a resin plate, a metal plate, a enamel plate, a glass plate, a coating plate, a film, etc. which is impermeable. Can be written on, and it is possible to easily erase the handwriting with a wet cloth such as a wet cloth, a wet tissue, or a wet blackboard wipe. Furthermore, the handwriting written on these writing surfaces is The present invention relates to a water-based ink for a writing board, which does not easily disappear in rainy water when left outdoors. In the present invention, the writing plate ink means an ink that can be written on a non-permeable writing surface such as the resin plate, the metal plate, the enamel plate, the glass plate, the coating plate and the film, and is a so-called white board. It does not mean an ink that is used only for simple things.

[0002]

2. Description of the Related Art Heretofore, there have been known many water-based ink compositions for writing boards, which are capable of erasing handwriting written on a non-absorbing surface. These aqueous ink compositions for writing plates are disclosed, for example, in JP-A-6-1228493 and JP-A-7-207212.
As disclosed in Japanese Patent Laid-Open No. 9-100433 and Japanese Patent Laid-Open No. 9-100433, it comprises a pigment, a resin, and a release agent.

[0003]

However, the above-mentioned conventional water-based inks for writing boards are capable of erasing handwriting on a writing surface that is non-permeable, but on the other hand, an aliphatic carboxylic acid is used as a release agent. Estel is, for example, JP-A-6-122.
In 849 and Japanese Patent Laid-Open No. 7-207212, 1
˜20% by weight, 1 to 1 in JP-A-9-100433
Since it contains 50% by weight, it easily disappears by touching the handwriting, which causes problems such as soiling hands and clothes and making the handwriting unreadable.
Further, when left outdoors, there is a problem that the handwriting gets wet and peels off in the rain. The present invention is
The above does not peel off just by rubbing, and when trying to erase, it can be easily erased with a wet wiping material such as a wet blackboard wipe, and the handwriting does not come off even when exposed to rain. An object is to provide a water-based ink for plates.

[0004]

The present invention is directed to a pigment, an extender pigment, an acrylic resin, polyvinyl alcohol or a water-soluble cellulose derivative, and a molecular weight of 600 to 6,000.
The water-based ink for a writing board is characterized in that it contains at least a paste or solid polyethylene glycol at room temperature, an aliphatic carboxylic acid ester, and water.

Each component of the present invention will be described in detail below. The pigment is used as a colorant and is a conventionally known azo pigment, nitroso pigment, anthraquinone pigment, indigoid pigment, phthalocyanine pigment, piazolone pigment, oxazine pigment, quinacridone pigment, perinone pigment. , Metal complex pigments, pyranthrone pigments, condensation pigments, flavantron pigments, quinophthalone pigments, flavone pigments, xanthene pigments and other organic pigments, carbon black, dark blue, red iron oxide, titanium oxide and other inorganic pigments, aluminum powder, brass From metal powder pigments such as powders, pigments, fluorescent pigments, pearl pigments, and the like, one or two or more kinds can be appropriately selected that can be stably dispersed as fine particles in the water-based ink for writing boards. Can be used. The amount used varies depending on the type of pigment and other ink components, but is preferably 1 to 40% by weight, more preferably 5 to 5% by weight based on the total amount of the aqueous ink for writing board.
It is 30% by weight.

Extending pigments are contained in an aqueous pigment dispersion liquid.
Generally, it imparts hiding power, glossiness, redispersibility, etc., but in the present invention, when used in combination with a pigment, it improves the hiding power, gloss, etc., compared with the use of a pigment alone, for improving handwriting. Which is used as an auxiliary agent for improving the redispersibility of the ink over time,
From the so-called colloid-treated products obtained by surface-treating the surfaces of conventionally known aluminum silicate, calcium carbonate and these extender pigments with resin acids, fatty acids, organic acids such as sulfonic acids, and salts such as amine salts and ammonium salts. One or two or more kinds of materials that can be stably dispersed in the water-based ink for writing boards can be appropriately selected and used. The amount used varies depending on the type of extender pigment and other ink components, but is 0.05 to 20 with respect to the total amount of the aqueous ink for writing boards.
Wt% is preferred, more preferably 0.1-15 wt%
Is.

The acrylic resin is used for the purpose of dispersing a pigment and an extender pigment, and can be used without particular limitation, but polyacrylic acid is neutralized with an alkaline substance such as sodium hydroxide, ammonia and alkanolamine. A water-soluble salt of polyacrylic acid such as sodium polyacrylate, ammonium polyacrylate, or alkanolamine salt of polyacrylic acid is preferably used. Specifically, durimer AC-10P (polyacrylic acid), AC-10SL (polyacrylic acid), AC-
10S (polyacrylic acid), the same AC-10L (polyacrylic acid) (the above polyacrylic acid is a type which is used after being neutralized with an alcal substance such as sodium hydroxide, ammonia, and alkanolamine), the same AC -10NP
(Polyacrylic acid sodium salt), AC-103 (polyacrylic acid sodium salt), AC-107 (polyacrylic acid sodium salt), AC-10N (polyacrylic acid sodium salt, AC-16H (polyacrylic acid) Acid alkanolamine salt), AC-10HN (polyacrylic acid sodium salt) (above, manufactured by Nippon Pure Chemical Co., Ltd.), Dydol DL (polyacrylic acid sodium salt), C-1.
000 (polyacrylic acid sodium salt) (all manufactured by Daido Kasei Co., Ltd.), Despex N-40 (polyacrylic acid sodium salt), A-40 (polyacrylic acid ammonium salt) (all, Allied Colloid Company Manufactured) and the like. These acrylic resins may be used alone or in combination of two or more. The amount of these acrylic resins used is preferably 1 to 10% by weight, more preferably 2 to 7% by weight, based on the total amount of the aqueous ink for a writing plate, as the solid content of the acrylic resin.

Polyvinyl alcohol or a water-soluble cellulose derivative is used as a dispersion stabilizer for pigments and extender pigments. Polyvinyl alcohol is a polymer compound obtained by saponifying polyvinyl acetate with an alkali, an acid, aqueous ammonia, etc., and has a good average degree of polymerization of about 300 to 700 and a degree of saponification of about 85 to disperse pigments and extender pigments. It is preferably 90 mol% partially saponified. Specifically, Gohsenol GL-03 (degree of polymerization of about 3
00, saponification degree 86.5 to 89.0 mol%), and GL-0
5 (degree of polymerization: about 500, degree of saponification: 86.5 to 89.0 mol%) (above, manufactured by Nippon Synthetic Chemical Industry Co., Ltd.), Kuraray Poval PVA-203 (degree of polymerization: about 300, degree of saponification: 86.5-8)
9.5 mol%), PVA-204 (polymerization degree of about 400,
Degree of saponification 86.5 to 89.5 mol%), PVA-205
(Polymerization degree: about 500, Saponification degree: 86.5-89.5 mol%)
(Above, Kuraray Co., Ltd.), Shin-Etsu Poval PA-05
(Polymerization degree of about 500, saponification degree of 86 to 90 mol%, manufactured by Shin-Etsu Chemical Co., Ltd.), DENKA POVAL B-03 (polymerization degree of about 3
00, saponification degree 87-89 mol%), B-05 (polymerization degree about 500, saponification degree 87-89 mol%) (above, manufactured by Denki Kagaku Kogyo Co., Ltd.), Unitika Poval UP040G (polymerization degree about 400, Saponification degree 86-90 mol%), same UP050
G (degree of polymerization: about 500, degree of saponification: about 87 to 89 mol%) (above, manufactured by Unitika Ltd.) and the like. Examples of the water-soluble cellulose derivative include hydroxyethyl cellulose obtained by reacting alkali cellulose with ethylene oxide or ethylene chlorohydrin, and hydroxypropyl cellulose obtained by reacting propylene oxide. Specifically, as hydroxyethyl cellulose, Tyrose H300p, H4000p, H10000p (above,
Clariant Polymer Co., Ltd., HEC Daicel SP
200, SP250, SP400, SP500,
SP550, SP600, SP750, SP80
0, SP850, SP900, EP600, E
P850, SE400, SE500, SE55
0, SE600, SE850, SE900 (all manufactured by Daicel Chemical Industries, Ltd.), Fujichem HECAL
-15F, AC-15F, AH-15F, AV-
15F, same AW-15F, same AW-15F, same AX-1
5F, same SV-25F, same SW-25F, same SX-25
F, SY-25F, SZ-25F, CF-G, C
F-V, CF-W, CF-X, CF-Y (all manufactured by Fuji Chemical Co., Ltd.), Nisso H.K. E. C. AL-15,
A-G-15, B-L-15, B-G-15, B-L-20, B-G-20, M-L-15 (all manufactured by Nippon Soda Co., Ltd.). ) And the like. As hydroxypropyl cellulose, Nisso HPC-SL, the same
L, same-M, same-H (above, Nippon Soda Co., Ltd. product), L-
HPCLH-11, LH-20, LH-21, L
H-22, LH-30, LH-31, LH-32
(Above, manufactured by Shin-Etsu Chemical Co., Ltd.) and the like. These polyvinyl alcohols or water-soluble cellulose derivatives can be used alone or in combination of two or more. The amount used varies depending on the type of pigment or extender pigment and other ink components, but is preferably 0.01 to 5% by weight, more preferably 0.05 to 3% by weight, based on the total amount of the aqueous ink for writing board. is there.

Polyethylene glycol is used for the purpose of imparting a coat-forming property, imparting a coat-fixing property to the writing plate surface, imparting erasability and imparting water resistance, and has a molecular weight of 600 to 6,
It must be paste or solid at room temperature of 000. If the molecular weight of polyethylene glycol is 600 or less, it is liquid at room temperature, so the fixability of the handwriting and the water resistance deteriorate, and if the molecular weight of polyethylene glycol is 6,000 or more, the water resistance improves. On the other hand, the handwriting becomes too hard and the erasability deteriorates. Specifically, Toho polyethylene glycol # 600 (molecular weight about 600), Toho polyethylene glycol # 1000 (molecular weight about 100
0), ibid # 1500 (molecular weight about 1,000), ibid # 15
40 (molecular weight about 1540), the same # 2000 (molecular weight about 2,000), the same # 4000 (molecular weight about 4,000),
Same # 6000 (Molecular weight: about 6,000), Lion Corporation
PEG # 600 (molecular weight about 600), # 1000
(Molecular weight about 1,000), # 1500 (Molecular weight about 1,
000), ibid # 1540 (molecular weight about 1540), ibid # 2
000 (Molecular weight about 2,000), the same # 4000 (Molecular weight about 4,000), the same # 6000 (Molecular weight about 6,000)
(Above, manufactured by Toho Chemical Industry Co., Ltd.), PEG600 (molecular weight about 600), 1000 (molecular weight about 1,000), 1500 (molecular weight about 1,000), 1540 (molecular weight about 1540), 2000 ( The molecular weight is about 2,000, the same is about 4000 (the molecular weight is about 4,000), the same is about 6000 (the molecular weight is about 6,000) (these are NOF Corporation). These polyethylene glycols may be used alone or in combination of two or more. The amount used is preferably 0.7 to 10% by weight, more preferably 1.0 to 9% by weight, based on the total amount of the water-based ink for a writing plate, although it depends on the ink component.

The aliphatic carboxylic acid ester is used for the purpose of a water resistance auxiliary agent for the coating film and is insoluble in the aqueous ink composition for writing boards as it is, but it is emulsified by using it together with the polyethylene glycol. Those to be dispersed are preferably used, and the ratio thereof is 0.002 to 0.5 by weight ratio with respect to polyethylene glycol. Specifically, the monobasic acid ester is a higher fatty acid ester such as butyl myristate, butyl stearate, cetyl 2-ethylhexanoate, and 2-piparic acid.
Octyldodecyl, ethyl oleate, 2-hexyldecyl isostearate, isocetyl myristate, isocetyl stearate, octyl palmitate, isopropyl isostearate, isopropyl myristate, isopropyl palmitate, isostearyl palmitate, myristyl myristate, cetyl palmitate. , Octyldodecyl myristate, ethyl linoleate, isopropyl linoleate, cholesteryl stearate, phytosteryl isostearate and the like, dibasic acid diesters such as diethyl sebacate, diisopropyl adipate, diisopropyl sebacate and the like, monohydric alcohol mono, or Examples of diesters include propylene glycol monostearate, propylene glycol monocaprylate, and dicaprylic acid. Examples of mono-, di- or triesters of trihydric alcohols such as ropylene glycol and propylene glycol dicaprate include trimethylolpropane trioctanoate, trimethylolpropane triisostearate, glyceryl tri-2-ethylhexanoate, and tri (capryl-capric acid). Examples include glycerin, animal oil-derived triglycerides, vegetable oil-derived triglycerides, and the like. These aliphatic carboxylic acid esters may be used alone or in combination of two or more. The amount used is preferably 0.01 to 0.6% by weight, and more preferably 0.02 to 0.5% by weight, based on the total amount of the water-based ink for a writing plate, although it varies depending on the ink component.

Further, in the water-based ink for a writing board according to the present invention, it is possible to use a lower alcohol as a drying accelerator which enhances the drying property of handwriting. Examples of the lower alcohol include ethanol, normal propyl alcohol, isopropyl alcohol, normal butyl alcohol, isobutyl alcohol and the like. The amount of the lower alcohol used should be such that the dispersibility of the ink is not deteriorated, and is preferably 0.5 to 15 parts by weight, more preferably 1 to 10 parts by weight.

In addition to the components shown above, if necessary, p
H additives, antiseptics, antifungal agents, wetting agents, viscosity modifiers, antifreezing agents, nib dry inhibitors, antifoaming agents, various solvents, etc. You can

The method for producing a water-based ink for a writing board of the present invention comprises mixing a required amount of each of the above-mentioned components with a homomixer,
It can be easily obtained by mixing and dispersing with a high speed stirrer such as a lab mixer or a disperser such as a ball mill, a sand mill or a bead mill.

[0014]

The water-based ink for writing boards of the present invention has a pigment, an extender pigment, an acrylic resin, polyvinyl alcohol or a water-soluble cellulose derivative, and a molecular weight of 600 to 6,000.
It consists of a film formed by mixing with paste or solid polyethylene glycol at room temperature of 0. Even when the polyethylene glycol is not included, a coating film is formed,
Since this coating film has a good fixing property to the writing surface, peeling does not occur only by rubbing. The coating film formed by mixing the polyethylene glycol becomes brittle, and the handwriting can be erased by wiping with a wet cloth. Further, the coating film formed only of the former resin swells and peels off the coating film which is wet with water due to rainfall or the like, but the coating film combined with the polyethylene glycol has a low hygroscopic property of the polyethylene glycol. Due to its nature, the coating film does not swell with water, making it difficult to peel off. Further, the aliphatic carboxylic acid ester insoluble in the ink composition covers the surface of the coating film to increase the hydrophobicity of the coating film and make it easy to repel water.

[0015]

EXAMPLES The present invention will be described in more detail below with reference to examples. The above components were stirred in a ball mill for 12 hours to obtain a water-based ink for writing plates.

[0016] The above components were stirred in a ball mill for 24 hours to obtain a water-based ink for writing plates.

[0017] The above components were dispersed in a ball mill for 48 hours to obtain a water-based ink for writing plates.

[0018] The above components were dispersed in a ball mill for 48 hours to obtain a water-based ink for writing plates.

[0019] The above components were dispersed in a ball mill for 12 hours to obtain a water-based ink for writing plates.

[0020] The above components were dispersed in a ball mill for 24 hours to obtain a water-based ink for writing plates.

[0021] The above components were dispersed in a ball mill for 48 hours to obtain a water-based ink for writing plates.

[0022] The above components were dispersed in a ball mill for 12 hours to obtain a water-based ink for writing plates.

[0023] The above components were stirred in a ball mill for 12 hours to obtain a water-based ink for writing plates.

Comparative Example 1 In Example 1, Toho polyethylene glycol #
An aqueous ink for a writing board was obtained in the same manner as in Example 1 except that 600 was changed to Toho polyethylene glycol # 400 (molecular weight: about 400).

Comparative Example 2 In Example 3, Toho polyethylene glycol #
A water-based ink for a writing plate was obtained in the same manner as in Example 5 except that water was used instead of 1540.

Comparative Example 3 In Example 6, Toho polyethylene glycol #
6000 to Toho polyethylene glycol # 1100
A water-based ink for a writing plate was obtained in the same manner as in Example 6 except that the amount was changed to 0 (molecular weight: about 11,000). The results are shown in Table 1.

[0027]

[Table 1]

* 1 Fixing test Write a square line of 5 × 5 cm on a white board made of enamel and a white board made of melamine resin, and after 10 minutes, rub the handwriting up to 10 times with your finger and measure the number of times until the handwriting disappears. did. > 10:10 rubbing does not change handwriting

* 2 Erasability test Writing a 5 x 5 cm square line on a white board made of enamel and a white board made of melamine resin, and after 1 day, wipe the handwriting up to 10 times with a wet cloth until the handwriting disappears. Was measured. > 10:10 Do not wipe the handwriting even if wiped

* 3 Water resistance test Write a 5 × 5 cm square line on a glass plate, dry it for 1 hour, leave the glass plate in an environment of 100% humidity for 1 hour, and spray it up to 10 times with a mist. After that, the number of times until the handwriting from the glass plate was peeled off was measured. The amount of atomized spray is 1 milliliter per time. > 10:10 No spray of handwriting from the glass plate even after spraying

[0031]

INDUSTRIAL APPLICABILITY As described above, the water-based ink for a writing plate of the present invention can be written on a writing surface that is impermeable, and the handwriting thereof is a wet wipe such as a wet cloth, a wet tissue or a wet blackboard wipe. It is also excellent in erasing with water, and has excellent water resistance so that when it is used outdoors, the handwriting is not erased even when exposed to rain.

Claims (5)

[Claims] 1. A pigment, an extender pigment, an acrylic resin,
A water-based ink for a writing board, which comprises at least polyvinyl alcohol or a water-soluble cellulose derivative, a polyethylene glycol having a molecular weight of 600 to 6,000 and paste or solid at room temperature, an aliphatic carboxylic acid ester, and water. 2. The water-based ink composition for a writing board according to claim 1, wherein the acrylic resin is a water-soluble salt of polyacrylic acid. 3. Polyvinyl alcohol having an average degree of polymerization of about 3
The water-based ink composition for a writing plate according to claim 1 or 2, which is a partial saponification type having a saponification degree of about 00 to 700 and a degree of saponification of about 85 to 90 mol%. 4. The water-based ink composition for a writing board according to any one of claims 1 to 3, wherein the water-soluble cellulose derivative is hydroxyethylulose or hydroxypropylcellulose. 5. The fatty acid carboxylic acid ester is a monobasic acid ester, a dibasic acid diester, a mono-, di- or triester of a dihydric alcohol, or a mono-, di-, or triester of a trihydric alcohol, which is aqueous for writing boards. The water-based ink composition for a writing plate according to any one of claims 1 to 4, which is contained in the ink in an amount of 0.02 to 0.5 part by weight.