JP3275020B2 - Water-based erasable marking pen ink composition - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a water-based erasable marking pen ink composition, and more particularly to a water-based, non-absorbing or non-permeable writing surface, typically a so-called white plate. The present invention relates to a water-based marking pen ink composition which is excellent in erasability of handwritings written in (1).

[0002]

2. Description of the Related Art Conventionally, handwriting written on a non-absorbable or impervious writing surface is wiped off from the writing surface by gently rubbing it with a dry cloth or soft paper to erase the handwriting. Various erasable marking pen ink compositions are known. Such a conventional erasable marking pen ink composition generally contains an additive called a release agent together with an organic solvent, a pigment and a resin.
No. 9149 discloses an erasable marking pen ink composition obtained by dissolving a substance selected from a surfactant and a saturated aliphatic carboxylic acid triglyceride together with an aliphatic dibasic acid ester and an aliphatic monobasic acid ester in an organic solvent. Is described.

However, as described above, such conventional erasable marking pen ink compositions use ketones or alcohols as solvents. Particularly, among these solvents, ketones are highly toxic, and among alcohols, methanol is highly toxic and has a bad smell. On the other hand, ethanol has relatively low toxicity,
This will increase raw material costs.

Therefore, for example, Japanese Patent Application Laid-Open No. Sho 60-17947.
No. 8 and JP-A-60-219273, a resin emulsion such as a polyvinyl acetate resin as a release agent is dissolved in water together with a dye or pigment as a colorant and a predetermined surfactant. There has been proposed an aqueous erasable marking pen ink composition containing the composition. However, since such a water-based ink composition uses a resin emulsion as a release agent, like a so-called strippable paint, in the handwriting on the non-absorbing surface, after its drying,
The above resin emulsion forms a continuous coating on the writing surface, and therefore, the handwriting is peeled into a continuous coating, and the handwriting is easily rubbed from the writing surface to the extent that the handwriting is rubbed lightly. It is hard to say that it does not peel and has excellent erasability.

Therefore, recently, various improvements have been proposed for aqueous erasable marking pen ink compositions. For example, JP-A-64-11174 and JP-A-1-188576 disclose water-soluble erasability using a water-soluble polyvinyl alcohol as a resin component for forming a film and using a silicone-based surfactant as a release agent. Ink compositions have been proposed. Also, Japanese Patent Application Laid-Open
Japanese Patent No. 252681 discloses a water-soluble resin or a resin which is originally water-insoluble but water-solubilized by salt formation with a base, such as a resin component for forming a film.
An aqueous erasable marking pen ink composition has been proposed, which uses a styrene-maleic anhydride resin, uses an aliphatic carboxylic acid ester, a higher hydrocarbon, or a higher alcohol emulsion at room temperature as a release agent.

Further, JP-A-2-117975 discloses that a polyvinyl acetal resin is used as a resin component.
An aqueous erasable marking pen ink composition using an ester compound of a polyalkylene glycol ether as a release agent has been proposed.

[0007]

However, the conventionally known water-based erasable marking pen ink compositions as described above have insufficient erasability and are not practically satisfactory. That is, the erasability of handwriting deteriorates with time, or depending on the environmental atmosphere, particularly, humidity conditions,
Erasability is inferior, and in the case of a white plate material, in particular, a resin plate or a painted plate, the erasability is inferior.

The present inventors have conducted intensive studies to solve the above-mentioned problems in the conventional water-erasable marking pen ink composition, and as a result, as a resin component for forming a film, a water-soluble polyvinyl acetal resin was used. With the use of an aqueous emulsion of a non-volatile aliphatic carboxylic acid ester which is liquid at normal temperature as a handwriting release agent, only the handwriting portion rubbed with a dry cloth or the like is easily peeled off from the writing surface. The present inventors have found that a water-based erasable marking pen ink composition having excellent erasability can be obtained, which has led to the present invention.

[0009]

The aqueous erasable marking pen ink composition according to the present invention comprises (a) water as a solvent, (b) a colorant dissolved or dispersed in water, and (c) a film-forming agent. -Soluble polyvinyl formal as a material
Resin, polyvinyl acetal resin (acetaldehyde
Cetal resin), polyvinyl butyral resin or these
A mixture of (d) an aqueous emulsion of a liquid aliphatic carboxylic acid ester which is hardly volatile at room temperature , and (e) a water-soluble resin or a water-insoluble resin as a film-forming auxiliary.
Emulsions or hydrosols, or inherently water-insoluble
However, it is characterized by containing a resin solubilized by a base with water .

[0010] In the aqueous erasable marking pen ink composition according to the present invention, water is used as a solvent.
The amount of water in the ink composition is usually in the range of 50 to 90% by weight, preferably 60 to 80% by weight. In the marking pen ink composition according to the present invention, a pigment is preferably used as the colorant. As a pigment,
Inorganic pigments such as carbon black, titanium oxide and iron oxide, and phthalocyanines such as copper phthalocyanine blue, azo, quinacridone, anthraquinone, dioxane, indigo, thioindigo, perinone, perylene, and indolenone Any of organic pigments such as azo-azomethine and the like may be used depending on the characteristics and use of the ink composition.

By the way, dispersions obtained by dispersing various pigments in water are already on the market, and in the present invention,
Such commercially available products can be preferably used. In the pigment dispersion, various resin dispersants, surfactants, and the like may be blended as a pigment dispersant. Therefore, even in the ink composition according to the present invention, such a resin, surfactant, or the like is used. May be contained. Pigment dispersants are known per se, and are usually 1 to 3 parts by weight based on 1 part by weight of pigment.
It is used in an amount of 00 parts by weight, preferably 5 to 100 parts by weight.

In preparing the aqueous erasable ink composition according to the present invention, an aqueous dispersion may be prepared by using a pigment in advance using a resin dispersant, and this may be mixed with other components to form an ink composition. . Here, a polyvinyl acetal resin can be preferably used as a resin dispersant.
In the present invention, a dye can also be used as a coloring agent. In this case, a water-soluble dye is preferably used as the dye.

In the present invention, the colorant as described above is usually contained in the ink composition in a range of 0.5 to 20% by weight, preferably in a range of 1 to 15% by weight. When the colorant is excessively contained, the viscosity of the ink composition is too high, so that the flow of the ink composition is deteriorated, the writing property is deteriorated, and the erasability is also reduced. On the other hand, when the content of the coloring agent is too small, the density of the handwriting is too low to obtain a practical marking pen ink composition.

The ink composition according to the present invention has a coating or layer made of a resin containing the above-mentioned coloring agent, which is written on a non-absorbing surface and, after water is volatilized, has a handwriting. It contains a water-soluble polyvinyl acetal resin so that it can be separated from a release agent layer described later. In general, a polyvinyl acetal resin can be obtained by reacting an aliphatic aldehyde with polyvinyl alcohol, but in such an acetalization reaction, the polyvinyl alcohol cannot be completely acetalized,
In the stage of producing polyvinyl alcohol by saponification, an acetyl group remains partially. Therefore, generally, the polyvinyl acetal resin has the following formula:

[0015]

Embedded image

(Wherein, R represents hydrogen or an alkyl group having 1 to 3 carbon atoms). The molecule has a considerable amount of hydroxyl groups and acetyl groups in the molecule together with the acetal structure. A polyvinyl acetal resin suitable for use in the present invention is a polyvinyl acetal resin in which R is hydrogen or an alkyl group having 1 to 3 carbon atoms in the above formula,
That is, a polyvinyl formal resin, a polyvinyl acetal resin (acetaldehyde acetal resin) , a polyvinyl butyral resin, etc., having a degree of acetalization of 5 to 4
0 mol% range, pH 7 ± 2, solid content 18 ± 4%
Is in the range of 4000 ± 3000 centipoise. As such a water-soluble polyvinyl acetal resin, a commercially available product can be obtained, and such a commercially available product can be suitably used in the present invention.

In the present invention, the water-soluble polyvinyl acetal resin is contained in the ink composition in an amount of 0.1 to 15% by weight, preferably 0.2 to 10% by weight. When the amount of the water-soluble polyvinyl acetal resin in the ink composition exceeds 15% by weight, the viscosity of the ink composition becomes excessively high, resulting in poor writability and poor erasability. However, when the amount is less than 0.1% by weight, the erasability of handwriting is inferior.

Next, in the ink composition according to the present invention, a hardly volatile aliphatic carboxylic acid ester which is liquid at normal temperature is contained in an aqueous emulsion state as a handwriting release agent. As the aliphatic carboxylic acid ester, a monobasic acid ester, a dibasic acid diester, or a trihydric alcohol, particularly a mono-, di-, or tri-ester of glycerin, is preferably used.

Particularly preferred examples include monobasic acid esters, especially higher fatty acid esters such as propyl myristate, butyl palmitate, butyl stearate,
Octyl stearate, butyl isostearate, dialkyl aliphatic dibasic acid dioctyl dodecane diacid, dipropyl adipate, dioctyl sebacate, dioctyl azelate, etc. Methylolpropane triisostearate and the like can be mentioned. These are used alone or as a mixture of two or more.

Further, in the present invention, if necessary,
As the release agent, an aqueous emulsion of a hardly volatile higher hydrocarbon which is liquid at ordinary temperature or a higher alcohol which is hardly volatile which is liquid at ordinary temperature may be used together with the aqueous emulsion of the aliphatic carboxylic acid ester. As the higher hydrocarbons,
Usually, what is called liquid paraffin or squalane is preferably used, but it may be partially oxidized, for example, as oxidized polyethylene wax.
The higher alcohol is not particularly limited, but, for example, hexyl alcohol, octyl alcohol, lauryl alcohol and the like are preferably used.

The above-mentioned aqueous emulsion of an aliphatic carboxylic acid ester or a higher hydrocarbon or higher alcohol can be prepared by a usual emulsification method.
Commercial products can also be used. In the ink composition according to the present invention, the aliphatic carboxylic acid ester as a release agent is contained in the ink composition in an amount of 1 to 20% by weight, preferably 2 to 15% by weight. When the amount of the aliphatic carboxylic acid ester in the ink composition is less than 1% by weight, sufficient handwriting erasability cannot be obtained. In addition, the handwriting is elongated, and the writing surface is stained. On the contrary, the erasability of the handwriting is reduced.

In the present invention, as described above,
When a higher hydrocarbon or a higher alcohol is used in combination with the above-mentioned aliphatic carboxylic acid ester as a release agent, the compounding amount is 1 to 20% by weight, preferably 2 to 15% by weight in the ink composition in total. Range. Furthermore,
In the ink composition according to the present invention, a water-soluble polyhydric alcohol is preferably blended as a release aid in order to enhance the effect of the release agent. Examples of such polyhydric alcohols include (poly) such as ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, dipropylene glycol, tripropylene glycol, polyethylene glycol having a molecular weight of about 200 to 600, and polypropylene glycol having a molecular weight of 1000 to 3000. In addition to alkylene glycol, glycerin, trimethylolpropane and the like can be mentioned. Such a polyhydric alcohol is blended in the ink composition in an amount of 20% by weight or less, preferably 10% by weight or less. Excessive addition of more than 20% by weight in the ink composition is not preferred because the viscosity of the ink composition becomes excessively high and the writability deteriorates.

In the ink composition according to the present invention, a conventionally known resin having a film-forming property at room temperature can be used as a resin component as a film-forming aid, in addition to the above-mentioned polyvinyl acetal resin. . In the present invention, such room-temperature film-forming resin, in particular, (1) water-insoluble resin, for example, polyvinyl acetate, vinyl acetate copolymer, alkyd resin, acrylic resin, emulsion or hydrosol such as urethane resin, or ( 2) Resins which are water-insoluble by nature but are water-solubilized by salt formation, such as vinyl acetate copolymer, acrylic resin, styrene-maleic anhydride resin, maleated oil, maleated polybutadiene, and maleic. (3) resins that are originally water-insoluble but are water-solubilized by salt formation, such as alkyd alkyd resins, maleated petroleum resins, maleated rosin ester resins, alkyd resins, urethane resins, etc. Originally, a water-soluble resin is preferably used.

Examples of the comonomer in the emulsion or hydrosol or the water-solubilized vinyl acetate copolymer include vinyl ester compounds other than vinyl acetate, such as vinyl propionate and vinyl versatate, and unsaturated carboxylic acids such as And acrylic acid, methacrylic acid, maleic acid, maleic anhydride, fumaric acid, itaconic acid, crotonic acid, citraconic acid and the like, or vinyl hydrocarbons such as ethylene, propylene, styrene and α-methylstyrene. . These may be mixed and used as a comonomer. Further, in addition to the above, esters of the unsaturated carboxylic acids such as methyl acrylate, ethyl acrylate, methyl methacrylate, dimethyl maleate and the like can also be used as a comonomer. Also,
The vinyl acetate copolymer may be a graft copolymer onto polyvinyl acetate.

Particularly preferred specific examples of the vinyl acetate copolymer include, for example, vinyl acetate-acrylic acid copolymer,
Vinyl acetate-methacrylic acid copolymer, vinyl acetate-styrene-acrylic acid copolymer, vinyl acetate-styrene-maleic anhydride copolymer, vinyl acetate-acrylic acid-methyl acrylate copolymer, vinyl acetate-methacrylic acid -Methyl acrylate copolymer, vinyl acetate-acrylic acid-ethyl acrylate copolymer, vinyl acetate-methacrylic acid-
Examples thereof include a methyl methacrylate copolymer and a vinyl acetate-maleic anhydride copolymer.

Emulsions and hydrosols of polyvinyl acetate and the above-mentioned vinyl acetate copolymer can be easily obtained as commercial products. Further, emulsions and hydrosols of alkyd resins and urethane resins can also be obtained as commercial products. Also, a resin that is originally water-insoluble but is water-solubilized by salt formation or the like is a resin that is originally water-insoluble and is made water-soluble by salt formation with an inorganic or organic base. Then, there may be mentioned alkali metal salts such as sodium and potassium, and organic salts such as ammonium salts and organic amine salts. Various water-solubilized resins can be obtained as commercial products.

For example, the water-solubilized alkyd resin is
An alkyd resin having a free carboxyl group obtained from an excessive amount of a polybasic acid and a polyhydric alcohol is neutralized with an alkali metal base, an ammonium base, an organic amine, and the like, and is made water-solubilized. These can be obtained as commercial products. For example, a water-solubilized urethane resin has, for example, a carboxyl group in a polymer main chain, and the carboxyl group is neutralized to form a salt with an alkali metal base, an ammonium base, an organic amine, or the like. These are also available as commercial products.

[0028] The inherently water-soluble resins include polyvinylpyrrolidone, a degree of polymerization of 100 to 3000,
A water-soluble synthetic resin such as polyvinyl alcohol having a saponification degree of 50 mol% or more can be preferably used. But,
Natural water-soluble resins such as gum arabic and celiac can also be used. The above resin is contained in the ink composition according to the present invention in a range of 0.1 to 15% by weight, preferably 0.3 to 10% by weight, as a resin component. When the resin is excessively contained, the viscosity of the ink composition is too high, so that the writability is deteriorated and the erasability is reduced. On the other hand, when the content of the resin is too small, the erasability of handwriting is inferior.

Among the various room-temperature film-forming resins described above, in the present invention, a water-insoluble resin emulsion or hydrosol, or a resin which is originally water-insoluble but is water-solubilized by salt formation or the like. Is preferably used. According to the ink composition containing such a room-temperature film-forming resin,
As described below, when written, such a resin contains a colorant together with the polyvinyl acetal resin described above, and forms a film as a carrier of the colorant, so that the handwriting is excellent in water resistance,
Further, it has stable erasability regardless of temperature and humidity conditions.

Further, the ink composition according to the present invention may contain various surfactants together with the water-soluble polyhydric alcohol described above or as a separate release aid.
As such a surfactant, any of anionic, nonionic, cationic and amphoteric surfactants can be used. However, nonionic surfactants such as carboxylic acid-based, sulfonic acid-based, sulfate-based, and phosphate-based surfactants having a polyoxyethylene chain, anionic surfactants, alkylbetaine-type amphoteric surfactants, and fluorine-based surfactants Surfactants and the like are preferably used. The surfactant is usually contained in an amount of 10% by weight or less, preferably 0.2 to 5% by weight. Excessive blending reduces the erasability of handwriting.

The handwriting of the ink composition according to the present invention on the non-absorbable or non-permeable penetrating surface is such that when the water evaporates, that is, when the handwriting dries, the polyvinyl acetal which is the above-mentioned film-forming agent is used. While the resin and the resin component as a film forming aid contain a colorant, a film is formed,
The emulsion of the aliphatic carboxylic acid ester as the release agent or the emulsion of the mixture of the aliphatic carboxylic acid ester and the higher hydrocarbon or the higher alcohol is destroyed, so that a continuous oil layer composed of the aliphatic carboxylic acid ester or the mixture thereof is non-dispersed. The handwriting has erasability because it is formed between the absorbent writing surface and the resin film.

Here, the above-mentioned surfactant as a release aid has an effect of assisting separation of the oily layer and the resin film containing a pigment in handwriting during writing. But,
The surfactant also has the effect of enhancing the leveling property during writing, eliminating uneven distribution of the release agent emulsion in the handwriting before drying on the writing surface, and imparting uniform erasability after the handwriting is dried. In particular, these effects are remarkable when a fluorine-based surfactant is used.

Furthermore, the ink composition according to the present invention is used as a drying accelerator for improving the drying property of handwriting, usually not more than 15% by weight based on the ink composition, so long as the emulsion contained in the ink composition is not destroyed. , Preferably 1 to 10% by weight of a lower aliphatic alcohol. Particularly, ethanol, propanol or butanol is preferably used.

[0034] In addition to the above, the ink composition may optionally contain, if necessary, any compound usually added to the aqueous ink composition.
It may contain a pH adjuster, a preservative, a preservative, and the like.

[0035]

The aqueous erasable marking pen ink composition according to the present invention comprises water as a solvent, a water-soluble polyvinyl acetal resin as a resin having film forming properties at room temperature, and a liquid at room temperature as a release agent. Since it is an aqueous ink composition in which a non-volatile aliphatic carboxylic acid ester is dispersed in an aqueous emulsion state, there is almost no problem of toxicity, odor, or pungent odor in the conventional oil-based ink composition. Moreover, the above-mentioned release agent forms a continuous oily layer on the writing surface after the handwriting has dried, and separates the resin film containing the coloring agent from the writing surface. Similarly, by gently rubbing the handwriting with a cloth, paper, or the like, only the rubbed portion can be easily peeled off and erased. Further, according to the ink composition of the present invention, since the release agent is a non-volatile liquid substance, even after a long time after writing, still between the writing surface and the resin layer containing the colorant. Since it exists, handwriting erasability is effectively maintained.

Further, since the ink composition of the present invention contains a polyvinyl acetal resin as a film-forming agent together with the above-mentioned release agent, it has been conventionally difficult to obtain sufficient erasability, especially on a white plate. Even in the case of a plastic plate or a painted plate typified by a melamine resin plate or a polyester resin plate, etc., it has excellent erasability of handwriting. Further, when the ink composition of the present invention contains an emulsion or a hydrosol of a water-insoluble resin, or a water-solubilized resin as a film-forming auxiliary, when writing, such a resin cooperates with the polyvinyl acetal resin. Since a handwriting is formed by forming a film while containing a coloring agent, the handwriting not only has excellent water resistance, but also has stable erasability regardless of the temperature and humidity conditions.

[0037]

EXAMPLES The present invention will be described below with reference to examples.
The present invention is not limited by these examples. In the following examples, the component amounts indicate% as an effective amount in the ink composition, and the balance is water.

Example 1 Colorant Phthalocyanine Green 2 Dispersant Ammonium salt of styrene-butyl acrylate-methacrylic acid copolymer 2 Film-forming agent polyvinyl acetal resin ¹⁾ 2 Film-forming aid Vinyl acetate-ethyl acrylate-acrylic acid Copolymer (hydrosol) 1 Release agent Isopropyl myristate (emulsion) 8 Surfactant Anionic surfactant 0.5 Preservative and fungicide (effective amount)

Example 2 Colorant Carbon black 5 Dispersant Acrylic resin ²⁾ 3 Film forming agent Polyvinyl acetal resin 1 Film forming aid Polyurethane (emulsion) ³⁾ 5 Release agent Butyl stearate (emulsion) 5 Dioctyl dodecane diacid ( Emulsion) 5 Surfactant Anionic surfactant 1 Preservative and fungicide (effective amount)

Example 3 Colorant Slen Blue 3 Dispersant Vinyl acetate-acrylic acid copolymer (hydrosol) ⁴⁾ 5 Film-forming agent Polyvinyl acetal resin 5 Film-forming auxiliary agent None Release agent Butyl laurate (emulsion) 4 Squalane ( Emulsion) 1 Surfactant Amphoteric surfactant 1.5 Preservative and fungicide (effective amount)

Example 4 Colorant Carbon black 3 Dispersant Vinyl acetate-acrylic acid copolymer (hydrosol) 3 Film forming agent Polyvinyl acetal resin 1.5 Film forming aid Polyurethane (emulsion) 4 Release agent Cetyl isooctanoate (emulsion) 8) Surfactant Nonionic surfactant 2 Preservative / antifungal agent (effective amount)

Example 5 Colorant Monoazolide 4 Dispersant Polyvinyl acetal resin 2 Film forming agent Polyvinyl acetal resin 0.5 Film forming aid Acrylic resin ⁵⁾ 2 Release agent Butyl palmitate (emulsion) 12 Lauryl alcohol (emulsion) 3 Interface Surfactant Nonionic surfactant 0.5 Preservative and fungicide (effective amount)

Example 6 Colorant Slen blue 3 Dispersant Polyvinyl acetal resin 1 Film forming agent Polyvinyl acetal resin 0.5 Film forming aid Polyurethane (emulsion) 1 Release agent Butyl isostearate (emulsion) 5 Surfactant Nonionic surfactant Agent 1 Preservative / antifungal agent (effective amount)

Example 7 Colorant Monoazolide 5 Dispersant Polyvinyl Alcohol 10 Film Forming Agent Polyvinyl Acetal Resin 2 Film Forming Aid Polyvinyl Acetate (Emulsion) ⁶⁾ 1 Release Agent Butyl Stearate (Emulsion) 10 Surfactant Nonionic Surfactant Agent 1 Preservative / antifungal agent (effective amount)

Example 8 Colorant Special Black TU Paste ⁷⁾ 20 Film-forming agent Polyvinyl acetal resin 4 Film-forming aid Water-solubilized alkyd resin 2 Release agent Octyl stearate (emulsion) 5 Liquid paraffin (emulsion) 2 Aid Polypropylene glycol (average molecular weight 1000) 0.5 Surfactant Nonionic surfactant 1 Antiseptic / antifungal agent (effective amount)

Example 9 Colorant Phthalocyanine Green 2 Dispersant Polyvinyl Acetal Resin 1 Film Forming Agent Polyvinyl Acetal Resin 1 Film Forming Auxiliary None Release Agent Cetyl stearate (emulsion) 4 Surfactant Nonionic surfactant 1 Preservative and fungicide (Effective amount)

Example 10 Colorant Carbon black 5 Dispersant Acrylic resin ²⁾ 4 Film forming agent Polyvinyl acetal resin 1.5 Film forming aid Acrylic resin ⁵⁾ 1 Release agent Dioctyl dodecane diacid (Emulsion) 8 Surfactant Nonionic Surfactant 0.5 Preservative and fungicide (effective amount)

Comparative Example 1 Colorant Phthalocyanine Green 2 Dispersant Ammonium salt of styrene-butyl acrylate-methacrylic acid copolymer 2 Film forming agent Vinyl acetate-ethyl acrylate-acrylic acid copolymer (hydrosol) 3 Release agent Myristin Isopropyl acid (emulsion) 8 Surfactant Anionic surfactant 0.5 Antiseptic / antifungal agent (effective amount)

Comparative Example 2 Colorant Carbon black 5 Dispersant Acrylic resin ²⁾ 3 Film forming agent Polyurethane (emulsion) 6 Release agent Butyl stearate (emulsion) 5 Dioctyl dodecane diate (emulsion) 5 Surfactant Anionic surfactant 1 Antiseptic and fungicide (effective amount)

Comparative Example 3 Colorant Slen blue 3 Dispersant Vinyl acetate-acrylic acid copolymer (hydrosol) 5 Film forming agent Vinyl acetate-acrylic acid copolymer (hydrosol) 5 Release agent Butyl laurate (emulsion) 4 Squalane (Emulsion) 1 Surfactant Amphoteric surfactant 1.5 Preservative and fungicide (effective amount)

Comparative Example 4 Colorant Carbon black 3 Dispersant Vinyl acetate-acrylic acid copolymer 3 Film forming agent Polyurethane (emulsion) 5.5 Release agent Cetyl isooctanoate (emulsion) 8 Surfactant Nonionic surfactant 2 Preservative Fungicide (effective amount)

Comparative Example 5 Coloring agent Monoazo compound 4 Dispersant Acrylic resin ²⁾ 2 Film forming agent Acrylic resin ⁵⁾ 2.5 Release agent Butyl palmitate (emulsion) 12 Lauryl alcohol (emulsion) 3 Surfactant Nonionic surfactant 0 .5 Preservatives and fungicides (effective amount)

Comparative Example 6 Colorant Slen Blue 3 Dispersant Polyurethane (Emulsion) 1 Film Forming Agent Polyurethane (Emulsion) 1.5 Release Agent Butyl Isostearate (Emulsion) 5 Surfactant Nonionic Surfactant 1 Antiseptic and Fungicide ( Effective dose)

Comparative Example 7 Coloring agent Monoazolide 5 Dispersant Polyvinyl alcohol 10 Film forming agent Polyvinyl acetate (emulsion) 3 Release agent Butyl stearate (emulsion) 10 Surfactant Nonionic surfactant 1 Antiseptic / antifungal agent (effective amount)

Comparative Example 8 Colorant Special Black TU Paste 20 Film Forming Agent Water Solubilized Alkyd Resin 6 Release Agent Octyl Stearate (Emulsion) 5 Liquid Paraffin (Emulsion) 2 Auxiliary Polypropylene Glycol (Average Molecular Weight 1000) 0.5 Surfactant Anionic surfactant 1 Antiseptic / antifungal agent (effective amount)

Comparative Example 9 Colorant Carbon black 5 Dispersant Acrylic resin ²⁾ 4 Film forming agent Acrylic resin ⁵⁾ 2.5 Release agent Dioctyl dodecane diacid (emulsion) 8 Surfactant Nonionic surfactant 0.5 Preservative Fungicide (effective amount) (Note) 1) Slesk K, Sekisui Chemical Co., Ltd., aqueous solution (solid content 20% by weight) 2) Hoshiros AW-36, manufactured by Hoshi Photo Chemical Co., Ltd. 3) Chuo Rika Kogyo Co., Ltd. Licabond GL-39, aqueous solution (solid content 30% by weight) 4) Licabond SA-L manufactured by Chuo Rika Kogyo Co., Ltd., aqueous solution (solid content 30% by weight) 5) Bonncoat ST-3 manufactured by Dainippon Ink and Chemicals, Inc.
726) Polysol HR-C manufactured by Showa Polymer Co., Ltd. 7) Aqueous dispersion of pigment manufactured by Hoechst Synthetic Co., Ltd. Using each of these ink compositions, write on enamel white plate or melamine resin white plate, Five minutes later, the dried handwriting was rubbed with a dry cloth under a load of 100 to 200 g, and the erasability (initial erasability) of the handwriting was examined. ◎ indicates that the handwriting was erased after 1 to 3 rubs (very good), and 極 め て indicates 4
Handwriting was erased in ~ 6 times (good), △ means rubbing number 7 ~
Handwriting was erased 9 times (slightly bad), x is 1 rubbing
This indicates that the handwriting was erased 0 times or more, or that the handwriting was not erased even 10 times or more. Table 1 shows the results.

[0057]

[Table 1]

──────────────────────────────────────────────────続 き Continued on front page (58) Field surveyed (Int. Cl. ⁷ , DB name) C09D 11/00-11/20

Claims (6)

(57) [Claims] (1) water as a solvent; (b) a colorant dissolved or dispersed in water; and (c) water-soluble polyvinyl formal as a film-forming agent.
Resin, polyvinyl acetal resin (acetaldehyde
Cetal resin), polyvinyl butyral resin or these
A mixture of (d) an aqueous emulsion of a liquid aliphatic carboxylic acid ester which is hardly volatile at room temperature , and (e) a water-soluble resin or a water-insoluble resin as a film-forming auxiliary.
Emulsions or hydrosols, or inherently water-insoluble
An aqueous erasable marking pen ink composition comprising a resin which is water-solubilized by a base . 2. The emulsion-forming agent according to claim 2, wherein the film-forming auxiliary is a water-insoluble resin.
Or hydrosol, or water-insoluble but salt
2. The resin according to claim 1, wherein the resin is a water-solubilized resin.
Aqueous erasable marking pen ink composition. 3. A higher hydrocarbons or aqueous erasable marking pen ink composition according to claim 1 or 2, characterized in that it comprises a higher alcohol together with aliphatic carboxylic acid ester as a release agent. 4. The aqueous erasable marking pen ink composition according to claim 1 or 2, characterized by containing a polyhydric alcohol as a release aid. 5. characterized in that it contains an aliphatic alcohol as a drying aid according to claim 1 or an aqueous erasable marking pen ink composition according to 2. 6. The method of claim 1 or 2 binomial aqueous erasable marking pen ink composition as claimed, characterized in that it contains a surfactant.