JP2003221542A - Water-based marking pen for writing board and ink composition used therefor - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a water-based marking pen ink composition having excellent erasability and visibility, and to provide a water-based marking pen in which the ink is charged and which is used for writing boards. <P>SOLUTION: This ink composition comprising water, a colorant, a polymer latex, and a releasing agent is characterized in that the colorant comprises at least one colorant selected from metal powder or colored resin fine particles having an average particle diameter of ≤15 μm and an inorganic pigment, organic pigment or fluorescent pigment having an average particle diameter of ≤5 μm, and that the releasing agent comprises at least one agent selected from the group consisting of aqueous emulsions selected from higher alcohols, liquid paraffin, squalane and dimethylpolysiloxane, liquid at the ordinary temperature, silicone-based surfactant and resin fine particles having an average particle diameter of ≤5 μm. The water-based marking pen for writing boards has an ink reservoir 3 containing an ink and a pen core 2 comprising a porous polyester core having a porosity of ≥58%, a porous foam member having open cells, or a writing brush. <P>COPYRIGHT: (C)2003,JPO

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a writing board surface such as a white board, a blackboard (black board) and a green board.
The present invention relates to an ink composition that can be easily erased with a dry cloth or a tissue after writing, and a water-based marking pen for a writing plate filled with the ink.

[0002]

2. Description of the Related Art A water-based ink for writing boards which can be erased with a dry cloth or tissue after writing is disclosed in, for example, Japanese Patent No. 2706.
No. 960, No. 2857577, No. 2957239,
No. 3,032,562, No. 3,158,309 and Japanese Patent Laid-Open No. Hei 7
No. 207212.

However, all of the erasable inks disclosed in these documents are white plates (so-called whiteboards) having a smooth plate surface or neon board plates (the plate surface is made of transparent resin).
For blackboards (black boards) and green boards for chalk, which are often used in schools and the like, the erasability itself is not satisfactory, and most of the inks have difficulty in visually recognizing writing lines.

Further, since it is difficult to see the reflected light on a smooth white plate, if a matte white plate having a reflectance of 60% or less is used,
The erase residue (stain) increased and it was almost unusable.

An erasable ink using a metal powder having a high specific gravity and poor dispersibility is hardly practically used since it is difficult to keep the colorant uniform because the colorant immediately settles in the ink. The only practical example is the one disclosed in U.S. Pat. No. 6,224,284, but the erasability and stability are not satisfactory either.
Furthermore, since the erasable ink using titanium oxide is inferior in dispersibility, an ink for filling type marking pen (Patent No. 2706) is used.
960) was difficult to use.

[0006]

SUMMARY OF THE INVENTION The present invention has been made in view of such drawbacks of the conventional water-based ink for writing plates, and has an excellent erasability and visibility. It is an object of the present invention to provide an article and an aqueous marking pen for a writing plate filled with the ink.

[0007]

Means for Solving the Problems As a result of intensive studies by the present inventor, erasability and visibility are significantly improved by blending a specific resin, a specific colorant and a specific release agent. And has come to complete the present invention,
The aqueous marking pen ink composition for a writing plate according to the present invention for solving the above-mentioned problems comprises water, a colorant, a polymer latex and a release agent, and the colorant has an average particle size of 15 microns or less. Of metal powder or colored resin fine particles, an inorganic pigment having an average particle size of 5 microns or less, an organic pigment or a fluorescent pigment, and the release agent is a higher alcohol liquid at normal temperature, liquid paraffin,
It is characterized by containing at least one selected from the group consisting of an aqueous emulsion selected from squalane or dimethylpolysiloxane, a silicone-based surfactant, and resin fine particles having an average particle size of 5 μm or less.

In order to solve the above-mentioned problems, an aqueous marking pen for a writing board according to the present invention has a batting containing ink, a porous polyester core having a porosity of 58% or more, and a porous material having open cells. A filling pen comprising a foam or a brush, the filling pad filled with the above ink composition, a porous polyester core having a porosity of 58% or more, and a porous foam having open cells. A valve type marking pen having a pen core composed of a body or a brush and a valve mechanism and filled with the above ink composition.

[0009]

BEST MODE FOR CARRYING OUT THE INVENTION Embodiments of the present invention will be described in detail below. The water-based marking pen ink for writing plates according to the present invention has a polymer latex having a film forming temperature of 0 ° C. or lower or a glass transition temperature of 0 ° C. or lower, and an average particle diameter of 1
It contains a metal powder or colored resin fine particles of 5 microns or less, a colorant which is an inorganic pigment, an organic pigment or a fluorescent pigment having an average particle size of 5 microns or less, a release agent, and water. The ink is preferably adjusted to a viscosity of 3 to 80 CPS.

The water-based marking pen for a writing board of the present invention comprises:
Polymer latex having a film forming temperature of 0 ° C. or lower or a glass transition temperature of 0 ° C. or lower, metal powder or colored resin fine particles having an average particle size of 15 μm or less, an inorganic pigment or an organic pigment having an average particle size of 5 μm or less Alternatively, it contains a colorant which is a fluorescent pigment, a release agent, and water, and has an ink viscosity of 3 to 8
It is characterized by being filled with a water-based marking pen ink for a writing plate adjusted to 0 CPS.

Each component of the marking pen ink according to the present invention is selected from the substances listed below.

As the coloring agent in the marking pen ink for writing plates of the present invention, metal powder or colored resin fine particles having an average particle diameter of 15 microns or less and inorganic pigments, organic pigments or fluorescent pigments having an average particle diameter of 5 microns or less are used. To be The content of the colorant is usually 1 to 50% by weight of the total amount of the ink composition.

Examples of the metal powder include aluminum powder and colored aluminum powder. Since aluminum powder reacts with water to generate hydrogen gas, it needs to be treated with a fatty acid and a surfactant, but it is actually available as an aqueous aluminum paste.

Examples of the colored resin fine particles include acrylic-styrene copolymers, acrylic urethane copolymers, benzoquanamine resins or styrene resins colored with dyes or pigments. Regarding these, commercially available products can be easily obtained.

Examples of the inorganic pigment include titanium oxide, carbon black, red husk, iron black and the like. Examples of organic pigments include azo-based, anthraquinone-based, phthalocyanine-based, dioxazine-based, monacridone-based, and polyazo-based pigments.

At present, various aqueous pigment dispersions are available for writing instruments, but those dispersed with a resin-based dispersant are more preferable from the viewpoint of erasability and stability. The use of a water-soluble dye is not preferable because an unerased residue occurs depending on the type of plate surface. As the fluorescent pigment, a commercially available aqueous dispersion is easily available.

The polymer latex used in the aqueous marking pen ink for writing plates of the present invention has a film forming temperature of 0 ° C. or less,
Alternatively, it has a glass transition temperature of 0 ° C. or lower. Specifically, styrene-butadiene copolymer, carboxylated styrene-butadiene copolymer, acrylonitrile-butadiene copolymer, carboxylated acrylonitrile-butadiene copolymer, chloroprene, methacrylic acid ester-butadiene copolymer, isobutylene- The latex is selected from isoprene copolymer, acrylic resin-based, silicone resin-based, natural rubber-based latex, etc., or two or more thereof are mixed and used.

Preferred examples include styrene-butadiene copolymer, carboxylated styrene-butadiene copolymer, acrylonitrile-butadiene copolymer or carboxylated acrylonitrile-butadiene copolymer latex. The polymer latex is 2 to 50% by weight, preferably 3 to 3 in terms of solid content in the ink.
Contains 5% by weight.

The release agent used in the marking pen ink for writing plates of the present invention includes higher alcohols which are liquid at room temperature,
It contains one or more selected from liquid paraffin, squalane or dimethylpolysiloxane emulsion, silicone-based surfactant, and resin fine particles of 5 μm or less. Its content is 0.5 to 25% by weight, preferably 3 to 20% by weight, based on the total amount of the ink composition.

Examples of higher alcohols include lauryl alcohol and tridecanol, which are less toxic. Emulsions of higher alcohol, liquid paraffin and squalane can be prepared by using a homogenizer as an emulsifier together with a sorbitan surfactant, a fatty acid soap and sodium alkylsulfate. Its content is 0.5 to 20% by weight in terms of pure content in the ink.

As the dimethylpolysiloxane emulsion, commercially available products KM-722, KM-740, KM-
780 (Shin-Etsu Chemical Co., Ltd.), TSM-630, TSM
-631, TSM-632 (manufactured by Toshiba Silicone Co., Ltd.) and the like can be used. Its content is 0.5 of the total amount of the ink composition.
To 20% by weight.

The silicone-based surfactant is a copolymer of dimethyl silicone and polyether and has an average molecular weight of 1,
It is preferably about 000 to 12,000. Examples of commercially available products include KF-351, KF-353 (manufactured by Shin-Etsu Silicone Co., Ltd.), TSF-4440, YSA-6403 (manufactured by Toshiba Silicone Co., Ltd.) and the like. The content is 0.5 to 20% by weight based on the total amount of the ink composition.

Examples of the resin fine particles having a particle size of 5 μm or less include polystyrene, acrylic-styrene copolymer, polymethylmethacrylate, acrylic-urethane copolymer and benzoguanamine resin. The content is 0.5 to 15% by weight of the total amount of the ink composition. When the polymer latex is formed into a film, the resin fine particles enter and weaken the soft and elastic resin film to facilitate erasing. Hollow resin fine particles are preferable in terms of erasability and ink dispersion stability. As a commercial item, Grandor PP-1100
(Manufactured by Dainippon Ink and Chemicals, Inc.), Lowpaque OP-84J
(Made by Rohm and Haas), JSR AE-866
(Manufactured by E-Tech Co., Ltd.) and the like.

Japanese Patent No. 2706960 and Japanese Patent Laid-Open No. 7-20
The fatty acid esters and fatty acid diesters, which are the plasticizers of the resin disclosed in Japanese Patent No. 7212, are absorbed with time (penetration) on the plate surface of the resin white plate, for example, nylon, polyester, acetate or fluororesin. do it)
Therefore, even if the initial erasability is good, the erasability with time deteriorates, which is not preferable.

The dispersant for the colorant used in the marking pen ink for writing plates of the present invention is selected from the following resin-based dispersants, amphoteric surfactants and polycarboxylic acid compounds, alone or, Two or more types are mixed and used. The content is 0.5 to 10% by weight based on the total amount of the ink composition.

As the resin-based dispersant, commercially available products such as Disperbic 180 and 192 (manufactured by BYK Chemie), Jonkryl 61-J, 62 and 682 (manufactured by Johnson Polymer Co., Ltd.) and the like can be used. As the amphoteric surfactant, commercially available products such as Amphitol 24B and 86B (manufactured by Kao Corporation) and Lipomin LA (manufactured by Lion Corporation) can be used. As the polycarboxylic acid compound, commercially available Disperbic (manufactured by Big Chemie), Aron A20
U, A6001 (manufactured by Toagosei Kagaku Co., Ltd.) and the like can be used.

In the composition of the present ink, in addition to the above-mentioned essential components, other additives usually used in water-based inks, for example, fluorinated surfactants for preventing cissing, preservatives, antibacterial agents, A pH adjusting agent and a water-soluble solvent such as ethylene glycol, diethylene glycol, propylene glycol, or glycerin as a moisturizing agent for preventing the pen core from drying can be added if necessary. Further, a lower alcohol such as ethanol or propanol can be added in the range of 1 to 10% by weight in order to improve the dryness of the handwriting.

As shown in FIG. 1, a padding type water-based marking pen for a writing board according to the present invention has a padding (ink tank) 3 containing ink, a fiber thickness of 7 to 30 denier and a porosity. It has a porous polyester core of 58% or more, and a pen core 2 made of a porous synthetic resin foam having open cells or a brush. In addition, 1 is a cap, 4 is a body,
5 is a tail plug.

The viscosity of the ink contained in the batting 4 is 5 to 2
It is preferable to adjust to 0 CPS. If it is 5 CPS or less, the stability of the ink is deteriorated. Further, when it is 20 CPS or more, the outflow of ink is deteriorated, and a blur occurs during writing. The conventional water-based marking pens for writing boards have an ink composition based on the assumption that the pen core for solvent-type marking pens is used as it is, and have various limitations (see, for example, Japanese Patent No. 2706960).

In the present invention, by devising the pen core,
A water-based marking pen for writing boards that is capable of writing stably even with bright metallic inks containing metallic powder and vivid pastel inks containing titanium oxide, and has good erasability and visibility. It came to completion.

As shown in FIGS. 2 (A) and 2 (B), the valve-type water-based marking pen for a writing board of the present invention has a porosity of 58% or more with a fiber thickness of 7 to 30 denier. Of a polyester core, a pen core 2 made of a porous synthetic resin foam having open cells or a brush, a urethane sponge 6 or felt wrapping the end of the pen core 2, a valve seat 7, a valve case (spring receiver) 8 , And a valve mechanism including a valve core (valve rod) 9 and a spring 10 (the structure of the valve seat portion is different between (A) and (B)).

The viscosity of the ink used is 10 to 80 CP.
It is preferable to adjust to S. In the present invention, by using a polymer latex with a specific dispersant or a specific release agent, a glitter metallic color ink containing metal powder, or a vivid pastel color ink containing titanium oxide, a blackboard or green We have completed a water-based marking pen for writing boards that allows stable writing on the board without scratching and has good erasability and visibility.

[0033]

The metal powder and titanium oxide in the ink gradually settle in the ink bottle, but in the batting, they exist stably due to the interaction between the dispersant, the polymer latex and the fibers of the batting. In addition, the release agent in the ink interacts with the polymer of the polymer latex as the water volatilizes in the handwriting written on the writing plate surface, forming a film that adheres weakly to the plate surface, forming a dry cloth or tissue. Brings handwriting that can be easily erased by light rubbing with.

[0034]

[Example] 1. Preparation of Release Agent (Emulsion) Mixtures of the respective components of Reference Examples 1 and 2 below were stirred and emulsified with a homogenizer to obtain release agents A and B. Reference Example 1 (Peeling agent A) Sodium oleate 3 parts Sodium lauryl sulfate 2 parts Tridecanol 40 parts Water 55 parts Reference Example 2 (Peeling agent B) Sorbitan surfactant OP80R 3 parts (Nippon Yushi Co., Ltd.) OT221 1 part Flow Paraffin 30 parts Water 66 parts

2. Preparation of Metal Powder Dispersion Mixtures of the respective components of Reference Examples 3 and 4 below were each applied to a disper and stirred and dispersed for 1 hour to obtain a metallic color dispersion. Reference Example 3 (silver color dispersion) Aluminum paste WB-0230 (manufactured by Toyo Aluminum Co., Ltd.) 11 parts Citric acid 0.5 part PH adjuster triethanolamine 3 parts Amphoteric surfactant Amphitol 86B (manufactured by Kao) 5 parts Water 80 .5 parts Reference Example 4 (blue metallic color dispersion) Blue aluminum paste F.70l (manufactured by Showa Aluminum Co., Ltd.) 11 parts Amphoteric surfactant Lipomin LA (manufactured by Lion Corp.) 3 parts PH adjuster Diethanolamine 3 parts Jonkuryl J- 1535 (manufactured by Johnson Polymer Co.) 2 parts water 81 parts

3. Preparation of sample inks Table 1 shows the compositions of the example inks and the comparative example inks.
A predetermined amount of pigment dispersion, polymer latex, dispersant and water are mixed, the mixture is stirred for 1 hour with a disper, and then components such as a release agent, a fluorosurfactant, a preservative and a moisturizer are added, The sample ink was obtained by further stirring for 1 hour.

The ink of Comparative Example 1 was obtained by replacing the colorant with a black pigment dispersion, and the ink of Comparative Example 2 was obtained by replacing the colorant of Example 5 with a water-soluble dye. The ink of No. 3 was obtained by replacing the release agent with a dioctyl dodecane nitrate emulsion (corresponding to the ink composition described in JP-A-7-207212), and the ink of Comparative Example 4 had a polymer latex in an acrylic resin emulsion and a white pigment. Each of which is replaced by resin fine particles (Patent No. 2706
(Corresponding to the ink composition described in Japanese Patent Publication No. 960).

[Table 1]

(Explanation of Raw Materials in Table 1) The explanation will be given according to the note numbers in the table. a. Master Fine MF5765 White (Solid content 6
0%, manufactured by Dainichiseika Kogyo Co., Ltd. b. SP Blue 6184 (solid content 30%, manufactured by Fuji Pigment Co.) c. LM-21 pink (solid content 51.5%, manufactured by Fuji Pigment Co.) d. SP Black 8052 (solid content 25%, manufactured by Fuji Dye Co., Ltd.) e. Styrene-butadiene copolymer latex, JSR
0561 (solid content 69%, glass transition point -63 ° C, JS
R company) f. Acrylonitrile-butadiene copolymer latex, Nipol LX-513 (solid content 45%, glass transition temperature -55 ° C, manufactured by Zeon Corporation) g. Carboxylated styrene-butadiene copolymer latex, JSR0545 (solid content 54%, glass transition temperature -31 ° C, manufactured by JSR Corporation) h. Styrene-acrylic resin copolymer emulsion, Aron HD-3 (solid content about 30%, manufactured by Toagosei Co., Ltd.) i. TSM-630 (37% active ingredient, Toshiba Silicone Co.) j. KF-351 (manufactured by Shin-Etsu Silicone Co., Ltd.) k. Acrylic resin hollow fine particle liquid AE-866 (solid content 2
0%, manufactured by E-Tech Co., Ltd. l. Dioctyl dodecanoate emulsion (Purity 3
Adjusted to 0%) m. Amphitol 24B (manufactured by Kao Corporation) n. Dipper Big 180 (manufactured by Big Chemie) o. Proxel XL-2 (manufactured by Abyssia) p. EF-122C (made by Tochem)

(Performance of Sample Ink) Erasability and Visibility Test A predetermined amount of each sample ink was filled in a batting type marking pen to prepare a sample pen. A white plate, a black plate coated with acrylic resin, a blackboard, and a green board were used as writing plates, and predetermined lines were drawn with each sample pen, and the erasability immediately after and after a lapse of time (2 weeks) was examined. To erase, use a commercially available blackboard wipe for 500
The sample was rubbed with a load of g and the number of rubs required to completely erase the handwriting was measured. The test results are shown in Table 2. As for the visibility, it was examined whether or not a character of 2 × 2 cm was written and it was clearly visible from a point 3 cm away.

[Table 2]

The contents of the evaluation symbols in Table 2 are as follows. Criteria for erasability ◯: Erasable by rubbing 1 to 5 times Δ: Erasable by rubbing 6 to 10 times ×: Not erased by rubbing 10 times Visibility standard (by visual inspection) ○: Good △: A little hard to see ×: Not visible

[0043]

EFFECTS OF THE INVENTION Since the water-based marking pen ink for writing plates of the present invention is water-based, it is natural that no odor is generated when it is used, but not only on a white plate, but also on a blackboard or a greenboard surface with a metallic appearance. Characters that are clear and clearly visible in color or pastel color can be written, and the handwriting is easily erased by rubbing with a dry erasing material not only immediately after writing but also after a long time.

[Brief description of drawings]

FIG. 1 is a diagram showing the structure of a batting type marking pen according to the present invention filled with an aqueous marking pen ink for a writing plate according to the present invention.

FIG. 2 is a view showing the structure of a valve type marking pen according to the present invention, which is filled with the water based marking pen ink for a writing plate according to the present invention.

[Explanation of symbols]

1 cap 2 pen core 3 ink 4 body 5 tail plugs 6 Urethane sponge 7 seat 8 valve case 9 valve core 10 springs

Claims (7)

[Claims] 1. A water-colorant, a polymer latex, and a release agent, wherein the colorant is a metal powder or colored resin fine particles having an average particle size of 15 microns or less, and an inorganic pigment having an average particle size of 5 microns or less. , An organic emulsion containing at least one selected from organic pigments or fluorescent pigments, and the release agent is an aqueous emulsion selected from higher alcohols, liquid paraffin, squalane, or dimethylpolysiloxane that are liquid at room temperature,
An ink composition comprising a silicone-based surfactant and at least one selected from the group consisting of resin fine particles having an average particle size of 5 microns or less. 2. The metal powder is aluminum powder or colored aluminum powder, and the aluminum powder or colored aluminum powder alone or 2
The ink composition according to claim 1, wherein at least one kind and at least one kind of colored resin fine particles, an inorganic pigment, an organic pigment or a fluorescent pigment, or two or more kinds are used together to give a metallic color. 3. The ink composition according to claim 1, wherein titanium oxide is used in combination with one or more of organic pigments, colored resin fine particles or fluorescent pigments to give a pastel color. 4. The ink composition, wherein the polymer latex is a styrene-butadiene copolymer latex or an acrylonitrile-butadiene copolymer latex having a film forming temperature of 0 ° C. or lower or a glass transition temperature of 0 ° C. or lower. The ink composition according to claim 1, wherein the ink composition is contained in an amount of 2 to 50% by weight. 5. The dispersant for the colorant is a resin-based dispersant,
The ink composition according to claim 1, which is at least one selected from an amphoteric surfactant and a polycarboxylic acid compound. 6. A batting containing ink and having a porosity of 58%.
A batting type marking pen filled with the ink composition according to claim 1, comprising the above-mentioned porous polyester core, a porous foam having open cells, or a pen core made of a brush. 7. The ink composition according to claim 1, comprising a porous polyester core having a porosity of 58% or more, a porous core having open cells or a pen core made of a brush, and a valve mechanism. Valve type marking pen.