JP6396766B2 - Marking pen - Google Patents

Description

The present invention relates to a marking pen incorporating a water-based ink composition for a writing board having excellent ink stability.

    Conventionally, in a water-based ink for a writing board written on a writing board (white board) made of a material such as enamel, glass, metal, or thermoplastic or thermosetting plastic, the handwriting formed on the writing board can be scratched and erased. For this purpose, a release agent (erasability imparting agent) is added. As the release agent, an oily material that is hardly volatile at room temperature such as an aliphatic carboxylic acid ester or an aqueous dispersion of an acrylic resin is used. Are added to an aqueous medium (for example, see Patent Documents 1 and 2).

Japanese Patent Publication No.7-119383 Japanese Patent Publication No. 8-16206

The oily substance emulsion described in Patent Document 1 is insoluble in an aqueous medium, but can be imparted with high scratch erasing performance by being blended with an aqueous ink in a dispersed state. However, ink separation or insoluble sedimentation may occur over time due to the difference in temperature during storage or the arrangement method.
In addition, the aqueous dispersion of acrylic resin described in Patent Document 2 has a low action as a release agent in a small amount and requires a large amount of addition, so that it is difficult to obtain ink stability over time.
Therefore, in any release agent, writing performance and erasing performance deteriorate over time.

The present invention is intended to solve the problems of conventional water-based ink compositions for writing boards, that is, a novel release agent (erasability imparting agent) having high solubility that can be stably maintained in an aqueous medium even after time. ) by using, without causing ink separation or sedimentation, there is provided a marking pen with a built-in writing board water based ink composition having excellent abrasion erasability and ink stability.

〔式中ＲはＣ_２Ｈ_４、Ｃ_３Ｈ_６、Ｃ_４Ｈ_８のいずれかを示し、整数であるｍ〜ｐは１≦ｍ＋ｎ＋ｏ＋ｐである。〕
更に、前記一般式におけるｍ〜ｐが、１≦ｍ＋ｎ＋ｏ＋ｐ≦４０の範囲にあること、前記消去性付与剤が、インキ組成物全量中０．５〜２０重量％の範囲で添加されることを要件とする。
更に、両末端変性シリコーン又はフッ素系界面活性剤を含有してなることを要件とする。更に、前記両末端変性シリコーン又はフッ素系界面活性剤が、インキ組成物全量中０．５〜５重量％の範囲で添加されること、前記両末端側鎖変性シリコーンのＨＬＢ値が７〜９の範囲にあることを要件とする。
更には、前記マーキングペンが、繊維チップ、フェルトチップ、プラスチックチップのいずれかから選ばれるマーキングペン用ペン先を筆記先端部に装着し、軸筒内部に収容した繊維束からなるインキ吸蔵体にインキを含浸させ、筆記先端部にインキを供給する構造を備える構造、または軸筒内部に直接インキを収容し、櫛溝状のインキ流量調節部材又は繊維束からなるインキ流量調節部材を介在させて筆記先端部に所定量のインキを供給する構造、又は軸筒内部に直接インキを収容して、弁機構により筆記先端部に所定量のインキを供給する構造のいずれかを備える前記いずれかに記載のマーキングペン。 The present invention incorporates a water-based ink composition for a writing board containing a colorant, water, a water-soluble and / or water-dispersible resin, and an alkylene oxide adduct of polyglycerin as an erasability imparting agent . Require a marking pen .
Furthermore, it is required that the alkylene oxide adduct of polyglycerol is at least one selected from alkylene oxide adducts of diglycerol represented by the following general formula (1).

[In the formula, R represents any of C ₂ H ₄ , C ₃ H ₆ , and C ₄ H ₈ , and m to p, which are integers, satisfy 1 ≦ m + n + o + p. ]
Further, m to p in the general formula is in the range of 1 ≦ m + n + o + p ≦ 40, and the erasability imparting agent is added in the range of 0.5 to 20% by weight in the total amount of the ink composition. And
Furthermore, it is a requirement that it contains a both-end modified silicone or a fluorosurfactant. Further, the both-end modified silicone or the fluorosurfactant is added in a range of 0.5 to 5% by weight in the total amount of the ink composition, and the HLB value of the both-end side chain-modified silicone is 7 to 9. Requirement to be in range.
Further, the marking pen has a marking pen pen tip selected from any one of a fiber tip, a felt tip, and a plastic tip attached to a writing tip, and an ink is stored in an ink occlusion body formed of a fiber bundle accommodated inside the shaft cylinder. With a structure for supplying ink to the tip of writing, or containing ink directly in the shaft tube, and interposing an ink flow rate adjusting member consisting of a comb groove-like ink flow rate adjusting member or fiber bundle. The structure according to any one of the above, comprising either a structure for supplying a predetermined amount of ink to the tip, or a structure for storing ink directly in the shaft cylinder and supplying a predetermined amount of ink to the writing tip by a valve mechanism. Marking pen.

According to the present invention, since the erasability imparting agent can be stably maintained in a dissolved state in an aqueous medium, it has high ink stability and excellent scratch erasability without causing separation or sedimentation of the ink even after time. It can provide a marking pen with a built-in writing board water based ink composition.
Further, by adding both terminal-modified silicones or fluorine-based surfactants together with the polyglycerin alkylene oxide adduct, the erasability can be dramatically improved, so that handwriting can be erased with a lighter force at the time of scrubbing. At the same time, it becomes a water-based ink composition for a writing board that can be surely scraped and erased without leaving handwriting on the board surface.

In the present invention, an alkylene oxide adduct of polyglycerin is added to an aqueous medium as an erasability imparting agent. Therefore, the alkylene oxide adduct of polyglycerin to be applied is one that can maintain a dissolved state in water at room temperature (25 ° C.).
In particular, as the polyglycerin serving as the main chain, those having a low degree of bonding such as diglycerin, triglycerin, tetraglycerin and the like are useful because the erasability imparting power increases.
Moreover, as an alkylene oxide adduct, a C1-C8 thing is preferable and a C2-C4 thing is especially suitable from dissolution stability being high.
Therefore, the compound represented by the above general formula (1) can be exemplified as a compound having particularly high erasability imparting power and dissolution stability.

M to p in the general formula (1) may be 1 ≦ m + n + o + p. Particularly, in the present compound in which diglycerin is applied as a main chain, those having 40 or less have extremely high dissolution stability in an ink state. This is more preferable.
The average molecular weight of the compound is particularly useful in the range of 200 to 3000, preferably 350 to 2500.

    The erasability imparting agent is contained in the range of 0.5 to 20% by weight, preferably 2 to 15% by weight, based on the total amount of ink. If the amount is less than 0.5% by weight, practically sufficient handwriting erasability cannot be obtained, and even if added in excess of 20% by weight, the improvement of the function as an erasability imparting agent is not recognized. Is not required.

    Other general erasability-imparting agents such as polyalkylene glycol fatty acid diester, fatty acid polyalkylene glycol monoether ester, dicarboxylic acid bis (polyalkylene glycol monoether) ester, fatty acid alkyl ester, polyglycerin fatty acid ester, silicone oil, alkyl vinyl ether Higher hydrocarbons, fatty acid potassium, polyhydric alcohol fatty acid esters, and emulsions of oily substances that are hardly volatile at room temperature described in Patent Document 1 may be used in combination as necessary.

    Furthermore, by adding both terminal-modified silicones or fluorosurfactants together with the polyglycerin alkylene oxide adduct, handwriting bleeding can be suppressed and erasability can be dramatically improved. In particular, when 0.5% by weight or more is added in the total amount of the ink composition, both terminal-modified silicones and fluorine-based surfactants can be oriented over the entire surface of the handwriting at the time of writing, and at the interface between the writing board surface and the handwriting. Can exist. Therefore, water-based ink composition for writing board that can erase the handwriting with a lighter force at the time of scrubbing eraser, and can surely scrub without leaving the handwriting on the board surface after aging, compared to the case of using polyglycerin alkylene oxide adduct alone. It becomes a thing.

The both-end-modified silicone and the fluorosurfactant, when added in an amount of less than 0.5% by weight in the total amount of the ink composition, act to suppress the bleeding of handwriting, and by adding 0.5% by weight or more, the above effect is achieved. In addition, in order to express the erasability improving effect, it is particularly preferable to add in the range of 0.5 to 5% by weight based on the total amount of the ink composition. Even if it is added in an amount exceeding 5% by weight, the above-mentioned effect is not improved.
The both-end-modified silicone and the fluorosurfactant can be widely used without limitation as long as they are water-soluble, but in the both-end side chain-modified silicone, the HLB value is particularly in the range of 7-9. Are particularly useful because of their high erasability improving effect due to their high orientation to the surface of the handwriting at the time of writing. Specific products include X22-6266 (HLB value: 8) manufactured by Shin-Etsu Chemical Co., Ltd., KF-6004 (HLB value: 9), Paintad 29 (HLB value: 7) manufactured by Toray Dow Corning. Can be mentioned.

    A water-soluble or water-dispersible resin is used as a handwriting fixing agent, and a water-soluble resin can also be used to impart ink viscosity. Specifically, cyanate-modified polyalkylene glycol, polyvinyl acetal, polyvinyl alcohol, polyvinyl pyrrolidone, partially saponified polyvinyl acetate, vinyl acetate / vinyl alcohol / acrylic acid ester copolymer, vinyl acetate / vinyl alcohol / methacrylic acid ester copolymer Examples include coalescence, gum arabic, and cellulose resin. The cyanate-modified polyalkylene glycol is preferably a copolymer of diisocyanate and polyalkylene glycol. Examples of suitable diisocyanates include tolylene diisocyanate, xylylene diisocyanate, isophorone diisocyanate, and hexylene diisocyanate. Examples of the polyalkylene glycol include those obtained by copolymerization using a single or a plurality of lower alkylene glycols such as ethylene glycol, propylene glycol, tetramethylene glycol and pentamethylene glycol, and particularly polyethylene glycol, polyethylene glycol / polypropylene. A glycol copolymer and polypropylene glycol are preferred.

    The resin is used in the range of 0.5 to 10% by weight, preferably 1 to 5% by weight, based on the total amount of the ink composition. If it is less than 0.5% by weight, the handwriting fixability at the time of writing is poor, and even if it exceeds 10% by weight, no further improvement is seen, so no further is required.

Examples of the colorant include organic pigments such as azo, anthraquinone, condensed polyazo, thioindigo, metal complex, phthalocyanine, perinone / perylene, dioxazine and quinacridone, carbon black, iron oxide, titanium white Inorganic pigments such as fluorescent pigments, and pigments such as fluorescent pigments, and dyes such as acidic dyes, basic dyes, and direct dyes that can be dissolved in an aqueous medium can be used. Of these, pigments are preferred because of their high erasability when the handwriting is rubbed with a dry eraser.
The colorant is used alone or in combination of two or more, and is applied in the range of 0.5 to 15% by weight, preferably 1 to 10% by weight in the ink composition.

    Further, the ink composition of the present invention may contain various additives such as a handwriting whitening inhibitor, a drying resistance imparting agent, a rust inhibitor, a viscosity modifier, a pigment dispersant, and a surfactant in addition to the above components as necessary. Agents can be used. Further, a small amount of a lower fatty alcohol such as ethanol or propanol may be added in order to accelerate the drying of the handwriting. The additive is a so-called conventional additive, and can be appropriately used as necessary from known compounds.

The water-based ink composition for a writing board is practically used by filling a marking pen having a pen tip attached to a writing tip.
The structure and shape of the marking pen itself are not particularly limited. For example, a marking pen pen tip such as a fiber tip, felt tip, plastic tip, etc. is attached to the writing tip, and from a fiber bundle accommodated inside the shaft tube The ink occlusion body is impregnated with ink, the ink is supplied to the tip of the writing, the ink is stored directly inside the shaft cylinder, and the ink flow rate adjustment member consisting of a comb groove-like ink flow rate adjustment member or fiber bundle is interposed And a marking pen having a structure in which a predetermined amount of ink is supplied to the writing tip, and a structure in which the ink is directly stored in the shaft cylinder and a predetermined amount of ink is supplied to the writing tip by a valve mechanism.
In addition to the cap-type marking pen provided with a cap that covers the pen tip, the marking pen has a knock-out type, a rotary type, a slide-type type intrusion mechanism, and the like that can accommodate the pen tip in the shaft cylinder. A marking pen of a formula may be used.

    The composition of the water-based ink composition for writing boards of Examples and Comparative Examples is shown in the following table. In addition, the numerical value in a table | surface shows a weight part.

The contents of the raw materials are shown below along the note numbers in the table.
(1) Aqueous pigment dispersion containing 20% carbon black and 8% polyvinyl alcohol (2) Aqueous pigment dispersion containing 20% Lake Red C (CI Pigment Red 53: 1) and 7% polyvinyl alcohol (3) ) Aqueous pigment dispersion containing 20% phthalocyanine green (CI Pigment Green 7) and 8% nonionic surfactant (4) Polyvinyl alcohol (saponification degree 78.5-81.5 mol%, polymerization degree 500) (5) Polyvinyl acetal, manufactured by Sekisui Chemical Co., Ltd., trade name: SREC KW-10 (25% active ingredient)
(6) Cyanate-modified polyoxyethylene resin, manufactured by Sanyo Chemical Co., Ltd., trade name: Melpol F-220
(7) Polyurethane resin, manufactured by Daiichi Kogyo Seiyaku Co., Ltd., trade name: Superflex 150 (active ingredient 30%)
(8) Polyoxypropylene polyglyceryl ether (average molecular weight 750, m to p in the general formula is m + n + o + p = 9)
(9) Polyoxypropylene polyglyceryl ether (average molecular weight 1000, mp in the general formula is m + n + o + p = 14)
(10) Polyoxyethylene polyglyceryl ether (average molecular weight 450, m to p in the general formula is m + n + o + p = 6)
(11) Polyoxyethylene polyglyceryl ether (average molecular weight 750, m to p in the general formula is m + n + o + p = 13)
(12) Emulsion of butyl stearate (active ingredient 20%)
(13) Acrylic / styrene copolymer emulsion (active ingredient 45%)
(14) Product name: Florard FC-430, manufactured by Sumitomo 3M Limited
(15) AGC Seimi Chemical Co., Ltd., trade name: Surflon S-241
(16) Made by Shin-Etsu Chemical Co., Ltd., trade name: KF-6004 (HLB value: 9)

Preparation of ink Ingredients other than the erasability imparting agent are put in a stirring vessel, stirred for 1 hour at 20 ° C. with a disper, then the erasability imparting agent is added, and further stirred (uniformly dispersed) to form an ink composition. I got a thing.

Production of Marking Pen A water-based marking pen was obtained by filling each of the ink compositions of Examples and Comparative Examples with a commercially available marking pen (manufactured by Pilot Corporation; WBMVM-20L) in an amount of 5 g.
The following tests were performed using the marking pen.

Erasability test Each marking pen was left in an environment of 25 ° C. for 60 days, then five consecutive circles were written on two types of writing boards (white boards), and the writing pen after being left at 25 ° C. for 1 hour. Then, the erasability when the reciprocation was made 5 times on the handwriting with a tissue paper on which 100 g and 50 g of weight were placed was visually observed.
As the writing board, an enamel plate having a surface gloss value of 70 ° gloss and a substrate surface coated with acrylic resin were used.
Ink Stability Test 5 g of each prepared ink was transferred to a sample bottle, covered, and left in an environment at 25 ° C. for 60 days. After standing for a period, the state of the ink inside was visually confirmed at room temperature.
The test results are shown in the following table.

The evaluation of symbols in the table is as follows.
Eraseability test A: The handwriting can be clearly erased by moving within 3 reciprocations.
○: The handwriting can be erased neatly.
X: The handwriting spreads, the white board becomes dirty, or a part of the handwriting cannot be erased and remains.
Ink stability test ○: No abnormality.
X: Aggregation and sediment are observed in the ink.

Claims (8)

A marking pen containing a water-based ink composition for a writing board, which contains a colorant, water, a water-soluble and / or water-dispersible resin, and an alkylene oxide adduct of polyglycerin as an erasability imparting agent. The marking pen according to claim 1, wherein the polyglycerin alkylene oxide adduct is one or more selected from diglycerin alkylene oxide adducts represented by the following general formula (1).

[In the formula, R represents any of C ₂ H ₄ , C ₃ H ₆ , and C ₄ H ₈ , and m to p, which are integers, satisfy 1 ≦ m + n + o + p. ] The marking pen according to claim 2, wherein m to p in the general formula is in a range of 1 ≦ m + n + o + p ≦ 40. The marking pen according to any one of claims 1 to 3, wherein the erasability imparting agent is added in a range of 0.5 to 20% by weight based on the total amount of the ink composition. The marking pen according to any one of claims 1 to 4, comprising a both-end-modified silicone or a fluorosurfactant. The marking pen according to claim 5, wherein the both-end-modified silicone or the fluorosurfactant is added in the range of 0.5 to 5% by weight in the total amount of the ink composition. The marking pen according to claim 5 or 6, wherein the HLB values of the both terminal-modified silicones are in the range of 7-9. The marking pen has a pen tip for a marking pen selected from a fiber tip, a felt tip, or a plastic tip attached to the writing tip, and impregnated with an ink occlusion body consisting of a fiber bundle housed inside the shaft tube. A structure having a structure for supplying ink to the writing tip, or containing ink directly in the shaft tube, and interposing an ink flow rate adjusting member composed of a comb groove-shaped ink flow rate adjusting member or a fiber bundle at the writing tip portion The structure according to any one of claims 1 to 7, comprising either a structure for supplying a predetermined amount of ink or a structure for storing ink directly in the shaft cylinder and supplying a predetermined amount of ink to the writing tip by a valve mechanism. Marking pen as described.