JP2017214519A - Oily marking pen ink composition for writing board and marking pen containing the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an oily marking pen ink composition for a writing board which achieves both high writing performance and erasability, the handwriting not being fixed even when a long period of time has elapsed after the handwriting has been formed allowing the handwriting to be erased with a light force even when a polyvinyl butyral resin is used and which allows peeling of the handwriting without scattering at the time of scratching, and is excellent in practicability such as a long-term use, and to provide a marking pen containing the same.SOLUTION: The oily ink composition for a writing board contains a pigment, an organic solvent, a polyvinyl butyral resin and one or more release agents selected from polyoxyalkylene glycerylether and polyoxyalkylene polyglyceryl ether. The marking pen contains the oily ink composition for a writing board.SELECTED DRAWING: None

Description

  The present invention relates to an oil-based marking pen ink composition for a writing board. Specifically, the present invention relates to an oil-based marking pen ink composition for a writing board capable of reliably erasing handwriting even after a long period of time, and a marking pen incorporating the same.

Conventionally, oil-based ink for writing board written on a writing board (so-called white board) made of a material such as enamel, metal, thermoplastic or thermosetting plastic imparts fixability of the handwriting formed on the writing board. For this purpose, a resin is added, and a release agent is added so that the handwriting can be rubbed and erased with a board eraser (an eraser made of nonwoven fabric or pile such as felt). As the resin, a polyvinyl butyral resin is suitably used because it can provide an appropriate fixing property to a writing board and pigment dispersibility. Various materials have been studied as the release agent, but fatty acid esters are widely used because of their high dissolution stability in ink.
When the polyvinyl butyral resin and the fatty acid ester are used in combination, initially high writing performance and erasing performance can be expressed, but the handwriting is fixed over time and is difficult to erase. In order to solve this problem, several techniques for improving erasability after aging by adding a surfactant have been disclosed (see, for example, Patent Documents 1 and 2).

JP-A-6-128522 JP-A-5-279615

  However, when the surfactant is added, the handwriting is prevented from fixing even after lapse of time, but the handwriting is stretched or scattered when it is rubbed with a board eraser. In some cases, the entire surface is soiled or the film cannot be peeled cleanly and erasability cannot be obtained.

  The present invention solves the problems of the oil-based ink composition for writing board using polyvinyl butyral resin, that is, even if a long time has passed after the formation of the handwriting, it can be erased with a light force without fixing the handwriting. The oil-based marking pen ink composition for a writing board excellent in practicality such as long-term use that can achieve both high writing performance and erasing performance because it can exhibit high erasability that it can be peeled off without being scattered during writing A built-in marking pen is provided.

〔式中のＸ，Ｙは、Ｃ_２Ｈ_４Ｏ、Ｃ_３Ｈ_６Ｏ、Ｃ_４Ｈ_８Ｏから選ばれるいずれか（但し、Ｘ,Ｙは異なる）であり、ａ＋ｂ＋ｃは３〜１００の整数であり、ａ＋ｂ＋ｃ+ｄは４〜１００の整数であり、ａ′＋ｂ′＋ｃ′は３〜５０の整数である。〕
更に、前記剥離剤が、インキ組成物全量中０．５〜１０重量％の範囲で添加されること、一塩基酸エステル及び/又は二塩基酸エステルから選ばれる一種以上を含むこと、前記有機溶剤がエチルアルコール、ｎ−プロピルアルコール、イソプロピルアルコールから選ばれる一種又は二種以上であることを要件とする。
更には、前記いずれかの筆記板用油性マーキングペンインキ組成物を内蔵してなるマーキングペンを要件とする。 The present invention relates to an oil-based marking pen ink composition for a writing board comprising a pigment, an organic solvent, a polyvinyl butyral resin, and at least one release agent selected from polyoxyalkylene glyceryl ether and polyoxyalkylene polyglyceryl ether. Is a requirement.
Furthermore, the polyoxyalkylene part of the release agent is one or more selected from polyoxyethylene, polyoxypropylene, and polyoxybutylene, and the release agent is represented by the following general formulas (1) to (3). It is a requirement that it is glyceryl ether shown by these.

[Wherein X and Y are any one selected from C ₂ H ₄ O, C ₃ H ₆ O, and C ₄ H ₈ O (provided that X and Y are different), and a + b + c is an integer of 3 to 100 A + b + c + d is an integer of 4 to 100, and a ′ + b ′ + c ′ is an integer of 3 to 50. ]
Furthermore, the release agent is added in the range of 0.5 to 10% by weight in the total amount of the ink composition, contains one or more selected from monobasic acid esters and / or dibasic acid esters, the organic solvent Is one or more selected from ethyl alcohol, n-propyl alcohol, and isopropyl alcohol.
Furthermore, the marking pen formed by incorporating the oil-based marking pen ink composition for any of the above-mentioned writing boards is a requirement.

  According to the present invention, even if a polyvinyl butyral resin that is particularly useful as a handwriting fixing resin is used, it can be erased with a light force even after a long period of time has elapsed after the formation of the handwriting, and it can be removed cleanly without scattering the handwriting at the time of scrub erasing. Therefore, high erasability can be expressed. Therefore, it is possible to provide an oil-based marking pen ink composition for a writing board excellent in practicality such as long-term use that can achieve both high writing performance and erasing performance, and a marking pen incorporating the same.

In the present invention, by adding at least one selected from polyoxyalkylene glyceryl ether and polyoxyalkylene polyglyceryl ether to the ink as a release agent, excellent erasure is achieved regardless of the initial time and time even when using a butyral resin. The property is obtained.
Usually, at the time of handwriting formation, the polyvinyl butyral resin forms a film on the writing surface to fix the handwriting, but conventional release agents have poor compatibility with the polyvinyl butyral resin, and between the film and the writing board. Since the erasing performance was imparted by the presence of the film, the film was fixed due to evaporation or decomposition over time or penetration into the writing surface.
On the other hand, the compound of the present invention as a release agent is highly compatible with the polyvinyl butyral resin because of its chemical structure, and therefore can be present in a uniform state in the coating, and can exhibit a permanent release effect. It becomes. Therefore, the high handwriting erasability equivalent to the initial value can be maintained even after the passage of time.

  The polyoxyalkylene glyceryl ether is a monoglyceryl ether having a polyoxyalkylene chain, and the polyoxyalkylene polyglyceryl ether is a polyglyceryl ether containing di, tri, tetra, etc. having a polyoxyalkylene chain. In addition, the structure of the portion to be the polyoxyalkylene chain is preferably composed of any one selected from polyoxyethylene, polyoxypropylene, and polyoxybutylene. Those having the above structure exhibit better compatibility, and particularly high temporal stability can be obtained.

Among the release agents, particularly preferred are glyceryl ethers represented by the general formulas (1) to (3). What is represented by the above general formula is highly compatible with the polyvinyl butyral resin and excellent in ink stability, and exhibits high peeling performance even in a small amount.
Specifically, polyoxyethylene glyceryl ether, polyoxypropylene glyceryl ether, polyoxyethylene polyoxypropylene glyceryl ether, polyoxybutylene polyoxyethylene polyoxypropylene glyceryl ether, polyoxypropylene diglyceryl ether, polyoxyethylene polyglyceryl ether And polyoxypropylene polyglyceryl ether.
More specific structures include polyoxyethylene (26) glyceryl ether, polyoxypropylene (10) glyceryl ether, polyoxypropylene (16) glyceryl ether, polyoxypropylene (50) glyceryl ether, polyoxypropylene (70). Glyceryl ether, polyoxyethylene (24) polyoxypropylene (24) glyceryl ether, polyoxybutylene (3) polyoxyethylene (8) polyoxypropylene (5) glyceryl ether, polyoxypropylene (9) diglyceryl ether, poly Oxyethylene (13) polyglyceryl ether, polyoxyethylene (20) polyglyceryl ether, polyoxypropylene (9) polyglyceryl ether, polyoxypropylene (14) polyglycer Rirueteru, polyoxypropylene (24) polyglyceryl ether and the like.

The polyoxyalkylene glyceryl ether or polyoxyalkylene polyglyceryl ether can be added in an amount of 0.5 to 10% by weight, preferably 0.5 to 8% by weight, based on the total amount of the ink composition.
By setting it as the said numerical range, the handwriting formed using the ink composition of this invention can maintain the outstanding erasability in a higher state even after time-lapse.

  Furthermore, other general-purpose release agents such as carboxylic acid esters, silicone surfactants, nonionic surfactants and the like can also be used in combination, for example, polyoxyalkylene alkyl ether sulfates, polyoxyalkylene alkylaryls. Examples include ether sulfates, polyoxyethylene alkyl ether phosphates or salts thereof, dibasic acid esters, monobasic acid esters, polyalkylene glycol esters, and the like.

In particular, monobasic acid esters and dibasic acid esters are preferably used in combination because they have high erasability at the beginning of writing and can be stably present when used in combination with the glyceryl ether. Furthermore, the aliphatic type is highly effective and more useful.
Specifically, CIO (cetyl isooctanoate), ICM-R (isocetyl myristate), ICIS (isocetyl isostearate), ISP (isostearyl palmitate), STO (isooctyl stearate), etc. as monobasic acid esters As dibasic acid esters, DINA (diisononyl adipate), DOA (di-2-ethylhexyl adipate), DTDA (ditridecyl adipate), DOS (di-2-ethylhexyl sebacate), DOZ (2-ethylhexyl azelate) ), DODN (di-2-ethylhexyl decanoate) and the like.

As said pigment, the general purpose pigment conventionally applied to oil-based ink is used suitably.
Specifically, inorganic pigments such as carbon black, ultramarine, titanium dioxide pigments, azo pigments, phthalocyanine pigments, indigo pigments, thioindigo pigments, selenium pigments, quinacridone pigments, anthraquinone pigments, selenium pigments, diketopyrrolo Organic pigments such as pyrrole pigments, dioxazine pigments, perylene pigments, perinone pigments, isoindolinone pigments, aluminum pigments, metal pigments whose surfaces are treated with colored resins, transparent or colored transparent films such as aluminum Metallic pigment, gold, silver, platinum, copper, with a thickness of 0.01 to 0.1 μm, obtained by peeling a metallic vapor deposited film such as aluminum formed on a substrate such as a metallic luster pigment, film, etc. Colloidal particles having an average particle size selected from 5 to 30 nm, fluorescent pigments, luminous pigments, thermochromic pigments Natural mica as a core material, synthetic mica, glass pieces, alumina, pearl pigment and the like to the surface of the transparent film pieces were coated with a metal oxide such as titanium oxide.
The pigment may be used alone or in combination of two or more, and is used in the range of 3 to 40% by weight in the ink composition.
In addition, general-purpose dyes such as organic solvent-soluble dyes classified as solvent dyes in the color index can be used in combination with the pigments.

As the resin used in the present invention, polyvinyl butyral resin (PVB) is used because it exhibits a pigment dispersion effect as well as handwriting fixability. In particular, those having a butyralization degree of 55 to 85 mol% are preferable, and specifically, S-REC BL-1, BL-1H, BL-2, BL-2H, BL-S, BX-L, BM-1, BM- 2, BM-5, BM-S, BH-3, BX-1, BX-5 (above, manufactured by Sekisui Chemical Co., Ltd.), Mobital B16H, B20H, B30T, B30H, B30HH, B45M, B45H (above, Kuraray Co., Ltd.) Manufactured) and the like. These can be used alone or in combination of two or more.
The content of the polyvinyl butyral resin can be added in the range of 1 to 10% by weight, preferably 2 to 8% by weight, and more preferably 3 to 6% by weight in the total amount of the ink composition.
Is desirable.

Along with the polyvinyl butyral resin, a general-purpose resin can be used in combination to impart handwriting fixability to the writing surface and ink viscosity.
Examples of the resin include cellulose resins such as ethyl cellulose and acetyl cellulose, and vinyl resins such as polyvinyl pyrrolidone, polyvinyl acetate, and vinyl pyrrolidone-vinyl acetate copolymer resin.
The resin may be added in the form of a processed pigment.

As the organic solvent, a volatile (low boiling point) organic solvent is suitably used, and even when writing on a whiteboard, the handwriting has excellent drying properties. Therefore, when the handwriting immediately after writing is touched, undried ink is used. A good handwriting can be formed without causing problems such as adhering to the hand or contaminating a blank portion where the handwriting on the writing surface is not formed.
Examples of the organic solvent include a lower aliphatic alcohol solvent or a glycol ether solvent, and it is preferably used as a main solvent (occupying 50% by weight or more of the total solvent).
The lower aliphatic alcohol solvent is methyl alcohol, ethyl alcohol, n-propyl alcohol, isopropyl alcohol, and the glycol ether solvent is ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether. More preferably, the lower aliphatic alcohol solvent is an aliphatic alcohol having 2 to 4 carbon atoms, and the glycol ether solvent is a glycol ether having 3 to 5 carbon atoms.
Among the organic solvents, ethyl alcohol, n-propyl alcohol, and isopropyl alcohol are particularly preferable.

  In addition, other solvents can be used in combination with the organic solvent, hydrocarbon organic solvents such as n-heptane, n-octane, isooctane, methylcyclohexane, ethylcyclohexane, toluene, xylene, ethylbenzene, methyl isobutyl ketone, methyl Ketone organic solvents such as n-propyl ketone, methyl n-butyl ketone, di-n-propyl ketone, n-butyl formate, isobutyl formate, n-propyl acetate, isopropyl acetate, n-butyl acetate, isobutyl acetate, ethyl propionate , Ester organic solvents such as n-butyl propionate, methyl butyrate, ethyl butyrate, methyl lactate, ethyl lactate, glycol solvents such as ethylene glycol, diethylene glycol, propylene glycol, benzyl glycol, benzyl alcohol, γ-butyro It can be exemplified a ton and the like.

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.
The additive is a so-called conventional additive, and can be appropriately used as necessary from known compounds.

The ink composition is practically used by filling a marking pen with a pen tip attached to the 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 oil-based marking pen ink compositions 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) Taitone R-7E manufactured by Sakai Chemical Co., Ltd.
(2) C.I. I. Pigment Orange 43 50%, polyvinyl butyral 50% processed pigment (3) C.I. I. Pigment Blue 60 45%, polyvinyl butyral 55% processed pigment (4) Sekisui Chemical Co., Ltd., trade name: ESREC BM-1
(5) Sekisui Chemical Co., Ltd., trade name: ESREC BL-S
(6) Ajinomoto Fine Techno Co., Ltd., trade name: Plenact 138S
(7) Daiichi Kogyo Seiyaku Co., Ltd., trade name: Hightenol 18E
(8) Polyoxypropylene (70) glyceryl ether (9) Polyoxyethylene (26) Glyceryl ether (10) Polyoxyethylene (24) Polyoxypropylene (24) Glyceryl ether

Preparation of ink Ingredients other than the release agent were put together with a solvent in a stirring vessel, and the mixture was stirred with 20 g of 2 mm glass beads at 20 ° C. for 2 hours at 20 ° C. Then, the release agent was added and further stirred for 5 minutes. The ink composition was obtained by removing the glass beads by filtering the thing with a mesh.

Production of Marking Pen The ink compositions of Examples 1 to 3 and Comparative Examples 1 to 3 were each filled with 7 g of a commercially available marking pen (manufactured by Pilot Corporation; CBML-25L) to obtain an oil-based marking pen. At the time of writing, it was written with the tip being pumped after shaking 30 times.
The ink compositions of Example 4 and Comparative Example 4 were each filled with 5 g of a commercially available marking pen (manufactured by Pilot Corporation; WMBM-12L) to obtain an oil-based marking pen.
The following tests were performed using each of the marking pens.

Erasability test Using each marking pen, write five spiral circles on various writing boards (green board for CBML-25L, white board for WMBM-12L), handwriting immediately after writing, and 20 ° C. The erasability when moving over the handwriting with a tissue paper having a weight of 100 g on the handwriting after leaving for 14 days 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.
The test results are shown in the following table.

The evaluation of symbols in the table is as follows.
Eraseability test ○: The handwriting can be erased by three movements.
Δ: A part of the handwriting remains after three movements.
X: More than half of the handwriting remains unerasable after three movements.

Claims (7)

  An oil-based marking pen ink composition for a writing board comprising a pigment, an organic solvent, a polyvinyl butyral resin, and one or more release agents selected from polyoxyalkylene glyceryl ether and polyoxyalkylene polyglyceryl ether.   The oil-based marking pen ink composition for a writing board according to claim 1, wherein the polyoxyalkylene part of the release agent is one or more selected from polyoxyethylene, polyoxypropylene, and polyoxybutylene. The oil-based marking pen ink composition for a writing board according to claim 1 or 2, wherein the release agent is glyceryl ether represented by the following general formulas (1) to (3).

[Wherein X and Y are any one selected from C ₂ H ₄ O, C ₃ H ₆ O, and C ₄ H ₈ O (provided that X and Y are different), and a + b + c is an integer of 3 to 100 A + b + c + d is an integer of 4 to 100, and a ′ + b ′ + c ′ is an integer of 3 to 50. ]   The oil-based marking pen ink composition for a writing board according to any one of claims 1 to 3, wherein the release agent is added in a range of 0.5 to 10% by weight based on the total amount of the ink composition.   The oil-based marking pen ink composition for a writing board in any one of Claims 1 thru | or 4 containing 1 or more types chosen from monobasic acid ester and / or dibasic acid ester.   The oil-based marking pen ink composition for a writing board according to any one of claims 1 to 5, wherein the organic solvent is one or more selected from ethyl alcohol, n-propyl alcohol, and isopropyl alcohol.   A marking pen comprising the oil-based marking pen ink composition for a writing board according to any one of claims 1 to 6.