JP6810539B2 - Oil-based ink composition, marking pen with built-in, and writing set - Google Patents

Description

The present invention relates to an oil-based ink composition. More specifically, the present invention relates to an oil-based ink composition capable of reliably erasing handwriting formed on a non-penetrating surface, a marking pen incorporating the composition, and a writing set .

Conventionally, in oil-based ink for a writing board, which is written on a writing board (so-called whiteboard or blackboard) made of a material such as hollow, metal, or plastic, a handwriting formed on the writing board so that writing and erasing can be repeated. A resin for imparting fixability to the paper is added, and a release agent for making the handwriting erasable by rubbing it with a board eraser (erasing portion made of felt or cloth) or the like is added.
Various materials have been studied as the release agent, but an aliphatic basic acid ester is widely used because of its high dissolution stability in ink, and as an improved invention thereof, erasability after aging is improved. In order to improve the technology, a technique for blending an erasing agent is disclosed (see, for example, Patent Documents 1 and 2).

Japanese Unexamined Patent Publication No. 2005-75893 Japanese Unexamined Patent Publication No. 2005-97368

In addition, a writing board equipped with a light source such as an LED is widely used in order to make the handwriting emit light and make it appear to emerge by irradiating the handwriting formed on the writing board with light, and this type of writing is used. Fluorescent color ink is used for the board.
A fluorescent dye or a fluorescent pigment is used as the colorant in the fluorescent color ink, but when the fluorescent dye is used, even if the above-mentioned aliphatic basic acid ester is used as the release agent, it is sufficiently removed by rubbing with an eraser. It is difficult to do so, and the brush strokes are scattered on the board surface due to rubbing and remain in a dispersed state, or the board surface is dyed. It is especially noticeable in handwriting after aging. Therefore, the remaining handwriting and the dyed part emit light when irradiated with light, and an afterimage is generated.
Furthermore, even if the erasable imparting agent of the above document was blended, the above-mentioned improvement in erasability was not observed in the system using the fluorescent dye.

INDUSTRIAL APPLICABILITY The present invention can exhibit high erasing performance that even when a fluorescent dye applicable to a light irradiation type writing board is used, the handwriting can be peeled off without being scattered at the time of scraping erasing, and the writing can be erased with a light force. It provides an oil-based ink composition having excellent practicality, a marking pen incorporating the composition, and a writing set .

The present invention contains a fluorescent dye, an organic solvent, a resin, a monobasic acid ester and a dibasic acid ester as a release agent, and the dibasic acid ester is an alkoxy group represented by R1-O-R2-. 3 Ri structure der having an ester group, wherein the dibasic acid ester relative to monobasic acid ester: 1 to 1: is added in an amount of two ranges, are written in transparent writing surface of the light irradiation type Ester oil-based ink composition is a requirement.
[R1 in the formula is an alkyl group having 3 to 8 carbon atoms, and R2 is any of 1 to 4 selected from an alkyl chain, an alkoxy chain, an alkyl chain and an alkoxy chain having 2 to 8 carbon atoms. It is a continuous organic chain in the range. ]
Further, a marking pen containing the oil-based ink composition is a requirement, and a writing set including the marking pen and a cursive having a transparent (transparent) impermeable writing surface is a requirement.
Further, it is required that the cursive is provided with a light source that emits light from the handwriting and emerges.
Further, it is required that the resin is a polyvinyl butyral resin.

According to the present invention, even when a fluorescent dye is used as a colorant, the handwriting can be peeled off without being scattered during scraping and erasing, and the entire handwriting can be erased with a light force, which is excellent in practicality of exhibiting high erasing performance. It is an oil-based ink composition. Therefore, it can be applied to a light irradiation type writing board or sheet material, and the writing portion can be made to stand out by imparting high luminescence to the handwriting without causing an afterimage even after repeated use.

According to the present invention, by adding a monobasic acid ester as a release agent and a specific dibasic acid ester to the ink together with the fluorescent dye, the ink can be reliably peeled off without scattering the brush strokes at the time of scraping and erasing. Therefore, excellent erasability can be obtained.
Specific examples of the monobasic acid ester serving as the release agent include CIO (cetyl isooctanoate), ICM-R (isocetyl myristate), ICIS (isocetyl isostearate), ISP (isostearyl palmitate), and STO (steare). Isooctyl acid) and the like. Aliphatic compounds are particularly effective and more useful.
When the resin forms a film on the writing surface to fix it as a handwriting during writing, the monobasic acid ester imparts erasing performance by being present between the film and the writing surface.

The Examples of the dibasic acid ester, at least one of an ester group, R 1 _-O-R 2 _- can be applied compound of structure having an alkoxy group represented by the.
The dibasic acid ester having the above structure becomes a release agent component that acts on the fluorescent dye and the resin by the alkoxy group having the specific structure. Therefore, by using it in combination with the monobasic acid ester, excellent fixability is exhibited at the time of writing, and at the time of erasing, the writing and erasing performance that the fluorescent dye is peeled off without remaining remains can be permanently exhibited. Become.

R ₁ constituting the alkoxy group is an alkyl group having 3 to 8 carbon atoms, and R ₂ is an organic having 1 to 4 continuous organic chains selected from an alkyl chain having 2 to 8 carbon atoms and an alkoxy chain. It is a chain in which an alkyl chain having 2 to 8 carbon atoms and an alkoxyl chain having 2 to 8 carbon atoms are continuous individually or in plural, and the alkyl chain and the alkoxyl chain are continuously continuous alternately or randomly.
Since the material having the above structure has high compatibility with the resin, it is possible to exhibit an appropriate plasticizing action on the handwriting. Therefore, the resin film (visible handwriting) in which the fluorescent dye is dispersed (compatible) is not cured, and the state suitable for abrasion peeling for a long period of time while maintaining the dispersed compatible state of the fluorescent dye. You can keep your handwriting with. Therefore, the handwriting can be easily and surely erased even after a lapse of time without causing an afterimage.
In particular, those in which R ₁ is a butyl group (that is, the alkoxy group terminal is a butoxy group) and R ₂ is an ethyl chain, an ethoxy chain, or an ethoxyethyl chain are long-term without limiting the type of resin or fluorescent dye. It is more preferable because the above-mentioned state can be expressed over a period of time.

Wherein R ₁ -O-R 2 _- as the alcohol to be reacted dibasic acid and esterified to form an alkoxy group represented by, as more suitable, for example, ethylene glycol isopropyl ether, ethylene glycol monobutyl ether, diethylene glycol Examples thereof include butyl ether, propylene glycol monobutyl ether, ethylene glycol isoamyl ether, and ethylene glycol monohexyl ether.

Examples of the dibasic acid that reacts with the alcohol to form a dibasic acid ester include succinic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, tartaric acid and the like. ..

Among the dibasic acid esters formed from the dibasic acid and alcohol, bis adipate (2-butoxyethyl), bis sebacate (2-butoxyethyl), bis adipate [2- (2-butoxyethoxy) ethyl) ] Is particularly useful because it can exhibit high effects regardless of the type of fluorescent dye, solvent, or monobasic acid ester.

The dibasic acid ester is blended in a ratio of 3: 1 to 1: 2 with respect to the monobasic acid ester (that is, 0.5 to 3 times the amount of the monobasic acid ester). Is preferable.
At the above ratio, the above-mentioned monobasic acid ester and dibasic acid ester are expressed in a state of high peeling action, and are particularly highly erased regardless of the composition of the fluorescent dye, solvent, resin, etc. and the usage environment. Sex is obtained.

Other general-purpose release agents such as carboxylic acid esters, silicone-based surfactants, and nonionic surfactants can also be used in combination. For example, sulfate esters of polyoxyalkylene alkyl ethers and polyoxyalkylene alkyl aryl ethers. Examples thereof include sulfuric acid esters, polyoxyethylene alkyl ether phosphoric acid esters, salts thereof, and compounds such as polyalkylene glycol esters.

The release agent can be added in the range of 3 to 30% by weight, preferably 5 to 25% by weight, based on the total amount of the ink composition.
Within the above numerical range, the handwriting formed by the ink composition using the fluorescent dye can be scraped and erased with excellent erasability.

As the fluorescent dye, a general-purpose oil-soluble fluorescent dye can be used, for example, Basic Yellow 1, Basic Yellow 40, Basic Red 1, Basic Violet 10, Basic Violet 11: 1, Acid Yellow 7, Acid Red 92, Acid Blue 9. , Dispers Yellow 121, Dispers Blue 7, Direct Yellow 85, Fluorocent Brightening Whitex WS52, Solvent Yellow 44, Solvent Blue 5, Solvent Green 7 and the like.
The fluorescent dye may be used alone or in combination of two or more, and is used in the range of 0.01 to 30% by weight in the ink composition.

Further, general-purpose pigments and dyes conventionally applied to oil-based inks can also be used in combination.
Specifically, the pigments include inorganic pigments such as carbon black, ultramarine blue, and titanium dioxide pigments, azo pigments, phthalocyanine pigments, indigo pigments, thioindigo pigments, slene pigments, quinacridone pigments, anthraquinone pigments, and slene pigments. , Diketopyrrolopyrrole pigments, dioxazine pigments, perylene pigments, perinone pigments, isoindolinone pigments and other organic pigments, aluminum powders and metal pigments whose surface is treated with a coloring resin, transparent or colored transparent films A metal glossy pigment on which a metal vapor deposition film such as aluminum is formed, a metal pigment having a thickness of 0.01 to 0.1 μm obtained by peeling off the metal vapor deposition film such as aluminum formed on a substrate such as a film, gold, and silver. , Platinum, Colloidal particles with an average particle diameter of 5 to 30 nm selected from copper, fluorescent pigments, phosphorescent pigments, thermochromic pigments, natural mica as core material, synthetic mica, glass pieces, alumina, surface of transparent film pieces Examples thereof include pearl pigments obtained by coating the above with a metal oxide such as titanium oxide.
In addition, examples of the dye include organic solvent-soluble dyes classified as solvent dyes in the Color Index.

The resin is used for fixing handwriting on the writing surface and imparting viscosity to the ink.
Examples of the resin include cellulosic resins such as ethyl cellulose and acetyl cellulose, and vinyl resins such as polyvinyl butyral, polyvinylpyrrolidone, polyvinyl acetate, and vinylpyrrolidone-vinyl acetate copolymer resin.
The resin may be added in the form of a processed pigment.

Among the resins, polyvinyl butyral resin (PVB) is more preferably used because it has good compatibility with the release agent and fluorescent dye of the present invention. In particular, those having a butyralization degree of 55 to 85 mol% are preferable, and specifically, Eslek 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, Sekisui Chemical Co., Ltd.), Mobital B16H, B20H, B30T, B30H, B30HH, B45M, B45H (above, Kuraray) Made) and the like. These can be used alone or in admixture 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, more preferably 3 to 6% by weight, based on the total amount of the ink composition.
Is desirable.

The organic solvent can be used as long as it is conventionally used for oil-based inks, but a volatile (low boiling point) organic solvent is preferable. Since the low boiling point organic solvent is excellent in the drying property of the handwriting when writing on the writing board, when the handwriting immediately after writing is touched, undried ink adheres to the hand or forms a handwriting on the writing surface. Good handwriting can be formed without causing problems such as contaminating the blank part that is not used.
Examples of the organic solvent include lower fatty alcohol solvents and glycol ether solvents, and it is preferable to use them as the main solvent (accounting for 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.

As another example of the organic solvent, hydrocarbon-based organic solvents such as n-heptane, n-octane, isooctane, methylcyclohexane, ethylcyclohexane, toluene, xylene, and ethylbenzene, methylisobutylketone, and methyln-propylketone. , Methyl n-butyl ketone, di-n-propyl ketone and other ketone organic solvents, n-butyl formate, isobutyl formate, n-propyl acetate, isopropyl acetate, n-butyl acetate, isobutyl acetate, ethyl propionate, n propionate. Ester-based organic solvents such as −butyl, methylbutyrate, ethylbutyrate, methyl lactate, and ethyl lactate, glycol-based solvents such as ethylene glycol, diethylene glycol, propylene glycol, and benzyl glycol, benzyl alcohol, γ-butyrolactone, and the like can be exemplified. It can also be used in combination with a low boiling organic solvent.

Further, in addition to the above components, various additions such as a handwriting whitening inhibitor, a drying resistance imparting agent, a rust preventive, a viscosity modifier, a pigment dispersant, and a surfactant are added to the ink composition of the present invention, if necessary. Agents can be used.
The additive is a so-called conventional additive, and can be appropriately used from known compounds as needed.

The ink composition is put into practical use by filling a marking pen with a pen tip attached to a writing tip.
The structure and shape of the marking pen itself are not particularly limited. For example, a pen tip for a marking pen such as a fiber tip, a felt tip, or a plastic tip is attached to the writing tip, and the fiber bundle housed inside the barrel is used. The ink storage body is impregnated with ink and the ink is supplied to the tip of the writing. The ink is directly stored inside the barrel, and the ink flow control member consisting of a comb groove-shaped ink flow control member and the fiber bundle is interposed. Examples thereof include 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 inside the barrel and a predetermined amount of ink is supplied to the writing tip by a valve mechanism.
In addition to a cap-type marking pen having a cap that covers the pen tip, the marking pen has a knock-type, rotary-type, slide-type, and other infestation mechanisms that allow the pen tip to be accommodated in the barrel. It may be a type marking pen.

The handwriting by the marking pen is formed by writing on a general-purpose writing board (whiteboard, blackboard, etc.), a film, a sheet, etc., which is a non-penetrating surface, and the handwriting is a board eraser (felt, cloth, etc.). Is scraped off with.
In particular, since the handwriting has fluorescence, it is preferable that the writing surface (cursive) has a dark color such as black or is transparent (transparent). By irradiating the handwriting written on these with light, the handwriting is visualized as if it emits light and emerges. Therefore, it can also be provided as a set with a cursive (having a dark color or a transparent non-penetrating writing surface) equipped with a light source such as an LED.
In the ink of the present invention, since the handwriting is surely removed without remaining scattered on the writing surface due to rubbing during erasing, the residue is formed without emitting light during light irradiation and forming an afterimage. Only the handwriting clearly emits light and emerges, which makes it excellent in rewriting.

The table below shows the composition of the oil-based ink compositions of Examples and Comparative Examples. The numerical values in the table indicate the parts by weight.

The contents of the raw materials are shown below according to the note numbers in the table.
(1) Made by Nippon Fluorescent Chemical Co., Ltd., trade name: NKS-1005 (mixture of basic yellow 40 and resin)
(2) Made by Nippon Fluorescent Chemical Co., Ltd., trade name: NKS-1007 (mixture of basic violet 11: 1 and resin)
(3) Made by Sekisui Chemical Co., Ltd., Product name: Eslek BL-1
(4) Cetyl isooctanoate (5) Isooctyl stearate (6) Bis sebacate (2-butoxyethyl)
(7) Bis adipate (2-butoxyethyl)
(8) Bis adipate [2- (2-butoxyethoxy) ethyl]
(9) Bis sebacate (2-ethylhexyl)
(10) Bis adipate (2-ethylhexyl)
(11) Bisisodecyl adipate (12) Diethyl succinate (13) Pentaglyceryl monostearate

Preparation of Ink An oil-based ink composition was obtained by mixing each raw material in the blending amounts of the above-mentioned Examples and Comparative Examples, and stirring and dissolving at 20 ° C. for 3 hours in a disper.

Preparation of Marking Pen An oil-based marking pen was obtained by filling 5 g of each of the ink compositions of the above-mentioned Examples and Comparative Examples with a commercially available marking pen (manufactured by Pilot Corporation; WMBM-12L).
The following tests were performed using each of the marking pens.

Erasability test Using each marking pen, draw five consecutive spiral circles on various writing boards (steel blackboard and transparent acrylic board), and handwriting immediately after writing and handwriting after leaving at 20 ° C for 14 days. On the other hand, the state of the writing surface when the handwriting was moved three times with a tissue paper on which a weight of 100 g was placed was visually observed. The observation location was determined by the LED irradiation state under a fluorescent lamp and in a dark place.
The test results are shown in the table below.

The evaluation of the symbols in the table is as follows.
Erasability test ○: Handwriting is erased and no afterimage occurs.
Δ: The handwriting is erased, but an afterimage is generated.
X: The handwriting cannot be completely erased and remains, and an afterimage also occurs.

Claims (5)

It contains a fluorescent dye, an organic solvent, a resin, a monobasic acid ester and a dibasic acid ester as a release agent, and the dibasic acid ester uses the alkoxy group represented by R1-O-R2- as an ester group. structure der having is, the 3 against dibasic acid ester monobasic acid ester: 1 to 1: is added in an amount of two ranges, oil-based ink composition that is written to the permeable writing surface of the light irradiation type Stuff.
[R1 in the formula is an alkyl group having 3 to 8 carbon atoms, and R2 is any of 1 to 4 selected from an alkyl chain, an alkoxy chain, an alkyl chain and an alkoxy chain having 2 to 8 carbon atoms. It is a continuous organic chain in the range. ] A marking pen containing the oil-based ink composition according to claim 1. A writing set comprising the marking pen according to claim 2 and a cursive having a transparent (transparent) non-permeable writing surface. The writing set according to claim 3, wherein the cursive is provided with a light source that emits light from the handwriting to emerge. The oil-based ink composition according to claim 1, wherein the resin is a polyvinyl butyral resin.