JP2010090276A - Oil-based marking pen ink composition - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an oil-based marking pen ink composition which excels in the stability of ink, does not damage writing properties even when a pen point is left exposed to the air for a long time, and can form clear handwriting excellent in dryness. <P>SOLUTION: The oil-based marking pen ink composition comprises a coloring agent, ethanol, a glycol ether-based organic solvent, a resin, and a polyglycerin fatty acid ester having an HLB of 5-12, wherein a mass ratio of the ethanol to the glycol ether-based organic solvent meets 9:1 to 7:3. <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

  The present invention relates to an oil-based marking pen ink composition. More specifically, the present invention relates to an oil-based marking pen ink composition that can form good handwriting even after the pen tip is exposed to the outside air for a long time.

Conventionally, marking pens containing oil-based inks cause the solvent to evaporate from the pen tip when exposed to the outside air for a long time, and the colorant or resin in the ink dries and solidifies, making it impossible to write or fading. There was a thing. Such a phenomenon is conspicuous in an ink composition using a highly volatile alcohol-based organic solvent as a main solvent, and there is a problem that it is difficult to form a clear handwriting because the handwriting tends to be whitened.
Attempts have been made to add polyglycerin fatty acid esters to impart dry resistance to this type of oil-based ink, but the effect of preventing whitening of handwriting is poor, and depending on the polyglycerin fatty acid esters used, Stability may be impaired (for example, refer patent documents 1 and 2).
JP 58-108270 A JP 2004-330456 A

  The present invention is intended to solve the problems of the conventional oil-based marking pen ink composition, that is, it is possible to form clear handwriting even when the pen tip is exposed to the outside air for a long time, and to improve the ink stability. It is intended to provide an excellent oil-based marking pen ink composition.

The present invention comprises a colorant, an ethyl alcohol and glycol ether organic solvent, a resin, and a polyglycerin fatty acid ester having an HLB of 5 to 12, wherein the mass ratio of the ethyl alcohol to the glycol ether organic solvent is 9: An oil-based marking pen ink composition satisfying 1 to 7: 3 is required.
Further, the glycol ether organic solvent is propylene glycol monomethyl ether or propylene glycol monoethyl ether, and the polyglycerin fatty acid ester is contained in 0.1 to 5% by mass in the total amount of the ink composition. And

  The present invention is an oil-based marking pen that is excellent in ink stability and can form clear and excellent handwriting without losing writing performance even if the pen tip is exposed to the outside air for a long time. An ink composition can be provided.

As the colorant, a dye or a pigment is used.
Examples of the dye include oil-soluble dyes, such as Bali First Black 3806 (CI Solvent Black 29), 3807 (Trimethylbenzylammonium salt of CI Solvent Black 29), Spirit Black SB (C.I. Solvent Black 5), Spiron Black GMH (CI Solvent Black 43), Bali First Red 1308 (Salt Form of CI Basic Red 1 and CI Acid Yellow 23), Bali First Yellow AUM ( CI Basic Yellow 2 and CI Acid Yellow 42 salt formation), Spiron Yellow C2GH (organic acid salt of CI Basic Yellow 2), Spiron Violet CRH (CI Solvent Violet) 8-1), Bali First Violet 1701 CI Basic Violet 1 and CI Acid Yellow 42 salt formation), Spiron Red CGH (organic salt of CI Basic Red 1), Spiron Pink BH (CI Solvent Red 82), Nigrosine Examples include Base EX (CI Solvent Black 7), Oil Blue 613 (CI Solvent Blue 5), Neozapon Blue 808 (CI Solvent Blue 70), and the like.
Examples of the pigment include azo, anthraquinone, condensed polyazo, indigo, thioindigo, metal complex, phthalocyanine, perinone, perylene, dioxazine, quinacridone, slen, anthraquinone, throne, Organic pigments such as diketopyrrolopyrrole, dioxazine, and isoindolinone, carbon black, aniline black, ultramarine, yellow lead, titanium oxide, iron oxide, and other inorganic pigments, and metal powder pigments such as aluminum, transparent Or a metallic luster pigment in which a metal-deposited film is formed on a colored transparent film, natural mica, synthetic mica, glass pieces, alumina as a core substance, and transparent metallic luster in which the surface of a transparent film piece is coated with a metal oxide such as titanium oxide A pigment etc. can be illustrated.

The organic solvent is made of ethyl alcohol and glycol ether solvent.
As the glycol ether solvent, glycol ethers having 3 to 5 carbon atoms, that is, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, and more preferably, Propylene glycol monomethyl ether and propylene glycol monoethyl ether are used.
The ethyl alcohol and the glycol ether organic solvent are blended in the ink composition in a mass ratio of 9: 1 to 7: 3.
When there is more ethyl alcohol than the said mass ratio, a handwriting will be easily whitened and it will become difficult to form clear handwriting.
On the other hand, if the amount of ethyl alcohol is less than the above mass ratio, when writing on a non-penetrating surface such as glass or plastic, the dryness of the handwriting is inferior. Or a contamination of a blank portion on which the handwriting on the writing surface is not formed is likely to occur.
The ethyl alcohol and glycol ether solvents are used as main solvents. Apart from this, as general-purpose organic solvents, benzyl alcohol, ethylene glycol, diethylene glycol, propylene glycol, benzyl glycol, methyl lactate, ethyl lactate, γ-butyrolactone, etc. Can be added in a category that does not impair the writing performance.

  Examples of the resin include rosin derivatives such as rosin, ester gum, rosin-modified maleic resin, ketone resins, alkylphenol resins, cellulose derivatives, maleic acid resins, styrene-maleic acid copolymers, vinyl acetate, vinyl butyral, vinyl pyrrolidone, etc. Examples include vinyl resin, phenol-modified xylene resin, xylene resin, terpene resin, terpene-phenol resin, acrylic resin, methacrylic resin, aliphatic hydrocarbon resin, alicyclic hydrocarbon resin, alkyd resin, etc. Used for imparting properties and viscosity.

The polyglycerin fatty acid ester has an HLB of 5 to 12, preferably 7 to 12, in order to improve the drying resistance of the nib. Even if the nib is exposed to the outside air for a long time, the nib surface The evaporation of the solvent from can be suppressed.
When the HLB of the polyglycerin fatty acid ester is less than 5, the solubility in a solvent is poor and precipitation occurs in the ink at a low temperature, making it difficult to express desired drying resistance or causing whitening. Moreover, when HLB exceeds 12, it becomes impossible to provide drying resistance.
Specific examples of the polyglycerol fatty acid ester include decaglycerol tristearate (HLB9.8), hexaglycerol monostearate (HLB11.6), hexaglycerol distearate (HLB9.9), and hexaglycerol tristearin. An acid ester (HLB7.0) and a tetraglycerin monostearate (HLB8.4) can be illustrated.
The polyglycerin fatty acid ester is added in an amount of 0.1 to 5.0% by mass, preferably 0.2 to 2.0% by mass, based on the total amount of the ink composition.
If it is less than 0.1% by mass, it is difficult to exhibit the desired drying resistance, and if it exceeds 5.0% by mass, the coating strength of the handwriting is lowered, or the ink viscosity is increased and the handwriting is liable to be blurred.
In the marking pen containing the ink composition of the present invention, the polyglycerin fatty acid ester precipitates to form a film on the surface of the nib as the solvent in the ink evaporates in a state where the nib is exposed to the outside air. The film suppresses evaporation of the solvent from the nib and is easily broken during writing, so that it is considered that the film satisfies dry resistance.
In addition, various surfactants such as phosphate ester surfactants may be added as necessary.

The oil-based marking pen ink composition is practically used by filling a marking pen with a pen tip attached to a writing tip.
When filling the marking pen, 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 shaft cylinder is used. A structure that supplies ink to the pen tip by impregnating ink into the ink occlusion body consisting of a fiber bundle housed inside, ink that is directly contained inside the shaft cylinder, and composed of a comb groove-shaped ink flow rate adjusting member or fiber bundle Examples include a structure in which ink is supplied to the pen tip through a flow rate adjusting member, and a marking pen in which ink is directly stored in the shaft cylinder and supplied to the pen 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 following table shows the composition of the oil-based marking pen ink composition.
In addition, the numerical value in a table | surface shows a mass part.

The contents of the raw materials are shown below along the note numbers in the table.
(1) Product name: Nigrosine Base EX, manufactured by Orient Chemical Industry Co., Ltd.
(2) Product name: Microlith Blue 4G-A, manufactured by Ciba Geigy Co., Ltd.
(3) Product name: Bali First Red 1308, manufactured by Orient Chemical Co., Ltd.
(4) Arakawa Chemical Industries, Ltd., trade name: Ketone Resin K-90
(5) Product name: Marquide 33, manufactured by Arakawa Chemical Industries, Ltd.
(6) Toho Chemical Industry Co., Ltd., trade name: Phosphanol RA-600

The oil-based marking pen ink compositions of Examples 1 to 3 and Comparative Examples 1 to 3 were obtained by mixing a predetermined amount of components, heating and stirring.
Each ink composition was impregnated into a fiber sizing ink occlusion body in which a polyester sliver was coated with a synthetic resin film, and accommodated in a shaft tube, and a marking-type fiber pen body was attached to the tip of the shaft tube to obtain a marking pen. .
The marking pen is provided with a detachable cap.
The following tests were performed using each of the marking pens.

Dry-up resistance test Each marking pen with its cap removed was left in a temperature-controlled room adjusted to 20 ° C and 60% RH for 2 hours, and then written on the paper. Observed.
Drying test Using each marking pen, writing was performed on a polyester film in an environment of 20 ° C. and 60% RH, and the drying time of the handwriting was examined.
Ink stability test The ink compositions prepared in each Example and Comparative Example were allowed to stand at 20 ° C for 30 days, and then the state of the ink was visually observed.
Whitening Test Using each marking pen, writing was performed on a polyester film in an environment of 20 ° C. and 80% RH, and the state of the handwriting after drying was visually observed.
The test results are shown in the following table.

The evaluation of symbols in the table is as follows.
Dry-up resistance test ○: Can be written.
X: Cannot be written.
Dryability test ○: Dry within 10 seconds.
X: It takes 10 seconds or more to dry.
Ink stability test ○: No precipitate is observed in the ink composition.
X: Precipitates are observed in the ink composition.
Whitening test ○: Whitening is not seen in the handwriting ×: The handwriting is whitened.

Claims (3)

  It consists of a colorant, an ethyl alcohol and glycol ether organic solvent, a resin, and a polyglycerol fatty acid ester having an HLB of 5 to 12, and the mass ratio of the ethyl alcohol to the glycol ether organic solvent is 9: 1 to 7: Oil-based marking pen ink composition satisfying 3   The oil-based marking pen ink composition according to claim 1, wherein the glycol ether organic solvent is propylene glycol monomethyl ether or propylene glycol monoethyl ether.   The oil-based marking pen ink composition according to claim 1 or 2, wherein the polyglycerin fatty acid ester is contained in an amount of 0.1 to 5% by mass in the total amount of the ink composition.