JPH09111176A - Oil-based ink composition for marking pen - Google Patents

Abstract

(57) Abstract: In a low-toxicity non-aromatic hydrocarbon solvent-based ink, an ink impermeable surface is obtained without increasing the ink viscosity to the extent that the continuous outflow of the ink from the pen tip of the marking pen is obstructed. Also, an oil-based ink for a marking pen that gives a handwriting with substantially no blur is obtained. SOLUTION: At least one silicone oil selected from cyclic polydimethylsiloxane, alkyl-modified silicone oil and terminal-modified polyether-modified silicone oil is added to the ink composition as an additive for suppressing handwriting bleeding on the ink impermeable surface. It is contained in the range of 0.01 to 3% by weight.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to an oil-based ink composition for marking pens.

[0002]

2. Description of the Related Art Xylene or a mixed solvent of xylene and ethylene glycol monoalkyl ether has been mainly used as a solvent for oil inks for marking pens of this type, but recently, due to problems such as toxicity and odor of these solvents, it has recently been used. In oil-based inks, an alcohol-based solvent mainly composed of ethanol and a non-aromatic hydrocarbon-based solvent mainly composed of an aliphatic and / or alicyclic hydrocarbon are mainly used. However, any of the oil-based inks using the alcohol-based solvent or the non-aromatic hydrocarbon-based solvent has a tendency that the bleeding of the handwriting is remarkable when written on the ink non-penetrating surface such as glass, plastic film and metal surface. There is. A method of suppressing bleeding by increasing the resin content in the ink to increase the ink viscosity has been taken, but there is a limit to increasing the ink viscosity due to the relationship with continuous ink outflow from the marking pen, It cannot be a bleeding control measure. It has been proposed to add various handwriting bleeding additives to the alcohol-based solvent ink (see, for example, Japanese Patent Laid-Open No.
No. 247400, addition of polyether-modified silicone oil) has not been proposed as an effective means for suppressing handwriting bleeding with respect to the non-aromatic hydrocarbon solvent ink.

[0003]

DISCLOSURE OF THE INVENTION The present invention suppresses bleeding of handwriting on a non-ink penetrating surface such as glass, plastic film, and metal surface, and maintains good continuous ink outflow from the pen tip of a marking pen. An oil-based ink composition for a marking pen using a non-aromatic hydrocarbon solvent is provided.

[0004]

The oil-based ink composition for a marking pen of the present invention is applicable to a colorant as an essential component, an organic solvent mainly containing an aliphatic hydrocarbon and / or an alicyclic hydrocarbon, and the above solvent. It contains a soluble resin and at least one silicone oil selected from cyclic polydimethylsiloxane, alkyl-modified silicone and terminal-modified polyether-modified silicone.

Examples of the colorant include solvent dyes, inorganic pigments, organic pigments, metallic luster pigments and fluorescent pigments which are generally used in marking inks. Solvent dyes include basic dye bases, organic acid salts thereof, salt-forming salts of basic dyes and acid dyes, amine salts of acid dyes, and the like, and specific examples include nigrosine base EX (C.I. 50).
415B), oil black HBB (C.I.2615)
0), Bali Fast Red 1308 (C.I. 191)
40 and C.I. I. 45160 salt-forming salt), Bali Fast Red 1355, Oil Pink 312 (C.I. 451)
70B resinate), Oil Yellow 101, 105,
107 (organic amine salt of CI Acid Yellow 42), oil orange 201 (CI 21250),
Oil orange 203, oil blue 613 (C.I.
Solvent Blue 5) (above, a product of Orient Chemical Industry Co., Ltd.), Spiron Yellow CGNH (CAS.N)
o. 103349-70-8), Spyron Yellow C2
GH (organic acid salt of CI Basic Yellow 2), spirone red CGH (organic acid salt of CI Basic Red 1), spirone violet CRH (CI 42)
535B) (these are products of Hodogaya Chemical Co., Ltd.), Oreosol Black AR (CI Solvent Black 5)
0), Rhodamine B base (C.I. 45170B)
(These are the products of Taoka Industry Co., Ltd.), Neo Pen Blue 80
8, Neptune Red Base 486 (above, BASF
Company's product) Savinyl blue GLS (product of Sand Company) and the like. Inorganic pigments such as carbon black and titanium dioxide pigments, organic pigments such as β-naphthol,
Examples thereof include insoluble azo pigments such as naphthol AS type, benzimidazolone type, acetoacetic anilide type and pyrazolone type, phthalocyanine pigments such as phthalocyanine blue, condensed polycyclic pigments such as slene, indigo, perinone and quinacridone type pigments. Examples of metallic luster pigments include aluminum powder pigments and bronze powder pigments.

The organic solvents used are mainly aliphatic hydrocarbons and / or alicyclic hydrocarbons. Specific examples of the aliphatic hydrocarbons include hexane, heptane, mineral spirits, and isoparaffin (for example, Isopar of Exxon Co.). Series) and the like, specific examples of alicyclic hydrocarbons include cyclohexane, methylcyclohexane, ethylcyclohexane, decalin and the like, and examples of mixed solvents of aliphatic and alicyclic hydrocarbons include Exsol D Exsol D series. These non-aromatic hydrocarbon solvents account for 85% by weight or more of the total solvent. As an auxiliary solvent, ethanol, propanol, isopropanol, which is compatible with the main solvent,
Even if one or more low toxicity alcoholic solvents selected from the group consisting of benzyl alcohol, propylene glycol monomethyl ether, hexylene glycol and octylene glycol are used in combination within the range of 5 to less than 15% by weight of the total solvent. Good.

As the resin soluble in the main solvent, alkylphenol resin, terpene resin, terpene-phenol resin, phenol-modified xylene resin, xylene resin,
Acrylic resin, methacrylic resin, aliphatic hydrocarbon resin,
Examples thereof include alicyclic hydrocarbon resins, alkyd resins, vinyl resins, polyester resins, vinyl alkyl ether resins, styrene-butadiene elastomers and the like.

The silicone oil used is one or more silicone oils selected from cyclic polydimethylsiloxane, alkyl-modified silicone oil and terminal-modified polyether-modified silicone oil. Here, the polyether-modified silicone generally refers to a side chain-modified polyether silicone represented by the following general formula (Formula 1).

Embedded image However, although this general polyether-modified silicone oil can be applied to oil-based inks mainly composed of alcohol-based solvents, it is difficult to apply it to oil-based inks mainly composed of non-aromatic hydrocarbon-based solvents, and also has a good effect in terms of function. Hard to get.
The terminal-modified polyether-modified silicone used in the present invention has a chemical structure represented by the following general formula (Formula 2).

Embedded image Specific examples of silicone oil include TSF404, TSF405, and TSF40 as cyclic polydimethylsiloxane.
6 (product of Toshiba Silicone Co., Ltd.), KF412 (product of Shin-Etsu Chemical Co., Ltd.) as an alkyl-modified silicone oil,
SH203, SH230 (Toray Dow Corning Silicone Co., Ltd. product), Silwet L-720, L-722 as terminal modified polyether modified silicone oil
(Product of Nippon Unicar Co., Ltd.) and the like.

Other solubilizing agents for solvent dyes include higher fatty acids such as oleic acid, higher alcohols such as myristyl alcohol, cetyl alcohol, stearyl alcohol, animal and vegetable oils such as castor oil and terpene oil, and acidic phosphates in small amounts as necessary. You may add. In the ink composition, the colorant, the organic solvent, the soluble resin and the silicone oil are used in the ranges of 2 to 30% by weight, 40 to 90% by weight, 3 to 30% by weight and 0.01 to 3% by weight, respectively. The dye solubilizer is added in an amount of 5% by weight or less in the ink composition, if necessary.

[0010]

BEST MODE FOR CARRYING OUT THE INVENTION In the ink, when the colorant is a dye, a predetermined amount of an organic solvent and a resin are appropriately charged in a container, and after stirring and dissolving while heating, each component is added, Prepared by stirring to homogenize. When using a pigment as a colorant, the pigment paste that has been previously subjected to a dispersion treatment in an organic solvent solution in which a resin is dissolved is stirred and sufficiently stirred,
After mixing, it is prepared by adding the other ingredients and stirring to homogenize.

[0011]

EXAMPLES Table 1 shows the compositions of the example inks and the comparative example inks. The numerical values of the compositions are expressed in parts by weight.

[Table 1] The contents of the raw materials in the table will be described along the note numbers. (1) Oleosol Black AR (trade name of Taoka Industry Co., Ltd.), C.I. I. Solvent Black 50 (2) Rhodamine B base (CI.45170B) (3) Spyron Yellow CGNH (trade name of Hodogaya Chemical Co., Ltd.), CAS. No. 103349-70-
8 (4) Oil Blue 613 (Orient Chemical Industry Co., Ltd.)
Trade name), C.I. I. Solvent Blue 5 (5) Black pigment dispersion consisting of 60 wt% carbon black, 17.5 wt% terpene resin (Picolite S1500, trade name of Rika Hercules Co., Ltd.), 2.5 wt% dispersant and 20 wt% methylcyclohexane. Paste (6) Octylphenol-aldehyde condensation resin (Hitanol 1501, Hitachi Chemical Co., Ltd., trade name, softening point 80-
100 ° C., acid value 85-100) (7) Alicyclic hydrocarbon resin (Alcon P-100, Arakawa Chemical Co., Ltd. trade name, softening point 100 ° C.) (8) YS resin PX-1150, Yasuhara Chemical (stock) )
Product name, softening point 115 ° C. (9) Ethylcyclohexane (10) Isoparaffin / cycloparaffin mixed solvent (Exol D-40, Exxon company product name, initial boiling point 153
(° C, dry point 196 ° C, aniline point 69 ° C) (11) Isoparaffinic solvent (Isopar H, Exxon Co. product name, initial boiling point 176 ° C, dry point 192 ° C, aniline point 84 ° C) (12) Cyclic polydimethylsiloxane (TSF405, trade name of Toshiba Silicone Co., Ltd.) (13) end-modified polyether-modified silicone oil (Silwet L-722, Nippon Unicar Co., Ltd.) (14) alkyl-modified silicone oil (KF412, Shin-Etsu Chemical ( Trade name) (15) Alkyl-modified silicone oil (SH203, Toray Dow Corning Silicone Co., Ltd. trade name)

The inks of Comparative Examples 1 to 4 are inks in which only the silicone oil is removed from the compositions of the Example inks having the corresponding numbers, and the weight of the ink is replenished with a solvent (ethylcyclohexane). A predetermined amount of each of the sample inks prepared by the above-mentioned ink preparation method was filled in a marking pen having the following structure to make a sample pen, and the sample pen was tested. The marking pen has a configuration in which a pen body holder to which a pen body made by binding acrylic fibers with a resin is fixed is attached to the tip of an aluminum cylindrical body that accommodates an ink storage body made of a polyester fiber bundle inside. is there.

With each of the sample pens, 20 ° C., 60% RH
Under the conditions described above, a straight line was drawn on each surface of the polyester film (PET film), glass and art paper, and the handwritings were visually observed to determine the degree of bleeding. Table 2 shows the test results.

[Table 2] The contents of the evaluation symbols in the table are as follows. ○: No bleeding was observed △: Some bleeding was observed ×: Marked bleeding

[0014]

INDUSTRIAL APPLICABILITY The oil-based ink composition for a marking pen of the present invention, in a low-toxicity non-aromatic hydrocarbon solvent type ink, increases the ink viscosity to such an extent that the continuous outflow of the ink from the nib of the marking pen is obstructed. Without causing bleeding on the ink-impermeable surface.

Claims (3)

[Claims] 1. A colorant as an essential component, an organic solvent mainly containing an aliphatic hydrocarbon and / or an alicyclic hydrocarbon, a resin soluble in the solvent, and a cyclic polydimethylsiloxane,
An oil-based ink composition for a marking pen, which contains at least one silicone oil selected from alkyl-modified silicone and terminal-modified polyether-modified silicone. 2. The oil-based ink composition for a marking pen according to claim 1, wherein the solvent comprises only an aliphatic hydrocarbon and / or an alicyclic hydrocarbon. 3. The solvent is 85 to 95% by weight in the total solvent.
Is an aliphatic hydrocarbon and / or an alicyclic hydrocarbon, and the balance is one or two alcohol solvents selected from ethanol, propanol, isopropanol, benzyl alcohol, propylene glycol monomethyl ether, hexylene glycol and octylene glycol. The oil-based ink composition for a marking pen according to claim 1, which comprises at least one kind.