JPH07268267A - Marking ink composition - Google Patents

Abstract

PURPOSE:To obtain a marking ink compsn. which can be used for writing on a flat impermeable surface and is excellent in erasability of written lines after aging by compounding at least a pigment, an org. solvent, a specific resin, a fatty acid ester (deriv.), and a specific compd. CONSTITUTION:A marking ink contains at least a pigment, an org. solvent (e.g. ethanol and isopropanol), a resin sol. in the solvent (e.g. polyvinyl butyral), a fatty acid ester (deriv.) (e.g. isopropyl myristate), and a sulfuric, acetic, or phosphoric ester of a polyoxyalkylene alkyl ether or its salt (e.g. sodium sulfate ester of polyoxyethylene-polyoxypropylene cetyl ether).

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a marking ink composition, more specifically the surface of which can be written on a writing plate such as a plastic plate, a metal plate, a enamel plate, a glass plate, or a baking resin plate, and The present invention relates to a marking ink composition that can be easily erased by lightly rubbing the handwriting with a dry cloth or a flexible paper as needed.

[0002]

2. Description of the Related Art The above marking ink composition comprises a pigment, an organic solvent, a resin soluble in the organic solvent and an additive for erasing. Various additives have been proposed. For example, Japanese Patent Publication No. 60-55553 discloses that
(A) Aliphatic dibasic acid ester and (B) polyoxyethylene alkyl ether sulfuric acid ester, polyoxyethylene alkylphenyl ether sulfuric acid ester, polyoxyethylene alkyl ether phosphoric acid ester, and polyoxyethylene alkylphenyl ether phosphoric acid ester It is disclosed to use one kind or two or more kinds together. JP-A-59-64680 discloses the combined use of (A) isopropyl myristate and (B) normal paraffin and isoparaffin.
JP-A-60-51764 discloses that (A) a higher aliphatic hydrocarbon such as liquid paraffin and mineral spirit, and (B) a sorbitan ester type nonionic surfactant and a polyoxyethylene alkyl ether phosphate ester type. It is disclosed to use in combination with either or both of the nonionic anionic surfactants.

[0003]

However, the above-mentioned conventional marking ink composition has the erasability of handwriting, in particular,
The erasability with time is insufficient. That is, there is a problem that a handwriting which has been written for a long time cannot be completely erased unless it is repeatedly rubbed with an eraser.

[0004]

The present invention is directed to a pigment, an organic solvent, a resin soluble in the organic solvent, a fatty acid ester or a derivative thereof, and a sulfuric acid, acetic acid or phosphoric acid ester of a polyoxyalkylene alkyl ether, or The gist is a marking ink composition containing at least those salts.

The pigment is stably dispersed as fine particles in the marking ink composition from conventionally known organic / inorganic and metal powder pigments, colored processed powder obtained by combining the pigment with resin powder and fluorescent pigment. What can be done can be appropriately selected and used. In particular, the processed pigment whose surface is coated with a resin can be preferably used from the viewpoints of dispersibility, stability over time, workability, and the fact that no other resin needs to be added to the marking ink composition. Although the amount used varies depending on the type of pigment and other ink components, it is 1 to 20% by weight, preferably 2 to 10% by weight, based on the marking ink composition.

Organic solvents include lower alcohol solvents such as methanol, ethanol, propanol, isopropanol and butanol, ketone solvents such as acetone, methyl ethyl ketone and methyl isobutyl ketone, ethyl acetate, normal propyl acetate, isopropyl acetate and normal butyl acetate. It is possible to use one solvent or a mixture of two or more solvents such as an ester solvent such as isobutyl acetate.
Various mixing ratios are determined in consideration of miscibility with other components to be used, and the amount used is 65 to 90% by weight, preferably 72 to 85% by weight based on the total amount of the marking ink composition. .

The resin is used for the purpose of imparting a film forming ability to the ink and imparting adhesion to the writing surface, viscosity of the ink and dispersion stability of the pigment. Any one that is soluble in the organic solvent can be used, but it is preferable to use a resin having a relatively low degree of polymerization in order to obtain the low viscosity required for the marking ink composition. Specifically, 1 of polyvinyl butyral or polyvinylpyrrolidone having an average degree of polymerization of 1000 or less, vinyl acetate resin, vinyl chloride-vinyl acetate copolymer, polyacrylic acid ester, shellac, ethyl cellulose, etc.
One kind or two or more kinds can be used, and the amount thereof is 1 to 20% by weight, preferably 2 to 10% by weight based on the total amount of the marking ink composition. When the pigment is a processed pigment, the resin in the pigment can be substituted.

The fatty acid ester or its derivative is used as a release agent that imparts a property of easily erasing the handwriting by rubbing. Specifically, isopropyl myristate, isooctyl myristate, isopropyl palmitate, isooctadecyl palmitate, ethyl linoleate, isopropyl linoleate, ethyl oleate,
Isostearyl caprylate, oleyl caprylate, dioctyl stearate, hexadecyl normal octanoate, cetyl normal octanoate, hexadecyl isooctanoate, cetyl isooctanoate, hexadecyl isooctanoate, diethyl sebacate, dioctyl sebacate,
Diisopropyl adipate, dibutyl adipate, dioctyl adipate, diisodecyl adipate, propylene glycol monocaprylate, hexadecyl 2-ethylhexanoate, stearyl 2-ethylhexanoate, tri-2
-Glyceryl ethylhexanoate or Unistar H334R
(Trimethylolpropane-mixed fatty acid triester of lauric acid and stearic acid, manufactured by NOF CORPORATION), H
310 (trimethylolpropane-capric acid triester, manufactured by NOF CORPORATION), 312R (trimethylolpropane-lauric acid triester, manufactured by NOF CORPORATION)
Made), NJERB TPO (trimethylolpropane-
1 such as caprylic acid triester, NOF Corporation
One kind or two or more kinds can be used. The amount used is 0.5 to 15% by weight with respect to the total amount of the marking ink composition,
It is preferably 3 to 13% by weight.

The sulfuric acid, acetic acid or phosphoric acid ester of polyoxyalkylene alkyl ether or a salt thereof is used in combination with the above-mentioned fatty acid ester or its derivative to improve the initial and erasability. Examples of the polyoxyalkylene alkyl ether include polyoxypropylene alkyl ether and polyoxyethylene polyoxypropylene alkyl ether. The sulfuric acid, acetic acid or phosphoric acid ester of polyoxyalkylene alkyl ether can be obtained by esterifying the above polyoxyalkylene alkyl ether with sulfuric acid, acetic acid or phosphoric acid by a conventionally known method.
Further, examples of the substance that forms a salt include ammonium, alkali metal, alkaline earth metal, and alkanolamine.

The polyoxyalkylene alkyl ether and the sulfuric acid, acetic acid or phosphoric acid ester or salts thereof are represented by the general formulas (1) to (3). The amount used is 0.2 to 8% by weight with respect to the total amount of the marking ink composition,
It is preferably 0.5 to 4% by weight.

An ester of polyoxypropylene alkyl ether or polyoxyethylene polyoxypropylene alkyl ether with sulfuric acid and a salt thereof are shown in Chemical formula 1.
An ester of polyoxypropylene alkyl ether or polyoxyethylene polyoxypropylene alkyl ether with acetic acid and a salt thereof are shown in Chemical formula 2. An ester of polyoxypropylene alkyl ether or polyoxyethylene polyoxypropylene alkyl ether with phosphoric acid and a salt thereof are shown in Chemical formula 3.

[0012]

Embedded image RO- (CH ₂ CHCH ₃ O) m- (CH ₂ CH ₂
O) nSO ₃ M

[0013]

Embedded image RO- (CH ₂ CHCH ₃ O) m- (CH ₂ CH ₂
O) nCH ₂ COOM

[0014]

[Chemical 3]

In the above formula, R represents an alkyl group or an alkylphenyl group. M is hydrogen, alkyl group, ammonium, alkanolamine, lithium, sodium,
An alkali metal atom such as potassium or an alkaline earth metal such as magnesium, calcium or barium is shown. m and n show the average addition mole number of propylene oxide and propylene oxide. That is, m represents a number of 1 or more and n represents a number of 0 or more.

In addition to the components shown above, various additives such as antiseptics, antifungal agents, wetting agents, viscosity modifiers, antifreezing agents, antifoaming agents, and various general activators may be added as necessary. You can also select and use it.

In the method for producing the marking ink composition of the present invention, the above-mentioned respective components are mixed in necessary amounts and mixed by a high speed agitator such as a homomixer or a lab mixer or a disperser such as a ball mill or a sand mill. It can be easily obtained by dispersing.

[0018]

Although it is not clear why the marking ink composition of the present invention is excellent in initial and erasability with time, it is presumed as follows. Writing by the marking ink composition of the present invention, when the solvent evaporates, most of the fatty acid ester as a release agent or its derivative is present between the resin film constituting the writing and the writing surface, and the erasability is improved. It is provided that sulfuric acid, acetic acid or phosphoric acid ester of polyoxyalkylene alkyl ether or a salt thereof is partially in the resin film and plasticizes the resin film to improve the erasability of handwriting. Since the other portion is mixed with the fatty acid ester or the derivative thereof, the erasability at the initial stage and the time course is improved by the synergistic action of the both.

[0019]

【Example】

Example 1 Fuji AS black (processed pigment, resin; polyvinyl butyral, manufactured by Fuji Dye Co., Ltd.) 8 parts by weight ethanol 65 parts by weight isopropanol 10 parts by weight isopropyl myristate 7 parts by weight polyoxyethylene polyoxypropylene cetyl ether sulfate 2 parts by weight of sodium ester The above components were stirred with a stirrer for 3 hours to obtain a marking ink composition.

Example 2 Fuji AS Red (Processed pigment, resin; polyvinyl butyral, manufactured by Fuji Dye Co., Ltd.) 7 parts by weight Ethanol 50 parts by weight Isopropanol 37 parts by weight Diisopropyl sebacate 9 parts by weight Polyoxyethylene polyoxypropylene decyl tetra 3 parts by weight of sodium phosphate ester of decyl ether The above components were stirred with a stirrer for 4 hours to obtain a marking ink composition.

Example 3 Fuji IK Blue (Processed pigment, resin; vinyl chloride-vinyl acetate copolymer, manufactured by Fuji Color Co., Ltd.) 5 parts by weight Methyl ethyl ketone 55 parts by weight Ethyl acetate 30 parts by weight Tri-2-ethylhexanoic acid Trimethylolpropane 6 parts by weight Polyoxyethylene polyoxypropylene octyl phenyl ether acetate ester 4 parts by weight The above components were stirred with a stirrer for 2 hours to obtain a marking ink composition.

Example 4 Phthalocyanine green 3 parts by weight Vinyl chloride-vinyl acetate copolymer (polymerization degree 300) 3 parts by weight Methyl ethyl ketone 42 parts by weight Ethyl acetate 42 parts by weight Isopropyl palmitate 3 parts by weight Diisopropyl adipate 3 parts by weight Polyoxy 2 parts by weight of phosphoric acid ester of ethylene polyoxypropylene oleyl ether The above components were dispersed in a ball mill for 6 hours to obtain a marking ink composition.

Example 5 Phthalocyanine blue 3 parts by weight Polyvinyl butyral (polymerization degree 630) 4 parts by weight Ethanol 50 parts by weight Isopropanol 27 parts by weight Diisopropyl adipate 9 parts by weight Propylene glycol dicaprate 4 parts by weight Sodium sulfate of polyoxypropylene cetyl ether 3 parts by weight The above components were dispersed in a ball mill for 5 hours to obtain a marking ink composition.

Comparative Example 1 A marking ink composition was prepared in the same manner as in Example 1 except that the sodium sulfate of polyoxyethylene polyoxypropylene cetyl ether was changed to 1 part by weight of normal paraffin and 1 part by weight of isoparaffin. Got

Comparative Example 2 In Example 4, sulfuric acid ester of polyoxyethylene polyoxyoleyl ether was used as Plysurf A208B.
A marking ink composition was obtained in the same manner as in Example 4 except that the phosphoric acid ester of polyoxyethylene alkyl ether manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd. was used.

The marking ink compositions obtained in the above Examples 1 to 5 and Comparative Examples 1 and 2 were filled in a batting type writing instrument to prepare samples, and erasability tests were conducted. The results are shown in Table 1.
Shown in.

[0027]

[Table 1]

* 1 Initial erasure test Write characters in a certain size on a writing board (enameling board and fluororesin board), dry it, and then use a dry cloth to abrade it with a load of 500 g. The number of times until it was erased was measured.

* 2 Erasability test with time Writing characters in a certain size on a writing board (enameling board and fluororesin board), leaving it for a month in the room, and then using a dry cloth on the handwriting, load 500g It was rubbed with and the number of times until the handwriting disappeared was measured.

[0030]

As described above, the marking ink composition according to the present invention can be written on a writing surface having a smooth surface and non-permeability, and its handwriting can be lightly rubbed with a cloth or the like. It is excellent in that it can be easily erased, and the erasability after leaving the handwriting for a long time is also good.

Claims (1)

[Claims] 1. A marking containing at least a pigment, an organic solvent, a resin soluble in the organic solvent, a fatty acid ester or a derivative thereof, and a sulfuric acid, acetic acid or phosphoric acid ester of polyoxyalkylene alkyl ether or a salt thereof. Ink composition.