JPH07292308A - Marking ink composition - Google Patents

Abstract

PURPOSE:To obtain a marking ink composition good in the erasabllity of letters written on a writing board such as a whiteboard (esp. made of resin) even after left to stand for a long time. CONSTITUTION:This marking ink composition comprises 2-10wt.% of an inorganic or organic pigment or metallic powder, 72-85wt.% of a lower alcohol such as methyl or ethyl alcohol, 2-10wt.% of a lower alcohol-soluble resin such as polyvinyl butyral, 3-13wt.% of an unsaturated fatty acid ester produced from an unsaturated fatty acid such as butyl linolenate or ethyl oleate and a <=7C aliphatic alcohol, and 0.2-4wt.% of a phosphoric or phosphorous ester, and an ammonium, alkali metal, alkaline earth metal or alkanolamine salt thereof.

Description

Detailed Description of the Invention

[0001]

INDUSTRIAL APPLICABILITY The present invention is capable of writing on a writing plate such as a resin plate, a metal plate, a enamel plate, a glass plate, a baking coating plate, etc., whose surface is smooth and impermeable, 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 Writing on a writing board as described above, and
The handwriting erasable marking ink composition comprises a pigment, a lower alcohol, a resin soluble in the lower alcohol, and an additive that imparts erasability. Various erasability imparting agents have been proposed. For example, JP-A-58-42672 discloses "(A) phosphoric acid ester or sulfuric acid ester of polyoxyethylene alkyl ether or polyoxyethylene alkylphenol ether, phosphoric acid alkyl ester or phosphorous acid alkyl ester, and ammonium or alkali metal thereof. A compound selected from the group consisting of an alkaline earth metal or an alkanolamine salt "and" (B) an ester of an aliphatic monocarboxylic acid having 6 or more carbon atoms and an aliphatic monohydric alcohol having 8 or more carbon atoms, It is disclosed that the compound having a total carbon number of 20 or more and having a carbon chain branched structure and / or an unsaturated bond in the molecule is used in combination. Further, Japanese Patent Publication No. 60-55553 discloses "(A) Aliphatic dibasic acid ester" and "(B) Polyoxyethylene alkyl ether sulfuric acid ester, polyoxyethylene alkylphenyl ether sulfuric acid ester, polyoxyethylene alkyl ester. One or more phosphoric acid esters of ethers and phosphoric acid esters of polyoxyethylene alkyl phenyl ethers "are disclosed in combination. further,
Japanese Patent Publication No. 62-9149 discloses "(A) aliphatic dibasic acid ester" and "(B) polyoxyethylene alkyl ether sulfate, polyoxyethylene alkylphenyl ether sulfate, and polyoxyethylene alkyl ether. A substance selected from the group consisting of a phosphoric acid ester, a phosphoric acid ester of polyoxyethylene alkylphenyl ether, a polyester having a molecular weight of 1000 to 5000 composed of polyglycol and a dibasic acid, and a triglyceride composed of a saturated fatty acid having 12 or less carbon atoms. ) "Ester of aliphatic monobasic acid having 20 or more carbon atoms in total" is disclosed.

[0003]

However, the conventional marking ink composition described above has an insufficient erasability on a writing plate made of resin. That is, there is a problem that the handwriting written on the resin writing plate cannot be completely erased even after being left for a long period of time and right after the writing, unless it is repeatedly rubbed with an eraser.

[0004]

The present invention comprises a pigment, a lower alcohol, a resin soluble in the lower alcohol, an alkyl ester of an unsaturated carboxylic acid having 7 or less carbon atoms,
The subject matter is a marking ink composition containing at least a phosphoric acid ester, a phosphorous acid ester, or a salt thereof.

Each component of the present invention will be described in detail below. The pigment is used as a coloring material, and a marking ink composition is selected from conventionally known organic, inorganic and metal powder pigments, colored powders obtained by combining dyes and pigments with resin powders and fluorescent pigments. Those which can be stably dispersed as fine particles therein can be appropriately selected and used. In particular, a processed pigment obtained by coating the surface of a pigment 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. The amount used varies depending on the type of pigment and other ink components, but is 1 to 20% by weight, preferably 2 to 10% by weight, based on the total amount of the marking ink composition.

The lower alcohol is used as a solvent and may be one or two of methyl alcohol, ethyl alcohol, normal propyl alcohol, isopyr alcohol, normal butyl alcohol, isobutyl alcohol, secondary butyl alcohol, tertiary butyl alcohol and the like. The above can be mixed and used. When two or more kinds are mixed and used, various mixing ratios are determined in consideration of miscibility with other components. 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.
Is.

The resin is used for the purpose of imparting a film-forming ability to the ink, adhering to the writing surface, viscosity of the ink, and dispersion stability of the pigment. Any one soluble in the organic solvent can be used, but it has a low viscosity (1 to 1) required for a marking ink composition usually used for writing boards.
In order to obtain 0 cps, 25 ° C.), it is preferable to use a resin having a relatively low degree of polymerization. Specifically, the average degree of polymerization is 10
It is possible to use one or more of polyvinyl butyral or polyvinylpyrrolidone of 00 or less, vinyl acetate resin, polyacrylic acid ester, shellac, ethyl cellulose, etc., or a mixture thereof in an amount of 1 with respect to the total amount of the marking ink composition. -20% by weight, preferably 2-10% by weight. When a processed pigment having the surface of the pigment coated with a resin is used as the pigment, the resin in the pigment can be substituted.

An alkyl ester of an unsaturated carboxylic acid having a carbon number of 7 or less is used as a release agent which imparts a handwriting property which can be easily erased by rubbing. This ester can be obtained by reacting an unsaturated carboxylic acid with an aliphatic alcohol having a carbon number of 7 or less by a conventional method. As the unsaturated carboxylic acid, oleic acid,
Examples thereof include linoleic acid, ricinoleic acid, and linolenic acid. Examples of aliphatic alcohols having 7 or less carbon atoms include methyl alcohol, ethyl alcohol, normal propyl alcohol, isopropyl alcohol, normal butyl alcohol, isobutyl alcohol, tertiary butyl alcohol, and normal alcohol. Examples thereof include pentyl alcohol, isopentyl alcohol, normal hexyl alcohol, isohexyl alcohol, normal heptyl alcohol, and isoheptyl alcohol. Among these esters, particularly preferable ones are ethyl oleate, ethyl linoleate, isopropyl linoleate, and butyl ricinoleate, and the use amount thereof is 0.5 to 15% by weight, preferably 3% with respect to the total amount of the marking ink composition. ~ 13% by weight.

The phosphoric acid ester, the phosphorous acid ester or salts thereof are used as a peeling aid for improving the initial and erasability of handwriting on a resin writing board by being used in combination with the above unsaturated fatty acid ester. is there. Examples of the phosphoric acid ester and its salt include phosphoric acid monoester (general formula: PO (OR) (OM) ₂ ), phosphoric acid diester (general formula: PO (OR) ₂ OM), and phosphoric acid triester (general formula: PO (RO)). ₃ ), and examples of the phosphite and its salt include phosphite monoester (general formula: (RO) P (OM) ₂ ), phosphite diester (general formula: (RO) POM or (RO) ₂ PM). = O) and a phosphorous acid triester (general formula: (RO) ₃ P). In the above general formula, R is an alkyl group having 12 or less carbon atoms, a phenyl group, an alkylphenyl group, an alkoxyalkyl group, an alkoxyphenyl group, an alkoxyalkylphenyl group, M is hydrogen, ammonium, an alkali metal,
Indicates an alkaline earth metal or alkanolamine.
Among these phosphoric acid esters, phosphorous acid esters and salts thereof, particularly preferred are tributoxyethyl phosphate, triphenyl phosphate, monobutyl phosphate and 2-ethylhexyldiphenyl phosphate, the amount of which is 0 based on the total amount of the marking ink composition. 0.1 to 8% by weight, preferably 0.2
~ 4% by weight.

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

The marking ink composition of the present invention is
It can be easily obtained by mixing the above-mentioned components in required amounts and mixing and dispersing them with a high-speed stirrer such as a homomixer or a lab mixer or a disperser such as a ball mill, a sand mill or a bead mill.

[0012]

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. The unsaturated fatty acid ester, which is a release agent, is present between the handwriting and the surface to be written, and exhibits erasability of the handwriting. Since the unsaturated fatty acid ester in the present invention is less likely to violate the resin, it has high erasability when written on a resin writing board, and since it is used together with phosphoric acid or phosphorous acid ester, the phosphoric acid or phosphorous acid ester The ester is mixed with the unsaturated fatty acid ester, and the synergistic action of the two improves the erasability in the initial stage and the time course.

[0013]

【Example】

Example 1 Phthalorocyanine green 3 parts Polyvinyl butyral 2 parts Ethyl alcohol 50 parts Normal propyl alcohol 42 parts Butyl linosinate 3 parts Tributoxyethyl phosphate 3 parts The above components are stirred for 6 hours in a ball mill to obtain a marking ink composition. It was

Example 2 Fuji AS Red 7 parts (processed pigment, pigment; lake red, 50% by weight, resin;
Polyvinyl butyral, 50% by weight, Fuji Pigment Co., Ltd.
Ethyl alcohol 50 parts Isopropyl alcohol 37 parts Ethyl oleate 9 parts Mixture of dibutyl phosphate and monobutyl phosphate 3 parts The above components were stirred for 4 hours with a stirrer to obtain a marking ink composition.

Example 3 Phthalocyanine blue 4 parts Polyvinyl butyral (polymerization degree: about 700) 4 parts Ethyl alcohol 44 parts Normal butyl alcohol 43 parts Isopropyl linoleate 6 parts Triphenyl phosphate 4 parts The above ingredients are dispersed in a ball mill for 5 hours. A marking ink composition was obtained.

Example 4 Fuji AS Black 8 parts (black processed pigment, pigment; carbon black, 50% by weight, resin; polyvinylpyrrolidonane, 50% by weight, manufactured by Fuji Dye Co., Ltd.) Ethyl alcohol 65 parts Normal propyl alcohol 10 Parts Ethyl linoleate 7 parts Tributoxyethyl phosphate 2 parts The above components were dispersed in a stirrer for 3 hours to obtain a marking ink composition.

Example 5 Carbon black 3 parts Polyvinyl butyral (polymerization degree 300) 4 parts Ethyl alcohol 50 parts Isopropyl alcohol 27 parts Ethyl linolenate 9 parts 2-Ethylhexyldiphenyl phosphate 3 parts The above ingredients are dispersed in a ball mill for 5 hours. A marking ink composition was obtained.

Example 6 Fuji AS Black 8 parts (black processed pigment, pigment; carbon book, 50% by weight,
Resin: polyvinyl butyral, 50% by weight, manufactured by Fuji Dye Co., Ltd. Ethyl alcohol 65 parts Isopropyl alcohol 10 parts Ethyl linoleate 7 parts Tributoxyethyl phosphite 2 parts The above components are stirred with a stirrer for 3 hours for marking ink. A composition was obtained.

Example 7 Phthalocyanine green 3 parts Polyvinyl butyral (polymerization degree of about 630) 2 parts Ethyl alcohol 50 parts Normal propyl alcohol 42 parts Butyl linosinate 3 parts Sodium monobutyl phosphate 3 parts The above ingredients are dispersed in a ball mill for 6 hours. To obtain a marking ink composition.

Example 8 Fuji AS Red 7 parts (processed pigment, pigment; lake red, 50% by weight, resin;
Polyvinyl butyral, 50% by weight, Fuji Pigment Co., Ltd.
Manufactured) Ethyl alcohol 50 parts Isopropyl alcohol 37 parts Butyl oleate 9 parts Diphenyl sodium phosphite 3 parts The above components were stirred with a stirrer for 4 hours to obtain a marking ink composition.

Comparative Example 1 Example 1 was repeated except that butyl linosine was replaced with dibutyl sebacate and monobutyl phosphate was replaced with Gafac RS-710 (polyoxyethylene alkyl ether phosphate ester, manufactured by Toho Chemical Industry Co., Ltd.). A marking ink composition was obtained in the same manner as in Example 1.

Comparative Example 2 A marking ink composition was obtained in the same manner as in Example 2 except that ethyl oleate was changed to isostearyl caprate in Example 2.

Comparative Example 3 Same as Example 5 except that ethyl linolenate was changed to 4 parts of dioctyl azelate, 5 parts of isooctadecyl palmitate and 2-ethylhexyldiphenyl phosphate was replaced with triglyceride caprate in Example 5. To obtain a marking ink composition.

Comparative Example 4 A marking ink composition was obtained in the same manner as in Example 8 except that butyl oleate was changed to octyl oleate in Example 8.

The marking ink compositions obtained in the above Examples 1 to 8 and Comparative Examples 1 to 4 were filled in a batting type writing instrument to prepare a writing instrument for testing, and an erasability test was conducted. The results are shown in Table 1.

[0026]

[Table 1]

* 1 Initial erasure test Write characters in a certain size on a writing board (enameling board and acrylic board) using the above-mentioned writing instrument for test, and after drying, load 500 g with a dry cloth on the handwriting. And the number of times until the handwriting was erased was measured.

* 2 Erasability test with time Using the above-mentioned writing instrument for writing, write letters on a writing plate (enameled plate and acrylic plate) in a certain size, leave it indoors for 1 month, and then dry the handwriting. Load 500g using cloth
And the number of times until the handwriting was erased was measured.

[0029]

As described above, the marking ink composition of the present invention can be written on a writing plate having a smooth and impermeable surface, and the handwriting can be easily erased by lightly rubbing it with a dry cloth or the like. In addition, it is excellent in erasability after aging, and particularly, even when written on a resin writing plate, the erasability is excellent.

Claims (1)

[Claims] 1. A pigment, a lower alcohol, a resin soluble in the lower alcohol, and an unsaturated carboxylic acid having 7 carbon atoms.
A marking ink composition comprising at least the following alkyl ester and a phosphoric acid ester, a phosphorous acid ester or salts thereof.