JP2007204609A - Marking ink composition for writing board - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a marking ink composition for writing board, suppressing occurrence of so-called ghost phenomenon in which a releasing agent for imparting erasing property after erasing handwriting remains, in the marking ink composition for writing board in which it can be drawn on a writing board and the handwriting written on the board can be readily erased. <P>SOLUTION: In the marking ink composition for writing board comprising at least a pigment, a lower alcohol, a polyvinyl butyral and a releasing agent, silicon dioxide particles are included. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

  The present invention relates to a marking ink composition for a writing board, and more particularly can be written on a writing board such as a resin plate, a metal plate, an enamel plate, a glass plate, and a baked coating plate having a smooth and impermeable surface. Further, the present invention relates to a marking ink composition for a writing board which can be easily erased by lightly rubbing the handwriting with a dry cloth, flexible paper, an erasing tool or the like as necessary. Furthermore, the present invention relates to a marking board marking ink composition capable of suppressing the so-called ghost phenomenon in which a release agent for imparting erasability remains on the writing board surface after erasing the handwriting and maintaining the writing board surface cleanly.

  Conventionally, a marking ink composition for a writing board mainly comprises a pigment, a lower alcohol, a resin soluble in the lower alcohol, and a release agent for imparting erasability.

  Various resins have been proposed as resins soluble in lower alcohols. For example, Patent Document 1 discloses the use of polyvinyl butyral resin, acrylic resin, styrene-acrylic copolymer resin, styrene-maleic acid copolymer resin, shellac, rosin-maleic acid copolymer resin, and the like. . Further, in Patent Document 2, in addition to polyvinyl butyral resin, vinyl pyrrolidone-vinyl acetate copolymer, polyvinyl acetate, arylsulfonamide-formaldehyde condensation resin, polyacrylic acid ester, ethyl cellulose, carboxymethyl cellulose, hydroxypropyl cellulose, etc. Use is disclosed. Patent Document 3 discloses the use of polyvinyl alcohol, cellulose, nitrocellulose, and methylcellulose in addition to polyvinyl butyral resin and polyvinyl acetate.

Various release agents for imparting erasability have also been proposed. For example, Patent Document 4 states that “phosphoric acid ester or sulfuric acid ester of polyoxyethylene alkyl ether or polyoxyethylene alkyl phenol ether, alkyl phosphoric acid ester or phosphorous acid alkyl ester, and their ammonium, alkali metal, alkaline earth metal or alkanol. A compound selected from the group consisting of amine salts "and" an ester of an aliphatic monocarboxylic acid having 6 or more carbon atoms and an aliphatic monohydric alcohol having 8 or more carbon atoms, having a total carbon number of 20 or more, And a compound having a branched structure of a carbon chain and / or an unsaturated bond therein. Patent Document 5 discloses “aliphatic dibasic acid ester” and “sulfuric acid ester of polyoxyethylene alkyl ether, sulfuric acid ester of polyoxyethylene alkylphenyl ether, phosphoric acid ester of polyoxyethylene alkyl ether, and polyoxyethylene alkylphenyl”. It is disclosed to use together with “one kind or two or more kinds of ether phosphate ester”. Patent Document 6 discloses “aliphatic dibasic acid ester” and “sulfuric acid ester of polyoxyethylene alkyl ether, sulfuric acid ester of polyoxyethylene alkylphenyl ether, phosphoric acid ester of polyoxyethylene alkyl ether, polyoxyethylene alkylphenyl”. “Substances selected from the group consisting of phosphoric esters of ethers, polyesters composed of polyglycols and dibasic acids with molecular weights of 1000 to 5000, and triglycerides composed of saturated fatty acids having 12 or less carbon atoms” and “aliphatic monobasic groups having 20 or more carbon atoms in total” It is disclosed to use three kinds together with “ester of acid”. Patent Document 7 discloses that “a fatty acid ester which is an ester of a monocarboxylic acid having 8 or more carbon atoms and an aliphatic monohydric alcohol having 8 or more carbon atoms”, “polyoxyethylene alkyl ether type nonionic surfactant and And / or a polyoxyethylene alkylphenol ether type nonionic surfactant ”is disclosed. Patent Document 8 uses “5 to 20% by weight of polyoxyethylene / polyoxypropylene monoalkyl ether which is liquid at normal temperature”, more preferably “group consisting of carboxylic acid ester and polyoxypropylene monoalkyl ether”. And 2-10% by weight of a liquid compound at room temperature selected from at least one selected from Further, Patent Document 9 discloses that at least selected from the group consisting of “polyoxyethylene / polyoxypropylene block copolymer 5 to 20% by weight which is liquid at normal temperature” and “carboxylic acid ester and polyoxypropylene alkyl monoalkyl ether”. It is disclosed that 2-10 wt% of a liquid compound at room temperature selected from one kind is used in combination.
JP 05-194903 A Japanese Patent Laid-Open No. 05-302051 Japanese Patent Application Laid-Open No. 07-228812 Japanese Patent Laid-Open No. 58-042672 Japanese Patent Publication No. 60-055553 Japanese Examined Patent Publication No. 62-009149 Japanese Examined Patent Publication No. 01-023513 JP 05-194903 A JP 05-194904 A

However, in the above-mentioned conventional marking ink composition for a writing board, if a release agent for imparting erasability is blended in the ink composition, the release agent for imparting erasability remains on the writing board surface after erasing the handwriting. A so-called ghost phenomenon occurs.
The present invention can erase the handwriting on a writing board such as a resin plate, a metal plate, an enamel plate, a glass plate, a baked coating plate, or the like, and a release agent for imparting erasure remains on the surface of the writing board after erasing the handwriting. An object of the present invention is to provide a marking ink composition for a writing board that suppresses the occurrence of a so-called ghost phenomenon.

  The gist of the present invention is a marking ink composition for a writing board containing silicon dioxide particles.

  It is presumed that the silicon dioxide particles adsorb and remove the above-mentioned components used as a release agent that causes the ghost phenomenon.

  The pigment used in the present invention is used as a colorant, and conventionally known organic pigments such as azo pigments, condensed polyazo pigments, phthalocyanine pigments, quinacridone pigments, indigo pigments, thioindigo pigments, and the like Among inorganic pigments such as carbon black, bitumen, bengara and titanium oxide, metal powder pigments such as aluminum powder and brass powder, colored processed powders combining these pigments and resin powders, fluorescent pigments and pearl pigments Therefore, those that can be stably dispersed as fine particles in the marking ink composition for a writing board can be appropriately selected and used. In particular, a processed pigment whose surface is coated with a resin can be preferably used from the viewpoints of dispersibility, stability over time, workability, and the need to add another resin to the marking ink composition for writing boards. Specific examples of processed pigments include Fuji AS Black 810, Red 58, Blue 650, Green 710, Orange 200, (manufactured by Fuji Dye Co., Ltd.), Micro Pigmo Black AMBK-2, Red AMRD- 2, Blue AMBE-2, Green AMGN-2, Orange AMOE-2, Yellow AMYW-2, Pink AMPK-2, Violet AMVT-2 (above, manufactured by Orient Chemical Co., Ltd.) is there. The amount used varies depending on the type of pigment and other ink components, but is 1 to 30% by weight, preferably 2 to 20% by weight, based on the marking ink composition for writing boards.

  The lower alcohol is used as a solvent and is selected from conventionally known alcohols having 4 or less carbon atoms such as methanol, ethanol, normal-propanol, isopropanol, normal-butanol, isobutanol, secondary butanol, and tertiary butanol. One kind or a mixture of two or more kinds can be used. The mixing amount is determined in consideration of miscibility with other components to be used, but is 50 to 90% by weight, preferably 55 to 85% by weight based on the total amount of the marking ink composition for writing board. % By weight.

  Polyvinyl butyral 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 material that is soluble in a lower alcohol can be used without particular limitation. As specific examples, Denkabutyral # 2000-L, # 3000-1, # 3000-2, # 3000-4, # 3000-K, # 4000-1, # 4000-2, # 5000- A, # 6000-C, # 6000-EP (manufactured by Denki Kagaku Kogyo Co., Ltd.), ESREC BL-1, BL-2, BL-5, BL-10, BL-S, BM -1, BM-2, BM-5, BM-S (Sekisui Chemical Co., Ltd.) can be used. It is 1 to 30% by weight, preferably 2 to 20% by weight, based on the total amount of the ink composition. If the amount used is small, no film is formed and the dispersion stability of the pigment becomes unstable. On the other hand, when the amount used is large, fixing to the plate surface becomes strong and the viscosity becomes high, which is not preferable as a marking plate marking ink. When the pigment is a processed pigment using polyvinyl butyral, it can be replaced by a resin in the processed pigment.

  The release agent is used for imparting the property that the handwriting can be easily erased by rubbing on the resin plate and good erasability after repeated erasing, and is not particularly limited as long as it is soluble in the lower alcohol. It can be used. Specifically, polyoxyethylene alkyl ether, polyoxyethylene alkyl phenyl ether, polyoxyethylene secondary alkyl ether, polyoxyethylene / polyoxypropylene alkyl ether, and sulfate, phosphate, glycerin fatty acid ester, Examples thereof include glycerin fatty acid ester, polyoxyethylene glycerin fatty acid ester, sorbitan fatty acid ester, polyoxyethylene sorbitan fatty acid ester, polyethylene glycol fatty acid ester, polyhydric alcohol fatty acid ester and the like, and one kind or a mixture of two or more kinds can be used. The amount used is 0.1 to 10% by weight, preferably 0.2 to 5% by weight, based on the total amount of the marking ink composition for a writing board.

  The silicon dioxide particles used in the present invention are used for the purpose of suppressing the occurrence of the ghost phenomenon, and conventionally known silicon dioxide particles can be used without any particular limitation, but in particular water or hydrocarbon solvents, A colloidal solution in which silicon dioxide particles are stably dispersed in an organic solvent such as a halogenated hydrocarbon solvent, alcohol solvent, ether solvent, ketone solvent, ester solvent, polyhydric alcohol solvent, etc. It can be preferably used in terms of stability and workability. In general, there are water-dispersed aqueous silica sols and organic solvent-dispersed organosilica sols. More specifically, silicon dioxide particles that are water-dispersed aqueous silica sols are used as Snowtex XS (silicon dioxide content 20%). , Particle diameter 4-6 nm), OXS (silicon dioxide content 10%, particle diameter 4-6 nm), S (silicon dioxide content 30%, particle diameter 8-11 nm), OS (silicon dioxide content 20) %, Particle diameter 8-11 nm), 20 (silicon dioxide content 20%, particle diameter 10-20 nm), 30 (silicon dioxide content 30%, particle diameter 10-20 nm), 40 (silicon dioxide content) 40%, particle diameter 10-20 nm), O (silicon dioxide content 20%, particle diameter 10-20 nm), N (silicon dioxide content 20%, particle diameter 10-20 nm), C ( Silicon oxide content 20%, particle size 10-20 nm), AK (silicon dioxide content 19%, particle size 10-20 nm), 50 (silicon dioxide content 48%, particle size 20-30 nm), O -40 (silicon dioxide content 40%, particle diameter 20-30 nm), CM (silicon dioxide content 30%, particle diameter 20-30 nm), 20 L (silicon dioxide content 20%, particle diameter 40-50 nm) OL (silicon dioxide content 20%, particle size 40-50 nm), XL (silicon dioxide content 40%, particle size 40-60 nm), ZL (silicon dioxide content 40%, particle size 70-100 nm) ), UP (silicon dioxide content 20%, particle size 40-100 nm), OUP (silicon dioxide content 15%, particle size 40-100 nm), PS-S (silicon dioxide) Content 19%, particle diameter 80-120 nm), PS-M (silicon dioxide content 20%, particle diameter 80-150 nm), MP-1040 (silicon dioxide content 40%, particle diameter 100 nm), MP-2040 (Silicon dioxide content 40%, particle diameter 200 nm), MP-3040 (silicon dioxide content 40%, particle diameter 300 nm), MP-4540M (silicon dioxide content 40%, particle diameter 450 nm) Quarton PL-1 (silicon dioxide content 12%, particle size 15 nm), PL-3 (silicon dioxide content 20%, particle size 35 nm), PL-7 (silicon dioxide content 20) %, Particle diameter of 70 nm), PL-20 (silicon dioxide content 24%, particle diameter of 220 nm) (manufactured by Fuso Chemical Industries, Ltd.) and the like. Silicon dioxide particles that are organic solvent-dispersed organosilica sols include methanol silica sol (methanol-dispersed silicon dioxide, silicon dioxide content 30%, particle size 10 to 20 nm), MA-ST-M (methanol-dispersed dioxide dioxide). Silicon, silicon dioxide content 40%, particle size 20-30 nm), EG-ST (ethylene glycol dispersed silicon dioxide, silicon dioxide content 20%, particle size 10-20 nm), EG-ST-ZL (ethylene glycol) Dispersed silicon dioxide, silicon dioxide content 20%, particle diameter 70-100 nm), IPA-ST (isopropanol dispersed silicon dioxide, silicon dioxide content 20%, particle diameter 10-20 nm), IPA-ST-UP (Isopropanol-dispersed silicon dioxide, silicon dioxide content 15%, Child diameter 40-100 nm), IPA-ST-ZL (isopropanol dispersed silicon dioxide, silicon dioxide content 30%, particle diameter 70-100 nm), NPC-ST-30 (n-propyl cellosolve dispersed silicon dioxide, Silicon dioxide content 30%, particle size 10-20 nm), DMAC-ST (dimethylacetamide dispersion type silicon dioxide, silicon dioxide content 20%, particle size 10-20 nm), MEK-ST (methyl ethyl ketone dispersion type silicon dioxide) , Silicon dioxide content 30%, particle diameter 10-20 nm), MIBK-ST (methyl isobutyl ketone dispersed silicon dioxide, silicon dioxide content 30%, particle diameter 10-20 nm), XBA-ST (xylene, n- Butanol mixed solvent dispersion type silicon dioxide, silicon dioxide content 30%, (Diameter 10-20 nm) PMA-ST (propylene glycol monomethyl acetate dispersion type silicon dioxide, silicon dioxide content 30%, particle diameter 10-20 nm) (manufactured by Nissan Chemical Industries, Ltd.), Quattron PL-1- MA (methanol-dispersed silicon dioxide, silicon dioxide content 20%, particle size 12 nm), PL-2-MA (methanol-dispersed silicon dioxide, silicon dioxide content 20%, particle size 20 nm), PL- 3-MA (methanol-dispersed silicon dioxide, silicon dioxide content 20%, particle size 30 nm), PL-5-MA (methanol-dispersed silicon dioxide, silicon dioxide content 20%, particle size 50 nm), PL-10-MA (methanol-dispersed silicon dioxide, silicon dioxide content 20%, particle diameter 90 nm), the same PL 30-MA (methanol-dispersed silicon dioxide, silicon dioxide content 20%, particle size 300 nm), PL-1-IPA (isopropanol-dispersed silicon dioxide, silicon dioxide content 20%, particle size 12 nm), PL-2-IPA (isopropanol-dispersed silicon dioxide, silicon dioxide content 20%, particle diameter 20 nm), PL-3-IPA (isopropanol-dispersed silicon dioxide, silicon dioxide content 20%, particle diameter 30 nm) PL-5-IPA (isopropanol dispersion type silicon dioxide, silicon dioxide content 20%, particle size 50 nm), PL-10-IPA (isopropanol dispersion type silicon dioxide, silicon dioxide content 20%, particle size) 90 nm), PL-30-IPA (isopropanol-dispersed silicon dioxide, Silicon fluoride content 20%, particle size 300 nm), PL-1-MEK (methyl ethyl ketone dispersion type silicon dioxide, silicon dioxide content 20%, particle size 12 nm), PL-2-MEK (methyl ethyl ketone dispersion type dioxide) Silicon, silicon dioxide content 20%, particle size 20 nm), PL-3-MEK (methyl ethyl ketone dispersion type silicon dioxide, silicon dioxide content 20%, particle size 30 nm), PL-5-MEK (methyl ethyl ketone dispersion type) Silicon dioxide, silicon dioxide content 20%, particle diameter 50 nm), PL-10-MEK (methyl ethyl ketone dispersion type silicon dioxide, silicon dioxide content 20%, particle diameter 90 nm), PL-30-MEK (methyl ethyl ketone) Dispersed silicon dioxide, silicon dioxide content 20%, particle size 300n m), PL-1-TOL (toluene-dispersed silicon dioxide, silicon dioxide content 20%, particle diameter 12 nm), PL-2-TOL (toluene-dispersed silicon dioxide, silicon dioxide content 20%, Particle diameter 20 nm), PL-3-TOL (toluene-dispersed silicon dioxide, silicon dioxide content 20%, particle diameter 30 nm), PL-5-TOL (toluene-dispersed silicon dioxide, silicon dioxide content 20) %, Particle diameter 50 nm), the same PL-10-TOL (toluene dispersion type silicon dioxide, silicon dioxide content 20%, particle diameter 90 nm), the same PL-30-TOL (toluene dispersion type silicon dioxide, containing silicon dioxide) 20%, particle size 300 nm) (above, manufactured by Fuso Chemical Industry Co., Ltd.). These silica sols can be used alone or in combination of two or more. The amount used is 0.1 to 30.0% by weight, preferably 1.0 to 20.0% by weight, based on the total amount of the marking ink composition for a writing board. When the amount used is small, there is no difference from the conventional case. When the amount used is large, the solid content of the handwriting becomes larger than the release agent imparting erasability and the handwriting cannot be erased. Further, when the viscosity increases and the applicator is filled, it becomes difficult to eject ink.

  In addition to the components shown above, if necessary, for example, resins such as polyvinyl pyrrolidone, vinyl acetate resin, polyacrylic acid ester, shellac, preservatives, antifungal agents, wetting agents, viscosity modifiers, antifreeze agents, pens Various additives such as an anti-drying agent, an antifoaming agent, various activators, and an organic solvent that does not interfere with the solubility of polyvinyl butyral can be appropriately selected and used.

Example 1
The method for producing a marking ink composition for a writing board according to the present invention comprises mixing the necessary amounts of the above components and mixing them with a high-speed stirrer such as a homomixer or lab mixer, or a dispersing machine such as a ball mill, sand mill or bead mill. It can be easily obtained by dispersing.

Solmix AP-4 (ethanol 85.5%, isopropanol 13.4%,
Mixed solution of acetone 1.1%, manufactured by Nippon Kasei Chemical Co., Ltd. 48.0 parts Isopropanol 33.0 parts Methanol silica sol (methanol-dispersed organosilica sol, silicon dioxide content 30%, particle size 10-20 nm, Nissan Manufactured by Chemical Industry Co., Ltd.) 2.0 parts BS-2 (polyoxyethylene (2) stearyl ether, Nikko Chemicals (
2.0 parts CIO (cetyl isooctanoate, manufactured by Nikko Chemicals Co., Ltd.) 7.0 parts Fuji AS Blue 650 (processed pigment coated with blue pigment with polyvinyl butyral, manufactured by Fuji Dye Co., Ltd.) 0 part The said component was stirred with the homomixer for 4 hours, and the blue marking ink composition for writing boards was obtained.

Example 2
Ethanol 48.0 parts Isopropanol 36.6 parts IPA-ST-UP (isopropanol-dispersed organosilica sol, silicon dioxide content 15%, particle size 40-100 nm, Nissan) Chemical Industry Co., Ltd.)
3.0 parts PBC-31 (polyoxyethylene (1) polyoxypropylene (4) cetyl ether, manufactured by Nikko Chemicals Co., Ltd.) 1.5 parts Sefsol-228 (propylene glycol dicaprylate, manufactured by Nikko Chemicals Co., Ltd.) 5.0 parts Pigment Red 53: 1 (red pigment) 1.5 parts Pigment Red 112 (red pigment) 1.5 parts Denkabutyral # 4000-1 (polyvinyl butyral, manufactured by Denki Kagaku Kogyo Co., Ltd.) 2.9 parts The above components were dispersed in a ball mill for 5 hours to obtain a red writing ink for a writing board.

Example 3
Ethanol 42.5 parts Isopropanol 31.0 parts Isobutanol 5.0 parts EG-ST-ZL (ethylene glycol dispersed organosilica sol, silicon dioxide content 20%, particle size 70-100 nm, Nissan Chemical Industries, Ltd.) Made)
5.0 parts Nonal 205 (polyoxyethylene nonylphenol ether, manufactured by Toho Chemical Co., Ltd.) 0.5 parts TDP-2 (dipolyoxyethylene (2) alkyl ether phosphoric acid, manufactured by Nikko Chemicals Co., Ltd.) 2.0 IPM-EX (isopropyl myristate, manufactured by Nikko Chemicals Co., Ltd.)
4.0 parts Fuji AS Black 810 (processed pigment coated with black pigment with polyvinyl butyral, manufactured by Fuji Dye Co., Ltd.) 10.0 parts The above ingredients are stirred with a stirrer for 4 hours, and black marking ink for writing board A composition was obtained.

Example 4
In the same manner as in Example 1, except that the methanol silica sol was MA-ST-M (methanol dispersed organosilica sol, silicon dioxide content 40%, particle size 20-30 nm, manufactured by Nissan Chemical Industries, Ltd.) A marking ink composition for a writing board was obtained.

Example 5
Except that IPA-ST-UP of Example 2 was changed to Snowtex UP (water-dispersed aqueous silica sol, silicon dioxide content 20%, particle size 40-100 nm, manufactured by Nissan Chemical Industries, Ltd.) A red marking ink composition for a writing board was obtained.

Example 6
EG-ST-ZL of Example 3 is MP-4540M (water-dispersed aqueous silica sol, silicon dioxide content 40%, particle diameter 450 nm, manufactured by Nissan Chemical Industries, Ltd.) 2.5 parts ethanol 45.0 parts A black marking ink composition for a writing board was obtained in the same manner as described above.

Comparative Example 1
A blue marking ink composition for a writing board was obtained in the same manner except that the solmix AP-4 was added instead of the methanol silica sol of Example 1.

Comparative Example 2
A red marking ink composition for a writing board was obtained in the same manner except that IPA-ST-UP in Example 2 was changed to 30.0 parts and isopropanol was changed to 9.6 parts instead.

Comparative Example 3
A black marking board marking ink composition was obtained in the same manner except that 0.5 part of EG-ST-ZL in Example 3 and 47 parts of ethanol were used instead.

  An applicator (EMWLM, manufactured by Pentel) was filled with the ink prepared in Examples 1 to 6 and Comparative Examples 1 to 3, and Test 1 was carried out using this as a sample. The results are shown in Table 1.

Test 1
Eraseability of handwriting Using each sample, writing was performed on a writing board (same as above) and dried, and a load of 25 g / cm ² was applied to the dry cloth to check the number of times the dry cloth moved until the handwriting could be erased.

Test 2
Eraseability of ghosts Further, a load of 25 g / cm ² was applied to the dry cloth, and the number of times the dry cloth moved until the erasable release agent residue so-called ghost could be erased was confirmed.

  As described above in detail, the marking ink composition for writing board according to the present invention is a marking board ink composition for writing board that can easily erase the handwriting. It is a marking ink composition for a writing board which suppresses generation | occurrence | production of what is called a ghost phenomenon in which an agent remains.

Claims (4)

A marking ink composition for a writing board containing silicon dioxide particles. The marking ink composition for a writing board according to claim 1, wherein the silicon dioxide particles are organic solvent-dispersed silicon dioxide. The marking ink composition for a writing board according to claim 1 or 2, further comprising polyvinyl butyral. The marking ink composition for a writing board according to any one of claims 1 to 3, further comprising a monohydric alcohol monofatty acid ester and / or a dihydric alcohol difatty acid ester.