JP2005132989A - Marking ink composition for writing board - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a marking ink composition for writing boards characterized in that it can be written on writing boards, the handwriting written on the boards can be readily erased, it is excellent in suppressing whitening of the handwriting, and bits of eraser debris cannot be easily scattered when it is erased . <P>SOLUTION: The marking ink composition for writing boards comprises at least a pigment, lower alcohol, polyvinyl butyral, and a release agent, which contains 0.01 to 3.0 wt.% hydroxypropyl cellulose. <P>COPYRIGHT: (C)2005,JPO&NCIPI

Description

  The present invention relates to a marking ink composition for a writing board, and more specifically, writing 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 non-permeable 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, if necessary. Furthermore, it is related with the marking ink composition for writing boards excellent in the whitening suppression of a handwriting.

  Conventionally, a marking ink composition for a writing board 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, vinyl pyrrolidone-vinyl acetate copolymer, polyvinyl acetate, arylsulfonamide-formaldehyde condensation resin, polyacrylic ester, ethyl cellulose, carboxymethyl cellulose, hydroxypropyl cellulose, etc. are used. Is disclosed. Patent Document 3 discloses the use of polyvinyl alcohol, cellulose, nitrocellulose, and methylcellulose in addition to polyvinyl butyral 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 “from the group consisting of carboxylic acid ester and polyoxypropylene monoalkyl ether”. It is disclosed that 2-10% by weight of a compound that is liquid at room temperature selected from at least one selected from the above is used in combination. Further, Patent Document 9 discloses that at least one 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% by weight of a liquid compound at room temperature selected from seeds 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 writing boards, when polyvinyl alcohol, ethyl cellulose, carboxymethyl cellulose, hydroxypropyl cellulose, etc. are used alone, the handwriting is difficult to dry and sticky. When rubbing with an erasing tool, there is a problem that the erasing tool spreads out in the form of stretching the handwriting around and cannot be erased. Ink compositions containing a release agent alleviate this problem, but especially when writing on a white writing board, when the handwriting dries, pigment aggregation occurs and the handwriting film is localized. Shrinkage occurs, causing fine cracks, and the white color of the writing board appears to pass through, and the handwriting after drying appears whitish (hereinafter referred to as whitening).
An object of this invention is to provide the marking ink composition for writing boards which suppressed generation | occurrence | production of the whitening of the handwriting in writing boards, such as a resin plate, a metal plate, an enamel plate, a glass plate, and a baking coating board.

  The present invention provides a marking ink composition for a writing board containing at least 0.01 to 3.0% by weight of hydroxypropylcellulose based on the total amount of the pigment, lower alcohol, polyvinyl butyral, release agent, and ink. It is what.

  Polyvinyl butyral has three components of vinyl acetal group, vinyl alcohol group, and vinyl acetate group in the molecular chain, and therefore has excellent solubility in solvents. Of these, the hydroxyl group in the vinyl alcohol group undergoes a cross-linking reaction with various functional groups, so that it has a three-dimensional structure and has a strong adhesive strength and coating strength. However, since the flexibility is lost as the coating film strength becomes stronger, the coating film is likely to be brittle and the handwriting is likely to be cracked. Hydroxypropyl cellulose is a substance having film forming ability and flexibility, and therefore has a function as a certain kind of binder. Therefore, by mixing and using hydroxypropyl cellulose and polyvinyl butyral, the brittleness of the polyvinyl butyral film is compensated, the film is made flexible and cracks are suppressed, and the whitening of the handwriting is suppressed. It seems to be.

  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 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. Specific examples of processed pigments include Fuji AS Black 810, Red 58, Blue 650, Green 710, Orange 210, (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, Orient Chemical Co., Ltd.) . 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.

  The lower alcohol is used as a solvent and has a carbon number such as conventionally known methyl alcohol, ethyl alcohol, normal-propyl alcohol, isopropyl alcohol, normal-butyl alcohol, isobutyl alcohol, secondary butyl alcohol, tertiary butyl alcohol, etc. From 4 or less alcohols, it can be used 1 type or in mixture of 2 or more types. The amount used is determined in various mixing ratios in consideration of miscibility with other components to be used, and is 50 to 90% by weight, preferably 55 to 85% by weight, based on the total amount of the marking ink composition. is there.

  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 (above, manufactured by Sekisui Chemical Co., Ltd.) can be used, and the amount used is a marking ink composition. It is 1-30 weight% with respect to the whole quantity, Preferably it is 2-20 weight%. 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 respective sulfuric acid ester, phosphoric acid ester, glycerin fatty acid ester, polyglycerin Examples thereof include fatty acid esters, polyoxyethylene glycerin fatty acid esters, sorbitan fatty acid esters, polyoxyethylene sorbitan fatty acid esters, polyethylene glycol fatty acid esters, polyhydric alcohol fatty acid esters, 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.

  Hydroxypropyl cellulose is used for the purpose of imparting adhesion to the writing surface, imparting ink viscosity, and imparting flexibility to the handwriting after drying, and suppressing the occurrence of whitening of the handwriting. Specific examples include Crucell L (molecular weight 95,000), G (370,000), M (850,000), H (1.15 million) (above, manufactured by Aqualon Co., USA), Nisso HPCSSL. Type (molecular weight 15,000-30,000), SL type (30,000-50,000), L type (550,000-70,000), M type (110,000-150,000), 1 type or 2 types or more, such as the same H type (250,000 to 400,000) (above, Nippon Soda Co., Ltd.) can be used. The amount used is 0.01 to 3.0% by weight, preferably 0.03 to 1.5% by weight, based on the total amount of the marking ink composition. When the amount used is small, there is no difference from the conventional case, and when the amount used is large, the handwriting becomes sticky or adheres to the writing surface and the erasability decreases. Also, the ink viscosity increases, and when the applicator is filled, it becomes difficult to eject the 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 hinder the solubility of hydroxypropyl cellulose can be appropriately selected and used.

  The method for producing the marking ink composition of the present invention comprises mixing the required amounts of each component described above, and mixing and dispersing 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. Can be obtained more easily.

Solmix AP-4 (mixed solution of ethanol 85.5%, isopropanol 13.4%, acetone 1.1%, manufactured by Nippon Kasei Kogyo Co., Ltd.) 49.8 parts Isopropanol 33.0 parts Crucell L (hydroxypropylcellulose) 0.29 parts BS-2 (polyoxyethylene (2) stearyl ether, manufactured by Nikko Chemicals Co., Ltd.)
2.0 parts CIO (cetyl isooctanoate, manufactured by Nikko Chemicals Corporation) 7.0 parts Fuji AS Blue 650 (processed pigment coated with blue pigment with polyvinyl butyral, manufactured by Fuji Dye Co., Ltd.) 8.0 parts Was stirred with a homomixer for 4 hours to obtain a blue marking ink composition.

Ethanol 48.0 parts Isopropanol 39.3 parts Crucell G (hydroxypropylcellulose, molecular weight 370,000, manufactured by Aqualon, USA)
0.3 part 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 0.0 part 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 marking ink composition.

Ethanol 47.0 parts Isopropanol 31.0 parts Isobutanol 5.0 parts Nisso HPC SSL (hydroxypropylcellulose, molecular weight 15,000-30,000, manufactured by Nippon Soda Co., Ltd.) 0.5 part Nonal 205 (Polyoxy) Ethylene nonylphenol ether, manufactured by Toho Chemical Co., Ltd.) 0.5 part TDP-2 (dipolyoxyethylene (2) alkyl ether phosphoric acid, manufactured by Nikko Chemicals Co., Ltd.) 2.0 parts IPM-EX (isopropyl myristate, 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 for 4 hours with a stirrer to obtain a black marking ink composition. Obtained.

  A red marking ink composition was obtained in the same manner except that Crucell G of Example 2 was Crucrucel M (hydroxypropylcellulose, molecular weight 850,000, manufactured by Aqualon, USA).

(Comparative Example 1)

A blue marking ink composition was obtained in the same manner except for the Crucell L of Example 1 except that Solmix AP-4 was added instead.

(Comparative Example 2)
A red marking ink composition was obtained in the same manner except that Denkabutyral # 4000-1 of Example 2 was replaced with 1.5 parts of Crucell G and 1.4 parts of isopropanol.

(Comparative Example 3)
A black marking ink composition was obtained in the same manner except that the amount of Nisso HPC SSL of Example 3 was 3.1 parts and ethanol was reduced instead.

  Test 1 was carried out using the inks prepared in Examples 1-4 and Comparative Examples 1-3. Moreover, these inks were filled in the applicator (EMWLM, manufactured by Pentel), and Test 2 was performed using this as a sample. The results are shown in Table 1.

Test 1
Comparison of whitening situation of handwriting Each ink was applied to a writing board (FB-115Wc, enamel plate surface, manufactured by KOKUYO Co., Ltd.) using an applicator (application thickness: 25 microns) under the conditions of 25 ° C. and 80%. After the dried film was covered with a transparent cellophane tape, the lightness of the film was measured with a color computer (NF777, manufactured by Nippon Denshoku Industries Co., Ltd.). The whitening state of the handwriting was confirmed in this comparison as an indicator that the higher the lightness, the more easily the handwriting looks white.

Test 2
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.

  As described above in detail, the marking ink composition for a writing board according to the present invention is a marking ink composition for a writing board in which whitening that occurs when writing on a writing board, particularly a white writing board, is suppressed.

Claims (2)

A marking ink composition for a writing board, comprising at least 0.01 to 3.0% by weight of hydroxypropylcellulose based on the total amount of pigment, lower alcohol, polyvinyl butyral, release agent, and ink. The marking ink composition for a writing board according to claim 1, wherein the hydroxypropylcellulose has a molecular weight of 600,000 or less.