JPH0468071A - Ink for marking pen used on writing board - Google Patents

Abstract

PURPOSE:To obtain the title ink which gives a readily dry-erasable writing, by mixing a coloring agent comprising a colored polymer which is a copolymer made by using maleic anhydride as one component and dyed with a cationic dye, a specified agent for imparting erasability, a resin, and a solvent. CONSTITUTION:A copolymer (a) made by using maleic anhydride as one component (e.g. methyl vinyl ether/maleic anhydride copolymer) and a cationic dye (b) selected from a basic dye classified in the Color Index or a dye based thereon are dissolved in a solvent (c) to bring into contact with each other, giving a coloring agent (A) comprising a colored polymer which is the component (a) dyed with the component (b). 1-30wt.% component A is mixed with 0.5-20wt.% agent for imparting erasability, selected from a dicarboxylic acid diester of polyalkylene glycol, a polyalkylene glycol ether ester of fatty acid, and a fatty acid diester and citric acid triester of polyalkylene glycol, a resin, and an organic solvent.

Description

DETAILED DESCRIPTION OF THE INVENTION Field of Industrial Application The present invention relates to marking pen ink for writing boards, and more particularly, handwriting written on a writing board made of a surface material impermeable to ink can be printed on a dry cloth or This invention relates to a marking pen ink for writing boards that has the ability to be easily erased by rubbing with an erasing material such as soft paper.

2. Description of the Related Art Many proposals have been made regarding this type of marking pen ink for writing boards (for example, Japanese Patent Publication No. 61-1989).
No. 25755, JP-A-61-246272, JP-A-6
4-79280). Although pigments are used as colorants in the inks of these inventions, they need to be dispersions with low viscosity in order to obtain sufficient interflow from the pen body. However, it is difficult to maintain stable dispersion over a long period of time with such a low viscosity dispersion.
Due to the distribution period from manufacture to use, and the long time between use and use, pigment sedimentation within the marking pen may cause poor writing due to clogging of the pen body, or if the pigment concentration within the pen body becomes high. There are many problems such as deterioration in erasability of handwriting.

On the other hand, inks that use dyes as colorants have the problem that the dye in the handwriting tends to stain the writing board material or get into minute recesses on the surface, contaminating the writing board surface.

Problems to be Solved by the Invention The present invention aims to provide a marking pen ink for a writing board that gives handwriting that is easy to dry erase on the writing board surface and is stable without coloring agent settling for a long period of time.

Means for Solving the Problems The marking pen ink for writing boards of the present invention comprises a colored polymer erasability imparting agent made by dyeing a cationic dye to a copolymer containing maleic anhydride as an essential component, a resin, and Contains an organic solvent.

Specific examples of the copolymer include diisobutylene-maleic anhydride copolymer, styrene-maleic anhydride copolymer, methyl vinyl ether-maleic anhydride copolymer,
Examples include ethylene-maleic anhydride copolymer.

Cationic dyes are selected from basic dyes classified as color indexes or dyes based on them, and their chemical structures include oxazine, doarylmethane, xanthine, azine, monoazo, disazo, cyanine, methine, thiazole, ketoimine, It is a dye with an acridine or thiazine structure.

The colored polymer is obtained by dissolving the copolymer and the dye in a solvent at room temperature or under heating and bringing them into contact with each other, thereby dyeing the maleic acid portion of the copolymer with the dye. The colored polymer may be separated from the solvent, purified, and used in the form of a powder, but if the solvent is subjected to ink cutting, it can also be prepared into an ink as it is without separation.

The colored polymer is used in the ink composition in an amount of 1 to 30% by weight, preferably 2 to 10% by weight.

The erasability imparting agent is a dicarboxylic acid polyalkylene glycol diester represented by the following general formula (1), - a fatty acid polyalkylene glycol ether ester represented by the mathematical formula (2), - a fatty acid polyalkylene glycol ether ester represented by the mathematical formula (3). It is a compound selected from fatty acid diesters of polyalkylene glycols and citric acid triesters represented by formula (4).

General formula (11% formula% General formula (2) R' COO-(C[IRICHR20), I-R-
Formula (3) %Formula% General formula (4) Here, X is an alkylene group, alkenylene group, or phenylene group having 1 to 34 carbon atoms, RIIRl is a hydrogen atom or a methyl group, and R is an alkyl group having 1 to 30 carbon atoms. or an aryl group, R'' is an alkyl group having 5 to 29 carbon atoms, R'' is an alkyl group, alkenyl group, hydroxyalkyl group, or hydroxyalkenyl group having 1 to 29 carbon atoms, and n is 1 to 29 carbon atoms.
The number 20 and Y each represent a hydrogen atom or an acetyl group.

In other words, -ooc-x-c in formula (1)
oo- is a dicarboxylic acid residue having 3 to 36 carbon atoms, specifically malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, superric acid, azelaic acid, sebacic acid, dodecanniic acid, tridecanniic acid, tetradecanoic acid,
It is an acid residue such as hexadecanoic acid, octadecanoic acid, eicosanniic acid, docosaniic acid, fumaric acid, maleic acid, malic acid, tartaric acid, phthalic acid, etc., and R'CO in formula (2) has 6 to 30 carbon atoms. is an acyl group, -R"CO in formula (3) is an acyl group having 2 to 30 carbon atoms,
Specifically, caproyl, capryloyl, cabrinoyl,
Groups such as lauroyl, myristroyl, valmitoyl, steacoyl, aracoyl, behenoyl, montanoyl, oleoyl, ercoyl, lilnoyl, υnoloyl, ricinoloyl, isocaprinoyl, inlauroyl, isomyristoyl, isobalmitoyl, isostearoyl, isoaracoyl, oxystearoyl, etc. can give.

The erasability imparting agent selected from these compounds is used in the ink composition in an amount of 0.5 to 20% by weight, preferably 2 to 10% by weight. Inks containing less than 0.5% by weight do not have sufficient erasability of handwriting on the writing board surface;
If the ink exceeds the viscosity, it will not be possible to obtain a smooth ink flow.

The resin is blended to provide handwriting with an appropriate thickness that is temporarily fixed to the surface of the writing board, and specifically includes cellulose derivatives such as ethyl cellulose, carboxymethyl cellulose, hydroxypropyl cellulose, and acetyl cellulose, and vinylpyrrolidone-acetic acid. Vinyl copolymers, polyvinyl butyral, vinyl chloride-vinyl acetate copolymers, vinyl polymers such as polyvinyl acetate, arylsulfonamide-formaldehyde condensation resins, styrene-maleic acid half ester copolymers, polyacrylic esters, etc. can give.

The organic solvent is a volatile solvent that dissolves or disperses the colored polymer, erasability imparting agent, and resin. glycol monomethyl ether), butyl glycol, propylene glycol monomethyl ether, glycol ethers such as propylene glycol monoethyl ether, esters such as butyl acetate, ethyl propionate, ethyl acetate, ketones such as methyl ethyl ketone, methyl isobutyl ketone, xylene, etc. N-methyl-2-pyrrolidone, 1,3-
High boiling point solvents such as dimethyl-2-imidazolidinone, dimethyl sulfoxide, and γ-butyrolactone are also used auxiliary.

Furthermore, it suppresses bleeding and repelling of ink on the writing board surface,
A surfactant is sometimes used for the purpose of uniformly distributing the erasability imparting agent in the handwriting and improving the peeling of the handwriting from the board surface. Specific examples of such surfactants include sulfuric acid alkyl ester salts, alkylbenzene sulfonates, alkylnaphthalene sulfonates, phosphoric acid alkyl ester salts, polyoxyethylene alkyl (or aryl) ether sulfate esters, polyoxyethylene alkyl (
or aryl) ether phosphoric acid ester, polycarboxylic acid salt, formaldehyde condensate of naphthalene sulfonic acid, polyoxyethylene alkyl (or aryl) ether, polyoxyethylene fatty acid ester, polyoxyethylene sorbitan fatty acid ester, glycerin fatty acid ester, fatty acid alkanol Amide, fatty acid alkylolamide ethylene oxide adduct, alkyl amine salt, quaternary ammonium salt, alkyl betaine, amine oxide, alkylimidacillin, polyether modified silicone, polyoxyethylene perfluoroether, perfluoroalkyl sulfonate, etc. are used in the ink composition in an amount of less than 10% by weight, preferably less than 2% by weight.

Function: Since the colored polymer exists in a dissolved state in the ink, it is maintained stably without settling over time unlike pigments. Furthermore, because the applied dye is dyed to the copolymer and the active dyed area is masked, and the colored polymer itself is a huge molecule, it may stain the surface of the writing board or It will not get into the minute holes in the surface and contaminate the board surface.

Furthermore, the combination of the colored polymer and the erasability imparting agent produces handwriting that does not adhere strongly to the surface of the writing board and is easily erased by light rubbing with a dry erasing material.

Example +11 Preparation of colored polymer 1-1) 500 m equipped with a stirrer, reflux condenser, and thermometer
200 g of methyl ethyl ketone in 40 flasks.

12 g of methyl vinyl ether-maleic anhydride copolymer (Gantresotsu AN-119, manufactured by GAF), chrysoidine base (Neshitune Orange Base 206BA)
(manufactured by SF) was added, stirred at room temperature for 1 hour, and dissolved.
The temperature was gradually raised and stirring was continued at 70 to 80°C for 10 hours.

After the treatment, the solvent was distilled off using a rotary evaporator and dried to obtain colored polymer A.

1-2) Add 200 g of ethanol and 4 g of Victoria Blue (C, 1,44045) to the above-mentioned apparatus, and stir for 1 hour at room temperature to dissolve. Then, the styrene-maleic anhydride copolymer (Sflip Set 520.
(manufactured by Monsando Kasei Co., Ltd.) was gradually added thereto, and the temperature was gradually raised to 70 to 80° C. for 10 hours. Then add ethanol and total! 250g, 8% of colored polymer B
An ethanol solution was obtained.

1-3) Rhodamine 6GCP (C,1,4
5160), methyl vinyl ether as a copolymer
An 8% ethanol solution of colored polymer C was obtained using a maleic anhydride copolymer in the same manner as in 1-2).

(2) Preparation of ink Table 1 shows the compositions of the example ink and the comparative example ink. Composition numbers represent parts by weight.

2-1) Preparation method Predetermined amounts of colorant, solvent, and resin are weighed, mixed, and stirred at room temperature for 2 to 5 hours. Next, an erasability imparting agent and surfactant are added, and the mixture is further stirred for 1 hour. A sample ink was obtained.

2-2) Explanation of Comparative Example Comparative Example 1 is an example in which a solvent dye was used in place of the coloring agent in Example 1.

Comparative Example 2 is a known method using a pigment as a coloring agent (Japanese Unexamined Patent Publication No. 61
-246272 publication) formulation example.

Comparative Example 3 is a known method using a pigment as a coloring agent (Japanese Unexamined Patent Publication No. 64
-79280 publication) formulation example.

2-3) Explanation of raw materials used (according to note numbers in Table 1) ■
Black dye (Paris First Blank 3806 Orient Chemical Industry) C,1,5olvent Black 2
9 ■ Black processing pigment (Fuji AS Black, Fuji Color @)
Carbon black surface treated with polyvinyl butyral■ Black processed pigment (Microlith Black C-A).

(Ciba Geigy) Carbon black surface-treated with cellulose derivative ■～■ is an erasability imparting agent ■ Methyl diglycol stearate C+Js
sCOO-(CHzCHzO)z-CHi■ Butyl triglycol laurate C+ +HzsCOO
-(CHzCHzO) 3-C4H9■ Butyl glycol diester dodecanoate C4H*0CHzCHzO
OC (CHz) +. C00CH2CH! 0C4H9■
Isooctanoic acid diester C of polyethylene glycol 200? HISCOO(CH2CH2O)SOCC? HIS
■ S-LEC BL-2 (Tasui Chemical Industry ■) ■ Styrene-maleic acid half ester copolymer (Oxilac 5R-101, Nippon Shokubai Chemical Industry ■) [Phase] to [Phase] are surfactants [Phase] Poly Phosphate ester of oxyethylene (Plysurf A-2085, Daiichi Kogyo Seiyaku ($1) ■ Sulfate ester of polyoxyethylene (Hitenol N-17, Daiichi Kogyo Seiyaku ■) ■ Polyoxyethylene oleyl ether (Emuldan 40B, Kao side) (3) Performance evaluation 3-1) Initial erasability Fill a marking pen with each sample ink, draw a predetermined line on the writing board surface of the enamel, and use a dry cloth to write 100 g.
The erasability of the handwriting was tested by rubbing it 5 times with a load of 2.

3-2) Performance over time After each sample marking pen was left standing for one month in three positions: upright (pen tip facing upwards), horizontally, and inverted (pen tip facing downwards), the writing performance was evaluated by writing on a writing board. The color density and erasability of handwriting were investigated.

The test results are shown in Table 2.

Effects of the Invention The marking pen ink for writing boards of the present invention has good erasability of initial handwriting, and since the coloring agent is a polymer and is dissolved in the ink, the marking pen ink filled with the ink can be easily left unused. Regardless of the situation, it may settle or be unevenly distributed at the bottom of the marking ben, worsening the interflow from the pen tip, or
The coloring agent does not enter the fine pores on the board surface and contaminate the board surface. In other words, both the advantages of pigment ink (good erasability) and the characteristics of dye ink (stability over time) are exhibited.

Claims (1)

[Claims] In a marking pen ink for writing boards containing a colorant, an erasability imparting agent, a resin, and an organic solvent, the colorant is a colored polymer obtained by dyeing a cationic dye into a copolymer containing maleic anhydride as one component. The erasability imparting agent is a dicarboxylic acid polyalkylene glycol diester, a fatty acid polyalkylene glycol ether ester,
A marking pen ink for writing boards, characterized by being a compound selected from fatty acid diesters of polyalkylene glycols and citric acid triesters.