JP2909775B2 - Water-based marking pen ink for writing boards - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

A large number of volatile organic solvent-based inks have been proposed as marking inks for writing boards. However, all of them have a problem of odor and safety during use. In order to solve these problems, water-based inks have recently been proposed (for example, JP-A Nos. 1-111174, 174577, and 188576).
And Japanese Patent Application Laid-Open Nos. 2-117975 and 124985) are common to these water-based inks, but the handwriting written on the ink-impermeable writing board surface is based on the volatile organic solvent-based ink. Drying is slower than handwriting of ink, and wiping is often performed in an undried state, causing a problem that the ink spreads on the plate surface and contaminates the plate surface. In order to accelerate the drying of the ink, a means of adding a volatile organic solvent such as ethyl alcohol has been proposed. However, in practice, a sufficient effect can be obtained unless the amount is relatively large (20 to 30% by weight or more). However, this leaves a problem for safety, which is the main purpose of the water-based ink.

[0002]

SUMMARY OF THE INVENTION The present invention is an aqueous-based ink in which all or most of the liquid component is water and does not substantially exhibit a flash point.
Immediately after drying, of course, even in an undried state, even after a lapse of time, it aims to provide a water-based marking pen ink for a writing board that gives a handwriting that can be easily and cleanly wiped off with a dry eraser such as cloth or soft paper. is there.

[0003]

The marking pen ink for a writing board according to the present invention comprises a pigment and a releasing agent dispersed or dissolved in an aqueous vehicle, and the releasing agent comprises (A) a dicarboxylic acid and a polyalkylene glycol monomer. A combination of at least one compound selected from alkyl ether diesters, fatty acid and polyalkylene glycol monoalkyl ether esters, polyalkylene glycol and fatty acid diesters, and polyether-modified silicone oils, and (B) silicone powder.

As the pigment, pigments generally used in marking inks and printing inks are used. Specifically, azo, anthraquinone, condensed polyazo, thioindigo, metal complex salt, phthalocyanine, perinone / perylene, Organic pigments such as dioxazine-based and quinacridone-based pigments, and inorganic pigments such as carbon black and iron oxide are used.
It is used in the range of 10 to 10% by weight.

[0005] Among the above release agents, the compounds described in Group A (hereinafter referred to as release agent A) are referred to as release agents A
The components that make up are described.

The dicarboxylic acids include malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, dodecandioic acid, tridecandioic acid, tetradecandioic acid, hexadecandioic acid, and octadecandioic acid. , Eicosantioic acid, docosantioic acid, fumaric acid, maleic acid, malic acid, tartaric acid, phthalic acid and the like.

As fatty acids, caproic acid, caprylic acid,
Capric acid, lauric acid, myristic acid, palmitic acid, stearic acid, arachiic acid, behenic acid, montanic acid, oleic acid, erucic acid, linoleic acid, linoleic acid, ricinoleic acid, isocapric acid, isolauric acid,
Examples include isomyristic acid, isopalmitic acid, isostearic acid, isoarachinic acid, oxystearic acid, and the like.

Polyalkylene glycols include polyethylene glycol and polypropylene glycol, and monoethers thereof include methyl, ethyl, propyl and butyl ether.

The polyether-modified silicone oil is a hydrophilic silicone oil of a type in which a part of the methyl groups of polydimethylsiloxane is substituted with a polyoxyalkylene group.

The release agent A is contained in the ink composition in an amount of 0.5 to 2
It is used in an amount of 0% by weight, preferably 2 to 10% by weight.

The silicone powder of the release agent B is selected from a powder of a silicone resin, a powder of a silicone elastomer, and a powder obtained by supporting a silicone oil at a high concentration on an inorganic carrier. Silicone powder accounts for 0.1 to 30% by weight, preferably 0.5 to 30% by weight of the ink composition.
It is used in the range of 10 to 10% by weight.

The aqueous vehicle comprises water and a water-soluble resin and / or a surfactant for dispersing the pigment or the silicone powder in water. Examples of the water-soluble resin include polyvinylpyrrolidone, partially saponified polyvinyl acetate, polyvinyl alcohol, polyvinyl acetal, a water-soluble acrylic resin, a water-soluble cellulose derivative, gum arabic, and the like. %, Preferably in the range of 0.5 to 10% by weight. Examples of the surfactant include a nonionic, anionic or cationic surfactant, a polymer surfactant, and a fluorine-based surfactant which are usually used for dispersing a pigment. , Preferably 0.1
To 3% by weight. Other additives such as small amounts of lower alcohols such as ethanol and propanol,
Preservatives, rust inhibitors, defoamers, pH adjusters and the like are used as necessary.

[0013]

EXAMPLES Table 1 shows the compositions of the inks of the examples.

[Table 1] The numerical values of the compositions in the table are expressed in parts by weight, and the contents of the raw materials are described below according to the note numbers. (All numerical values are% by weight.) 1. Aqueous paste containing 20% carbon black and 6% polyvinyl alcohol 2. Aqueous paste containing 10% indanthrone blue (CI pigment blue 60) and 3% polyvinyl alcohol Paste 3. Aqueous paste containing 20% Lake Red C (CI Pigment Red 53: 1), 7% polyvinyl alcohol 4.20% carbon black, 8% nonionic surfactant (polyoxyethylene nonyl phenyl ether) , 2
4. Aqueous paste containing 5% anionic surfactant 5. Silicone elastomer powder (spherical, particle size distribution: 1.0 to 2.1 μm) Silicone resin powder (Tospearl 120; Toshiba Silicone Co., Ltd.) 7.8% aqueous silicone resin powder dispersion (X-5
2-660; Shin-Etsu Chemical Co., Ltd.) 8. Powder in which silicone oil 12500CS is supported on an inorganic carrier (Trefle F-250; Dow Corning Toray Silicone Co., Ltd.) Silicone resin powder (spherical, particle size distribution 0.
(3 to 0.7 μm) 10. 10. Adipic acid triethylene glycol monomethyl ether diester 11. Oleic acid triethylene glycol monobutyl ether ester 12. Isocaprylic acid diester of polyethylene glycol 400 Polyether-modified silicone oil (L-760
2; Nippon Unicar Co., Ltd.) Polyoxyethylene alkyl phenyl ether 15. 15. Phosphoric acid esters of polyoxyethylene alkyl phenyl ether 16. Polycarboxylic acid type polymer activator (Demoll EP; Kao Corporation) 17. Fluorinated surfactant (Surflon S-141; Asahi Glass Co., Ltd.) Partially saponified polyvinyl acetate (SMR-10M;
Shin-Etsu Chemical Co., Ltd.) 19. Hydroxypropyl cellulose (HPC-L; Nippon Soda Co., Ltd.)

Each example ink was prepared according to the following formula. Example 1 A predetermined amount of a resin and water are mixed and stirred by a stirrer until the resin is dissolved. Next, a silicone powder and a surfactant are added, and the mixture is treated with a sand mill for 1 hour. Thereafter, the pigment paste was charged, mixed, and stirred with a disper for 1 hour. Further, an additive was added and stirring was continued for 1 hour to obtain a sample ink. Example 2 A predetermined amount of a silicone powder, a surfactant and water are mixed and treated with a sand mill for 1 hour to obtain a dispersion. The pigment paste was added to the dispersion, and the mixture was stirred for 1 hour with a disper. Then, an additive was added and the mixture was further stirred for 1 hour to obtain a sample ink. Example 3 All components were mixed and stirred with a disper for 1 hour to obtain a sample ink. Examples 4 and 5 Prepared according to the ink formulation of Example 1.

[0015] Three prior art water-based inks were then prepared as comparative inks for the samples of the comparative tests. Comparative Example 1 An ink having a composition obtained by removing the silicone powder from the ink composition of Example 1 (an ink described in JP-A-2-117975) Comparative Example 2 An ink containing a polyether-modified silicone oil and a water-insoluble inorganic powder as a release agent (JP-A-1-188576)
Comparative Example 3 An ink described in Japanese Patent Application Laid-Open No. H10-150, in which 10 parts of an aqueous dispersion of 25% quinacridone pigment was used instead of lactimine color black as the water-dispersible pigment. Ink containing water-soluble inorganic powder (Japanese Unexamined Patent Publication (Kokai) No. 2-124985)
The inks of Example 1 described in the above-mentioned publications (10 parts of a 20% aqueous solution of sullen blue were used in place of the lactimine color scarlet for the water-dispersible pigment) were prepared in accordance with the description in each publication.

Test of Sample Ink Performance (Erasability of Handwriting on Writing Board) Test Each test ink was filled into a marking pen, and a predetermined line was drawn on the engraved writing board. The erasability afterwards was examined. The erased state was observed after rubbing 5 times with a 100 g load using a dry cloth. The test results are shown in Table 2.

[Table 2] The evaluation symbols in the table are as follows. Erasability of handwriting in the undried state ○ Almost completely erased △ Slightly contaminated surface × Stained surface is extremely contaminated Erasability of dry handwriting ○ Almost completely erased △ Slight on surface Traces remain

[0017]

The handwriting on the writing board surface with the water-based marking pen ink according to the present invention is contaminated by the excellent lubricating action of the silicone powder that is movable in the handwriting even when wiped off in the wet state. Can be wiped off cleanly by rubbing with a dry eraser. In addition, mainly release agent A which is in the handwriting and inhibits the adhesion of the handwriting to the plate surface
In the same manner, handwriting which dries on the plate surface and has passed for a long time can be easily erased similarly by rubbing with a dry eraser. While maintaining the erasure performance of dry handwriting required for writing board ink in this way, when the undried handwriting on the writing board surface seen in the conventional aqueous base ink is rubbed with an erasing material The problem of plate surface contamination that occurred was eliminated.

Claims (1)

(57) [Claims] 1. A marking pen ink for a writing board in which a pigment and a release agent are dispersed or dissolved in an aqueous vehicle, wherein the release agent is (A) a diester of dicarboxylic acid and polyalkylene glycol monoalkyl ether, and a fatty acid and polyester. Water-based marking for a writing board, which is a combination of at least one compound selected from an ester of an alkylene glycol monoalkyl ether, a diester of a polyalkylene glycol and a fatty acid, and a polyether-modified silicone oil, and (B) silicone powder. Pen ink.