JPH01318074A - Ink for writing utensil - Google Patents

Abstract

PURPOSE:To obtain an ink for writing utensil which is odorless and nontoxic, can give a writing utensil which, even when left uncapped for a long time, does not become scratchy and can give a writing peelable in a continuous film on a resin surface by specifying the emulsion so that it may satisfy specified requirements for a solid content, a viscosity and a surface tension. CONSTITUTION:This ink for writing utensil comprises an emulsion used as an aqueous peelable coating agent (e.g., polyvinyl acetate emulsion), a colorant, a surfactant used as a surface tension modifier, a polyglyceroil fatty acid ester (e.g., decaglycerol monolaurate) and water, wherein the solid content of said emulsion is 5-40wt.% based on the total weight of the ink for writing utensil, the viscosity is 60cP/25 deg.C or below, and the surface tension is 20-38dyn/cm. This ink is freed from odor and toxicity due to an organic solvent, can give a writing utensil which, even when left uncapped for a long time, does not become scratchy due to drying of its pen point, is good in retention of a writing put on a non-absorbing surface, and can give a writing which can be easily and continuously peeled from a resin plate or a coated surface.

Description

Detailed Description of the Invention (Field of Industrial Application) The present invention relates to a water-based ink for writing instruments, and more particularly, the present invention relates to a water-based ink for writing instruments, and more specifically, the handwriting on a non-absorbing surface has the performance of a strippable paint, and it The present invention relates to a water-based ink for writing instruments that can be ejected from a writing instrument having a molded nib or the like.

(Prior art) Conventionally, strippable paints are made of ethyl cellulose,
Organic solvent-soluble compositions such as polyvinyl acetate resin, butyral resin, vinyl acetate-acrylic acid ester copolymer, emulsion-type compositions such as polyvinyl acetate emulsion, butyral resin emulsion, or polyvinyl alcohol Water-soluble type compositions are known, such as temporary surface protection for automobiles, aircraft, mechanical parts, metal household appliances, iron and non-ferrous metal products, glassware, plastic molded products, rubber products, etc. It is a coating material whose film can be completely removed just before using these products, and it is applied by spray painting, brush painting, dipping, etc. in the same way as regular paints. .

Recently, strippable paints have been added with pigments and/or dyes and are being used as colored strippable paints for decorative purposes such as glass windows, but conventional painting methods such as spray painting and brush painting Although it is possible to paint large areas in color, it is difficult to paint details and fine patterns.

On the other hand, for detailed painting and fine pattern painting, ordinary oil-based paint markers can be used successfully, but these are difficult to remove, and when erasing, it is necessary to use an organic solvent used in the ink or an oil-based paint marker. It is quite troublesome, such as having to use a solvent that is soluble in the ink.
Because organic solvents were used, their odor and toxicity were problems.

In addition, as an oil-based ink for writing instruments that can be erased on non-absorbent surfaces, there is marker ink for whiteboards, but this makes the adhesion of handwriting to the whiteboard extremely low, making it difficult to easily remove handwriting from paper, cloth, etc. Therefore, it is erased even by touching it with a hand or finger, and the retention of handwriting is extremely weak. Furthermore, in order to weaken the adhesion, the handwriting itself is erased. Since the cohesive force is kept low, when erasing, the eraser dust (powder) of the handwriting scatters and contaminates hands, clothes, and surrounding areas, and since it uses an organic solvent, it cannot be used with oil-based paint markers. It had similar odor and toxicity problems.

Therefore, the inventor of the present invention has developed a method that has no odor or toxicity, improves the retention of handwriting (paint film) on a non-absorbent surface, makes it possible to peel it off completely continuously in a film form at any time, and has fine details. We have previously proposed an ink for writing instruments that can be ejected from writing instruments that have a fiber nib or a resin-molded nib so that painting and fine patterns can be colored (Japanese Patent Application Laid-open No. 179478/1983).

(Problem to be Solved by the Invention) However, if a writing instrument using the above-mentioned ink is left without a cap for a long time, since the ink uses a resin emulsion, the solvent in the ink will evaporate and There was a problem in that a resin film was formed on the pen tip, making handwriting more likely to become blurred.

(Means for Solving the Problems) Therefore, the present invention aims to improve the above-mentioned problems, and provides an emulsion used as an aqueous peelable coating material, and a coloring agent.

An ink for a writing instrument comprising at least a surfactant used as a surface tension modifier, a polyglycerin fatty acid ester, and water, and having the following conditions. The gist is an ink for writing instruments that allows continuous peeling of handwriting.6 <Conditions> - The solid content of the emulsion is 5 to 40% by weight based on the total amount of ink for writing instruments.

-Viscosity must be 60 cps/25°C or less.

・Surface tension is 20-38 dyne/cm
To be.

The present invention will be explained in detail below.

The emulsion used as the aqueous strippable coating material is a binder for the ink and exhibits the strippability of the ink, and is used as a strippable paint. Known acrylic acid ester emulsion,
Styrene-butadiene resin emulsion, butyral resin emulsion, ethylene-vinyl acetate emulsion,
Styrene-acrylic acid ester emulsion etc. can be used.

In order to maintain good handwriting (paint film) and enable continuous peeling, it is preferable that the solid content of the emulsion in the ink is high, but if the viscosity of the ink is too high, the ink will bleed from the pen tip. It is preferable for the emulsion to have a low viscosity since this will reduce discharge. Taking the above points into consideration, and as a result of various studies, it is necessary that the solid content of the emulsion is 5 to 40% by weight based on the total amount of ink for writing instruments. This is because if it is less than 5% by weight, the retention and continuous releasability of handwriting (coating film) will be poor, and if it exceeds 40% by weight, the ink discharge will be reduced. Further, in order for the emulsion in the ink to form a continuous coating film at least at room temperature after writing, it is desirable that the MFT (minimum film forming temperature) is 25° C. or lower. In addition, a small amount of a plasticizer or a film forming agent (for example, a high boiling point solvent such as butyl carpitol, butyl carpitol acetate, hexylene glycol, etc.) can be appropriately added in order to lower the MFT and improve film forming properties. .

As the coloring agent, known dyes and/or pigments conventionally used in writing instrument inks can be used, but examples of pigments include cellulose acetate, polymethyl methacrylate, nylon,
Resin powder such as polystyrene, polyethylene, polypropylene, benzoguanamine resin, carbon black,
Black pigments such as aniline black and iron black; yellow pigments such as Hansa yellow, benzidine yellow, and permanent yellow; red pigments such as Bengara, cadmium red, permanent red, and lake red; Composite pigments can be obtained by mixing and grinding pigments such as blue pigments, green pigments such as chrome green, cobalt green, and phthalocyanine green.

It is particularly preferably used, and the amount used is preferably 3 to 30% by weight based on the total amount of the ink.

The polyglycerin fatty acid ester, which is a feature of the present invention, is used to prevent handwriting from becoming blurred even when left without a cap for a long time. Acids, esters such as isostearic acid, oleic acid, lylunic acid, and esters of hexaglycerin such as lauric acid, myristic acid, stearic acid, isostearic acid, oleic acid, and lylunic acid are used, and the amount used is 0.3
~10% by weight is preferred.

Surfactants as surface tension adjusting agents adjust the surface tension of ink and enable the ink to be applied well to various surfaces. , amphoteric surfactants can be used, and the surface tension of the ink is 20 to 38 d y n as described later.
The amount used may be adjusted so that it falls within the range of e/cm.

Next, to explain the physical properties that the ink for writing instruments of the present invention should have, the surface tension is 20 to 38 dyne/cm;
The viscosity must be 60 cps/25°C or less.

That is, when the surface tension is less than 20 dyne/cm, handwriting tends to bleed when used as a general marker on paper, cloth, etc., and when it exceeds 38 dyne/cm, the surface to be coated is made of polyethylene resin, polypropylene, etc. If the resin has low polarity such as resin, the leveling property of the handwriting will be poor and it will be easy to repel, and the viscosity will be 6.
This is because if the temperature exceeds Q c p s / 25° C., ink ejection from the resin pen nib or resin molded nib becomes poor, and handwriting tends to become blurred.

In addition to the above-mentioned components, there are also dispersants and wetting agents that help disperse pigments, silicone oil emulsions that improve releasability, and 1. , -720. L-7001, L-7002,
Water-soluble silicone block copolymers such as L-7600, L-7604 (manufactured by Nippon Unicar), wax emulsions, Pluronic L-44, Pluronic L-61
, L-62. Same L-64. Same L-101, Same L-12
1, P-84, P-103, F-68, F-6
8. F-88, (manufactured by Asahi Denka Kogyo ■), Emulgen PP-150, PP-230, PP-250, P-290 (Kao Soap Nt!5), Pronon 1
02, 104, 15, 201, 204, 20
8 (more than 1 manufactured by Nippon Oil & Fats), Newport PE-61,
PE-68, PE-71, PE-74, PE-
85, polyoxyethylene polyoxypropylene block polymers such as PE-88 and PE-108 (manufactured by Sanyo Chemical Industries, Ltd.), Ftardient 200,
251 (or above, ■NEOS*), F-TOP BF12
1. EF122A, EF122B, EF123B
, EF352, EF501 (manufactured by Shinshu Kasei), Megafac F~142D, F-144D, F
-171, F-1'17 (manufactured by Dainippon Ink & Chemicals) and other water-soluble ethylene oxide-added fluorinated surfactants; release agents; plasticizers for improving the physical properties of coating films; You can also add small amounts.

The ink for a writing instrument of the present invention is formed into an ink by mixing and dissolving or mixing and dispersing the above-mentioned components, and then used by filling it into a writing instrument having a fiber nib or a resin-molded nib.

(Function) The ink for writing instruments according to the present invention uses polyglycerin fatty acid ester as an essential component of the ink, so if the pen is left without a cap for a long time, the polyglycerin fatty acid ester will form a thin film on the nib. This prevents the formation of a resin film on the pen tip by suppressing the evaporation of solvent (particularly water) from the pen tip, which is thought to prevent blurring of handwriting.

(Examples) The present invention will be explained in more detail based on Examples below.
"Parts" indicate "parts by weight."

11L Polysol PS 20 parts (manufactured by Showa Kobunshi ■, polyvinyl acetate emulsion, solid content 50%
, MFT12°C) MA-100, 8 parts (manufactured by Mitsubishi Chemical Corporation, carbon black, pigment) Span20 1 part (manufactured by Kao Atlas ■, nonionic surfactant.

Surface tension regulator) Decaglin 1-L 3 parts (manufactured by Nikko Chemicals ■, Decaglyceryl monolaurate) Water 6
8 parts Butyl carpitol acetate 3 parts (film forming aid) 2 parts Digit C-20 (manufactured by Gooh Kagaku Kogyo ■, wax emulsion, peelability imparting agent) M i s s 22 1 part (SC
(manufactured by HWEGMANN, West Germany, wetting and dispersing agent) Among the above components, the pigment was dispersed in water and the wetting and dispersing agent in a conventional manner, and then other components were mixed to obtain a black ink.

Daiarashi Primal AC-38230 parts (manufactured by Nippon Acrylic Chemical, acrylic acid ester emulsion, solid content 50%, MFT 7°C) Phthalocyanine blue (pigment) 6 parts NIKKO
L NP-51 parts (manufactured by Nikko Chemicals n, anionic surfactant, surface tension regulator) Decagrin 2-8 8 parts (manufactured by Nikko Chemicals n, decaglyceryl distearate) Water 6
7 parts L-720 2 parts (manufactured by Nippon Unicar, water-soluble silicone block copolymer, release agent) Hexylene glycol (film-forming aid) 2 parts Dispe
rbyk 1 part (BYK-Malli
(manufactured by Nckrodt, West Germany, wetting and dispersing agent) A blue ink was obtained using the above ingredients in the same manner as in Example 1.

Tairyu Kitachi Policy/L/EVA P-120 part (Showa Kobunshi H
Ethylene-vinyl acetate emulsion, solid content 50%
, MFT3℃) Kronos KR-38012 parts (Titan Kogyo ■, titanium oxide, pigment) NIKKOL
SLS 1 part (manufactured by Nikko Chemicals,
Anionic surfactant, surface tension regulator) Hexagrin 1-L 3 parts (manufactured by Nikko Chemicals ■, hexaglyceryl monolaurate) Water
60 copies Megafuck F-142D 1 copy (
Dainippon Ink Chemical Co., Ltd., water-soluble ethylene oxide-added fluorine-based surfactant, release agent) Hexylene glycol 2.5 parts (film-forming aid) Disperbyk 1.5 parts (BYK-
(Manufactured by Mallinckrodt, West Germany, wetting and dispersing agent) A white ink was obtained without using the above ingredients in the same manner as in Example 1.

Lost Storm Sot Policy 7L/EVA P-150 Part (Showa Kobunshi ■
Ethylene-vinyl acetate emulsion, solid content 50%
, MFT3℃) Crystal violet (dye)
10 parts Emulbon T-201, 5 parts (manufactured by Toho Chemical Industry ■, nonionic surfactant, surface tension modifier) Hexagrin 1-M 1 part (manufactured by Nikko Chemicals ■, hexaglyceryl monomyristate) Water 4
0 parts Megafac F-142D 1 part (manufactured by Dainippon Ink & Chemicals ■, water-soluble ethylene oxide-added fluorine surfactant, release agent) Hexylene glycol 2.5 parts (film-forming aid) Disperbyk 1. Part 5 (BYK-
(manufactured by Mallinckrodt, West Germany, wetting and dispersing agent) The above components were mixed and stirred to obtain a purple ink.

Comparative Examples 1 to 4 were inks obtained in the same manner as in Examples 1 to 4 above, except that the polyglycerin fatty acid ester was removed and its water was added. .

(Effects) The physical properties of the inks obtained in Examples 1 to 4 and Comparative Examples 1 to 4 and the nib drying properties of writing instruments with fiber nib filled with each ink are shown in Table 1. As shown.

When the inks of Examples 1 to 4 above were filled into a writing instrument with a fiber nib and written on a non-absorbing surface such as a glass plate, aluminum plate, iron plate, polyethylene plate, etc., the handwriting was clear and after drying, the handwriting was I rubbed it, but it didn't go away. Furthermore, when cellophane tape was attached to one end of the handwriting and removed after two months, the handwriting easily and continuously turned into a film and peeled off. Also, when written on paper, no bleeding occurred.

Incidentally, although a writing instrument having a fiber nib was filled with a commercially available strippable paint, no paint was discharged. Also, when I wrote on a non-absorbent surface with a commercially available oil-based pigment type whiteboard marker and rubbed it with one finger after drying, the handwriting disappeared.

Table 1 Book 1: Surface tension was measured using a Junoui surface tension meter.
Measured at 5°C.

Book 2: Viscosity was measured at 25°C using a B-type viscometer.

*3: Pen tip dryness resistance is measured when the writing instrument is heated at 25℃ and humidity 40%.
After being left in an environmental test chamber for 48 hours, writing was performed and the handwriting was observed.

O: Uniform and good handwriting Δ: Slightly blurred in the early stages of writing ×: Blurred As explained in detail above, the ink for writing instruments of the present invention has no odor or toxicity due to organic solvents, and can be used for a long time without a cap. Even if left for a long time, the pen tip will not dry and the handwriting will not become blurred, and handwriting written on a non-absorbent surface will retain well, and handwriting on a resin plate or painted resin surface will be easy and continuous. It is removable.

Patent applicant: Bentel Co., Ltd.

Claims (1)

[Claims] An emulsion used as an aqueous strippable coating;
An ink for writing instruments comprising at least a colorant, a surfactant used as a surface tension regulator, a polyglycerin fatty acid ester, and water, having the following conditions:
An ink for writing instruments that allows continuous peeling of handwriting. <Conditions> - The solid content of the emulsion is 5 to 40% by weight based on the total amount of writing instrument ink. -Viscosity must be 60 cps/25°C or less. -Surface tension is 20 to 38 dyne/cm.