JPS58201864A - Aqueous ink for ball point pen - Google Patents

Abstract

PURPOSE:An aqueous ink for ball point pens, containing a specific mercaptobenzothiazole derivative, having improved abrasion preventing effect between metallic balls and tips and lubricity, and capable of giving good writing conditions. CONSTITUTION:An aqueous ink prepared by incorporating preferably 0.01-3wt% mercaptobenzothiazole derivative of formulas I and/or II (R is lower alkyl, H or halogen; M is H, NH4 or alkali metal; n is an integer 1-5), e.g. 3-mercaptobenzothiazole or an adduct thereof with 1-5 mole ethylene oxide, with an aqueous ink. EFFECT:Improved abrasion resistance even with tips made from a synthetic resin, e.g. polycarbonate, other than metal, and remarkably extended writing distances with smooth writing conditions.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a water-based ink for a ballpoint pen, and more particularly to a water-based ink for a ballpoint pen that has excellent lubricity and has a smooth writing feel.

Conventional water-based inks for ballpoint pens use glycol solvents, glycol ether solvents, and yv alcohol ether ester i-agents as evaporation inhibitors.

A water-soluble dye such as a direct dye, an acid dye, or a basic dye is dissolved in an aqueous solution of a water-soluble organic solvent such as an amine solvent, and a preservative and an anion are added as appropriate.

Alternatively, low viscosity water-based inks are made by adding nonionic surfactants, but these water-based inks lack lubricity and have high friction between the ball and the chip. 1 Synthetic resin or metal chips Abrasion occurs and the ball becomes loose, resulting in blurred handwriting and difficulty in memorizing smoothly.
When writing, abrasion noise occurs between the ball and the tip.

There was a problem that the writing quality was not smooth.

The present inventors aimed to solve the problems mentioned above.

The present invention was completed as a result of intensive research.

That is, the present invention provides water-based ink with the following general formula (I) and/or
The gist of the invention is a water-based ink for ballpoint pens containing a mercaptobenzothiazole derivative represented by (Ill).

(Rid, lower alkyl group, H1)-logen group 1M.

Indicates H, NH4, and alkali metal. ) (R is a lower alkyl group, L).logen group, n is.

Indicates an integer from 1 to 5. ) It is not clear why the water-based ink of the present invention has excellent lubricity and has the effect of preventing friction between the ball and the chip and preventing wear of the chip, but it is thought to be as follows.・Ru.

Mercaptobenzothiazole derivatives represented by general formulas (II and (II)) have a mercapto group, which is a polar group, and therefore chemically or physically adsorb to metals.As a result, the non-polar groups are directed outward. It is thought that a thin film formed on the metal surface lowers the coefficient of wear between the tip and the ball and has a lubricating effect.

The present invention will be explained in detail below.

Specific examples of the mercaptobenzothiazole derivative represented by general formula (I) include 3-mercaptobenzothiazole, 3-mercapto-methylbenzothiazole, 3-mercaptomethylbenzothiazole, and their ammonium salts and alkali metal salts. be.

Specific examples of the mercaptobenzothiazole derivative represented by the general formula (Ir) include 1 to 5 moles of ethylene oxide adduct of two-color mercaptobenzothiazole, and ethylene oxide 1 of 3-mercaptomethylbenzothiazole.
~5 molar adduct.

Examples include adducts of 6-mercaptochlorobenzothiazole with 1 to 5 moles of ethylene oxide.

These can be used alone or in combination, and if the amount used is 0.01 weight less than the total amount of water-based ink, the effect will not be noticeable, and if it is more than 6 weight parts, insoluble matter will remain in the ink. Tashi.

0.01 to 6 because the viscosity increases and ink discharge becomes poor.
A weight range is preferred.

Furthermore, most of the water-soluble dyes such as ordinary acid dyes, direct dyes, and basic dyes can be used as dyes that can be used as colorants in the ink of the present invention. The dyes are Mitsui Nylon Black GL (0,1,15711), Water Black Φ21 (0,1,15985, j2090.4274)
5 mixed dye), Nigrosine N B cone, (OL
I.

50420), Eosin FA (0,1,,45380
).

Eisenerythron (0,1,4543(] )l
Dictator 2 ji/(0, 1, 19140), 70 ki 5
- Shin PB (0,1,45410), Suminol Milling Yellow MR (0,1,22910L Brilliant Blue FOP (0,1,42090), Soluble Blue BO (0,1,42755), etc. Kayaras Black Gconc is a direct dye.

(0,1,35255), Direct Deep Black EX (O,1,50255), Direct First Black conc, (0,1,27720) + Direct First Black B (0,I.

35435), Diamond First Orange WS (0,1,29156), Direct Blue 2
13 (0,1,22610), 7 Talocyanine Pul G Conch (0,1,22311), and Direct Sky Blue 5 B (0,1,24400).

These can be used alone or in combination. or,
Auramine 0 (Cj, I.

Ba51c Yel low2) + Astrazone Yellow 7 GLL (0,T, Ba5ic Yellow
21) + Astrazone Golden Yellow G L (0
,1,Basic 6-Yellow 28), Astrazone Yellow Brown GG L (0,■-Ba'sic Ora
nge30).

Rodamiy 6 G CP (0,1,Ba5ic R
edl).

, 6 Rama Zenda Pace (0,1,Ba5ic几ed9
) + Methyl violet (0,1, Ba5ic ■1
olet 1).

Crystal Violet EX-PDR (0, I.

B a s i c V i o I e t 3
), o-damin B (0,I.

Ba5ic V, 1olet 10) + Eisen Victoria Pure Blue B OH (0, 1, Bas i
c Blue7), Malachite Green-7 (0-1, Ba
5ic Green 4), etc., and can be used alone or in combination.

The amount of these water-soluble dyes to be used is preferably 05 to 305 to 30 parts by weight based on the total amount of the ink. This is because if it is less than 0.05% by weight, the ink concentration cannot be achieved, and if it is more than 600 parts by weight, the ink viscosity is too high, which may result in poor ink discharge when filled into a ballpoint pen.

Next, the water-soluble organic solvents used in the present invention include ethylene glycol, fluoropylene gelicol, diethylene glycol, triethylene glycol, thiodiethylene glycol, 1,3-phthanediol, glycerin, ethylene glycol monomethyl ether, and ethylene glycol monomethyl ether. Examples include ethyl ether, diethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol diethyl ether/l/, ethylene glycol monoethyl ether acetate, formamide, sulfolane, sorbitan, acetin, etc. One type or two or more types may be used. The amount of these water-soluble organic solvents to be used is preferably 10 to 400 to 40 parts by weight based on the total amount of the ink.

Also, water is the main solvent, and how much should it be used?

A weight ratio of 28 to 89.5 based on the total amount of ink is preferable.

If necessary, penetrants such as anionic or nonionic surfactants, preservatives such as sodium pentachlorophenol, phenol, and formalin, and water-soluble polymers for viscosity adjustment may be selected and used as appropriate. be.

Hereinafter, the present invention will be explained in more detail with reference to Examples, where "part" simply means "1 part by weight".

Example 1 Eiseneosin GH (0,1,45380)
4.0 parts ethylene glycol 6
0.0 part 6-mercapto-benzothiazole
1.0 part pentachlorophenol
02 parts Neugen P O81 parts (manufactured by Daiichi Kogyo Seiyaku ■, nonionic surfactant) Water
6
4.7 parts Water and ethylene glycol in the above ingredients 50~
Eiseneosin GH was heated to 60°C.

5-Mercapto-benzothiazole, pentachlorophenol, and Neugen P were sequentially added, and after stirring for 2 hours and 9 minutes, the mixture was filtered to obtain a red water-based ink.

Comparative Example 1 A red water-based ink was obtained in the same manner as in Example 1, except that 6-mercapto-benzothiazole in Example 1 was removed and water was added in the same amount.

Husband January-1 Kayaras Black G Conch 10 parts (0,1
, 35225, Nippon Kayaku ■) propylene glycol
10.0 parts thiodiglycol
10.0 parts 6-mercapto-methylbenzothiazole 02 parts Neugen p
After heating 0.1 part of the above ingredients to 40 to 60°C and stirring for about 2 hours, a black water-based ink was obtained.

Comparative Example 2 A black water-based ink was obtained in the same manner as in Example 2, except that water was added instead of 3-mercapto-methylbenzothiazole in Example 2.

Example 3 10- Example 4 Soluble Blue Daiwatadrazine<c. x. 1q14aj
s. o part 3-mercapto-benzothiazole
0,5 parts 5-mercapto-chlorobenzothiazole 1.5 parts 5 mole adduct of ethylene oxide Ethylene glycol 20.0 parts Sulfolane 10.0 parts Water
62
．． 0 parts A green water-based ink was obtained using the above ingredients in the same manner as in Example 2.

Example 5 A green water-based ink was obtained in the same manner as in Example 4, except that 05 parts of 3-mercapto-benzothiazole in Example 4 was changed to 25 parts, and 62.0 parts of water was changed to 60.0 parts.

The inks obtained in Examples 1 to 5 and Comparative Examples 1 and 2 above were applied to a commercially available metal tip ballpoint pen (tip material: brass.
Ball material: Tungsten carbide-containing steel. Ball diameter 0. 6 ms) and left in a constant temperature room at 70°C with a cap for 10 days. Writing distance. Table 1 shows the results of testing for unpleasant sounds during writing.

Table-1 *1. Writing distance Using a commercially available autorotating continuous writing force measuring device (Rasenki), the writing speed was 7 cm/sec. Load 1 0 0, 9.

The writing distance was measured by continuous writing at an angle of 70 degrees until a misalignment occurred.

*2. Uncomfortable sounds When writing down the unpleasant sounds on the paper, those that produced unpleasant sounds were classified as "present," and those that did not were classified as "absent."

As described above, when the ink of the present invention is used in a water-based ballpoint pen, it has excellent abrasion prevention effects and lubricity between the metal ball and the tip, and has excellent durability even when the tip is made of a synthetic resin other than metal, such as polycarbonate. This is a water-based ink for ballpoint pens that is abrasive and, as a result, has a significantly extended writing distance for smooth writing.

Patent applicant: Bentel Co., Ltd. 16 one

Claims (1)

[Scope of Claims] A water-based ink for a ballpoint pen, comprising a water-based ink containing a mercaptobenzothiazole derivative represented by the following general formula (I) and/or (1). (R represents a lower alkyl group IHI, and a halogen group JM represents H+ N H' + alkali metal.) (R represents a
Lower alkyl group, Hl)・logen group, n is. Indicates an integer from 1 to 5. )