JPH11100539A - Oil based ink composition for ballpoint-pen - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain an oil based ink compsn. for a ballpoint-pen hardly causing faintness and patches at the first start in writing even after the long period storage. SOLUTION: This compsn. contains at least 10-45 wt.% colorant such as a dye or a pigment, 35-80 wt.% solvent such as a glycolic solvent, glycol ether solvent and alcoholic solvent, 5-50 wt.% resin, and 0.5-5 wt.% trimethylol tri-2- ethyl hexanoate.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to an oil-based ink composition used for a ball-point pen. Specifically, the present invention relates to an oil-based ink composition for a ball-point pen, which has little blur when starting to write even after storage for a long period of time, that is, so-called first brush blur, and has a smooth writing feel.

[0002]

2. Description of the Related Art Conventionally, oil-based ink compositions for ballpoint pens have been developed by using coloring materials such as dyes and pigments, solvents such as glycols, glycol ethers and high-boiling alcohols, ketone resins, xylene resins and rosin-derived resins. And a resin mainly for adjusting viscosity and flow characteristics such as polyvinylpyrrolidone and polyvinyl butyral as required. In the case of using glycols, glycol ethers, high-boiling alcohols, etc. as solvents, the dye or resin in the ink composition precipitates because of their hygroscopicity, and the amount of ink discharged from the pen tip And the ink inside the socket of the ball or ballpoint pen tip is corroded by the ionized dye and oxygen in the air, resulting in a decrease in the amount of ink discharged from the pen tip, resulting in writing blur. And, in extreme cases, writing becomes impossible. Many proposals for solving this problem are known. For example, addition of an ethylene oxide adduct of an aliphatic amine (JP-B-39-27676)
), Combined use of a glycol solvent and a fatty acid ester (Japanese Patent Publication No. 40-3378), addition of oleyl ether or ester of polyethylene glycols (Japanese Patent Application Laid-Open No. 55-54).
No. 370), a combination use of an antioxidant and a corrosion inhibitor (Japanese Patent Publication No. Sho 5)
8-10436) and the like.

[0003]

However, in spite of the various proposals mentioned above, the quality of the ink composition for ballpoint pens has not been sufficiently satisfied. In particular, the first brush after storage for a long time was extremely insufficient. The present invention, even after long-term storage,
An object of the present invention is to provide an oil-based ink composition for a ball-point pen that has little initial brush blur and a smooth writing feel.

[0004]

SUMMARY OF THE INVENTION The gist of the present invention is to provide an oil-based ink composition for a ball-point pen containing at least a coloring material, a solvent, a resin, and trimethylolpropane tri-2-ethylhexanoate.

The details will be described below. As the coloring material, oil-soluble dyes conventionally used in oil-based ink compositions for ballpoint pens are often used, but other conventionally known dyes and pigments can also be used.

Examples of oil-soluble dyes include Rhodamine B base (CI. 45170B, manufactured by Taoka Dyestuff Manufacturing Co., Ltd.), Soldan Red 3R (CI. 21260, manufactured by Chugai Kasei Co., Ltd.), and methyl violet 2B base ( C.I.
42535B, National Anilin, USA
e Div. , Victoria Blue F4R (C.I.
I. 42563B), nigrosine-based LK (CI.
50415) (above, manufactured by BASF, Germany), Balifast Yellow # 3104 (CI. 13900A),
Bali First Yellow # 3105 (CI. 1869)
0), Orient Spirit Black AB (CI.5)
0415), Bali Fast Black # 3804 (C.I.
I. 12195), Bali Fast Yellow # 110
9, Bali First Orange # 2210, Bali First Red # 1320, Bali First Blue # 160
5, Bali Fast Violet # 1701 (all manufactured by Orient Chemical Co., Ltd.), Spiron Black GMH
Special, Spiron Yellow C-2GH, Spiron Yellow C-GNH, Spiron Red C-GH, Spiron Red C-BH, Spiron Blue BPNH, Spiron Blue C-RH, Spiron Violet C-RH, S.P.
P. T. Orange 6, S.I. P. T. Blue 111 (both manufactured by Hodogaya Chemical Industry Co., Ltd.) and the like.

As the pigments, PRINTEX 95, 7
5, 45, P, XE2 (all made by Degussa Japan Co., Ltd.), # 2400B, # 1000, # MCF8
8, MA100, MA7, MA11, # 50, # 40,
# 30, CF9, # 20B (Mitsubishi Kasei Kogyo Co., Ltd.), RAVEN7000, 2000, 12
Carbon blacks such as 00, 1000, 500, 410, and 14 (all manufactured by Columbia Carbon Japan Co., Ltd.), titanium oxides such as P25 (manufactured by Nippon Aerosil Co., Ltd.), black iron oxide, and yellow iron oxide , Red iron oxide, ultramarine,
Inorganic pigments such as cobalt blue, chrome green, and chromium oxide, Hansa Yellow 10G, 5G, 3G, and 4,
GR, A, Benzidine Yellow, Permanent Yellow NCG, Tartrazine Lake, Quinoline Yellow,
Sudern 1, Permanent Orange, Indus Ren Brilliant Orange GN, Permanent Brown FG, Para Brown, Permanent Red 4R, Fire Red, Brilliant Carmine 6B, Bordeaux 5B, Thioindigo Red, Fast Violet B, Dioxazine Violet, Alkaline Blue Lake, Phthalocyanine Organic pigments such as blue, indigo, acid green lake, and phthalocyanine green are exemplified.

These coloring materials can be used alone or in combination. The amount used is preferably from 10 to 45% by weight based on the total amount of the oil-based ink composition for ball-point pens.

Solvents include glycol solvents such as ethylene glycol, diethylene glycol, propylene glycol and hexylene glycol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, ethylene glycol monohexyl ether, ethylene glycol monophenyl ether. , Diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, diethylene glycol monohexyl ether, diethylene glycol monophenyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol mononormal butyl ether, propylene glycol Monophenyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol mononormal butyl ether, dipropylene glycol monophenyl ether, tripropylene glycol monomethyl ether, tripropylene glycol monoethyl ether, tripropylene glycol mononormal Glycol ether solvents such as butyl ether and tripropylene glycol monophenyl ether; alcohol solvents such as benzyl alcohol, α-methylbenzyl alcohol, lauryl alcohol, tridecyl alcohol, isododecyl alcohol, and isotridecyl alcohol; and propylene glycol Methyl ether acetate, propylene glycol diacetate, N-methyl Tyl-2-pyrrolidone and the like can be used.

These solvents can be used alone or as a mixture. The use amount thereof is preferably 35 to 80% by weight based on the total amount of the oil-based ink composition for a ballpoint pen.

Resins are added to improve fixability, prevent hand-through of handwriting, adjust viscosity and promote dissolution of dyes. Condensed resins of ketones such as cyclohexanone, acetophenone and urea with formaldehyde, and cyclohexanone Condensed resins and their hydrogenated resins, maleic acid resins, copolymers of styrene and maleic ester,
A copolymer of styrene and acrylic acid or an ester thereof,
Polyvinyl pyrrolidone, polyvinyl butyral, polyvinyl acetal, polyamide which is a condensate of a polymerized fatty acid and polyamines, epoxy resin, polyvinyl alkyl ether, cumarone-indene resin, polyterpene, xylene resin, rosin-based resin and hydrogenated product thereof, rosin-modified Maleic acid resin, vinyl pyrrolidone-vinyl acetate copolymer, polymethacrylic acid ester, polyacrylic acid polymethacrylic acid copolymer, polyoxyethylene and phenol resin.

These resins can be used alone or as a mixture. The amount used is preferably from 5 to 50% based on the total amount of the oil-based ink composition for a ballpoint pen.

[0013] Trimethylolpropane tri-2-ethylhexanoate is used for the first brush of an oil-based ink composition for ball-point pens to prevent fading and improve the writing quality. The amount used to obtain the effect of preventing the first brush from blurring in terms of quality is 0.5 to 5% by weight based on the total amount of the oil-based ink composition for a ballpoint pen.
Is preferred.

In addition to the above-mentioned essential components, a lubricant such as castor oil, a polyoxyethylene adduct of castor oil, polyoxyethylene alkylamine, molybdenum disulfide, a preservative, a fungicide, a rust inhibitor, a dispersant, etc. It may be appropriately selected and used.

For the preparation of the oil-based ink composition for a ballpoint pen, a conventionally known method for producing an ink composition can be applied. That is, when a dye is used as a colorant, an oil-based ink composition for a ballpoint pen can be obtained by dissolving each component with a stirring and mixing machine, and when a pigment is used, another pigment is used with a dispersion and mixing machine. By dispersing together with the components, an oil-based ink composition for a ballpoint pen can be obtained. During the production, heating to dissolve solids such as dyes and using a filter to remove coarse particles such as pigments are particularly preferable methods.

[0016]

The oil-based ink composition for ball-point pens of the present invention is excellent in prevention of initial brush rubbing and excellent writing quality because trimethylolpropane tri-2-ethylhexanoate has excellent compatibility with dyes and other organic solvents. In particular, the best writing quality is due to the presence of three side-chain ethyl groups and ester bonds in the molecule.
It is thought that this is because of the smooth flow even in the ink which is a mixture of various chemical compositions.

[0017]

EXAMPLES Examples and comparative examples will be described below. Example 1 Spiron Violet C-RH (Dye, Hodogaya Chemical Industry Co., Ltd.) 16 parts by weight Bali First Black # 3802 (Dye, Orient Chemical Industry Co., Ltd.) 10 parts by weight Ethylene glycol monophenyl ether 26 parts by weight Benzyl alcohol 20 parts by weight Resin SK (ketone resin, manufactured by Huls AG (Germany)) 13 parts by weight Polyvinylpyrrolidone 4 parts by weight Trimethylolpropane tri-2-ethylhexanoate 3 parts by weight Oxyethylene dodecylamine 8 parts by weight After heating and stirring at 80 ° C. for 4 hours, the mixture was filtered under warm pressure to obtain a black oil-based ink composition for a ballpoint pen.

Example 2 Spiron Black GMH Special (Dye, Hodogaya Chemical Industry Co., Ltd.) 15 parts by weight Bali First Violet # 1701 (Dye, Orient Chemical Industry Co., Ltd.) 11 parts by weight Benzyl alcohol 30 parts by weight Propylene Glycol 12 parts by weight Ethylene glycol monophenyl ether 12 parts by weight Halon 110H (ketone resin, manufactured by Honshu Chemical Industry Co., Ltd.) 12 parts by weight Trimethylolpropane tri-2-ethylhexanoate 1 part by weight Polyoxyethylene (10) hydrogenated castor oil 4 3 parts by weight oxyethylene dodecylamine 3 parts by weight The above components were heated and stirred with a stirrer (80 ° C., 4 hours), and then filtered under warm pressure to obtain a black oil-based ink composition for a ballpoint pen.

Example 3 Balifast Blue # 1607 (Dye, manufactured by Orient Chemical Industry Co., Ltd.) 30 parts by weight Ethylene glycol monophenyl ether 30 parts by weight Benzyl alcohol 16 parts by weight Halon 110H (described above) 12 parts by weight tri-2-ethyl Trimethylolpropane hexanoate 2 parts by weight Polyoxyethylene (5) dodecylamine 10 parts by weight The above components were heated and stirred with a stirrer (80 ° C., 3 hours), and then filtered under warm pressure to give a blue oil-based ink composition for a ballpoint pen. I got

Example 4 P. T. Orange 6 (Dye, Hodogaya Chemical Industry Co., Ltd.) 15 parts by weight Spiron Red C-GH (Dye, Hodogaya Chemical Industry Co., Ltd.) 15 parts by weight Spiron Yellow C-2GH (Dye, Hodogaya Chemical Industry Co., Ltd.) 3 parts by weight Hexylene glycol 20 parts by weight Benzyl alcohol 20 parts by weight Propylene glycol monomethyl ether 10 parts by weight Halon 110H (described above) 10 parts by weight Polyvinylpyrrolidone 1 part by weight Trimethylolpropane tri-2-ethylhexanoate 0.5 parts by weight Poly 5.5 parts by weight of oxyethylene (20) octadecylamine The above components were heated and stirred with a stirrer (70 ° C., 6 hours), and then filtered under warm pressure to obtain a red oil-based ink composition for a ballpoint pen.

Example 5 Varifast Blue # 1607 (Dye, manufactured by Orient Chemical Industry Co., Ltd.) 30 parts by weight Ethylene glycol monophenyl ether 30 parts by weight Benzyl alcohol 17 parts by weight Halon 110H (described above) 10 parts by weight tri-2-ethyl Trimethylolpropane hexanoate 5 parts by weight Polyoxyethylene (5) dodecylamine 8 parts by weight After heating and stirring the above components with a stirrer (80 ° C., 3 hours), filtration under warm pressure is performed, and a blue oil-based ink composition for a ballpoint pen is used. I got

Comparative Example 1 A black oil-based ink composition for a ballpoint pen was obtained in the same manner as in Example 1, except that oleic acid was used instead of trimethylolpropane tri-2-ethylhexanoate.

Comparative Example 2 In Example 2, polyoxyethylene (10) was used instead of trimethylolpropane tri-2-ethylhexanoate.
A black oil-based ink composition for a ballpoint pen was obtained in the same manner as in Example 2 except that the hardened castor oil was used.

Comparative Example 3 A red oil-based ink composition for a ballpoint pen was obtained in the same manner as in Example 3, except that castor oil was used in place of trimethylolpropane tri-2-ethylhexanoate.

A first brush rub test was performed on the oil-based ink compositions for ball-point pens obtained in Examples 1 to 5 and Comparative Examples 1 to 3. Table 1 shows the results.

Preparation of Test Samples: The oil-based ink compositions for ball-point pens obtained in Examples 1 to 5 and Comparative Examples 1 to 3 were commercially available using an oil-based ball-point pen (BK100, Pentel Co., Ltd.).
And the pen tip is made of a stainless steel tip and a cemented carbide ball), and 0.3 g was filled in the same writing implement as a test sample.

First brush rub test 1: After writing each test sample by hand, the cap was removed and the temperature was 50
It is left for 24 hours under the condition of 30 ° C. and 30% humidity. After taking it out, it is left for 2 hours in a room at a temperature of 22 ° C. and a humidity of 60%, and is returned to room temperature. The length from the start of the writing to the position of the handwriting that can be written normally is measured with a ruler (unit: mm).

First brush rub test 2: After writing each test sample by hand, the cap was taken off and the temperature was 40
It is left for 3 months under the condition of 50 ° C. and 50% humidity. After taking it out, it is left for 2 hours in a room at a temperature of 22 ° C. and a humidity of 60%, and is returned to room temperature. The length from the start of the writing to the position of the handwriting that can be written normally is measured with a ruler (unit: mm).

Writing taste test: Monitor 1 randomly selected
0 persons rated each test sample on a five-point scale for writing taste. The evaluation was 5 if the writing quality was excellent, 1 if the writing quality was poor, and 2 to 4 in the middle. The evaluation points were averaged for each of the test samples, and the writing taste was evaluated.

[0030]

[Table 1]

[0031]

As described above in detail, the oil-based ink composition for a ball-point pen according to the present invention has an excellent effect that almost no initial brush blur occurs even when stored for a long period of time.

Claims (1)

[Claims] 1. An oil-based ink composition for a ballpoint pen, comprising at least a coloring material, a solvent, a resin, and trimethylolpropane tri-2-ethylhexanoate.