JPH07102205A - Oil-based ball-pen ink composition - Google Patents

Abstract

(57) [Summary] [Structure] A colorant, an organic solvent, and a polymethacrylic acid ester represented by the following general formula (Formula 1), and a viscosity of 100.
To 3,000 cp oil-based ball-pen ink composition. [Chemical 1] [Effect] Even if you write with a small amount of ink, it has excellent wash fastness when written on cloth, and it produces dark handwriting and less bleeding.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an oil-based ball-pen ink composition suitable for writing instruments containing at least a coloring material, an organic solvent and a resin, and particularly suitable for writing on cloth.

[0002]

2. Description of the Related Art Ink compositions for general writing instruments use dyes and pigments as coloring materials, and dissolve and / or dissolve these coloring materials in a solvent.
Alternatively, a resin is added for dispersion, and if necessary, a resin is added for improving fixability or viscosity adjustment, and a surfactant or the like is added for improving solubility or dispersion stability. Here, the resin of the ink composition is important because it is closely related to the fastness of handwriting and the viscosity is closely related to penetrability of handwriting and blurring.

In particular, in an ink composition whose main writing target is cloth, since the handwriting is often repeatedly washed in the presence of a detergent or the like, the washing resistance of the handwriting is extremely important. Ketone resins, polyvinyl butyral, nitrocellulose, etc. are known as resins for imparting the robustness of handwriting, but with polyvinyl butyral and nitrocellulose, there is a problem in dissolution stability, There was a possibility that the dissolution system would collapse over time. And, the durability of the handwriting when washing is not satisfactory only by using the ketone resin, and in order to have the washing fastness, a large amount of ink is discharged onto the cloth as the writing object, The focus was on enhancing wash fastness by allowing the ink to penetrate sufficiently. Therefore, it is necessary to use an ink that easily infiltrates the fibers of the cloth, and a writing instrument having a structure in which an ink absorber having a viscosity of 10 cp or less is soaked in an ink occluding body is used.

[0004]

However, when writing on a cloth with a writing instrument in which a low-viscosity ink is impregnated in the above-mentioned ink occlusion body, the cloth has a much rougher texture than paper. However, there was a drawback that it was extremely bleeding. Those written with a small amount of ink in order to prevent this bleeding were not satisfactory in washing fastness.

Therefore, according to the present invention, even if a small amount of ink is used for writing, it is excellent in fastness to washing when written on cloth,
The purpose was to develop an ink that produces dark handwriting and has less blurring.

[0006]

According to the present invention, in order to provide fastness to washing with washing, strong washing resistance can be imparted without having to rely on ink permeation between cloth fibers with a low viscosity ink. Starting from the search for substances, the possibility was found in the polymethacrylic acid ester represented by the following general formula (Formula 2). Then, by using a ball-pen ink in which the ink appears as the ball rotates, an ink with less blurring is completed even when writing is stopped or slowly written. Furthermore, the ink viscosity is 100 to 3000 cp.
It was found that by doing so, the purpose could be achieved more completely. That is, the gist of the present invention is an oil-based ball ink composition comprising at least a coloring material, an organic solvent and a polymethacrylic acid ester represented by the following general formula (Formula 2).

[0007]

[Chemical 2]

Examples of such polymethacrylic acid ester include polyethyl methacrylate, polypropyl methacrylate, polybutyl methacrylate, hexyl polymethacrylate, cyclohexyl polymethacrylate, polymethylcyclohexyl methacrylate, cyclopentyl polymethacrylate, poly Examples include isooctyl methacrylate, polyethylhexyl methacrylate, polylauryl methacrylate, methacrylethyl-butyl methacrylate copolymer, butyl methacrylate-lauryl methacrylate copolymer and the like, which may be used alone or in combination of two or more. Good. Since these polymethacrylic acid esters have appropriate flexibility and adhesiveness, when used as a resin for ink for cloth writing, an ink having sufficient resistance to bending and washing can be obtained.

The content of the polymethacrylic acid ester represented by the above general formula (Formula 1) in the oil-based ball-pen ink is preferably 2 to 35% by weight, and more preferably 3 to 25% by weight. If it is less than 8% by weight, the washing resistance is not sufficient, and if it is more than 25% by weight, the viscosity of the ink becomes too high and the ink becomes uncomfortable and the ink penetrates into the cloth unfavorably. This is because.

The oil-based ball-pen ink composition of the present invention comprises
In particular, when used as an ink composition for oil-based ballpoint pens for cloth writing, the ink viscosity is 100 to 3000 cps (60
Less than 0 cp is measured by Tokimec ELD viscometer standard cone rotor-1 rpm, and 600 cp or more is measured by Tokimec ELD viscometer ST rotor 20.
Measured at rpm. It is desirable to set the temperature within the range of 25 ° C. If the ink viscosity is less than 100 cp, the handwriting when writing on the cloth tends to be smeared, and further it becomes difficult to hold the ink in the hollow cylinder for the ball-point pen, and there is a drawback of leakage, and if it is higher than 3000 cp, the ink cloth will not penetrate. This is because the washing resistance tends to be poor due to insufficient amount.

The oil-based ball-pen ink composition of the present invention comprises
As the colorant, dyes and pigments conventionally used in oil-based ball-pen ink compositions can be used without any limitation. Specific examples of the dyes include Varifer-Steaello # 3104 (C.I. 13900A), Vari-Fastello- # 3105 (C.I. 18690).
Rhodamin B base (C.I.45170B), Soldane red 3R (C.I. 21260), methyl violet 2B base (C.I. 42535B), Victoria Bull-F4R (C.I. 42563B). , Orient-
Split Black AB (C.I. 50415), Nigrosine Base LK (C.I. 50415), Variffer
Stroblac # 3804 (C.I. 12195), manufactured by Orient Chemical Industry Co., Ltd., oil-based dye Varifer-Stello- # 1109, orange # 2210, red # 132.
0, Bull- # 1605, Violet # 1701 and the like.

As the pigment, Printex 150
T, 140U, 95, 85, 75, 45, P, XE2, (all from Degussa Japan Co., Ltd.),
# 2400B, # 2200B, # 1000, # 900,
# MCF88, MA600, MA100, MA7, MA
11, # 50, # 45, # 40, # 32, # 30, CF
9, # 20B, # 4000B (above, manufactured by Mitsubishi Kasei Co., Ltd.), Raven 7000, 5000, 35.
00, 2000, 1500, 1200, 106
0, 1035, 1000, 850, 780, 500, 430, 420, 410, 22 and 1
4, the same 825 Oil Beads, the same H20, the same C,
Carbon black such as Conductex 975, 900, SC (above, Colombian Carbon Japan Co., Ltd.), titanium oxide such as P25 (Nippon Aerosil Co., Ltd.), black iron oxide, yellow iron oxide. Inorganic pigments such as red iron oxide, ultramarine blue, cobalt blue, chrome green, and chromium oxide, Hansaero-10G, 5G, 3G, and 4, GR, A, benzinjero, permanent hero-NCG , Tartrazine lake, Quinoline yellow, Sudan 1, Permanent orange, Induslen Brilliant orange GN, Permanent brown FG, Para brown, Permanent red 4R, Fire red, Brilliant car Min BS, pyrazolone red, lake red C, quinacridone red, brilliant car
Organic pigments such as Min 6B, Bord-5B, Thioindigo Red, Fast Violet B, Dioxane Violet, Alkaline Blue Lake, Phthalocyanine Blue, Indigo, Acid Green Lake, Phthalocyanine Green, BS-605. , 607 (all manufactured by Toyo Aluminum Co., Ltd.), Bronze Powder-P-555, and P-77.
7 (above, manufactured by Nakajima Metal Foil Industry Co., Ltd.) and the like. In addition to these, fluorescent pigments and other known organic fluorescent pigments can be used. The above-mentioned coloring agents can be used alone or in combination with others, and the amount thereof is preferably 5 to 35% by weight with respect to the total amount of the oil-based ball-pen ink composition, although it varies depending on the color tone and the like. Further, a dye, a pigment and a disperse pigment may be mixed and used.

The solvent can be used without particular limitation as long as it can dissolve the polymethacrylic acid ester well and can dissolve or disperse the coloring material well. Specific examples of the solvent include benzyl alcohol, propylene glycol, 1,
Examples of the organic solvent include 3-butanediol, 2-phenoxyethanol, hexylene glycol, oleic acid, and ethylene glycol dibutyl ether. The above organic solvents may be used alone or in combination of two or more.

The ink composition of the present invention comprises a color material which is an essential component, an organic solvent, and a polymethacrylic acid ester represented by the above general formula (Formula 2). In addition to the essential components, various viscosity modifiers and surfactants can be used. For example, as a viscosity modifier,
Ketone resin, xylene resin, polyethylene oxide,
Polymer compounds such as rosin, rosin derivatives, terpene-based resins, coumarone-indene resins, polyvinyl butyral, and polyvinylpyrrolidone, and silicon oxide fine particles, higher fatty acid metal salts, and thixotropy-imparting agents, and also surfactants. As the agent, fatty acid salts, higher alcohol sulfate ester salts, liquid fatty acid sulfate ester salts, anionic surfactants such as alkylallyl sulfonates, polyoxyethylene alkyl ethers, sorbitan alkyl esters, polyoxyethylene Nonionic surfactants such as sorbitan alkyl esters are mentioned.

The oil-based ball-pen ink composition of the present invention containing the polymethacrylic acid ester represented by the above general formula (Formula 2) as an essential component is a commonly used oil-based ball-point ink composition.
Since it has a lower viscosity than Rupen ink, it is preferably incorporated into a writing instrument having a cap having a structure in which a seal packing is applied to the pen tip to prevent ink leakage.

[0016]

When writing on various cloths with the oil-based ball-pen ink composition of the present invention, there are few blemishes and it is easy to write, and it also has good washfastness with little discoloration even after repeated washing with detergent. The reason why the handwriting is obtained is considered as follows.

Since these polymethacrylic acid esters represented by the above general formula (Formula 2) have appropriate flexibility and adhesiveness, when they are used as a resin for ink for cloth writing, their handwriting is , Without using a large amount of ink for writing, that is, with a small amount of penetration into the cloth, sufficient resistance to bending and washing can be obtained. Further, in a writing instrument having an oil-based ball-pen structure, the ink is transferred to the writing object mainly with the rotation of the ball, so that the writing may be stopped,
Even when writing slowly, a small amount of ink is ejected, which helps to prevent blurring. In addition, increase the ink viscosity to 1
The effect becomes more certain by setting it to 00 to 3000 cp. That is, by setting the ink viscosity to 100 cp or more, it is possible to further prevent the rapid spread of the ink in the cloth and to allow the ink to soak into the cloth appropriately.
It is both hard to stain and resistant to washing.

[0018]

EXAMPLES The present invention will be described in detail below with reference to Examples. In Examples and Comparative Examples, "part" means "part by weight".
Indicates.

Example 1 2-phenoxyethanol 46 parts Benzyl alcohol 23 parts Varifast Black # 3806 (Orient Chemical Co., Ltd. oil dye) 15 parts Polybutyl methacrylate (average molecular weight 54000) 10 parts Sarcosine OH (manufactured by Nikko Chemicals Co., Ltd., surfactant) 4 parts The above components were mixed, heated to 120 to 130 ° C., stirred for 5 hours, and then filtered to obtain a black ink having a viscosity of 8449 cp.

Example 2 Hexylene glycol 80 parts 1,3-butanediol 40 parts Printex # 35 (Orient Chemical Co., Ltd., oil dye) 12 parts Polypropyl methacrylate (average molecular weight 45000) 10 Part Nikkor CO-20TX (manufactured by Nikko Chemicals Co., Ltd., surfactant) 4 parts The above components are mixed and heated to 120 to 130 ° C., stirred for 5 hours, and then three times with three rolls. Roll well,
4 with SCR20B type centrifuge manufactured by Hitachi, Ltd.
Centrifugation was performed at 000 rpm for 30 minutes to remove the lower layer precipitate to obtain a black ink having a viscosity of 77 cp.

Example 3 2-phenoxyethanol 46 parts Benzyl alcohol 23 parts Varifast Black # 3806 (Orient Chemical Co., Ltd. oil dye) 15 parts Polybutyl methacrylate (average molecular weight 54000) 10 parts Sarcosine OH (manufactured by Nikko Chemicals Co., Ltd., surfactant) 4 parts The above components were mixed, heated to 120 to 130 ° C., stirred for 2 hours, and then filtered to obtain a black ink having a viscosity of 350 cp.

Example 4 2-phenoxyethanol 46 parts Benzyl alcohol 23 parts Varifast Black # 3806 (Orient Chemical Co., Ltd. oil dye) 15 parts Polybutyl methacrylate (average molecular weight 54000) 15 parts Sarcosine OH (manufactured by Nikko Chemicals Co., Ltd., surfactant) 4 parts The above components were mixed, heated to 120 to 130 ° C., stirred for 2 hours, and then filtered to obtain a black ink having a viscosity of 820 cp.

Example 5 2-phenoxyethanol 46 parts Benzyl alcohol 23 parts Varifast Black # 3806 (oil dyestuff manufactured by Orient Chemical Industry Co., Ltd.) 10 parts Polybutyl methacrylate (average molecular weight 54000) 27. 7 parts Sarkosin OH (manufactured by Nikko Chemicals Co., Ltd., surfactant) 4 parts The above components were mixed, heated to 120 to 130 ° C., stirred for 2 hours, and then filtered to obtain a black ink having a viscosity of 2950 cp.

Example 6 2-phenoxyethanol 80 parts Benzyl alcohol 40 parts Nigrosine EX (Olympic Chemical Co., Ltd. oil dye) 17 parts Polypropyl methacrylate (average molecular weight 45000) 20 parts Sarcosin OH (sunlight) 4 parts by Chemicals Co., Ltd., surfactant) The above components were mixed, heated to 120 to 130 ° C., stirred for 5 hours, and then filtered to obtain a black ink having a viscosity of 230 cp.

Example 7 2-Phenoxyethanol 80 parts Benzyl alcohol 40 parts Nigrosine EX (manufactured by Orient Chemical Industry Co., Ltd., oily dye) 12 parts Polypropyl methacrylate (average molecular weight 45000) 11.9 parts Sarcosin OH (Nikko Chemicals Co., Ltd., surfactant) 4 parts The above components were mixed, heated to 120 to 130 ° C., stirred for 5 hours, and then filtered to obtain a black ink having a viscosity of 105 cp.

Example 8 2-phenoxyethanol 80 parts benzyl alcohol 40 parts Nigrosine EX (oil dye, manufactured by Orient Chemical Industry Co., Ltd.) 17 parts Polypropyl methacrylate (average molecular weight 45000) 30 parts Sarcosin OH (sunlight) Chemicals Co., Ltd., Surfactant 4 parts The above components were mixed, heated to 120 to 130 ° C., stirred for 5 hours, and then filtered to obtain a black ink having a viscosity of 720 cp.

Example 9 2-phenoxyethanol 80 parts Benzyl alcohol 20 parts Nigrosine EX (oil dye, manufactured by Orient Chemical Industry Co., Ltd.) 15 parts Ethyl methacrylate-lauryl methacrylate copolymer (copolymerization ratio 2 : 8 (average molecular weight 85,000) 30 parts Sarcosin OH (manufactured by Nikko Chemicals Co., Ltd., surfactant) 4 parts The above components are mixed, heated to 120 to 130 ° C., stirred for 5 hours, and filtered to give a viscosity of 2480 cp. Of black ink was obtained.

Example 10 2-phenoxyethanol 80 parts Benzyl alcohol 20 parts Nigrosine EX (Oil dyestuff manufactured by Orient Chemical Industry Co., Ltd.) 15 parts Ethyl methacrylate-lauryl methacrylate copolymer (copolymerization ratio 2 : 8 (average molecular weight 85,000) 20 parts Xylene resin (manufactured by Mitsubishi Gas Chemical Co., Inc., HP-120) 5 parts Sarcosine OH (manufactured by Nikko Chemicals Co., Ltd., surfactant) 4 parts Mixing the above components, 120 to After heating to 130 ° C. and stirring for 5 hours, a black ink having a viscosity of 1960 cp was obtained by filtering.

Example 11 2-phenoxyethanol 25.5 parts Benzyl alcohol 5.1 parts Vari-Fast Blue- # 2606 (oil dye, manufactured by Orient Chemical Industry Co., Ltd.) 4 parts Polypropyl methacrylate (average molecular weight) 45000) 9.6 parts The above components were mixed, heated to 120 to 130 ° C., stirred for 3 hours, and then filtered to obtain a skyble-color ink having a viscosity of 264 cp.

Example 12 2-phenoxyethanol 25.5 parts Benzyl alcohol 5.1 parts Varifa-Stojello # 4120 (oil dye, manufactured by Orient Chemical Industry Co., Ltd.) 4 parts Polypropyl methacrylate (average molecular weight) 45000) 9.6 parts The above components were mixed, heated to 120 to 130 ° C., stirred for 3 hours, and then filtered to obtain a yellow ink having a viscosity of 264 cp.

Comparative Example 1 An example except that 40.9 parts of a ketone resin (manufactured by Hitachi Chemical Co., Ltd.) and 0.6 part of polyvinylpyrrolidone K-90 were used in place of the polybutyl methacrylate of Example 1 1
A black ink having a viscosity of 8580 cp was obtained in the same manner as in.

Comparative Example 2 A black ink having a viscosity of 71.5 cp was obtained in the same manner as in Example 2 except that 10 parts of a ketone resin was used instead of 10 parts of polypropyl methacrylate in Example 2.

Comparative Example 3 A black ink having a viscosity of 132 cp was obtained in the same manner except that 10 parts of a ketone resin (manufactured by Hitachi Chemical Co., Ltd.) was used in place of the polybutyl methacrylate of the ink of Example 1.

Comparative Example 4 A black ink having a viscosity of 4510 cp was obtained in the same manner, except that 35.6 parts of polybutyl methacrylate was used instead of 27.7 parts of polybutyl methacrylate in the ink of Example 3.

Comparative Example 5 Polypropyl methacrylate 11.9 of the ink of Example 5
A black ink having a viscosity of 77 cp was obtained in the same manner except that 7.1 parts of polypropyl methacrylate was used instead of parts.

The inks of the above-mentioned Example 1 and Comparative Example 1 were hand-printed on a cotton cloth using a silk printing plate, and this cotton cloth was left at room temperature for 1 day. In addition, the above-mentioned Example 2 and Comparative Example 2 were compared with the tip knock type paint marker (MMP5-A).
D, manufactured by Pentel Co., Ltd. Further, the above Examples 3 to 12 and Comparative Examples 3 to 5 were manufactured by Pentel Co., Ltd.
The parts of Lupen K-106 were filled. The following tests 1 and 2 were performed on these and evaluated. The results are shown in Table 2 to Table 4.
Shown in.

Test 1: cloth writing test; cotton cloth (Kanakin 3
No .: JIS dye fastness test (JIS L 0803 compliant)), and handwritten with the above-mentioned oil-based ballpoint pen, and visually observed bleeding at the time of writing, handwriting density, and strikethrough state on back surface of cloth. The evaluation of the test results is as shown in Table 1.

[0038]

[Table 1]

Test 2: cloth writing test; cotton cloth (Kanakin 3
No .; for JIS dye fastness test (JIS L 0803
The handwriting written in (Compliance)) was subjected to a washing test for 1 hour at 40 ° C. using P & G detergent Ultra-Ariele 5 g / 1 l, and the result was visually evaluated in comparison with an unwashed product. ⊚: No discoloration ○: Less discoloration △: Significant discoloration ×: Severe discoloration

[0040]

[Table 2]

[0041]

[Table 3]

[0042]

[Table 4]

[0043]

INDUSTRIAL APPLICABILITY As described above, the oil-based ballpoint pen ink of the present invention is excellent in fastness to washing when written on a cloth even when written with a small amount of ink, and produces a dark handwriting and less bleeding. Is.

Claims (2)

[Claims] 1. An oil-based ballpoint pen ink composition comprising at least a coloring material, an organic solvent and a polymethacrylic acid ester represented by the following general formula (Formula 1). [Chemical 1] 2. The ink has a viscosity of 100 to 3000 c.
The oil-based ball-pen ink composition according to claim 1, which is in the range of p.