JP3010773B2 - Ink composition - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a low-toxic ink composition having excellent handwriting fixability.

[0002]

2. Description of the Related Art Conventionally, an ink composition used for a marking pen or the like includes an aqueous ink composition containing a water-soluble dye and water as main components, and an oil-soluble dye, an oil-soluble resin and a solvent as main components. Oil-based ink compositions.

It has been proposed to use a low-toxic aliphatic alcohol having 4 or less carbon atoms as a solvent for an oil-based ink composition.

[0004]

However, when water or an aliphatic alcohol having 4 or less carbon atoms is used as a solvent, a film made of a resin soluble in these solvents has a weak adhesive property, and the film formed on the non-absorbing surface of the handwriting does not adhere. There was a problem that fixability was weak. An object of the present invention is to obtain an ink composition having sufficient fixability to a non-absorbing surface by using water or an aliphatic alcohol having 4 or less carbon atoms as a solvent.

[0005]

SUMMARY OF THE INVENTION The present invention provides a colorant, a solvent comprising water or an aliphatic alcohol having 4 or less carbon atoms,
The gist of the present invention is an ink composition comprising at least a copolymer of styrene and an organic acid soluble in the solvent or a salt thereof, and a polyvinyl alkyl ether soluble in the solvent. The details will be described below.

As the coloring material, dyes and pigments can be used. As the dye, C.I. I. Acid Red 52, C.I. I. Acid Blue 1, C.I. I. Acid Black 2, 12
Acid dyes such as C.3; I. Direct Black 19,
C. I. Direct dyes such as Direct Blue 86, C.I.
I. Basic Blue 7, C.I. I. Basic Red 1
Water-soluble dyes such as basic dyes such as C.I. I. Solvent Black 7, 123, C.I. I. Solvent Red 8, 49 and C.I. I. Solvent Blue 2, 2
5, 55, 70, C.I. I. Solvent Green 3,
C. I. Solvent Yellow 21, 61, C.I. I. Solvent Orange 37, C.I. I. And oil-soluble dyes such as Solvent Violet 8 and 21. They are,
They can be used alone or in combination. When water is used as a solvent, a water-soluble dye is used.When an aliphatic alcohol having 4 or less carbon atoms is used as a solvent, it is preferable to use an alcohol-soluble dye. Insoluble dyes can also be used. It is preferable to use 2 to 20% by weight of the ink composition.

As pigments, ocher, barium yellow, navy blue,
Inorganic pigments such as cadmium red, titanium oxide, red iron oxide, iron black, carbon black, etc., azo pigments, condensed polyazo pigments, phthalocyanine pigments, quinacridone pigments, indigo pigments, thioindigo pigments, nitroso pigments, nitro pigments Conventionally known pigments such as organic pigments such as pigments, basic dye pigments, acid dye pigments, vat dye pigments, mordant dye pigments and natural dye pigments are exemplified. These can be used alone or in combination of two or more.
It is preferable to use 2 to 20% by weight based on the total amount of the ink composition. In particular, when a pigment is used as a coloring material, a processed pigment having a resin-coated surface can be preferably used from the viewpoints of dispersibility, stability over time, and workability. Specific examples thereof include Labester, Dirac TN (all manufactured by Dainippon Ink and Chemicals, Inc.), Polybride N (manufactured by Nippon Oil & Fats Co., Ltd.), and Hi-Corp (manufactured by Tokusetsu Kogyo Kogyo). Can be

Further, metal powder can be used as a coloring material. Specifically, gold, silver, copper, iron, platinum, nickel, aluminum, tungsten, cobalt, titanium, magnesium, tantalum, molybdenum, tin, lead, zinc, zirconium and alloys such as brass, nickel silver, copper -Titanium, silver-gold, iron-cobalt, iron-nickel, etc., and these can be used alone or in combination.

Water or an aliphatic alcohol having 4 or less carbon atoms is used as a solvent. In addition to water, aliphatic alcohols having 4 or less carbon atoms include methyl alcohol, ethyl alcohol, normal propyl alcohol, isopropyl alcohol, and the like. Normal butyl alcohol, isobutyl alcohol and tertiary butyl alcohol are exemplified. These may be used alone or in combination. It is preferable to add 50 to 90% by weight based on the total amount of the ink composition.

The copolymer of styrene and an organic acid soluble in the above-mentioned solvent or a salt thereof and polyvinyl alkyl ether are
It is used in combination to obtain a handwriting having excellent fixability.

Examples of the copolymer of styrene and an organic acid or a salt thereof include Johnson Krill 67, 678, and 682 (all manufactured by Johnson Co., Ltd.) and Spraval A954F.
(Manufactured by BASF, West Germany) and styrene-acrylic acid copolymers, and Suprapearl AP20 and AP30 (above,
Styrene-maleic acid copolymers such as those manufactured by BASF, West Germany, or alkali metal salts such as sodium and potassium, ammonium salts, and amine salts. Examples of polyvinyl alkyl ethers include Lutonal M40 and A50 (all manufactured by BASF, West Germany).

The amount of the copolymer of styrene and an organic acid or a salt thereof and polyvinyl alkyl ether is preferably 0.2 to 20% by weight based on the total amount of the ink.
The usage ratio of the copolymer of styrene and the organic acid or the salt thereof to the polyvinyl alkyl ether is preferably from 7: 3 to 3: 7.

Further, in addition to the above-mentioned components, various additives such as a preservative, a fungicide, a wetting agent, a viscosity modifier, a freeze stabilizer, an antifoaming agent, and a surfactant may be added as required. You can also use it selectively.

In particular, in the case of an ink composition using an aliphatic alcohol having 4 or less carbon atoms as a solvent, a phenol resin, a ketone resin, a rosin resin, a butyral resin, or the like can be used. To give a specific example, tamanol 100S and 510 (manufactured by Arakawa Chemical Industries, Ltd.), hitanol 1501 and 2501 (manufactured by Hitachi Chemical Co., Ltd.) and the like as phenol resins, and ketone resins as ketone resins, respectively. K-90 (Arakawa Chemical Industry Co., Ltd.), Halon 11
0H (manufactured by Honshu Chemical Co., Ltd.)
Herculin D, pentaline 255, 261 (both manufactured by Rika Hercules Co., Ltd.), gum rosin WW and the like are used as butyral resins as denka butyral # 2000-
L, # 3000-1, # 3000-2, # 300
0-4, # 3000-K (above, Denki Kagaku Kogyo Co., Ltd.)
Manufactured). These may be used alone or as a mixture of two or more, and it is preferable to use 1 to 20% by weight of the total amount of the ink composition.

The ink composition is prepared by mixing and stirring using a commonly known stirrer when a dye is used as a coloring material, and using a generally known dispersing machine when using a pigment. It can be easily obtained by mixing and dispersing.

[0016]

The ink composition according to the present invention uses a copolymer of styrene and an organic acid, which forms a hard film, and a polyvinylalkyl ether having tackiness in combination. Since it is excellent in solubility, it is possible to obtain handwriting excellent in fixability.

[0017]

The present invention will be described below in more detail with reference to examples. In the Examples and Comparative Examples, the term "parts" means "parts by weight".

Example 1 C. I. Solvent Blue 70 6.0 parts Methyl alcohol 10.0 parts Ethyl alcohol 72.0 parts Joncryl 67 4.0 parts Lutenal M40 (polyvinyl methyl ether) 8.0 parts The above components are stirred with a stirrer for 3 hours and blue. An ink composition was obtained.

Example 2 C.I. I. Solvent Red 8 10.0 parts Methyl alcohol 65.0 parts Benzyl alcohol 10.0 parts Suprapearl A954F 10.0 parts Lutenal A50 (polyvinyl ethyl ether) 5.0 parts The above components are stirred with a stirrer for 3 hours to obtain a red ink. A composition was obtained.

Example 3 C. I. Solvent Violet 21 4.0 parts Normal propyl alcohol 20.0 parts Ethyl alcohol 71.5 parts Suprapearl A954F 2.0 parts Lutonal M40 2.0 parts Florard FC-431 0.5 parts (Fluorine surfactant, Sumitomo 3M ( The above components were stirred with a stirrer for 4 hours to obtain a purple ink composition.

Example 4 C.I. I. Solvent Green 3 7.0 parts Normal propyl alcohol 20.0 parts Ethyl alcohol 59.0 parts Suprapearl A954F 6.0 parts Lutenal M40 5.0 parts Gum rosin WW 3.0 parts The above components are stirred for 4 hours with a stirrer. A green ink composition was obtained.

Example 5 C.I. I. Solvent Yellow 21 5.0 parts Butyl alcohol 15.0 parts Ethyl alcohol 65.0 parts Suprapearl A954F 10.0 parts Lutenal A50 5.0 parts The above components were stirred with a stirrer for 4 hours to obtain a yellow ink composition. .

Example 6 Phthalocyanine Blue 6.0 parts Ethanol 50.0 parts Isopropyl alcohol 30.0 parts Suprapearl A945F 5.0 parts Lutenal A50 5.0 parts Denkabutyral # 2000-L 4.0 parts For 3 hours to obtain a blue ink composition.

Example 7 C.I. I. Acid Black 2 6.0 parts Ethyl alcohol 10.0 parts Water 78.0 parts Joncryl 61J 4.0 parts Lutenal M40 2.0 parts The above components were stirred with a stirrer for 3 hours to obtain a black ink composition. .

Example 8 C.I. I. Pigment Black 7 7.0 parts Ethylene glycol 2.0 parts Water 79.0 parts Suprapearl A954F sodium salt 8.0 parts Lutenal M40 5.0 parts The above components are dispersed with a disperser for 3 hours to obtain a black ink composition. Obtained.

Example 9 C.I. I. Direct Black 19 4.0 parts Methyl alcohol 20.0 parts Water 72.0 parts Joncryl 62 10.0 parts Lutenal M40 4.0 parts The above components were stirred with a stirrer for 4 hours to obtain a black ink composition. .

Example 10 C.I. I. Acid Red 87 7.0 parts Methyl alcohol 10.0 parts Ethyl alcohol 10.0 parts Ammonium salt of Suprapearl AP20 10.0 parts Lutonal M40 8.0 parts Water 58.0 parts The above components are stirred with a stirrer for 4 hours. Thus, a red ink composition was obtained.

Example 11 C.I. I. Acid Blue 1 5.0 parts Ethyl alcohol 10.0 parts Water 72.0 parts Joncryl 61J 5.0 parts Lutenal A50 8.0 parts The above components were stirred with a stirrer for 4 hours to obtain a blue ink composition. .

Comparative Example 1 Example 1 was repeated, except that Joncryl 67 was added and methyl alcohol was added.
A blue ink composition was obtained.

Comparative Example 2 The procedure of Example 2 was repeated except that Rutonal A50 was used and methyl alcohol was added.
A red ink composition was obtained.

Comparative Example 3 A black ink composition was obtained in the same manner as in Example 7, except that water was added, except for Joncryl 61J.

Comparative Example 4 A black ink composition was obtained in the same manner as in Example 8, except that Rutonal M40 was used and water was added.

[0033]

Using the ink compositions obtained in Examples 1 to 11 and Comparative Examples 1 to 4, a peelability test (rubbing off with hand oil), a bending test and a test for handwriting tackiness were performed. Done. The results are shown in Tables 1 and 2.

Peelability (rubbing off with hand oil) Test Examples 1 to 6 and Comparative Examples 1 and 2 use a fiber core as a pen point,
A writing instrument using a batting (Mark Pentel MS50, manufactured by Pentel) is filled with each of the ink compositions of the Examples and Comparative Examples, and a straight line is written on a non-absorbing surface (using a polypropylene film or an iron plate), and written for 10 minutes or more. After standing, the handwriting was rubbed perpendicularly to a straight line with one finger (11 testers), the number of times until it completely disappeared was measured, and the average value was calculated. In Examples 7 to 11 and Comparative Examples 3 and 4, a writing implement using a fiber core as a pen tip and batting (sign pen S
520, manufactured by Pentel) and filled with the aqueous ink compositions of the Examples and Comparative Examples, written straight on a non-absorbing surface (using a polypropylene film or an iron plate), and left for 20 minutes or more. The finger was rubbed perpendicularly to a straight line with one finger (11 testers), and the number of times until it completely disappeared was measured, and the average value was calculated.

Bending test: A writing instrument is assembled in the same manner as in the peeling test, and a straight line is arranged on a polypropylene film to be written. After standing for 20 minutes or more, the film is bent. The state of the handwriting at the bent portion was observed. ：: Handwriting is not affected by bending. 筆: Handwriting has slightly cracked. ×: Handwriting has cracks and peeling.

Stickiness of handwriting: A writing instrument was assembled in the same manner as in the peelability test, a straight line was written on a polypropylene film, and after standing for 20 minutes or more, the handwriting was touched with a finger to determine the presence or absence of tackiness. ○: no stickiness ×: sticky

[0037]

[Table 1]

[0038]

[Table 2]

As described in detail above, the ink composition according to the present invention has low toxicity, excellent fixability of handwriting, and has no stickiness to handwriting and is practically usable. Is excellent.

──────────────────────────────────────────────────続 き Continuing from the front page (72) Inventor Katsuhisa Oda 229-1 Kamitamari, Tamari-mura, Niibari-gun, Ibaraki Prefecture Pentel Co., Ltd. Examiner at Ibaraki Plant Naoko Matsumoto (56) References JP-A-1-193378 (JP, A) JP-A-53-83809 (JP, A) JP-A-60-173063 (JP, A) JP-A-58-196275 (JP, A) (58) Fields investigated (Int. Cl. ⁷ , DB name) ) C09D 11/00-11/20

Claims (1)

(57) [Claims] 1. A colorant, a solvent comprising water or an aliphatic alcohol having 4 or less carbon atoms, a copolymer of styrene and an organic acid soluble in the solvent or a salt thereof, and a solvent soluble in the solvent. An ink composition comprising at least a polyvinyl alkyl ether.