JPS60135467A - Ball point ink - Google Patents

Abstract

PURPOSE:To provide the titled ink which enables ball point pens to be used as a capless pen, gives excellent feeling in writing and can be written with a high density, by incorporating liquid polyethylene glycol or polypropylene glycol in a water ink. CONSTITUTION:The titled ball point ink is botd. by incorporating liquid polyethylene glycol and/or polypropylene glycol in a ball point ink consisting of a water-soluble dye, a water-soluble org. solvent (e.g. ethylene glycol), a water- soluble high-molecular material having stringiness (e.g. polyethylene oxide having an MW of 500,000 or above) and not more than 10wt% (based on the total quantity of ink) water. The ink gives excellent feeling in writing as an conventional water based ball point ink, its nib is not dried when ball point pens are left to stand without cap as in conventional oil based ball point ink and the ink gives handwriting having higher density than that obtd by conventional oil based ball point ink.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to an ink for a ballpoint pen that can be used without a cap like an oil-based ballpoint pen, has an excellent writing feel, and has a handwriting density higher than that of an oil-based ballpoint pen.

Conventionally, there are two types of ink for ballpoint pens. That is, an oil-based ink consisting of an oil-soluble dye, an oil-based solvent such as phenylselonorp or benzyl alcohol nato, and a resin dissolved in this oil-based solvent, and an aqueous ink consisting of a water-soluble dye and an aqueous solvent whose main solvent is water. With ink.

The former has the advantage that since most of the solvents in the ink have a high boiling point of 200'C or higher, it will not dry out on the tip of a ballpoint pen even if left for a long time without using a cap. It had the disadvantage of poor writing feel.

Although the latter has an excellent writing feel, there is a problem in that if the ballpoint pen is left without a cap for a long period of time, the ink dries at the pen tip.

Therefore, the applicant has developed a new ballpoint pen that has an excellent writing feel like a conventional water-based ballpoint pen, but does not dry out the tip of the ballpoint pen even when left without a cap like a conventional oil-based ballpoint pen. provided ink. (Japanese Patent Application No. 58-917/; No. 9) The present invention relates to improving the handwriting density of the above-mentioned ballpoint pen ink.

That is, 1 the present invention comprises a water-soluble dye, a water-soluble organic solvent, a water-soluble polymer having sailing properties, and 10% of the total amount of ink.
The gist of the present invention is to provide an ink for a ballpoint pen, which is characterized in that the ink for a Luhole pen contains less than % by weight of water and contains liquid polyethylene glycol and/or polypropylene silicate.

The present invention will be explained in detail below.

Suitable water-soluble dyes used in the present invention include direct dyes, acid dyes, food colorings, and basic dyes, which have high color burr, can produce deep handwriting with a small amount, and have excellent dissolution stability. Preferably. Specific examples include: Direct Thip Planok 1
9), Direct fly rack AB (same 32)l
Tyrektoff Test Plank B (22), Kayaku Direct Brilliant Yellow G (0, 1, Direct Yellow 4), Eisen Primula Yellow 50 L H (2
6), Eisen Primula Yellow G OL H (44)
l Tirect Fast Erotic (50), Kayaku Direct Scarle Soto B (C, 1, Tirec Tolenodo 3)
7), Eisen Direct 7 String F) I (Same 1
), Eisen Primula Elo Le Soto GSH (same 4) I
Eisen Direct Roteurinresodo BH (31)
, Eisen Primula Red 4BH (81), Direct Fast Scarlet 488 (23), Kayaku Direct Scarlet 3B (39), Eisen Primula Pink 2BLH (75), Kayaku Direct Sky Blue 6 B (0, 1, Direct Blue 1) l Eisen Direct Sky Blue 5BH (15), Mitsui Direct Pull-28N (6) 1 Kayaras Splat Turquoise Blue FBL (+99), Water Blue #3 (86), Kayaras Blue 〇〇〇c (same 78)
, direct dyes such as Kayaras Spura Prue FF2OL (106), Negro/N (0, 1, 77 Nodoplanoku 2 Otori, Suminol Milling Black 8BX (24), Kayanor Milling Black VLG (26), Suminol Milling Black NB (29), Eisen Opal Plano L W H (52), Water Black +87-L (154), Fast Yellow (0,1,
Annod xo-9), Minoia/Radfast Yellow G
(17th), Suminol Fast Yellow NR (19th)
, Water Yellow #1 (same 23).

Suminol Fast Yellow R (25), Metanyl Yellow (56), Water Yellow #6 (liJ 42)
), Suminol Fastlet GG (0,1, Acid Orange 19) I Naphthol Orange (1m20),
Suminol Milling Oren: ;R (45), Water Orange #18 (56), Solar Red RB (
C! , 1. Abnodred 7), Solarbin (ll
'lJ 14), new = + comb 7 (M 18
) + A/Norodamine G (5Q), Erythrosin (51), Kayaqua 7 Norodamine FB (52), Tsuju-Tale Noto #2 (87), 'Z-
a-Tarpink #2 (92), Eisen Rose Bengal (94), Suminol Brilliant Scarlet DH (97), Mythiasis Violenoto 6 B
N (0, 1, Annod Violet 15), Mitsuia 7 Annod Purple BN (17), Patent Blue V
(0,1a/throat blue 1), patent blue AF (
Same 7) l Water Blue #9 (same 9), Water Blue #116 (same 15) l Orienton Louvre Blue
080 (22), S Soy Nylon 7 Astopull ~ (E
(M2S), Suminol 7 Asto Plue 3G (Sminol 27
), Daiwa Digo Carmine (74).

Water Blue #115 (9o), Orienton Lupulpur-08B (93), 77 Sodo Brilliant Milling Green B (0,1, Acid Green 9)
Acidic dyes such as Sunset Yellow (C, 1, Food Yellow 3), Amaranth ((:!, 1.7 = Dread 9)
Food colorants such as 1 Food Green No. 2 (0° ■, Food Green 2) and basic dyes include C, 1, Be-7 Nokuekuchi-1, C, I.

Bae/Tsukuero 2. C, 1, Bentsquerow + 1
, 0.1. Bentsuk Orange 2, 0.1 Basic Orange + 4, C, I Basic Orange 15.0
．． 1. Bentsk Orange 21. O, 1, Bei Sonoku Orenshi 22, 0.1. -Neetsunoclet 11C,
I Hennokrenodo 21C9 ■ Benzkled 8. O
, 1, Be/Tsu Cred 9. O, 1, BA/TSCRED 12, 0. I Basic Red 13.0°I, Hannok Violet 1. O', 1. Bentzk Violet 3+ 0.1. 7 nokuno (iore soto 7,, O, 1,
Bennock Violet 10, 0. ．． 1. b/
Tsuku Violet + 4, O, 1, He-7 Noku Flu-
3,0,i, Bendsk Blue 5.0. I Basic Blue 7, O, 1, Basic Blue 9.0.1゜B/
Tsuku Blue 24. C, 1, Be-7 Noku Blue 25, C,
I basic blue 26,9■, benzuk green 1
', O, 1, Pe-7 Soku Green 4 ° C, 1, -<-n, Ku Brown 1, 0.1 Basinoku Kuburanoku 2, etc., and there is one type or two or more types that do not chemically react. The amount used is preferably 5 to 40% by weight based on the total amount of the ink, considering the handwriting density and dissolution stability for a ballpoint pen.

Water-soluble organic solvents that dissolve water-soluble dyes well and are chemically stable can be used, but the ink dries at the tip of a ballpoint pen.

In consideration of the stability of the ink over time, those that evaporate at a boiling point of 150° C. or higher are particularly preferably used.

To give specific examples, polyhydric alcohols and derivatives thereof include ethylene glycol, diethylene glycol,
Propylene glycol, dipropylene glycol, tril
J ethylene / IJ: + -l, to IJ methylene glycol, 1,5-phthylene gelicol, tetramethylene glycol, thiodiglycol, hequinolene gelicol, glycol serine, diethylene glycol diethyl ether ethylene glycol monobutyl ether, diethylene glycol monomethyl Ether Lengericol Motuptyle Ether, ) IJI-F-Lengericol Monomethyl Ether, -Dipropylene Glycol Monomethyl Ether, Schiff 90 Hirun Glycol Monoethyl Etheno l'l Trif'0 Pyrene Glycol Monomethyl Ether &. ! Examples of the nitrogen-containing solvent include monoethanolamine, jetanolamine, triethanolamine, 2-pyrrolidone, N-methyl-2-pyrrolidone, dimethyl sulfoxide, and sulfolane.

Tetrahydrofurfuryl alcohol, gamma-butyrolactone, etc. can be used alone or as a mixture of 2tJII or more, and the amount of the additive is 10 to 85% by weight based on the total amount of the ink.

The water-soluble polymer having stringability used in the present invention is suitable for ballpoint pen ink.

This is necessary to prevent the ink from running out even when writing quickly. A specific example is polyvinylpyrrolidone.
90. Examples include hydroquinopropyl cellulose [H], polyethylene oxide with a molecular weight of 500,000 or more,
These water-soluble bacterial molecules having thread-spinning properties can be used singly or as a mixture of two or more, and the amount used is not particularly limited, but is preferably from 0.1 to 10% by weight.

Furthermore, the ink discharge is stabilized. Other water-soluble polymers can be added for purposes such as adjusting viscosity, adjusting ink viscoelasticity, and improving handwriting characteristics. Any polymer can be used as long as it is soluble in water and a mixture of two or more of the water-soluble organic solvents mentioned above. Specific examples of water-soluble polymers that can be used in the present invention include polyethylene oxide, polypropylene/oxide, polyvinylpyrrolidone, carboquine methylcellulose, hydroxyprobylcellulose, hydroxyethylcellulose, methylcellulose,
Ethylcellulose, polyacrylamide, polyacrylic acid.

Examples include sodium polyacrylate, polyvinyl alcohol methacrylate, alcohol-soluble alkyd resin, etc.1 These water-soluble polymers can be used alone or as a mixture of two or more that do not cause a chemical reaction, and the amount used This is because the viscosity and viscoelasticity of the ink change significantly depending on the type and molecular weight of the polymer used.

It is not particularly limited.

The ballpoint pen ink used in the present invention has a water content of 10% by weight or more, and when the ballpoint pen is left unused without using the camp.

Moisture in the ink evaporates from the nib of the ballpoint pen, that is, the gap between the ball and the ball holder, and the viscosity inside the ball holder increases.

The handwriting may become blurred, the ink may not continue, and the performance of the ballpoint pen will be significantly reduced.

For this reason, it is better to reduce the water content in the ballpoint pen ink as much as possible, and it needs to be at most 10% by weight, preferably at most 1% by weight, based on the total amount of the ink.

The purpose of using liquid polyethylene glycol and/or polypropylene glycol, which is the gist of the present invention, is to stabilize the dissolution of dyes at high concentrations.

If the amount of dye is increased and the dye concentration is increased, the proportion of the water-soluble organic solvent in the total amount of the ink will inevitably decrease. Therefore, dyes and water-soluble polymers, as well as solid additives, must be dissolved in the reduced water-soluble organic solvent.
Ink stability is significantly reduced. However, by using water-soluble liquid polyethylene glycol or polypropylene glycol, the amount of water-soluble heavy molecules added for thickening can be reduced because they themselves have considerably higher viscosity. Furthermore, since the water-soluble liquid polyethylene glycol and polypropylene glycol easily dissolve water-soluble dyes, the amount of solvent in the overall ink increases.

Therefore, it improves the dissolving power of the dye.

The ballpoint pen ink of the present invention also has a good writing feel.

1w as needed to improve handwriting performance and performance over time.
1. Cationic, nonionic, and anionic surfactants 1. Rust inhibitors such as benzotriazole, various amide compounds, sodium dehydroacetate, nodium omazi/zinc omazine, formalin, and sodium pentachlorophenol.

Phenol 1 Preservatives and fungicides such as dioxin paraben, inorganic fillers such as finely divided silicon dioxide and calcium carbonate, humectants such as urea, ethylene urea and sorbitol,
PL-1 regulators such as sodium carbonate, sodium hydroxide, acetic acid, hydrochloric acid, oxalic acid, etc. can also be added to the ballpoint pen ink of the present invention.

The present invention will be explained below based on seven examples.
"Parts" indicates "parts by weight."

Example 1 (black ink) Victoria B'lue FB (0,1,Ba
5ic 80 parts Blue 26 Birdy 7 Dye Chemicals Methyl Violet FN (C, 1, Ba5
ic 10.0 parts Violet 1 Manufactured by Bardishu Dye Chemicals ■) Ohrysoidine B (C, 1, Ba5ic
8.0 parts Orange 2 Birdy 7 Dye chemicals ■
) Melachite Green (C, T, Ba5i
c 5.0 parts G r e e port 4 manufactured by Hodogaya Chemical Industry ■) HPO (H) (manufactured by Nippon Soda ■, hydro 02 parts xypropyl cellulose, stringable water-soluble polymer) +IPC (SL) (Japan Made by Soda ■, 6B, O part Doroquinglovil cellulose thickening water-soluble polymer) Nonal 204 (manufactured by Toho Chemical ■, 20 parts nonionic surfactant) Diethylene glycol 26.0 parts Propylene glycol 150 parts Thiodiglycol 50 Part Polyethylene Glycol 300 16.8 parts (average published 100) Among the above compositions, RPC (H) and HP C! (SL
) in polyethylene glycol 500 heated to 60-70°C and stirred.

Then, by passing it through a roll mill 4 to 5 times, a rubbery, transparent gel-like material is obtained. Also, in another container, 50 to 60
Add the dye and surfactant to the heated thiodiglycol, polyethylene glycol, and diethylene glycol solution at C and stir for 1 hour. Then, add the roll-milled gel and stir for 2 hours while maintaining 50 to 60゛CK. The desired black ink was obtained by stirring.

Example 2 (blue ink) Victoria Pure Blue BOH (Hodogaya 180 parts manufactured by Kagaku Kogyo ■) Methyl Violet FN 2.0 parts PV
PK-90 (+t'Lihynyruby C11, 0 parts Ridone, stringable aqueous polymer) HP C (H) 0.1 parts HPC (SL) 10. O parts Naimeen L201 (manufactured by NOF ■ 2B part, nonionic surfactant Agent] Diethylene glycol 25.0 parts Propylene glycol 45.0 parts Thiodiglycol 50 parts Polypropylene glycol (average molecular weight 224 molecules 75
0) The above components were treated in the same manner as in Example 1 to obtain the desired blue ink.

Example 3 Of the composition of Example 1, polyethylene glycol 300
The desired black ink was obtained in the same manner as in Example 1, except that 68 parts of the 100% polypropylene glycol (average molecular weight 750) was added.

The inks obtained in Examples i and 2.3 above were filled using the parts of commercially available oil-based ballpoint pens according to the procedure for assembling a normal ballpoint pen. After that, in order to confirm the effect, we added the same commercially available black ink oil-based ballpoint pen as used in the above assembly as a comparative product, and tested the writing taste, drying of the pen tip, first stroke fading, continuous writing, smearing, and handwriting density tests. went.

The results are shown in the table below.

*Each test method except writing feel was conducted using the method shown in JIS 86069 ballpoint pen medium, and '4 writing taste was determined by a sensory test.

※※ Written using the method used in the continuous writing test in Example 1.3 and a commercially available oil-based ballpoint pen for 200 m.
The center of the handwritten area near 00 m was measured with a 5-point color difference meter, and the Y value was determined.

As described above, the ballpoint pen ink according to the present invention has the same dry nib blurring performance and continuous writing performance as normal oil-based ballpoint pens, has the same smearing performance, and has excellent handwriting that cannot be obtained with normal oil-based ballpoint pens. It has density and writing feel.

Patent applicant: Bentel Co., Ltd.

Claims (1)

[Claims] A ballpoint pen ink consisting of a water-soluble dye, a water-soluble organic solvent, a water-soluble polymer having threadability, and a water content of 10% by weight or less based on the total amount of the ink is mixed with liquid polyethylene glycol and/or polypropylene glycol. An ink for a ballpoint pen characterized by containing the following.