JPS6136383A - Ink for wire dot printer of ink type - Google Patents

Abstract

PURPOSE:The titled ink having improved drying resistance at a printer head, chroma, color concentration, etc. of printing, comprising specific dye, a water- soluble organic solvent, water urea, cationic activator, specific amine salt, and ethylene oxide addition type activator. CONSTITUTION:The aimed ink comprising (A) acid dye and/or direct dye, (B) a water-soluble organic solvent, (C) water, (D) urea(derivative), (E) a cationic activator and one or more of 4-12C amine hydrochloride, sulfate, formate, acetate, and lactate, and (F) an ethylene oxide addition type activator. EFFECT:Having improved color reproducibility and water resistance when color recording image is formed by color mixing method of subtractive color process by the use of black, yellow, magenta, and cyanic ink.

Description

Detailed Description of the Invention (Industrial Application Field) The present invention moves ink attached to the wire surface forward by sliding the wire back and forth, and transfers the ink attached to the wire surface to a printing medium. Regarding ink for ink-type wire dot printers, more specifically, black and yellow.

The present invention relates to an ink for ink-type wire dot printers that has excellent color reproducibility and water resistance when forming a color recorded image by a subtractive color mixing method using Mazenk and/or Unink.

(Prior art) An ink-type wire dot printer that moves ink adhered to the wire surface forward by sliding the wire back and forth and transfers the ink adhered to the wire surface to a printing medium is a printer that uses a wire that taps an ink ribbon with a wire. Unlike ribbon-type wire dot printers, which print by using liquid ink, the ink is guided to the printer head in a liquid state.
Since the physical properties of the ink, such as one color vI4, can be selected relatively freely, the print quality and color tone of the print can be changed freely, making it suitable for color printing.

(Problems to be solved by the invention) However, in general, 1. Inks using acidic dyes and/or direct dyes become unclear when the prints get wet with water after being printed on one sheet of paper. That is, there was a problem of poor water resistance.

Furthermore, due to the mechanism of ink-type wire dot printers, the ink is exposed to the air in the printer head, so if the printer is left in a stopped state as soon as the ink evaporates, the ink will evaporate. It is a known drawback that the head gradually dries up and when you try to restart the operation, the wire becomes difficult to move or solid ink is deposited on the head, making it difficult to print smoothly at the initial stage. Ta.

Therefore, attempts have been made to use aliphatic polyhydric alcohols and their derivatives as wetting agents for the purpose of suppressing drying of the ink, but although the drying of the ink can be suppressed to some extent, the printer is not operated for more than two days. When left for a long time, ink solids were observed to be deposited on the head, and the initial printing was extremely unstable when operation was resumed.

Therefore, the first objective of the present invention is to
When forming color recorded images using subtractive color mixing using magenta and cyan inks, the print medium has sufficient saturation and color density, and the print does not become unclear even when wet with water, and has good water resistance. There are many ways to obtain ink for ink-type wire dot printers.

A second object of the present invention is to provide an ink-type wire dot printer that prevents ink from drying in the printer head as much as possible and allows smooth initial printing of printers that have been out of operation for a long period of time. The purpose is to obtain ink.

(Means for solving problems) The present inventor aimed to obtain an ink for the above purpose.

The present invention was finally completed as a result of detailed studies on the mechanism of an ink-type wire dot printer and the composition of ink suitable for it.

That is, 1 the present invention comprises: an acid dye and a direct dye; a water-soluble organic solvent; water; urea and/or a derivative thereof; a cationic activator, a hydrochloride of an amine having 4 to 12 carbon atoms;
Sulfates, formates.

The gist of the present invention is an ink for an ink-type wire dot printer, which is characterized by comprising at least one of acetates and lactates; and an ethylene oxide-added activator.

(Function) It is not clear why the ink for ink-type wire dot printers of the present invention is suitable for use in wire dot printers, but it is speculated as follows.

The sulfonic and carboxyl groups of acid dyes and direct dyes and the cationic activators and the basic moieties of hydrochlorides, sulfates, formates, acetates, and lactates of amines having 4 to 12 carbon atoms form salts. hand.

It is poorly soluble in water, or becomes insoluble and hydrophobic.

The water resistance of printing is improved, and the hydrophobic groups in the ethylene oxide-added activator capture the salt-formed dyes, and the hydrophilic groups in the ethylene oxide-added activator form hydrogen bonds with water. The resultant salt-formed dye is solubilized. That is, the ethylene oxide-added activator forms micelles in an aqueous solution and envelops and solubilizes the colorant, resulting in better solubility than K, and as a result, it is believed that the print has sufficient saturation and color density. Further, it is considered that the drying of the ink in the printer head is prevented as much as possible due to some kind of synergistic effect between the slow drying property of urea and/or its derivatives and the salt-forming dye and the ethylene oxide-added activator.

(Structure of the invention) The present invention will be explained in detail below.

Acid dyes and direct dyes are used as coloring agents.One example is Eiseneosin GH (C, 1,45380).

Water Black Kaoru 21 (0, i, 15985°42
090.4274.5 mixed dye), Nigronon NB Conc (0,1,50420), Orient Water Black Sho 181-L (manufactured by Orient Chemical ■), Water Blue S 9 (c, i.

42090), Water Pink Book 2 (0,1゜45410), Kayaftatrazine (C!, 1゜1)
9140) + Suminol Milling Brilliant Red B (C, 1, 18134), Podgaya 7 Throat Brilliant Milling Green B (C,
1,42100), Kaya/, Ie. −〇()(0,1,
+8965), Orient Water Yellow $6 (
C! , 1.22910-8), and water blank Ki 100-L (C!, 1.3
5255), Direct Deep Black XA (manufactured by Sumitomo Chemical), Direct First Black Conch (
C, 1, 27720).

Orient Water Blue GS (C, R, 742
oo).

Orient Water Blue Sasa 117~L (0,174
There are 200 liquid types), which can be used alone or in combination, and the amount used is preferably 10 to 10% by weight of pure dye based on the total amount of ink. This is 10
If it is less than 10% by weight, the print density will be low and difficult to see, making it impractical. If it is more than 10%, the solid concentration in the ink will become too high, making it easy for the ink to dry in the printer head. .

The water-soluble organic solvent used in the present invention prevents ink from drying,
It is used for the purpose of promoting the dissolution of dyes, to give a specific example.

Ethylene glycol, glycol/glycol.

13-butanediol, 14-putenol diethylene glycol, triethylene glycol-/' + tetraethylene/glycol, ciflobylene glycol, methyl seronorb, ethyl seronorb, butyl seronorb, methyl seronorbu decatate, ethyl seronorp acetate , dimethylcelonorb, diglyme, glycerin, methylcarpitol, polyhydric alcohols such as carpitol and derivatives thereof, formamide, dimethyl sulfokide, tetrahydrofurfuryl alcohol, tetrahydrofurandimethanol.

Diacetone alcohol, 2-pyrrolidone, N-methyl-
2-pyrrolidone, 4-butyrolactone.

Sulfolane, thiogetanol, monoethanolamine, jetanolamine, triethanolamine, ethylene carbonate, phlopylene carbonate, morpholine, 1-(2-hydroquinoethyl)-piperazine, etc., one or two types. It can be used as a mixture of the above, and the amount used is preferably 5 to 40% by weight based on the total amount of the ink.

The amount of water used as the main solvent is 40 to 8% of the total amount of ink.
0% by weight is desirable.

Urea and/or its derivatives used in the present invention are mainly used for the purpose of promoting dye dissolution and preventing drying in the printer gutter, and are used in combination with water-soluble dyes and water-soluble organic solvents. As a result, it exhibits a particularly remarkable effect in preventing dryness in the printer head section. Specific examples of urea and its derivatives that can be used in the invention include urea, ethylene urea, tetramethyl urea, thiourea, and ethylene oxide/de adducts to urea. It is desirable that the amount is 20% by weight or less.

Cationic activators and hydrochlorides, sulfates, formates, acetates, and lactates of amines having 4 to 12 carbon atoms are used to improve water resistance.

Examples of cationic activators include Cationogen L (manufactured by Daiichi Kogyo Seiyaku ■), Cation AB, Cation 13B (manufactured by NOF ■), and Emco KCC-9 (Nikko Chemicals 1).
N), Ansbootx ()-40, -h-J-Suru CI3-50. -hff-/Ill TB (manufactured by Toho Chemical@), Cortamine 24P.

r-pin D-B6P, Sir'-C kC-dQ (manufactured by Kao Atlas ■), Alucard 20-75, Fcard c/42 (manufactured by Lion ■) XHQ○30
5. XI (CO402 (more than Morley Geno II)
Alkylpicolium salt types such as I-Gyo Seiyaku ■), Positono B (Hana, manufactured by TE Atlas ■), and Tekitol l'
I (Daiichi 1: Manufactured by Industrial Pharmaceutical Co., Ltd.) Elect-le $500
(+: Made of 1 bottle of oil and fat) and other polyamines, soft
$706 (Made with E1 oil)・, Demarfa-4O
Imidanosu 7 derivatives such as 0 (manufactured by Toho Chemical Co., Ltd.), Niregan PD (manufactured by Nippon Oil & Fats Co., Ltd.), and Anstex C-1.
60゜Anstex C-200 (manufactured by Toho Chemical)
.

Specific examples of amine salts having 4 to 12 carbon atoms include butyl amine salts, which are primary amines;
, amylamine, hexylamine/l hebutylamine, octylamine, caprylamine, secondary amines such as dipropylamine, dibutylamine, butylpropylamine, and tertiary amines such as triethylamine, tripropylamine, and tributylamine.

Butyldiethylamino, butyldipropylamine, propyldibutylamine, ethyldibutylamine, aromatic amino/o, m, p-phenylenediamine,
Benzyl 7 Mi7. Hydrochloride and sulfate such as OH-9p-toluidine.

Examples include formate, acetate, and lactate, which can be used alone or in combination, and the amount used is 01 to 20% by weight based on the total amount of ink, and if it is less than 01% by weight, the water resistance effect is weak. If it is more than 20% by weight, the odor may be too strong or the viscosity may be too high, so it is more preferably 05 to 1.
It is 0% by weight.

The ethylene oxide addition type activator is a dye salt formed and insolubilized with at least one of the above-mentioned cationic activator, hydrochloride, sulfate, formate, acetate, and lactate of an amine having 4 to 12 carbon atoms. It is used as a solubilizer, and specific examples include polyoxy/ethylene alkyl ether types such as Ny-Kol 1515 (manufactured by Nippon Nyukazai ■) and Emulgen +47 (manufactured by Kao Atlas ■), and Liponox NO (manufactured by Kao Atlas ■). Made by Lion ■).

Polyoxygen/ethylene alkylphenol ether type such as Emulgen 810 (manufactured by Kao Atlas ■) and Ny-Cole 25 (manufactured by Nippon Nyukazai ■).

Polyoxyethylene norbiqune derivatives such as Tween 20 (manufactured by Kao Atlas ■) and Emanone 3199 (
Kao Atlas ■), En7atsu) 0/2 (Lion ■
(manufactured by Lion) ;'z Which polyoxy/ethylene acyl ether type, polyoxy7 ethylene polyoxy/propylene pronoc polymer type such as Emulgen PP-130 (manufactured by Kao Atlas ■), Enmite (manufactured by Lion ■), Levalin (Bayer Polyoxyethylene-added amide types such as those manufactured by Kao Corporation), polyoxyethylene-added amine types such as Esoduomine (manufactured by Lion ■), and polyoxyethylene/higher alcohol types such as Emulgen 709 (manufactured by Kao Atlas ■).

There are special nonionic polyoxyethylene conductors such as Emulgen A-90 (manufactured by Kao Atlas ■) and Nucor 607 (manufactured by Nippon Nyukazai ■), and these can be used alone or in combination, and the amount used is If it is less than 1% by weight based on the total amount of ink, solubilization may not be sufficient.
If the content is 0% by weight or more, the handwriting may appear tinged, so the content is preferably 1 to 30% by weight, more preferably 2 to 20% by weight.

In addition, polyvinyl alcohol may be added to the ink of the present invention for the purpose of adjusting the viscosity of the ink, if necessary.

Polyvinylpyrrolidone, polyoxy/ethylene.

A small amount of water-soluble polymers such as methylcellulose, hydroquine ethylcellulose, hydroquinopropylcellulose, polyethyleneimine, and gelatin can also be added.

In addition to the above-mentioned components, various anionic compounds are added to the ink for the purpose of adding a wetting effect to the ink, smoothing the ink supply to the ink-impregnating member, and also improving the adhesion of the ink to the wire in the printing head. and/or a penetrating agent such as a nonionic surfactant of not more than 3% by weight based on the total amount of ink, and formalin, phenolpentachlorophenol sodium, dehydroacetic acid to prevent ink flow inhibition due to mold growth and ink decay. Sodium, 12-
A small amount of a preservative and a fungicide such as benzointhiazolin-6-one may be added as appropriate, and when the ink comes into contact with metal parts, benzotriazole, ethylenediaminetetraacetic acid, etc. may be added as necessary to prevent metal corrosion. Corrosion and rust preventive agents such as salt can also be added as appropriate.

The ink of the present invention is prepared by appropriately selecting, mixing, and dissolving the above-mentioned ink components.

(Example) The present invention will be explained in more detail in the following Example (C). In the Example, "part" means 1 part by weight.

Example 1 Water Plano, Rizen 181-L i6.4 parts (Orient Kagaku fmH, 2oX Norikino 1 item) Water Yellowness 6 0.5 parts (Orient Kagaku fmH, 2oX Norikino 1 item) Water Yellow 6 0.5 parts (Orient Kagaku fmH, 2 o

Ethylene glycol 10.0 parts
Basic
50 parts Broxel XI, -220 parts (manufactured by I-No-I Japan@).

12-penzoinothyanolin=5-one) Lobethylamine hydrochloride 19 parts (manufactured by Nippon Fine Chemical ■) Levalin (ethine rheoxide-added activator, manufactured by Bayer AG) Δ8s total I OC 1.0 parts Mix the above components After adjusting the pH to +0.7 with a 25% aqueous sodium hydroxide solution and stirring at 20 to 25°C for 2 hours, insoluble matter was filtered out using a membrane filter (manufactured by Sartorius, 0.211). Separately, viscosity L77
cP, surface tension 53 dyn/(a black ink was obtained.

Comparative Example 1 Water Black #181-1. 219 parts Water Yellow 16 06 parts Ethylene glycol 10.0 parts
5 parts Pruxel Ml
Manufactured with viscosity +, 55 cP + surface tension 65dy
A black ink of n/Cm was obtained.

Example 2 Suminol Milling Brilliant Leno M H ((l Yukagaku ■, C, 1, 2, 5 parts + 81
34) Water pink $2 o, 5 parts (
Orient Chemical @C,I.

Ethylene glycol 12. o section
Basic
7 o parts Broxel XL-22, 0 parts Encard C/12 (cationic activator).

Made by Lion #) 28 parts Leverin 75 parts total
10 Oo part Mix each of the above components and 25% hydroxide) IJum aqueous solution (trowel p I-1 was replaced with IjQ, and an ink was prepared in the same manner as in Example 1 to give a viscosity of 2.54 cp and a surface tension. 37 d
A magenta ink of y++/Ca was obtained.

Comparative Example 2 Suminol Milling Brilliant Red 13 5.3 parts Water Pink #2 07 parts Ethylene Glycol +2.0 parts Genus
70 parts Broxel XL -22,0 parts Total 1000 parts Same as Example 2 from each of the above ingredients! Please fix it.

A magenta ink with a viscosity of 149 cP and a surface tension b 1 dyn/(i) was obtained.

Examples & Water Blue Potato 3 0.7 parts (C, 1° manufactured by Orient Chemical ■) Water Blue Good 9 -11 parts (C, I manufactured by Orient Chemical ■).

Annod Brilliant Milling Part 05 Green B
(manufactured by Eisen ■ 0.1.42jOO) Ethylene glycol 12.0 parts
7 parts Broxel X L -22,0 parts
647 total 1000 parts The above components were mixed and 25% hydroxide) The pH was adjusted to 110 with an aqueous IJ solution, and an ink was prepared in the same manner as in Example 1, with a viscosity of 2. j 4 cP surface tension 39 dy
Ink of 777 colors of n/(a) was obtained.

Comparative Example 5 Water Blue Ichiban 5 0.9 parts Water Blue Book 9 15 parts Acid Brilliant Milling 06 parts Green B Ethylene Glycol +2.0 parts
Basic
70 parts Broxel XL-22, D total 100.0 parts Prepared in the same manner as in Example 5 using each of the above ingredients.

Viscosity 1.49 cP Surface tension 62 dyn/Ca 7
Obtained dark colored ink.

Example 4 Kayasil Yellow GG 2.8 parts (manufactured by Nippon Kayaku ■, 0.l.

Acid Yellow 17) Ethylene glycol 100 parts urine
Basic
50 parts Broxel XL-22, 0 parts XHOO5056, 4 parts Emulgen 147 (ethylene oxide addition type activator,
(Manufactured by Kao Atlas ■) 56 parts Total 100.0 parts The above components were mixed, the pH was adjusted to 77 with a 25% aqueous sodium hydroxide solution, and an ink was prepared in the same manner as in Example 1, and the viscosity J was 96 cP. Surface tension 41 dyn/
A yellow ink of Ca was obtained.

Comparative Example 4 Kayanol Yellow GG 3.7 parts ethylene glycol 120 parts urine urea
50 parts Broxel XL -22.0 parts water
775 parts Total: 1000 parts A yellow ink having a viscosity of 1.51 cP and a surface tension of 65 dyn/Om was obtained using the above components in the same manner as in Example 4.

(Effect of the invention) Examples 1 to 4. The inks of Comparative Examples 1 to 4 were used in an ink-type wire dot printer to perform printing and ink planning. The results are shown in the table below.

Each evaluation was performed in the following manner.

(υ Drying of the head: After printing with the prototype printer for 10 minutes, it was left indoors for 5 days, and then.

Printing was performed again, and judgment was made based on the change in color tone of the print and the presence or absence of fading.

(○: good, △: problematic, X: poor) (2) Color tone of print: As a substitute test, print on inkjet paper (ST-704A, manufactured by Jujo Paper ■) as a test piece, visually judge, evaluated.

(3) Water resistance of printing The test piece used for two-tone evaluation was immersed in water for 1 hour, air-dried indoors, and visually judged and evaluated.

As described above, the ink of the present invention is optimal as an ink for ink-type wire dot printers, having excellent drying resistance in the printer head, print saturation, single-color density, and print water resistance.

Claims (1)

[Claims] With an acid dye and/or a direct dye; With a water-soluble organic solvent;
Water; Urea and/or a derivative thereof; A cationic activator, at least one of hydrochloride, sulfate, formate, acetate, and lactate of an amine having 4 to 12 carbon atoms; Ethylene oxide addition type An ink for an ink-type wire dot printer, comprising at least an activator.