JP3304500B2 - Emulsion ink for thermosensitive stencil printing and printing method - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a heat-sensitive stencil emulsion ink, and more particularly to a heat-sensitive stencil emulsion ink which can be colored by heat and a printing method.

[0002]

2. Description of the Related Art Stencil printing is widely used as a simple printing method for printing tens to hundreds of sheets.
In this method, stencil printing master comprising an ink passage of the porous support, such as a thermoplastic film and washi, giving infrared flash, a heat <br/> corresponding to the character image image by a thermal head thermally The printed film is obtained by perforating a plastic film, passing ink from the perforated portion, and transferring the ink to paper or the like.

In such a stencil printing method, it is possible to print many identical character images using the same master and ink, but different characters and images are individually printed on a part of each printed matter. Or the name of each recipient cannot be individually printed on a postcard or the like. Conventionally, in such a case, a method has been adopted in which a character image is individually written manually at a place where writing is required, or a sticker, a label, or the like is attached. However, such a method has a drawback that when the number of prints increases, the work becomes complicated and the efficiency deteriorates.
Further, in the printing method using the conventional stencil printing emulsion ink, new characters and images cannot be developed by applying heat to the obtained stencil printed matter. Conventionally, a method of individually printing the names of individual recipients by a word processor is known, but in such a method, a ribbon tape for thermal transfer is required as a consumable,
It was uneconomic.

[0004]

SUMMARY OF THE INVENTION It is an object of the present invention to solve the above-mentioned problems of the prior art, and to print different character images one by one on a large number of printed materials by thermal printing. An object of the present invention is to provide a thermosensitive coloring type stencil printing emulsion ink and a printing method that can enjoy the color development and color change of characters.

[0005]

The first invention of the present application is directed to a water-in-oil emulsion ink comprising an oil phase and an aqueous phase, wherein the emulsion ink comprises a water-in-oil emulsion ink comprising an oil phase and an aqueous phase. Mutually by heat
Contains leuco dye and developer that melt and mix to form color
The present invention relates to a thermosensitive stencil printing emulsion ink comprising the leuco dye in an aqueous phase and the developer in an oil phase . The second invention of the present application is to print a character image using the emulsion ink for stencil printing, and then print the heat-sensitive area portion with the heat-sensitive coloring type stencil emulsion ink according to claim 1, or a stencil printing emulsion ink. multi print a character image and a heat sensitive area part using the heat-sensitive color forming stencil printing emulsion inks simultaneously
After obtaining several prints, each of the heat sensitive areas of the prints
Printing method characterized by forming a character image different applies heat corresponding to the character image with a thermal printer les continuously.

The water-in-oil (W / O) emulsion ink of the present invention contains a leuco dye as a color former component and a developer component as an acidic substance. When melted and mixed, the leuco dye changes from colorless to colored. After stencil-printing the heat-sensitive area portion with the heat-sensitive coloring type stencil printing emulsion ink of the present invention to obtain a large number of printed matter, on each heat-sensitive area part of the printed matter,
For example, by applying the information of characters and images stored in a database such as a word processor as heat by a thermal printer equipped with a heating device such as a thermal head, different characters and images can be easily continuously printed on the heat-sensitive area of each printed material. Can be written.

The leuco dye used in the present invention is not particularly limited, and dyes used for general thermal paper, for example, leuco dyes such as fluoran, triphenylmethane and spiropyran are preferably used. Specifically, 3-cyclohexylamino-6-chlorofluoran, 3-dimethylamino-5,7-dimethylfluoran, 3-dimeramino-7-chlorofluoran, 3-dimethylamino-7-methylfluoran, 3-dimethylamino-7,8-benzfluoran, 3-dimethylamino-6-methyl-7-chlorofluoran, 3-pyrrolidino-6-methyl-7-anilinofluoran, 3-diethylamino-7- ( o-chloroanilino) fluoran, 3-
Dibutylamino-7- (o-chloroanilino) fluoran, 3- (N-methyl-N-amyl) amino-6-methyl-7-anilinofluoran, 3- (N-methyl-N-
Cyclohexyl) amino-6-methyl-7-anilinofluoran, 3-diethylamino-6-methyl-7-anilinofluoran, 3-morpholino-7- (N-propyl-trifluoromethylanilino) fluoran, 3 -Pyrrolidino-7-trifluoromethylanilinofluoran, 3-pyrrolidino-7- (di-p-chlorophenyl)
Methylaminofluoran, 3-diethylamino-5-chloro-7- (α-phenylethylamino) fluoran,
3-diethylamino-5-methyl-7- (α-phenylethylamino) fluoran, 3-diethylamino-7-
Piperidinofluoran, 3,3-bis (p-dimethylaminophenyl) -phthalide, 3,3-bis (p-dibutylaminophenyl) -phthalide, 3,3-bis (p-dimethylaminophenyl) -6 -Dimethylaminophthalide, 3,3-bis (p-dimethylaminophenyl) -6
-Diethylaminophthalide, 3,3-bis (p-dimethylaminophenyl-6-chloroaminophthalide, 6'-
Chloro-8'-methoxy-benzoindolino-pyrrospirane, 6'-bromo-3'-methoxy-benzoindolino-pyrrospirane and the like can be mentioned.

Examples of the color developer used in the present invention include various acidic substances which react with the leuco dye upon heating to develop color, such as phenolic substances and organic or inorganic acidic substances. Specifically, salicylic acid, 3
-Isopropylsalicylic acid, 3-cyclohexylsalicylic acid, 4,4'-isopropylidene diphenol (bisphenol A), 4,4'-isopropylidenebis (2
-Chlorophenol), 4,4'-isopropylidenebis (2,6-dibromophenol), 4,4'-isopropylidenebis (2-methylphenol), 4,4'-
Cyclohexylidenebisphenol, 4,4'-cyclohexylidenebis (2-methylphenol), 4-phenylphenol, 4-hydroxydiphenoxide, α-
Naphthol, β-naphthol, 3,5-xylenol,
Thymol, 4-hydroxyacetophenone, catechol, resorcin, hydroquinone, pyrogallol, phloroglysin, 2,2'-methylenebis (4-chlorophenol), 2,2'-dihydroxydiphenyl, ethyl p-hydroxybenzoate, p-hydroxybenzoate Propyl acid, butyl p-hydroxybenzoate, benzyl p-hydroxybenzoate, p-chlorobenzyl p-hydroxybenzoate, p-methylbenzyl p-hydroxybenzoate, benzoic acid, 1-hydroxy-2-naphthoic acid , 2-
Hydroxy-6-naphthoic acid, 4-hydroxydiphenylsulfone, bis (4-hydroxyphenyl) sulfide, 2-hydroxy-p-toluic acid, tartaric acid, oxalic acid, maleic acid, citric acid, succinic acid, boric acid, clay And activated clay.

[0009] In the thermosensitive coloring type stencil printing emulsion ink of the present invention , the aqueous phase contains a leuco dye and an oil phase.
Contains a color developer . Leuco dye and developer are combined with aqueous phase
Emulsion by separate inclusion in separate phases of the oil phase
Emulsion inks are easier to manufacture, and emulsion inks are cheaper.
The qualification is improved . The use ratio of the leuco dye and the developer is usually in the range of 1 to 10 parts by weight, preferably 2 to 5 parts by weight, based on 1 part by weight of the leuco dye. The proportion in the emulsion ink is preferably 20 to 50% by weight based on the solid content of the emulsion ink.

The emulsion ink of the present invention is of the W / O type. The oil phase component contains, in addition to the developer, a solvent, a non-volatile oil, a resin, an emulsifier, and the like .
Water-soluble additives such as a water-soluble resin, an electrolyte, a fungicide, and an antioxidant can be contained in addition to the ico dye . As the solvent in the oil phase component, Nisseki No. 4 solvent, Nisseki 6
No. Solvent, Nisseki Isosol 400, high boiling petroleum solvents such as Ink Solvent 240, etc., as non-volatile oil, machine oil, spindle oil, olive oil,
Castor oil and the like, and examples of the resin include an alkyd resin, a petroleum resin, a phenol resin, a maleic resin, and a rosin-modified resin thereof. As the emulsifier, a nonionic surfactant is preferably used, and sorbitan monolaurate, sorbitan monopalmitate,
Oleic acid monoglyceride, oleic acid diglyceride,
Higher alcohols, alkyl phenols and the like can be mentioned.

Examples of the water-soluble resin in the aqueous phase component include methyl cellulose, polyvinyl alcohol, carboxymethyl cellulose and the like. Examples of the electrolyte include sodium sulfate and sodium borate. Examples of the fungicide include phenol and sorbin. Acid, dehydroacetic acid, methyl p-oxybenzoate and the like, and as the antioxidant,
Examples thereof include dibutylhydroxytoluene and butylhydroxyanisole.

The emulsion ink of the present invention may contain a hot-melt component in order to enhance the color development sensitivity of the leuco dye and the color developer. Examples of the hot-melt component include fatty acid esters, fatty acid amides, waxes and the like.
Compounds having a melting point of about 150 ° C. are preferred. Specific examples thereof include benzoic acid-4-benzyl ester, benzoic acid-4-methoxyphenyl ester, lauric amide, stearic amide, caproic amide, carnauba wax, montan wax, polyethylene wax and the like. The amount of these hot melt components is usually 1 to 10 parts by weight, preferably 1 to 3 parts by weight, per 1 part by weight of the leuco dye.

In order to prepare an emulsion ink containing a leuco dye which is a thermosensitive coloring component and a developer, 90 to 30 parts by weight of an oil phase component is added to, for example, 10 to 70 parts by weight of an oil phase component as in a normal emulsion ink. By gradually adding and emulsifying the aqueous phase component. The leuco dye, which is a thermosensitive coloring component, and the developer are combined with an aqueous phase component or an oil phase component , respectively.
The inclusion in minute, when preparing the aqueous phase or oil phase
Each of the heat-sensitive coloring components may be mixed, or a dispersion of the heat-sensitive coloring components is prepared in advance using a solvent, a dispersant, a resin, or the like used in the oil phase or the aqueous phase, and this is dispersed in the oil or aqueous phase. May be added .

The heat-sensitive coloring type stencil printing emulsion ink of the present invention is used for printing a heat-sensitive area for writing a different character image on a part of a printed matter. The heat-sensitive area portion of each printed matter printed is, for example, created by a word processor or the like in advance, and is individually heat-printed by a thermal printer based on the information of the character image stored in the database to express a character image and the like. The printing of the heat-sensitive area may be performed after printing the character image with normal stencil printing ink, or simultaneously printing the character image and the heat-sensitive area using the normal ink and the heat-sensitive ink of the present invention at the same time. Is also good. For example, after printing a large number of the same pattern on a postcard or the like using a simple stencil printing machine such as Print Gokko (trade name of Riso Kagaku Kogyo Co., Ltd.), the emulsion ink of the present invention is written in a place where the address, name, etc. of the recipient are written. By printing the heat sensitive area by using the thermal printer with the thermal printer, it is possible to easily print individual recipient names and the like continuously.

According to such a method, the working efficiency is remarkably improved, a ribbon tape for thermal transfer is not required unlike the prior art, and even if the formation of a character image in the heat-sensitive area fails, the area is not affected. The heat-sensitive emulsion ink of the present invention can be overprinted and reused, which is economical. Various colors can be developed by appropriately selecting a coloring component in the emulsion ink.

Hereinafter, the present invention will be described in detail with reference to examples, but the present invention is not limited to these examples.
In addition, the part in an example means a weight part.

【Example】

[0017]

Example 1 7 parts of 4,4'-isopropylidene diphenol, 35 parts of an alkyd resin, 50 parts of Nisseki No. 6 solvent and 8 parts of sorbitan monooleate were mixed and thoroughly kneaded with a three-roll mill. Oil phase component. Next, 20 parts of 3- (N-cyclohexyl-N-methyl) amino-6-methyl-7-anilinofluoran, 2 parts of methylcellulose and water 78
Part of the mixture was pulverized and dispersed by a sand mill to obtain a liquid D. 10 parts of the obtained liquid D, 5 parts of ethylene glycol and 8 parts of water
Five parts were mixed to obtain an aqueous phase component. While gradually adding 70 parts of the water phase component to 30 parts of the oil phase component, the mixture was stirred and emulsified to prepare an emulsion ink. Postcard with Print Gokko PG-10 using the obtained emulsion ink
All solid printing was performed to a size of 10 cm × 10 cm. I
After drying the ink, a word processor (Fujitsu
Crisp when printed with thermal printing using ASIC 30AX (registered trademark)
A black image was obtained.

Example 2 3- (N-cyclohexyl-N-methyl) amino-6
10 parts of methyl-7-anilinofluoran, 10 parts of stearic acid amide, 2 parts of methylcellulose and 78 parts of water were mixed, and the mixture was pulverized and dispersed by a sand mill to obtain an E liquid. The mixture was mixed to form an aqueous phase component. Next, while gradually adding 70 parts of the aqueous phase component to 30 parts of the oil phase component used in Example 1 , the mixture was stirred and emulsified to prepare an emulsion ink. After performing stencil printing using the obtained emulsion ink in the same manner as in Example 1, when performing thermal printing with a word processor, a clear image was obtained.

Example 3 In Example 2 , 3- (N-cyclohexyl-N-methyl) amino-6-methyl-7-anilinofluoran was changed to 3-dimethylamino-7,8-benzfluoran. An emulsion ink was prepared in the same manner as in Example 2 except for the above. When a latent image of a character was stencil-printed with Print Gocco PG-10 using this emulsion ink, and the printed portion was heated with a household iron, clear red characters were obtained.

Example 4 The emulsion ink obtained in Example 3 was mixed with HM yellow ink for Print Gocco PG-10 (manufactured by Riso Kagaku Co., Ltd.), and stencil printing was performed on Print Gocco PG-10 using this mixed ink. To obtain a yellow image. Next, when this portion was thermally printed with Oasis 30AX, clear red characters appeared on the yellow background.

[0022]

[0023]

According to the thermosensitive coloring type stencil printing emulsion ink and the printing method of the present invention, after stencil printing is performed, a different character image can be easily added to a part of the printed matter, and the stencil printing can be performed. Then, by heating, a character image of another color can be obtained.

──────────────────────────────────────────────────続 き Continuation of the front page (56) References JP-A-5-93161 (JP, A) JP-A-5-271592 (JP, A) JP-A-57-167380 (JP, A) 181572 (JP, A) JP-A-1-301770 (JP, A) JP-A-4-91172 (JP, A) JP-A-64-14284 (JP, A) JP-A-57-90085 (JP, A) JP-B-48-2111 (JP, B1) (58) Field surveyed (Int. Cl. ⁷ , DB name) B41M 5/26 B41L 13/04 C09D 11/00 C09D 11/02

Claims (2)

(57) [Claims] 1. A water-in-oil emulsion ink comprising an oil phase and a water phase, wherein the emulsion ink is exposed to heat.
Leuco dyes that melt and mix with each other to form color
A colorant, the leuco dye in an aqueous phase, and the developer in an oil phase.
A thermosensitive coloring type stencil printing emulsion ink characterized by containing . 2. After printing a character image using the emulsion ink for stencil printing, printing a heat-sensitive area with the emulsion ink for thermosensitive coloring type stencil printing according to claim 1.
Alternatively, a stencil printing emulsion ink and the thermosensitive coloring type stencil printing emulsion ink were simultaneously used to print a character image and a heat-sensitive area portion to obtain a large number of printed matter.
Thereafter, heat corresponding to the character image is applied to each of the heat-sensitive areas of the printed material by a thermal printer to obtain different character images.
A printing method comprising forming an image continuously .