JPH0720733B2 - Thermochromic printed matter - Google Patents

Description

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a printed matter in which the color of a printed image changes with a change in temperature, and more specifically, a printed matter obtained by process printing, in which the printed image changes from a black-and-white image to a natural color. It relates to a thermochromic print that reversibly changes to an image.

2. Description of the Related Art There have been many proposals for thermochromic printed matter, but as a printed matter by process printing, there is a disclosure in JP-A-55-63293. According to the above disclosure, the printed image changes from natural color to colorless or 1 to 3 colors of the black ink which make up a natural color image and 1 to 3 colors of black ink become colorless due to temperature change, and reversible to an image composed of the remaining 3 to 1 colors. The present invention relates to a thermochromic printed matter that changes with time.

DISCLOSURE OF THE INVENTION Problems to be Solved by the Invention As described above, the thermochromic printed matter disclosed above exhibits reversible thermochromic conversion from natural color to colorless or from natural color to an image in which some of the colors are decolorized. Of course, it is a colorless matter, but it is a printed matter that gives the impression of an unfinished image even in an image in which some of the colors have disappeared. It is a printed matter that exhibits a reversible change between the two aspects of the picture of the picture and the picture of the completed natural color.

The present invention is different from the above-described mode of discoloration, in which a black-and-white printed image is reversibly changed from a black-and-white printed image to a natural-colored image due to a temperature change, and both images before and after the change are perceived as a completed image. It is an object of the present invention to provide a thermochromic printed matter which exhibits a change between two aspects with a natural color image.

Means for Solving the Problems The thermochromic printed matter of the present invention is a printed matter obtained by process printing using cyan, magenta, yellow obtained from color separation of an original image and, if necessary, 3 or 4 plates for black. , Cyan, magenta, and yellow colorants and thermochromic colorants singly or in combination, which are the complementary colors of the cyan, magenta, and yellow colors, and three types that reversibly change from orange, green, and purple to colorless. And 3 kinds of thermochromic black inks containing each of the thermochromic colorants and the black inks, if necessary, are overprinted on the substrate by the plate of the corresponding color.

The three thermochromic black inks or (1) a cyan colorant and a thermochromic colorant that reversibly changes from orange to colorless due to a temperature change (even if it is alone, it shows a change from yellow to colorless). It may be a combination of a thermochromic colorant and a thermochromic colorant exhibiting a change from red to colorless. Hereinafter, this type of thermochromic colorant is abbreviated as ○ color thermochromic colorant).
An ink that reversibly changes from black to cyan when the temperature changes, (2) an ink that contains a magenta colorant and a green thermochromic colorant and that changes from black to magenta when the temperature changes, and (3) An ink that contains a yellow colorant and a purple thermochromic colorant and that changes from black to yellow due to a temperature change.

Further, the corresponding color plates are the process plate for cyan for the thermochromic black ink containing cyan, the process plate for magenta for the thermochromic black ink containing magenta, and the thermochromic black containing the yellow colorant. It means that the process version for yellow is used for the ink.

As the colorant, a pigment or dye conventionally used in printing ink is used.

The thermochromic colorant is an electron-donating color-changing organic compound, an electron acceptor of the organic compound (hereinafter simply referred to as an electron acceptor), and a compound serving as a medium for determining the temperature at which the two color reaction reactions occur. A reversible thermochromic composition consisting of three components (hereinafter abbreviated as discoloration temperature adjusting agent) or a thermochromic colorant in the form of microcapsules containing the composition, which are disclosed in Japanese Examined Patent Publication No. 44908,60-15667,15668,312
35,52189, JP-A-57-167380, 59-156790, 60-228589,61
Each component constituting the thermochromic composition, which is disclosed in Japanese Patent Publication No. 53388, is as follows.

Electron-donating color-forming organic compounds are triphenylmethanephthalides, indolephthalides, polyarylcarbinols, leuco auramines, acyl auramines, aryl auramines, rhodamine B lactams, indolines, spiropyrans. And a fluoran compound, which is a substantially colorless pigment forming a color with an acid (electron acceptor as Lewis acid). (Hereinafter abbreviated as dye former) As electron acceptors, phenol compounds and their metal salts, aromatic carboxylic acids and aliphatic carboxylic acids having 2 to 5 carbon atoms and their metal salts, acidic phosphoric acid esters and their Metal salts, 1,2,3-triazole and its derivatives,
Examples thereof include halohydrins having 2 to 5 carbon atoms and their derivatives, urea and thiourea and their derivatives, boric acid and boric acid esters and their metal salts, and 1-hydroxytriazole and its derivatives.

Discoloration temperature adjusting agents include alcohols such as decyl alcohol, lauryl alcohol, myristyl alcohol, cetyl alcohol, stearyl alcohol, behenyl alcohol, oleyl alcohol, isostearyl alcohol, hexamethylenediol, heptyl laurate, stearyl myristate, propyl palmitate, stearin. Esters such as ethyl acid lauryl benzoate, dicetyl adipate, lauric acid, myristic acid, palmitic acid,
Aliphatic carboxylic acids having 6 or more carbon atoms such as adipic acid and their anhydrides, ethers such as didecyl ether and didodecyl ether, ketones such as laurone, diheptyl ketone, stearone and benzophenone, stearamide, laurin Examples thereof include compounds having a boiling point of 150 ° C. or higher, such as acid amides and acid amides such as bisstearic acid amide.

In the thermochromic composition, the above three components, that is, the dye former, the electron acceptor and the color changing temperature adjusting agent are mixed in a weight ratio of 1: 0.1 to 10: 1 to 100, and melted at 80 to 100 ° C. to obtain a homogenous compatible solution. It is obtained by

The orange, green and purple thermochromic colorants may be used alone or may be composed of a mixture of a plurality of thermochromic colorants. The toning is carried out by stages of the composition or by mixing in the form of microcapsules. Further, the black toning of the thermochromic black ink disperses or dissolves the pigment or dye described below in the composition, or adds the dye or pigment to the ink containing the orange, green or purple thermochromic colorant. Or,
Alternatively, it is performed by mixing inks prepared separately.

Even if the color change temperature of each thermochromic colorant is slightly different,
The species may be the same and the others may be different, or the three species may be the same.

Next, cyan, magenta, yellow and black colorants will be described.

Phthalocyanine blue (CIPigmen
t Blue 15), Alkaline Blue G toner (CIPigment B)
lue 18), dark blue (CI Pigment Blue 27), etc., and as a dye, Carbanol Blue GX-FS (CI Vat
Blue 42) and the like.

Toluidine Red (CIPigment)
Red 3), Naphthol Carmine FB (CIPigment Red
5), anthocin 3B lake (CIPigment Red 66), naphthol red FGR (CIPigment Red 112), etc., and as the dye, rhodamine 6GCP (CIBasic Red
1), Sumilite Supura Brown 3RL (CIDirect Red 8
4) etc.

As a yellow pigment, Fast Yellow G (CIPigment Ye
llow 1), Fast Yellow 10G (CIPigment Yello
w), Disazo Yellow AAMX (CIPigment Yellow 1
3), Disazo Yellow AOAA (CIPigment Yellow 17)
Direct Pure Yellow as a dye
5G (CIDirect Yellow), Acid Fast Yellow 2
GL (CIAcid Yellow 29), etc.

In the three types of thermochromic black ink, the thermochromic colorant and the colorant are used in a weight ratio of 100: 0.01 to 50.

Carbon black (CIPigment Bl
ack 7), aniline black (CIPigment Black 1) and the like.

Black ink is not required, but it is used to reproduce the original image as a well-defined image.

A thermochromic black ink is obtained by combining the thermochromic colorant and the colorant described above and dispersing or dissolving them in a vehicle, or by mixing an ink containing each coloring component.

There are various types of printing inks that can be applied, such as cooling solidification type, evaporation drying type, permeation drying type, precipitation drying type, gelation drying type, oxidation polymerization type, heat curing type, moisture curing type, and UV curing type. The ink vehicle is composed of natural resin, naturally processed resin, synthetic resin, wax, solvent and the like.

The amount of the coloring component contained in the printing ink is 100
About 1 to 50 parts by weight of the thermochromic colorant, and the colorant 0.
It is in the range of 001 to 25 parts by weight.

Further, additives such as antioxidants, ultraviolet absorbers, plasticizers and antiblocking agents which are commonly used for modifying printing ink may be added.

Next, a printing ink vehicle will be exemplified.

Cooling and solidifying type (wax type) Carnauba wax, paraffin wax, microcrystalline wax, etc.

Evaporative drying type (resin / solvent type) rosin, maleated rosin, gelac, casein, styrene-maleic acid copolymer, acrylic resin, alkyd resin, cellulose derivative, petroleum hydrocarbon resin, low molecular weight polyethylene, polystyrene, polyacetic acid Vinyl, vinyl acetate-vinyl chloride copolymer, polyvinyl alcohol / petroleum solvent, aromatic solvent, alcohol solvent, ester solvent or ketone solvent, or water.

Gelation dry type (emulsion type) Vinyl polymer latex, vinyl copolymer latex, acrylic resin emulsion, synthetic rubber latex and the like.

Permeation dry type (resin / petroleum solvent) rosin, rosin derivative / machine oil, spindle oil, kerosene, etc.

Oxidation polymerization type Polymerized linseed oil, tung oil, dehydrated castor oil, oily deer oil, soybean oil modified alkyd resin, palm oil modified alkyd resin,
Flaxseed oil modified alkyd resin, etc.

Thermosetting epoxy resin, amino resin, heat-reactive unsaturated hydrocarbon resin, etc.

UV curable polyether acrylate, polyester acrylate, epoxy resin modified acrylate, etc.

Using the printing ink having the above-mentioned structure, process printing is carried out with an intaglio, letterpress, planographic or stencil plate according to the type and application of the substrate to be described later to obtain a thermochromic printed matter.

The base material is paper, cloth, non-woven fabric, plastics, ceramics, wood, glass, ceramics, stone plates, metal, etc.,
A transparent protective layer may be provided on the surface of the printing layer.

The thermochromic printed matter of the present invention has cyan and magenta which are complementary colors of each color in the temperature range below the color changing temperature of the orange, green and purple thermochromic colorants in the printed image. By complementing each other with the yellow colorant and the yellow colorant, each thermochromic ink has a black color, and as a whole, the original image has a black-white reproduction appearance. In the temperature range exceeding the color change temperature, the orange, green and purple are colorless, and the printed image is a natural color composed of three primary colors of cyan, magenta and yellow (four colors when black ink is used). It takes on the appearance of a reproduction of the original picture consisting of images.

Therefore, if the color change temperature is set to, for example, 40 to 50 ° C,
At room temperature around 20 ° C, the printed matter shows a black and white image, and when heat of 50 ° C or higher is applied, the printed matter becomes a natural color image, and when left at room temperature, it becomes the original black and white image. Also, if the discoloration temperature is set to 5 to 10 ° C, the printed matter exhibits a natural color image at room temperature around 20 ° C, and if cold heat is applied by means such as putting in a refrigerator, the image becomes black and white, and left at room temperature. If you do, the original color image will change again.

Here, when the three types of thermochromic colorants have slightly different color changing temperatures, the change gradually appears as the temperature changes. However, when the color changing temperatures are almost the same, the change appears sharply. Make the effect more prominent.

Example 1 Table 1 shows the composition, color change temperature, color change mode and form (whether microcapsule form or non-capsule form) of the thermochromic colorant for the printing ink used for preparing the thermochromic printed matter.

The contents of the dye former in Table 1 are as follows.

(A) 6-bismethoxyfluorane (b) 3-diethylamino-5,6-benzofluorane (c) 3- (4'-diethylaminophenyl) -3-
(1'-Ethyl-2'-methylindol-3'-yl) phthalide (d) 3-chloro-6-cyclohexylaminofluorane (e) 2- (N-phenyl-N-methylamino) -6-
(Np-tolyl-N-ethylamino) fluorane (f) 3-bis (4-dimethylaminophenyl) -6
-Dimethylaminophthalide The cyan dyes in the table are carbanol blue GX-FS (C.
I.Vat Blue 42), magenta dye is Rhodamine 6GCP (C.
I.Basic Red 1) was used respectively.

The following printing inks were prepared using the thermochromic colorant, thereby preparing thermochromic printed matter. All parts below are parts by weight.

Example 1 50 parts of thermochromic colorant A, 40 parts of the same B, cyan pigment (CIPigm
5 parts of ent Blue 15) was kneaded with 400 parts of an epi-bis type epoxy resin (molecular weight 390) to obtain a thermochromic black ink I which changed from black to cyan at 55 ° C.

Similarly, 40 parts of the thermochromic colorant A, 45 parts of the same C, 2 parts of magenta pigment (CI Pigment Red 66) and 380 parts of epoxy resin were kneaded, and the thermochromic black ink II changed from black to magenta at 55 ° C II. , 95 parts of the thermochromic colorant B, 45 parts of the same C, 4 parts of yellow pigment (CIPigment Yellow 1) and 400 parts of epoxy resin were kneaded, and thermochromic black ink III that changes from black to yellow at 60 ° C, respectively. Obtained.

Separately, 8 parts of carbon black was kneaded into 200 parts of epoxy resin to prepare a black ink.

100 of each of the thermochromic black inks I, II, III and black ink
2.5 parts of a curing agent, diethylenetriamine, was added to each of the parts, and a corresponding plate of a screen plate for cyan, magenta, yellow, and black obtained by color-separating the original image was used and overprinted on the surface of the mug.

The printed image on the surface of the obtained mug exhibited a black-and-white image at 55 ° C or lower and a natural color image at 60 ° C or higher, and was reversible.

Example 2 100 parts of thermochromic colorant D was kneaded with 120 parts of epoxy resin to obtain thermochromic black ink IV which changed from black to blue at 55 ° C.

When the thermochromic black ink I in Example 1 was replaced with the above IV and printed, the printed image showed the same color change as in Example 1.

Example 3 100 parts of thermochromic colorant E, cyan pigment (CI Pigment Blue
18) 35 parts were dispersed in 650 parts of 15% styrene-maleic anhydride copolymer ammonia aqueous solution to obtain a thermochromic black ink V which changes from cyan color to black at 15 ° C.

Similarly, the thermochromic colorant F4 20 parts, the magenta pigment (C.
I.Pigment Red 66) 2 parts by weight is dispersed in 750 parts of a 15% styrene-maleic anhydride copolymer aqueous solution to change from magenta to black at 15 ° C. 15 parts of G400 parts, 24 parts of yellow pigment (CI Pigment Yellow 1)
% Styrene-maleic acid copolymer aqueous solution dispersed in 600 parts, thermochromic black ink that changes from yellow to black at 15 ℃ VI
Got I.

Thermochromic black inks V, VI, VII using gravure plates for cyan, magenta, yellow and black created by color separation of the original image
Also, the water-based black ink was overprinted on a 20 μm thick aluminum foil laminated high quality paper. The obtained printed matter showed a black-and-white image below 15 ° C, and a natural color image above 15 ° C.

When the printing paper was applied as a label to each of the aluminum and PET drinking water containers, the temperature range and the remaining amount of the contents were displayed by a black and white image and a color image.

Example 4 200 parts of the thermochromic colorant H was dispersed in 800 parts of a 10% shellac-hydroalcoholic solution to obtain a thermochromic black ink VIII.

The thermochromic black ink VI in Example 3 was used as the black ink VI.
The printed matter printed in place of II exhibited the same color change as the printed matter of Example 3.

Example 5 Thermochromic colorant I 400 parts, cyan pigment (CIPigment B
lue 1) 0.5 part, polymerized linseed oil 400 parts, and rosin-modified phenolic resin 150 parts were kneaded to obtain a thermochromic black ink IX exhibiting black below 30 ° C and blue above 30 ° C.

Similarly, the thermochromic colorant J 400 parts, polymerized linseed oil 400
Part, 100 parts of rosin-modified phenolic resin, and kneaded at 30 ℃
Black at less than 30%, thermochromic black ink X that exhibits magenta color at 30 ° C or higher, thermochromic colorant K 400 parts, fast yellow 10G
(CIPigment Yellow 3) 2 parts, polymerized linseed oil 400 parts,
120 parts of a rosin-modified phenolic resin was kneaded to obtain a thermochromic black ink XI exhibiting black at less than 30 ° C and yellow at 30 ° C or more.

Carbon black in a vehicle of thermochromic black inks IX, X, XI, polymerized linseed oil, and rosin-modified phenolic resin, using offset plates for cyan, magenta, yellow, and black ink, respectively, created by color separation of the original image. The black ink in which the ink was dispersed was overprinted on high-quality paper to obtain a thermochromic printing paper. This printing paper changes the image from black and white to color depending on the body temperature, and is useful for books with pictures, securities requiring forgery prevention, or forgery prevention seals.

Example 6 Thermochromic Colorant I of Thermochromic Black Ink V, and Thermochromic Colorant H of Thermochromic Black Ink VIII in place of Thermochromic Colorant E
In place of the thermochromic colorant J, and the thermochromic colorant K of the thermochromic black ink VII in place of the thermochromic colorant K to obtain thermochromic black inks XII, XIII, and XIV, respectively. .

The black inks XII, XIII, XIV and the water-based black ink were heat-shrinkable with a vinyl chloride film (20 μm thickness, shrinkage ratio) using cyan, magenta, yellow, and gravure plates for black ink created by color separation of the original image. 40%) was overprinted on the surface to obtain a heat-shrinkable vinyl chloride film having a black-and-white image below 30 ° C and a printed image showing a color image above 30 ° C. This shrinkable film is applied for decoration of writing instruments.

In addition, although a hard vinyl chloride film with a thickness of 0.2 mm is used as a base material for overprinting in the same manner as above, a plate laminated with a 2 mm thick white vinyl chloride sheet while pressing at 180 ° C. for 10 minutes is useful as an underlay. is there.

Example 7 Thermochromic Colorant I 160 parts, dark blue (CIPigment Blue 27)
80 parts were dispersed in 290 parts of an acrylic ester resin emulsion to obtain a thermochromic black ink XV that exhibits black at temperatures lower than 30 ° C and blue at temperatures higher than 30 ° C. Similarly, thermochromic colorant J2
Disperse 00 parts in 300 parts of acrylic acid ester resin emulsion, thermochromic black ink XVI showing black below 30 ° C and magenta color above 30 ° C, thermochromic colorant K200 parts, yellow pigment (CIPigment Yellow) 3) 4 parts of this was dispersed in 300 parts of an acrylic ester resin emulsion to obtain a thermochromic black ink XVII exhibiting black at temperatures lower than 30 ° C and yellow at temperatures higher than 30 ° C.

Using the screen plates for cyan, magenta, yellow and black ink created by color separation of the original image, the black ink XV, XV
Black inks obtained by dispersing carbon black in I, XVII and the acrylic ester resin emulsion were overprinted on cotton cloth T-shirts, respectively, to obtain T-shirts with a printed image that changed from black-white to color at body temperature. In the same manner, handmade items such as handkerchiefs with heat-discolorable printed images, gloves, socks, etc. were obtained.

EFFECTS OF THE INVENTION As described above, the printed matter of the present invention not only enjoys the surprisingness that it reversibly changes from a black and white image to a natural color image due to temperature change, but also each image before and after the change is a completed image. Therefore, it can be said that each color has the value of an ordinary printed matter, and is one printed matter having images of two colors. As described above, not only the printed matter itself is useful, but also an article in which the printed matter is combined can be greatly added.

Claims (1)

[Claims] 1. A printed matter obtained by process printing using 3 or 4 types of plates for cyan, magenta, yellow and, if necessary, black obtained by color separation of an original image, each of cyan, magenta and yellow colorants. And each of the three types of thermochromic colorants that reversibly change from orange, green, and purple, which are complementary colors of cyan, magenta, and yellow, which are composed of a thermochromic colorant alone or in combination, to colorless. Three types of thermochromic black ink and black ink, if necessary, are overprinted on the substrate by the corresponding color plates, and the thermochromic color reversibly changes from a black-and-white image to a natural color image due to temperature change. Printed matter.