JPS5933187A - Heat-sensitive transfer medium - Google Patents

Abstract

PURPOSE:To provide a heat-sensitive transfer medium capable of obtaining a high-density image and transferred images repeatedly, which is constituted of a transfer master sheet provided with a transfer layer comprising a leuco dye and a receiving sheet provided with a receiving layer comprising a color developer, wherein the transfer layer and/or the receiving layer contains specified compounds. CONSTITUTION:The transfer sheet provided with the transfer layer comprising a leuco dye (e.g., crystal violet lacton) as a main constituent on a base such as a paper and the receiving sheet provided with the receiving layer comprising a color developer (e.g., 4-tert-butylphenol) having a melting point of not higher than 200 deg.C as a main constituent on a base are provided, and at least one compound of formulas I -V [wherein each of R<1>, R<2> is 10-30C alkyl; each of R<2>, R<6>, R<11> is 1 30C alkyl; each of R<4>, R<5> is H, lower alkyl; each of R<7>, R<8> is H, halogen, lower alkyl (alkoxy); R<9> is 1-30C alkyl, (substituted)aryl; each of R<10>, R<12> is H, halogen, lower alkyl; n is 0.1] (e.g., decylacetamide) is incorporated in the transfer layer and/or the receiving layer, thereby obtaining the objective heat-sensitive transfer medium.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a thermal printing medium on which an image with a single height can be obtained and on which images can be transferred many times. ．． in. ．． be.

Traditionally, internal organs? As a thermal transfer medium, is it thermal sublimation? A transfer sheet with transfer material 1 provided on a support. and a receiver that receives a sublimation dyed image by thermal printing from the back side of the sheet. −・． Those consisting of storage sheets, . A type of transfer/-1 in which a transfer layer of a monochromatic material and a pigment or dye is provided on a support and a receiving sheet is known.・! The paper image on the top is not very durable, and is a transferred image. ．． Must apply O.111. on top: must be applied after O. Those of other companies contain pigments or... Because it is a transfer layer with dye dispersed in it, it is possible to obtain high-density images.・: If a large amount of pigment is included for the purpose, the transfer efficiency will be lowered, making it difficult to obtain a high density image. If a large amount of thermofusible material is used to increase sensitivity, a large amount of the thermofusible material will migrate to the receiving sheet 1 side, making it difficult to peel off the transfer sheet and receiving note smoothly. First, there were drawbacks such as the image areas of thin lines becoming unclear.

．． ．． :: At the bottom, substances that react with each other and develop color due to heat are supported on separate supports, and these substances are mutually supported.
i crystal:. Goods. ，? 1? One. ,a? , Uu? ? ·body. Although it is not well known, this kind of thing is a reactive type) because of 《Is it just a picture during face-to-face contact? If the copying layer simply transfers to the receiving layer, sufficient coloring reaction will not occur, resulting in a low-density image, and sufficient reaction will not be promoted. If so, the image on the receiving sheet 1 will be a more dense image, but the coloring reaction will also proceed on the transfer sheet 1, and the image formation will be slight. The point is. Is recognized.

The present invention is described above. Ω species. In comparison to skewered thermal transfer media, it is possible to provide a thermal transfer medium that has higher thermal sensitivity and can provide high-quality images, and also allows a small amount of dye components to be transferred from the transfer layer to the receiving layer. The purpose of the present invention is to provide a heat-sensitive transfer medium that allows high-density transfer images to be obtained multiple times through transfer.

That is, according to the present invention, a transfer sheet 1. has a transfer layer containing a leuco dye as a main component, and a receiving sheet 1. There is provided a thermal transfer medium, characterized in that the transfer layer and/or the receiving layer contains at least one compound represented by the following general formulas (1) to (V).

General formula (1) R,'NTTqOR. ”,.(1), (wherein R,1 is an alkyl group having 10 to 30 carbon atoms, R2
is an argyl group having 1 to 30 carbon atoms) General formula (II) (R, .3 is an alkyl group having 10 to 30 carbon atoms, R
4, R4 is hydrogen or lower alkyl. ) General formula (
lI1) (wherein, .R6 is an ano-kyl group having 1 to 30 carbon atoms, l,
R7, Rl8 are hydrogen, halogen, lower alkyl group or lower alkoxy group, n is O or 1) general formula (
IV) (wherein R,' is an ylekyl group having 1 to 30 carbon atoms or a substituted or unsubstituted phenyl group, R10 is hydrogen,
General formula (V) (In the formula, B, , I1 is an alkyl group having a carbon prime number of 1 to 30, and R12 is hydrogen, halogen, or a lower argyl group.) In the above, the alkyl group includes a saturated or unsaturated alkyl group, and the lower alkyl group includes a carbon number of 1 to 6.
It includes things like . No Rogen has... chlorine, bromine,
Substituted aryl groups include iodine and fluorine, and substituted aryl groups include alkyl groups, alkoxy groups, a. This includes a phenyl group substituted with a substituent such as a halogen group or a halogen group.

In the thermal transfer medium of the present invention, a receiving sheet is stacked on a transfer sheet so that the receiving layer is in contact with the transfer layer (dye layer) of the transfer sheet, and the back side of the transfer sheet 1 or the receiving sheet 1. A desired colored image is formed on the surface of the receiving sheet 1 by the heat transfer from behind. When the transfer layer and the receptor layer are brought into contact with each other and heated as described above, only a portion of the dyeing in the transfer layer is transferred to the receptor layer by the thermal melt of the color developer in the receptor layer. By using Transfer No. 1 and sequentially replacing only the receiving sheets, it is possible to obtain a large number of copies with high-density images.

In the present invention, as described above, specific compounds represented by the general formulas (+) to (v) (hereinafter, transfer It is characterized by containing at least one type of auxiliary agent). By adding this transfer aid to the transfer layer and/or the receiving layer, when the transfer layer and the receiving layer are brought into contact with each other and heated, the reaction between the leuco dye transferred from the transfer layer to the receiving layer and the color developer is facilitated. and provides clear, high-density images. That is, the transfer aid exhibits the following effects.

(1) The coexistence of a dye binder lowers the melting point of the transfer layer. (This includes not only the decrease in the melting point of the dye, but also the decrease in the melting point when the painting power aid is melted; that is, the dye dissolves into the molten transfer aid.) (2) Color developer and It becomes eutectic and lowers the melting point.

(3) In reality, (1) and (2) occur simultaneously, lowering the melting point of the reaction system as a whole. ? In the present invention, the transfer aid described above can be added to one or both of the transfer layer and the receiving layer, but in the case of the present invention, it is preferable to add it to at least the transfer layer to obtain a good image. It is preferable because it strengthens the transfer. The amount of transfer aid used is O. 1 to 50 parts by weight.

Specific examples of the transfer aid used in the present invention are shown below.

N of the acid amine P used in the present invention represented by the above general formula
Among the substituents, examples of compounds of general formula (1) and general formula (II) are as follows.

decylacetamide 12 decylnarobionamide 1, undecylacetamide lξ, u/decylzolopionamide, lauryl acetamide, laurylzolopionamide P1 tridecyl acetamide? Toamihi, ``1・Ridecilpionamide P, Myristyl acetamide, Myristylzolopionamide R, Pentadecyl acetamide 1・Ami P1 Takuntadecilpamine P, ?noξ Lumitylacetamide, Norξru 5
Tilpromonamide, walnutylbutyramide, hezotylacetamide P1 heptylpropylene amide, stearyl acetamide 171 stearylzolopylene amide P, stearyl butyramide J stearyl nonoleramide, stearyl cazolone amide P , stearyllaurinamide, stearylnoξlumitinamide, stearylstearinamide, nonadecylacetamide, nonadecylzologionamide, phenylacetamide P5 phenylprobionamide, hehenylstearinamide, undecanoic acid methylamide, undecanoic acid ethylamide, lauric acid methyl?
Ruamide,? Lauric acid ethylamide, tridecanoic acid methylamide, tridecanoic acid ethylamide, myristic acid methylamide, myristic acid ethylamide, K methylamide F + 1 pentadecanoic acid ethylnamide, methyl palmitic acid IF, y'i lumitic acid dimethylamide, ξ butyl rumitate + mi + Q , stearic acid methinocytemide, stearic acid ethylamide reverse 1, stearic acid propylamide, stearic acid butylamide, stearic acid dimethylamide, metheteric acid diethylamide, stearic acid dibutynoC amide P1 nonadecanoic acid methylamide, nonadecanoic acid ethylamide 1, phenic acid methylamide, Methylamide oleate P, ethylamide oleate.

Among the N-substituted acid amides represented by the above general formula, those represented by the general formula (■) include, for example, N-stearinpenzamide'pJ-7ξlumity-2-chloropenzamide, N-stearinoleni-2-methoxypenzamide, AmiP,N-stearyl-4-methylpenzami1,N-
ξ-methyl-2.4-i Methylpenzamide, N-pehenylbenzamide, N-behenyl-2-methylbenzamide, N-stearylphenylacetylamide, N-
Examples include behewata noremei and ruacetylamide. Among the enzymatic amide substituted compounds Ω represented by the general formula of Zenmei, examples of the compounds represented by the general formula (■) and the general formula (v) include φ′. N-cyclohexyl acetamide, N-cyclohexyl compound. mil♂, N-cyclohexyl stearic acid amide 15, N-7 chlorohexyl esteramide, N-7 cyclohexyl-2-methylbenzamide 1:',
N-zochlorohexyl-2-chloromethane 1:″, N
-cyclohexyl-2,4-dimethylbenzami+:'
, N-cyclohexyl ξ rumitate amyl', N-(
2-1 lorohexyl).・Nξrumitic acid amino}', N
l-(,2-methinohexyl)steer. Examples include amyl phosphoric acid P, N-stearyl hexahi P-benzami 15'.

The transfer layer used in the present invention is one in which a transfer layer containing a leuco dye as a main component is provided on a support such as paper, composite paper, or plastic film. Roy in this case. As the co-dye, any dye conventionally used for pressure-sensitive paper or thermal paper can be used, and l-IJ phenylmethane-based, fluoran-based, phenothiazine-based, auramine-based, and spiropyran-based dyes are preferably used. Ru. these!
An example of the realm of Ikosomesashi is shown below. ．． 3.3-bis(p-dimethylaminophenyl)monophtali+:,,13,. a-bis(p-dimethylaminoenyl)-6. -, dintylaminophthalene (also known as crystalline pyolet lactone), :u, :3-bis(p
-4methylaminophenyl')-6-4ethylaminophthaliP, 3,3-bis(p-nomethylaminophenyl)
-6-chlorophthali)y, 3Il13-bis(p-dibutylaminophenyl)phthalide, 3-cyclohexylamino-6-chlorofluoran, 3-(N.+N-diethylamino)-5-methy/l/-7 -(N,N-)pendylamino)fluorane, 3-)methylamino5,7
-Dimethylfluorane. , 3-diethylamino-7-methylfluoran, . 3--, It ethylamino-7,8
-penzfluorane, 3-diethylamine-6-methyl-7-chlorofluorane, 3-pyrrolidino-6-methyl=7-anilinof-olane, 2={N-(3'-1-,
Lifluoromethylphenyl)amino l-6-)ethylaminofluorane, 2,(.3.6-bis(-)ethylamino)-9-(o-k o/l/γ=17-)#zanthyl benzoic acid lactam}, 3-diethyl urea ≧ no 7-(o-
chloroanilino) fluorane, 3-dibutylamino-7
-(o-chloroanilino)fluoran, 3-N-methyl-N-amylamino-6-methyl-7-anilinofunoviolan, :3-N. monomethyl-N-chlorohexylamino-6-methyl-7-anilinofluorane, 3-(,2
'-hydroxy-47-dimethylaminophenyl)-3
, (2',monomethoxy-5'.-chlorophenyl)phthalito, 3-(2'-hyFoxy-4'-dimethyla.
Mino. , phenyl)-73-(2'1-me1-kin-5'
1-ditrophenyl)phthalyl1, 3-(2'-hydroxy-47-diethylaminophenyl')-3-(2'-methoxy-5'-methylphenyl)phthalyl', 3-(2
'monomethoxy4'-dimethylaminophenyl)-3-
(2'-hydroxy'/-4'-1'lo-57-methylphenyl)phthalide.

In the present invention, the leuco dye is applied to the support.
Normally 0.3~50f/m2, preferably 0.5~30f
//Used at a rate of about pn2.

The receptor sheet used in the present invention is one in which a receptor layer containing a color developer for the leuco dye is provided on a support such as paper, synthetic paper, or plastic film. In this case, as the color developer, an electron-accepting substance such as a phenolic substance, an organic acid or a salt or ester thereof, etc. is used.
From the viewpoint of practicality, those having a melting point of 200° C. or lower are preferably used. Specific examples of color developers preferably applied in the present invention are shown below. Note that the numbers in brackets indicate the melting point.

4-t. ert-butylphenol (98), 4-hyP
roxidiphenyl ether (84), ]-naphthol (
98), 2-naphthol (121), methyl-4-hyP
Roxypenzoate (131)%'4-Hydroxyacetophenone (109), 2. ．． , 2'-dihydoxydiphenyl ether (79), 4-phenylphenol (
I66), 4=Ierj-octylcatechol (+09
), 2,2'-dihi-1groxydiphenyl (103),
4.4'-methylenepisphenol (160'), 2,
2'-methylenebis(4-chlorophenol) (16
4), 2,2' dimethylenebis(4-methyl-6.-t
crt-butylphenonyl') (125), 4',4'
-isozolopylidene dilaenol (156), 4,4'
-isozolopylidene bis(2-chlorophenol) (9
0), 4,4'-inzolopylidene bis(2,6-dibromophenol) (172), 4,4'-isopropylidene bis(2-t:er't-butylphenol) (1
10), 4,4'-isopropylidene bis(2-methylphenol) (]36), 4,? 4'-isopropylitempis (2+”--)methylelephenol) (168)
,．． 4,4'-SeC-butylidene diphenol (1.
19), 4,4′-Secondary Ptylidenepis (2-
methylphenol) (L42), 4,4'-cyclohexylidene diphenol (180), 4,4'-cyclohexylidene bis(2-methylphenol) (1.84)
, salicylic acid (I63), salicylic acid methalyl ester (74), salicylic acid phenacyl ester (110)
, 4-hibiloxybenzoic acid methyl ester (131),
4-hydroxybenzoic acid ethyl ester (116) J'
4-Hydroquine benzoic acid proyl ester (9s), 4
-Hydoxybenzoic acid improvil ester (86),
'4-Macrodrogysibenzoic acid butyl ester (7T), 4
-HiIF'0 xybenzoic acid isoazole ester (5(1
), /l-Hi'IF Roquin benzoin e/phenyl ester (178), s-hyde xybenzoate:benzoic acid benzyl ester (II+), 4-hilp+'+4-benzoic acid cyclohexyl ester (1]9 ), 5-hydroxysalicylic acid (206), 5-chlorsalicylic acid (172), 3-chlorsalicylic acid (]'78), thiosalicylic acid (464
), 2-chloro-5-nitrobenzoic acid (165), 4-
Methoxyphenol (53), 2-hydroxybenzyl alcohol (87), 2,5-dimethylphenol (7
5), benzoic acid ('122), orthotoluic acid (10
7), me〉toluic acid (+i+), ・guratoluic acid (
181), orthochlorobenzoic acid (142'), metaoxybenzoic acid (200), 2.4-dihi]? 4-benzophenone (1)
33), 2,”'4-dihydroxyrepenzophenone (1
44), 2-Nafl・Itsuk・Assid (+s4), 1
-hi + y logic 2 - naphtoic acid F' (195
), 3,4-dihyroxybenzoic acid ethyl ester (1
28), 3.4-Proquinbenzoic acid:;enyl ester (189L4-Proquinbenzoic acid)
0. ), zalisylzalisile} ('148), phthalic acid monoquaternyl ester (107).

Further, in the present invention, the receiving layer may contain a porous filler. When the receiving layer contains a porous filler, the heat-melting reaction component from the transfer layer quickly transfers to the receiving sheet side, and image formation is removed on the receiving sheet side, and a small amount of transfer occurs. Also, the coloring reaction between the dye and the color developer is sufficiently carried out on the porous filler, and a significantly high density of the colored image is achieved. in this case,
What about porous fillers? The condition is that it has a certain amount of oil absorption, specifically 50ml! /1002(JISK
5101 law) is”2,? Preferably 150ml!
/1oo2 or more? things are used. Examples of this porous filler include inorganic and organic fine powders such as silica, aluminum silicate, alumina, aluminum hydroxide, magnesium hydroxide, urea monophor → phosphorus resin, and styrene resin. The thorns are color developer 1 weight = i
On the other hand, it is used in a proportion of 0.05 to 10 parts by weight, especially,
It is preferable to use it in a range of 0.1 to 3 parts by weight from the viewpoint of thermal sensitivity and image density. ? When the transfer layer or receiving layer is provided on the support, commonly used mixtures are used, such as Eha, Holihyur alcohol, Mel, Kiseno I/Rome, Hypokin ethyl cellulose, and Calze. Hydroxymethylcellulose, polyvinylpyrrolidone, polynacrylnag β, polyacrylic acid, Denzon, gelatin, styrene, vinyl chloride-vinyl acetate, polybutylene, methacrylate, and other water-soluble silicone, organic soluble, soluble or aqueous emulsion formation You can read the book on sex. 'Honhaimei's thermal transfer media is prepared by dissolving each of the above-mentioned layer-forming components together with a solvent such as water in a pulverizing and mixing means such as a ball mill or Natliter to prepare each layer-forming liquid. Dry coverage on support 0.3
It can be obtained by applying the coating so that it becomes ~30 f//m2.

The transfer layer provided on the surface of the transfer sheet 1 used in the present invention may be a so-called plain (no image) layer provided uniformly over the entire surface of the support;
It may be provided in advance in the form of a desired image. A transfer sheet having an image-free transfer layer can be obtained by simply applying a transfer layer forming liquid to the surface of a support.

On the other hand, those with an image-like transfer layer have a
It can be obtained by applying the transfer layer forming liquid in the form of a desired image (including letters) by letterpress printing or gravure printing, or by applying the transfer layer forming liquid to the surface of the image-free transfer layer of the above-mentioned transfer sheet. , overlap the appropriate support surfaces such as paper, synthetic paper, plastic film, etc. The non-image transfer layer of the transfer sheet 1 is pressed from the support side or the transfer sheet 1 side in an image-like manner using a typewriter, iron tF, etc., or a heat suppressing means such as a thermal head or a thermal pen. can be obtained by imagewise attachment to the surface of other suitable supports.

In order to carry out the thermal transfer of the present invention, for example, an image-like transfer layer. A transcription that has. When using =1., a receptor layer of -1. is applied to the surface of this transfer layer until the receptor layer is in contact with the surface of the transfer layer. This can be done by stacking them like this and passing them between heated rolls. Transfer sheet 1 with an image transfer layer
When using a transfer sheet, it can be done by overlaying the receiving layer of a receiving sheet on the surface of the transfer layer of the transfer sheet and directly heating printing using a thermal printer from the back side of the transfer sheet. stomach. In this method, the receiving layer of the receiving sheet is placed on the transfer layer of the transfer sheet, and the original drawing written in black ink is placed on the back side of the transfer sheet. This can be done by selectively heating only the black image area at a high temperature (in this case, both the transfer sheet and the receiving sheet must be transparent to infrared rays ).

In such thermal transfer according to the present invention, the above-mentioned operation is repeated using the same transfer sheet.
Therefore, a large number of copies can be easily obtained. In addition, when obtaining multicolor copies, create transfer sheets that use one ico-dye of different tones as the main coloring component, such as transfer sheet 1 with blue leuco dye and transfer sheet 1 with red leuco dye. However, if a transfer image is formed on the same receiving sheet by transfer, nine colored images of blue and red can be formed on the same sheet.

In the present invention, since the leuco dye and its color developer are contained in separate supports, the problem of blurring of coloring power during production and storage, which was seen with conventional thermal paper, can be avoided. Furthermore, the resulting copy contains only a color developer and no leuco dye in the non-image area, so no color development occurs even if it is heated (i.e. , fully fixable). Furthermore, it is also economical because high-density images and a large number of copies can be obtained with a small amount of heating energy.

The present Akanemei will be explained in more detail with reference to Examples.

Example 1 After dispersing a composition consisting of 209 N-stearylbenzamide, 5 t of ethyl cellulose, and 2,002 t of water using a Zeel mill for 24 hours, a polyester with a thickness of 12 μm was roughened using a wire sprayer. After coating on the surface of the film and drying, the amount of adhesion is jOf/m.
A No. 2 transfer sheet was created (Transfer Sheet A-1). A transfer sheet was also prepared in the same manner except that stearyl acetamide was used instead of N-stearylpenzamide (transfer sheet A-2). On the other hand, transfer sheets were prepared in the same manner except for N-stearylpe/Tsami 1 for comparison (transfer sheet c-i.) Next, the coated surfaces of these transfer sheets were brought into contact with high-quality paper. Then, applying printing pressure from a typewriter from behind the high-quality paper, the transfer print sheets 81', A-2', and O, which are mirror images, are printed.
il. ' were created respectively. On the other hand, 4-hydroxybenzoic acid n-butyl ester 20f Silica fine particles 10F Polyvinyl alcohol 3f Water 100? After dispersing the composition for 24 hours using a ball mill, it was coated on the surface of high-quality paper (35 g/m2) using a wire parr and dried to form a receiving sheet (B
-1) was created.

The surface of each of the transfer printing sheets was brought into contact with the receptor layer of the receptor cartridge obtained in this manner, and when heated by passing between heated rolls at 95°C from the back side of the receptor cartridge, a blue colored image was formed. Obtained. The resulting image density was also measured using a Macbeth densitometer (RD-514). The values are shown in Table-1.

As shown in Table 1, the image density of the present invention is superior to that of the comparative example. Furthermore, the above-mentioned operation was carried out 10 times from the transfer image sheet (A-x') produced using the above-mentioned transfer sheet} (A-+).
The transferred images were obtained several times, but the density was almost the same as that of the first image.

Example 2 The transfer sheet of Example 1 except that 3-diethylamino-6-chlorofluorane was used in place of the crystal and S iolet lactone, and N-cyclohexylzo-pionamide was used in place of N-stearylpenzamide. A transfer sheet (A.-3) for red coloring was created in the same manner as in Example 1, and a transfer print sheet (A.-3') having a mirror image for red coloring was created in the same manner as in Example 1. did.

The surface of the receiving sheet (B-1) having a clear blue image obtained in Example 1 and the transfer image sheet (B-1) obtained in this example
A-3') was brought into contact with the surface of the transfer coloring sheet, and when the back side of the transfer coloring sheet was passed through a heating roll at a temperature of 120°C in the same manner, a clear red image was formed, and two images of blue and red were formed. A color transfer image was obtained.

Example 3 The transfer layer surface of the transfer sheet (A.-1.) obtained in Example 1 was stacked so as to be in contact with the receiving layer surface of the receiving sheet 1-(B-1.), and thermal heat was applied from the back surface of the transfer sheet. When printed using a thermal printer with a built-in head, a clear blue image was obtained on the receiving sheet.

Example 4 Receiving sheet from which a blue image was obtained according to Example 3 and Example 2
When a similar transfer sheet for red color development was overlapped and printed using a thermal printer in the same manner as in Example 3, a clear red image was formed, and a two-color image of blue and red was formed. I got it.

Patent applicant Ricoh Co., Ltd. Representative Patent Attorney Toshiaki Ikeura

Claims (1)

[Claims] (1) Consisting of a transfer master sheet having a transfer layer containing a leuco dye as a main component, and a receiving sheet having a receiving layer containing a color developer as a main component having a melting point of 200°C or less for the leuco dye, the transfer layer and A thermal transfer medium characterized in that/or the receiving layer contains at least one compound represented by the following general formulas (+) to (V). ? General formula 0)・RINHCOR21(I) (In the formula, R1' is an alkyl group having 10 to 30 carbon atoms, ■2
is an alkyl group having 1 to 30 carbon atoms) General formula (')' (wherein 3 is an alkyl group having 10 to 30 carbon atoms, R4,
R5 is hydrogen or a lower alkyl group) general formula (III
) (In the formula, ■゜ is an alkyl group having 1 to 30 carbon atoms, ■", R
8 is hydrogen, halogen, lower alkyl tree or lower alkoxy group, n is O or 1) general formula (I1/)"
"(In the formula, R9 is an alkyl group having 1 to 30 carbon atoms or a substituted or unsubstituted aryl group, and 1° is an atom, a halogen, or a lower alkyl group)" General formula (V) (In the formula, Rl1 is an alkyl group having 1 to 30 carbon atoms, R12
is hydrogen, halogen or lower narkyl group)