JPS623985A - Ink sheet for thermal transfer recording - Google Patents

Abstract

PURPOSE:To obtain an extremely excellent anti-blocking property, by providing a layer of a material obtained by cross-linking and hardening a specified hydrogen-modified polysiloxane by active radiations in a predetermined thickness on the side on which heat is applied. CONSTITUTION:The layer obtained by cross-linking and hardening a hydrogen- modified polysiloxane of formula (1), (2) or (3), wherein m is an integer of 4-1,000, n is an integer of 5-50 and p : q = 85 : 15 - 3 : 97, by active radia tions is provided on the side on which heat is applied. If the value of m, n, p or q is less than the predetermined range, exudation or the like may occur at an end part of the ink sheet in stacked condition where the processing thick ness is large, whereas if the value is in excess of the range, restrictions as to materials are generated. UV rays, electron rays or the like can be used as the active radiations. The thickness of the layer in the hardened state is set to be 0.02-1mum. Accordingly, blocking can be prevented from occurring where the ink sheet is rolled or stacked.

Description

DETAILED DESCRIPTION OF THE INVENTION (Field of Industrial Application) The present invention relates to thermal transfer recording ink sheets 1 to 1, and more particularly relates to an ink sheet forming and covering a part of a recording medium used in a transfer type thermal recording device. Regarding 1~.

(Prior art) In recent years, the spread and progress of information devices has been remarkable, especially personal computers, A-Fiscom, etc. - Evening, word processor? As printers become more popular, the number of printers installed in them is rapidly increasing.

Thermal transfer printers, which are lightweight, low-priced, and highly reliable, are capable of recording by applying a predetermined amount of heat to the ink sheet to avoid transferring the ink to the recording paper. Line -) #].

There are several methods for this thermal transfer, and a typical one uses a thermal head for the hot/cold stamp ++n, and a wax layer containing pigment is placed on the sheet (J, thermal head thermal/cold applying section is covered). Melt transfer method on T-7 paper,
Similarly, there is a method in which a sublimable dye is contained in a binder and the dye is sublimated and diffused transferred by applying heat to a thermal head, and as a heating method, there is a method in which electrical heating is performed through an ink sheet.

All of these require higher sensitivity, ie, high speed printing, etc., and '+A', which naturally has a relatively low melting point, must be used as the ink layer. However, due to the convenience of installing this ink sheet into a printer, it is not possible to make it into a cartridge, and it is forced to take the form of a 1-roll or a stack of sheets, and in this state, the +A advantage, which has a relatively low melting point, is used. is used in the ink layer, so J,
This causes so-called plotting, which causes migration and peeling of the ink layer, or integration due to lateral seepage, or
There is a problem that the ink sheet and the end of the ribbon may fall off.

[Problems to be Solved by the Invention 1)] The problems to be solved by the present invention are the 111 problems of conventional ink sheets, that is, the problems that occur when the ink sheet is in the form of a roll or a stack of sheets. This is an attempt to solve the problems based on so-called blocking.

[Failure to solve the problem]

The above problem is that on the side of the ink sheet where heat and cooling are applied,
Preferably, the layer consisting of a specific hydrogen-modified polysiloxane cured by actinic radiation has a thickness of 0.
．． 02- Solved by forming with IP. That is, in the present invention, the following general formula (where n is an integer of 5-50) or (TII) (where p: q = 85 + 15-3: 97) is applied to the side to which heat is applied.
The present invention relates to a thermal transfer recording ink sheet 1 consisting of forming a layer consisting of a cross-linked cured product of polysiloquiline using actinic radiation.

Originally, as a backside treatment for this type of ink sheet 1-, there is a treatment to improve the problems that occur when applying heat and cold. In other words, there is an attempt to eliminate the sticking phenomenon caused by the softening of the ink sheet base material by covering it with a heat-resistant bamboo material or by improving the slippage of the base material. -13359, JP-A-54i-146790, JP-A-56-155794,
JP-A-57-129789, JP-A-58-171992
, JP-A No. 511-187396, etc., which use silicon-based compounds. However, these are all processes for instantaneous phenomena during the recording of heat application, and when heat is applied! 1 momentary softening of the base material or (,
1. Treatments to improve slipperiness, and these treatments are greatly influenced by IJ, the thermal characteristics of the base material, or the friction surface properties of the base H.

On the other hand, the problem of preventing blots and blistering that the present invention aims to solve is the problem of peelability after a period of time.
The blocking prevention method of the present invention is essentially completely different from the above-mentioned conventional processing that deals with instantaneous phenomena when heat is applied, and the effects of the conventional processing are the same as those of the present invention. It is completely unknown whether or not it is effective when used in I-.

[Effect]

As the hydrodiene-modified polysiloxane represented by the general formula (T) (where m is an integer of 4-100017) used in the present invention, the number m of repeating units of dimethyl ziro 1 sane is 4-100.
0 is adopted.

Further, as the hydrogen polysiloxane having the general formula (IT) (where n is an integer of 5 to 50), a methylsiloxane having 0 repeating units of 5 to 50 is used.

Also, the general formula (III) --- (III) (however, in the formula, D: Q = 85: 15-3: 97)
As the hydrogen-modified polysiloxane represented by, the ratio of repeating units p and q of methylsiloxane and dimethylsiloxane is p:q=85:15-3
:9γ is used. 'These +n,
If n, p and q do not reach the above-mentioned predetermined ranges, oozing of the edges of the lumber may occur during stacking if the treated thickness is large.

In addition, if it exceeds the above range, there may actually be restrictions in terms of material r1.Specific examples of these include terminal-hydrogen-modified polydimethylsiloxane PS 53
7 (m: 4), PS 542 (m: 2)
30), PS 543 (m: 380),, P
s 545 (Ill: 840), polymethylhydroxy[1xane P S' 120 (n: 35),
Polymethylhide [1 siloxane] polymer PS123
．． 5 (Q = 15-18%>, PS 12
3 ((1=65-70%), PS 122,5<q
=45~50%)'tpS'124.5(Q
=96-97%). These may be used alone or in combination of two or more.

The active (II discharge copper wire) used in the present invention is as follows.

Radiation sources such as ultraviolet light and electron beams can be used.

When ultraviolet rays are used, the photoreaction initiators and/or sensitizers used in ordinary ultraviolet curing are used.

Various substances commonly used as initiators and sensitizers for UV-curable paints can be used.9 For example, benzoin,
Benzoin methyl ether, benzoin ethyl ether, penzoin impyl ether, benzoin butyl ether, 2-methylbenzoin, penzohenone, Michler's ketone, benzyl, benzyl dimethyl ketal,
Anthopyanone, methylanthraquinone, shea t'! Chill, I? Examples include tophenone, Schiffnil disulfide, anthracene, etc., and those in which these are combined with small amounts of sensitizers such as amines.

In addition, in the present invention, other polymers or A ribomer compounds can be used in combination, and in this case, the other polymer and t] are, for example, -I-tyrene copolymers such as ethylene-vinyl acetate and ethylene-acrylic. Coalescence, polystyrene, styrene-butadiene T polymer, rubbers, I? Lulose derivatives, butyral, polyvinyl alcohol, polyamide, polycarbonate, polyvinyl chloride, boxymelamine, polyester, polyether polyurethane,
Examples include A-ribomer-like compounds having one-coupled structure and the like, and these are usually used in fH at a ratio of 0.5 to 80% by weight.

Furthermore, the present invention does not preclude the use of inorganic additives. At this time, inorganic additives are used, for example, to avoid a decrease in thermal conductivity, and in the case of energization 711 heat, etc., the conductivity ↑
Preferred specific examples include metal powders such as silver, copper, iron, aluminum, etc., metal oxide powders such as alumina, titanium white, glass, etc., and inorganic salt powders such as calcium carbonate 11,1ifI. acid l-
18, horns, etc. can be removed, and the use of A is about 10-80 parts by weight based on the total amount of modified polysiloyarin and other additives. It's a turtle.

-1- When forming a cured product layer of the Hyde-n-di-tin modified polysiloxane represented by the general formula (T to ■) on the side of the ink sheet to which heat is applied, The reaction initiator is applied as it is or diluted with an appropriate inert solvent (2) and is formed on a predetermined portion of the ink sheet by an appropriate means such as a coating means.Then, actinic radiation is irradiated by a conventional means to cause crosslinking and curing. The inert solvent in this case is preferably one with a boiling point of 5o-15oC from the viewpoint of workability, and specific examples include toluene, xylene, hexane, ethyl acetate, butyl acetate, a1.=
Examples include ton, methyl ethyl ketone, methyl isobutyl ton, and the like. In the order of forming the cured product layer of the Hydrogen modified polysiloxane of the present invention, after the ink layer is provided on the base material, = b m <, and beforehand, the Hydrogen modified polysiloxane is applied to the base material. Set up a cured layer of siloxane U1
After that, an ink layer is applied (J is also 1).

The coating thickness is in the range of 0.02-IP, preferably 0.05-0.4iP as the thickness of the cured product;
Uniform effect is 1 below 02P! If the ink sheet exceeds 17 A, the sensitivity of the ink sheet decreases, which is not desirable.

Curing of activated open cotton can be done at high speed without heating, and its T power potential is very large.

As an ink sheet for forming a cured product layer of the Hydrogen Hentai Bamboo Borishiroki Ff of the present invention, the limited t!
Any of the various types that have been used in the past can be used. Among these, the effects of the present invention are particularly noticeable in the melt-transfer type. These ink sheets are not particularly limited as mentioned above, but will be explained by taking as an example a melt transfer type ink sheet that is preferably used in the present invention.2-12. 60. An ink layer prepared from paraffin wax or stell wax having a melting point of about -100°C and a coloring material together with a softener and a filler as a thermal conductivity improver is applied to a thickness of about 2-20°C. I can give examples of things that I have written.

A wide variety of coloring materials can be used, including pigments listed in the Yoriyoshi table in the Dye Handbook (published by Maruzen Co., Ltd., 1910), pigments such as carbon black, direct dyes, Various dyes such as disperse dyes, basic dyes, and acid dyes can be used.

In particular, yellow coloring materials are preferably those having a chlorphenylazo group, magenta coloring materials are preferably having naphtholazo groups, and cyan coloring materials are preferably having a phthalocyanine structure.

As the softening agent, those conventionally used can be used, such as T-tyrene-vinyl acetate, ethylene-based Jξ polymers such as ethylene-acrylic, polystyrene, styrene-butadiene copolymers, rubbers, cellulose derivatives, butyral, Polyvinyl alcohol, polyamide, polycarbonate, polyvinyl chloride, 1-boxy melamine, polyester, poly-I--methylpolyurethane and -A above
Examples include substances that can be easily melted by heat, such as ribomer core compounds, or lubricating oil.

Fillers such as 17 that have been used in the past can be used, such as metal powders such as silver, copper, iron, alumina 18, etc.
Specific examples include metal oxide powders such as alumina, titanium white, glass, etc., and inorganic salt powders such as calcium carbonate, sulfuric acid, sulfuric acid, clay, etc.

〔Example〕

EXAMPLES The present invention will be specifically described below with reference to Examples.

Example 1 Paraffin wax #155 (softening point 69°G) 100
Heavy lifting part and carbon black MA-8,20 weight part 1
The mixture was melted and mixed and dispersed at 00° C. to prepare a black ink.

Hola 1-mel]~]-teing was carried out on the shim at a thickness of 4/L4 (comparison material). Place this ink sheet on the front and back sides.
The sheets were stacked, sandwiched between two glass plates, and heated in a constant temperature bath at 50° C. under a weight of 50,090.

-6 Ink sheets 1 to 1 of the present invention include Chisso Co., Ltd. 11J Hyde l]diene-modified polysiloxane PS 120 (n = 35), and hydrogen-modified polysiloxane ioo and benzyl dimethyl to the m part. A 1% toluene solution containing 5 parts of ketal was applied and air dried. Next, ultraviolet rays were irradiated for 20 seconds at a distance of 10 cm using a BOvt/cm high-pressure mercury lamp for crosslinking and curing. The thickness of this cured product is 0.2. It was LL. (Product of the present invention). Five ink sheets of the present invention were stacked alternately on the front and back sides in the same manner as above, sandwiched between two glass plates, and 5 sheets were stacked at the same time as the above comparative material under a weight of 500 g.
It was heated in a constant temperature bath at 0°C. When the two materials were taken out after heating for 24 hours, blocking had occurred in the comparison material, and when attempts were made to peel them off, random transfer of the ink to the back surface was observed. -6 No deterioration was observed in the ink sheet having the cured material layer of hydrocarbon modified resin [11 lean] on the back surface even when the ink sheet was peeled off.

Example 2 Acid value wax NFS-9125 (softening point 63°C) 100
Part by weight and β-naphthol/azo type face 1!1p erm
anent Carmine F B B (')
A magenta hot melt ink was prepared by melting and mixing and dispersing 2.7 parts by weight at 100°C.

This ink was hot-melt coated on a polyester film with a thickness of 6/A-2 to a thickness of 4P under heating (comparative data). As in Example 1, 5 sheets of this ink sheet were stacked alternately on the front and back sides, sandwiched between two glass plates, and
0470Heat it in a constant temperature bath at 50℃ under weight. -6 As the ink sheet 1 of the present invention, on the back side of the above ink sheet, Chisso Co., Ltd. tl Hydrogen-modified polysiloxane PS 542 (m -250) and hydrogen-modified polysiloxane-17 = 100 parts by weight were mixed with benzyl. A 1% toluene solution containing 5 parts by weight of dimethyl ketal was applied and air-dried. Next, using an 80 W/cm high pressure mercury lamp, ultraviolet rays were irradiated for 20 seconds at a distance of 1 ocm to effect crosslinking and curing. The thickness of this cured product was 0.2.

Five ink sheets of the present invention were stacked alternately on the front and back sides in the same manner as above, sandwiched between two glass plates, and heated in a constant temperature bath at 50° C. under a weight load of 500 q at the same time as the above comparative material. When Ryoshi 1111 was taken out after heating for 24 hours,
The comparative material had some blocking, and when I tried to peel it off, I found that the ink was randomly transferred to the back side. -Hydrodiene-modified polyester of Riki's invention [21] No deterioration was observed in the ink sheet having a cured product layer of xane on the back surface even when it was peeled off.

〔effect〕

As can be seen from the above examples, the ink sheet of the present invention exhibits extremely excellent blocking resistance.

(further)

Claims (5)

[Claims] (1) On the side where the amount of heat is applied, there are the following general formulas ▲ Numerical formulas, chemical formulas, tables, etc. ▼ (However, m is an integer from 4 to 1000) ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (However, n is 5- 50 integers) or ▲ Numerical formulas, chemical formulas, tables, etc. ▼ (However, in the formula, p:q = 85:15-3:97) Made by crosslinking and curing hydrogen modified polysiloxane with active radiation. A thermal transfer recording ink sheet formed by forming a layer of a cured product. (2) The thermal transfer recording ink sheet according to claim 1, wherein the layer made of the cured product of the hydrogen-modified polysiloxane has a thickness of 0.02 to 1 μm. (3) The thermal transfer recording ink sheet according to claim 1 or 2, wherein the ink sheet is of a melt transfer type. (4) The claim that the melt transfer type ink sheet is prepared from a paraffin wax or ester wax having a melting point of 60-100°C and a coloring material on a 2-12μ polyester film base material. The thermal transfer recording ink sheet according to item 3. (5) Claims 1 to 4, wherein the coloring material contained in the ink sheet is a yellow coloring material having a chlorphenylazo group, a magenta coloring material having a naphtholazo group, or a cyan coloring material having a phthalocyanine structure. The thermal transfer recording ink sheet according to any one of the above.