JPS62294592A - Thermal transfer recording sheet - Google Patents

Abstract

PURPOSE:To improve the running property of a thermal head at the time of high energy recording, by providing a cured film of a silicone resin, which is formed by the addition reaction of organopolysiloxanes, to a base film. CONSTITUTION:In a thermal transfer recording sheet wherein a thermal transfer coloring material layer is provided to one surface of a base film, a cured film of a silicone resin, which is formed by the addition reaction of organopolysiloxane having a vinyl group directly bonded to a silicon atom and organopolysiloxane having a hydrogen atom directly bonded to a silicon atom, is formed to the other surface of the base film by a method wherein a mixture of organopolysiloxanes is mixed with a curing catalyst as it is or after diluted with a proper solvent to prepare a coating solution which is, in turn, applied to the base film and dried before subjected to heat treatment for curing. Inorg. or org. fine particles, a surfactant, an antistatic agent and a viscosity control agent, etc. may be added to the coating solution as other additives.

Description

Detailed Description of the Invention 3. Detailed Description of the Invention (Field of Industrial Application) The thermal transfer recording sheet of the present invention is useful for color recording in 100-person terminals such as facsimile machines, printers, and copying machines, which are rapidly becoming popular in recent years. It can be advantageously used for color recording of television images, etc.

(Prior Art) Various methods such as electrophotography, inkjet, and g-thermal transfer recording are being considered for color recording such as color recording in the above-mentioned OA terminals and color recording of television images, but thermal transfer recording The method is based on maintainability of the equipment, ease of operation,
This method is advantageous over other methods in that the equipment and consumables are inexpensive.

In the thermal transfer recording method described above, an image receptor is placed on the ink-coated surface of a thermal transfer recording sheet coated with ink that covers all of the coloring materials, and the back side of the thermal transfer recording sheet is heated by a thermal head to form a thermal transfer recording sheet. Recording is performed by transferring the coloring material inside to the image receptor.

Such thermal transfer recording methods include a melting transfer recording method using a thermal transfer recording sheet coated with a heat-melting ink, and a sublimation transfer recording method using a thermal transfer recording sheet coated with an ink containing a sublimable dye.

In this type of thermal transfer recording method, the thermal transfer recording sheet is heated to a high temperature by a long head, so if the base film of the thermal transfer recording sheet has insufficient heat resistance,
The base film becomes thermally fused and the thermal head becomes unable to run, making it impossible to record. Therefore, in order to improve the heat resistance of the base film, it has been proposed to provide a protective film of various heat-resistant resins.
74195), and it has also been proposed to add a lubricant, a surfactant, etc. to the above-mentioned protective layer in order to further improve the running properties of the thermal head (Japanese Patent Laid-Open No. 1983-1999).
146790, JP-A-56-155794, and JP-A-E7-129789).

However, recently, in this recording method, in order to increase the recording speed, even higher energy than before is applied to the thermal head, which places a heavy burden on the thermal transfer sheet. It is not always possible to obtain sufficient thermal performance and excellent running performance. In particular, thermal transfer recording sheets using a sublimation type thermal transfer recording method using sublimable dyes require higher energy during recording than thermal transfer recording sheets using a bath melting type thermal transfer recording method using heat-melting inks. Furthermore, thermal transfer recording sheets processed by the conventionally proposed method cannot provide sufficient runnability for a thermal head.

(Problems to be Solved by the Invention) An object of the present invention is to provide a thermal transfer recording sheet with good running properties on a thermal head.

(Means for Solving the Problems) The present inventors have conducted studies on improving the running properties of thermal heads in thermal transfer recording sheets, and have found that silicone resin formed by an addition reaction of organopolysiloxanes to a base film. It has been found that by providing a cured film of the present invention, it is possible to obtain a thermal transfer recording sheet that exhibits very good running properties of a thermal head even during high-energy recording.

That is, the thermal transfer recording sheet of the present invention is a thermal transfer recording sheet having a heat transferable coloring material layer on one side of a base film, which is formed by an addition reaction of organopolysiloxanes on the other side of the film. It is characterized by having a cured silicone resin.

The addition reaction-curing organopolysiloxane used to form the cured film in the present invention has high reactivity, so it can form a complete cured film under mild conditions, and the formed cured film has extremely high heat resistance. In addition, the thermal transfer recording sheet of the present invention has excellent lubricity unique to silicone resins, so the thermal transfer recording sheet of the present invention has excellent running properties of a thermal head even during high-energy recording.

The organopolysiloxanes that can form a cured film of silicone resin through an addition reaction used in the present invention include vinyl groups, radical polymerization initiators such as benzoyl peroxide, etc. Alternatively, silico-addition polymerization reaction occurs upon irradiation with ultraviolet rays, electron beams, etc. Among siliconolganopolysiloxanes, those having a vinyl group directly bonded to silicon atoms, in addition to the above-mentioned addition polymerization reaction, An organopolysiloxane with a methyl group directly bonded to a ditertiary
A cured film of silicone resin can be formed by carrying out an addition reaction as shown in the following formula using a vulcanizing agent such as butyl peroxide or dicumyl peroxide. ).

RRRR1R3R' The above addition reaction of an organopolysiloxane having a vinyl group directly bonded to a silicon atom and an organopolysiloxane having a methyl group is used in the production of methylvinyl silicone rubber, and each of the above Various types of organopolysiloxanes are manufactured or commercially available), and they can be used in the present invention.

An organopolysiloxane having a vinyl group directly bonded to a silicon atom can also undergo an addition reaction with an organopolysiloxane having a hydrogen atom directly bonded to a silicon atom under a certain type of catalyst as shown in the following formula. , a cured film of silicone resin can be formed (R1- in the following formula
R5 and R11 to R15 each represent an alkyl group, a phenyl group, or the like. 15 '15 '1
2 '1! i'15R12RRRRR Platinum is used as a catalyst for such a reaction.

Examples include tutaladium, rhodium, or compounds thereof, and platinum-based materials are usually used.

Specifically, chloroplatinic acid, alcohol-modified chloroplatinic acid,
Examples include congres of chloroplatinic acid and olefins, solid platinum supported on carriers such as wood, platinum black, alumina, and silica.

The above reaction is used for crosslinking silicone rubber, etc., and can be carried out at low temperatures and in a short time, so it is mainly used for low temperature vulcanization W (LTV) silicone rubber, but also for release paper, etc. Since various types of organopolysiloxanes mentioned above are manufactured and commercially available,
In the present invention, they can be used. Examples of commercially available organopolysiloxanes include:
Tone Silicone Co., Ltd. Tone Silicone 5
RX-211, 5D-7220, 5D-7226, 5R
X-318, SRX-345, SRX-357, 8
RX-370, DX-24-5100, Shin-Etsu Silicone KS-770, KS-77 manufactured by Shin-Etsu Chemical Co., Ltd.
2, KS-841, KS-774, KS-778, KE
-103, KE-106, KE-104, KE-120
1, KE-1202, KE-1204, KE-1205
,KE-1206,KE-1300,KE-1600
etc. can be mentioned.

In these commercially available products, an organopolysiloxane having a vinyl group and an organopolysiloxane having a hydrogen atom directly bonded to a silicon atom are already mixed.
They are used with a curing catalyst added at the time of use.

Among the main methods for curing and converting silicone resin in the present invention, addition of organopolysiloxane having a vinyl group directly bonded to a silicon atom and organopolysiloxane having a hydrogen atom directly bonding to a silicon atom. The method using a reaction is particularly advantageous in that a cured film can be formed at a low temperature in a short time, and the organopolysiloxane used is easily available in various commercial products.

The base film of the thermal transfer recording sheet of the present invention is subjected to an addition reaction between the organopolysiloxane having a vinyl group directly bonded to a silicon atom and the organopolysiloxane having a hydrogen atom directly bonded to a silicon atom. In order to completely form a cured film of silicone resin, the mixture of the above-mentioned organopolysiloxanes can be applied as is or after being diluted with a suitable bath agent, mixed with a curing catalyst and applied.
Adjust this and apply this 8! Kff on base film L
i cloth.

It may be dried and then heat treated for hardening.

For dilution, aromatic bath agents such as toluene and xylene, ketone solvents such as methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone, aliphatic solvents such as hexane and heptane, and esters such as ethyl acetate and butyl acetate are used. Cellosolve type solvents such as methylcellonlube and ethyl cellosolve are used.

The amount of curing catalyst used is 0.0% relative to the organopolysiloxane.
It is appropriate to use it in a range of 0.001 to 10% by weight.

In addition to the above-mentioned components, organic or inorganic fine particles, surfactants, antistatic agents, viscosity modifiers, etc. may be added to the coating liquid, and in some cases, within the range that does not impair the purpose of the present invention. Other heat-resistant resins may also be blended.

As a method of applying the above-mentioned coating liquid, for example, "Coating Method J" by Yuji Harasaki (1979, published by Maki Shoten)
This can be carried out using a gravure coater, reverse roll coater, wire percoater, air doctor coater, etc. described in .

After coating and drying, it is necessary to perform heat treatment to accelerate the hardening of the coating film.
It is about 0 seconds to 1 hour. Of course, when the temperature is high, a short time is sufficient, and when the temperature is low, a long time is required. If the curing is insufficient, a cured film with sufficient heat resistance and strength will not be obtained, the adhesion to the base film will be insufficient, good running properties of the thermal head will not be obtained, and the thermal head This may cause dirt to be added to the surface of the image, resulting in a decrease in the image quality of the transferred record.

The thickness of the cured film formed in the present invention is 0.01
~10 μm is appropriate, and VCO-1~2 Jim is preferred.

Examples of the base film used in the thermal transfer recording sheet of the present invention include polyethylene terephthalate film, polyamide film, polyaramid film, polyimide film, polyetherimide film, polycarbonate film, polyphenylene sulfide film,
Polysulfone film, polyether sulfide film.

Although polyetheretherketone film, cellophane, triacetate film, polypropylene film, etc. can be used, polyethylene terephthalate film is particularly advantageous from the viewpoints of mechanical strength, one-dimensional stability, heat resistance, economic efficiency, and the like. The thickness of these base films is 1~
30 .mu.m is one equivalent "c", but 2 to 15 .mu.m is particularly preferred.

The formation of the coloring material layer in the thermal transfer recording sheet of the present invention is as follows:
In the case of a sublimation type thermal transfer recording sheet, the ink is prepared by dissolving or dispersing the sublimable dye and a binder resin with good heat resistance in a suitable solvent.The ink is applied to the base film and dried. In the case of a melt-type thermal transfer recording sheet, an ink is prepared by dissolving or dispersing a coloring matter such as a pigment or dye in a heat-melting substance using a solvent if necessary, and this ink is applied to a base film. Just dry it.

Examples of the sublimable dyes used in the above-mentioned sublimation type thermal transfer recording sheet include nonionic azo-based, anthraquinone-based, azomethine-based, methine-based, indoaniline-based, naphthoquinone-based, quinophthalone-based, and nitro-based dyes. Examples of binder resins include polycarbonate resins, polysulfone resins, polyvinyl butyral resins, polyarylate resins, polyamide resins, polyaramid resins, polyimide resins, polyetherimide resins, and cellulose resins such as acetyl cellulose, methyl cellulose, ethyl cellulose, etc. It will be done. As a solvent,
Aromatic solvents such as toluene and xylene, ketone solvents such as methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone, ester solvents such as ethyl acetate and butyl acetate, alcohol solvents such as Impropatol, f-tanol, and methyl cellosolve, and chloride. Methylene.

Halogen bath agents such as trichloroethylene and chlorobenzene, ether bath agents such as dioxane and tetrahydrofuran, and amide solvents such as dimethylformamide and N-methylpyrrolidone are used. The pigments used in melt-type thermal transfer recording sheets include inorganic pigments such as carbon black and silica, various organic pigments such as azo and condensed polycyclic pigments, and dyes such as acidic pigments containing sulfonic acid groups. Dyes, basic dyes, metal complex dyes.

Oil-soluble dyes etc. are used. Next, the heat-melting substance is preferably a solid or semi-solid substance with a melting point of 40 to 120°C, such as Karnapawassu and Montanwasu.

Jisoo. Microcrystalline wax, wood wax.

Examples include oil-based synthetic waxes. As a solvent,
The same materials as in the case of the above-mentioned sublimation type thermal transfer recording sheet can be mentioned.

In addition to the above-mentioned components, each of the above inks may contain organic or inorganic non-sublimable fine particle dispersants, antistatic agents, antiblocking agents, and antifoaming agents, if necessary.

Antioxidants, viscosity modifiers, etc. can be added.

These inks can be applied in the same manner as described above for applying the heat-resistant protection Jd, and the appropriate coating film thickness is 0.1 to 5 μm in dry film thickness.

In addition, in the production of the recording sheet of the present invention, in order to improve the adhesion between each layer formed by the above-mentioned coating and the base film, the surface of the base film is subjected to corona treatment, polyester resin, cellulose resin, etc. An undercoat treatment with a resin such as oil, polyvinyl alcohol, urethane resin, or polyvinylidene chloride may be performed.

(Effects of the Invention) The thermal transfer recording sheet of the present invention can run well even during high-energy recording without fusion of the thermal to the base film, and there is no adhesion of debris to the thermal head. It is possible to obtain transfer recordings of high image quality.

(Examples) The present invention will be explained in detail below using Examples, but these Examples are not intended to limit the present invention.

"Part" in the examples means "1 part by weight".

Example 1 a) Preparation of a thermal transfer recording sheet A biaxially oriented polyethylene terephthalate film (6 thicknesses) was used as a base film, and a heat-resistant slipping layer was formed on one side of the film by the following method.

Specifically, 10 parts of Toray Silicone SRX-211 (trade name, manufactured by Toray Silicone Co., Ltd.), which is an addition reaction type silicone for release paper, and a platinum-based catalyst Toray Silicone SRX-212CAT (trade name,
(manufactured by Toray Silicone Co., Ltd.) 0.36 parts, surfactant KF-351 (trade name, manufactured by Shin-Etsu Chemical Co., Ltd.)
0.09 parts, n-hexane 40 parts, toluene 49.55
Apply a coating liquid that softens the parts, and after drying, heat at 120°C.
was heat-treated for 30 minutes to form a heat-resistant slippery layer with a thickness of about 0.2 μm.

The other side of the base film of this sheet is coated with ink 6a consisting of 5 parts of sublimable dye (C, 1,5olvant Blue 95), 10 parts of polysulfone resin, and 85 parts of chlorobenzene, dried, and inked to a thickness of about 1 μm. A coloring material layer was formed to produce a thermal transfer recording sheet.

b) Preparation of image receptor Water-bathable polyester resin Pyronal MD-1200 (
Trade name, manufactured by Toyobo Co., Ltd., Tg = 67°C) (solid content: 34%) K After coating on 150 μm thick polypropylene synthetic paper, it was kept dry to form a dyed M layer of about 7 μm thickness. Furthermore, crosslinkable silicone KS is added to the surface.
-841 (trade name, manufactured by Shin-Etsu Chemical Co., Ltd., silicone content 30%) II and catalyst PL-3 (trade name, manufactured by Shin-Etsu Chemical Co., Ltd.) 0.011 Toluene 29.17
'(f') The mixture was uniformly mixed and applied to a wet film thickness of approximately 6 μm, and after drying, it was further heated in an oven at 100° C. for 30 minutes to produce an image receptor.

C) Transfer Recording Results The color material layer side of the above thermal transfer recording sheet and the resin coated side of the above recording paper were overlapped, and the heat resistant slipping layer side (/C3dot/w
0.4w,'d for a thermal head with heating resistor density of m
A power of t was applied for a /4' pulse width of 1 to 10 msec, and the whole test line was tested.

The results showed that the sheets exhibited good runnability without any fusion, and records with good gradation could be obtained.

Examples 2 to 6 Various coating liquids shown in Table 1 were prepared in place of the coating liquid of Example 1 as coating liquids for the thermolubricious layer, and the coating liquids of the present invention were prepared using the layer forming treatment method shown in Table 1. A thermal transfer recording sheet was prepared.

Using each of the obtained sheets, thermal transfer recording was carried out in the same manner as in Example 1 except for the above. The results showed good running performance with no fusion between the head and seat.
Please make sure you are able to record good gradation.

1 below.

Table 1

Claims (3)

[Claims] (1) A thermal transfer recording sheet having a heat transferable coloring material layer on one side of a base film, having a cured film of silicone resin formed by an addition reaction of organopolysiloxanes on the other side of the film. A thermal transfer recording sheet featuring: (2) The cured film is a cured film of a silicone resin formed by an addition reaction between an organopolysiloxane having a vinyl group directly bonded to a silicon atom and an organopolysiloxane capable of an addition reaction with the vinyl group. A thermal transfer recording sheet according to claim 1. (3) A cured film of silicone resin that is formed by an addition reaction between an organopolysiloxane having a vinyl group directly bonded to a silicon atom and an organopolysiloxane having a hydrogen atom directly bonded to a silicon atom. A thermal transfer recording sheet according to claim 1.