JPH023892Y2 - - Google Patents

Description

[Detailed explanation of the idea] The present invention relates to a heat-sensitive recording material.

The thermosensitive recording method has been widely used in recent years due to its simplicity and maintenance-free equipment. As heat-sensitive recording materials used in heat-sensitive recording systems, those using leuco dyes and phenolic compounds, and transfer ribbons for thermal transfer coated with dye ink are known. Among these, it has been proposed to pre-form a heat-sensitive recording layer only on required parts of the base material, but in this method, heat-sensitive recording layers of different shapes are provided on base materials of different sizes depending on the application. There is a need. Also, when trying to record a multicolor image in which images of different hues are superimposed using the conventional thermal recording method, it is possible to use a transfer tape that transfers only the thermally printed portion, but once the transfer is performed, the If an attempt is made to transfer the image to the transfer body again, the image that has already been transferred may be reversely transferred to the transfer tape used for the next transfer, or even if the image is not reversely transferred, the image may be destroyed. be. Alternatively, in a system using a leuco dye, even if a transparent substrate is used, it is not preferable because color develops throughout.

The present invention was developed to overcome the drawbacks of the prior art described above, and includes a release layer and a release layer on the surface of the base material.
The gist of the present invention is a heat-sensitive recording material characterized in that a heat-sensitive recording layer and an adhesive layer are sequentially provided, and the adhesive layer contains a lubricant and a release agent.

Hereinafter, the present invention will be explained in detail using the drawings.

FIG. 1 is a schematic cross-sectional view showing the structure of the heat-sensitive recording material of the present invention. The heat-sensitive recording material shown in FIG. 1 has a release layer 2, a heat-sensitive recording layer 3, and an adhesive layer 4 sequentially provided on the surface of a base material 1, and the adhesive layer contains a lubricant and a mold release agent. .

To explain the base material and each layer in the above, various materials can be used as the base material 1, but as described later, the heat-sensitive recording material of the present invention is one that is transferred onto a separate base material after image formation. Therefore, use a material that can withstand the heat and/or pressure during transfer, and the heat and impact of thermal printing during image formation. Specifically, ledger paper, capacitor paper,
Paper such as tissue paper, high quality paper, and paperboard, plastic film such as cellophane, polyester, polycarbonate, and cellulose triacetate, synthetic paper, or metal foil, and any composite of the above materials can be used.

Next, to explain the release layer provided on the surface of the base material 1 as described above, the release layer has adhesiveness to the base material and holds the heat-sensitive recording layer described below.
Any material may be used as long as it can peel off the heat-sensitive recording layer when heated, such as cellulose resin such as cellulose acetate resin, cellulose acetate butyrate resin, etc.
Paints prepared by known coating methods using paints containing resins such as melamine resins, acrylic resins, and epoxy resins as vehicles, and paints made by adding thermal release agents such as lecithin, silicone, wax, etc. to known paints. Examples include those provided using.

Next, the heat-sensitive recording layer 3 can be formed using a composition containing, for example, a diazo compound, an alkaline substance, a coupling agent, other additives, and a binder.

In the above, examples of the diazo compound include:
Those described in Japanese Patent Publication No. 55-49730 can be used, or diazosulfonates corresponding to these can also be used.

As a coupling agent, the general formula is I can give an example of what is expressed as . However, in the above, R ¹ , R ² , R ³ , R ⁵ are hydrogen, an alkyl group, an aryl group, an alkoxy group, a sulfonic acid or sodium sulfonate group, an alkylamino group, an arylamino group, an amino group, a carboxylic acid group, a carboxylic acid ester group or a halogen, R ⁴ is an alkyl group, an aryl group, or a heterocycle,
R ⁶ is a sulfonic acid or sodium sulfonate group or a carboxyl group, R ⁷ and R ⁸ are R ¹ ,
The same as R ² , R ³ or R ⁵ and a hydroxyl group, X is a halogen, m is an integer of 1 to 3, n
is 1 or 2. Among the above, coupling agents belonging to (A) and (B) give blue or red dyes, those belonging to (C) give brown or blue dyes, and (D) and (E)
Those belonging to the following formula give red or yellow dyes. You can also use something like this.

Specifically, resorcinol and its derivatives 4
- 1-phenyl-3 which is benzoylresorcinol, 2-methylresorcinol, 5-methylresorcinol, diresorcinol and diresorcinol sulfide, phloroglycin, pyrazolones;
-Methyl--pyrazolone, 4,4'-bis(1-phenyl-3-methyl-5-pyrazolone), 1-
(4'-sulfophenyl)-3-methyl-5-pyrazolone, naphthols include 2-hydroxy-
3-naphthoic acid-2'-ethoxyanilide, 2-hydroxy-3-naphthoic acid-2',5'-dimethoxyanilide, 2-hydroxy-3-naphthoic acid-
2'-Methoxy-5-nitroanilide, 2-hydroxy-3-naphthoic acid-2-methyl-4-chloroanilide, 2-hydroxy-3-naphthoic acid-morpholinopropioamide, 2-hydroxy-3-
Naphthoic acid ethanolamide, dihydroxynaphthalene, 2-hydroxy-3-naphthoic acid naphthamide, 1,8-dihydroxynaphthalene-3
(or 4)-sodium sulfonate, sodium 1-hydroxy-8-benzoylaminonaphthalene-3-sulfonate, sodium 1-hydroxy-8-phenylaminonaphthalene-4-sulfonate, 1-hydroxy-8-methylamino Sodium naphthalene-5-sulfonate, sodium 1-hydroxynaphthalene-4-sulfonate, 2,8
- Sodium dihydroxynaphthalene-6-sulfonate.

Examples of acidic coupling agents include 2-hydroxy-3-naphthoic acid, 2-hydroxy-6-naphthoic acid, 2-hydroxy-1-naphthoic acid, 2-hydroxy-1-naphthoic acid,
6-dihydroxybenzoic acid, 2,4-dihydroxybenzoic acid, 3,5-dihydroxybenzoic acid,
2,4,6-trihydroxybenzoic acid and cyanoacetic acid, as well as m-hydroxyphenylurea,
N,N-ethylenebisacetoacetamide, 2,
6-dihydroxyacetophenone, acetoacetanilide, 2,4,6-trihydroxyacetophenone, N-benzylacetoacetamide, catechol, acetoacetic benzamide, or alternatively 2,4-dihydroxybenzoic acid ethanolamide, 3,5 -Dihydroxybenzoic acid ethanolamide and the like can also be used.

As coupling agents it is also possible to use compounds which have in their structure a group in the form of a metal carboxylate salt as well as a coupling position. To give a specific example,
2-hydroxy-1-naphthoic acid, 2-hydroxy-3-naphthoic acid, 2-hydroxy-4-naphthoic acid, 2-hydroxy-6-naphthoic acid, 2,
3- (or 2,4-, 2,5-, 2,6-, 3,
4-,3,5-)dihydroxybenzoic acid, 2,
3,4- (or 2,4,6-, 3,4,5-)
Trihydroxybenzoic acid, 2-hydroxyanthracene-3-carboxylic acid, 3-hydroxybenzofuran-2-carboxylic acid, 2-hydroxycarbazole-3-carboxylic acid, 2-hydroxy-a-
Benzocarbazole-3-carboxylic acid, 1-
(4'-sulfophenyl)-3-carboxy-5-pyrazolone, 4,4'-methylenebis-(3-hydroxy-2-naphthoic acid)-2-(or 3-,4
-) metal salts of aromatic compounds such as acetoacetaminobenzoic acid, 3-(or 4-, 5-, 6-)acetoacetaminosalicylic acid, 5,5'-carboxyacetoacetobenzidide.

Metals that form salts include monovalent or polyvalent metals such as lithium, sodium, potassium, calcium, magnesium, strontium, barium, aluminum, chromium, manganese, iron, cobalt, nickel, copper, zinc, or cadmium. You can choose whatever you like.

Among the compounds listed as compounds having a coupling position and a group in the form of a metal carboxylic acid salt in the structure, particularly preferred are 2-hydroxy-1-naphthoic acid, 2-hydroxy-3-naphthoic acid, 2, 4-dihydroxybenzoic acid, 4-
acetoacetaminobenzoic acid or 4-acetoacetaminosalicylic acid, calcium, zinc,
Salts of strontium, manganese or cadmium.

Organic or inorganic alkaline substances,
A basic compound or a thermally decomposable alkali generator that generates an alkali by thermal decomposition can be used, and examples of organic compounds include urea, thiourea, aminopyridine, imidazole, phenylimidazole, guanidine, diphenylguanidine, and diphenylguanidine. -0
- As inorganic products such as tolylguanidine,
NH ₄ HCO ₃ , NH ₄ H ₂ PO ₄ , (NH ₄ ) ₂ HPO ₄ ,
Examples include (NH ₄ ) ₃ PO ₄ and NaHNH ₄ PO ₄ .

As other components, it is desirable to add an acidic stabilizer in order to improve the storage stability of the diazo compound and the rate of photodecomposition during the fixing operation.
Monovalent to divalent or more fatty acids, specifically citric acid, oxalic acid, malonic acid, malic acid, adipic acid, maleic acid, etc. can be mentioned.

The binder is preferably (a) soluble in water, methanol or ethanol, which is a solvent for the diazo compound, and (b) softens or melts to an extent that facilitates the coloring reaction of the diazo compound during thermal printing. Can be mentioned. Polyvinyl alcohol, polyvinyl butyral,
polyvinyl acetal, polyvinyl formal,
Epoxy, polyacrylic acid, polymethacrylic acid,
Polymethacrylic acid ester, polyacrylate,
polyamide, polyvinyl chloride, polyvinyl acetate,
Synthetic or natural resins such as vinyl chloride/vinyl acetate copolymer, cellulose acetate, cellulose acetate butyrate, melamine, polyvinylpyrrolidone, gelatin, and casein can be mentioned. It is more preferable to use a binder having an acidic residue in terms of stabilizing the diazo compound and accelerating the rate of photodecomposition during fixing. Examples of such binders include styrene/maleic acid copolymer, isobutylene/ It is preferable to use a maleic acid copolymer or a vinyl chloride-vinyl acetate-maleic acid ternary copolymer resin.

A solvent or diluent is added to the above-described diazo compound, alkaline substance, coupling agent, other components, and binder to prepare a composition for forming a heat-sensitive recording layer.

In the above, the blending ratio of the diazo compound and the coupling agent is 1/0.5 to 1/5, more preferably 1/3 to 1/2. Further, the blending ratio of the diazo compound and the binder is 1/1 to 1/20, more preferably 1/3 to 1/10. The degree of alkalinity of the alkaline substance varies depending on the type of alkaline substance used, so it cannot be generalized, and it must be determined after conducting preliminary tests as appropriate. The minimum amount is sufficient to create an atmosphere where people feel comfortable.

However, as will be described later, the layer containing the alkaline substance may be separated from the layer containing the alkaline substance (for example, by the reference numeral 3 in FIG. 3).
For layer A), the alkaline substance/binder is 1/0.5 to 1/5, preferably 1/0.5 to 1/5.
It is about 2.

The composition prepared as described above is coated on the surface of the release layer on one side of the base material using a known coating method, such as gravure coating, roll coating, air knife coating, kiss coating, spray coating, continuous coating, dip coating, or spinner coating. coat, wheeler coat, brush coating, solid coat by silk screen, wire bar coat, flow coat, gravure printing, gravure offset printing, lithographic offset printing, die lithography, letterpress printing, intaglio printing, jet printing, silk screen printing, static The heat-sensitive recording layer is formed by applying by electroprinting to a thickness of about 1 to 5 μm.

As the heat-sensitive recording layer, in addition to the above-mentioned type that develops color under alkaline conditions, it is also possible to use one that develops color under neutral conditions; one example is 2,5-diethoxy(dimethoxy)-4-(4-tolylmercapto)benzenediazonium chloride as a diazo compound. The heat-sensitive recording layer may be constructed using the above-mentioned alkaline material without containing an alkaline substance.

Further explaining the adhesive layer 4 provided on the surface of the heat-sensitive recording layer 3, the adhesive composition forming the adhesive layer 4 is a thermoplastic resin such as polyvinyl acetate, polyester, polyester polyol, vinyl chloride/acetic acid. We use resins such as vinyl copolymers, polyacrylic acids, polyacrylic esters, polymethacrylic esters, ethylene/vinyl acetate copolymers, and even epoxy resins with UV curability in consideration of their adhesion to the heat-sensitive recording layer. and select
It can be formed by diluting it with an appropriate solvent and applying it using a known coating method, and preferably has transparency. The thickness of the adhesive layer 4 is not particularly limited, but is approximately 5 to 50 μm.

Since the heat-sensitive recording material of the present invention performs heat recording from above the adhesive layer 4, it is desirable that the adhesive layer 4 further contains a lubricant and a mold release agent.

The typical substances that serve as lubricants are metal soaps, that is, metal salts of fatty acids such as lauric acid and stearic acid, but there are also the following substances.

Organic tin fatty acid salts such as dibutyl-tin dilaurate, dibutyl-tin dinonylate, fatty acid amides such as stearylamide, palmitylamide, oleylamide, bis fatty acid amides, higher ketones such as stearone, higher alcohols and their derivatives such as myristyl alcohol, cetyl alcohol. , stearyl alcohol, polyethylene glycol, polyglycerol, hydrocarbons such as liquid paraffin, paraffin wax, microwax, polyethylene with a low degree of polymerization, as well as natural waxes such as carnauba wax, candelilla wax, beeswax, spermaceti wax, privet wax, montan wax.

Furthermore, the term "mold release agent" refers to an agent that is generally used for the purpose of improving mold release during processing of rubber or plastic. A wide variety of substances can serve as mold release agents, but the main ones include mineral oils, such as petroleum ethers, vegetable oils, such as olive oil or castor oil, petrolatum or lanolin, fatty acids, especially alkanoic or alkenoic acids having 11 to 24 carbon atoms, and The ester especially has 6 carbon atoms.
Esters with ~24 alkyl or alkenyl, esters of phosphites, especially phenyl or alkyl (8 to 13 carbon atoms), fatty acid esters of glycerin-sorbitan condensates, alkenoyl (7-21 carbon atoms) amino acid esters, fluorocarbons and These include Teflon and silicone.

To carry out thermal recording using the above-described thermal recording material, thermal printing is first performed from the adhesive layer side of the thermal recording material. The thermal head used for thermal printing can be of any type, such as line or matrix dot type, segment type, thermal type type, or thermal pen type, and the thermal energy required is 0.1 to 5 mJ per dot. be.

When diazo sulfonate is used as the diazo compound in the heat-sensitive recording layer, exposure to ultraviolet rays for activation is preferably carried out prior to thermal printing, thereby increasing the recording sensitivity.

After thermal printing is performed, the heat-sensitive recording layer is irradiated with ultraviolet rays to decompose the diazo compound in the areas where thermal printing has not been performed, fixing the image, and preventing unnecessary fogging from occurring thereafter. The ultraviolet rays used for fixing and activation may be those emitted from light sources such as ultra-high pressure mercury lamps, high pressure mercury lamps, low pressure mercury lamps, carbon arcs, xenon arcs, metal halide lamps, and the like.

After thermal printing and fixing are performed as described above, the adhesive layer is placed on another base material so that it is in contact with the other base material, and the adhesive layer is placed on another base material by heating and pressurizing it with a heat press or by irradiating it with ultraviolet rays. After the transfer, the base material of the heat-sensitive recording material is peeled off. Other base materials can be selected and used as appropriate depending on the purpose, and examples include the following: (a) Form paper, thin paper, parchment paper, high-quality paper, art paper, etc. Paper, coated paper, paperboard, etc., (b) polyethylene film, polypropylene film, ionomer film, polyvinyl chloride film, polyvinylidene chloride film, polyvinyl alcohol film, polyethylene terephthalate film, polycarbonate film, nylon film, polystyrene film, ethylene Plastic film, plastic sheet or plastic plate such as vinyl acetate copolymer film, ethylene vinyl alcohol copolymer film, cellulose diacetate film, cellulose triacetate film, polysulfone film, polyimide film, (c) stainless steel, aluminum, copper,
Metal foil or plate made of lead, tin, etc., (d) natural fibers,
Woven or non-woven fabrics made of fibers such as chemical fibers and glass fibers, (e) Inorganic boards such as glass, concrete, and ceramics, (f) Wooden boards such as wood, plywood, and particle board, (g) Above (a) to (f) ) materials are laminated as appropriate. Among these, art paper, coated paper, white polyester film, etc. are exemplified to obtain high-quality images, and when transparency is required, transparent plastic film or sheet is preferable. Among transparent plastic films, polyester, A material with excellent heat resistance such as polycarbonate is preferred.

By changing the components of the heat-sensitive recording layer of the heat-sensitive recording material of the present invention, for example, by changing the coupling agent to give an appropriate coloring hue, it can be layered one after another on other substrates after thermal printing and fixing. When transferred, images with different hues appear mixed and visible.
This produces an effect similar to multicolor printing. Although the effect is similar to multicolor printing, it is not simply a matter of arranging areas of different hues, but is also recorded on a heat-sensitive recording material that uses predetermined color separation filters to produce yellow, red, indigo, and black colors. However, if the images are transferred onto the same substrate in the same register, an image resembling a so-called color photograph can also be obtained.

As an application example of the heat-sensitive recording material of the present invention, it may be divided into two layers, a layer 3A containing an alkaline substance and a layer 3B containing a substance other than the alkaline substance, as shown in FIG. The order of forming the layers 3A and 3B may be as shown in FIG. 2, or the layers 3A and 3B may be interchanged. Note that layer 3 containing an alkaline substance
In order to more efficiently isolate the alkaline substance from substances other than the alkaline substance in the layer 3B, A is preferably formed by dispersing the alkaline substance in the binder rather than by dissolving it in the binder.

Further, as described above, when a thermosensitive recording layer is constructed using a diazo compound that develops a neutral color, it may be divided into a layer containing the diazo compound and a layer containing a coupling agent.

According to the present invention, the obtained image can be transferred in an appropriate size to an appropriate position on an appropriate substrate according to the purpose, so it is possible to transfer the obtained image in advance to each substrate of different materials and sizes. Moreover, there is no inconvenience in forming the heat-sensitive recording layer after determining its size and position. In addition, according to the present invention, the obtained image can be transferred onto another base material in a layered manner, so that it is possible to transfer the obtained image onto another base material, which is different from the conventional case where a heat-sensitive recording layer is provided in advance, in which only one type of coloring hue is produced, or when reverse transfer is performed when using a transfer tape. No such inconvenience will occur.

Examples are given below to more specifically explain the present invention.

Example 1 A releasable paint, a sensitive paint, and an adhesive paint having the following compositions were prepared.

Peelable paint Cellulose acetate resin…5 parts by weight (Daicel Chemical Industries, LAC) Methyl cellosolve…25 parts by weight Methyl ethyl ketone…15″ Toluene…15″ Soybean lecithin…0.5″ Sensitive paint 2,5-diethoxy-4-(4 ′-Tolylmercapto)-benzenediazosulfonate sodium
...1 part by weight 2-hydroxy-3-naphthoic acid calcium salt
...1.5" Cellulose acetate propionate resin ...5" (Manufactured by Eastman Kodatsu, CAP482-05) Toluene 20" Ethanol 20" Methyl cellosolve 5" Adhesive paint Polyester resin ...5 parts by weight (Manufactured by Toyobo, Pylon 200) PVC / Vinyl acetate copolymer resin…5″ (manufactured by Union Carbide, VAGH) Methyl ethyl ketone…7″ Toluene…20″ Polyethylene wax…2″ (manufactured by BASF, AF) Mold release agent…2 parts by weight (MOLDWIZ F-57) Above Using each paint, a release layer was first applied to the surface of a 25 μm thick transparent polyester film by gravure coating using a releasable paint so that the film thickness was 0.5 μm, and then a release layer was applied using a sensitive paint by roll coating. A heat-sensitive recording material was prepared by providing a sensitive layer with a thickness of 3 μm over the release layer, and further overlapping the sensitive layer with an adhesive layer with a thickness of 2 μm by roll coating using an adhesive paint.

Thermal printing is performed from the adhesive layer side of the resulting heat-sensitive recording material using a line dot type thermal printer with an energy of approximately 1.3 mJ per dot.
After fixing with a Xe flash with an energy of 1000 J, the adhesive layer side of the heat-sensitive recording material was brought into contact with high-quality paper and bonded by heat using a hot plate at a temperature of about 170°C under a load of about 20 kg, and then a polyester film was bonded. When the paper was peeled off, a blue image with a reflection density of 1.03 was transferred to the high-quality paper.

Example 2 2-Hydroxy- in the sensitive coating composition of Example 1
3-naphthoic acid calcium salt to 2-hydroxy-
Heat-sensitive recording materials were prepared in the same manner as in Example 1, except that 1-naphthoic acid calcium salt was used and the acetoacetaminosalicylic acid calcium salt was used, respectively, and the two types obtained above were used. Thermal printing was performed on each of the thermal recording material obtained in Example 1 and the thermal recording material obtained in Example 1.
After fixing, when the images were transferred one after another onto high-quality paper, each image was transferred, and the overlapping parts of each image had the effect of color mixing, i.e., red, blue, yellow, and green. An image consisting of seven colors including , orange, purple, and reddish black was obtained.

Example 3 A sensitive material paint and an adhesive paint having the following compositions were prepared.

Sensitive paint (A) p-diethylaminobenzenediazochloride... 1/2zncl ₂ double salt 1 part by weight PVC/vinyl acetate/maleic acid copolymer resin
…2.5 parts by weight Methyl ethyl ketone …12.5″ Ethanol…5″ Sensitive paint (B) Phloroglucinol…10 parts by weight Diphenylguanidine…1″ Acrylic resin…11″ (Rohm and Haas, Paraloid B-67) Cyclohexane…99 ″ Paint for adhesives Cyclized rubber…10 parts by weight (Thermolite N) Polyethylene wax…1″ (BASF, AF) Soybean lecithin…1″ Cyclohexane…88″ Transparent polyester with a thickness of 25 μm as in Example 1 After providing a release layer on the film, the film was sequentially formed on the release layer by roll coating using a sensitive material paint (A) and a sensitive material paint (B) so that the film thicknesses were 1 μm and 2 μm, respectively, and then the above-mentioned An adhesive layer with a coating thickness of 1 μm was provided by roll coating using the following adhesive paint.

Thermal printing and
When fixed and transferred onto high-quality paper, the reflection density was 1.40.
A dark brown image was obtained.

[Brief explanation of the drawing]

1 and 2 are cross-sectional views showing an embodiment of the present invention. 1...Base material, 2...Peeling layer, 3...Thermosensitive recording layer, 4...Adhesive layer.

Claims (1)

[Scope of utility model registration request] 1. A heat-sensitive recording material, characterized in that a release layer, a heat-sensitive recording layer, and an adhesive layer are sequentially provided on the surface of a base material, and the adhesive layer contains a lubricant and a release agent.