JPH05238128A - Thermosensitive and pressure sensitive recording sheet and its manufacture - Google Patents

Abstract

PURPOSE:To improve recording density during thermosensitive recording laminating a pressure sensitive recording layer consisting of a microcapsule which contains a coloring agent and a thermosensitive recording layer containing a developer and a coloring agent on one surface of a support. CONSTITUTION:A pressure sensitive recording layer of a single laminar microcapsule which contains at least, either of developer or coloring agent, or of such microcapsules applied in a mixed form, an aqueous polymer intermediate layer, a silicone resin layer, a viscous layer, an intermediate support and a thermosensitive recording layer containing a coloring agent and a developer are sequentially laminated on one surface of a support to obtain a thermosensitive and pressure sensitive recording sheet. The preferable silicone resin layer is one cured by irradiating a silicone compound having at least, one or more selected from among an acryloyl group, a methacryloyl group and an epoxy group, using a high energy beam, either ultraviolet ray or an electron beam. It is preferable to laminate an additional overcoat layer.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a heat-sensitive pressure-sensitive recording sheet, in which an aqueous polymer intermediate layer, a silicone resin layer, a self-coloring type pressure-sensitive recording layer of a single form provided on a support, An adhesive layer, an intermediate support, and a heat-sensitive recording layer, which are sequentially provided, are heat-sensitive pressure-sensitive recording sheets having peeling property, non-exposure of recording, recordability of different information, water resistance, chemical resistance, oil resistance, A heat-sensitive pressure-sensitive recording sheet which can be used as a recording sheet of a type having scratch resistance and dust generation suppressing ability, as a recording sheet for labels, slips, correspondence, postcards, entertainment items, and clean rooms.

[0002]

2. Description of the Related Art The pressure-sensitive recording layer used in the present invention is a self-coloring type pressure-sensitive recording layer, which has been developed from so-called carbonless copying paper. It is also called a hand paper. Its composition is colorless dye (hereinafter referred to as color former)
The step of applying the coating material of the microcapsules encapsulating on the support, and further applying the electron-accepting substance (hereinafter referred to as a developer) such as acidic clay, phenol resin, organic acidic substance on the coating. Manufacturing process by two-layer coating consisting of two steps (including coating order reversed)
Alternatively, there is known a method (Japanese Patent Publication No. 47-16096) in which the components of the above-mentioned two steps, or one of the microcapsules, is uniformly mixed and coated by one layer. In such a self-coloring type pressure-sensitive recording sheet, since the total amount of the color-developing agent and the color-developing agent are in the vicinity of each other, it is easy to obtain a dark color density, but it is not intended due to friction during manufacturing or handling. There is a problem that undesired color stain is likely to occur.

The self-coloring type pressure-sensitive recording sheet is destined to satisfy both the practically required coloring performance and the suppression of unnecessary coloring stains under the conditions under which it is used. Efforts are being made to satisfy both of the conflicting properties of colored stains. Further, such a self-coloring type pressure-sensitive recording sheet is often used for sticking continuous slips to luggage or as a lower sheet, and therefore, water resistance, oil resistance, stain resistance, recording property, etc. are required at the same time. However, it was extremely difficult to satisfy those conditions at the same time. Furthermore, if one of them is used for pasting in a continuous slip, the lower paper must be a release paper, so it is often used in the lowermost layer in the slip structure, and it naturally has a low color density. there were. In such a configuration, release paper of the same area is required,
For example, not only is the release paper ejected when labels are applied continuously, but it is a great obstacle to work.
In general, release paper cannot be recycled, so there is a problem in disposal,
Further, there is a problem in that the combined thickness of the pressure sensitive paper and the release paper becomes thick when used. Furthermore, the pressure-sensitive information recorded on the self-coloring pressure-sensitive recording sheet is inevitably highly open to the public, and if you want to hide the information content, you must put it in a separate bag. It was

Up to now, for example, a recording sheet having a plastic layer formed by a melt-laminating method or a method of providing a laminate layer by a vacuum contact method on the recording layer of a self-coloring type pressure-sensitive recording sheet (Japanese Patent Publication No. Sho 49-10857). (Japanese Utility Model Laid-Open No. 52-149709) and examples of providing a release layer on these protective layers are known. However, in reality, when a protective layer is provided by fusion lamination or laminating, unnecessary color stains can be prevented, but only unsatisfactory results are obtained at the expense of the originally required color development performance. It was the actual situation that was not done. Further, since these methods basically assume that the pressure-sensitive recording portion is exposed, the problem of non-disclosure of recording cannot be solved.

In another method, a soluble polymer solution is applied onto a self-coloring type pressure-sensitive recording layer and dried to form a film, but a protective layer having a small thickness can be formed, but the microcapsules are destroyed to cause remarkable color fog. Or the microcapsules were surrounded by the resin, the original self-coloring type pressure-sensitive recording property was almost lost, and both the color density and the color developing speed were decreased to unacceptable levels.

[0006]

SUMMARY OF THE INVENTION Therefore, an object of the present invention is to reduce the color fog caused by friction without sacrificing the original color developability in the pressure-sensitive recording property, and at the same time, the water resistance and the oil resistance. In addition to these functions, the thermal head is capable of performing thermal recording on the surface without leaving any effect on the pressure-sensitive recording layer. Another object is to provide a heat-sensitive pressure-sensitive recording sheet.

[0007]

The present inventors have found the present invention as a result of intensive research to solve the above problems. That is, a microcapsule containing at least one of a color former and a color developer is independently laminated on one surface of a paper or film support, or a pressure-sensitive recording layer formed by mixing and coating, a water-based recording layer. A heat-sensitive pressure-sensitive recording sheet comprising a molecular intermediate layer, a silicone resin layer, an adhesive layer, an intermediate support, a color-developing agent, and a color-developing agent which develops color by contacting with the color-developing agent. It is the invention of the manufacturing method. The silicone resin used in the present invention is preferably a silicone resin in which at least one acryloyl group, methacryloyl group, or epoxy group is introduced at the terminal or side chain of the molecular main chain of polydialkylsiloxane, and contains an inorganic pigment. May be. An overcoat layer may be provided on the heat-sensitive recording layer, or an undercoat layer may be provided below the heat-sensitive recording layer.

In this heat-sensitive pressure-sensitive recording sheet, the silicone resin provided on the recording surface does not soak into the pressure-sensitive recording layer due to the action of the aqueous polymer intermediate layer, and a small amount of the silicone resin maintains surface releasability. A high color density can be obtained. The silicone resin itself exhibits not only releasability from the adhesive layer but also high water resistance, and the aqueous polymer intermediate layer exhibits high oil resistance. Further, when the heat-sensitive recording layer, the intermediate support and the adhesive layer are used as the label, not only the release paper is unnecessary but there is not only a cost merit, but also the unnecessary release paper need not be discharged, and the silicone resin layer is not necessary. Since it also serves as an overcoat layer, the overlaid layer becomes thin, and color can be developed with good recording density during pressure-sensitive recording, and it has excellent gloss, scratch resistance, and abrasion resistance on the printed surface Since it has an adhesive layer and an intermediate support, the pressure-sensitive recorded information can be exposed to the outside and can be handled without being exposed. If necessary, the thermal recording layer and the intermediate support can be peeled off to make the inside sense. You can read the pressure-recorded information. In addition to the internal pressure-sensitive recording on the intermediate support by pressure, thermal recording can be performed using a thermal head, and different information can be recorded on the surface intermediate support and on the internal pressure-sensitive recording section. It is a thing. This function can simultaneously record, for example, an address on the front surface of one postcard and information that the other person does not want to be seen inside the concealed postcard.

The details of the present invention will be described below. As the support used in the heat-sensitive pressure-sensitive recording sheet of the present invention, and the intermediate support, general paper such as glassine paper, high-quality paper, art paper, coated paper and cast paper can be used,
Raw materials commonly used in papermaking, such as wood pulp, synthetic pulp, fillers, sizing agents, paper-strengthening agents, and dyes, can be used as necessary. In addition, plastic sheets such as polyethylene, polypropylene, polyethylene terephthalate, and polyamide, and synthetic paper or non-woven fabric made of these synthetic fibers, or a laminated paper, a metal foil, or a metal foil laminated with a synthetic resin on one side or both sides Paper, a laminated product with a synthetic resin film, mica paper, glass paper, etc. can also be used. These plastic sheets and synthetic resins can be made opaque with inorganic or organic pigments.

The pressure-sensitive recording layer that can be used in the present invention is not particularly limited, and any conventionally known one can be used. For example, a method of microencapsulation, a wall material of the microcapsule, a color former, an oil dissolving the color former, a color developer, an adhesive, a microcapsule protective agent, and the like. Examples of the microencapsulation method include a coacervation method (US Pat. No. 2,800,458), an interfacial polymerization method (Japanese Patent Publication No. 47-1763, etc.), an in situ polymerization method (Japanese Patent Publication No. 51-9079, etc.). Etc. can be used.

Polyurethane, polyurea, epoxy resin, urea / formalin resin, melamine / formalin resin, etc. can be used as the wall material of the microcapsule.

As the color former used in the pressure-sensitive recording layer or the heat-sensitive recording layer, triallylmethane compounds, diarylmethane compounds, xanthene compounds, thiazine compounds, spiropyran compounds, etc. can be used. There is no particular limitation as long as it is used as a material or a heat-sensitive recording material.

As the oil for dissolving the color former, aromatic synthetic oils such as diarylalkane series, alkylnaphthalene series, alkylated biphenyls, hydrogenated terphenyls, and aliphatic synthetic oils such as kerosene, naphtha, paraffin oil and chlorinated paraffins are used. Oils, cottonseed oil, soybean oil, vegetable oils such as linseed oil and the like can be used.

As the protective agent for the microcapsules, cellulose powder, starch particles, talc, calcined kaolin, calcium carbonate and the like can be used.

The color developer used in the pressure-sensitive recording layer includes
Clays (eg acid clay, attapulgite etc.), organic acids (eg aromatic carboxy compounds such as salicylic acid or metal salts thereof), mixtures of organic acids and metal compounds, acidic polymers (eg phenol / formaldehyde resins, salicylic acid series) Resin or metal salts of these)
Etc. can be used. As the developer used in the heat-sensitive recording layer, an electron-accepting substance generally used in heat-sensitive recording materials is used, and in particular, a phenol derivative, an aromatic carboxylic acid derivative or a metal compound thereof, N, N'-diarylthiourea. A derivative or the like is used. Of these, particularly preferred are phenol derivatives, and specifically, 1,1-bis (p-hydroxyphenyl) propane, 2,2-bis (p-hydroxyphenyl) propane, 2,2-bis (p -Hydroxyphenyl) butane, 2,2-bis (p
-Hydroxyphenyl) hexane, bisphenol sulfone, bis (3-allyl-4-hydroxyphenyl)
Sulfone, 4-hydroxy-4'-isopropyloxydiphenyl sulfone, 3,4-dihydroxy-4 '
-Methyldiphenyl sulfone, diphenol ether, benzyl p-hydroxybenzoate, propyl p-hydroxybenzoate, butyl p-hydroxybenzoate and the like can be mentioned.

Further, in order to further improve the sensitivity, N-hydroxymethylstearic acid amide as a sensitizer,
Waxes such as stearic acid amide and palmitic acid amide, naphthol derivatives such as 2-benzyloxynaphthalene, biphenyl derivatives such as p-benzylbiphenyl and 4-allyloxybiphenyl, 1,2-bis (3-methylphenoxy) ethane, Polyether compounds such as 2,2′-bis (4-methoxyphenoxy) diethyl ether and bis (4-methoxyphenyl) ether. Carbonic acid such as carbonic acid diphenyl, oxalic acid dibenzyl, oxalic acid di (p-chlorobenzyl) ester, or an oxalic acid diester derivative can be added.

In the present invention, as the binder used for forming the pressure-sensitive recording layer, the aqueous polymer intermediate layer, the undercoat layer and the overcoat layer, starch, cellulose derivatives such as hydroxyethyl cellulose, methyl cellulose, ethyl cellulose and carboxymethyl cellulose are used. , Protein such as casein and gelatin, aqueous natural polymer such as saccharose such as oxidized starch and ester compound starch, polyvinyl alcohol, modified polyvinyl alcohol, polyvinylpyrrolidone, polyacrylic acid, sodium polyacrylate, acrylic acid amide / acrylic acid Ester copolymer, acrylic acid amide / acrylic acid ester / methacrylic acid terpolymer, styrene /
Water-soluble synthetic polymer compounds such as alkali salts of maleic anhydride copolymers, latex, polyacrylamide, styrene / maleic anhydride copolymers and latexes, water-soluble alkali salts of ethylene / maleic anhydride copolymers, etc. Adhesive, polyvinyl acetate, polyurethane, polyacrylic acid ester, styrene / butadiene copolymer, acrylonitrile / butadiene copolymer, methyl acrylate /
Butadiene copolymer, acrylonitrile / butadiene /
Examples thereof include acrylic acid copolymers, latexes of ethylene / vinyl acetate copolymers, electron beam curable resins, and ultraviolet curable resins.

Pigments used in the pressure-sensitive recording layer, the aqueous polymer intermediate layer, the undercoat layer, the overcoat layer or the silicone resin layer include diatomaceous earth, talc, kaolin, calcined kaolin, calcium carbonate, magnesium carbonate, Examples thereof include titanium oxide, zinc oxide, silicon oxide, aluminum hydroxide, urea-formalin resin and the like.

In addition, zinc stearate as an auxiliary agent,
Higher fatty acid metal salts such as calcium stearate. Waxes such as paraffin, oxidized paraffin, polyethylene, oxidized polyethylene, stearamide, and castor wax. Further, a dispersant such as sodium dioctyl sulfosuccinate and a sulfonic acid-modified polyvinyl alcohol, an ultraviolet absorber such as a benzophenone type or a benzotriazole type, a surfactant, a fluorescent dye and the like are added as necessary.

In the pressure-sensitive recording material of the present invention, as a method for forming the pressure-sensitive recording layer, there are known blade coating method, air knife coating method, gravure coating method, roll coating coating method, bar coating method, drop curtain coating method and the like. Coating methods are available.

Further, in the field of pressure-sensitive recording material manufacturing, a back coat is applied to prevent curling, a conductive treatment is applied to prevent jamming, and an undercoat layer is provided between the support and the pressure-sensitive recording layer. Various known techniques can be added as necessary.

Further, as the constitution of the present invention, calcium carbonate, talc, silica, clay, barium sulfate, magnesium carbonate are provided between the support and the pressure-sensitive recording layer or between the intermediate support and the heat-sensitive recording layer in order to obtain the color density. , Magnesium silicate, lead sulfate, white lead, zinc white, zinc sulfide, satin white, titanium oxide, antimony oxide, mica, bentonite, calcium silicate, gypsum, inorganic pigments such as aluminum hydroxide or polystyrene, polyvinyltoluene, styrene There is no problem in providing an undercoat layer containing a fine powder organic pigment such as / divinylbenzene copolymer, polymethylmethacrylate, urea / formaldehyde polymer, or polyethylene.

An aqueous polymer intermediate layer composed of an aqueous polymer may be provided between the pressure sensitive recording layer and the silicone resin layer. Examples of the aqueous polymer mentioned here include the following substances.

As natural polymers and semi-synthetic polymers, modified starch compounds such as starch, oxidized starch, etherified starch, dialdehyde starch, esterified starch, alginic acid compounds such as sodium alginate and propylene glycol alginate, casein,
Examples thereof include modified cellulose compounds such as gelatin, pullulan, dextran, chitin, chitosan, gum lattex, gum arabic, funori, natural gum, dextrin, methylcellulose, ethylcellulose, hydroxycellulose and carboxymethylcellulose. As the synthetic polymer, completely saponified or partially saponified polyvinyl alcohol, acetoacetylated polyvinyl alcohol, esterification products of polyvinyl alcohol and polyvalent carboxylic acid, carboxy modified polyvinyl alcohol, sulfonic acid modified polyvinyl alcohol, olefin modified Modified polyvinyl alcohol compounds such as polyvinyl alcohol, nitrile modified polyvinyl alcohol, amide modified polyvinyl alcohol, pyrrolidone modified polyvinyl alcohol, polyethylene glycol, polyacrylic acid amide, polyacrylic acid, ammonium polyacrylate, sodium polyacrylate, etc. Polyacrylic acid compound, polyvinylpyrrolidone, polyethyleneimine, polyvinyl ether, polymaleic acid copolymer, polyacrylamide, Such as soluble alkyd resins. In addition, styrene /
Use an emulsion in which synthetic polymers such as maleic anhydride copolymer, styrene / butadiene copolymer, butadiene / methacrylate copolymer, acrylonitrile / butadiene / acrylic acid latex, etc. are dispersed in water instead of the aqueous polymer solution. You can As an aqueous polymer,
The above polymers may be used alone or as an aqueous solution in which they are mixed together with an antifoaming agent, a dispersant, etc., if necessary.

The silicone resin release agent for forming the silicone resin layer used in the present invention is a silicone resin (mainly polydimethylsiloxane) or a solution thereof.
An aqueous emulsion, preferably a silicone resin that is cured by heating, ultraviolet rays or electron beams,
Besides, various silicone compounds having the same function, fluorine compounds, compounds containing a long-chain alkyl group, and the like can be used. The ultraviolet or electron beam curable silicone resin is a resin in which an acryloyl group or a methacryloyl group is introduced at the terminal or side chain of the molecular main chain of a general silicone resin, and is a silicone-containing acrylate, a silicone-containing methacrylate or a derivative thereof. .. The product names are FM0711, FM0721, FM0725, PS58
3 (above, Chisso Corporation), KP-600, X-62-
7100, X-62-7112, X-62-7140,
X-62-1144, X-62-1153, X-62-
7157, X-62-1158, KNS-5200, X
-62-7166, X-62-7168, X-62-7
177, X-62-7180, X-62-7181, X
-62-7192, X-62-7200, X-62-7
203, X-62-7205, X-62-7931 (above, Shin-Etsu Chemical Co., Ltd.), RC149, RC300, RC
450, RC802, RC710, RC720 (above,
(Goldschmitt), EBECRYL350, EB
ECRYL1360 (above, Daicel UCB Ltd.) etc. are mentioned. Furthermore, acrylates or methacrylates containing long-chain alkyl groups and their silicone-modified compounds are also good ultraviolet or electron beam curable release agents. These can be used alone or in combination of two or more. In addition, these silicone resins have the purpose of increasing the surface strength of the silicone resin layer,
Alternatively, for the purpose of improving the curability, a general ultraviolet curable resin or an electron beam curable resin is used as a curing aid.
It can be used by mixing within a range that does not excessively affect the peel strength.

Typical examples of the ultraviolet curable or electron beam curable resin used in the present invention include (1) polyester acrylates and polyester methacrylates such as Aronix M-5300, Aronix M-5400 and Aronix M-. 5500, Aronix M-5600, Aronix M-5700, Aronix M-6100, Aronix M-6200,
Aronix M-6300, Aronix M-650
0, Aronix M-7100, Aronix M-80
30, Aronix M-8060, Aronix M-8
100 (above, product name of Toagosei Chemical Industry Co., Ltd.), Viscoat 700, Viscoat 3700 (above, product name of Osaka Organic Chemical Industry Co., Ltd.), Kayarad HX-220, Kayarad HX-620 (above, Nippon Kayaku ( Stock name) etc.

(2) Urethane acrylate and urethane methacrylate, for example, Aronix M-1100, Aronix M-1200, Aronix M-1210,
Aronix M-1250, Aronix M-126
0, Aronix M-1300, Aronix M-13
10 (above, product name of Toagosei Chemical Industry Co., Ltd.), viscoat 812, viscoat 823, biscoat 823 (above, product name of Osaka Organic Chemical Industry Co., Ltd.), NK ester,
U-108-A, NK ester, U-4HA (above, Shin Nakamura Chemical Co., Ltd. trade name), etc. are mentioned.

(3) Monofunctional acrylate, monofunctional methacrylate, vinylpyrrolidone, acryloyl compound, acrylamide compound For example, methyl acrylate, ethyl acrylate, butyl acrylate, 2-ethylhexyl acrylate,
2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl acrylate, tetrahydrofurfuryl acrylate, phenoxyethyl acrylate, cyclohexyl acrylate,
Cyclohexyl methacrylate, acryloyl morpholine, benzyl acrylate, glycidyl methacrylate, N, N-dimethylaminoethyl acrylate, N,
N-dimethylaminoethyl methacrylate, N, N-diethylaminoethyl methacrylate, butoxyethyl acrylate, vinylpyrrolidone, acrylamide ether compound and the like. Ethylene oxide-modified phenoxyphosphoric acid acrylate Ethylene oxide-modified butoxylated phosphoric acid acrylate, and other product names of Toagosei Kagaku Kogyo Co., Ltd. are Aronix M-101 and Aronix M-
102, Aronix M-111, Aronix M-1
13, Aronix M-114, Aronix M-11
7, Aronix M-152, Aronix M-154
And so on.

(4) Polyfunctional acrylate, polyfunctional methacrylate, for example, 1,6-hexanediol diacrylate, 1,6-hexanediol dimethacrylate,
Neopentyl glycol diacrylate, diethylene glycol diacrylate, polyethylene glycol diacrylate, polyethylene glycol dimethacrylate, polypropylene glycol diacrylate, polypropylene glycol dimethacrylate, pentaerythritol diacrylate, dipentaerythritol hexaacrylate, isocyanuric acid diacrylate, pentaerythritol triacrylate , Isocyanuric acid triacrylate, trimethylolpropane triacrylate, trimethylolpropane trimethacrylate, ethylene oxide modified pentaerythritol tetraacrylate, propylene oxide modified pentaerythritol tetraacrylate, propylene oxide modified dipentaerythritol polyacrylate Relate, ethylene oxide-modified dipentaerythritol polyacrylate, such acrylate esters of pentaerythritol acrylate adduct. The product names of Toagosei Co., Ltd. are Aronix M-210 and Aronix M-21.
5, Aronix M-220, Aronix M-23
0, Aronix M-233, Aronix M-24
0, Aronix M-245, Aronix M-30
5, Aronix M-309, Aronix M-31
0, Aronix M-315, Aronix M-32
0, Aronix M-325, Aronix M-33
0, Aronix M-400, Aronix M-45
0, TO-458, TO-747, TO-755, TH
IC. TA2 etc. are mentioned. These can be used alone or in combination of two or more.

The photoinitiators used in the present invention, especially when using the ultraviolet curing method, include acetophenones such as di- and trichloroacetophenone, benzophenone, Michler's ketone, benzyl, benzoin, benzoin alkyl ether, benzyl dimethyl ketal and tetra. There are methyl thiuram monosulfides, thioxanthones, azo compounds and the like, which are selected from the viewpoints of the type of polymerization reaction of the radiation curable resin, stability, suitability with an ultraviolet irradiation device, and the like. The amount of the photoinitiator used is usually 0. It is in the range of 1 to 5%. In addition, a storage stabilizer such as hydroquinone may be used in combination with the photoinitiator.

For the purpose of preventing sticking or blocking, the resin forming these silicone resin layers can contain organic or inorganic pigments, such as kaolin, calcined kaolin, talc, pyrophyllite, diatomaceous earth, calcium carbonate, water. Examples thereof include aluminum oxide, magnesium hydroxide, magnesium carbonate, titanium oxide, barium carbonate, urea-formalin resin, and plastic beads such as styrene.

The coating amount of the silicone resin layer and the coating amount of the aqueous polymer intermediate layer are not limited, but it is desired that the coating amount be thinner for the purpose of avoiding a reduction in writing pressure, and preferably 0.2 g / m ² to. It is 10 g / m ² or less, more preferably 0.5 g / m ^{2 to} 3 g / m ² or less. Examples of the method for applying the silicone resin of the present invention and the resin forming the intermediate layer include a gravure roll and transfer roll coater, a bar coater, a roll coater, an air knife coater, a U comma coater, and an AKKU coater.
Smoothing coater, micro gravure coater, air knife coater, reverse roll coater, 4 or 5 roll coater, blade coater, dip coater, bar coater, rod coater, kiss coater, gate roll coater, squeeze coater, falling curtain coater, slide coater, Any coater such as a die coater may be used.

Examples of the adhesive used in the present invention include acrylic resins, natural and synthetic rubbers, styrene / butadiene copolymers, polyvinyl acetate, vinyl acetate / ethylene copolymers, starches, silicone compounds, glue, casein, Resins such as polyvinyl alcohol, polyurethane and polyurethane can be used alone or in the form of solution, aqueous solution or emulsion. The method of setting these pressure-sensitive adhesives may be any method such as heat drying, hot melt, ultraviolet ray curing, electron beam curing, etc., but as a matter of course, in the case of a thermal method, thermal fogging of the heat sensitive recording layer It must be taken into consideration.

In the heat-sensitive pressure-sensitive recording sheet according to the present invention, these supports, or pressure-sensitive recording layers, aqueous polymer intermediate layers, cured silicone resin layers, intermediate supports, undercoat layers, heat-sensitive recording layers, overcoats. It can be used by printing characters or a tint block on the coat layer. Further, in the present invention, surface treatment such as corona treatment for improving the adhesiveness and wettability may be performed without any problem.

The heat-sensitive pressure-sensitive recording sheet of the present invention has a color former layer, a developer layer, a protective coating layer, an adhesive layer, a release layer, a printing layer, an ink receiving layer, a writing layer, on the front surface or the back surface thereof. A heat-sensitive color developing layer, an ink jet receiving layer, a toner receiving layer, a magnetic recording layer, a thermal transfer ink receiving layer and the like can be provided alone or simultaneously. Further, the heat-sensitive pressure-sensitive recording sheet of the present invention can be used as a series of copy sheets in combination with other pressure-sensitive recording sheets, carbon copying sheets, adhesive sheets, printing sheets, transparent films and the like.

The ultraviolet irradiation device used in the present invention is as follows:
For example, there are a low-pressure mercury lamp, a medium-pressure mercury lamp, a high-pressure mercury lamp, a metal halide lamp, and the like, and there is an ozoneless type that generates less ozone. Generally, a plurality of lamps having an output of 30 w / cm or more are used in parallel.

The electron beam irradiation used in the present invention has an accelerating voltage of 100 to 1000 KV, more preferably an electron beam accelerator of 100 to 300 KV, in terms of penetrating power and hardening power.
It is preferable that the absorbed dose in one pass is 0.5 to 20 Mrad. If the accelerating voltage or the electron beam irradiation dose is lower than this range, the electron beam penetrating power is too low to perform sufficient curing, and if it is higher than this range, not only the energy efficiency deteriorates, but also the resin, There are unfavorable effects on quality such as decomposition of additives and reduction of strength of base paper.

The electron beam accelerator may be, for example, an electro curtain system, a scanning type, a double scanning type or the like. Further, in the electron beam irradiation step, the synthetic resin film, metal foil, metal drum or the like may be brought into close contact with the overcoat layer to cure the overcoat layer while transferring the surface shape thereof.

During electron beam irradiation, if the oxygen concentration is high, the curing of the electron beam curable resin is hindered, so nitrogen,
Oxygen concentration is less than 600ppm, preferably 400ppm by replacing with inert gas such as helium and carbon dioxide.
Irradiation is preferably performed in an atmosphere suppressed below.

The heat-sensitive pressure-sensitive recording sheet of the present invention can be recorded on the heat-sensitive recording surface and the pressure-sensitive recording surface by a commonly used heat-sensitive printer or pressure-sensitive printer, respectively. As a matter of course, the recorded contents may be different between the heat-sensitive recording and the pressure-sensitive recording, or may be the same.
The order of recording may be either heat-sensitive recording or pressure-sensitive recording. Pressure-sensitive recording may be performed after peeling off the intermediate support including the heat-sensitive recording layer and the adhesive layer.

[0041]

In this heat-sensitive pressure-sensitive recording sheet, the silicone resin does not seep into the pressure-sensitive recording layer due to the action of the aqueous polymer intermediate layer, and a high color density can be obtained with surface releasability. In addition, since release paper is not required, there is a cost advantage.Since the silicone resin layer also functions as an overcoat layer, the overlapped thickness becomes thin, and it is possible to develop color with good recording density during pressure-sensitive recording, gloss and water resistance. Since it has excellent properties, chemical resistance, and scratch resistance, and also has an adhesive layer and a coating layer on the release layer, the pressure-sensitive information is disclosed to the outside and handled without being exposed, and if necessary a thermal recording layer is used. By peeling off the intermediate support, the information pressure-sensitively recorded inside can be read. Further, by heat-sensitive recording using a thermal head, information different from that of the internal pressure-sensitive recording portion can be recorded on the surface of the intermediate support.

[0042]

The present invention will be described in detail below with reference to examples, but the contents of the present invention are not limited to the examples. All parts and percentages shown below are by weight. Further, the value indicating the smear amount is the smear amount after drying unless otherwise specified.

Preliminary Operation 1 (Preparation of Self-Coloring Type Pressure Sensitive Recording Layer) Microcapsules containing a color-forming agent used for the self-coloring type pressure-sensitive recording layer were prepared by mixing 10 parts of crystal violet lactone with Hisol SAS N-296 (Nippon Petrochemical Co., Ltd. ) Made 9
It was heat-dissolved in 0 part to obtain an internal phase oil. Melamine 10 parts and 37
% Formalin 25 parts was heated together with 100 parts of water to obtain a melamine / formalin initial polycondensate. Then, the internal phase oil was added to a 5% aqueous solution of styrene / maleic anhydride copolymer 150.
Emulsified into the emulsion, the above melamine / formalin polycondensate was added to this emulsion, and the liquid temperature was maintained at 70 ° C. for 2 hours to obtain a microcapsule dispersion liquid containing a color former having a melamine / formalin resin film. .. The average particle size of the obtained microcapsules was about 6 μm.

The coating material for the self-coloring type pressure-sensitive recording layer was prepared by the following formulation. The unit is dry weight part. Coloring agent-encapsulating microcapsules 110 parts Developer (PR26298 manufactured by Sumitomo Dures Co., Ltd.) 60 parts Starch particles 280 parts Kaolin clay 70 parts Oxidized starch 100 parts

The self-coloring type pressure-sensitive recording sheet was prepared as follows. That is, a self-coloring type pressure-sensitive recording layer having the above composition was coated on a high-quality paper having a basis weight of 40 g / m ^{2 in} an amount of 8 g /
A pressure-sensitive recording sheet of a self-coloring type was obtained by coating so as to be m ² .

Preliminary Operation 2 (Preparation of Thermosensitive Recording Layer) Mixtures having the following compositions were pulverized and dispersed by a sand mill until the average particle size became about 1 μm, and the liquids A and B were mixed.
Liquid] was prepared. [Solution A] 3- (N-methyl-N-cyclohexyl) amino-6-methyl-7-anilinofluorane 42 parts 10% aqueous polyvinyl alcohol solution 20 parts water 40 parts [Solution B] Bisphenol A 52 parts 2-benzyloxynaphthalene 50 parts 10% aqueous polyvinyl alcohol solution 50 parts water 100 parts Next, using the prepared [A liquid] and [B liquid], a heat-sensitive coating liquid was prepared with the following formulation. [Liquid A] 50 parts [Liquid B] 250 parts Zinc stearate (40% dispersion liquid) 25 parts 10% aqueous polyvinyl alcohol solution 216 parts Calcium carbonate 50 parts Water 417 parts

Example 1 Formaldehyde was mixed as a curing agent on the recording surface of a self-coloring type pressure-sensitive recording sheet prepared in Preliminary operation 1 using an air knife coater as an aqueous polymer intermediate layer.
% Gelatin solution was applied, set, dried and cured. UV-curable silicone resin (made by Shin-Etsu Chemical,
The product was coated with a reverse roll coater (trade name: KNS5200) at a rate of 0.8 g / m ^{2 using a} reverse roll coater, and an ultraviolet irradiation device (Rapid Cure, manufactured by USHIO INC.) Was used. Furthermore, 10 g / m ^{2 of} an adhesive resin IRR84 (containing 5% by weight of Irgacure 651 as a reaction initiator) manufactured by Rad Cure Specialties Co., Ltd. was used as an adhesive.
It was applied by an offset gravure coater so that The above heat-sensitive coating liquid was applied at a dry coating amount of 6 g / m ^{2 using} a high-quality paper having a basis weight of 40 g / m ² as an intermediate support.
^It was coated so as to have a thickness of ² , dried and supercalendered to obtain a heat-sensitive recording sheet comprising an intermediate support and a heat-sensitive recording layer. The surface of the intermediate support on which the pressure-sensitive adhesive layer and the heat-sensitive recording layer were not applied was overlaid to obtain a desired heat-sensitive pressure-sensitive recording sheet.

Example 2 20% by weight of calcium carbonate (manufactured by Shiraishi Calcium, Whiten SB, was used on the recording surface of the self-coloring type pressure-sensitive recording sheet prepared in Preliminary operation 1 by using an air knife coater as an aqueous polymer intermediate layer. 10% polyvinyl alcohol solution mixed with (1) was applied and dried. In addition, electron beam curable silicone resin (trade name X-62-7, manufactured by Shin-Etsu Chemical Co., Ltd.
192) with 5 reverse roll coater 0.6g / m
^It is applied so that it becomes ^2, and it is introduced into an electron beam irradiation device (made by Nisshin High Voltage, Curetron) and the electron beam acceleration voltage 2
It was cured by irradiation with an electron beam at 00 kV and an absorbed dose of 3 Mrad.
On top of that, an adhesive (BPS817 manufactured by Toyo Ink Co., Ltd.
0) was applied with a comma coater so as to be 10 g / m ² and dried. A high-quality paper having a basis weight of 40 g / m ² was coated with a polyvinyl alcohol suspension containing 20% by weight of calcium carbonate particles so as to be 1 g / m ² , dried, and then supercalendered. The coating solution was applied so that the dry coating amount would be 6 g / m ² , dried and supercalendered to obtain a thermosensitive recording sheet comprising an intermediate support and a thermosensitive recording layer. Further, a polyvinyl alcohol suspension containing 20% by weight of calcium carbonate particles was applied as an undercoat layer on the heat-sensitive recording layer so as to have a concentration of 1 g / m ^2, and after drying, an overcoat layer was provided to perform supercalender treatment. The surface of the intermediate support on which the pressure-sensitive adhesive layer and the heat-sensitive recording layer were not applied was overlaid to obtain a desired heat-sensitive pressure-sensitive recording sheet.

Example 3 A 4% polyethylene glycol solution as an aqueous polymer intermediate layer was applied to the recording surface of the self-coloring pressure-sensitive recording sheet prepared in Preliminary operation 1 with an air knife coater and dried by heating. A silicone resin emulsion (manufactured by Shin-Etsu Chemical Co., Ltd., trade name KM763) was coated thereon with a blade coater to a dry weight of 0.6 g / m ^2, and dried by heating.
Furthermore, a urethane acrylate resin (made by Toagosei Kagaku Kogyo, Aronix M1
210: M115 (7: 3 mixed resin) was applied with a comma coater to 10 g / m ² , and was superposed with an intermediate support having a heat-sensitive recording layer shown below, and an electron beam irradiation device (Nisshin High Voltage) was used. Manufactured by Curetron) and cured by electron beam irradiation with an electron beam accelerating voltage of 200 kV and an absorbed dose of 3 Mrad to obtain a desired heat and pressure sensitive recording sheet. As an intermediate support, a high-quality paper having a basis weight of 40 g / m ² was coated with a polyvinyl alcohol suspension containing 20% by weight of aluminum hydroxide particles so as to have a concentration of 1 g / m ² , dried, and then heat-sensitive. An intermediate support having a heat-sensitive recording layer is prepared by applying the coating solution so that the dry coating amount is 6 g / m ^2, and after drying, applying an overcoat layer having the same composition as the undercoat layer, drying and supercalendering. Got the body

Comparative Example 1 The self-coloring type pressure-sensitive recording sheet obtained in Preliminary operation 1 was used for evaluation without providing a silicone resin layer.

Comparative Example 2 A thermosetting silicone resin solution (trade name KL-838, manufactured by Shin-Etsu Chemical Co., Ltd.) was applied to a self-coloring type pressure-sensitive recording sheet obtained in Preliminary operation 1 and a low temperature curing type platinum catalyst (trade name). CAT
PL-8) was mixed at 1%, coated with a gravure roll so as to have a solid content of 0.6 g / m ^2, and heat-cured with a hot air circulation dryer at 100 ° C. Furthermore, 10 g of an adhesive (BPS8170, manufactured by Toyo Ink) on it with a comma coater.
/ M ² and the heat sensitive recording layer and the same heat sensitive recording sheet as in Example 1 were superposed as an intermediate support to obtain the desired heat and pressure sensitive recording sheet.

Comparative Example 3 The self-coloring type pressure-sensitive recording sheet prepared in Preliminary operation 1 was coated with a low-density polyethylene (about 7 μm) at the minimum coating thickness (about 7 μm) that could be continuously produced on the recording surface using a polyethylene melt laminator. Density 0.918 g / cm ³ ,
Melt index 7) is laminated and a thermosetting silicone resin (Shin-Etsu Chemical Co., Ltd., trade name KL-
838) is a low temperature curing platinum catalyst (trade name CAT PL-
8%) was mixed with 1% and the solid content was 0.6 g with a gravure roll.
/ M ² and heat-cured with a hot air circulation dryer at 60 ° C, and an adhesive (Toyo Ink, B
PS8170) was applied with a comma coater to 10 g / m ² and used as a thermosensitive recording layer and an intermediate support in Example 2.
The same heat-sensitive recording material as in above was overlaid to obtain the desired heat-sensitive pressure-sensitive recording sheet.

Test: Examples 1 to 3 and Comparative Examples 1 to 3
The heat-sensitive pressure-sensitive recording sheet obtained in 1. was evaluated for color density, color speed, printability, abrasion resistance, oil resistance, and water resistance. The respective results are shown in Table 1.

[Pressure-sensitive color density] The color density of each heat-sensitive pressure-sensitive recording sheet was measured by printing with a heat-sensitive printer first, then applying a constant weight from the top of the heat-sensitive recording layer, and then peeling off the intermediate support. The pressure-sensitive color printing surface was exposed and the color density was measured with a Macbeth reflection densitometer. Based on the color density of the self-coloring type pressure-sensitive recording sheet prepared in the preliminary operation, 90% or more in relative value was excellent, 70% or more and less than 90% was average, and less than 70% was inferior.

[Heat-sensitive color density] Used for pressure-sensitive color density test
The color density of the heat-sensitive recording part of the test piece
It was measured with a meter. Thermal recording paper using the same coating liquid (grammage 70
g / m ² The same color with a thermal printer,
90% or more in relative value based on concentration, 70% or more 9
Less than 0% was average and less than 70% was inferior.

[Color development speed] The color development speed was judged by giving superiority or inferiority depending on the color development condition in the above color density test. Immediately after the pressurization, when the intermediate support was peeled off, the case where the record was sufficiently readable was rated as excellent, and the case where it took 2 minutes or more for the reading to be rated as poor.

[Abrasion resistance] The abrasion resistance was judged by lightly rubbing the intermediate support surface of each heat-sensitive pressure-sensitive recording sheet with steel wool, peeling off the intermediate support, and coloring the recording surface. Excellent when there is no obstacle due to friction on the recording surface, average when there are several colors developed due to friction,
The more difficult it was to read, the worse it was due to friction or the inability to read the records.

[Oil resistance and water resistance] Oil resistance and water resistance are measured by dropping one drop of xylene or water on the recording surface with the intermediate support of each heat and pressure sensitive recording sheet peeled off. , It was judged by the time to seep into the back side.

[Printability] When a dot impact printer not equipped with an ink ribbon is used to print from above the intermediate support, the characters that have been colored can be clearly printed without breaks, and the characters that have been colored have breaks. The case was considered inferior.

[Exposure] In the test of the printability, the case where the record printed by the printer could not be read as it was was judged as excellent, and the case where it could be read was judged as poor.

[0061]

[Table 1]

Evaluation: The heat-sensitive pressure-sensitive recording sheets obtained in Examples 1 to 3 were free from the occurrence of color fog due to rubbing and were water resistant as compared with the self-coloring pressure-sensitive recording sheet (Comparative Example 1). It has excellent properties, oil resistance, and printability, and is comparable to self-coloring pressure-sensitive recording sheets in terms of color density and color development speed, and the contents of pressure-sensitive recording can be hidden by an intermediate support. It was a thing. The intermediate support has good releasability, and the heat-sensitive recording layer provided thereon can record information other than pressure-sensitive recording, and the heat-sensitive recording portion can be used as a label if necessary. Met.

On the other hand, as a comparison, in the case of not having the aqueous polymer intermediate layer obtained in Comparative Examples 2 and 3 and the case of using the polyolefin laminate intermediate layer, heat-sensitive recording is possible, but pressure-sensitive recording is possible. There are obstacles such as impeding the color development of the recording and poor printability. In the case of the self-coloring type pressure-sensitive recording sheet having no intermediate support (Comparative Example 1), it is obvious that not only there are problems in water resistance, oil resistance and abrasion resistance but also there is no concealment of recording. is there.

[0064]

In the heat-sensitive pressure-sensitive recording sheet of the present invention, the silicone resin provided on the recording surface does not soak into the pressure-sensitive recording layer due to the action of the aqueous polymer intermediate layer, and the surface releasability is reduced by a small amount of the silicone resin. It is possible to obtain a high color density while maintaining. The silicone resin itself exhibits high water resistance, and the aqueous polymer intermediate layer exhibits high oil resistance. Further, since the release paper is unnecessary, not only is there a cost advantage when used as a label, but it is not necessary to discharge the release paper unnecessarily. Since the silicone resin layer also functions as an overcoat layer, the thickness of the layer is thin and the color can be developed with good recording density during pressure-sensitive recording, and the gloss, scratch resistance, and abrasion resistance of the printed surface are excellent, and the release layer Since it has an adhesive layer and an intermediate support on top of it, it is possible to handle pressure-sensitive recorded information without exposing it to the outside,
Moreover, the pressure-sensitive recorded information can be read by peeling off the intermediate support, if necessary. Further, the heat-sensitive recording layer provided on the intermediate support allows heat-sensitive recording by a thermal head, and different information can be recorded in the internal pressure-sensitive recording section. As described above, the present invention can be used in many applications such as continuous slips, pasting slips, labels, direct mails, correspondences such as postcards, recordings, and dust-free recording papers, and has great practical significance. is there.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁵ Identification code Office reference number FI technical display location 6956-2H B41M 5/18 Z

Claims (6)

[Claims] 1. A pressure-sensitive recording layer in which microcapsules containing at least one of a color former and a developer are individually laminated on one surface of a support, or mixed to form a coating, and a water-based recording layer. A heat-sensitive pressure-sensitive recording sheet comprising a molecular intermediate layer, a silicone resin layer, an adhesive layer, an intermediate support, a color-developing agent, and a heat-sensitive recording layer containing a color-developing agent that develops color by contacting with the color-developing agent. .. 2. The silicone resin layer has at least one acryloyl group, methacryloyl group, or epoxy group at the terminal or side chain of the polydialkylsiloxane molecular main chain.
The heat-sensitive pressure-sensitive recording sheet according to claim 1, wherein the heat-sensitive pressure-sensitive recording sheet comprises a layer obtained by curing a silicone compound having one or more species with ultraviolet rays or at least one high energy ray selected from electron rays. 3. The heat-sensitive pressure-sensitive recording sheet according to claim 1, further comprising an overcoat layer on the heat-sensitive recording layer. 4. The heat-sensitive pressure-sensitive recording sheet according to claim 1, further comprising an undercoat layer under the heat-sensitive recording layer. 5. A step of providing a pressure-sensitive recording layer by laminating microcapsules each encapsulating at least one of a color former and a color developer individually on one surface of a support, or by coating them in a mixture. A step of applying an aqueous polymer solution on the recording layer to provide an aqueous polymer intermediate layer, a step of applying a silicone resin on the aqueous polymer intermediate layer to provide a silicone resin layer,
A step of applying a pressure-sensitive adhesive to the silicone resin layer or the intermediate support to form a pressure-sensitive adhesive layer, and a step of applying a heat-sensitive recording layer containing a color-developing agent and a color-developing agent that develops color by contacting the color-developing agent to the intermediate support, A method for producing a heat-sensitive pressure-sensitive recording sheet, which comprises producing a heat-sensitive pressure-sensitive recording sheet by combining the steps of integrating an intermediate support and a silicone resin layer via an adhesive layer. 6. The heat-sensitive pressure-sensitive recording sheet according to claim 3, wherein in the step of providing the silicone resin layer, the silicone resin is cured by at least one high energy ray selected from ultraviolet rays and electron beams. Production method.