JPH08127172A - Laminated pressure sensitive recording sheet - Google Patents

Abstract

PURPOSE: To provide a laminated pressure sensitive recording sheet having a stable releasability. CONSTITUTION: An opaque coating sheet in which a pressure sensitive recording layer solely laminated or mixed with both or one of microcapsulated coloring reagent and developer and coated one side of a support and water borne polymer coating layer is provided on the other side surface is integrated via a thermoplastic resin laminated layer. Thus, the releasing strength in the case of releasing the opaque sheet is extremely stable. Even if the laminating conditions are slightly irregular, the strength is not extremely altered, and a laminated pressure sensitive recording sheet of stable quality is obtained. Further, information can be recorded in a pressure sensitive recording part by pressurizing, and when the opaque sheet is released to disclose the inner information, the opaque sheet is not readhered at all.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a laminated pressure-sensitive recording sheet, in which a self-developing pressure-sensitive recording layer of a single form provided on a support is covered with an opaque coating via a thermoplastic resin laminate layer. It is a laminated type pressure-sensitive recording sheet with internal coloration provided with a sheet, and the opaque coating sheet has releasability, and has a non-exposure of recording, water resistance, chemical resistance, oil resistance, and scratch resistance. It is a laminated pressure-sensitive recording sheet that can be used as a recording sheet, particularly as a recording sheet for slips, messages, entertainment items, and clean rooms, which has excellent performance in terms of preventing re-adhesion and retaining information.

[0002]

2. Description of the Related Art The pressure-sensitive recording layer used in the present invention is a self-coloring pressure-sensitive recording type, which is developed from so-called carbonless copying paper. Also called paper. Its composition is a process of applying a coating of microcapsules containing a colorless dye (hereinafter referred to as a color former) on a support, and electron-accepting properties of acid clay, phenol resin, organic acid substances, etc. on the coating. Substance (hereinafter referred to as developer)
The manufacturing method by two-layer coating consisting of two steps (including the reverse coating order) and the above-mentioned 2
Ingredients, or any one of the ingredients is microencapsulated, mixed evenly, and applied in a single layer to prepare a coating (Japanese Patent Publication No.
No. 7-16096) is known. In such a self-coloring pressure-sensitive recording sheet, since a color former and a developer are present in the vicinity, it is easy to obtain a printed image with high color density, but unintentional and unintentional due to friction during manufacturing or handling. There is a problem that colored stains are likely to occur.

The self-coloring 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 conflicting properties of dirt. In addition, the pressure-sensitive information recorded on the self-coloring pressure-sensitive recording sheet is inevitably exposed 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 method of providing a laminate layer by a vacuum adhesion method on a recording layer of a self-coloring pressure-sensitive recording sheet (Japanese Patent Publication No. Sho 49-10857) or a recording having a plastic layer by a melt lamination method. Sheets (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 lamination, unnecessary color stains can be prevented, but basically it is premised that the pressure-sensitive recording portion is exposed. The issue of record secrecy could not be resolved. Further, a heat-sealable or thermoplastic resin coating layer is provided on the recording layer of the self-coloring pressure-sensitive recording sheet, and the back surface is overlaid with an opaque coating sheet coated with a hot-melt type or thermoplastic type heat-sealable adhesive, Method of integrating by hot pressing (Japanese Utility Model Laid-Open No. 2-2173, Japanese Utility Model Laid-Open No. 3-116974)
However, if it is hot pressed enough to be integrated, color fog in the pressure-sensitive recording layer will be lost and the commercial value will be lost, or if a resin with an adhesive strength much weaker than the adhesive strength is used, it will be adhered with a light press. There was no choice but to integrate by force. Although this type of pressure-sensitive recording sheet has the concealment of the recording, it can be easily re-adhered by simply re-pressing it, so that the confidentiality of the recording is low.

The applicants of the present invention have previously prepared a pressure-sensitive recording in which a color former or a color developer in which both or one of them is microencapsulated is individually laminated or mixed on one surface of a support. Using a pressure-sensitive recording sheet in which the layer and the opaque coating sheet are integrated via a thermoplastic resin laminate layer,
It was found that these problems could be solved by increasing the adhesive strength between the pressure-sensitive recording layer and the thermoplastic resin laminate layer and weakening the adhesive strength between the opaque coating sheet and the thermoplastic resin laminate layer, but it was manufactured in a wide range. In this case, there was a problem that the peelability of the web in the width direction was large, the peelability when peeling the opaque coating sheet was likely to vary, and local strong adhesion sites were recognized. It is considered that this is because the opaque coated sheet is often formed from paper made of pulp, so that the surface in contact with the thermoplastic resin laminate layer is not uniform. When the thermoplastic resin is laminated, if the unevenness of the surface of the opaque coating sheet that comes into contact with the laminate is large, the contact area with the laminating resin becomes large, and it becomes sensitive to fluctuations in the laminating temperature, pressing pressure and the like. This is not preferable in terms of quality, because it appears as a variation in peel strength depending on the part in the width direction of the laminate. Also, even if the average value of the 180 degree peeling test is such that the adhesive strength falls within the allowable range, it may be microscopically considered to be due to the unevenness of the fibers constituting the opaque coating sheet, but the portion exceeding the allowable adhesive strength There is. Such a portion may cause the pressure-sensitive recording layer to develop color, which is not preferable as a recording sheet.
If the press pressure at the time of lamination is reduced in order to avoid such a microscopic excessive adhesion, the adhesiveness itself of the opaque coating sheet deteriorates, causing a fatal defect as a product such as peeling of the top paper.

[0006]

SUMMARY OF THE INVENTION Therefore, an object of the present invention is to provide a laminated pressure-sensitive recording sheet having an opaque coating sheet, without sacrificing its original color developability, while the opaque coating sheet is laminated under the manufacturing conditions. Shows a stable peeling property even with slight fluctuations in the film, there is no unnecessary coloration at the time of peeling due to the presence of microscopic excessive adhesion sites, and information is not disclosed. The present invention provides a laminated pressure-sensitive recording sheet which has a confidentiality property of preventing re-adhesion, has a good adhesion of a thermoplastic resin laminate layer in actual use, and can prevent recording modification and contamination.

[0007]

Means for Solving the Problems As a result of intensive studies on the above problems, the present inventors have found the following solution. That is, a color-forming agent or a color-developing agent, both or one of which is microencapsulated, is singly laminated on one side of a support, or is mixed and applied. In a laminated pressure-sensitive recording sheet integrated via a laminate layer, a laminated pressure-sensitive recording sheet having an aqueous polymer coating layer on the surface of the opaque coating sheet on the side in contact with the thermoplastic resin laminate layer. It is an invention. The term “aqueous polymer” as used herein means both a water-soluble polymer and a water-dispersible polymer such as latex. Further, an inorganic pigment or an organic pigment may be mixed and used in the aqueous polymer coating layer.

The details of the present invention will be described below. In the laminated pressure-sensitive recording sheet of the present invention, when the thermoplastic resin laminate layer is melt extruded, the self-coloring pressure-sensitive recording sheet and the opaque coating sheet can be integrated, and the adhesive strength of the thermoplastic resin laminate layer (release Intensity) on the pressure sensitive recording sheet side and the opaque coated sheet side,
It is possible to peel off the opaque coating sheet which has a relatively weak adhesive strength with the thermoplastic resin laminate layer.

In the present invention, examples of the aqueous polymer forming the aqueous polymer coating layer include, but are not limited to, the followings.

As the water-soluble polymer, starches (starch, oxidized starch, esterified starch, phosphate esterified starch, hydroxyethylated starch, acetylated starch, cationized starch, dextrin, etc.), natural polymeric polysaccharides (Agar, xanthan gum, pullulan, chitosan, star gum, guar gum, gum arabic, gum tragacanth, alginic acid derivative, etc.), casein, gelatin, (modified) polyvinyl alcohol (completely saponified, partially saponified, esterified, carboxy modified, cationic modified, Acetoacetyl-modified, sulfonic acid-modified, amide-modified, nitrile-modified, various other modified polyvinyl alcohol, etc.), polyvinyl ethers (polyvinyl methyl ether, etc.), polyvinyl pyrrolidone, acrylic polymer (polyacrylic acid, Liacrylamide, polyacrylic acid esters, polyacrylic acid salts, etc.), cellulosic polymers (methyl cellulose, ethyl cellulose, carboxymethyl cellulose, hydroxyethyl cellulose, etc.), polyacryloylmorpholine, polyethylene glycol, polyethylene glycol diamine, water-soluble epoxy compounds, water-soluble Alkali of polyester, polyethyleneimine, polyallylamine, acrylamide / acrylic acid ester copolymer, acrylamide / acrylic acid ester / methacrylic acid terpolymer, isobutylene / maleic anhydride copolymer, styrene / maleic anhydride copolymer Salts, alkali salts of ethylene / maleic anhydride copolymers, styrene / acrylic acid copolymers and the like.

Examples of water-dispersible polymers include styrene / butadiene copolymers, acrylonitrile / butadiene copolymers, methyl acrylate / butadiene copolymers, ethylene / vinyl acetate copolymers, vinyl acetate / acrylic acid (esters). Latex polymers such as copolymers, acrylonitrile / butadiene copolymers, acrylonitrile / butadiene / acrylic acid copolymers, polyethylene, polyvinyl acetate, polyurethane, vinylidene chloride, polychloroprene emulsion, etc.

These aqueous polymers may be used alone or in combination of two or more.

The aqueous polymer coating layer may contain one or more inorganic pigments or organic pigments, if necessary, in order to finely control the adhesiveness to the thermoplastic resin laminate layer.

Examples of the inorganic or organic pigments include kaolin, calcined kaolin, clay, calcined clay, talc, pyrophyllite, diatomaceous earth, calcium carbonate, silica, aluminum hydroxide, magnesium hydroxide, magnesium carbonate, titanium dioxide and titanium dioxide. Coated mica, titanium black,
Titanium yellow, barium sulfate, barium carbonate, lithopone, molybdenum white, zinc white, zinc sulfide, gypsum, lead white, ultramarine blue, navy blue, cobalt blue, carbon black, iron black, zinc oxide, cobalt oxide, silicon oxide, azo pigment, Examples thereof include, but are not limited to, phthalocyanine pigment, dye lake, silicone particles, starch particles, urea-formalin resin particles, melamine resin particles, styrene beads, and benzoguanamine resin particles.

If desired, the aqueous polymer coating layer may contain a surfactant or a lubricant.

The coating amount of the aqueous polymer coating layer varies depending on the smoothness and air permeability of the opaque coating sheet to be used, the type and thickness of the thermoplastic resin laminate layer, and the processing conditions. It is preferably in the range of 1 to 30 g / m ² . If it is less than this range, the aqueous polymer coating layer is not sufficiently formed, and if it is more than this range, the recording density is lowered when pressure-sensitive printing is performed, which is not preferable as a recording sheet.

When a self-coloring pressure-sensitive recording sheet in which the thickness of the thermoplastic resin laminate layer is within a certain range and the pressure-sensitive recording layer has a high color-developing property, the opaque coating sheet almost disperses the writing pressure, Since it transmits without absorbing, high color density is obtained at the time of pressure-sensitive recording, and the gloss, scratch resistance, and abrasion resistance of the printed surface are excellent, and an opaque coating sheet is provided on the thermoplastic resin laminate layer. Therefore, the pressure-sensitive recorded information can be handled without being exposed to the outside and exposed, and the opaque coated sheet can be peeled off as necessary to read the pressure-sensitive recorded information inside. Further, the information once disclosed has a characteristic that it cannot be hidden again (preventing re-adhesion).

As the resin constituting the thermoplastic resin laminate layer, polyethylene (low density, medium density, high density, linear low density polyethylene), polypropylene, polytrimethylpentene, polybutene, ethylene vinyl acetate copolymer, ethylene ethyl General-purpose melt extrusion resins such as acrylate copolymer, ethylene acrylic acid copolymer, ethylene methyl acrylate copolymer, ethylene vinyl alcohol copolymer, ethylene methacrylic acid copolymer and its salts, vinyl chloride, vinylidene chloride, etc. They can be used alone or as a mixture. The mixing method is not particularly limited, and any method can be used. For example, a extruder for a kneader, a heating kneading roll, a Banbury mixer, a predetermined amount of a polyolefin resin using a kneader,
Then, if necessary, various additives (release agent, slip agent, pigment, antioxidant, neutralizing agent, etc.) are added and melt-mixed, and then the mixture is crushed and pelletized, or a so-called extruder is used. It is possible to use, for example, a method of directly charging and extrusion coating in the state of a simple blend, or a method of using a mixed resin obtained by copolymerizing one component with another component at the time of polymerizing one polyolefin resin.

Further, by setting the thickness of the thermoplastic resin laminate layer in the range of 10 to 50 μm, the glossiness, scratch resistance, and gloss of the printed surface can be obtained without lowering the color developability of the pressure-sensitive recording layer.
Not only does it improve abrasion resistance, but it also functions as a release layer that is released from the opaque coated sheet. When the thickness of the thermoplastic resin laminate layer is smaller than this range, when the opaque coating sheet is peeled off, a laminate layer floating occurs in which the thermoplastic resin laminate layer is peeled off from the pressure-sensitive recording layer, or
The background may be fogged on the pressure-sensitive recording layer, which may make it difficult to read the record. When the thickness of the thermoplastic resin laminate layer is thicker than this range, the recording density is lowered when pressure-sensitive printing is performed, which is not preferable as a recording sheet.

To integrate the pressure-sensitive recording layer and the opaque coating sheet with a thermoplastic resin laminate, a general laminator such as a melt extrusion die, a T die or a multi-layer simultaneous extrusion die can be used. As a pretreatment for the melt extrusion, a known treatment for improving adhesion such as corona treatment or flame treatment may be performed on the opaque coating sheet provided with the pressure-sensitive recording layer or the aqueous polymer coating layer. As a matter of course, the adhesiveness and the releasability can be controlled by changing the degree of surface treatment of the pressure-sensitive recording layer and the opaque coating sheet. At the time of laminating by melt extrusion, either the support having a pressure-sensitive recording layer or the opaque coating sheet may be positioned on the cooling roll side or the press roll side, but a pressure-sensitive recording layer having particularly high color-developing sensitivity is provided. When used, it is preferable to use an opaque cover sheet on the press roll side.

It is possible to use a known technique such as adding titanium dioxide or a cyanine pigment and its dispersant, or an antioxidant to the resin forming the thermoplastic resin laminate layer. .

The adhesive strength with the thermoplastic resin laminate layer is a relative comparison between the pressure sensitive recording layer side and the opaque coating sheet side, but preferably the adhesive strength of the thermoplastic resin laminate layer on the pressure sensitive recording layer side. Is 100gf / 15m in 180 degree peeling test with Tensilon universal tensile tester
It is preferable that the adhesive strength (peeling strength) is m or more.
If the adhesive strength of the thermoplastic resin laminate layer is less than this range, a peeling problem of the thermoplastic resin laminate layer may occur during recording, transportation and the like. Further, if it is more than this range, even if the thermoplastic resin laminate layer is forcibly peeled off, the pressure-sensitive recording layer develops color, so that the adhesive strength is sufficient.

In principle, the adhesive strength between the opaque coating sheet and the thermoplastic resin laminate layer is less than the adhesive strength between the thermoplastic resin laminate layer and the pressure-sensitive recording layer, but the opaque coating sheet can be peeled off, but too much. If the adhesive strength is too close, the thermoplastic resin laminate layer may float (partially peel off) from the pressure-sensitive recording layer, or the pressure-sensitive recording layer may develop color or become opaque when the opaque coating sheet is peeled off. Depending on the thickness of the cover sheet, the opaque cover sheet may be broken when peeled off. Such troubles differ in the adhesive strength range generated depending on the thickness and type of the opaque coating sheet, the thickness of the thermoplastic resin laminate layer, or the color developability of the pressure-sensitive recording layer.
It is preferable that the adhesive strength (peeling strength) is smaller than 80 gf / 15 mm in the 0 degree peeling test.

The variation in peel strength between the opaque coating sheet and the thermoplastic resin laminate layer in the width direction of the web is 10 gf / 15 mm as a difference between the maximum peel strength and the minimum peel strength in order to provide uniform quality. It is preferably within the range. When it exceeds this range, when the opaque coating sheet is actually peeled off, the difference in peeling feeling depending on the sample becomes remarkable, and quality control in manufacturing becomes difficult.

Between the pressure-sensitive recording layer and the thermoplastic resin laminate layer, if necessary, polyvinyl alcohol, gelatin, polyacrylic acid and salts thereof, various latexes such as casein, starch and rubber latex for improving adhesion. The aqueous polymer intermediate layer can be provided in a coating amount range that does not reduce the pressure-sensitive recording sensitivity.

As the support and the opaque cover sheet used in the self-coloring pressure-sensitive recording sheet of the present invention, general paper such as glassine paper, high-quality paper, art paper, coated paper, cast paper and the like can be used. Raw materials usually used in papermaking, such as pulp, synthetic pulp, fillers, sizing agents, paper-strengthening agents, and dyes, can be used as necessary. Also, plastic sheets such as polyethylene, polypropylene, polyethylene terephthalate, polyamide, polyvinyl chloride, polyvinylidene chloride, and polymethylpentene, and synthetic paper or non-woven fabric made of these synthetic fibers, or a laminate in which synthetic resin is laminated on one side Paper, metal foil, or a laminated product of metal foil and paper,
It is also possible to use vapor-deposited paper, holographically treated opaque sheets, laminated products with synthetic resin films, mica paper, glass paper and the like. These supports can be made opaque with inorganic or organic pigments, inks, toners and the like.

In the method of the present invention, the base paper based on natural pulp including waste paper pulp, which is advantageously used, includes
Various polymer compounds and additives can be contained. For example, starch, starch derivatives (cationized starch, phosphate esterified starch, oxidized starch, etc.), polyacrylamide, polyvinyl alcohol, polyvinyl alcohol derivatives (completely saponified, partially saponified,
Carboxyl-modified, cation-modified, other various modified polyvinyl alcohol), gelatin (alkali-treated, acid-treated, various modified gelatin) and other dry paper strength enhancers, star gum, alginic acid derivatives and other natural polymer polysaccharides, higher fatty acid metal salts , Rosin derivatives, dialkyl ketones, alkenyl or alkyl succinic anhydrides, epoxidized higher fatty acid amides, organic fluoro compounds, dialkyl ketene dimer emulsions and other sizing agents, polyamide polyamine epichlorohydrin resins, melamine resins, urea resins, epoxidized polyamide resins Wet strength enhancer, stabilizer, pigment, etc.
Dyes, antioxidants, optical brighteners, various latexes, inorganic electrolytes (sodium chloride, sodium sulfate, sodium phosphate, calcium chloride, lithium chloride, magnesium chloride, magnesium sulfate, barium chloride, etc.), pH adjusters, sulfuric acid bands And a fixing agent such as aluminum chloride, a filler such as calcium carbonate, kaolin, talc, and clay, and an additive such as an organic conductive agent may be appropriately combined and contained. These contents may be dispersed in the pulp slurry at the paper making stage, may be added at the tab size after paper making, and the solution may be applied by various coaters. However, in all cases the concentration of residual surfactant must be below 800 ppm.

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 microcapsulation method, a microcapsule wall material, a color former or an oil dissolving the color former, a color developer, an electron beam curable resin, a microcapsule protective agent, or the like. As the microencapsulation method, a coacervation method (US Pat. No. 2,800,458 etc.),
An interfacial polymerization method (Japanese Patent Publication No. 47-1763 etc.), an in situ polymerization method (Japanese Patent Application Laid-Open No. 51-9079 etc.) and the like can be used.

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

As the color former, triallylmethane compounds, diarylmethane compounds, xanthene compounds,
A thiazine-based compound, a spiropyran-based compound, or the like can be used and is not particularly limited as long as it is generally used for a pressure-sensitive recording 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, aliphatic synthesis 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.

Examples of developers include 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, An acidic polymer (for example, phenol-formaldehyde resin, salicylic acid-based resin, or a metal salt thereof) or the like can be used.

In the present invention, as the binder used for forming the pressure-sensitive recording layer, starch, cellulose derivatives such as hydroxyethyl cellulose, methyl cellulose, ethyl cellulose and carboxymethyl cellulose, protein such as casein and gelatin, oxidized starch, ester compound. Aqueous natural polymer compounds such as saccharose such as starch, polyvinyl alcohol, modified polyvinyl alcohol, polyvinylpyrrolidone, polyacrylic acid, sodium polyacrylate, acrylic acid amide / acrylic acid ester copolymer, acrylic acid amide / acrylic acid ester / Water-soluble synthetic polymer such as methacrylic acid terpolymer, alkali salt of styrene / maleic anhydride copolymer, latex, polyacrylamide, styrene / maleic anhydride copolymer Compounds and latexes, water-soluble polymers such as alkali salts of ethylene / maleic anhydride copolymers, polyvinyl acetate, polyurethane, polyacrylic acid esters, styrene / butadiene copolymers, acrylonitrile / butadiene copolymers, acrylics Examples thereof include latex such as methyl acid / butadiene copolymer, acrylonitrile / butadiene / acrylic acid copolymer, ethylene / vinyl acetate copolymer and the like.

Pigments used in the pressure-sensitive recording layer or the thermoplastic resin laminate layer include diatomaceous earth, talc, kaolin, calcined kaolin, calcium carbonate, magnesium carbonate, titanium oxide, zinc oxide, silicon oxide and aluminum hydroxide. , Urea-formalin resin and the like.

In addition, zinc stearate as an auxiliary agent,
Waxes such as higher fatty acid metal salts such as calcium stearate, paraffin, oxidized paraffin, polyethylene, oxidized polyethylene, stearamide, castor wax, etc., dispersant such as sodium dioctylsulfosuccinate, sulfonic acid modified polyvinyl alcohol, benzophenone type, UV absorbers such as benzotriazole
Furthermore, a surfactant, a fluorescent dye, etc. are added as needed.

In the laminated pressure-sensitive recording sheet of the present invention,
As a method for forming the aqueous polymer coating layer and the pressure-sensitive recording layer, a blade coater, an air knife coater, a gravure coater, a microgravure coater, a roll coater, a bar coater, a falling curtain coater, a rod coater, a die coater, a comma coater, a lip coater. A coating method using a known coater such as the above is possible.
The pressure-sensitive recording layer is preferably smoothed.

Further, 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 in 1) can be added as necessary.

Further, as a constitution of the present invention, calcium carbonate, talc, silica, clay, barium sulfate, magnesium carbonate, magnesium silicate, between the support and the pressure-sensitive recording layer are used in order to obtain a high color density. Inorganic pigments such as lead sulfate, lead white, zinc white, zinc sulfide, satin white, titanium oxide, antimony oxide, mica, bentonite, calcium silicate, gypsum, aluminum hydroxide, or polystyrene,
It suffices to provide an undercoat layer containing fine organic pigments such as polyvinyltoluene, styrene / divinylbenzene copolymer, polymethylmethacrylate, urea / formaldehyde polymer and polyethylene.

The laminated pressure-sensitive recording sheet of the present invention is
The pressure-sensitive recording surface, the thermoplastic resin laminate surface, the surface of the opaque coating sheet, or the back surface of the laminated pressure-sensitive recording sheet, a color-developing layer or a developer layer or both for pressure-sensitive recording, a protective coating layer, A peeling layer, a printing layer, a tint block printing layer, a toner receiving layer, an ink receiving layer, a thermosensitive recording layer, a writing layer, a magnetic recording layer and the like can be provided alone or simultaneously. Also,
The laminated pressure-sensitive recording sheet of the present invention includes other pressure-sensitive recording sheets, back carbon copying sheets, adhesive sheets, printing sheets,
It can be used as a series of copy sheets in combination with a transparent film or the like. Part or all of the recording sheet of the present invention, such as die cutting, separation of a part of the opaque coating sheet,
There is no problem with making perforations and feed holes for printers.

[0041]

In the laminated pressure-sensitive recording sheet of the present invention, the pressure-sensitive recording layer and the opaque coating sheet are integrated by the thermoplastic resin laminate layer, and the pressure-sensitive recording layer and the thermoplastic resin laminate layer are firmly adhered to each other. However, the opaque cover sheet is relatively weakly adhered, and the opaque cover sheet can be separated (peeled) from the support having the thermoplastic resin laminate layer and the pressure-sensitive recording layer with a light force. By providing the aqueous polymer coating layer on the side of the opaque coating sheet that contacts the thermoplastic resin laminate layer, the side of the opaque coating sheet that contacts the thermoplastic resin laminate layer becomes more homogeneous, and not only is the peelability less uneven In addition, the tolerance for fluctuations in the resin temperature during lamination is widened, and stable peeling quality can be obtained. Once the opaque coated sheet is separated from the thermoplastic resin laminate layer, the thermoplastic resin laminate layer is already cooled and solidified, so that it is not easily re-bonded. Since the thermoplastic resin laminate layer transmits the writing pressure with almost no dispersion and absorption, a high color density can be obtained at the time of pressure sensitive recording, and the gloss, scratch resistance, and abrasion resistance of the printed surface are excellent. Since it has a thermoplastic resin laminate layer and an opaque cover sheet, the pressure-sensitive recorded information can be handled without being exposed or exposed to the outside, and the opaque cover sheet can be peeled off as necessary to make the inside sense. You can read the pressure-recorded information. Further, for the reason described above, the information once disclosed has a characteristic that it cannot be hidden again (anti-redeposition property).

[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% shown below are based on weight. Also,
Unless otherwise noted, the value indicating the smear amount is the smear amount after drying.

Example 1 As the pressure-sensitive recording paper, a commercially available high-sensitivity self-coloring pressure-sensitive recording paper (manufactured by Mitsubishi Paper Mills, Diaself, MCD N130, basis weight 130 g / m ² ) was used. As the opaque coating sheet, a single-sided cast paper having a basis weight of 70 g / m ² is used, and an aqueous solution of polyvinyl alcohol (manufactured by Nippon Synthetic Chemical Industry Co., Ltd., Gohsenol NM-11) is used as a coating solution for the aqueous polymer coating layer on the non-cast surface. The coating amount was 4 g / m ² and the coating was heated and dried to form an aqueous polymer coating layer. Corona treatment was applied to the pressure-sensitive recording surface, and low-density polyethylene (density: 0.918 was used as a thermoplastic resin laminate layer using a melt extrusion die.
g / cc, MFR: 12 g / 10 minutes) and high-density polyethylene (density: 0.955 g / cc, MFR: 37 g / 1
(0 minutes) is melt-extruded at a press linear pressure of 40 kg / cm so that the mixture becomes 15 g / m ^2, and the pressure-sensitive recording layer and the aqueous polymer-coated surface of the opaque coating sheet are bonded as the bonding surface, and the purpose is A laminated pressure-sensitive recording sheet of was obtained.

Example 2 A target laminated pressure-sensitive recording sheet was obtained in the same manner as in Example 1 except that styrene / butadiene copolymer latex (made by Asahi Kasei Corporation) was used instead of polyvinyl alcohol.

Example 3 An intended laminated pressure-sensitive recording sheet was obtained in the same manner as in Example 1 except that the coating liquid formulation for the aqueous polymer coating layer was changed as follows in terms of solid content. Gohsenol NM-11 (PVA manufactured by Nippon Synthetic Chemical Industry Co., Ltd.) 60 parts Escalon 1500 (calcium carbonate manufactured by Sankyo Flour Mills Co., Ltd.) 40 parts Microsol KE-511 (pigment dispersant manufactured by Mutual Chemical Co., Ltd.) 1 part

Comparative Example 1 A laminated pressure-sensitive recording sheet was obtained in the same manner as in Example 1 except that the non-cast surface of the opaque coating sheet was used without providing the aqueous polymer coating layer.

Comparative Example 2 A laminated pressure-sensitive recording sheet was obtained in the same manner as in Comparative Example 1 except that melt extrusion was performed at a press linear pressure of 20 kg / cm.

Comparative Example 3 The opaque coating sheet was not subjected to the aqueous polymer coating layer, but was previously size-pressed with an alkyl ketene dimer (manufactured by Japan PMC, surface sizing agent SS-362). Other than that was manufactured in the same manner as in Example 1 to obtain a laminated pressure-sensitive recording sheet.

Comparative Example 4 A laminated pressure-sensitive recording sheet was obtained in the same manner as in Comparative Example 3 except that melt extrusion was performed at a pressing linear pressure of 20 kg / cm.

Comparative Example 5 A self-coloring pressure-sensitive recording paper was laminated using a multi-layer coextrusion die so that low-density polyethylene was arranged on the pressure-sensitive recording paper side and polypropylene on the opaque coating sheet side. The non-cast surface of the opaque coating sheet was used without providing the aqueous polymer coating layer. Other than that was manufactured in the same manner as in Example 1 to obtain a laminated pressure-sensitive recording sheet.

Test: Color development, releasability, variation in releasability in the web width direction of the laminated pressure-sensitive recording sheets obtained in Examples 1 to 3 and Comparative Examples 1 to 5, self-coloring pressure-sensitive recording paper. Of the laminate was evaluated. The respective results are shown in Table 1 below.

[Coloring property] The color density of each laminated pressure-sensitive recording sheet has an impact after one sheet of pressure-sensitive upper paper (NCR upper paper N50 manufactured by Mitsubishi Paper Mills) is superposed on the opaque coating sheet. Printing was performed by applying a constant weight with a printer, the opaque coating sheet was then peeled off to expose the color printed surface, and the color density was measured with a Macbeth RD919 reflection densitometer.

[Peelability / Variation of Peelability] When peeling the opaque coating sheet of each laminated pressure-sensitive recording sheet from the thermoplastic resin laminate layer, 180 degree peel strength (sample width) using a Tensilon universal testing machine 15 mm). The average value of the peel strength of the samples sampled from 10 positions in the web width (1200 mm) direction was taken as the measured value of the peel property. The opaque cover sheet cannot be peeled off,
When the opaque coated sheet was broken during peeling, the measurement was impossible. In addition, as an index of variation in peelability, 10
The maximum peel strength and the minimum peel strength of the samples at various locations are shown.

[Background color development at the time of peeling] The presence or absence of unnecessary color-developing stains on the self-coloring pressure-sensitive recording paper at the time of peeling the opaque coating sheet was judged.

[Laminated Adhesiveness] The adhesiveness of the thermoplastic resin laminated layer to the self-coloring pressure-sensitive recording paper was evaluated. An incision was made in a sample piece having a width of 30 mm, and peeling of the laminate from the self-coloring pressure-sensitive recording paper was attempted by hand from the incision.

[0056]

[Table 1]

Evaluation: In the laminated pressure-sensitive recording sheets obtained in Examples 1 to 3, the thermoplastic resin laminate layer was sufficiently adhered to the pressure-sensitive recording layer, and only the opaque coating sheet was peeled off neatly when peeled off. In addition, the opaque coated sheet had a uniform and good peeling property, the variation in the peeling property in the web width direction was small, and the thermoplastic resin laminate layer was still adhered to the pressure-sensitive recording layer. All the pressure-sensitive recording layers after peeling off the opaque coating sheet have good color development, and there is no background fog when peeling off the opaque coating sheet. I had one.

On the other hand, the laminated pressure-sensitive recording sheet obtained in Comparative Example 1 cannot be put to practical use by adhering it to the thermoplastic resin laminate layer to the extent that the opaque coating sheet is difficult to peel off. It was Further, the laminated pressure-sensitive recording sheet obtained in Comparative Example 2 was prepared by lowering the pressing pressure at the time of lamination so that the opaque coated sheet could be peeled off. Peeling occurred, unnecessary coloration was observed during peeling, and the variation in peeling was large. In Comparative Example 3, the opaque coating sheet is preliminarily size-pressed so that the opaque coating sheet can be peeled off. However, the variation in peeling is large, and unnecessary stability of the background color is observed. Was lacking. In Comparative Example 4, an opaque coating sheet subjected to size press treatment was used, and the pressing pressure during lamination was further lowered, and unnecessary color development during peeling could be avoided, but a laminate layer and self-coloring feeling were obtained. The adhesiveness of the pressure recording paper was poor, and the variation in peeling was large. In Comparative Example 5, by applying the co-extrusion laminating method, the adhesiveness between the self-coloring pressure-sensitive recording paper and the laminate layer and the unnecessary color development at the time of peeling were improved, but the peeling variation was unavoidable.

[0059]

In the laminated pressure-sensitive recording sheet of the present invention, the pressure-sensitive recording layer and the opaque coating sheet are integrated by the thermoplastic resin laminate layer, and the opaque coating sheet and the thermoplastic resin laminate layer are formed with a light force. It can be separated (peeled) from the support having a pressure recording layer. The peel strength has little variation in the width direction of the web, and it is possible to eliminate a portion that is excessively adhered microscopically, so that stable peelability without unnecessary background coloration at the time of peeling can be obtained. Further, the pressure-sensitive recorded information can be handled without being exposed to the outside and exposed, and the opaque cover sheet can be peeled off as necessary to read the pressure-sensitive recorded information inside, which was once disclosed. Information cannot be hidden again (anti-redeposition property)
It is characterized by the fact that it can be used for many purposes such as continuous slips, pasting slips, labels, correspondences such as postcards, recordings, and dust-free recording paper.

Claims (2)

[Claims] 1. A pressure-sensitive recording layer and an opaque coating sheet, each of which is formed by laminating a color-forming agent or a color-developing agent, both or one of which is microencapsulated, individually on one surface of a support, or by mixing and coating them. In a pressure-sensitive recording sheet integrated with a thermoplastic resin laminate layer, a laminated pressure-sensitive recording sheet having an aqueous polymer coating layer on the surface of the opaque coating sheet on the side in contact with the thermoplastic resin laminate layer. . 2. The laminated pressure-sensitive recording sheet according to claim 1, wherein the aqueous polymer coating layer contains an inorganic pigment or an organic pigment.