WO2001076884A1

WO2001076884A1 - Method for producing information recording material and coating liquid for use therein

Info

Publication number: WO2001076884A1
Application number: PCT/JP2001/002497
Authority: WO
Inventors: Yasuro Yokota; Masato Shiraishi
Original assignee: Mitsubishi Paper Mills Ltd.
Priority date: 2000-04-11
Filing date: 2001-03-27
Publication date: 2001-10-18
Also published as: DE10196052T1

Abstract

A method for producing an information recording material, characterized in that (1) a coating liquid film having a plurality of layers is subjected to curtain flow coating wherein an intermediate coating liquid layer is arranged between two coating liquid layers which form a high viscosity liquid upon contacting or mixing with each other, (2) a coating liquid film having a plurality of layers is subjected to curtain flow coating wherein at least one set of adjacent layers gradually form a high viscosity liquid after contacting or mixing with each other, (3) the surface of a supporter is first coated with water or an aqueous liquid and then, before the supporter is dried, a coating liquid film having a plurality of layers is subjected to curtain flow coating, and (4) a coating liquid film having a plurality of layers is subjected to curtain flow coating, wherein a coating liquid layer containing 90 wt % or more of water is arranged as the layer nearest to the surface of a supporter. The method allows the production with good productivity of an information recording material which is excellent especially in qualities relating to application and has excellent various properties.

Description

Specifi cations tf Report How to use iH recording materials

[0 0 0 1]

Technology

The present invention relates to a method for producing an information recording material and a coating liquid used for the method. More specifically, the present invention relates to a method for producing an information recording material such as a heat-sensitive recording material having excellent coating properties and excellent properties, such as an ink jet recording material, with high productivity, and a coating liquid used in the method. It is.

[0200] Information recording materials provided with an information recording layer for recording information on a support are used in a wide range of fields. A wide variety of such information recording materials have been put into practical use, such as pressure-sensitive recording materials, heat-sensitive recording materials, photosensitive and heat-sensitive recording materials, photosensitive and pressure-sensitive recording materials, thermal transfer recording materials, and inkjet recording materials. In recent years, these information recording materials have been used in which two or more layers are provided on a support due to demand for higher performance and higher performance.

[0 0 0 3]

A thermosensitive recording material generally has a thermosensitive recording layer containing a component that develops a color when heated on a support, and is heated with a thermal head, a hot pen, a laser beam, or the like. Thereby, a color image can be obtained.

[0 0 0 4]

Such a thermosensitive recording material has the advantages of being able to record with a relatively simple device, being easy to maintain, and having no noise. For example, a measurement recorder, a facsimile, a printer, and a computer. It is used in a wide range of fields, such as terminal devices for labels, vending machines for labels, and ticketes. In addition, in order to obtain better color density, sensitivity, image stability, multiple colors, etc., not only a single thermosensitive recording layer, but also one or more protective layers and / or underlayers Thermal recording materials coated with two or more thermal recording layers have also been put to practical use. [0 0 0 5]

The ink jet recording method is a recording method for recording images and characters by attaching minute droplets of ink ejected from an ink jet recording apparatus to an ink jet recording material. Ink-jet recording materials used for this purpose may be those that are not coated with an ink-receiving layer, such as uncoated paper. When a fine image is desired, the support is provided with an ink receiving layer. In recent years, with the diversification of uses, high performance printing such as colorization and high-speed printing, more ink has been ejected, and higher capacity ink absorption and higher printing density have been required. Became. In order to meet such requirements, conventional single-layer ink-receiving layers cannot provide sufficient performance, and ink-jet recording materials provided with two or more ink-receiving layers have also been put to practical use. [0 0 0 6]

Conventionally, in an information recording material comprising two or more layers laminated on a support, layers are formed by coating and drying one layer at a time. Methods such as blade coating, rod coating, and reverse roll coating are used.However, information recording materials made by such a method have poor coating quality, seepage into the lower layer of the coating solution, and In addition to problems such as pinholes in the upper layer due to repelling during coating, quality variations during long-time continuous coating, problems such as limited high-speed coating and reduced productivity resulting from multiple coatings. is there.

[0 0 0 7]

In contrast to these coating methods, the curtain coating method disclosed in Japanese Patent Publication No. 49-24313, for example, forms a free-falling curtain of the coating solution and collides it with a support to apply the coating solution. It is known that coating quality is good and suitable for high-speed coating. Further, by forming a paint film composed of a plurality of coating liquid films and applying the film to the curtain, it is possible to simultaneously apply a plurality of layers, thereby greatly improving productivity of multi-layer coating. In the simultaneous multi-layer coating using the curtain coating method, it is necessary to apply a coating film composed of a plurality of coating liquid films on a support, and then dry and solidify without disturbing the layer structure. If the layer structure is disturbed during drying and inter-layer mixing occurs, The function of the layer is not sufficiently exhibited, and various characteristics of the information recording material deteriorate. Conventionally, in the field of photographic light-sensitive materials, etc., in which multilayer simultaneous coating is performed by force coating, gelatin is usually contained as a binder in a coating solution, and the coating film is transferred onto a support. Immediately after cooling, the gelatin in the coating solution gels due to cooling and the coating solution is immobilized, so that mixing between layers does not occur.

[0 0 0 8]

On the other hand, in the case of information recording materials, for example, in the case of heat-sensitive recording materials, there is a problem that various properties such as color development and image stability are greatly deteriorated if gelatin is added so that the coating solution is immobilized by cooling. However, in the case of ink jet recording materials, the ink absorption capacity and absorption speed may not be sufficiently obtained.In addition, a method of immobilizing a coating liquid using a material other than gelatin without impairing these characteristics has been proposed. It has not been found, and it has not been possible to prevent interlayer mixing in the same manner as in the case of the photosensitive material.

[0 0 0 9]

By the way, unlike the photographic light-sensitive material, the support used for the information recording material often uses a highly water-absorbing support such as paper, or a layer having a very high water absorption is coated in advance. There are many cases. When a paint film composed of a plurality of coating liquid films is curtain-coated on such a support, water in the lowermost coating liquid constituting the paint film moves into the support or a layer that has been previously coated. Accordingly, the water in the upper layer coating solution moves to the lower layer side. At this time, there was a problem that components other than water contained in each layer also moved into the lower layer due to the movement of water, and mixing between the layers occurred.

[0 0 1 0]

Disclosure of 昍

A first object of the present invention is to overcome such disadvantages of the prior art and to produce information recording materials such as heat-sensitive recording materials and ink jet recording materials with excellent coating quality and various characteristics with high productivity. Another object of the present invention is to provide a coating liquid suitably used in this method.

[0 0 1 1]

The present inventors have conducted intensive studies to achieve the above object, and as a result, (1) An intermediate coating liquid film is provided between two coating liquid films which, when contacted or mixed, has a high viscosity, for isolating the two coating liquid films. By coating the paint film as quickly as possible to form the information recording layer, (2) in forming a part or all of the layers constituting the information recording material by applying a paint film consisting of multiple layers to the curtain, At least one pair of adjacent two layers constituting a paint film composed of a plurality of layers to be curtain-coated is configured to have a structure in which the viscosity is temporarily increased upon contact or mixing. In forming a part or all of the plurality of layers constituting the material by applying a paint film composed of a plurality of layers, the water or the aqueous liquid is applied to the surface of the support on the side where the paint is formed, and then dried. Immediately cover the paint film (4) When forming a part or all of the plurality of layers constituting the information recording material by curtain-coating a paint film composed of a plurality of layers, It has been found that the first object can be achieved by using a coating liquid containing 90% by weight or more of the total weight of the coating liquid as the lowermost coating liquid constituting the coating film.

[0 0 1 2]

The above-mentioned 3 (2), which comprises a combination of three coating liquids having a specific property, the coating liquid used in the method of (1), and a combination of two coating liquids having a specific property. It has been found that the second object can be achieved by the coating liquid used in the method (1).

[0 0 1 3]

The present invention has been completed based on such findings.

That is, the present invention

(1) In a method for manufacturing an information recording material having an information recording layer provided on a support, an intermediate coating for isolating the two coating liquid films between the two coating liquid films which increases in viscosity when contacted or mixed. A method of manufacturing an information recording material (hereinafter referred to as a manufacturing method I) characterized by forming an information recording layer by curtain coating a plurality of paint films provided with a liquid film;

(2) In a method for manufacturing an information recording material in which an information recording layer is provided on a support, a part or all of a plurality of layers constituting the information recording material is formed by curtain-coating a paint film composed of a plurality of layers. In this case, a paint film composed of a plurality of layers for applying the curtain is formed. A method for producing an information recording material, characterized in that at least one pair of adjacent two layers increases in viscosity over time when contacted or mixed (hereinafter referred to as Production Method II);

(3) In a method for producing an information recording material having a chinho recording layer provided on a support, a part or all of a plurality of layers constituting the information recording material is coated with a paint film composed of a plurality of layers. Manufacturing the information recording material, wherein water or an aqueous liquid is applied to the surface of the support on which the coating film is formed, and the coating film is immediately formed in a undried state by curtain coating. Method (hereinafter referred to as production method III),

(4) In a method for manufacturing an information recording material in which an information recording layer is provided on a support, a part or all of a plurality of layers constituting the information recording material is formed by curtain coating a paint film composed of a plurality of layers. Wherein the lowermost coating liquid constituting the coating film composed of a plurality of layers to be coated with the curtain contains 90% by weight or more of water based on the total weight of the coating liquid. (Hereinafter referred to as Production Method IV),

(5) Two coating liquids that increase in viscosity when contacted or mixed, and are used for an intermediate coating liquid film for isolating these coating liquid films, and are in contact with or mixed with the above two coating liquids. A coating liquid used in the above-mentioned production method I (hereinafter referred to as coating liquid I), which is a combination with a coating liquid that does not increase the viscosity;

(6) The coating liquid used in the above-mentioned production method II (hereinafter referred to as coating liquid II), which comprises a combination of two coating liquids that temporarily increase viscosity when contacted or mixed.

Is provided.

[0 0 1 4]

施ままま! ^!

In the method for producing an information recording material according to the present invention, a part or all of the plurality of layers constituting the information recording material are produced by applying a paint film composed of a plurality of layers, and then drying. The type of layer formed by curtain coating is not particularly limited, and examples thereof include an undercoat layer, a heat-sensitive recording layer, and a protective layer for a thermal recording material, and an undercoat layer and an ink-receiving layer for an ink jet recording material. A series of these adjacent layers are applied simultaneously by force coating. Specific examples of the layers to be simultaneously coated include, for the heat-sensitive recording material, a combination of an undercoat layer and a heat-sensitive recording layer, a combination of a heat-sensitive recording layer and a protective layer, a combination of an undercoat layer, a heat-sensitive recording layer and a protective layer, 2 or more different types of underdrawing Combination of layers, combination of two or more different types of heat-sensitive recording layers, combination of two or more different types of protective layers, undercoat layer and ink receiving layer for ink jet recording materials, multiple ink receiving layers, etc. And other combinations are not particularly limited.

[0 0 1 5]

Examples of the curtain coating device used for curtain-coating a paint film composed of a plurality of layers on a support include an extrusion hopper type curtain coating device and a slide hopper type curtain coating device, and are not particularly limited. The slide hopper type curtain coating apparatus disclosed in Japanese Patent Publication No. 491-2431, which is used for photosensitive materials, can be particularly preferably used. By using this slide hopper type curtain coating apparatus, a coating film composed of a plurality of layers can be easily applied.

[0 0 1 6]

When a plurality of layers constituting an information recording material are applied using a normal information recording material coating liquid using these force coating devices, these coating liquids are similar to those of a photographic light-sensitive material. Since the coating solution gels and does not immobilize the coating solution, interlayer mixing gradually progresses from immediately after the coating until the drying is completed. If interlayer mixing occurs, the function of each layer cannot be sufficiently exhibited, and an information recording material having good various properties cannot be obtained. For example, in the case of a heat-sensitive recording material, when the undercoat layer and the heat-sensitive recording layer are simultaneously coated in multiple layers by force coating, and the undercoat layer and the heat-sensitive recording layer are mixed, the color density is reduced. When the heat-sensitive recording layer and the protective layer are simultaneously coated in multiple layers by force coating, and the heat-sensitive recording layer and the protective layer are mixed, a decrease in the color density, a decrease in the protective layer's barrier property, and the occurrence of a printing failure may occur. Problems arise. In addition, in the case of an ink jet recording material, when a plurality of ink receiving layers are mixed, a reduction in color density, a decrease in ink absorption capacity, and an absorption speed occur. When interlayer mixing occurs in this way, the function of each layer cannot be sufficiently exhibited.

[0 0 1 7]

In the method of manufacturing the information recording material of the present invention, there are four embodiments of manufacturing methods I to IV in order to prevent such interlayer mixing, and each manufacturing method will be described below. [0 0 1 8]

First, in the method I for producing an information recording material of the present invention, in order to prevent interlayer mixing, an intermediate layer which separates the two coating liquid films between the two coating liquid films whose viscosity increases upon contact or mixing. Curtain coating of multiple layers of coating film with coating liquid film is applied and dried. If the inter-layer mixing progresses during drying, part of the two layers sandwiching the intermediate coating liquid layer will mix with the intermediate coating liquid layer, and if further mixing proceeds, the two layers sandwiching the intermediate coating liquid layer and the intermediate coating liquid layer Becomes a mixed state and the viscosity increases. As a result, further inter-layer mixing is suppressed, and although part of the two coating liquid films that increase in viscosity when contacted or mixed are mixed, most of these layers are not mixed at all and the function of each layer is reduced. It can be fully demonstrated.

[0 0 1 9]

The intermediate coating liquid used in the method for producing an information recording material according to the present invention is characterized in that the two coating liquid films sandwiching the intermediate coating liquid layer are brought into contact with or mixed with each other before the coating film is applied to the support, and the viscosity is increased. It is used for the purpose of preventing. Therefore, the intermediate coating liquid must not be in contact with or mixed with the two coating liquids sandwiching the intermediate coating liquid layer to increase the viscosity. In addition, the intermediate coating liquid must not prevent the two coating liquids sandwiching the intermediate coating liquid layer from having high viscosity when contacting or mixing. The intermediate coating liquid can be used without any particular limitation as long as it has the above characteristics and is suitable for force coating. The intermediate coating liquid is preferably one that does not hinder the function of each of the two coating liquid layers sandwiching the intermediate coating liquid layer.

[0 0 2 0]

If an intermediate coating liquid layer is not provided and the two coating liquid films, which increase in viscosity when contacted or mixed, are in contact with each other, the high viscosity is applied before applying to the support, and the coating is not applied. Function, or the layer structure is disturbed even if it can be applied. In addition, a similar phenomenon occurs when the thickness of the intermediate coating liquid layer is insufficient, so that an intermediate layer sufficient to prevent the two coating liquid films from coming into contact with each other before being applied to the support. Layer thickness is required.

[0 0 2 1]

A coating liquid that increases in viscosity when two coating liquids sandwiching the intermediate coating liquid layer come into contact with or mixed with each other can be used without any particular limitation. If the two coating liquids to be applied across the intermediate coating liquid layer do not have the function of contacting or mixing to increase the viscosity, By separately adding an appropriate additive to each of these two coating solutions, a function of increasing the viscosity by contacting or mixing can be exhibited.

[0 0 2 2]

The combination of additives contained in the two coating liquids to increase the viscosity when the two coating liquids come into contact with or mixed with each other includes a positively charged high molecular compound, a negatively charged low molecular compound, and a negatively charged compound. Highly charged high molecular compound and positively charged low molecular compound, Positively charged high molecular compound and negatively charged high molecular compound, Positively charged low molecular compound and negatively charged low molecular compound, Polyvalent metal Examples thereof include, but are not limited to, a polymer compound which reacts with the ion to make it insoluble.

[0 0 2 3]

Examples of the positively charged polymer compound include oligomers and polymers of primary to tertiary amines or quaternary ammonium salts, and specifically, dimethylamine, ebi-chlorohydrin polycondensate, and acrylamide-diallylamine. Examples thereof include a polymer, a polyvinylamine copolymer, chitosan, and salts thereof, but are not limited to these examples.

[0 0 2 4]

Examples of the negatively charged polymer compound include an oligomer or a polymer containing a carboxyl group, a sulfone group, a sulfino group, and the like. Specific examples include polyacrylic acid, acrylic acid copolymer, and polymethacrylic acid. Acid, Methacrylic acid copolymer, Polyvinyl sulfonic acid, Vinyl sulfonic acid copolymer, Polyvinyl sulfinic acid, Alginic acid, Carrageenan, Pectin, Phacelan, Carboxymethylcell mouth, Heparin, Chondroitin sulfate, Xanthan gum, Arabic Examples include gums, guagams, and salts thereof, but are not limited to these examples.

[0 0 2 5]

Examples of the polymer conjugate which is insolubilized by reacting with a polyvalent metal ion include alginic acid, potassium oxymethylcellulose, pectin and salts thereof, but are not limited to these examples. There is no.

[0 0 2 6] Examples of the negatively charged low molecular weight compound include inorganic acids such as hydrochloric acid, sulfuric acid, and nitric acid, and organic acids such as carboxylic acids, sulfonic acids, and sulfino acids, but are not limited to these examples. There is no.

[0 0 2 7]

Positively charged low molecular weight compounds include inorganic bases such as sodium hydroxide, potassium hydroxide, and ammonium, and organic bases such as primary to tertiary amine and quaternary ammonium salts such as dicyandiamide, dimethyldiarylammonium chloride, and the like. Etc. can be shown, but the present invention is not limited to these examples.

[0 0 2 8]

Examples of the polyvalent metal ion include a calcium ion, a magnesium ion, an aluminum ion, a zinc ion, a boron-iron ion, and the like, but are not limited to these examples.

[0 0 2 9]

It is also preferable that the substance added to each coating liquid to increase the viscosity when these two coating liquids come into contact with or mixed with each other can increase the viscosity with a smaller amount. Further, it is preferable that the time until the viscosity becomes high after contact or mixing is shorter.

[0 0 3 0]

The coating liquid I of the present invention is a coating liquid used in the production method I, and includes two coating liquids that increase in viscosity when contacted or mixed, and an intermediate coating for isolating these coating liquid films. It is used for a liquid film and comprises a combination of the above two coating liquids and a coating liquid which does not increase in viscosity even when they are in contact with or mixed with each other.

[0 0 3 1]

The two coating liquids that become highly viscous upon contact or mixing include, as additives, a positively charged polymer compound and a negatively charged low molecular compound, and a negatively charged polymer compound and a positively charged polymer compound. Low molecular compounds, positively charged high molecular compounds and negatively charged high molecular compounds, positively charged low molecular compounds ^) and negatively charged low molecular compounds, or reacting with polyvalent metal ions It is preferable to separately include them so as to form a combination of insoluble polymer compounds.

[0 0 3 2] In the information recording material manufacturing method II of the present invention, in order to prevent interlayer mixing, at least one pair of adjacent two layers constituting a coating film composed of a plurality of layers to be curtain-coated are contacted or mixed.調製 Prepared and applied to increase viscosity temporarily. Adjacent two layers that increase in viscosity over time when contacted or mixed must be one that gradually increases in viscosity after contact or mixing. If the two layers instantaneously increase in viscosity after contact or mixing, the layer structure of the coating film is disturbed or the coating film itself cannot be formed between the time when the coating film composed of multiple layers is formed and the time when it is applied to the support. . Therefore, the speed and degree of viscosity increase after the two layers are in contact with or mixed with each other need to be adjusted according to the coating liquid or device to be applied so that the layer structure is not disturbed before being applied to the support. . After being applied to the support, the viscosity increases due to contact or mixing, and most of these layers do not mix at all and exhibit a good layer separation state.

[0 0 3 3]

A combination of coating liquids that gradually increases in viscosity after contact or mixing can be used without particular limitation. If the two coating liquids do not have the function of gradually increasing the viscosity temporarily after contact or mixing, contact or mixing can be carried out by adding appropriate additives to these coating liquids separately. The function of gradually increasing the viscosity over time can be exhibited.

[0 0 3 4]

Specific examples of combinations of additives to be included in the coating liquid in order to gradually increase the viscosity of the two coating liquids after contact or mixing include a lipoxyl group capable of dissolving by reacting with an alkali. Examples include, but are not limited to, combinations of polymer emulsion and polymer.

[0 0 3 5]

Examples of the emulsion of a polymer containing a carboxyl group that dissolves by reacting with an alkali include an emulsion of a copolymer of acrylic acid, methacrylic acid, maleic acid, fumaric acid and other monomers. Such emulsions are not water-soluble due to the low degree of dissociation of the carboxyl groups contained in the polymer in the acidic-neutral region, and exist as emulsions. When an alkali is added to the solution, the carboxyl group is dissociated and the water solubility of the emulsion is expressed. The degree gradually rises. The rate of increase in viscosity can be controlled by the particle size of the emulsion, the content of carboxyl groups, and the like.

[0 0 3 6]

It is also preferable that the substance to be added in order to gradually increase the viscosity over time after the two coating liquids come into contact with or mixed with each other can be made more viscous with a smaller amount of addition.

[0 0 3 7]

By the way, when a plurality of layers constituting an information recording material are simultaneously coated in multiple layers by using the above-mentioned force coating apparatus, the surface tension of the uppermost layer of the coating liquid is usually lower than the surface tension of the lower layer of the coating liquid. It is important to prevent the phenomenon of repelling, in which the top layer shrinks above the lower layer, causing defects in the top layer. Here, the uppermost layer indicates a layer furthest from the support, and the lower layer indicates a layer closer to the support. For adjusting the surface tension, a method of adding a surfactant to the coating liquid to reduce the surface tension is used. Conversely, it is very difficult to increase the surface tension of the coating solution, and this is not generally performed. For this reason, it is necessary to add a large amount of surfactant to the uppermost coating liquid to reduce the surface tension.However, in information recording materials, for example, in thermal recording materials, a large amount of surfactant is added to the coating liquid. When added, various properties such as color development and image stability may be deteriorated, and it is difficult to control the wettability of water or oil on the heat-sensitive recording material. In the case of the ink jet recording material, the target quality may not be obtained because the ink absorbency and the print density are greatly affected. As described above, the method of preventing the repelling of the uppermost layer due to the addition of the surfactant has a disadvantage that the performance of the information recording material is limited.

[0 0 3 8]

In the production method II of the information recording material of the present invention, it is possible to make the surface tension of the uppermost coating liquid higher than the surface tension of the adjacent lower coating liquid. After the uppermost layer coating liquid and the adjacent lower layer coating liquid come into contact with or mixed with each other, the viscosity of the uppermost layer is reduced with time to prevent the uppermost layer from shrinking on the lower layer and causing a phenomenon of repelling. Can be. [0 0 3 9]

The rate at which the coating liquid of the uppermost layer and the coating liquid of the adjacent lower layer are increased in viscosity after contact or mixing is required to be high enough to prevent the phenomenon of repelling. For this reason, the rate and degree of viscosity increase after contact or mixing are adjusted according to the coating liquid or equipment to be applied so that the repelling phenomenon can be prevented and the layer structure is not disturbed before being applied to the support. There is a need.

[0 0 4 0]

The coating liquid II of the present invention is a coating liquid used in this production method II, and is composed of a combination of two coating liquids which, when contacted or mixed, increase in viscosity with time. It is preferable that the two coating liquids separately contain, as additives, a combination of an emulsion and a polymer of a polymer containing a ruboxyl group, which are capable of reacting and dissolving with an alkali. Further, those composed of a combination of coating liquids having different surface tensions are preferable.

[0 0 4 1]

Next, in the production method III of the Qianho recording material of the present invention, in order to prevent inter-layer mixing, water or an aqueous liquid is applied in advance to absorb the water on the support before the force coating is performed. Prompt, where it is done curtain coating is done. Thereby, when the coating layer is curtain-coated, the movement of moisture to the support side is suppressed, and most of the coating layer does not mix at all and a good layer separation state is exhibited.

[0 0 4 2]

In the present invention, a coating film is formed by applying a curtain using a curtain coating apparatus. Before forming the coating film, water or an aqueous liquid is applied to the surface of the support on the side where the coating film is formed. The liquid to be applied may be water alone, but is preferably an aqueous liquid using a material that can be dissolved or dispersed in water.

[0 0 4 3]

The material that can be dissolved or dispersed in water is not particularly limited, and examples thereof include the following materials.

[0 0 4 4]

Water-soluble polymers such as starch-based polymers, polyvinyl alcohol-based polymers, gelatin-based polymers, polyacrylamide-based polymers, cellulose-based polymers, etc., emulsions and latexes such as petroleum resin emulsions, and ethylene Emuljo of a copolymer containing at least acrylic acid (or methacrylic acid) Or latex, styrene-butadiene, styrene-acrylic, vinyl acetate-acrylic, ethylene-vinyl acetate, butadiene-methylmethacrylate copolymers and emulsions of carboxy-modified copolymers thereof Tex and the like. Alkali metal salts such as sodium chloride and potassium chloride, alkaline earth metal salts such as calcium chloride and barium chloride, colloidal metal oxides such as colloidal silica, and organic antistatic agents such as polystyrene sulfonate Pigments, such as clay, kaolin, calcium carbonate, talc, barium sulfate, titanium oxide, etc., pH regulators such as hydrochloric acid, phosphoric acid, citric acid, caustic soda, other coloring pigments, coloring dyes, fluorescent brightening An additive such as an agent may be appropriately combined and contained.

[0 0 4 5]

In this production method III, there is no particular limitation on a device for applying water or an aqueous liquid to the surface of the support, and a known coating device, for example, a pressure type fountain, a jet fountain, a hooded nip, or a roll as a device having a different liquid contacting method. Equipment such as metalling, load-measurement, and force-setting, commonly known equipment such as blades, rods, roll nips, and air-knives as coating amount adjustment devices, or use these as appropriate Combined devices can be used.

[0 0 4 6]

Furthermore, in the method IV for producing an information recording material of the present invention, in order to prevent interlayer mixing, the lowermost coating liquid constituting a coating film composed of a plurality of layers to be curtain-coated is 90% of the total weight of the coating liquid. Contains more than 10% water. If the lowermost coating liquid contains 90% by weight or more of water based on the total weight of the coating liquid, even if the water in the coating liquid moves to the support or the lower layer previously applied, Since the lower layer has a sufficient amount of water in the coating liquid, it is difficult for water to move from the upper layer, and the upper layer is dried before the progress of interlayer mixing, thereby preventing interlayer mixing.

[0 0 4 7]

The component of the lowermost coating solution is not particularly limited as long as it contains 90% by weight or more of water based on the total weight of the coating solution. Therefore, the lowermost layer coating liquid may be a layer coating liquid indispensable for realizing the function of the information recording material, and for the purpose of preventing interlayer mixing, A layer not directly related to the function of the information recording material may be provided as the lowermost layer.

[0 0 4 8]

It is preferable that the lowermost layer of the coating liquid contains a component that is capable of figuring after drying, since the movement of water can be more effectively suppressed. Specific examples of components that form a film after drying include polyvinyl alcohols, starches, celluloses, polyacrylamides, styrene Z maleic anhydride copolymer copolymers, and ethylene / maleic anhydride copolymers. Water-soluble polymers such as alkali salts of poly (acrylic acid), polyacrylic acid, polymethacrylic acid, polyacrylic acid ester, polymethacrylic acid ester, styrene / butadiene copolymer, acrylonitrile / butadiene copolymer, ethylene Z vinyl acetate Synthetic resin emulsions such as copolymers, acrylamide / acrylic ester copolymers, acrylamide / acrylic ester / methacrylic acid terpolymers and the like. [0 0 4 9]

The drying method according to the method of manufacturing the Qianho recording material I to IV of the present invention is not particularly limited, but specific examples include a method of blowing heated air, a method of blowing dehumidified air, a method of irradiating infrared rays, and a method of irradiating infrared rays. Examples include a method of irradiating a wave, and these can be used in combination.

[0 0 5 0]

The method for producing the information recording material of the present invention The coating liquid of the multiple layers constituting the coating film applied by the methods I to IV is used with its viscosity and surface tension adjusted to reduce interlayer mixing during curtain application. Is done. The smaller the difference in the viscosity of the coating liquid of each layer, the less the mixture between the layers, and the difference in the viscosity of the coating liquid of each layer is preferably 10 OmPa · s or less. If the surface tension of the lower coating liquid is smaller than that of the upper coating liquid, the upper coating liquid film will repel the lower coating liquid film, and a uniform coating film will be formed. This is not preferable because the coating quality may deteriorate and the coating quality may deteriorate. When the surface tension of the coating liquid in each layer is the same, repelling phenomena are less likely to occur. It is particularly preferable to set the upper layer to be smaller than the lower layer so as to obtain better coating quality. When three or more layers are simultaneously coated, it is preferable to adjust the surface tension so as to gradually decrease from the lowermost layer, that is, the layer closest to the support to the uppermost layer farthest from the support. However, in the method II for producing an information recording material of the present invention, the coating solution of the uppermost layer and the coating solution of the lower layer adjacent thereto are used. This is not the case with regard to the surface tension.

[0 0 5 1]

In order to adjust the viscosity of the coating solution, various thickeners such as polyvinyl alcohol, starch, carboxymethyl cellulose, and other water-soluble polymers such as acryl-based emulsions are mixed with the coating solution to increase the viscosity. It is possible to raise the viscosity by increasing the partial concentration, or conversely, take measures to dilute the coating solution to lower the viscosity. [0 0 5 2]

In order to adjust the surface tension of the coating solution, anionic surfactants such as carboxylate, sulfonate, ester sulfate, and phosphate ester, ether type, ester type, ester type, and nitrogen-containing An arbitrary amount of a nonionic surfactant such as a mold, an amphoteric surfactant such as beinine, an aminocarboxylate, or an imidazoline derivative can be mixed with the coating solution.

[0 0 5 3]

The method for producing the information recording material of the present invention, the coating liquid of a plurality of layers constituting the coating film applied by the coating liquids I to IV includes a pigment dispersant, a thickener, a fluidity improver, an antifoaming agent, a foam inhibitor, Release agents, foaming agents, penetrants, coloring dyes, coloring pigments, fluorescent whitening agents, antioxidants, preservatives, anti-bubbling agents, water-proofing agents, wet paper strength agents, dry paper strength agents, etc. It can also be appropriately compounded.

[0 0 5 4]

Each layer of the information recording material produced by the information recording material production methods I to IV of the present invention can contain an arbitrary binder. Specific examples of the pinda include starches, hydroxyethyl cellulose, methyl cellulose, ethyl cell mouth, carboxymethyl cellulose, gelatin, casein, polyvinyl alcohol, modified polyvinyl alcohol, polyacrylic acid, polymethacrylic acid, polyacrylic acid ester, Polymer acrylate, polysodium acrylate, polyethylene terephthalate, polybutylene terephthalate, chlorinated polyester, aryl resin, furan resin, ketone resin, oxybenzoyl polyester, polyase resin Polyetheretherketone, polyethersulfone, polyimide, polyamide, polyamideimide, polyaminobismaleimide, polymethylpentene, polyphene Nylene oxide, polyphenylene sulfide, polyphenylene sulfone, polysulfone, polyarylate, polyallyl sulfone, polybutadiene, polycarbonate, polyethylene, polypropylene, polystyrene, polyvinyl chloride, polyvinylidene chloride, polyacetic acid Vinyl, polyurethane, phenolic resin, urea resin, melamine resin, melamine formalin resin, benzoguanamine resin, bismaleimid triazine resin, alkyd resin, amino resin, epoxy resin, unsaturated polyester resin, styrene / butadiene copolymer, acrylonitrile butadiene Copolymer, methyl acrylate // butadiene copolymer, ethylene Z-vinyl acetate copolymer, acrylate acrylate acrylate copolymer, amide acrylate Acrylic acid ester / methacrylic acid terpolymer, styrene / maleic anhydride copolymer alkaline salt, ethylene / maleic anhydride copolymer alkaline salt or ammonium salt, other polyolefin resins, etc. These can be used alone or in combination of two or more.

[0 0 5 5]

The support used for the Qianho recording material manufactured by the information recording material manufacturing methods I to IV of the present invention may be any of transparent, translucent, and opaque, such as paper, various nonwoven fabrics, woven fabrics, Female fat film, synthetic resin laminated paper, synthetic paper, metal foil, ceramic paper, glass plate, etc., or a composite sheet combining these can be used arbitrarily according to the purpose, but is not limited thereto. .

[0 0 5 6]

Any layer of the information recording material produced by the method I to IV for producing the information recording material of the present invention may contain, if necessary, diatomaceous earth, talc, kaolin, calcined kaolin, calcium carbonate, magnesium carbonate, titanium oxide. Inorganic and organic pigments such as zinc oxide, silicon oxide, aluminum hydroxide, urea-formalin resin, and other higher fatty acid metal salts such as zinc stearate and calcium stearate, paraffin, paraffin oxide, polyethylene, Waxes such as polyethylene oxide, stearic acid amide, and cascade, dispersants such as sodium dioctyl sulfosuccinate, surfactants, and fluorescent dyes can also be contained. [0 0 5 7] In addition, an antioxidant and an ultraviolet absorber can be added for the purpose of improving light resistance. Examples of the antioxidant include, but are not particularly limited to, hindered amine antioxidants, hindered phenol antioxidants, and sulfide antioxidants. Examples of UV absorbers include organic UV absorbers such as benzotriazole-based UV absorbers, salicylic acid-based UV absorbers, and benzophenone-based UV absorbers, and inorganic UV absorbers such as zinc oxide, titanium oxide, and cerium oxide. Examples include, but are not particularly limited to, UV absorbers.

[0 0 5 8]

The components of the heat-sensitive recording material produced by the method I to IV for producing the information recording material of the present invention, which are colored by heating, are not particularly limited, and include, for example, a generally colorless or pale-colored electron-donating dye precursor and an electron-accepting dye. A combination of an aromatic isocyanate compound and an imino compound, a combination of a colorless or pale-color electron-donating dye precursor and an aromatic isocyanate compound, a combination of a metal compound and a coordination compound, Examples include a combination of a diazonium salt and a coupler. A combination of a colorless or pale-color electron-donating dye precursor and an electron-accepting compound, a combination of an aromatic isocyanate compound and an imino compound, in terms of good properties such as color development and image stability. Usually, a combination of a colorless or light-colored electron-donating dye precursor and an aromatic cyanocyanate compound is particularly preferably used.

[0 0 5 9]

In the thermal recording material produced by the method I to IV for producing the information recording material of the present invention, any layer in the thermal recording material contains a material capable of recording information electrically, magnetically or optically. You may let it. The surface on which the heat-sensitive recording layer is provided or the surface on the opposite side may have ink receiving properties for ink jet recording. In addition, a back coat layer may be provided on the surface opposite to the surface on which the heat-sensitive recording layer is provided for the purpose of preventing curling and electrification, and may be subjected to adhesive processing or the like. Further, the surface of the thermal recording layer may be printed with UV ink or the like.

[0 0 6 0]

In the heat-sensitive recording material manufactured by the method I to IV for manufacturing the information recording material of the present invention, in order to perform printing with a laser beam, any layer and support in the heat-sensitive recording material The body can contain a light-to-heat conversion material.

[0 0 6 1]

In the ink jet recording material produced by the information recording material production methods I to IV of the present invention, an ink receiving layer may be provided on both surfaces of the support. Any layer in the inkjet recording material may contain a material capable of recording information electrically, magnetically, or optically. In addition, a pack coat layer may be provided on the surface opposite to the surface on which the ink receiving layer is provided for the purpose of curling prevention, antistatic treatment, and the like, and may be subjected to adhesive processing or the like.

[0 0 6 2]

Hereinafter, the present invention will be described with reference to examples, but the present invention is not limited to these examples. In the examples, “part j” and “%” indicate “part by weight” and “% by weight” unless otherwise specified.

[0 0 6 3]

Example 1

[0 0 6 4]

(A-1) Preparation of coating solution for thermal recording layer

A mixture having the following composition was dispersed in a ball mill, and A-1-1, 1, A-2, and A-1-3 solutions having a volume average particle size of 1 μm and A-1 having a volume average particle size of 2 m were used. Four liquids were obtained. [0 0 6 5]

A— 1-1 liquid:

3-Dibutylamino-1 6-methyl-1 7-anilinofluorane 40 parts Polyvinyl alcohol 10% aqueous solution 20 parts Water 40 parts

[0 0 6 6]

A— 1— 2 liquids:

4,4'-bis (hydrophenyl) sulfone 80 parts Polyvinyl alcohol 10% aqueous solution 40 parts Water 80 parts

[0 0 6 7] A-1-1 three liquid:

2-Benzyloxy naphthene 80 parts Polyvinyl alcohol 10% aqueous solution 40 parts Water 80 parts [0068]

A— 1—4 liquid:

Calcium carbonate (Shiraishi Kogyo Callite SA) 80 parts Sodium polyacrylate 1 part Water 79 parts [0069]

A-1-1, A-2, A-1-3, A-1-4 solutions obtained as above, 600 parts of 10% aqueous polyvinyl alcohol solution, 200 parts of 10% aqueous sodium alginate solution, water 105 parts and 0.67 parts of a fluorinated surfactant (SAFLON S-1111 manufactured by Asahi Glass) were mixed to prepare a coating solution for the heat-sensitive recording layer.

[0070]

(B-1) Preparation of intermediate coating liquid

An intermediate coating solution was prepared by mixing 1500 parts of a 0.5% aqueous solution of hydroxymethyl methylcellulose and 0.80 parts of a fluorine-based surfactant (Saflon S-111 manufactured by Asahi Glass).

[0071]

(C-1) Preparation of protective layer coating liquid

A mixed solution having the following composition was dispersed by a ball mill to obtain a solution C having a volume average particle size of 1 m. [0072]

C— 1 solution:

Aluminum hydroxide (Showa Denko Hijilight H42) 6 parts Silane-modified polyvinyl alcohol (Kuraray R2105) 0.1 part Water 13.9 parts

[0073]

C-1 solution obtained as above, 25% dispersion of 40% zinc stearate, 10% 1000 parts of an aqueous polyvinyl alcohol solution, 10 parts of calcium chloride, 234 parts of water, and 0.90 part of a fluorosurfactant (Saflon S-111 manufactured by Asahi Glass) were mixed to prepare a protective layer coating liquid.

[0074]

(D-1) Preparation of thermal recording material

The thermosensitive recording layer coating solution, intermediate coating solution, and protective layer coating solution prepared in (A-1), (B-1), and (C-1) were heat-recorded from below using a slide hopper type curtain coating device. In the order of recording layer coating solution, intermediate coating solution and protective layer coating solution, the flow rate per curtain width lm is heat-sensitive recording layer coating solution 400 OmlZmin, intermediate coating solution 200 m1 / min, protective layer coating solution 400 OmlZmi A coating film of n was formed, coated on a high-quality paper of 60 g / m ² at a coating speed of 200 m / min, and dried to prepare a thermosensitive recording material. In addition, when the coating solution for the heat-sensitive recording layer and the coating solution for the protective layer in this example were mixed, the viscosity was increased.

[0075]

Example 2

Example 1 Instead of using 200 parts of a 10% aqueous sodium alginate solution in (A-1), 200 parts of a 10% aqueous solution of chitosan lactate was used, and instead of using 10 parts of calcium chloride in (C-11), 28 parts were used. A thermosensitive recording material was produced in the same manner as in Example 1 except that 10 parts of aqueous ammonia was used. In addition, when the coating liquid for the heat-sensitive recording layer of this example and the coating liquid for the protective layer were mixed, the viscosity was increased.

[0076]

Example 3

Example 1 A thermosensitive recording material was produced in the same manner as in Example 1 except that 10 parts of a 90% aqueous lactic acid solution was used instead of 10 parts of Shiridani calcium in (C-1). In addition, when the coating solution for the heat-sensitive recording layer and the coating solution for the protective layer in this example were mixed, the viscosity was increased.

[0077]

Example 4

Example 1 Instead of using 200 parts of a 10% aqueous sodium alginate solution in (A-1), 200 parts of a 10% aqueous solution of chitosan lactate was used, and in (C-11), 1000 parts of a 10% aqueous solution of polyvinyl alcohol and calcium chloride were used. Use 10 parts and 234 parts of water A thermosensitive recording material was produced in the same manner as in Example 1 except that 800 parts of a 10% aqueous solution of polyvinyl alcohol, 200 parts of an aqueous solution of 10% sodium alginate and 244 parts of water were used instead. In addition, when the coating liquid for the thermosensitive recording layer and the coating liquid for the protective layer of this example were mixed, the viscosity was increased.

[0078]

Example 5

(E-1) Preparation of coating solution for lower ink receiving layer

A mixed solution having the following composition was stirred with a homomixer to prepare a lower-ink receiving layer coating solution.

[0079]

Lower ink receiving layer coating liquid:

Synthetic amorphous silica (Mizukasil P78D manufactured by Mizusawa Chemical) 28 parts

10% aqueous solution of polyvinyl alcohol 40 parts

10% sodium alginate aqueous solution 15 parts Water 117 parts Fluorosurfactant (Saflon S-111 manufactured by Asahi Glass)

(F-1) Preparation of intermediate coating liquid

An intermediate coating solution was prepared by mixing 1500 parts of a 0.5% aqueous solution of hydroxymethylmethylcellulose and 0.4 part of a fluorine-based surfactant (Saflon S-111 manufactured by Asahi Glass).

[0081]

(G-1) Preparation of coating liquid for upper ink receiving layer

The mixed solution having the following composition was stirred with a homomixer to prepare a coating liquid for an upper ink receiving layer.

[0082]

Upper layer ink receiving layer coating liquid:

Synthetic amorphous silica (Tokuyama Fine Seal X37B) 21 parts

63 parts of 10% polyvinyl alcohol aqueous solution Cationic polymer (Sumitomo Chemical Industries Sumireze Resin 1001)

14 parts Water 102 parts Fluorosurfactant (SAFLON S-111 manufactured by Asahi Glass) 0.002 parts [0083]

(H-1) Preparation of ink jet recording material

The lower ink receiving layer coating solution, intermediate coating solution, and upper ink receiving layer coating solution prepared in (E-1), (F-1) and (G-1) were prepared using a slide hopper type force coating device. From the lower layer side, the lower ink receiving layer coating liquid, the intermediate coating liquid, and the upper ink receiving layer coating liquid, in this order, the flow rate per force-ten width lm is 7200 ml / min for the lower ink receiving layer, 4 Oml / min for the intermediate coating liquid. Then, a coating film of 210 Oml / min of the upper ink receiving layer coating liquid was formed, applied on a high quality paper of 60 g / m ² at a coating speed of 40 m / min, and dried to prepare an ink jet recording material. When the coating liquid for the lower ink receiving layer and the coating liquid for the upper ink receiving layer in this example were mixed, the viscosity increased.

[0084]

Example 6

Example 5 Instead of using 15 parts of a 10% aqueous sodium alginate solution in (E-1), 15 parts of an aqueous lactate solution of 10% chitosan was used, and instead of using 102 parts of water in (G-1), 96 parts of water were used. An ink jet recording material was prepared in the same manner as in Example 5, except that 6 parts of 28% aqueous ammonia was used. In addition, when the coating liquid for the lower ink receiving layer and the coating liquid for the upper ink receiving layer in this example were mixed, the viscosity was increased.

[0085]

Example 7

Example 5 Instead of using 40 parts of a 10% aqueous solution of polyvinyl alcohol, 15 parts of a 10% aqueous solution of sodium alginate and 117 parts of water in (E-1), 55 parts of a 10% aqueous solution of polyvinyl alcohol and 6 parts of 28% aqueous ammonia Example 5 except that 111 parts of a 10% aqueous solution of chitosan and 48 parts of a 10% aqueous solution of polyvinyl alcohol were used instead of 63 parts of a 10% aqueous solution of polyvinyl alcohol in (G-1), using 111 parts of water and 111 parts of water. In the same manner as described above, an ink jet recording material was produced. In addition, When the coating liquid for the lower-ink receiving layer and the coating liquid for the upper-ink receiving layer in this example were mixed, a high viscosity was produced.

[0 0 8 6]

Comparative Example 1

A heat-sensitive recording material was produced in the same manner as in Example 1 (C-11) except that 10 parts of water was used instead of 10 parts of calcium chloride. The viscosity of the heat-sensitive recording layer coating liquid and the protective layer coating liquid of this comparative example did not increase when mixed.

[0 0 8 7]

Comparative Example 2

Example 1 Except that in Example (A-1), instead of using 600 parts of a 10% aqueous solution of polyvinyl alcohol and 200 parts of a 10% aqueous solution of sodium alginate, 800 parts of a 10% aqueous solution of polyvinyl alcohol was used. In the same manner as in Example 1, a thermosensitive recording material was produced. The viscosity of the coating solution for the thermosensitive recording layer and the coating solution for the protective layer in this comparative example did not increase even when mixed.

[0 0 8 8]

Comparative Example 3

Instead of using 600 parts of a 10% aqueous solution of polyvinyl alcohol and 200 parts of a 10% aqueous solution of sodium alginate in Example 1 (A-1), 800 parts of a 10% aqueous solution of polyvinyl alcohol was used. A heat-sensitive recording material was prepared in the same manner as in Example 1 except that 10 parts of water was used instead of 10 parts of Shiridani calcium in C-1). It should be noted that the coating liquid for the heat-sensitive recording layer and the coating liquid for the protective layer of this comparative example did not increase in viscosity even when mixed. [0 0 8 9]

Comparative Example 4

Example 5 Except that in Example (E-1), 55 parts of a 10% aqueous solution of polyvinyl alcohol was used instead of 40 parts of an aqueous solution of 10% polyvinyl alcohol and 15 parts of an aqueous solution of 10% sodium alginate. In the same manner as in Example 5, an ink jet recording material was produced. In addition, even if the coating liquid for the lower ink receiving layer and the coating liquid for the upper ink receiving layer were mixed in this comparative example, the viscosity did not increase.

[0 0 9 0] Comparative Example 5

Example 5 An ink jet recording material was produced in the same manner as in Example 5 except that 15 parts of a 10% aqueous solution of lactate of chitosan was used instead of 15 parts of an aqueous solution of sodium alginate in (E-1). In addition, even if the lower ink receiving layer coating liquid and the upper ink receiving layer coating liquid of this comparative example were mixed, the viscosity did not increase.

[0091]

Comparative Example 6

Example 5 Instead of using 40 parts of a 10% aqueous solution of polyvinyl alcohol and 15 parts of a 10% aqueous solution of sodium alginate in (E-1), 55 parts of a 10% aqueous solution of polyvinyl alcohol was used. An ink jet recording material was prepared in the same manner as in Example 5 except that 15 parts of a 10% aqueous solution of chitosan lactate and 48 parts of a 10% aqueous solution of polyvinyl alcohol were used instead of using 63 parts of an aqueous solution of polyvinyl alcohol. In addition, even if the lower ink receiving layer coating liquid and the upper ink receiving layer coating liquid of this comparative example were mixed, the viscosity did not increase.

[0092]

Test 1 Printing with thermal head on thermal recording material

The thermal recording material prepared in Examples 1 to 4 and Comparative Examples 1 to 3 was applied with an applied pulse of 1.2 ms using an Okura Electric thermal facsimile printing tester (TH-PMD) with a TDK print head (LH4409). At an applied voltage of 20 volts, printing was performed with a width of 5 cm and a length of 5 cm, and the density of the printed portion was measured using a densitometer (Macbeth RD918). Further, the color development of the printed portion was visually observed. The results are shown in Table 1. [0093]

Test 2 Barrier test of protective layer of thermal recording material

Pulse applied to the thermal recording materials prepared in Examples 1 to 4 and Comparative Examples 1 to 3 using an Okura Electric thermal facsimile printing tester (TH-PMD) with a TDK print head (LH4409) for 1.2 ms. With an applied voltage of 20 volts, printing was performed with a width of 5 cm and a length of 5 cm. Next, castor oil was applied to the printed area, and two hours later, the density of the portion where the castor oil was applied was measured using a densitometer (Macbeth RD918). The results are shown in Table 2. [0094]

Test 3 Printing on an ink jet recording material using an ink jet printer The ink jet recording materials prepared in Examples 5 to 7 and Comparative Examples 4 to 6 were blackened using a Seiko Epson Color Ink Jet Printer (PM750C). The ink was printed 5 cm wide and 5 cm long, and the density of the printed area was measured using a densitometer (Macbeth RD918). Further, the color development of the printed portion was visually observed. Table 3 shows the results.

[0095]

table 1

[0096]

Table 2

[0075] Table 3

[0 0 7 6]

In Tables 1 to 3, as shown in Examples 1 to 7, a plurality of layers having an intermediate coating liquid film provided between two coating liquid films which increase in viscosity when contacted or mixed, separating the two coating liquid films. By forming the information recording layer by curtain coating the paint film of No. 1, an information recording material having good coating quality and excellent various properties could be obtained with high productivity.

[0 0 7 7]

In Comparative Examples 1 to 3, the heat-sensitive recording layer and the protective layer were in a mixed state, a low color density was obtained, and the barrier property of the protective layer was very low. In Comparative Examples 4 to 6, the lower ink receiving layer and the upper ink receiving layer were in a mixed state, and only a low color density was obtained.

[0 0 7 8]

Example 8

[0 0 7 9]

(A-2) Preparation of coating solution for thermal recording layer

A mixture of the following composition was dispersed in a ball mill, and A—2-1, A—2-2, A—2-3 liquid with a volume average particle diameter of 1 m and A—2—4 with a volume average particle diameter of 2 m A liquid was obtained. [0 0 8 0]

A-2-1 liquid:

[0 0 8 1] A— 2— 2 liquids:

4,4'-bis (hydroxyphenyl) sulfone 80 parts Polyvinyl alcohol 10% aqueous solution 40 parts Water 80 parts

A-2-3 liquid:

2-benzyloxynaphthene 80 parts Polyvinyl alcohol 10% aqueous solution 40 parts Water 80 parts

A— 2— 4 fluids:

Calcium carbonate (Callite SA manufactured by Shiroishi Industry) 80 parts Sodium polyacrylate 1 part Water 79 parts [0084]

A-2-1, A-2-2, A-2-3, A-2-4 liquids obtained as above, 600 parts of 10% aqueous solution of polyvinyl alcohol, and 30% solids Mix 67 parts of a polymer containing carboxyl group (Sannopco SN — Thickener 926), 238 parts of water, and 0.67 parts of a fluorine-based surfactant (Asahi Glass S-FLON S-111) that reacts and dissolves. A coating solution for the heat-sensitive recording layer was prepared.

[0085]

(B-2) Preparation of protective layer coating liquid

A mixed solution having the following composition was dispersed by a ball mill to obtain a B-2 solution having a volume average particle diameter of 1 m.

[0086]

B—Two liquids:

Aluminum hydroxide (Showa Denko Hijilight H42) 6 parts Silane-modified polyvinyl alcohol (Kuraray R2105) 0.1 part Water 13.9 parts [0087]

Solution B-2 obtained as described above, 25 parts of a 40% zinc stearate dispersion, 1000 parts of a 10% aqueous solution of polyvinyl alcohol, 10 parts of 28% aqueous ammonia, 234 parts of water, and a fluorinated surfactant (Asahi Glass Co., Ltd.) 0.90 parts of 1 Flon S-111) was mixed to prepare a coating solution for the protective layer.

[0088]

(C-1 2) Preparation of thermal recording material

Using a slide hopper type curtain coating device, apply the heat-sensitive recording layer coating solution and the protective layer coating solution from the lower layer side using the heat-sensitive recording layer coating solution and the protective layer coating solution prepared in (A-2) and (B-2). in the flow rate per curtain width lm is heat-sensitive recording layer coating liquid 4000MlZmin, paint film coercive Mamoruso coating liquid 400 Oml / mi n is formed, on fine paper of 60 g / m ² at a coating speed 200 m / min And dried to prepare a heat-sensitive recording material. When the coating solution for the heat-sensitive recording layer of this example and the coating solution for the protective layer were mixed, the viscosity gradually increased with time.

[0089]

Example 9

[0090]

(D-2) Preparation of undercoat layer coating liquid

A mixed solution having the following composition was stirred with a homomixer to prepare an undercoat layer coating solution. [0091]

Undercoat layer coating liquid:

Calcined Kaolin (Ensilhard Ansilex) 100 parts

24 parts of 50% styrene butadiene copolymer latex

10% starch aqueous solution (Nippon Shokuhin Kako MS 4600) 60 parts Sodium polyacrylate 2 parts

28% ammonia water 10 parts Water 106 parts Fluorinated surfactant (Saflon S-111 manufactured by Asahi Glass) 0.51 part [0092] (E— 2) Preparation of coating solution for thermal recording layer

Example 8 A heat-sensitive recording layer coating liquid was prepared in the same manner as in (A-2).

[0093]

(F-2) Preparation of thermal recording material

The undercoat layer coating solution and the heat-sensitive recording layer coating solution prepared in (D-2) and (E-2) were applied to the undercoat layer coating solution and the heat-sensitive recording layer coating solution from below using a slide hopper type curtain coating device. In this order, a coating film of 4000 ml / min of the undercoat layer coating liquid and 400 Oml / min of the thermal recording layer coating liquid is formed at a coating speed of 20 Om / min at a coating speed of 20 Om / min. ² was coated on high quality paper and dried to prepare a heat-sensitive recording material. When the undercoat layer coating liquid and the heat-sensitive recording layer coating liquid of this example were mixed, the viscosity gradually increased with time.

[0094]

Example 10

[0095]

(G-2) Preparation of undercoat layer coating liquid

A coating solution for an undercoat layer was prepared in the same manner as in Example 9 (D-2).

[0096]

(H-2) Preparation of thermosensitive recording layer coating liquid

[0097]

(1-2) Preparation of protective layer coating liquid

A protective layer coating solution was prepared in the same manner as in Example 8 (B-2).

[0098]

(J-2) Preparation of thermal recording material

Using the slide hopper type curtain coating device, apply the undercoat layer coating solution, thermal recording layer coating solution and protective layer coating solution prepared in (G-2), (H-2) and (I-2) to the lower layer side. The flow rate per curtain width lm is 4000 ml / min for the undercoat layer, 4000 ml / min for the thermal recording layer, and the coating solution for the protective layer. Forming a 4000 ml / min coating film, 200 m coating speed The heat-sensitive recording material was prepared by applying the composition at 60 g / m ² on high quality paper at / min and drying. When the undercoat layer coating solution and the thermosensitive recording layer coating solution of this example were mixed, the viscosity gradually increased with time. Further, when the coating solution for the heat-sensitive recording layer and the coating solution for the protective layer in this example were mixed, the viscosity gradually increased over time.

[0099]

Example 1 1

(K-2) Preparation of lower ink receiving layer coating liquid

The mixed solution having the following composition was stirred with a homomixer to prepare a lower-ink receiving layer coating solution.

[0100]

Lower layer ink receiving layer coating liquid:

10% aqueous solution of polyvinyl alcohol 40 parts Emulsion of carboxyl-containing polymer that dissolves by reacting with 30% solids alkali

(San Nopco SN-Sicna 926) 5 parts Water 127 parts Fluorinated surfactant (Surflon S-111 from Asahi Glass) 0.04 parts [0101]

(L-2) Preparation of coating liquid for upper ink receiving layer

[0102]

Upper layer ink receiving layer coating liquid:

Synthetic amorphous silica (Tokuyama Fine Seal X37B) 21 parts

63% 10% aqueous polyvinyl alcohol solution Cationic polymer (Violet resin 1001 manufactured by Sumitomo Chemical Co., Ltd.)

14 parts

28% ammonia water 10 parts Water 92 parts Fluorosurfactant (Saflon S-111 manufactured by Asahi Glass) 0.002 parts [0103]

(M-2) Preparation of inkjet recording material

Apply the lower ink receiving layer coating liquid and upper ink receiving layer coating liquid prepared in (K-2) and (L-2) from the lower layer side using a slide hopper type curtain coating device. In the order of the ink receiving layer coating liquid, the flow rate per unit width of lm is 720 OmlZmin for the lower ink receiving layer and 210 Oml / m for the upper ink receiving layer.

A 1 n paint film was formed, coated on high-quality paper at 60 g / m ² at a coating speed of 40 m / min, and dried to prepare an ink jet recording material. When the coating liquid for the lower ink receiving layer and the coating liquid for the upper ink receiving layer in this example were mixed, the viscosity gradually increased with time.

[0104]

Comparative Example 7

Example 8 Instead of using 67 parts of an emulsion (Sannobuco SN-Thickener 926) containing a carboxyl group and dissolving by reacting with an alkali having a solid content of 30% in (A-2), 67 parts of water was used. A heat-sensitive recording material was produced in the same manner as in Example 8, except that 10 parts of water was used instead of 10 parts of 28% aqueous ammonia in (B-2). The viscosity of the coating solution for the heat-sensitive recording layer and the coating solution for the protective layer in this comparative example did not increase even when mixed.

[0105]

Comparative Example 8

Example 8 Instead of using 67 parts of a carboxyl-containing polymer emulsion (Sannobuco SN—Thickener 926) and 238 parts of water, which were dissolved in (A-2) by reacting with an alkali having a solid content of 30%, 10% Sodium alginate aqueous solution

200 parts and 105 parts of water were mixed, and 10 parts of calcium chloride was used instead of 10 parts of 28% ammonia water in (B-2) to prepare a coating solution for the heat-sensitive recording layer and a protective layer. The viscosity of the coating solution for the heat-sensitive recording layer and the coating solution for the protective layer in this comparative example instantly increased when mixed. The coating liquid for the heat-sensitive recording layer and the coating liquid for the protective layer of this comparative example were applied in a slide hopper type Using a device, a coating film with a heat-sensitive recording layer coating liquid of 4000 ml / min and a protective layer coating liquid of 4000 ml / min per unit width lm in order of thermal recording layer coating liquid and protective layer coating liquid from the lower layer side. However, a paint film could not be formed, and a thermal recording material could not be produced.

[0106]

Comparative Example 9

Example 9 Instead of using 10 parts of 28% ammonia water in (D-2), 10 parts of water was used, and in (E-2), a polymer containing a carboxyl group that was dissolved by reacting with an alkali having a solid content of 30% was used. A thermosensitive recording material was prepared in the same manner as in Example 9 except that 67 parts of water was used instead of 67 parts of Emulsion (San Nopco SN—Thickener 926). The viscosity of the undercoat layer coating liquid and the heat-sensitive recording layer coating liquid in this comparative example did not increase even when they were mixed.

[0107]

Comparative Example 10

Example 9 An undercoat layer coating liquid was prepared in the same manner as in (D-2). Next, instead of using 67 parts of a carboxyl-containing polymer emulsion (Sannobuco SN-Sicna-1 926) and 238 parts of water in Sickle Example 9 (E-2), which reacts with an alkali having a solid content of 30% and dissolves, A thermosensitive recording layer coating liquid was prepared in the same manner as in Example 9 except that 201 parts of a 10% aqueous solution of chitosan and water 104 were used. The viscosity of the undercoat layer coating liquid and the heat-sensitive recording layer coating liquid of this comparative example immediately increased upon mixing. Using the slide hopper type curtain coating device, the undercoat layer and the heat-sensitive recording layer coating liquid of this comparative example were applied in order from the lower layer side to the undercoat layer coating liquid and the heat-sensitive recording layer coating liquid. An attempt was made to form a paint film with a thermal recording layer coating liquid of 4000 ml / min and a protective layer coating liquid of 4000 ml / min. However, a paint film could not be formed, and a thermal recording material could not be produced.

[0108]

Comparative Example 11

Example 10 Instead of using 10 parts of 28% ammonia water in (G-2), 10 parts of water was used, and in (H-2), carboxy dissolved by reacting with an alkali having a solid content of 30% was dissolved. 67 parts of water was used instead of using 67 parts of emulsion polymer (Sannopuco SN-Signer 926) containing a polymer group, and 10 parts of water was used instead of using 10 parts of 28% ammonia water in (1-2). In the same manner as in Example 10, a thermosensitive recording material was produced. Even when the undercoat layer coating liquid and the heat-sensitive recording layer coating liquid of the present example were mixed, the viscosity did not increase, and even when the heat-sensitive recording layer coating liquid and the protective layer coating liquid of the present example were mixed, the viscosity was high. Did not change.

[0109]

Comparative Example 12

Example 11 Instead of using 5 parts of a carboxyl group-containing polymer emulsion (Sannopco SN-Sicina 926), which was dissolved in (K-2) by reacting with an alkali having a solid content of 30%, 5 parts of water was used. An ink jet recording material was produced in the same manner as in Example 11, except that 10 parts of water was used instead of using 10 parts of 28% ammonia water in (L-12). In addition, even when the coating liquid for the lower ink receiving layer and the coating liquid for the upper ink receiving layer in this example were mixed, the viscosity did not increase.

[01 10]

Comparative Example 13

Example 11 Instead of using 5 parts of a carboxyl group-containing polymer emulsion (Sannobuco SN-Sixna 1926) which reacts with an alkali having a solid content of 30% in (K-1 2) to dissolve, and 127 parts of water, Using 15 parts of 10% aqueous sodium alginate solution and 117 parts of water, and using 10 parts of calcium chloride instead of 10 parts of 28% ammonia water in (L-2), the lower layer ink receiving layer coating liquid and upper layer ink A coating liquid for a receiving layer was prepared. The viscosity of the lower-ink-receiving layer coating liquid and the upper-ink-receiving layer coating liquid of this comparative example immediately increased when mixed. The lower ink receiving layer coating liquid and the upper ink receiving layer coating liquid of this comparative example were applied to the lower ink receiving layer coating liquid and the upper ink receiving layer coating liquid in order from the lower layer using a slide hopper type curtain coating device. Attempts to form a paint film with a flow rate of 7200 ml / min for the lower ink receiving layer, and a coating of 210 OmlZmin for the upper ink receiving layer.However, a paint film could not be formed, and ink jet recording material was produced. Things could not be done.

[01 1 1] Test 4 Printing with thermal head on thermal recording material

The thermal recording materials prepared in Examples 8 to 10 and Comparative Examples 7, 9, and 11 were pulsed using a thermal facsimile printing tester (TH-PMD) manufactured by Okura Electric Co., Ltd. with a print head (LH4409) manufactured by TDK. Printed 5 cm wide and 5 cm long at 1.2 milliseconds and an applied voltage of 20 volts, and the density of the printed area was measured using a densitometer (Macbeth RD918). Further, the color development of the printed portion was visually observed. The results are shown in Table 4.

[0112]

Test 5 Barrier test of protective layer of thermal recording material

Pulses applied to the thermal recording materials prepared in Examples 8 and 10 and Comparative Examples 7 and 11 using a thermal facsimile printing tester (TH-PMD) manufactured by Okura Electric with a printing head (LH4409) manufactured by TDK. Two milliseconds, an applied voltage of 20 volts, and a 5 cm wide and 5 cm long print were performed. Next, castor oil was applied to the printed portion, and two hours later, the density of the portion where the castor oil was applied was measured using a densitometer (Macbeth RD918). The results are shown in Table 5.

[0113]

Test 6 Printing on ink jet recording material with ink jet printing The ink jet recording material produced in Example 11 and Comparative Example 12 was used with Seiko Epson's color jet printing material (PM750C). A black ink was used to print 5 cm wide and 5 cm long, and the density of the printed area was measured using a densitometer (Macbeth RD918). Further, the color development of the printed portion was visually observed. Table 6 shows the results.

[0114]

Table 4

[0 1 1 5]

Table 5

[0 1 1 6]

Table 6

[0 1 1 7]

In Tables 4 to 6, as shown in Examples 8 to 11, at least one pair of adjacent two layers constituting a coating film composed of a plurality of layers is a coating that becomes highly viscous over time when contacted or mixed. By forming the information recording layer by curtain coating the material film, it was possible to obtain an information recording material having good coating quality and excellent characteristics with high productivity.

[0 1 1 8]

In Comparative Example 7, the heat-sensitive recording layer and the protective layer were in a mixed state, so that only a low color density was obtained and the protective layer had very poor parier. In Comparative Example 8, when the coating liquid for the heat-sensitive recording layer and the coating liquid for the protective layer contacted each other on a slide hopper type coating head, the viscosity increased at the same time, and the fluidity of the coating liquid was lost. Was not generated, and a heat-sensitive recording material could not be obtained. In Comparative Example 9, The undercoat layer and the thermosensitive recording layer were mixed, and only a low color density was obtained. In Comparative Example 10, when the undercoat layer and the heat-sensitive recording layer coating solution were brought into contact with each other on the slide hopper type force coating head, the viscosity increased at the same time, and the fluidity of the coating solution was lost. Was not generated, and a heat-sensitive recording material could not be obtained. In Comparative Example 11, the undercoat layer and the heat-sensitive recording layer and the heat-sensitive recording layer and the protective layer were in a mixed state, so that only a low color density was obtained and the protective layer had very low parability. In Comparative Example 12, the lower ink receiving layer and the upper ink receiving layer were in a mixed state, and only a low color density was obtained. In Comparative Example 13, the lower ink-receiving layer and the upper ink-receiving layer contacted the heat-sensitive recording layer coating liquid on the slide hopper type coating head, and at the same time, the viscosity of the coating liquid increased, and the fluidity of the coating liquid was lost. No paint film consisting of layers was formed, and an ink jet recording material could not be obtained. [01 19]

Example 12

[0120]

(A— 3) Preparation of coating solution for thermal recording layer

Disperse a mixture of the following composition in a ball mill, and mix A-3-1, A-3-1, A-3-3 with an average particle size of 1 zm and 3-1-4 with a volume average particle size of 2 jnm. Obtained. [012 1]

A— 3-1 solution:

3-Dibutylamino-6-methyl-7-anilinofluoran 40 parts Polyvinyl alcohol 10% aqueous solution 20 parts Water 40 parts

[0 122]

A— 3— 2 liquids:

[0 123]

A— 3— 3 liquids: 2-Benzyloxy naphthene 80 parts Polyvinyl alcohol 10% aqueous solution 40 parts Water 80 parts

[0124]

A— 3— 4 liquids:

Calcium carbonate 80 parts Sodium polyacrylate 1 part Water 79 parts

[0125]

A-3-1, A-3-2, A-3-3, A-3-4 liquids obtained as above, 600 parts of 10% aqueous solution of polyvinyl alcohol, and 30% solids 67 parts of a polymer containing a carboxyl group (Sannobuco SN — Thickener _{9 26} ), which reacts and dissolves, 67 parts of water, 238 parts of water, and 0.67 parts of a fluorinated surfactant (SAFLON S-111 from Asahi Glass) The mixture was mixed to prepare a coating solution for the heat-sensitive recording layer having a surface tension of 3 OmN / m.

[0126]

(B-3) Preparation of protective layer coating liquid

A mixed solution having the following composition was dispersed in a ball mill to obtain a B-3 solution having a volume average particle diameter of 1 m.

[0127]

B—3 liquids:

Aluminum hydroxide 6 parts Sodium polyacrylate 0.1 part Water 13.9 parts [0128]

The B-3 solution obtained as above, 25 parts of 40% zinc stearate dispersion, 1000 parts of 10% aqueous polyvinyl alcohol, 10 parts of 28% aqueous ammonia, and 234 parts of water were mixed, and the surface tension was 35 mN / m. Was prepared.

[0129] (C-1 3) Preparation of thermal recording material

Apply the heat-sensitive recording layer coating solution and the protective layer coating solution prepared in (A-3) and (B-3) from the lower layer side using a slide hopper type 1 force-coating device from the lower layer side. In the order of the coating liquid, a flow rate per curtain width of 1 m forms a coating film of the thermal recording layer coating liquid of 4000 ml / min and the protective layer coating liquid of 400 Oml / min. It was coated on m2 ^high quality paper and dried to produce a heat-sensitive recording material. When the coating solution for the heat-sensitive recording layer of this example and the coating solution for the protective layer were mixed, the viscosity gradually increased with time.

[0130]

Example 13

[0131]

(D-3) Preparation of undercoat layer coating liquid

A mixed solution having the following composition was stirred with a homomixer to prepare a coating solution for an undercoat layer having a surface tension of 3 OmNm.

[0132]

Undercoat layer coating liquid:

100 parts of calcined kaolin

24 parts of 50% styrene butadiene copolymer latex

10% starch aqueous solution 60 parts Sodium polyacrylate 2 parts

28% ammonia water 10 parts Water 106 parts Fluorinated surfactant (Surflon S-111 manufactured by Asahi Glass Co.) 0.51 parts [0133]

(E-3) Preparation of coating solution for heat-sensitive recording layer

Example 12 (A-3) In the same conditions as in Example 12 (A-3), except that the fluorosurfactant (Surflon S-11 1 made by Asahi Glass) was changed to 0.67 parts without addition. A coating solution for the heat-sensitive recording layer having a surface tension of 4 OmN / m was prepared.

[0134] (F-3) Preparation of thermal recording material

The undercoat layer coating solution and the heat-sensitive recording layer coating solution prepared in (D-3) and (E-3) were applied to the undercoat layer coating solution and the heat-sensitive recording layer coating from the lower layer side using a slide hopper type curtain coating device. in order liquid curtain width lm per undercoat layer flow coating solution 4000 ml / min, the heat-sensitive recording layer coating solution 4000 ml Zm in the paint film is formed, at a coating speed 200 m / m in the 60 g / m ² A thermosensitive recording material was prepared by coating and drying on high quality paper. When the undercoat layer coating liquid and the heat-sensitive recording layer coating liquid of this example were mixed, the viscosity gradually increased with time.

[0135]

Example 14

[0136]

(G-3) Preparation of undercoat layer coating liquid

A mixed solution having the following composition was stirred with a homomixer to prepare a coating solution for an undercoat layer having a surface tension of 3 OmN / m.

[0137]

Undercoat layer coating liquid:

100 parts of calcined kaolin

24 parts of 50% styrene butadiene copolymer latex

10% starch aqueous solution 60 parts Sodium polyacrylate 2 parts Water 116 parts Fluorinated surfactant (Saflon S-111 manufactured by Asahi Glass) 0.51 part [0138]

(H-3) Preparation of heat-sensitive recording layer coating liquid

Under the same conditions as in Example 12 (A-3), a thermosensitive recording layer coating liquid having a surface tension of 30 mN / m was prepared.

[0139]

(1-3) Preparation of protective layer coating liquid

Example 12 A protective layer coating liquid having a surface tension of 35 mN / m was prepared under the same conditions as in (B-3). did.

[0140]

(J-1 3) Preparation of thermal recording material

Apply the undercoat layer coating solution, thermal recording layer coating solution and protective layer coating solution prepared in (G-3), (H-3) and (1-3) from the lower layer side using a slide hopper type curtain coating device. Undercoat layer coating solution, thermal recording layer coating solution, protective layer coating solution, in order of flow rate per tenth of lm, undercoat layer coating solution 400 Oml / min, thermal recording layer coating solution 4000 ml / min Then, a coating film of a protective layer coating liquid of 400 Oml / min was formed, coated on a high-quality paper of 60 g / m ² at a coating speed of 20 Om / min, and dried to prepare a heat-sensitive recording material. When the coating solution for the heat-sensitive recording layer of this example and the coating solution for the protective layer were mixed, the viscosity gradually increased over time.

[0141]

Example 15

(K-1 3) Preparation of coating liquid for lower ink receiving layer

The mixed solution having the following composition was stirred with a homomixer to prepare a lower-ink receiving layer coating solution having a surface tension of 35 mN / m.

[0142]

Lower ink receiving layer coating liquid:

Synthetic amorphous silica 28 parts 10% polyvinyl alcohol aqueous solution 40 parts Carboxyl-containing polymer emulsion that reacts and dissolves with 30% solids alkali

(Sannobuco SN-Thickna 926) 5 parts Water 127 parts Fluorosurfactant (Surflon S-111 manufactured by Asahi Glass) 0.04 parts [0143]

(L-3) Preparation of upper layer ink receiving layer coating liquid

A mixture having the following composition was stirred with a homomixer to prepare a coating liquid for an upper ink receiving layer having a surface tension of 40 mN / m. [0144]

Upper layer ink receiving layer coating liquid:

Synthetic amorphous silica 21 parts

63% 10% aqueous solution of polyvinyl alcohol Cationic polymer (Sumireze resin 1001 manufactured by Sumitomo Chemical Co., Ltd.)

14 parts

28% ammonia water 10 parts Water 90 parts Polyoxyethylene alkylphenol-based surfactant

(Nikko Chemical NP-20) 0.4 parts

[0145]

(M-3) Preparation of ink jet recording material

Coating liquid for lower ink receiving layer and upper ink receiving layer prepared in (K-1 3) and (L 1-3) Using a liquid slid hopper type curtain coating device, lower layer ink receiving layer coating liquid and upper layer ink receiving from lower layer side In the order of layer coating liquid, the flow rate per unit width of lm forms a coating film of lower ink receiving layer coating liquid 720 Oml / min and upper ink receiving layer coating liquid 210 Oml / min, coating speed 4 Om The ink was applied onto a high quality paper of 60 g / m ² at / min and dried to prepare an ink jet recording material. When the coating liquid for the lower ink receiving layer and the coating liquid for the upper ink receiving layer in this example were mixed, the viscosity gradually increased over time. [0146]

Comparative Example 14

[0147]

Example 12 In (A-3), 67 parts of water was used instead of 67 parts of an emulsion of a polymer containing a carboxyl group (Sannopco SN—Sicna 926) which dissolves by reacting with an alkali having a solid content of 30%. To prepare a coating solution for the heat-sensitive recording layer with a surface tension of 3 OmN / m, and apply a protective layer coating with a surface tension of 35 mN / m using 10 parts of water instead of 10 parts of 28% ammonia water in (B-3). A heat-sensitive recording material was prepared under the same conditions as in Example 12 except that a liquid was prepared. The viscosity of the coating solution for the heat-sensitive recording layer and the coating solution for the protective layer in this comparative example did not increase when mixed. [0148]

Comparative Example 15

[0149]

Example 13 Instead of using 10 parts of 28% aqueous ammonia in (D-3), using 10 parts of water, a surface tension of 3 OmN / m was prepared as an undercoat layer coating solution. Emulsion of a polymer containing a carboxyl group that dissolves by reacting with 0% alcohol (Sannobuco SN—Thickener 926) A thermosensitive recording layer with a surface tension of 4 OmN / m using 67 parts of water instead of 67 parts A heat-sensitive recording material was produced under the same conditions as in Example 13 except that a coating liquid of Example 13 was produced. The viscosity of the undercoat layer coating liquid and the heat-sensitive recording layer coating liquid of this comparative example did not increase even when mixed.

[0150]

Comparative Example 16

[0151]

Example 14 In Example 3 (H-3), instead of using 67 parts of a polymer containing carboxyl groups (Sannobuco SN-Sicina 926), which was dissolved by reacting with an alkali having a solid content of 30%, 67 parts of water was used. A thermosensitive recording layer coating solution with a surface tension of 3 OmN / m was prepared using the protective layer with a surface tension of 35 mN / m using 10 parts of water instead of using 10 parts of 28% ammonia water in (1-3). A heat-sensitive recording material was prepared in the same manner as in Example 14 except that a coating liquid was prepared. Even when the coating solution for the heat-sensitive recording layer of this example and the coating solution for the protective layer were mixed, the viscosity did not increase.

[0152]

Comparative Example 17

EXAMPLE 15 Instead of using 5 parts of a carboxyl group-containing polymer emulsion (San Nopco SN-Sicina 926) which reacts with an alkali having a solid content of 30% and is dissolved in (K-3), 5 parts of water is used. Prepare a lower layer ink receiving layer coating liquid with a surface tension of 35 mN / m, and use 10 parts of water instead of 10 parts of 28% ammonia water in (L-13) to receive an upper layer ink with a surface tension of 4 OmN / m. An ink jet recording material was prepared in the same manner as in Example 15 except that a layer coating liquid was prepared. In addition, even if the lower-ink-receiving layer coating liquid and the upper-ink-receiving layer coating liquid of the present example were mixed, high viscosity was not obtained. Was.

[0153]

Comparative Example 18

[0154]

Example 12 In Example (A-3), 67 parts of water was used instead of 67 parts of a carboxyl group-containing polymer emulsion (Sannopco SN-Thickna 926) which was dissolved by reacting with an alkali having a solid content of 30%. To prepare a coating solution for the heat-sensitive recording layer having a surface tension of 3 OmNZm. In (B-3), instead of using 10 parts of 28% ammonia water, use 10 parts of water, and further use a fluorinated surfactant (Saflon made by Asahi Glass). A thermosensitive recording material was prepared under the same conditions as in Example 12 except that 0.9 part of S-111) was added to prepare a protective layer coating solution having a surface tension of 25 mN / m. The viscosity of the heat-sensitive recording layer coating liquid and the protective layer coating liquid of this comparative example did not increase even when they were mixed.

[0155]

Comparative Example 19

[0156]

Example 13 Instead of using 10 parts of 28% ammonia water in (D-3), a coating solution for an undercoat layer having a surface tension of 30 mN / m was prepared using 10 parts of water. Emulsion of a polymer containing a carboxyl group that dissolves by reacting with 0% alcohol (San Nopco SN-Thickener 926) Instead of using 67 parts, use 67 parts of water and further use a fluorine-based surfactant (Asahi Glass Co., Ltd.) A heat-sensitive recording material was prepared under the same conditions as in Example 13 except that 1.4 parts of 1-fluorocarbon S-111) was added to prepare a coating solution for the heat-sensitive recording layer having a surface tension of 28 mN / m. The viscosity of the undercoat layer coating liquid and the heat-sensitive recording layer coating liquid of this comparative example did not increase even when they were mixed.

[0157]

Comparative Example 20

[0158]

Example 14 In Example (H-3), instead of using 67 parts of a carboxyl group-containing polymer emulsion (San Nopco SN—Sicna 926) which reacts and dissolves with an alkali having a solid content of 30%, 67 parts of water was used. Thermal recording with surface tension of 30 mN / m A recording layer coating solution was prepared, and instead of using 10 parts of 28% aqueous ammonia in (1-3), 10 parts of water was used, and a fluorochemical surfactant (Saflon S-111 manufactured by Asahi Glass) was added in 0.9. A heat-sensitive recording material was produced under the same conditions as in Example 14, except that a protective layer coating solution having a surface tension of 25 mN / m was produced by adding the same. It should be noted that even when the coating solution for the heat-sensitive recording layer and the coating solution for the protective layer of this example were mixed, the viscosity did not increase.

[0159]

Comparative Example 21

Example 15 Instead of using 5 parts of a carboxyl-containing polymer emulsion (Sannobuco SN-Sicina 926) which dissolves by reacting with an alkali having a solid content of 30% in (K-3), 5 parts of water was used. A lower-ink receiving layer coating solution with a surface tension of 35 mNZm was prepared using water, and instead of using 10 parts of 28% ammonia water in (L-3), 10 parts of water was used, and a polyoxyethylene alkylphenol-based surfactant was used. The ink jet recording material was prepared under the same conditions as in Example 15 except that 2 parts of (Nikko Chemical NP-20) were used instead of 0.4 part to prepare a coating liquid for the upper ink receiving layer having a surface tension of 28 mN / m. Produced. In addition, even when the coating liquid for the lower ink receiving layer and the coating liquid for the upper ink receiving layer were mixed in this example, the viscosity did not increase.

[0160]

Test 7 Printing with thermal head on thermal recording material

Example 12-14, Comparative Example 14-: Okura Electric Thermal Facsimile Printing Tester (TH-PMD) with TDK printing head (LH4409) on the thermal recording material prepared in L6, 18-20 With an applied pulse of 1.2 milliseconds and an applied voltage of 20 volts, printing was performed with a width of 5 cm and a length of 5 cm, and the density of the printed area was measured using a densitometer (Macbeth RD918). Further, the color development of the printed portion was visually observed. The results are shown in Table 7.

[0161]

Test 8 Pariah test of protective layer of thermal recording material

The thermal recording materials prepared in Examples 12 and 14 and Comparative Examples 14, 16, 18, and 20 were applied using a thermal facsimile printing tester (TH-PMD) manufactured by Okura Electric with a printing head (LH4409) manufactured by TDK. Pulse 1.2 ms, applied voltage 20 volts, Printing was performed with a width of 5 cm and a length of 5 cm. Next, the food wrap was brought into contact with the printed area, and after 6 hours, the density of the area where the food wrap was brought into contact was measured using a densitometer (Macbeth RD918). The results are shown in Table 8.

[0162]

Test 9 Writing with a water-based vane on thermal recording material

Examples 12 to: 14 and Comparative Examples 14 to 16, 18 to 20 The non-printed portions of the heat-sensitive recording materials were written with a water-based ben (Teranish Kagaku Kogyo pension pen black), and the writability was visually observed. The results are shown in Table 9.

[0163]

Test 10 Printing on inkjet recording material by ink jet printing The ink jet recording material manufactured in Example 15, Comparative Examples 17 and 21 was manufactured using a color jet printing product manufactured by Seiko Epson (PM750C). Using a black ink, printing was performed 5 cm in width and 5 cm in length, and the density of the printed area was measured using a densitometer (Macbeth RD918). Further, the color development of the printed portion was visually observed. The results are shown in Table 10.

[0164]

Table 7

[0165] Table 8

[0167]

Table 10

[0168]

In Tables 7 to 10, as shown in Examples 12 to 15, in the two layers of the uppermost layer and the lower layer adjacent to the uppermost layer constituting the paint film composed of a plurality of layers, the surface tension of the coating liquid of the uppermost layer is lower than that of the adjacent layer. Higher than the surface tension of the lower layer coating liquid, and the uppermost layer coating liquid and the adjacent lower layer coating liquid Curtain coating of a paint film that temporarily increases viscosity when it comes into contact with or mixes with it to form an information recording layer has made it possible to obtain high-performance information recording materials with good coating quality and high performance. .

[0 1 6 9]

In Comparative Example 14, the coating liquid for the protective layer was repelled on the coating liquid for the heat-sensitive recording layer, so that only a uniform color density was obtained and the barrier property of the protective layer was very low. In Comparative Example 15, the heat-sensitive recording layer coating solution was repelled on the undercoat layer coating solution, and uniform color development was not obtained. In Comparative Example 16, the coating liquid for the protective layer was repelled on the coating liquid for the heat-sensitive recording layer, and only a uniform color density was obtained, and the protective layer had very low "rear" property. In Example 17, the upper layer ink-jet receiving layer coating solution was repelled on the lower layer ink-jet receiving layer coating solution, resulting in uneven color development.Comparative Examples 18 to 20: Uniform color formation was obtained. However, since more surfactant was added to the uppermost layer of the coating solution, the writing performance with the water-based pen was poor.In Comparative Example 21, uniform color development was obtained, but the upper layer ink-receiving layer formed a coating solution. The color density was low due to the addition of many surfactants.

[0 1 7 0]

Example 16

[0 1 7 1]

(A-4) Preparation of coating solution for thermal recording layer

A mixture of the following composition was dispersed with a pole mill, and A-4-1 solution, A-4-2 solution, A-4-3 solution with volume average particle diameter of 1〃m and A- solution with marrow average particle size of 2 zm 4—4 liquids were obtained.

[0 1 7 2]

A—4-1 solution:

3-Dibutylamino-1 6-methyl-7-anilinofluorane 40 parts Polyvinyl alcohol 10% aqueous solution 20 parts Water 40 parts

[0 1 7 3]

A— 4-2 liquid: 4, 4'-bis (hydroxyphenyl) sulfone 80 parts Polyvinyl alcohol 10% aqueous solution 40 parts Water 80 parts

[0174]

A— 4— 3 liquids:

2-benzyloxynaphthalene 80 parts Polyvinyl alcohol 10% aqueous solution 40 parts Water 80 parts

[0175]

A— 4— 4 liquids:

Calcium carbonate (Callite SA manufactured by Shiroishi Kogyo) 80 parts Sodium polyacrylate 1 part Water 79 parts

[0176]

A-4-1 solution, A-4-2 solution, A-4-3 solution, A-4-4 solution, A-4-4 solution, 600 parts of 10% aqueous polyvinyl alcohol solution, 305 parts of water, fluorine 0.67 parts of a surfactant (Saflon S-111 manufactured by Asahi Glass) was mixed to prepare a coating solution for the heat-sensitive recording layer.

[0177]

(B-4) Preparation of protective layer coating liquid

A mixed solution having the following composition was dispersed by a ball mill to obtain a solution B having a volume average particle size of 1 m. [0178]

B—4 liquids:

Aluminum hydroxide (Heijilite H42 manufactured by Showa Denko) 6 parts Sodium phosphate 0.1 parts Water 13.9 parts

[0179]

Solution B-4 obtained as above, 25 parts of 40% zinc stearate dispersion, 1000 parts of 10% aqueous polyvinyl alcohol solution, 244 parts of water and fluorine-based surfactant 0.90 parts of (Saflon S-111 manufactured by Asahi Glass) were mixed to prepare a coating solution for a protective layer.

[0180]

(C-14) Preparation of thermal recording material

Have a slide Dohoppa type curtain coating apparatus immediately after the air knife coater, subsequently the equipment has a drying equipment, water over 60 g / m ² fine paper under the conditions of a coating speed 20 OmZmin Apply 30 gZm ² using an air-knife type coating device, and immediately apply the coating solution for heat-sensitive recording layer and protective layer prepared in (A-4) and (B-4) using a slide hopper type curtain coating device. , From the lower layer side, in order of the thermal recording layer coating liquid and the protective layer coating liquid, the flow rate per curtain width lm is 400 OmlZmin in the thermal recording layer coating liquid and 400 Oml / min of the protective layer coating liquid. Then, it was dried to produce a thermosensitive recording material.

[0181]

Example 17

(D-4) Preparation of aqueous polyvinyl alcohol solution

A mixture of the following composition was stirred with a mixer while heating with steam. When the temperature reached C, the mixture was only stirred with a mixer for 30 minutes, and then cooled naturally to 30 ° C to produce an aqueous liquid.

Polyvinyl alcohol (PVA 117 made by Kuraray) 5 parts Water 95 parts

[0182]

(E-4) Preparation of thermal recording material

It has a slide Dohoppa type curtain coating apparatus immediately after the air-one knife coater, followed by equipment having a drying equipment, on the quality paper of 60 g / m ² in terms of coating speed 20 Om / min The aqueous liquid prepared in (D-4) was applied at 30 g / m ² using an air-knife coating device, and immediately, the heat-sensitive recording layer coating liquid prepared in (A-4) and (B-4) was applied. Using a slide hopper type curtain coating device, the protective layer coating solution was applied from the lower layer side in the order of the thermal recording layer coating solution and the protective layer coating solution. min _N protective layer coating liquid 400 Oml / min coating film Formed, coated and dried to produce a thermosensitive recording material.

[0183]

Example 18

(F-4) Preparation of aqueous solution of styrene-butylene copolymer latex

A mixed liquid having the following composition was stirred by a mixer to prepare an aqueous liquid.

43% styrene-butadiene copolymer latex (Nippon Zeon LX 415 A) 11.6 parts Water 88.4 parts

[0184]

(G-4) Preparation of thermal recording material

Have a slide Dohoppa type curtain coating apparatus immediately after the air knife coater, subsequently to a drying facility are facilities, on fine paper of 60 g / m ² in terms of coating speed 20 Om / min Apply the aqueous liquid prepared in (F-4) at 30 g / m ² with an air-knife type coating device, and immediately apply the heat-sensitive recording layer coating liquid prepared in (A-4) and (B-4). Using a slide-paper type force-coating device, the flow rate of the heat-sensitive recording layer coating solution and the protective layer coating solution was measured in order from the lower side, and the flow rate per force width of lm was 400 ° C. A coating film of 4000 m1 / min was formed and applied, and dried to prepare a thermosensitive recording material.

[0185]

Example 19

(H-4) Preparation of aqueous starch liquid

A mixture of the following composition was stirred with a mixer while heating with steam.When the liquid temperature reached 90 ° C, the mixture was only stirred with a mixer for 30 minutes, and then cooled naturally to 30 ° C to produce an aqueous liquid. .

Phosphated starch (MS4600 manufactured by Japan Food Processing Co., Ltd.) 5 parts Water 95 parts

[0186]

(1-4) Preparation of thermal recording material

A slide hopper type curtain coating device is provided immediately after the air knife type coating device. And, subsequently to the facilities has a drying equipment, the air knife coater and the aqueous solution prepared in over 60 g / m ² fine paper under the conditions of a coating speed 20 OmZmin (H- 4) 30 g / m ² was coated Te, immediately (A- 4), the heat-sensitive recording layer coating solution prepared by (B-4), a protective layer coating solution by using a slide Dohoppa type curtain coating apparatus, the heat-sensitive recording from the lower side In the order of layer coating liquid and protective layer coating liquid, the flow rate per curtain width lm is heat-sensitive.Form a coating film of recording layer coating liquid 4000 ml / min and protective layer coating liquid 4000 ml / min. A recording material was produced.

[0187]

Example 20

(J-1 4) Preparation of aqueous solution of aluminum hydroxide

A mixed solution having the following composition was stirred with a homomixer to prepare a seven-component solution.

Sodium phosphate 0.1 part Aluminum hydroxide (Heijilite H42 manufactured by Showa Denko) 5 parts Polyvinyl alcohol (PVA 117 manufactured by Kuraray) 10% aqueous solution 5 parts Water 89.9 parts

[0188]

(K-1 4) Preparation of thermal recording material

Have a slide Dohoppa type force one polymethylpentene coating apparatus immediately after the air-one knife coater, subsequently the equipment has a drying equipment, 60 g / m ² fine paper under the conditions of a coating speed 20 Om / min 30 g / m ² coated with the aqueous solution by air one knife coater manufactured by (J-4) on the immediately (A- 4), a heat-sensitive recording Sonuri prepared in (B-4) Using a slide hopper type curtain coating device, the flow rate of the thermosensitive recording layer coating liquid and the protective layer coating liquid in the order of 1 m from the lower layer side was measured using a slide hopper type curtain coating device. A coating film of 1 / min, 400 Oml / min of coating liquid for the protective layer was formed and applied, and dried to prepare a thermosensitive recording material.

[0189]

Comparative Example 22

The heat-sensitive recording layer coating solution and the protective layer coating solution prepared in (A-4) and (B-4) were applied from the lower layer side using a slide hopper type curtain coating device. In the order of the liquid, a flow rate per curtain width of 1 m forms a coating film of 4000 ml / min of thermal recording layer coating liquid and 400 Oml / min of protective layer coating liquid. It was coated on m2 ^high quality paper and dried to produce a heat-sensitive recording material. [0190]

Comparative Example 23

(S-4) Preparation of coated base paper

The aqueous solution prepared in (D- 4), 30 gZm ² was coated on fine paper of 60 g / m ² in terms of coating speed 200 m / min by air one knife coating device of the coating apparatus, their It was dried as it was to produce a coated base paper.

[0191]

(T-1 4) Preparation of thermal recording material

Next, using only the slide hopper type curtain coating apparatus of the coating apparatus, the heat-sensitive recording layer coating liquid and the protective layer coating liquid prepared in (A-4) and (B-4) were used using a slide hopper type curtain coating apparatus. Then, from the lower layer side, in order of the thermal recording layer coating liquid and the protective layer coating liquid, a coating film with a flow rate of 400 Oml / min for the thermal recording layer and 400 Oml / min for the protective layer The thermosensitive recording material was formed on the coated base paper prepared in (S-4) at a coating speed of 20 Om / min and dried. [0192]

Comparative Example 24

(U-4) Preparation of coated base paper

(F- 4) the aqueous solution prepared in, 30 g / m ² coated on fine paper of 60 g / m ² in terms of coating speed 200 m / min by air one knife coating device of the coating apparatus Then, it was dried as it was to prepare a coated base paper.

[0193]

(V— 4) Preparation of thermal recording material

Next, using only the slide hopper type curtain coating device of the coating device, the heat-sensitive recording layer coating solution and the protective layer coating solution prepared in (A-4) and (B-4) were used by using a slide hopper type curtain coating device. The flow rate per 1 m width of the heat-sensitive recording layer is 4000 ml / min. A coating film of 400 Oml / min was formed, coated on the coated base paper prepared in (U-4) at a coating speed of 20 OmZmin, and dried to prepare a thermosensitive recording material.

[0194]

Comparative Example 25

(W-4) Preparation of coated base paper

Apply 30 g / m ^{2 of} the aqueous liquid prepared in (J-4) onto 60 g / m ² high-quality paper at a coating speed of 200 m / min using the air-knife coating device of the coating device. Then, it was dried as it was to prepare a coated base paper.

[0195]

(X-4) Preparation of thermal recording material

Next, using only the slide hopper type curtain coating apparatus of the coating apparatus, the heat-sensitive recording layer coating liquid and the protective layer coating liquid prepared in (A-4) and (B-4) were used using a slide hopper type curtain coating apparatus. Then, from the lower layer side, in order of the thermal recording layer coating liquid and the protective layer coating liquid, a coating film with a flow rate of 400 Oml / min for the thermal recording layer and 400 Oml / min for the protective layer The thermosensitive recording material was formed by applying it on a coating base paper prepared at (W-4) at a coating speed of 200 m / min and drying. [0196]

Test 11: Printing on thermal recording material with thermal head

The thermal recording materials prepared in Examples 16 to 20 and Comparative Examples 22 to 25 were applied with a 1.2 mm pulse by using a thermal facsimile printing tester (TH-PMD) manufactured by Okura Electric with a print head (LH4409) manufactured by TDK. Printing was performed for 5 cm in width and 5 cm in length for 20 seconds with an applied voltage of 20 volts, and the density of the printed area was measured using a densitometer (Macbeth RD918). Further, the color development of the printed portion was visually observed. The results are shown in Table 11.

[0197]

In Table 11, the print density was represented by the following criteria. ◎ indicates that the print density is particularly high, 〇 indicates that the print density is high, Δ indicates that the print density is practically feasible, X indicates that the print density is low, or that the print is not uniform and impractical. Is shown.

[0198] Table 11

[0 1 9 9]

Rating:

In Table 11, as shown in Examples 16 to 20, water or an aqueous liquid was applied to the surface on the side where the coating film was formed, and the coating film was immediately curtain-coated in an undried state to form an information recording layer. By forming, an information recording material having good coating quality and excellent various properties could be obtained with good productivity.

[0 2 0 0]

In Comparative Examples 22 and 25, the heat-sensitive recording layer and the protective layer were in a mixed state, and only a lower color density was obtained as compared with Examples 16 to 20. It was in a shaggy state. In Comparative Example 23, a high print density was obtained, but after coating with the air-knife type coating device at the production stage, drying once, and then using the slide hopper type curtain coating device with the heat-sensitive recording layer coating solution. The process of applying the coating liquid for the protective layer requires two separate applications, resulting in poor productivity. In Comparative Example 24, an aqueous coating was formed on the surface of the aqueous liquid, and the coating liquid for the heat-sensitive recording layer and the protective layer was prevented from spreading evenly.

[0 2 0 1]

Example 2 1

(L-1 4) Preparation of coating liquid for lower ink receiving layer A mixed solution having the following composition was stirred with a homomixer to prepare a lower-ink receiving layer coating solution.

Synthetic amorphous silica (Mizukasil P 78 D, manufactured by Mizusawa Chemical) 28 parts

10% aqueous solution of polyvinyl alcohol 40 parts Water 132 parts Fluorinated surfactant (Saflon S-111 manufactured by Asahi Glass) 0.04 parts

[0202]

(M-4) Preparation of coating liquid for upper ink receiving layer

Synthetic amorphous silica (Tokuyama Fine Seal X37B) 21 parts

10% Polyvinyl alcohol aqueous solution 63 parts Cationic polymer (Violet Resin 1001 manufactured by Sumitomo Chemical Co., Ltd.) 14 parts Water 102 parts Fluorinated surfactant (Surflon S-111 manufactured by Asahi Glass) 0.002 parts

[0203]

(N-4) Preparation of inkjet recording material

Have a slide Dohoppa type curtain coating apparatus immediately after the air knife coater, subsequently to a drying facility are facilities, on fine paper of 6 0 g / m ² in terms of coating speed 4 OmZm in Apply 30 g / m ^{2 of} water with an air-knife coating device, and immediately slide the lower ink receiving layer coating solution and upper ink receiving layer coating solution prepared by (L-14) and (M-4). Using a hopper-type curtain coating device, the flow rate per 1 m of curtain width was changed to 720 Oml / min for the lower ink receiving layer coating liquid from the lower layer side in the order of the lower ink receiving layer coating liquid and the upper ink receiving layer coating liquid. A coating film of 210 Om 1 / min was formed and applied to the upper layer ink receiving layer coating liquid, and dried to prepare an ink jet recording material.

[0204]

Example 22

(0-4) Preparation of ink jet recording material Have a slide Dohoppa type force one polymethylpentene coating apparatus immediately after the air-one knife coater, subsequently the equipment has a drying equipment, 6 Og / m ² of fine and conditions of a coating speed 40 m / m in 30 g / m ^{2 of} the aqueous liquid prepared in (D-4) was applied on paper with an air-knife type coating device, and immediately the lower ink receiving layer prepared in (L-4) and (M-4) Using a slide hopper-type curtain coating device, the coating liquid and the upper ink receiving layer coating liquid were applied in order from the lower layer side to the lower ink receiving layer coating liquid and the upper ink receiving layer coating liquid. A coating film of a lower ink receiving layer coating liquid of 7200 ml / min and an upper ink receiving layer coating liquid of 2100 ml / min was formed and applied, and dried to prepare an ink jet recording material.

[0205]

Example 23

(P— 4) Preparation of ink jet recording material

Immediately after the air-knife type applicator, there is a slide hopper type curtain applicator, followed by a drying facility.6 Og / m2 ^high quality paper at an application speed of 40 m / min. The aqueous liquid prepared in (F-4) was applied on the surface of the substrate with an air knife type coating device at 3 Og / m ² , and immediately the coating liquid for the lower ink-receiving layer prepared in (L-14) and (M-4) Using a slide hopper type curtain coating device, the upper ink receiving layer coating liquid is applied in order from the lower layer side to the lower ink receiving layer coating liquid and the upper ink receiving layer coating liquid, and the flow rate per curtain width lm is lower ink receiving layer. A coating film of coating liquid 720 Oml / min, upper layer ink receiving layer coating liquid 2100 ml / min was formed and applied, and dried to prepare an ink jet recording material.

[0206]

Example 24

(Q-4) Preparation of inkjet recording material

Immediately after the air-knife type applicator, there is a slide hopper type curtain applicator, followed by a drying facility, which is capable of coating 6 Og / m2 ^high quality paper at a coating speed of 40 m / min. (H- 4) with an aqueous solution to 3 Og / m ² coated with an air knife coater produced above, immediately (L-4), the lower ink-receiving layer coating solution prepared by (M-4), Slide hopper type curtain coating device for upper layer ink receiving layer coating liquid The flow rate per curtain width lm is 7200 ml / min for the lower ink receiving layer and the upper ink receiving layer coating liquid is 2100 ml / min in the order of the lower ink receiving layer coating liquid and the upper ink receiving layer coating liquid from the lower layer side. A / min paint film was formed, applied, and dried to produce an ink jet recording material.

[0207]

Example 25

(R-4) Preparation of inkjet recording material

Have a slide Dohoppa type force one polymethylpentene coating apparatus immediately after the air-one knife coater, followed by equipment having a drying equipment, high-quality paper of 6 Og / m ² in terms of coating speed 40 m / min (J-4) aqueous solution was 3 Og / m ² coating by air one knife coater and produced by over immediately (L-4), the lower ink-receiving layer coating prepared by (M-4) Using the slide hopper type curtain coating device, the lower ink receiving layer coating liquid and the upper ink receiving layer coating liquid in order from the lower layer. A coating film of an ink receiving layer coating liquid of 720 Oml / min and an upper ink receiving layer coating liquid of 2100 ml / min was formed, applied and dried to prepare an ink jet recording material.

[0208]

Comparative Example 26

The lower ink receiving layer coating liquid and the upper ink receiving layer coating liquid prepared in (L-4) and (M-4) were applied to the lower ink receiving layer coating liquid and the upper ink using a slide hopper type force coating device. The flow rate per curtain width lm is 7200 ml / min, the upper ink receiving layer coating liquid is 210 Oml /, and the flow rate per curtain width lm is lower ink receiving layer coating liquid from the lower layer side in order of lower ink receiving layer coating liquid and upper ink receiving layer coating liquid. A coating film of min. was formed, and 6 Og / m ^{2 was} applied under the conditions of a coating speed of 40 mZmin and dried to prepare an ink jet recording material.

[0209]

Comparative Example 27

(Y-4) Preparation of coated base paper

Apply the aqueous liquid prepared in (D-4) with the air knife coating device of the coating device At a speed of 40 m / min, 30 g / m ^{2 was} coated on high quality paper of 60 g / m ² and dried as it was to prepare a coated base paper.

[0210]

(Z-4) Preparation of inkjet recording material

Then, using only the slide hopper type force coating device of the coating device (L-4) and (M-4), the lower layer ink receiving layer coating solution and the upper layer ink receiving layer coating solution prepared by (M-4) were used as slide hopper type curtains. Using a coating device, the flow rate per 1 m of curtain width was 7200 ml / min for the lower ink receiving layer coating liquid, and the upper ink receiving layer coating liquid for the lower ink receiving layer coating liquid and the upper ink receiving layer coating liquid in order from the lower layer. A coating film of 210 Oml / min was formed, applied to the coated base paper prepared in (Y-4) at a coating speed of 40 m / min, and dried to prepare an ink jet recording material.

[02 11]

Comparative Example 28

(AA-4) Preparation of coated base paper

The aqueous solution prepared in (F-4), 30 g / m 2 coated on fine paper of 60 g / m ² in terms of coating speed 40 m / min by air one knife coating device of the coating apparatus Then, it was dried as it was to prepare a coated base paper.

[0212]

(AB-4) Preparation of ink jet recording material

Next, using only the slide hopper type curtain coating device of the coating device, the lower ink receiving layer coating solution and the upper ink receiving layer coating solution prepared by (L-14) and (M-4) were applied to the slide hopper type curtain coating device. The flow rate per 1 m of curtain width is the ink receiving layer coating liquid, and the flow rate per curtain width lm is the lower ink receiving layer coating liquid in the order of the lower ink receiving layer coating liquid and the upper ink receiving layer coating liquid from the lower layer side. A coating film of 720 Oml / min, upper ink receiving layer coating liquid of 210 Oml / min was formed, applied to the base paper prepared in (AA-4) at a coating speed of 4 Om / min, dried and dried. A jet recording material was prepared.

[0213]

Comparative Example 29 (AC-4) Preparation of coated base paper

The aqueous liquid prepared in (J-4) was applied at 30 g / m ² on a high-quality paper of 60 g / m ² at an application speed of 40 m / min using an air knife coating device of the coating device, It was dried as it was to produce a coated base paper.

[0214]

(AD-4) Preparation of ink jet recording material

Next, the coating liquid for the lower ink receiving layer and the coating liquid for the upper ink receiving layer prepared in (L-14) and (M-4) were prepared using only the slide hopper type force coating apparatus of the coating apparatus. Using a force coating device, the flow rate per curtain width lm is 720 Oml / min, and the upper ink is the lower ink receiving layer coating liquid and the upper ink receiving layer coating liquid in order from the lower layer. A coating film of the receiving layer coating liquid 210 OmlZmin was formed, applied to the base paper prepared in (AC-4) at a coating speed of 40 m / min, and dried to prepare an ink jet recording material.

[0215]

Test 12: Printing on ink jet recording material by ink jet pudding The ink jet recording materials prepared in Examples 21 to 25 and Comparative Examples 26 to 29 were replaced with a color jet pudding made by Seiko-Ebson (PM750C). 5 cm in width and 5 cm in length were printed with black ink, and the density of the printed portion was measured using a densitometer (Macbez RD918). In addition, the color development of the printed portion was visually observed. The results are shown in Table 12.

[0216]

In Table 12, the print density was represented by the following criteria. ◎ indicates that the print density and ink absorbency are particularly high, 〇 indicates that the print density and ink absorbency are high, Δ indicates that the print density and ink absorbency are practically possible, and X indicates the print density and ink absorbency. This indicates that ink absorption is low or printing is not uniform, making it impractical.

[0217] Table 1 2

[0 2 1 8]

Rating:

In Table 12, as shown in Examples 21 to 25, water or an aqueous liquid was applied to the surface on the side where the coating film was formed, and the coating film was immediately applied in an undried state to record information. By forming the layer, it was possible to obtain an information recording material having good coating quality and excellent various properties with good productivity.

[0 2 1 9]

In Comparative Example 26, as in Comparative Example 22, the lower ink receiving layer and the upper ink receiving layer were in a mixed state, and the color density was slightly lower. In Comparative Example 27, the absorptivity of the ink was deteriorated, and the print density was high but bleeding occurred. In Comparative Example 28, a hydrophobic film was formed on the surface of the aqueous solution, which prevented the lower-ink receiving layer coating solution and the upper-ink receiving layer coating solution from spreading evenly. Color unevenness was caused by repelling. In Comparative Example 29, the ink penetrated deeply into the recording material, resulting in lower color development.

[0 2 2 0]

Example 26

[0 2 2 1]

(A— 5) Preparation of coating solution for thermal recording layer

A mixture of the following composition was dispersed in a ball mill, and A- 5-1 A-5-2, A-5-3 liquid and A-5-4 liquid with volume average particle size were obtained. [0222]

A— 5— 1 solution:

3-Dibutylamino-6-methyl-17-anilinofluorane 40 parts Polyvinyl alcohol 10% aqueous solution 20 parts Water 40 parts

[0223]

A— 5— 2 liquids:

4, 4'-bis (hydroxyphenyl) sulfone 80 parts Polyvinyl alcohol 10% aqueous solution 40 parts Water 80 parts

[0224]

A— 5— 3 liquids:

[0225]

A— 5— 4 fluids:

[0226]

A-5-1, A-5-2, A-5-3, A-5-4 solution obtained as above, 600 parts of 10% aqueous solution of polyvinyl alcohol, 2260 parts of water, fluorinated surfactant (Saflon S-111 manufactured by Asahi Glass Co., Ltd.) 1. Four parts were mixed to prepare a heat-sensitive recording layer coating solution having a water content of 90%.

[0227]

(B-5) Preparation of protective layer coating liquid

Disperse a mixture of the following composition in a ball mill, and apply a B-5 solution with a volume average particle size of 1 m. Obtained.

[0228]

B—5 liquids:

Aluminum hydroxide (Heijilite H42 manufactured by Showa Denko) 6 parts Sodium polyacrylate 0.1 part Water 13.9 parts

[0229]

Solution B-5 obtained as described above, 25 parts of a 40% zinc stearate dispersion, 1000 parts of a 10% aqueous solution of polyvinyl alcohol, 244 parts of water, and a fluorine-based surfactant (Surflon S-111 manufactured by Asahi Glass) 0. 90 parts were mixed to prepare a protective layer coating solution. [0230]

(C-5) Preparation of thermal recording material

Using a slide hopper type curtain coating device, apply the heat-sensitive recording layer coating solution and the protective layer coating solution from the lower layer side using the heat-sensitive recording layer coating solution and the protective layer coating solution prepared in (A-5) and (B-5). in a flow rate thermosensitive recording layer coating solution per force one Ten width lm 9000MlZmin, paint film coercive Mamoruso coating liquid 400 Oml / mi n is formed, 60 g / m ² fine paper at a coating speed of 200 m / min Was coated on the substrate and dried to prepare a heat-sensitive recording material.

[0231]

Example 27

[0232]

(D-5) Preparation of lowermost layer coating liquid

A lowermost layer coating liquid having the following composition and a water content of 99.5% was prepared.

[0233]

Lowermost coating liquid:

Water 99.5 parts Fluorinated surfactant (Surflon S-111 manufactured by Asahi Glass) 0.5 part [0234]

(E-5) Preparation of coating solution for thermal recording layer

Example 26 Liquid A—5—1, A-5-2, A—5—3, Ec—5—4 of (A—5) E-5-1, E-5-2, E-5-3, and E-5-4 were prepared under the same conditions as above. E-5-1, Ε-5-2, E-5-3, E-5-4 solutions obtained as above, 600 parts of 10% aqueous polyvinyl alcohol, 305 parts of water, fluorinated surfactant ( 0.67 parts of Surflon S-111 manufactured by Asahi Glass Co., Ltd. were mixed to prepare a heat-sensitive recording layer coating solution having a water content of 77.5%.

[0235]

(F-5) Preparation of protective layer coating solution

A protective layer coating solution was prepared under the same conditions as in Example 26 (B-5).

[0236]

(G-5) Preparation of thermal recording material

The lowermost layer coating liquid, thermal recording layer coating liquid and protective layer coating liquid prepared in (D-5), (E-5) and (F-5) were applied from the lower layer side using a slide hopper type curtain coating device. In the order of lower layer coating liquid, thermal recording layer coating liquid, and protective layer coating liquid, the flow rate per curtain width lm is 2000 ml / min for the lowermost layer coating liquid, 4000 m 1 / min for the thermal recording layer coating liquid, and 4000 for the protective layer coating liquid. A coating film of in 1 / min was formed, coated on high-quality paper of 60 gm ² at a coating speed of 200 m / min, and dried to prepare a thermosensitive recording material.

[0237]

Example 28

[0238]

(H-5) Preparation of lowermost layer coating liquid

A lowermost layer coating solution having a water content of 90% having the following composition was prepared.

[0239]

Lowermost coating liquid:

Polyvinyl alcohol 9.5% aqueous solution 99.5 parts Fluorinated surfactant (Surflon S-111 manufactured by Asahi Glass) 0.5 part [0240]

(1-5) Preparation of coating solution for heat-sensitive recording layer

Example 27 Under the same conditions as in (E-5), a heat-sensitive recording layer coating liquid having a water content of 77.5% was prepared. [0241]

(J-1 5) Preparation of protective layer coating liquid

[0242]

(K-5) Preparation of thermal recording material

Apply the lowermost layer coating solution, heat-sensitive recording layer coating solution, and protective layer coating solution prepared in (H-5), (1-5), and (J-5) to the lower layer side using a slide hopper type force coating device. To the lowermost layer coating liquid, thermal recording layer coating liquid, and protective layer coating liquid, the flow rate per curtain width lm is 200 Oml / min for the lowermost layer coating liquid, 400 Oml / min for the thermal recording layer coating, and protection. forming a Sonuri liquid 4000 m 1 / min paint film, coated on fine paper of 60 g Zm ² at a coating speed 200 m / min, to prepare a heat-sensitive recording material is dried.

[0243]

Example 29

[0244]

(L-5) Preparation of lowermost layer coating liquid

A mixed solution having the following composition was stirred with a homomixer to prepare a lowermost layer coating solution having a water content of 90%.

Aluminum hydroxide (Heijilite H42, manufactured by Showa Denko) 10 parts Polyvinyl alcohol 10% aqueous solution 10 parts Fluorinated surfactant (Saflon S-111 from Asahi Glass) 0.5 part Water 95 parts

[0246]

(M-5) Preparation of coating solution for heat-sensitive recording layer

Example 27 Under the same conditions as in (E-5), a heat-sensitive recording layer coating liquid having a water content of 77.5% was prepared.

[0247]

(N-5) Preparation of protective layer coating liquid A protective layer coating solution was prepared under the same conditions as in Example 26 (B-5).

[0248]

(0-5) Preparation of thermal recording material

The lowermost layer coating liquid, thermal recording layer coating liquid and protective layer coating liquid prepared in (L-5), (M-5) and (N-5) were applied from the lower layer side using a slide hopper type curtain coating device. In the order of lower layer coating liquid, thermal recording layer coating liquid, and protective layer coating liquid, the flow rate per curtain width lm is the lowest layer coating liquid 2000 ml / min, thermal recording layer coating liquid 4000 ml / min protective layer coating liquid 4000 ml / min. A coating film of min was formed, coated on high-quality paper of 60 g / m ² at a coating speed of 200 m / min, and dried to prepare a heat-sensitive recording material.

[0249]

Example 30

[0250]

(AA-5) Preparation of coating liquid for lower ink receiving layer

A mixed solution having the following composition was stirred with a homomixer to prepare a lower layer ink receiving layer coating solution having a water content of 90%.

[0251]

Lower layer ink receiving layer coating liquid:

Synthetic amorphous silica (Mizukasil P78D manufactured by Mizusawa Chemical) 28 parts Polyvinyl alcohol 10% aqueous solution 40 parts Water 253 parts Fluorinated surfactant (Surflon S-111 manufactured by Asahi Glass) 0.08 parts [0252]

(BA-5) Preparation of coating liquid for upper ink receiving layer

A mixed solution having the following composition was stirred with a homomixer to prepare a coating liquid for an upper-ink receiving layer.

[0253]

Upper layer ink receiving layer coating liquid:

Synthetic amorphous silica (Tokuyama Fine Seal X37B) 21 parts

14 parts Water 102 parts Fluorosurfactant (Surflon S-111 manufactured by Asahi Glass) 0.002 parts [0254]

(CA-5) Preparation of ink jet recording material

The lower ink receiving layer coating liquid and the upper ink receiving layer coating liquid prepared in (AA-5) and (BA-5) were applied from the lower layer side to the lower ink receiving layer coating liquid using a slide hopper type curtain coating device. In the order of the upper ink receiving layer coating liquid, the flow rate per 1 m of curtain width is 11600 ml / min for the lower ink receiving layer coating liquid and 2100 ml / min for the upper ink receiving layer coating liquid, and the coating speed is 40. An ink jet recording material was prepared by coating on high quality paper of 60 g / m ² at m / min and drying.

[0255]

Example 31

[0256]

(DA-5) Preparation of lowermost layer coating solution

Under the same conditions as in Example 27 (D-5), a lowermost layer coating solution having a water content of 99.5% was prepared.

[0257]

(EA-5) Preparation of coating solution for lower ink receiving layer

A mixed solution having the following composition was stirred with a homomixer to prepare a lower-ink receiving layer coating solution having a water content of 84%.

[0258]

Lower layer ink receiving layer coating liquid:

Synthetic amorphous silica (Mizukasil P78D manufactured by Mizusawa Chemical) 28 parts Polyvinyl alcohol 10% aqueous solution 40 parts Water 132 parts Fluorosurfactant (Surflon S-111 manufactured by Asahi Glass) 0.04 parts [0259] (FA-5) Preparation of coating liquid for upper ink receiving layer

Example 30 A coating liquid for an upper ink receiving layer was prepared under the same conditions as in (BA-5). [0260]

(GA-5) Preparation of ink jet recording material

The lowermost coating solution, lower ink receiving layer coating solution, and upper ink receiving layer coating solution prepared in (DA-5), (EA-5) and (FA-5) were prepared using a slide hopper type curtain coating device. In order from the lower layer side, the lower layer ink receiving layer coating liquid and the upper layer ink receiving layer coating liquid, the flow rate per curtain width lm is the lowermost layer coating liquid 2000ml / min, the lower layer ink receiving layer coating liquid 7200ml / min, the upper layer ink receiving layer forming a coating film of the coating liquid 210 OmlZmin, coated on fine paper coating speeds 40 m / min at 60 g / m ^2, to prepare a Inkujiwetto recording material is dried.

[0261]

Example 32

[0262]

(HA-5) Preparation of the lowermost coating liquid

Example 28 A lowermost layer coating liquid having a water content of 90% was prepared under the same conditions as in (H-5). [0263]

(I A-5) Preparation of coating liquid for lower ink receiving layer

Under the same conditions as in Example 31 (EA-5), a coating solution for a lower ink receiving layer having a water content of 84% was produced.

[0264]

(JA-5) Preparation of coating liquid for upper ink receiving layer

A coating solution for an upper ink receiving layer was prepared under the same conditions as in Example 31 (FA-5). [0265]

(KA-5) Preparation of inkjet recording material

The lowermost layer coating solution, lower layer ink receiving layer coating solution, and upper layer ink receiving layer coating solution prepared in (HA-5), (IA-5) and (JA-5) were prepared using a slide hopper type curtain coating device. In the order of the lower ink receiving layer coating liquid and the upper ink receiving layer coating liquid from the lower layer side, the flow rate per force width lm is the lowermost layer coating liquid 200 Oml / min, the lower ink receiving layer The coating solution 720 Oml / mi n upper Inku receiving layer coating liquid 210 Oml / mi n paint film is formed, coated on fine paper of 60 gZm ² at a coating speed 40 m / mi n, Inkujietsuto recorded dried Materials were made.

[0266]

Example 33

[0267]

(LA-5) Preparation of lowermost layer coating solution

Example 29 A lowermost layer coating solution having a water content of 90% was prepared under the same conditions as in (L-5). [0268]

(MA-5) Preparation of coating liquid for lower ink receiving layer

Under the same conditions as in Example 31 (EA-5), a coating solution for a lower ink receiving layer having a water content of 84% was prepared.

[0269]

(NA-5) Preparation of upper ink receiving layer coating liquid

Example 30 A coating solution for an upper ink receiving layer was prepared under the same conditions as in (BA-5). [0270]

(OA-5) Preparation of ink jet recording material

The lowermost layer coating solution, lower layer ink receiving layer coating solution, and upper layer ink receiving layer coating solution prepared in (LA-5), (MA-5) and (NA-5) were prepared using a slide hopper type force coating device. The flow rate per curtain width lm is 200 Oml / min for the lowermost ink receiving layer and 720 Oml / mi for the lower ink receiving layer in order of the lower ink receiving layer coating liquid and the upper ink receiving layer coating liquid from the lower layer side. n, upper Inku receiving layer coating liquid 210 to form a coating film of OML / mi n, coated on fine paper coating speeds 40 m / min at 60 g / m ^2, to prepare a Inkujedzuto recording material was dried .

[0271]

Comparative Example 30

[0272]

(AB-5) Preparation of coating solution for heat-sensitive recording layer

Example 27 Under the same conditions as in (E-5), a heat-sensitive recording layer coating liquid having a water content of 77.5% was applied. Produced.

[0273]

(BB-5) Preparation of protective layer coating liquid

[0274]

(CB-5) Preparation of thermal recording material

Using a slide hopper type curtain coating device, apply the heat-sensitive recording layer coating solution and the protective layer coating solution in order from the lower layer side using the slide hopper type curtain coating device. in force one flow rate per ten width lm form a heat-sensitive recording layer coating solution 400 Oml / mi n, protective layer coating solution 400 Oml / mi n paint film, coating speed 20 Om / min with 60 g / m ² Was coated on a high-quality paper and dried to prepare a heat-sensitive recording material.

[0275]

Comparative Example 31

[0276]

(DB-5) Preparation of lowermost layer coating solution

A lowermost layer coating solution having the following composition and a water content of 80% was prepared.

[0277]

Lowermost coating liquid:

Polyvinyl alcohol 19.5% aqueous solution 99.5 parts Fluorinated surfactant (Surflon S-111 manufactured by Asahi Glass) 0.5 part [0278]

(EB-5) Preparation of coating solution for heat-sensitive recording layer

Under the same conditions as in Example 27, a thermosensitive recording layer coating liquid having a water content of 77.5% was prepared. [0279]

(FB-5) Preparation of protective layer coating liquid

[0280]

(GB-5) Preparation of thermal recording material

(DB-5), (EB-5), bottom layer coating liquid prepared with (FB-5), thermal recording Using a slide hopper type curtain coating device, the flow rate per curtain width lm of the coating liquid for the lowermost layer, the coating liquid for the heat-sensitive recording layer, and the coating liquid for the protective layer is applied in order from the lower layer side. lowermost layer coating liquid 2000 ml / min, the heat-sensitive recording layer coating solution 400 OML / min, coating film of the protective layer coating solution 400 Oml / mi n is formed, of 60 g / m ² fine paper at a coating speed of 200 m / min It was applied on top and dried to produce a thermosensitive recording material. [0281]

Comparative Example 32

[0282]

(HB-5) Preparation of lowermost layer coating liquid

A mixed solution having the following composition was stirred with a homomixer to prepare a lowermost layer coating solution having a water content of 80%.

[0283]

Lowermost coating liquid:

Hydride Aluminum (Heijilite H42, Showa Denko) 20 parts Polyvinyl alcohol 10% aqueous solution 20 parts Fluorosurfactant (Asahi Glass S-FLON S-111) 0.5 parts Water 72 parts

[0284]

(I B-5) Preparation of coating solution for thermal recording layer

Example 27 A coating solution for a heat-sensitive recording layer having a water content of 77.5% was prepared under the same conditions as in (E-5).

[0285]

(JB-5) Preparation of protective layer coating liquid

[0286]

(KB-5) Preparation of thermal recording material

Apply the lowermost layer coating liquid, thermal recording layer coating liquid and protective layer coating liquid prepared in (HB-5), (IB-5) and (JB-5) from the lower layer side using a slide hopper type curtain coating device. In the order of the lowermost layer coating liquid, thermal recording layer coating liquid, and protective layer coating liquid, the flow per curtain width lm Amount lowermost layer coating solution 2000 ml / min, the heat-sensitive recording layer coating solution 400 OML / min, coating film of the protective layer coating solution 400 OML / min to form, on fine paper of 60 gZm ² at a coating speed 200 m / min And dried to prepare a heat-sensitive recording material.

[0287]

Comparative Example 33

[0288]

(LB-5) Preparation of coating liquid for lower ink receiving layer

[0289]

(MB-5) Preparation of coating solution for upper ink receiving layer

Under the same conditions as in Example 30 (BA-5), a coating liquid for an upper ink receiving layer was prepared. [0290]

(NB-5) Production of inkjet recording material

The lower ink receiving layer coating liquid and the upper ink receiving layer coating liquid prepared in (LB-5) and (MB-5) were applied from the lower layer side to the lower ink receiving layer coating liquid using a slide hopper type curtain coating device. In the order of the upper ink receiving layer coating liquid, a flow rate per curtain width lm is 720 Oml / min for the lower ink receiving layer coating liquid and 210 Oml / min for the upper ink receiving layer coating liquid. Om / min was applied on high quality paper of 60 g / m ² and dried to prepare an ink jet recording material.

[0291]

Comparative Example 34

[0292]

(0B-5) Preparation of lowermost layer coating liquid

A lowermost layer coating liquid having a water content of 80% was prepared under the same conditions as in Comparative Example 31 (DB-5). [0293]

(PB-5) Preparation of lower ink receiving layer coating liquid

Under the same conditions as in Example 31 (EA-5), a coating solution for a lower ink receiving layer having a water content of 84% was prepared. [0294]

(QB-5) Preparation of coating liquid for upper ink receiving layer

Example 30 A coating solution for an upper ink receiving layer was prepared under the same conditions as in (BA-5). [0295]

(RB-5) Preparation of inkjet recording material

The lowermost coating solution, lower ink receiving layer coating solution, and upper ink receiving layer coating solution prepared in (OB-5), (PB-5) and (QB-5) were prepared using a slide hopper type curtain coating device. From the lower layer side, the lower layer ink receiving layer coating liquid and the upper ink receiving layer coating liquid in order of the flow rate per lm width of the lowermost layer coating liquid 2000 ml / min, lower ink receiving layer coating liquid 720 Oml / min, upper layer A coating film of the ink receiving layer coating liquid of 210 Oml / min was formed, coated on a high-quality paper of 60 g / m ² at a coating speed of 40 m / min, and dried to prepare an ink jet recording material.

[0296]

Comparative Example 35

[0297]

(SB-5) Preparation of lowermost layer coating solution

Under the same conditions as in Comparative Example 32 (HB-5), a lowermost layer coating solution having a water content of 80% was prepared. [0298]

(TB-5) Preparation of coating solution for lower ink receiving layer

A coating solution for an upper ink receiving layer was prepared under the same conditions as in Example 31 (EA-5). [0299]

(UB-5) Preparation of coating liquid for upper ink receiving layer

Example 30 A coating solution for an upper ink receiving layer was prepared under the same conditions as in (BA-5). [0300]

(VB-5) Preparation of inkjet recording material

The lowermost coating liquid, lower ink receiving layer coating liquid, and upper ink receiving layer coating liquid prepared in (SB-5), (TB-5), and (UB-5) were prepared using a slide hopper type curtain coating device. From the lower layer side, the lower layer ink receiving layer coating liquid and the upper layer ink receiving layer coating liquid in order, the flow rate per lm width of the lower layer coating liquid is 200 Oml / min, the lower layer ink receiving layer Coating liquid 720 OML / min, the upper ink-receiving layer coating solution 2100 ml / mi n paint film is formed, Inkujietsuto recording material coating, dried over fine paper of 60 gZm ² at a coating speed 40 m / min Was prepared.

[0301]

Test 13 Printing with thermal head on thermal recording material

The thermal recording materials prepared in Examples 26 to 29 and Comparative Examples 30 to 32 were applied with a 1.2 mm pulse by using a thermal facsimile printing tester (TH-PMD) manufactured by Okura Electric with a print head (LH4409) manufactured by TDK. Printing was performed with a width of 5 cm and a length of 5 cm at an applied voltage of 20 volts for a second, and the density of the printed portion was measured using a densitometer (Macbeth RD 918). Further, the color development of the printed portion was visually observed. The results are shown in Table 13.

[0302]

Test 14 Barrier test of protective layer of thermal recording material

The thermal recording materials prepared in Examples 26 to 29 and Comparative Examples 30 to 32 were applied with a pulse of 1.2 mm using a thermal facsimile printing tester (TH-PMD) manufactured by Okura Electric with a print head (LH4409) manufactured by TDK. Seconds, 5 cm wide and 5 cm long were printed with an applied voltage of 20 volts. Next, castor oil was applied to the printed area, and two hours later, the density of the portion where the castor oil was applied was measured using a densitometer (Macbeth RD918). Table 14 shows the results.

[0303]

Test 15 Printing on an ink jet recording material using an ink jet pudding The ink jet recording material prepared in Examples 30 to 33 and Comparative Examples 33 to 35 was used for printing using ink jet printing pulp (PM750C) manufactured by Seiko Epson. Printing was performed 5 cm in width and 5 cm in length with rack ink, and the density of the printed area was measured using a densitometer (Macbeth RD918). In addition, the color development of the printed portion was visually observed. The results are shown in Table 15.

[0304] Table 13

[0305]

Table 14

[0307]

In Tables 13 to 15, as shown in Example 26 33, The lowermost coating liquid constituting the coating film is coated with a coating film containing water of 90% by weight or more of the total weight of the coating solution by curtain coating to form an information recording layer, so that coating quality is excellent. An information recording material having excellent properties was obtained with high productivity.

[0 3 0 8]

In Comparative Examples 30 to 32, the heat-sensitive recording layer and the protective layer were in a mixed state, a low color density was obtained, and the barrier property of the protective layer was very low. In Comparative Examples 33 to 35, the lower ink receiving layer and the upper ink receiving layer were in a mixed state, and only a low color density was obtained.

[0 3 0 9]

卜の

According to the method of the present invention, an information recording material having particularly good coating quality and excellent properties can be manufactured with high productivity by a multilayer coating method using curtain coating. The information recording material obtained by the method of the present invention is used as a heat-sensitive recording material, an ink-jet recording material, a magnetic recording material, or the like.

Claims

The scope of the claims

1. In a method for producing an information recording material having an information recording layer provided on a support, an intermediate coating for isolating the two coating liquid films between the two coating liquid films whose viscosity increases upon contact or mixing. A method for producing an information recording material, characterized in that an information recording layer is formed by applying a plurality of layers of a paint film provided with a liquid film with force.

2. The method for producing an information recording material according to claim 1, wherein the information recording material is a thermosensitive recording material.

3. The method for producing an information recording material according to claim 1, wherein the Qian information recording material is an ink jet recording material.

4. In a method for producing an information recording material in which an information recording layer is provided on a support, a part or all of a plurality of layers constituting the information recording material is formed by curtain-coating a paint film composed of a plurality of layers. In producing the information recording material, at least one pair of adjacent two layers constituting a coating film composed of a plurality of layers to be coated with a coating is highly viscous over time when contacted or mixed. Method.

5. At least one pair of adjacent two layers constituting a paint film composed of a plurality of layers to be curtain-coated is composed of an uppermost layer and a lower layer adjacent thereto, and the surface of the coating liquid of the uppermost layer The method for producing an information recording material according to claim 4, wherein the tension is higher than the surface tension of the adjacent coating liquid.

6. The method for producing an information recording material according to claim 4, wherein the information recording material is a thermosensitive recording material.

7. The method for producing an information recording material according to claim 4, wherein the information recording material is an ink jet recording material.

8. In a method for manufacturing an information recording material having an information recording layer provided on a support, a method for forming a part or all of a plurality of layers constituting the information recording material by curtain coating a paint film comprising a plurality of layers. A method for producing an information recording material, wherein water or an aqueous liquid is applied to the surface of a support on which a coating film is to be formed, and the coating film is immediately formed by curtain coating in an undried state.

9. The method for producing an information recording material according to claim 8, wherein the information recording material is a thermosensitive recording material. Law.

10. The method for producing an information recording material according to claim 8, wherein the information recording material is an ink jet recording material.

1 1. In a method for manufacturing an information recording material having an information recording layer provided on a support, a part or all of a plurality of layers constituting the information recording material is formed by applying a paint film composed of a plurality of layers by curtain coating. Wherein the lowermost coating liquid constituting the coating film composed of a plurality of layers to be coated with the curtain contains water in an amount of 90% by weight or more of the total weight of the coating liquid. .

12. The method for producing an information recording material according to claim 11, wherein the information recording material is a thermosensitive recording material.

1 3. The method for producing an information recording material according to claim 11, wherein the information recording material is an ink jet recording material.

14. Two coating liquids that increase in viscosity when contacted or mixed, and an intermediate coating liquid J3 for isolating these coating liquid films. 4. The coating liquid used in the production method according to claim 1, comprising a combination with a coating liquid that does not increase viscosity.

15. Two coating liquids that have high viscosity when contacted or mixed are added as positively charged polymer compound and negatively charged low molecular compound, and negatively charged polymer compound. Reacts with positively charged low molecular compounds, positively charged high molecular compounds and negatively charged high molecular compounds, positively charged low molecular compounds and negatively charged low molecular compounds, or polyvalent metal ions 15. The coating liquid according to claim 14, wherein the coating liquid is separately contained so as to form a combination of high molecular compounds that are insolubilized by the application.

16. The coating liquid used in the production method according to any one of claims 4 to 5, comprising a combination of two coating liquids whose viscosity increases with time when contacted or mixed.

17. Two coating liquids, each containing as an additive, a combination of an emulsion and a polymer containing a carboxyl group that dissolves by reacting with an alkali so that they are separately included. The coating liquid according to claim 16.