WO1997015454A1

WO1997015454A1 - Non-carbon pressure-sensitive copy paper

Info

Publication number: WO1997015454A1
Application number: PCT/JP1996/003119
Authority: WO
Inventors: Nobuhiro Kagota; Hironori Wada
Original assignee: Mitsubishi Paper Mills Ltd.
Priority date: 1995-10-26
Filing date: 1996-10-25
Publication date: 1997-05-01
Also published as: JP3373213B2; DE19681069B4; DE19681069T1

Abstract

Non-carbon pressure-sensitive copy paper comprising a base; a cationic resin layer; an ink receiving layer containing a cationic resin and an inorganic pigment: a surface-treated layer coated with a solution having a specific Cobb sizing degree; and a pigment layer, all the layers being on the side for ink jet recording of the base. Alternatively, the paper comprises a base containing cationic resin, and a color former-containing microcapsule layer on the base opposite the side for ink jet recording. Ink jet recording can be carried out with excellent image density and image clarity without spoiling the characteristics as non-carbon pressure-sensitive copy paper. Moreover, ink dries fast and does not ooze out at a high humidity or due to adhesion of water droplets, so this no-carbon paper is suited to ink jet recording property.

Description

Description No-carbon pressure-sensitive copying paper

Technical field

The present invention relates to a carbonless pressure-sensitive copying paper having a pressure-sensitive recording function and an ink-jet recording function of forming a color image by a reaction between an electron-donating color former and an electron-accepting developer. More specifically, the present invention relates to the characteristics of carbonless pressure-sensitive copying paper when ink jet recording is performed using a water-based ink on the surface of the support opposite to the microforce layer of the carbonless pressure-sensitive copying paper. Ink jet recording with excellent image density and image clarity without impairing ink quality, as well as quick drying of ink and control of ink bleeding due to high humidity conditions or adhesion of water droplets The present invention relates to carbonless pressure-sensitive copying paper having good suitability. Skill

No-carbon pressure-sensitive copying paper is described in, for example, U.S. Pat.Nos. 2,505,470, 2,505,489, 2,548,366, 2,550,471, 2,712,507, 2,730,456, 2,730,457, 34,18250, and 34,182,050. As described in the specification of US Pat. No. 3,672,935, basically, an electron-donating color former (hereinafter, referred to as a color former) is dissolved in a high-boiling-point solvent and encapsulated in microcapsules. It contains an upper paper (hereinafter referred to as CB) coated with a coating layer containing it on the back surface of the support, and an electron acceptor (hereinafter referred to as a developer) which reacts with the color former to form a color. When the lower paper (referred to as CF) with the coating layer coated on the surface of the support is superimposed on each other and printed with an appropriate pressure, the color former flows out of the microcapsules containing the color former on the upper paper and transfers to the lower paper. The developer layer is colored and a copy image can be obtained simultaneously with printing under pressure.

When a large number of copies are desired, the above-described middle paper coated with the colorant-containing layer on the surface of the support and coated with the microcapsule-containing layer containing the color former on the back surface is used as the upper paper and the lower paper. The required number of sheets are inserted and used in between. In addition, a layer containing a microcapsule containing a color former and a layer containing a color developer were formed on the same surface of the support as a laminated or mixed layer. Plain paper transfer-type pressure-sensitive copying paper with a self-coloring type pressure-sensitive copying paper (self), a microcapsule containing a color former, a microcapsule containing a developer, and a coating layer containing wax on the back surface of the support is carbon-free. It is well known as one form of pressure copy paper. Many methods for producing microcapsules containing a color former are known, and representative methods include the following various methods.

(1) A coacervation method using a polyion complex of gelatin-arabia rubber (U.S. Pat. Nos. 2,804,577 and 2,800,558).

(2) An interfacial polymerization method in which an insoluble film is formed at an interface between a hydrophilic liquid serving as a dispersion medium and a hydrophobic liquid to be included.

(3) An in situ polymerization method in which an initial condensate such as melamine-formaldehyde resin or urea-formaldehyde resin is added from the side of the hydrophilic liquid serving as a dispersion medium, and then converted into a resin and converted into a capsule. No. 68, No. 47-231 165, Japanese Unexamined Patent Publication No. 48-57992, No. 51-0979, No. 54-25 27 No. 7 publication).

As microcapsules, synthetic resin capsules are frequently used because raw materials are supplied cheaply and stably, high-concentration microcapsules can be obtained, and the manufacturing process is simple.

Carbonless pressure-sensitive copying paper is used in a wide variety of applications, including office slips, delivery slips, unified slips, contract documents, and consumer paper. In general, forms are printed on a printing press after printing a large amount of the same pattern in a frame, and then setting the upper paper, medium paper, and lower paper, etc., to finish the form.However, different information for each set is printed at the same time as the frame printing. Recently, there has been an increasing demand for printing. This is also referred to as “variable information reprinting.” By installing a reprinting unit in a part of the printing press, it is possible to connect to the convenience store and read out personal information, barcodes, serial numbers, etc. Information is additionally printed continuously.

As this additional printing unit, an electronic photography method using a laser beam for writing and a jet recording method are known. Among them, the ink jet recording method has high printing accuracy, low noise, and high-speed printing. It has the characteristic that it can be used for multi-color printing. / P96 / 03119 In addition, for carbonless pressure-sensitive copying paper coated with a microcapsule such as a microcapsule containing a color former or a microcapsule containing a developer, the support on the side different from the microcapsule-containing layer Printing on the surface is generally performed, and in practice, it is performed by offset printing or letterpress printing. However, in such a printing method, pressure is applied to the support during printing, and a part of the microcapsules is destroyed, which may cause the generation of color stain. For this reason, it was necessary to select a printing method capable of reducing the pressure load on the support as much as possible. In particular, for plain paper transfer type carbonless pressure-sensitive copying paper containing a color former-containing microcapsule and a developer-containing microcapsule in the same coating layer, capsule destruction tends to appear as color stain, so printing on it Caution was required. The ink jet recording method records fine characters and the like by jetting small droplets of ink on a recording sheet, such as paper, based on various operating principles. The ink density is high, the color tone is bright and vivid, ink is absorbed quickly, ink does not flow out or bleeds even when printing dots overlap, and the printing dots spread more than necessary in the horizontal direction In addition to high image reproducibility such as not being large and the surrounding area being smooth and not blurred, from the viewpoint of storability, water droplets may be generated for some reason due to the storability of image quality under high humidity conditions and printed matter. The image is required to be water-resistant when it adheres and to be preserved for a long period of time, and to have image storability such that the image does not discolor or fade when exposed to light.

Due to such demands, some proposals have been made as to image quality for coated paper or high-quality paper dedicated to ink jet recording. For example, an ink-receiving layer serving as a void layer containing a silica-based pigment as a main component has been provided on the surface of the support to improve the ink absorption (Japanese Patent Application Laid-Open No. 52-9744). No. 58-172, 495, etc.). Further, in order to increase the ink absorption by the ink receiving layer and to obtain a print dot having a high print dot density and no ink bleeding, Japanese Patent Application Laid-Open Nos. -157 proposes to mix non-colloidal silica powder. Furthermore, focusing on the fact that the color and sharpness depend on the distribution state of the dye in the ink in the ink receiving layer, a proposal has been made to use a specific additive that adsorbs the dye component (Japanese Patent Application Laid-Open No. 554-1444). No. 2). Also, several methods have been proposed for improving the water resistance of dyes. For example, Japanese Patent Application Laid-Open No. Sho 56-84692 discloses a method of incorporating a polycationic polymer electrolyte into a surface, JP-A-55-150396 discloses a water-resistant method for forming a dye and a dye in a water-soluble ink. Further, in order to simultaneously improve the water fastness and light fastness of a dye, Japanese Patent Application Laid-Open No. Sho 61-13989 discloses an example of an ink jet recording sheet characterized by containing a basic oligomer. It is shown. Japanese Unexamined Patent Publication (Kokai) No. Sho 64-8085 discloses a recording material for ink jet recording in which water resistance and light resistance are improved by using a vinylamine copolymer containing no one unit of (meth) acrylic acid monomer. An example is shown.

However, ink jet printing on pressureless copying paper or reprinting by ink jet recording of variable information has just begun to be studied, and general no-carbon printing has been used. When ink jet printing is performed on pressure-sensitive copying paper, especially on the surface of the support opposite to the micro-pressurized layer of the upper paper, since there is no coating layer, image density, image sharpness, etc. The printing quality is poor, the ink has poor drying properties, and the ink oozes out under high humidity conditions and due to the adhesion of water droplets.

The present inventors have attempted to improve the ink jet printing suitability of a no-strength pressure-sensitive copying paper by the above-mentioned conventionally known technique, but without impairing the characteristics as a carbonless pressure-sensitive copying paper. Sufficient inkjet printability could not be obtained. Disclosure of the invention

Under such circumstances, the present invention provides a carbonless pressure-sensitive copying paper having a pressure-sensitive recording function and an ink-jet recording function of forming a colored image by the reaction between an electron-donating color former and an electron-accepting developer. When performing ink jet recording using a water-based ink on the surface of the support opposite to the microcapsule layer, the image density and image sharpness can be improved without impairing the characteristics of carbonless pressure-sensitive copying paper. Excellent ink jet recording is possible, as well as excellent ink jet recording, fast drying of ink, and suppression of ink bleeding due to high humidity conditions or adhesion of water droplets. In addition, it is an object of the present invention to provide a no-strength pressure-sensitive copying paper having suitability for high-speed printing and suitability for additional printing on a printing press.

The present inventors have conducted intensive studies to develop a carbonless pressure-sensitive copying paper having the above-mentioned excellent functions, and as a result, a color image was formed by a reaction between an electron-donating color former and an electron-accepting developer. Applying specific treatment to the surface of the support on the side where the ink jet recording is performed (the side opposite to the microcapsule-containing layer) in the non-pressure-sensitive pressure-sensitive copying paper having the pressure-sensitive recording function and the ink-jet recording function to be formed It has been found that the object can be achieved by the above or by performing a specific treatment on the support itself, and based on this finding, the present invention has been completed.

That is, the present invention

(1) A colorless image formed by the reaction between an electron-donating color former and an electron-accepting color developer. A non-carbon pressure-sensitive copying paper characterized in that a cationic resin layer is provided on the surface of a support on which recording is performed, and a layer containing microcapsules containing an electron-donating color former is provided on the other surface. ),

(2) A colorless image formed by the reaction between an electron-donating color former and an electron-accepting color developer.For carbonless pressure-sensitive copying paper having a pressure-sensitive recording function and an ink-jet recording function, A non-carbon pressure-sensitive copying paper characterized in that a microcapsule-containing layer containing an electron-donating color former is provided on one side of a support containing 1 to 10% by weight of a cationic resin. Invention),

(3) Ink jet recording is performed on a non-carbon pressure-sensitive copying paper having a pressure-sensitive recording function and an ink jet recording function, which forms a color image by the reaction between an electron-donating color former and an electron-accepting developer. Carbon-free pressure-sensitive copying characterized in that an ink receiving layer containing a cationic resin and an inorganic pigment was provided on the surface of the support on the side to be processed, and a microcapsule-containing layer containing an electron-donating color former was provided on the other surface. Paper (third invention),

(4) Forming a colored image by the reaction between an electron-donating color former and an electron-accepting color developer. Ink-jet recording side of carbonless pressure-sensitive copying paper having a pressure-sensitive recording function and an ink jet recording function. Using a surface weight treatment solution, a 5% by weight aqueous solution of isopropyl alcohol compliant with JISP 8140 is used. A carbon-free pressure-sensitive copying paper characterized in that a surface treatment layer having a second cup size of 20 to 60 g / m ² is provided, and a microcapsule-containing layer containing an electron-donating color former is provided on the other surface. Invention), and

(5) Forming a colored image by the reaction between an electron-donating color-forming agent and an electron-accepting color-developing agent. On the surface of the support on which recording is performed, a pigment coating layer with a 10-second cobb size of 20-80 g / m ² using a 5% by weight aqueous solution of isopropyl alcohol according to JIS P8140 is provided. Another object of the present invention is to provide a carbonless pressure-sensitive copying paper (fifth invention), which is provided with a microcapsule-containing layer containing an electron-donating color former. BEST MODE FOR CARRYING OUT THE INVENTION

The carbonless pressure-sensitive copying paper of the present invention (the first to fifth inventions) has a pressure-sensitive recording function of forming a color image by a reaction between an electrochromic coloring agent and an electron-accepting developer. Having a microcapsule-containing layer containing an electrogenic color-forming agent on one side of the support, and the other side having characteristics suitable for performing ink jet recording. have.

In addition, the ink jet printing in the present invention refers to printing on a drop-on-demand type / continuous type using a water-soluble ink by a printing machine such as a brin, a facsimile or a copier, or as part of a line of a form printing machine. Includes printing with an ink jet printer.

Further, examples of the pulp used for the support in the present invention include NBKP, LBKP, NBSP, LBSP, GP, TMP, waste paper, and the like. Use by mixing. Depending on the purpose, synthetic fibers can be incorporated. As a support for carbonless pressure-sensitive copying paper, one having a basis weight of about 30 to 100 g / m ² is generally used, and one having a basis weight of about 40 to 60 g / m ² is mainly used. Have been.

In addition, fillers such as kaolin, talc, calcium carbonate and titanium oxide, dyes, sizing agents, fixing agents, wet strength agents, dry strength agents, etc., commonly used in papermaking are also used. It can be used as needed.

Water-soluble inks used for ink jet recording usually use direct dyes or acid dyes.To improve the water resistance of the ink jet recording area, a reaction between the anionic portion of the dye and a cationic substance is required. Dye fixing and water resistance treatment are effective. However, in terms of the light fastness of the ink jet recording part, a low molecular weight, strong thione t, tertiary or quaternary cationic substance tends to promote the fading of the recording part. In addition, when a low molecular weight cationic substance was used, there was a tendency for the color image of the carbonless pressure-sensitive copying paper to fade (called a desensitizing effect) under long-term storage conditions.

Therefore, in order to improve image storability such as water resistance and light resistance of the ink jet recording section without impairing the color image formed on the carbonless pressure-sensitive copying paper, at least the ink jet recording is performed in the first invention. In the second invention, a cationic resin layer is internally added to the support, and in the third invention, a cationic resin layer is provided on the surface of the support on which ink jet recording is performed. An ink receiving layer containing a cationic resin and an inorganic pigment is provided.

The cationic resin used in the first, second and third inventions has a chemical structure of a primary to tertiary amine or a quaternary ammonium salt which dissociates when dissolved in water to exhibit a cationic property. Oligomer ゃ Polymer.

Examples of the cationic resin include dimethylamine / epiclorhydrin addition polymer, acrylamide / diarylamine salt copolymer, dimethyldiallylammonium chloride / S〇2 copolymer, and diarylamine salt. ₍₂ ) copolymer, dimethyldiarylammonium chloride polymer, polymer of arylamine salt, quaternary salt polymer of dialkylaminoethyl (meth) acrylate, polycondensate of dicyandiamide / formalin, polycondensate of dicyandiamide / diethylenetriamine, Examples thereof include a polyvinylamine copolymer, but are not limited thereto. Of these, particularly preferred examples include a dimethylamine / ebichlorohydrin addition polymer, an acrylamide / diallylamine salt copolymer, and a polyvinylamine copolymer.

As a polymer obtained by polycondensation of dimethylamine and epichlorohydrin The one having an average molecular weight of about 300 to 1000 is used.

As the polyvinylamine copolymer, those obtained by copolymerizing N-vinylformamide and acrylonitrile are preferable. In order to obtain sufficient water resistance, the content of vinylamine units is preferably at least 20 mol%. Further, in order to sufficiently obtain the fixing property of the polyvinylamine copolymer to the support or the coating layer, it is preferable that the average molecular weight is 500 000 or more.

The polyvinylamine copolymer used in the present invention is a polymer as exemplified in JP-A-58-23809 and JP-A-1-040694.

As monomers for producing a polyvinylamine copolymer, N-vinylacetamide, N-vinylpropionamide, N-methylvinylcarbamate, N-vinylcarbamic acid other than N-vinylformamide And isopropyl N-vinylcarbamate. In addition, monomers copolymerized with N-vinylformamide include (meth) acrylic acid esters of acrylonitrile, alcohols having 1 to 4 carbon atoms and (meth) acrylic acid, acrylamide, and (meth) acrylic acid. Acids and the like can be exemplified, and particularly preferred are acrylonitrile and acrylamide.

One of these cationic resins may be used, or two or more thereof may be used in combination.

In the carbonless pressure-sensitive copying paper of the first invention, a layer made of the above cationic resin is provided on the surface of the support on which ink jet recording is to be performed. A resin layer may be provided, and a microcapsule-containing layer containing a color former may be provided thereon.

When a cationic resin layer is provided on the surface of the support, a water-soluble polymer compound can be used together with the cationic resin, if desired. Examples of the water-soluble polymer compound include various starches or derivatives thereof, cellulose derivatives, polyvinyl alcohol or modified products thereof, polyacrylamide compounds, modified polyvinyl acetate products, and styrene-acrylic acid, or olefins. Examples include natural or synthetic various high molecular compounds such as polymers such as maleic acid, acrylic acid, and styrene-maleic acid. To provide a cationic resin layer on the surface of the support, an aqueous liquid containing the cationic resin and a water-soluble polymer compound used as desired is added to the aqueous solution containing Size Presco, Gaitor Co, Blade Co, It can be applied and dried using general methods such as Rodco overnight, Airknife night, Gravureco night, and Sprayco night.

Dry coverage to the support of the cationic resin, 0 per side. 1 to 2.0 range g / m ² is an appropriate amount, can not be obtained sufficient image water resistance when less than this, than this Even if it is increased, no further effect of improving the water resistance of the image can be obtained, and the preservation of the color image of the carbon-free pressure-sensitive copying paper may be impaired. Is also not preferred.

On the other hand, in the carbonless pressure-sensitive copying paper of the second invention, the support to which the cationic resin is internally added is used as the support, but the amount of the cationic resin to be added is 1 to 1 per pulp solid content. It is in the range of 10% by weight. If the internal addition amount is less than 1% by weight, sufficient image water resistance cannot be obtained. If the internal addition amount exceeds 10% by weight, the effect of improving image water resistance cannot be obtained for that amount. This may impair the storage stability of the color image, and is economically disadvantageous.

Further, in the non-strength one-pong pressure-sensitive copying paper of the third invention, an ink receiving layer containing the cationic resin and the inorganic pigment is provided on a surface of a support on which ink jet recording is performed, and Thereby, the effect of the cationic resin as a dye fixing agent becomes remarkable, and the water resistance is further improved. As the inorganic pigment, those generally used as coating pigments can be used, but it is preferable to use a pigment having a large specific surface area and a high liquid absorbing ability.

In particular, by using an ultrafine inorganic pigment having an average primary particle diameter of 100 nm or less as the inorganic pigment, the water resistance can be further improved. It is preferable to use an ultrafine inorganic pigment having a characteristic capable of adsorbing a dye in terms of image quality and color development.

Examples of the ultrafine inorganic pigment having an average primary particle diameter of 100 nm or less for use in the present invention include silica (colloidal silica), alumina or alumina hydrate (alumina sol, colloidal alumina, cationic aluminum oxide or the like). And surface-treated cationic colloidal silica, aluminum silicate, magnesium silicate, magnesium carbonate, and the like. It is more preferable if the primary particles are porous, but non-porous. Even if it is porous, it is preferable that it coagulates at the time of preparation of the coating liquid or coagulates at the time of coating and drying to form a porous surface coating surface on the pulp fiber surface.

These inorganic pigments may be used alone or in a combination of two or more.

In addition, in addition to the cationic resin and the inorganic pigment, the ink receiving layer may further include a surface sizing agent for improving printing density, resolution, printing durability, and the like, if desired, a water-soluble polymer binder, a dye, A fluorescent whitening agent, a dye fixing agent, a surface strength improver and the like can be contained. Here, examples of the surface sizing agent include polymers such as styrene-monoacrylic acid, olefin-maleic acid, acrylic acid, and styrene-maleic acid used in normal paper production. Examples of the water-soluble polymer binder include, for example, polyvinyl alcohol, modified polyvinyl acetate, silyl-modified polyvinyl alcohol, polyvinyl butyral, polymethyl methacrylate, polyurethane resin, unsaturated polyester resin, vinyl chloride monoacetate copolymer Synthetic resin binders such as alkyd resin, styrene-butadiene copolymer latex, methylmethacrylate tobutadiene copolymer latex, acrylic acid and methacrylic acid polymer or copolymer latex, ethylene vinyl acetate copolymer latex, etc. Aqueous binders such as thermosetting synthetic resins such as urea resins, oxidized starch, etherified starch, cellulose derivatives such as carboxymethylcellulose and hydroxyethyl cellulose, gelatin, large Bean proteins, casein and the like.

In order to provide an ink receiving layer on the surface of the support, an aqueous solution containing the above-described chaotic resin, inorganic pigment, and various optional components used as needed is subjected to a size press, a gel coater, a bill blade coater, It may be applied and dried using a general method such as a blade mailing size press, a short time dwell coater, a rod ditch, an air knife ditch, a power doodle ditch, or the like.

The coating amount of the ink受珲layer, 0. 5~ 1 0 g / m 2 range are preferred, particularly 2 / JP96 / 03119

A range of ~ 6 g / n ^ is preferred. Further, the content of the cationic resin in the ink receiving layer is preferably in the range of 10 to 50% by weight, and particularly preferably in the range of 20 to 30% by weight. Such an ink-receiving layer has excellent dye fixing properties, quick drying of the ink, and also has excellent water resistance and light resistance.

Next, in order to instantly dry the water-soluble ink used in ink jet printing immediately after ink jet printing, the ink must be quickly penetrated into the printing surface of the non-carbon pressure-sensitive copying paper, and the machine must be heated by hot air or microwaves. It is desirable to promote drying by a selective drying method.

In order to increase the ink permeability to the printing surface, in the fourth invention, the surface of the support on which the ink jet recording is performed is coated with a surface sizing solution using a 5 weight according to JISP 8140. A surface treatment layer having a 10 second cop size degree (hereinafter abbreviated as a 10 second cup size degree) of 20 to 60 g / m ² using a% isopropyl alcohol aqueous solution is provided.

Further, in order to improve the ink drying property and the printing quality, in the fifth invention, the 10-second cup sizing degree is set to 20 to 80 g / m 2 on the surface of the support on which the ink jet recording is performed. ² is provided.

Here, the 10-second cup size defines the cup size after 10 seconds according to JISP 8140. In the present invention, the ink having a high permeability and the ink for jet recording are used. As a model, a 5% by weight aqueous solution of isopropyl alcohol is used. The cup size is represented by the weight of the liquid to be absorbed and retained per unit area within a certain period of time.

In the fourth aspect of the present invention, when the 10-second cup size of the surface treatment layer is less than ² Og / m ^{2, the} drying speed is low and the water resistance of the ink-jet printed image is insufficient. Also, 6 0 g / m ^2. However fast drying speed after Inkujietsuto printing exceeds, fast coating liquid penetration due to micro turnip cell containing coating solution coating, coatability is insufficient, carbonless pressure-sensitive copying When used as paper, coloring stains are likely to occur, and the performance as carbonless pressure-sensitive copying paper is insufficient from the viewpoint of stain resistance. Drying of the ink, water resistance of the printed image, from the standpoint of stain resistance when used as carbonless pressure-sensitive copying paper, 1 0 seconds Cobb sizing degree is preferably in the range of 3 0~5 0 g / m ² . As a means for adjusting the 10-second cobbsizing degree, there are a method using an internally added sizing agent of the support and a method of providing a surface treatment layer.Either of these methods can obtain the intended effect. from the viewpoint of the effect, 1 0-second cup sizing degree by performing the surface sizing treatment 6 0~1 ² 0 g / m 2 about support and 1 0 seconds Cobb sizing degree 2 Less than six 0 g A method of providing a surface treatment layer of / m is adopted. By the 1 0-second Cobb sizing degree of the surface of the support itself and 6 0~ 1 2 0 g / m 2 extent, good comb absorbable Inkujiwe' preparative recording Inku to the support interior and surface treatment By setting the 10-second cup sizing degree of the layer to 20 to 60 g / n ^, the ink absorption on the ink-jet printing surface can be improved, and the ink can be used as a pressure-sensitive copying paper. Good stain resistance can be obtained.

Adjustment of the 10 second cup sizing degree on the surface of the support itself can be performed by using an internally added sizing agent. Here, as the internal sizing agent, a sizing agent such as a rosin emulsion size, an alkyl ketene dimer system, an alkenyl succinic acid system, and a petroleum resin system, which is used for ordinary acidic paper and neutral paper, is used. be able to.

In the fourth invention, as the surface sizing agent used in the surface sizing solution used for forming the surface treatment layer, those used in ordinary papermaking can be used. For example, various starches or derivatives thereof, cellulose derivatives Natural or synthetic polymers such as poly (vinyl alcohol) or modified products thereof, polyacrylamide compounds, modified polyvinyl acetate, styrene-monoacrylic acid, olefin-maleic acid, acrylic acid, styrene-maleic acid, etc. Various polymer compounds can be mentioned. One of these surface sizing agents may be used, or two or more thereof may be used in combination.

Examples of the method of providing a treatment layer on the surface of the support using the surface sizing agent treatment solution include Size Presco overnight, Gate Luco overnight, Blade co overnight, Rodco night, Air knife coater, Gravure Common methods such as overnight and spray can be used.

On the other hand, in the fifth aspect, the 10-second cob size of the pigment coating layer provided on the surface of the support is in the range of 20 to 80 g / m ² . If the 10-second cobb size is less than ²⁰ g / m ² , the ink drying property and water resistance of the image are poor, and if it exceeds 80 g / m ² , The coating suitability of the microcapsule-containing coating liquid becomes insufficient, and when used as a no-strength pressure-sensitive copying paper, coloring stains are likely to occur. Ink drying property, water resistance of the printed image, from the standpoint of stain resistance when used as carbonless pressure-sensitive copying paper, 1 0 seconds Cobb sizing degree of pigment coating layer 3 0~5 0 g / m ² Is preferable. Also in this case, similarly to the case of the fourth invention, a support having a surface with a 10-second cob size of about 60 to 120 g / m ² is preferably used.

Examples of pigments used in the pigment coating layer include heavy calcium carbonate, light calcium carbonate, calcium sulfate, kaolin, calcined kaolin, talc, aluminum hydroxide, aluminum silicate, magnesium oxide, magnesium carbonate, magnesium sulfate. And ordinary inorganic or organic white pigments such as zinc oxide, activated clay, finely divided silicic acid, titanium oxide, calcium silicate, and urea-formaldehyde resin. These may be used alone or in combination of two or more. Examples of binders used in the pigment coating layer include styrene-butadiene-based copolymer latex, acrylonitrile-butadiene-based copolymer latex, vinyl acetate-based, acrylic latex, and alkali-thickened latexes thereof. Tex, gelatin, albumin, casein, starch, arsenic starch, oxidized starch, etherified starch, esterified starch, sodium alginate, arabia gum, carboxymethylcellulose, polyvinyl alcohol, polyvinylpyrrolidone, polyacrylic acid, Polyacrylamide, ethylene-maleic anhydride copolymer, isobutylene-maleic anhydride copolymer, styrene-maleic anhydride copolymer, methylvinyl ether-maleic anhydride copolymer, methylcellulose, etc. Natural Or a water-soluble binder such as a synthetic or semi-synthetic polymer compound. These can be used alone or as a mixture of several types.

In order to form a pigment coating layer on the surface of the support, it is necessary to use the above pigment, binder and optional dispersant, surfactant, ultraviolet absorber, fluorescent brightener, thickener, defoamer, etc. A pigment coating solution containing various known additives is applied to a normal coating machine (coater), for example, Air Knife Co., Blade Co., Rod Co., Barco., Barco. The substrate may be coated with a substrate, a gate roll, an overnight, a size press, an gravure coater, a curtain coater or the like, and dried. The dry coating amount is usually 1 to 20 g / m ² , preferably 2 to 8 g / m ² .

Further, in the fourth and fifth inventions, as described in the first to third inventions, the water resistance of the ink jet recording unit can be improved without impairing the color image of the carbonless pressure-sensitive copying paper. To improve image storability such as light fastness, a cationic resin is added to the above surface sizing solution or pigment coating solution, and a cationic resin is added to the surface treatment layer or pigment coating layer formed on the support surface. It is preferable to include a resin. As the cationic resin, the same resins as those exemplified in the first to third inventions can be used. Further, dry coverage to the support surface of the cationic resin is 0. 1~2. O g / m 2 range is preferred. If the amount is less than 0.1 g / m ² , the effect of improving image storability may not be sufficiently exhibited, and if it exceeds 2.0 g / m ² , the coloring performance as carbonless pressure-sensitive copying paper. May be impaired.

In the carbon-free pressure-sensitive copying paper of the present invention (first to fifth inventions), the microcapsule-containing layer containing the electron-donating color former, which is provided on the surface of the support opposite to the side on which ink jet recording is performed, comprises It is composed of microcapsules containing a color former and binders used as needed, capsule protective agents, and various auxiliaries. Examples of the electron-donating color former used in the microcapsules include the following color formers known in the art.

(1) Triarylmethane compounds: 3,3-bis (p-dimethylaminophenyl) -16-dimethylaminophthalide (crystal 'violet' lactone), 3,3-bis (p-dimethylamino) Phenyl) phthalide, 3- (p-dimethylaminophenyl) 1-3- (1,2-dimethylindole-3-yl) phthalide, 3- (p-dimethylaminophenyl) 13- (2- Methylindole-3-yl) phthalide, 3- (p-dimethylaminophenyl) -1-3- (2-phenylindole-3-yl) phthalide, 3,3-bis-1- (1 , 2-Dimethylindole-3-yl) -1-5-dimethylaminophthalide, 3,3-bis (1,2-dimethylindole-3-yl) -16-dimethylaminophthalide, 3,3-bis (9-ethylcarbazole-1-3-yl) 5- dimethyl § amino phthalide, 3, 3-bis one

(2-Phenylindole-3-yl) -1-5-dimethylaminophthalide, 3-p-dimethylaminophenyl 3- (1-methylvirol-2-yl-6-dimethyl Such as ruaminophthalide,

(2) Diphenylmethane compounds: 4,4,1-bis-dimethylaminobenzhydrinbenzyl ether, N-halophenylleucouramine, N-2,4,5-trichlorophenylleucouramine, etc. ,

(3) Xanthene compounds: rhodamine B-anilinolactam, rhodamine B-p-di-troinilinolactam, rhodamine B-p-coupro-lo-anilinolactam, 3-getylamino-17-dibenzylaminofluoran, 3-getylamino One 7-octylaminofluoran, 3-getylamino-7-phenylfluoran, 3-getylamino-7-3,4-dichloroanilinofluoran, 3-getylamino-17- (2-chloroanilino) fluoran, 3- Getylamino-6-methyl-7-anilinofluoran, 3-piperidino 6-methyl-7-anilinofluoran, 3-ethylethyltriamino-1-6-methyl-17-, 2) nofluoran,

3-Ethyl tri-amino-6-methyl-7-phenethylfluoran, 3-methylethylamino 7- (412 troarilino) fluoran, etc.

(4) Thiazine compounds: benzoyl leucomethylene blue, p-nitrobenzoyl leucomethylene blue, etc.

(5) Spiro compounds: 3-methyl-1-spirodinaphthopyran, 3-ethylethylspirodinaphtopyran, 3,3'-dichlorospirodinaphtopyran, 3-benzylspirodinaphtopyran, 3-methylnaphthrophine naphthopyran, —Methoxyben V) —Spiropyran, 3-propylspirodibenzopyran, etc.

Further, the color formers described in JP-A-63-230387 and in "Colorants", Vol. 61, No. 5, pp. 292-302 (1988), "Dyes for pressure-sensitive recording paper" are also mentioned. Can be

Further, a coloring agent which produces a colored image having an absorption wavelength at 600 to 1000 nm can be used. These are described, for example, in Japanese Patent Publication Nos. 58-5940, 58-5940, 499-1479, 63-511113, 41-5064, 5065, and 5065. No. 5066, No. 4-1 5068, JP-A-51-90608, No. 62-243652, No. 62-257970, No. 62-288078, No. 63-102975, No. 63-37158, Id 63— 154389, 63-185684, JP-A-2-188291, 2-231190, 4-173288, 4-212882, 4-224991, 4-251785, 4-251785, 4 Compounds described in JP-A-272889 and JP-A-5-32040 can be exemplified.

These color formers may be used alone or in combination of two or more, depending on the use and desired properties, and may be used alone or in combination.

These color formers are usually encapsulated in a state of being dissolved in a hydrophobic medium, and the hydrophobic medium is not particularly limited as long as it is used for ordinary carbonless pressure-sensitive copying paper. To give a concrete example,

(a) Aromatic hydrocarbons: diarylethane, alkylbiphenyl, alkylphenyl, alkylnaphthylene, triarylmethane, diphenylalkane, hydroanthracene, hydrophenanthrene, dibenzyltoluene, etc.

(b) Mineral oil: kerosene, paraffin, naphthenic oil, chlorinated paraffin, etc.

(c) Vegetable oil: cottonseed oil, corn oil, coconut oil, etc.

(d) Alcohol: oleyl alcohol, tridecyl alcohol, benzyl alcohol, 1-phenylethyl alcohol, glycerin, etc.

(e) Organic acids: oleic acid, etc.

(f) Ester: dimethyl phthalate, getyl phthalate, di-n-butyl phthalate, dioctyl phthalate, getyl adipate, propyl adipate, di-n-butyl adipate, dioctyl adipate, etc.

(g) Organic phosphate compounds: tricresyl phosphate, tributyl phosphite, triptyl phosphite toxide, etc.

(h) Ethers: Phenylsitol Sorb, Benzyl Cavitol, Polypropylene glycol, Propylene glycol monophenyl ether, etc.

(i) Amide: N, N-dimethyllauramide, N, N-dimethylstearamide, N, N-dihexyloctylamide, etc.

(j) Ketone: diisobutyl ketone, methylhexyl ketone, etc.

(k) Alkyl carbonate: ethylene carbonate, propylene carbonate, etc. These hydrophobic media may be used alone or in combination of two or more depending on the application and desired properties, and may be used alone or in combination.

When the color former is microencapsulated, various components commonly used in conventional microcapsules of ordinary carbonless pressure-sensitive copying paper, for example, an ultraviolet absorber, a light stabilizer, an antioxidant, etc., may be added to the internal phase if desired. May be dissolved.

The microencapsulation method used in the present invention is not particularly limited, but microcapsules formed by a coacervation method using gelatin, gum arabic, etc., generally, when mixed with latex, the film is destroyed. Therefore, it is desirable to use the interfacial polymerization method, in situ polymerization method, or microbial microencapsulation method.

The emulsifier used for the ensitu polymerization encapsulation is preferably a polymer electrolyte. Specifically, styrene-maleic anhydride copolymer, styrene-benzyl methyl methacrylate-maleic anhydride copolymer, para-alkylstyrene-maleic anhydride copolymer, nucleus monoalkyl-substituted styrene-monomaleic anhydride Acid copolymer, nucleated dialkyl-substituted styrene-maleic anhydride copolymer, styrene-maleic anhydride monoalkyl ester copolymer, ethylene-maleic anhydride copolymer, polystyrenesulfonic acid, polyacrylic acid, acrylic acid-acrylic acid ester An aqueous solution of a copolymer or the like, or a mixed aqueous solution thereof is used.

The emulsifier used for the interfacial polymerization encapsulation may be an aqueous solution of polyvinyl alcohol, carboxymethylcellulose, hydroxyethyl cellulose, various starches (wheat, potato, corn, etc.), or a mixture thereof, in addition to the above-mentioned in situ encapsulation. Aqueous solutions are also used. Further, a known substance having a nonionic, cationic or zwitterionic surface activity may be added to such an extent that no problem occurs in the encapsulation step, and these substances may be used in combination.

The size (average diameter) of the microcapsules containing the color former used in the present invention is preferably in the range of 0.1 to 20 / m, particularly preferably in the range of 1 to 10 m. The coating amount of the color former is not particularly limited, but is preferably 5 to: L0000 mg / m2, particularly preferably 20 to 300 mg / m2, from the viewpoint of color development performance. It is in the range of ² . In order to form a layer containing microcapsules containing a color former on the surface of the support, it is usually necessary to use water. A method is used in which an aqueous coating solution is prepared, applied, and dried. The aqueous coating liquid is added to the color-encapsulating agent-encapsulated microcapsule dispersion obtained by the above method, if necessary, with a latex-based binder, a water-soluble binder, a capsule protective agent (stilt), a white pigment, a surfactant, It is prepared by adding various auxiliaries known in the art, such as foaming agents, thickeners, preservatives, coloring agents and the like. The content of capsules in the capsule coating liquid is usually adjusted to 5 to 80 parts by weight based on 100 parts by weight (solid part) of the coating liquid.

Specific examples of latex-based binders include styrene-butadiene-based copolymer latex, acrylonitrile-butadiene-based copolymer latex, vinyl acetate-based, acrylic latex, and alkali-thickened latexes thereof. Can be Examples of the water-soluble binder include gelatin, albumin, casein, starch, arsenic starch, oxidized starch, etherified starch, esterified starch, sodium alginate, arabia gum, carboxymethylcellulose, polyvinyl alcohol, polyvinyl alcohol, Polyacrylic acid, polyacrylamide, ethylene-maleic anhydride copolymer, ibbutylene-maleic anhydride copolymer, styrene-maleic anhydride copolymer, methyl vinyl ether-maleic anhydride copolymer, methyl cellulose, etc. Natural, synthetic or semi-synthetic polymer compounds, etc. c These may be used in combination. Usually, the amount of these used is preferably in the range of 5 to 100 solid parts by weight, particularly preferably in the range of 5 to 50 solid parts by weight, based on 100 parts by weight of micro force busel dry solids. .

As the capsule protective agent (stilt) used in the present invention, known ones such as wheat starch granules, corn starch granules, pea starch granules, various plastic pigments, and pulp powders are preferably exemplified. (Average diameter) is preferably in the range of 1 to 100 m, particularly preferably in the range of 15 to 3. When a white pigment is added to the microcapsule-containing layer, for example, calcium carbonate, aluminum hydroxide, zinc oxide, titanium oxide, kaolin, talc and the like can be used.

As for the coating method, the coating is performed using a normal coating machine (Koichi Yuichi). Specific coating machines include Air Knife Coater, Braider Coater, Rodco Coater, Bar Coater, Mouth Coater, Size Presco Coater, Gravureco Coater, Rikko Co., Ltd. Or the like is used. The developer used in combination with the carbonless pressure-sensitive copying paper according to the present invention is a carbon-free pressure-sensitive copying paper having a coated layer. The developer is coated on a support as an aqueous or non-aqueous coating liquid. An aqueous coating solution is usually used. In addition to the developer, various known auxiliaries such as binders, pigments, dispersants, surfactants, ultraviolet absorbers, fluorescent brighteners, thickeners, and antifoaming agents are added to the coating liquid. Then, it is coated on the support using the coating machine as described above.

Examples of the electron-accepting color developer include, but are not particularly limited to, compounds having a phenolic hydroxyl group, inorganic solid acid compounds, organic solid acid compounds, and the like. The well-known thing used is mentioned. For example, a novolak type phenol resin and its polyvalent metal salt, a salicylic acid derivative and its polyvalent metal salt, a salicylic acid resin and its polyvalent metal salt and the like can be mentioned.

The salicylic acid derivative is a compound having at least one aromatic substituent, specifically, 3-phenylsalicylic acid, 5-phenylsalicylic acid, 3-benzylsalicylic acid, 5-benzylsalicylic acid, 3— ( Methylbenzyl) salicylic acid, 5 — (Hi-methylbenzyl) salicylic acid, 3 -— (hi, hi-dimethylbenzyl) salicylic acid, 5 — (hi, hi-dimethylbenzyl) salicylic acid, 3,5-diphenyl salicylic acid, 3,5-di (1-methylbenzyl) salicylic acid, 3,5-dibenzyl salicylic acid, 3,5-di (α, "-dimethylbenzyl) salicylic acid, 3,5-di (4-methylbenzyl) salicylic acid, etc. And polyvalent metal salt compounds thereof can also be used.

As the salicylic acid resin and its polyvalent metal salt, all of the above-mentioned compounds can be used. For example, the salicylic acid derivative and styrene, o.mp-methylstyrene, hexamethylstyrene, 5-methylstyrene, etc. And a polyvalent metal salt of a salicylic acid resin obtained by a Friedel-Crafts reaction of a styrene derivative having a molar ratio of 1: 0.5 to 10 under a strong acid catalyst. Examples of the polyvalent metal include Ca, Mg, Al, Zn, and Mn, and the use of a zinc salt is most preferable. These developers may be used in combination of two or more.

Examples of the pigment used in combination with the color developing agent include heavy calcium carbonate, light calcium carbonate, calcium sulfate, kaolin, calcined kaolin, talc, and hydroxide hydroxide. Normal inorganic or organic white pigments such as lumidium, aluminum silicate, magnesium oxide, magnesium carbonate, magnesium sulfate, zinc oxide, activated clay, finely divided silica, titanium oxide, calcium silicate, urine-formaldehyde resin, etc. Are mentioned. These developers and pigments are applied on a support together with an adhesive as needed.However, an intermediate coating layer composed of a pigment, an adhesive, and the like is formed on the support to provide a developer layer. Is also good.

The amount of the developer coating solution applied to the support and the content of the developer in the developer coating layer are not particularly limited, but usually, from the viewpoints of color developing performance and economy, The coating amount is preferably 2 to 20 g / m ² , more preferably 3 to 15 g / m ² , and the content of the color developer in the coating layer is preferably 2 to 80% by weight. More preferably, it is 5 to 40% by weight.

The carbonless pressure-sensitive copying paper of the present invention also includes plain paper transfer-type carbonless pressure-sensitive copying paper, and the plain paper transfer-type carbonless pressure-sensitive copying paper includes a color former, a microcapsule, and a microcapsule. A coating layer was formed using microcapsules containing a colorant, wax, and other additives as necessary. Since the coloring agent and the developing agent are separately microencapsulated and mixed in the same coating layer, coloring stains are likely to occur due to relatively weak pressure, and in particular, there is a tendency for stains to occur easily due to pressure during printing. The use of the ink jet recording method has made it possible to prevent the occurrence of coloring stains.

The microcapsules enclosing a color former can be obtained by the above-mentioned materials and methods, and the microcapsules encapsulating a developer can be obtained by microencapsulating the above-mentioned developer by a usual method. As the color developer, a novolak-type phenol resin, a salicylic acid derivative, a salicylic acid resin, or a polyvalent metal salt thereof is preferable as the color developer in terms of color development and ease of microcapsulation.

Examples of waxes include animal waxes such as confidential, whale, Chinese, lanolin, candelilla wax, carnauba wax, wood, rice wax, and other plant waxes, montan wax, ozokerite, Mineral waxes such as ceresin, paraffin wax, petroleum-based waxes such as microcristine phosphorus wax, montan wax derivatives, paraffin wax derivatives, microcriss / Saturation of modified waxes such as phosphorous wax derivatives, hydrogenated waxes such as caster wax and opal wax, low molecular weight polyethylene waxes and their derivatives, stearic acid amide, behenic acid amide ethylene bis stearic acid amide, etc. Examples include fatty acid amide waxes, unsaturated fatty acid amides such as oleic acid amide, linoleic acid amide, ricinoleic acid amide, and linolenic acid amide.

Further, a polyvinyl ether-based compound can be added as needed. The amount of addition is preferably from 0.01 to 10% by weight, particularly preferably from 0.01 to 5% by weight, based on the entire coating layer. As a result, it is possible to reduce unnecessary color stains on the coating layer surface generated after the press printing.

As the water-soluble ink used for performing ink jet printing on the carbonless pressure-sensitive copying paper of the present invention, a general ink commercially available together with an ink jet printer can be used. Such a water-soluble ink contains at least one selected from a water-soluble acid dye and a water-soluble direct dye as a dye, and if necessary, further includes a wetting agent, a dye dissolving agent, a preservative, and a fungicide. Etc. are contained.

As the above-mentioned water-soluble dye, a dye having an anionic water-soluble group such as a sulfonic acid group in the dye molecule is generally used. Such an ink is applied to the surface of the support of the carbonless pressure-sensitive copying paper of the present invention. When adhering to or adsorbing to the surface, the anion groups in the ink and the cations of the cationic resin on the surface of the support are combined to form an insoluble salt, thereby improving the water resistance of the image and improving the light resistance. Conceivable.

Next, the present invention will be described in more detail with reference to examples, but the present invention is not limited to these examples.

The properties of the pressure-sensitive copying paper were evaluated according to the following methods.

(1) Water resistance

Using a color ink jet printer Yuichi (trade name: MJ-700 V2C, manufactured by Epson), characters and S-line printing were performed with black ink on the surface different from the colorant coating layer, and that part was printed. One drop of distilled water was dropped, left to dry, and the degree of bleeding was visually determined. The evaluation criteria are as follows: A is good, fairly good, B is practically acceptable, C is practically problematic, and D is poor. (2) Light fastness

Using a color ink jet printer (trade name: MJ-700V2C, manufactured by Epson Corporation), characters and X-rays are printed with black ink on the surface different from the colorant coating layer, and the printed surface is exposed to sunlight for 8 hours. After exposure, the degree of fading was visually determined. As evaluation criteria, A is good, B is practically acceptable, C is slightly practical, and D is poor.

(3) Print bleed

Character printing was performed using black ink on a surface different from that of the color former coating layer using a color ink Bling Yuichi (trade name: MJ-700V2C, manufactured by Epson Corporation), and bleeding of the printing was visually determined. . As the evaluation criteria, A is good, B is practically acceptable, C is somewhat practical, and D is poor.

(4) Storage

The upper paper obtained in Examples and Comparative Examples was superimposed on commercially available paper under the pressure of carbonless copying paper (Mitsubishi NCR Paper N-40, manufactured by Mitsubishi Paper Mills), and after printing with a typewriter, two sheets were set. And left under the conditions of 40 ° 80% RH. Twelve hours later, the color fading of the colored characters by a typewriter printing was visually determined. As the evaluation criteria, A is good, B is at a level that is practically acceptable, C is somewhat practical, and D is unsatisfactory.

(5) Dryness

Immediately after printing on a different surface from the colorant-coated layer using a color ink jet printer (trade name: MJ-700V2C, manufactured by Epson Corporation), use a finger to print the characters and lines printed with black ink. The degree of rubbing and drying was visually determined. As evaluation criteria, A is good, fairly good, B is practically acceptable, C is practically acceptable, and D is poor.

(6) Print density

Using a color ink jet printer (trade name: MJ-700V2C, manufactured by Epson Corporation), printing was performed with black ink on the surface different from the color former coating layer, and the print density was visually judged. As the evaluation criteria, A is good, B is practically acceptable, C is somewhat practical, and D is poor. (7) Cup size

The cup sizing degree was determined based on the pressure-sensitive paper base paper provided with the support surface and the surface treatment layer, and the pressure-sensitive paper base paper provided with the pigment coating layer, by the method based on JISP 8140, by 5% by weight isopropyl alcohol. The cup size after 10 seconds was measured using an alcohol aqueous solution.

(8) Stain resistance

The superposed pressureless copying paper obtained in Examples and Comparative Examples and Ichisaka's Noichi Carbon pressure-sensitive copying paper under paper (Mitsubishi NCR Paper N-40, manufactured by Mitsubishi Paper Mills) were overlaid. Rubbing was performed with a load of 00 g / cm ² applied, and the stain on the lower paper side was visually determined. As evaluation criteria, A is good, fairly good, B is practically acceptable, C is practically acceptable, and D is poor.

Preparation Example 1

Preparation of microcapsule solution containing color former

As a coloring agent, 4 parts by weight of 3,3-bis- (p-ethylaminophenyl) -16-dimethylaminophthalide was used as a diarylbenzene solvent (Hisol SASN-296: Nippon Petrochemical Co., Ltd.) 9 A hydrophobic solution dissolved in 6 parts by weight was prepared. To 220 parts by weight of a 5% by weight aqueous solution of styrene-maleic anhydride copolymer, 180 parts by weight of the above-mentioned hydrophobic solution was gradually added under strong stirring, and 50% by weight of Coulter / Counter was added. Stirring was continued until the volume average diameter became 5 xm to obtain an emulsion. Separately, an aqueous solution of a melamine-formaldehyde precondensate obtained by heating and dissolving 11 parts by weight of melamine, 21 parts by weight of a 37% by weight aqueous solution of formaldehyde and 28 parts by weight of water is added to the emulsion, and . The mixture was stirred at a temperature of C for 2 hours to prepare a microcapsule solution containing a coloring agent. Preparation Example 2

m Preparation of microcapsule solution

As a developer, 60 parts by weight of p-phenylphenol-formalin resin was dissolved in 140 parts by weight of diisopropyl naphthalene to obtain a developer solution. Ethylene mono-maleic anhydride copolymer 100% by weight aqueous solution 100 parts by weight, urea 100 parts by weight, resorcin 1 part by weight and water 200 parts by weight were mixed to form a solution, and the developer was added thereto. The solution is emulsified and dispersed until the 50% volume average diameter on the Coulter Counter reaches 5 m. To continue to obtain an emulsion. To this, 25 parts by weight of a 37% by weight aqueous solution of formalin was added, and the system temperature was set to 55 ° C. with stirring, and the mixture was reacted for 2 hours to prepare a capsule solution containing a developing agent-containing microphone opening.

Preparation Example 3

Preparation of color former coating solution

To 70 parts by weight of wheat starch and 35 parts by weight of styrene-butadiene copolymer latex (manufactured by Nippon Synthetic Rubber Co., Ltd.) as solids were added to 100 parts by weight of solid content of the microcapsule liquid containing the color former obtained in Preparation Example 1 as solids. A coating solution was obtained.

Preparation Example 4

Preparation of Coating Liquid for Plain Paper Transfer Type Pressure Sensitive Copy Paper

100 parts by weight of the microcapsule solution containing the color developing agent obtained in Preparation Example 1 as a solid content, 180 parts by weight of the microcapsule solution containing the color developing agent obtained in Preparation Example 2 as a solid content, and solidified paraffin wax emulsion 120 parts by weight, 100 parts by weight of wheat starch, and 80 parts by weight of styrene-butadiene copolymer latex (manufactured by Nippon Synthetic Rubber Co., Ltd.) as a solid content, to give a total solid content of 20% by weight. The pH was adjusted to 6 to prepare a coating solution for plain paper transfer type pressure-sensitive copying paper.

Example 1

A PF I mill was used to mix LBKP beaten to a freeness of 380 ml CSF and NBKP beaten to 450 m1 CSF in a weight ratio of 7: 3. 10% by weight, Okutama Industry Co., Ltd.), 10% by weight of sulfuric acid band, 0.6% by weight of alkyl ketene dimer (Product name: Size Pine K 903, Arakawa Chemical Co., Ltd.) 0.1% by weight, amphoteric starch (Product name) : Cat o3210, manufactured by Oji National Co., Ltd.) was added in an amount of 0.8% by weight to produce a base paper having a basis weight of 60 g / m ² .

Dimethylamine'epichlorohydrin addition polymer (trade name: Polyfix 601; manufactured by Showa Polymer Co., Ltd.) was applied on both sides of the base paper at a dry weight of 0.8 g / m ² per one side and a phosphorylated ester (product name: MS # 4600, so that the per side 0. 8 g / m ² by Nihon Shokuhin Kako Co., Ltd.) dry coverage, deposited with Onmashi down size press apparatus as a mixed aqueous solution, subjected to machine calendering treatment Support Produced. One side of the support was coated with the color former coating liquid obtained in Preparation Example 3 using an air knife coater so that the dry adhesion amount was 4 g / m ^2, and the carbon black pressure-sensitive copying was performed. Paper on paper was obtained.

Example 2

Paper on carbon-free pressure-sensitive copying paper was obtained in the same manner as in Example 1 except that the dry adhesion amount of the dimethylamine-epiclorhydrin addition polymer was changed to 0.1 g / m ² . Example 3

A paper on a pressureless copying paper was obtained in the same manner as in Example 1 except that the dry adhesion amount of the dimethylamine-epiclorhydrin addition polymer was changed to 2.0 g / m ² . Example 4

In the same manner as in Example 1 except that a polyvinylamine copolymer (trade name: Himax SC-700, manufactured by Hymo) was used instead of the dimethylamine-epiclorhydrin addition polymer, Paper on carbon pressure sensitive copy paper was obtained.

Example 5

In the same manner as in Example 1 except that an acrylamide / diallylamine salt copolymer (trade name: Sumireze Resin 9557, manufactured by Sumitomo Chemical Co., Ltd.) was used in place of the dimethylamine 'epichlorohydrin addition polymer, A paper on carbonless pressure-sensitive copying paper was obtained. Example 6

A paper for monocarbon pressure-sensitive copying paper was obtained in the same manner as in Example 1 except that the dry adhesion amount of the dimethylamine-epiclorhydrin-added S compound was 0.05 g / m ² . Example 7

Paper on carbonless pressure-sensitive copying paper was obtained in the same manner as in Example 1, except that the dry adhesion amount of the dimethylamine-epiclorhydrin addition polymer was 2.5 g / m. Comparative Example 1

In the same manner as in Example 1 except that hexadecyltrimethylammonium chloride (trade name: Cationic PB-40, manufactured by NOF Corporation) was used in place of the dimethylamine 'epichlorhydrin addition polymer, Paper on carbon pressure sensitive copy paper was obtained. Comparative Example 2

Dimethylamine 'Ebichlorohydrin addition polymer instead of alkyl (coconut) A paper on carbonless pressure-sensitive copying paper was obtained in the same manner as in Example 1 except that dimethyl benzylammonium chloride (trade name: Cation F 2 -50, manufactured by Nippon Yushi) was used.

With respect to the carbonless pressure-sensitive copy paper on paper obtained in Examples 1 to 7 and Comparative Examples 1 and 2, water resistance, light resistance, print blur, and storage stability were evaluated. Table 1 shows the results. Table 1 Example Water resistance Light resistance Printability Storage stability Example 1 A A A A

Example 2 B B B A

Example 3 A A 'B B

Example 4 A A A A A

Example 5 A A A A A

Example 6 C B B A

Example 7 A B C C

Comparative Example 1 D D B D

Comparative Example 2 D D B D

As can be seen from Table 1, in Examples 1 to 5 in which an appropriate amount of the cationic resin was used, good properties were exhibited in each item such as water resistance, light resistance, print bleeding, and storage stability. In Example 6 where the amount was small, the water resistance was slightly poor, and in Example 7 where the amount was large, the bleeding of the ink jet recording characters was large, and the preservability of the colored characters of the carbonless pressure-sensitive copying paper was also somewhat insufficient. . In Comparative Examples 1 and 2 in which a quaternary ammonium salt, which is a low molecular weight cationic compound, was used instead of the cationic resin, water and light resistance of the ink jet recording portion were not obtained, and the carbonless feeling was not obtained. Imprint The image storability of the paper was also insufficient.

Example 8

A PF I mill is used to mix LBKP beaten to 38 Oml CSF with NBKP beaten to 450 m1 CSF in a 7: 3 ratio by weight. LIN, ALTER ABAD I) 3% by weight, sulfate band 2% by weight, rosin sizing agent 0.3% by weight, and dimethylamine 'epichlorhydrin polycondensate (trade name: Polyfix) 601 (manufactured by Showa Kobunshi) was added internally at 3% by weight to produce a base paper having a basis weight of 60 g / m ² . On one side of the obtained base paper, apply the color former coating solution obtained in Preparation Example 3 using an air-knife coater so that the dry adhesion amount becomes 4 g / m ^2, and perform carbonless pressure-sensitive copying. Paper on paper was obtained.

Example 9

A carbon-free pressure-sensitive copy paper was obtained in the same manner as in Example 8, except that the internal addition amount of the dimethylamine / ebichlorohydrin addition polymer was changed to 1% by weight.

Example 10

A carbon-free pressure-sensitive copying paper was obtained in the same manner as in Example 8, except that the internal addition amount of the dimethylamine'epichlorohydrin addition polymer was changed to 10% by weight.

Example 11

A carbonless feeling was obtained in the same manner as in Example 8 except that a polyvinylamine copolymer (trade name: Himax SC-700, manufactured by Hymo) was used instead of the dimethylamine / epiclorhydrin addition polymer. A paper on pressure copy paper was obtained.

Example 12

The procedure of Example 8 was repeated, except that acrylamide-diallylamine salt copolymer (trade name: Sumireze Resin 957, manufactured by Sumitomo Chemical Co., Ltd.) was used instead of the dimethylamine-epiclorhydrin addition polymer. Paper on pressure-sensitive copy paper was obtained. Comparative Example 3

Paper on carbonless pressure-sensitive copying paper was obtained in the same manner as in Example 8, except that the internal addition amount of the dimethylamine′-ebichlorohydrin addition polymer was 0.5% by weight.

Comparative Example 4 Paper on carbonless pressure-sensitive copying paper was obtained in the same manner as in Example 8, except that the internal addition amount of the dimethylamine / epiclorhydrin addition polymer was 15% by weight.

Comparative Example 5

The procedure of Example 8 was repeated except that hexadecyltrimethylammonium chloride (trade name: Cationic PB-40, manufactured by NOF Corporation) was used instead of the dimethylamine-epichlorhydrin addition polymer. Paper on carbon pressure sensitive copy paper was obtained. Comparative Example 6

In the same manner as in Example 8 except that alkyl (coconut) dimethylbenzylammonium chloride (trade name: cation F2-50, manufactured by Nippon Yushi) was used in place of the dimethylamine'epichlorohydrin addition polymer. The paper on Noi Carbon pressure-sensitive copy paper was obtained.

The papers on the carbonless pressure-sensitive copying paper obtained in Examples 8 to 11 and Comparative Examples 3 to 6 were evaluated for water resistance, light resistance, print blur, and storage stability. Table 2 shows the results. Table 2 Example Water resistance Light resistance Print bleed Preservation Example 8 AAAA Example 9 BBBA Example 1 0 ABAB Example 1 1 AAAA Example 1 2 AAAA Comparative Example 3 CBBA Comparative Example 4 ACCC Comparative Example 5 DDBD Comparative Example 6 DDBD As can be seen from Table 2, in Examples 8 to 12 in which an appropriate amount of the cationic resin was used, good characteristics were exhibited in each item such as water resistance, light resistance, print blur, and storage stability. In Comparative Example 3 in which the amount used is less than 0.1% by weight, the water resistance is poor, and in Comparative Example 4 in which the amount exceeds 10% by weight, the ink jet recording characters are liable to bleed, and there is no force. The preservability was also insufficient. In Comparative Examples 5 and 6, in which an amine quaternary salt, which is a low molecular weight thione compound, was used in place of the cationic resin, water resistance and light resistance of the ink jet recording portion could not be obtained. The image storability of the duplicating paper was also insufficient.

Example 13

Except that plain paper transfer type coating liquid obtained in preparations 4 instead of color former coating solution 4 g / m ² was 6 g / m ² coated in the same manner as in Example 1, plain paper transfer type No pressure and pressure sensitive copying paper was obtained.

Comparative Example 7

Plain paper transfer type in the same manner as in Comparative Example 1 except that 6 g / m ^{2 of the} coating liquid for plain paper transfer type obtained in Preparation 4 was used instead of the color former coating liquid 4 g / m ² No carbon pressure-sensitive duplicating paper was obtained.

The plain paper transfer type carbonless pressure-sensitive copying papers obtained in the above Examples 13 and Comparative Example 7 were evaluated for water resistance, light resistance, print bleeding and storage stability. Table 3 shows the results. Table 3 Example ¹ water resistance light resistance printing bleeding; storability Example 1 3 AAAB

Comparative Example 7 D D B D

As can be seen from Table 3, the plain paper transfer type with a support using a cationic resin In Example 13 using carbonless pressure-sensitive copying paper, good results were obtained in each of the evaluation items.However, instead of the cationic resin, an amine quaternary salt, which is a low molecular weight cationic compound, was used. In Comparative Example 7, the water resistance and light resistance of the ink jet recording unit were not obtained, and the image storability of the carbonless pressure-sensitive copying paper was insufficient. Application example 1

On a non-capsule coating surface of the carbonless pressure-sensitive copying paper obtained in Examples 1 and 8, a high-speed ink jet printer (trade name: S6240J, Uchida Yoko) was used to apply 10 As a result of printing at a speed of O m / min, there was no stain on the printed surface. In addition, no color development was observed even when the developing agent solution of acetone was applied to the microcapsule coating surface, and it was confirmed that the microcapsules were not destroyed by printing.

Comparative application example 1

As a result of performing letterpress solid printing at a speed of 10 Om / min on a non-capsule coating surface of the non-carbon pressure-sensitive copying paper obtained in Example 1 and Example 8 at a speed of 10 Om / min, a printing surface was obtained. No stain was seen, but when the acetone solution of developer was applied to the microcapsule coating surface, the microcapsule surface corresponding to solid printing developed a faint color, and the microcapsules were destroyed by printing. Was confirmed.

From the results of Application Example 1 and Comparative Application Example 1, the microcapsule coating surface suffers capsule destruction when printing on the back side in form printing such as letterpress printing, but there is no force capsule destruction in ink jet printing. It was found to be suitable for printing on carbonless pressure-sensitive copying paper having a microcapsule coating layer.

Example 14

Pulp solids obtained by mixing LBKP beaten to a freeness of 38 O ml CSF with a PFI mill and NBKP beaten to 450 m1 CSF with a ratio of 7: 3 by weight On the other hand, 10% by weight of light calcium carbonate (trade name: TP121, manufactured by Okutama Kogyo Co., Ltd.), 0.6 pounds of sulfuric acid band, alkyl ketene dimer (trade name: Size Pine K900) 3, 0.1% by weight of Arakawa Chemical Co., Ltd.) and 0.8% by weight of amphoteric starch (Cat 0 3 210, manufactured by Oji National Co., Ltd.), with a basis weight of 50 g / m ² Base paper was made.

On one side of the obtained base paper, cationic colloidal silica was used as an ultrafine inorganic pigment. (Product name: Snowtex-1 AK (3), manufactured by Nissan Chemical Co., Ltd., primary particle diameter: 10 to 20 nm) 100 parts by weight, water-soluble polymer compound as adhesive (Product name: PVA 117, Kuraray Co., Ltd.) 10 parts by weight, dimethylamine'epiclorhydrin addition polymer as dye fixing agent (Polyix 61, manufactured by Showa Polymer Co., Ltd.) The solution was applied to a dry solid content of 3 g / m ² using a roll coater, dried, and machine calendered. / m ² to obtain paper on carbonless pressure-sensitive copy paper.

Example 15

Paper on a non-carbon pressure-sensitive copying paper was obtained in the same manner as in Example 14 except that the coating amount of the ink receiving layer coating liquid was changed to 0.5 g / m ² .

Example 16

Paper on a non-carbon pressure-sensitive copying paper was obtained in the same manner as in Example 14, except that the coating amount of the ink receiving layer coating liquid was changed to 8 g / m ² .

Example 17

A carbon-free pressure-sensitive copy paper was obtained in the same manner as in Example 14 except that the addition amount of the dimethylamine 'epichlorohydrin addition polymer was changed to 10 parts by weight.

Example 18

Example 14 was repeated in the same manner as in Example 14 except that a polyvinylamine copolymer (trade name: Himax SC-700, manufactured by Hymo) was used in place of the dimethylamine 'epichlorohydrin addition polymer. A paper on carbonless pressure-sensitive copying paper was obtained.

Example 19

In the same manner as in Example 14 except that an acrylamide-diallylamine salt copolymer (trade name: Sumireze Resin 9557, manufactured by Sumitomo Chemical Co., Ltd.) was used instead of the dimethylamine-epichlorhydrin addition polymer, A paper on no-strength pressure-sensitive copying paper was obtained. Example 20

Example 14 Except that the average primary particle diameter of the ultrafine inorganic pigment used in Example 4 was 65 nm (trade name: Snowtex YL, average particle diameter 50 to 80 nm, manufactured by Nissan Chemical Industries, Ltd.) In the same manner as in 14, a paper on carbonless pressure-sensitive copying paper was obtained. Example 2 1

On a non-carbon pressure-sensitive copying paper in the same manner as in Example 14 except that the ultrafine inorganic pigment was changed to alumina hydrate (Cataloid AS-3, manufactured by Sekiyu Kasei Kogyo Co., Ltd., primary particle diameter: about 10 nm). I got the paper.

Example 22

Example 1 except that colloidal silica having an average primary particle diameter of 300 nm (trade name: Snowtex PST-3, manufactured by Nissan Chemical Industries, primary particle diameter: 300 ± 30 nm) was used as the inorganic pigment. In the same manner as in 4, a paper on carbonless pressure-sensitive copying paper was obtained. Example 23

Paper on carbonless pressure-sensitive copying paper was obtained in the same manner as in Example 14, except that light calcium carbonate (trade name: Yumapal TP-123, manufactured by Okutama Kogyo) was used as the inorganic pigment.

Example 2 4

The ink receiving layer coating liquid was a 6% by weight mixture of 30 parts by weight of dimethylamine'epiclorhydrin addition polymer and 10 parts by weight of a water-soluble polymer compound (trade name: PVA117, manufactured by Kuraray Co., Ltd.). A carbon-free pressure-sensitive copy paper was obtained in the same manner as in Example 14 except that coating, drying and machine calendering were performed so that the dry solid content was 0.3 g / n ^.

Comparative Example 8

Paper on carbonless pressure-sensitive copying paper was obtained in the same manner as in Example 14 except that the ink receiving layer was not applied in Example 14.

Comparative Example 9

Paper on carbonless pressure-sensitive copying paper was obtained in the same manner as in Example 14, except that the dimethylamine'epichlorohydrin addition polymer was not used as the coating liquid for the ink receiving layer.

Comparative Example 10

In the same manner as in Example 14 except that hexadecyltrimethylammonium chloride (trade name: Cationic PB-40, manufactured by NOF Corporation) was used instead of the dimethylamine-epichlorhydrin addition polymer. Thus, paper on carbonless pressure-sensitive copying paper was obtained. Comparative Example 1 1

In the same manner as in Example 14 except that alkyl (coconut) dimethylbenzylammonium chloride (trade name: cation F2-50, manufactured by Nippon Yushi) was used instead of the dimethylamine-ebichlorohydrin addition polymer, Paper on carbon pressure sensitive copy paper was obtained.

The dryness, print density, water resistance, light resistance and storage stability of the paper on carbonless pressure-sensitive copying paper obtained in Example 14 24 and Comparative Example 8 11 were evaluated. The results are shown in Table 4. Table 4 Example Dry color Print density Water resistance J Light resistance I Gourmet Example 1 4 AAAAA Example 1 5 A, A'BAA Example 1 6 AAABB Example 1 7 AABAA Example 1 8 AAAAB Example 1 9 AAAAB Example 2 0 BBABA Example 2 1 BBBAA Example 2 2 BBBBA Example 2 3 BBAAA Example 2 4 CCCBA Comparative Example 8 DDDCA Comparative Example 9 ABDBA Comparative Example 1 0 ABCDD Comparative Example 1 1 ABCDD As can be seen from Table 4, by providing an appropriate amount of an ink-receiving layer containing a cationic resin and an inorganic pigment on the surface of the support (Examples 14 to 23), non-capsules of carbon-free pressure-sensitive copying paper were obtained. When ink jet printing is performed on the coating layer surface, it is possible to obtain a resin having excellent water resistance as compared with the case where no cationic resin is used, and excellent in drying property and water resistance as compared with the case where no inorganic pigment is used. However, when the coating amount of the ink receiving layer is small, as described in Example 24, it is difficult to sufficiently exert the above effects. In Comparative Examples 10 and 11 in which a low molecular weight ammonium quaternary salt was used instead of the cationic resin, the light resistance after printing was poor. It was also found that when a low molecular weight ammonium quaternary salt was used, the color image of the non-carbon pressure-sensitive coloring paper had a tendency to fade (desensitize) and to be faint.

Example 2 5

Plain paper transfer mold was prepared in the same manner as in Example 14 except that 6 g- / m ^{2 of} the plain paper transfer mold coating liquid obtained in Preparation Example 4 was applied instead of the color former coating liquid 4 g / m ^2. No carbon pressure sensitive copy paper was obtained.

Comparative Example 1 2

Except that plain paper transfer type coating solution obtained in Preparation Example 4 instead of the color former coating solution 4 g / m ² was 6 g / m ² coated in the same manner as in Comparative Example 8, the plain paper transfer type NO A carbon pressure sensitive duplicating paper was obtained.

The dryness, print density, water resistance, light resistance and storage stability of the plain paper transfer type no carbon pressure-sensitive copying paper obtained in Example 25 and Comparative Example 12 were evaluated. Table 5 shows the results. Table 5 Example Drying property Print density Water resistance Light resistance Storage stability Example 25 A A A A A

Comparative Example 1 2 DDDCA From Table 5, it can be seen that, by providing an ink receiving layer containing a cationic resin and an inorganic pigment on the surface of the support, the ink jet printing was performed on the non-capsule coating layer surface of plain paper transfer type carbonless pressure-sensitive copying paper. It was found that the drying property, print density, water resistance, and light resistance were superior to those without the ink receiving layer.

Application example 2

Using a high-speed ink jet printer (trade name: S6240J, Yoko Uchida), apply 10 Om / min to the non-capsule coating surface of the carbonless pressure-sensitive copy paper obtained in Examples 14 and 25. As a result of printing at the speed, there was no stain on the printing surface. In addition, no color development was observed even when the developing agent solution of acetone was applied to the microcapsule coating surface, and it was confirmed that the microcapsules were not destroyed by printing.

Comparative application example 2

As a result of letterpress printing at a rate of 10 Om / min on a non-capsule coated surface of the carbonless pressure-sensitive copying paper obtained in Examples 14 and 25 using a form printing machine, the printed surface was contaminated. Although no microcapsules were observed, when the acetone solution of the developer was applied to the microcapsule coating surface, the microcapsule surface corresponding to solid printing developed a faint color, and the microcapsules could be destroyed by printing. confirmed.

Based on the results of Application Example 2 and Comparative Application Example 2, the microcapsule coating surface suffers capsule destruction when printing on the back side in form printing such as letterpress printing, but does not break in ink jet printing. It was found to be suitable for printing carbon black pressure-sensitive copy paper having a capsule coating layer.

Examples 26 to 28

Pulp obtained by mixing LBKP beaten to 38 Oml CSF and NBKP beaten to 450 m 1 CSF in a ratio of 7: 3 by weight on a PF I mill The light calcium carbonate (trade name: TP121) 12% by weight of Okutama Kogyo Co., Ltd., 0.6% by weight of sulfuric acid band, 0.08% by weight of alkyl ketene dimer (trade name: Size Pine K 903, Arakawa Chemical Co., Ltd.), amphoteric starch (trade name: Cat o3210, manufactured by Oji National Co., Ltd.) was added in an amount of 0.8% by weight to produce a base paper having a basis weight of 60 g / m ² . Then, this base paper was oxidized starch (trade name: MS 3800, manufactured by Nippon Shokuhin Kako) 3% by weight, styrene-based cationic sizing agent (trade name: ba 0.05% by weight (Example 26), 0.06% by weight (Example 27), 0.08% by weight (Example 28), polyvinylamine copolymer (trade name: Himax SC-700) Surface treated with a surface sizing solution containing 2% by weight to provide a surface treatment layer on one side of the base paper, and base paper for carbonless pressure-sensitive copying paper (hereinafter abbreviated as base paper for pressure-sensitive paper). I got

Next, on the opposite side of the pressure-sensitive paper base paper and the surface treatment layer side thereof, the air-knife-co-overcoat was used to apply the coloring agent coating solution prepared in Preparation Example 3 to a dry adhesion amount of 4 g / m ^2. Then, carbonless pressure-sensitive copying papers of Examples 26 to 28 were obtained.

Example 29

1% by weight of alkyl ketene dimer and 0.06% by weight of styrene-based cationic sizing agent. Instead of polyvinylamine copolymer, acrylamide-diarylamine salt copolymer (trade name: Sumireze) Resin 957, manufactured by Sumitomo Chemical Co., Ltd.), a pressure-sensitive paper base paper was obtained in the same manner as in Example 26, and the color former coating solution prepared in Preparation Example 3 was dried using an air knife coater. Coating was performed so that the adhesion amount was 4 g / m- 'to obtain a carbonless pressure-sensitive copy paper.

Example 30

For pressure-sensitive paper in the same manner as in Example 29 except that hexadecyltrimethylammonium chloride (trade name: Cationic PB-40, manufactured by NOF CORPORATION) was used instead of the acrylamide-diallylamine salt copolymer. After obtaining the base paper, apply the color former coating solution prepared in Preparation Example 3 using an air knife to the head so that the dry adhesion amount is 4 g / nr '. I got the paper.

Comparative Example 13

A PF I mill was used to mix LBKP beaten to a freeness of 380 ml CSF and NBKP beaten to 450 m1 CSF at a weight ratio of 7: 3. The pulp solid content was adjusted to light calcium carbonate (trade name: TP121, 12% by weight of Okutama Kogyo Co., Ltd., 0.6% by weight of sulfuric acid band, 0.08% by weight of alkyl ketene dimer (trade name: Size Pine K 903, Arakawa Chemical Co., Ltd.), amphoteric starch (trade name: cat O3210, Oji National Co., Ltd.) basis weight was added 0.8% by weight is papermaking of 6 0 g / m ² base paper, the surface of a base paper subjected to surface treatment with water instead of the surface sizing solution A treatment layer was provided to obtain a base paper for pressure-sensitive paper. Subsequently, the color former coating solution prepared in Preparation Example 3 was applied to the opposite surface of the surface treatment layer using an air-knife coater to a dry adhesion amount of 4 g / nr '. A pressure-sensitive copy paper was obtained.

Comparative Example 1 4

A pressure-sensitive paper base paper was obtained in the same manner as in Comparative Example 13 except that a mixed surface size liquid of 3% by weight of oxidized starch and 0.10% by weight of a styrene-based cationic sizing agent was used as the surface size liquid. The color former coating solution prepared in Preparation Example 3 was applied using Air Knife Co., Ltd. to a dry adhesion amount of 4 g / m ² to obtain a carbonless pressure-sensitive copying paper.

The monocarbon pressure-sensitive copying papers obtained in Examples 26 to 30 and Comparative Examples 13 and 14 were evaluated for the degree of cup size, drying property, water resistance and stain resistance. Table 6 shows the results. Table 6 Cove size

Dryness! Water resistance I Stain resistance Support surface Surface treatment layer Example 2 6 8 0 6 0 AAB Example 2 7 8 0 5 0 Α to Α 'A, A' Example 2 8 8 0 2 0 Β Β A Example 2 9 6 0 3 0 Α 'to Β A, A Example 3 0 6 0 3 0 Α' to Β Β A Comparative example 1 3 8 0 8 0 ADD Comparative example 1 4 8 0 1 0 DDA

From the results in Table 6, the cup size in the surface treatment layer for ink jet printing is shown. When the density is 20 g / m ² or more, the drying property during ink jet printing is excellent, and when the density is 60 g / m ² or less, the coating suitability of the The stain resistance of the paper was good. In addition, the water resistance of the ink-jet printed portion was good when a cationic compound was added, and especially when a cationic resin was added.

Example 3 1 to 36

Alkyl ketene dimer is 0.05-0.12% by weight, styrene-based cationic sizing agent is 0.05-0.08% by weight, and instead of oxidized starch, phosphate esterified starch (trade name: MS 4600, Example 26 was used except that dimethylamine / ebichlorohydrin addition polymer (trade name: Polyfix 601; manufactured by Showa Polymer) was used instead of the polyvinylamine copolymer. In the same manner as in the above, a base paper for pressure-sensitive paper was obtained. Subsequently, the coloring agent coating solution prepared in Preparation Example 3 was applied to the opposite surface of the surface treatment layer using an air knife to achieve a dry adhesion amount of 4 g / m ² , The carbonless pressure-sensitive copying papers of Examples 31 to 36 were obtained. In addition, corresponding to Examples 31 to 36, the alkyl ketene dimer was 0.06% by weight, 0.06% by weight, 0.08% by weight, 0.1% by weight, and 0.05% by weight, respectively. , 0.12% by weight, and the styrenic cationic sizing agents are 0.05% by weight, 0.08% by weight, 0.06% by weight, 0.08% by weight, 0.06% by weight, and 0.05% by weight, respectively. % By weight.

Comparative Examples 15 and 16

0.05% by weight (Comparative Example 15), 0.14% by weight (Comparative Example 16) of the alkyl ketene dimer, 0.055% by weight (Comparative Example 15), 0.08% by weight of the styrene-based cationic sizing agent (Comparative Example 15) A base paper for pressure-sensitive paper was obtained in the same manner as in Example 26, except that Comparative Example 16) was repeated, except that a dimethylamine-epiclorhydrin addition polymer was used instead of the polyvinylamine copolymer. Subsequently, the color former coating solution prepared in Preparation Example 3 was applied to the opposite surface of the surface treatment layer using Air Nifco Co., Ltd. so as to have a dry adhesion amount of 4 g / m ² . Comparative carbon papers of Comparative Examples 15 and 16 were obtained.

The carbonless pressure-sensitive copying papers obtained in Examples 31 to 36 and Comparative Examples 15 and 16 were evaluated for the degree of cobb size, drying property, water resistance and stain resistance. Conclusion The results are shown in Table 7. Table 7 Cobb size degree

^ Dryability :; Water resistance i Stain resistance Support surface Surface treatment layer Example 31 120 60 A A B

Example 32 120 40 A, A A 'Example 33 80 40 Α' to Β A 'A' Example 34 60 20 Β A 'A

Example 35 140 60 A, A B

Example 36 50 30 Β A 'to B A

Comparative Example 15 140 70 A A D

Comparative Example 16 40 10 D B A

From the results of Table 7, the cup size of the support surface is a 60~120g / m ^2, and when the cup size degree of 20 to 60 g / m ² in the surface treatment layer, in Inkjet Printing It has good drying properties and suitability for color former coating, and has good stain resistance as a no-strength one-bon pressure-sensitive copying paper. Even if the degree of cup size on the surface of the support is out of the range of 60 to 120 g / m ² , if the degree of cup size on the surface treatment layer is 20 to 60 g / m ² , it is relatively good. Although characteristics can be obtained, it can be seen that the characteristics are slightly inferior to the case where both conditions are satisfied.

Example 37

Pulp obtained by mixing LBKP beaten to 38 Oml CSF and NBKP beaten to 450 m 1 CSF in a ratio of 7: 3 by weight on a PF I mill The light calcium carbonate (trade name: TP121) , Manufactured by Okutama Industry Co., Ltd.) 10% by weight, sulfuric acid band 0.6% by weight, alkyl ketene dimer (trade name: Size Pine K903, manufactured by Arakawa Chemical Co.) 0.08% by weight, amphoteric starch (trade name: Cat o3210, Oji National) 8% by weight was added to produce a base paper having a basis weight of 60 g / m ² . Next, the base paper was subjected to a surface treatment using a mixed surface size liquid containing 3% by weight of oxidized starch and 0.05% by weight of a styrene-based cationic sizing agent to provide a surface treatment layer on the base paper. Furthermore, 10 parts by weight of polyvinyl alcohol (PVA117, manufactured by Kuraray) and 100 parts by weight of cationic colloidal silica (trade name: SNOTEX AK, manufactured by Nissan Chemical), dimethylamine'epichlorhydrin addition polymer (trade name) : Polyfix 601) A pressure-sensitive paper base paper having a pigment-coated layer was obtained by applying 5 g / m ^{2 of} a pigment coating liquid containing 20 parts by weight. Subsequently, the color former coating liquid prepared in Preparation Example 3 was applied to the opposite side of the pigment coating layer of the pressure-sensitive paper base paper using an air-knife coater so that the dry adhesion amount became 4 g / m ^2. After coating, a carbon-free pressure-sensitive copy paper was obtained.

Example 38

Cationic colloidal silica, using Sunote box YL instead of SNOWTEX AK, 4 after the other in which a pigment coating layer of g / m ² was obtained pressure sensitive paper base paper in the same manner as in Example 37 Using an air knife coater, the color former coating solution prepared in Preparation Example 3 was applied to a dry adhesion amount of 4 g / m ² to obtain a carbonless pressure-sensitive copy paper.

Example 39

Precipitated calcium carbonate instead of the cationic colloidal silica (trade name: evening Mapa - Le TP 123, Okutama Kogyo Co., Ltd.) using, in the same manner as in Example 37 except that provided a pigment coating layer of 5 g / m ² After obtaining the base paper for pressure-sensitive paper, the color former coating solution prepared in Preparation Example 3 was applied using an air knife to obtain a dry adhesion amount of 4 g / m ^2, and carbonless A pressure-sensitive copy paper was obtained.

Example 40

Pressure-sensitive paper was prepared in the same manner as in Example 37 except that light calcium carbonate (trade name: Priliant 15, made of Shiraishi calcium) was used instead of the cationic colloidal silica, and a 3 g / m ² pigment coating layer was provided. After obtaining base paper, use Air Knife Ko Then, the color former coating solution prepared in Preparation Example 3 was applied so as to have a dry adhesion amount of 4 g / m ² , to obtain a carbonless pressure-sensitive copying paper.

Example 4 1

Kaolin instead of the cationic colloidal silica (trade name: Kaoburai DOO, Ti ele Kaol in Co.) using sensitive similarly except having a pigment coating layer of 3 g / m ² Example 3 7 After obtaining the base paper for pressing paper, apply the color former coating liquid prepared in Preparation Example 3 using Air-Knife Co., Ltd. to a dry adhesion amount of 4 g / m ^2, and perform pressure-sensitive copying without carbon. I got the paper.

Comparative Example 1 7

In the same manner as in Example 37 except that a force-olin (trade name: Ultra White 90, manufactured by Shiraishi Kogyo) was used instead of the cationic colloidal silica, and a pigment coating layer of 4 g / m ² was provided. After obtaining a base paper for pressure-sensitive paper, using an air knife call evening one, the color former coating solution prepared in preparation example 3 was applied to a dry coating weight 4 g / m ^2, no force one Bonn A pressure-sensitive copy paper was obtained.

The carbonless pressure-sensitive copying papers obtained in Examples 37 to 41 and Comparative Example 17 were evaluated for the degree of cup size, drying property, water resistance and stain resistance. The results are shown in Table 8.

Table 8 Cobb size degree

Example Drying property: Water resistance; Stain resistance

Support surface! Pigment coating layer Example 3 7 8 0 8 0 A A 'A'

Example 3 8 8 0 5 0 A A A A,

Example 3 9 8 0 4 0 Α 'A A'

Example 4 0 8 0 3 0 A, A, A,

Example 4 1 8 0 2 0 BB ¹ A '

Comparative Example 1 7 8 0 1 0 C C A,

As can be seen from Table 8, the drying property after ink jet printing is better when the degree of cup size in the pigment coating layer is larger, and if it is less than ²⁰ g / m2, sufficient drying property cannot be obtained. Was. In terms of water resistance, the effect of adding the cationic resin was remarkable. In addition, it was found that the larger the cup size in the pigment coating layer, the better the water resistance. Industrial applicability

The carbonless pressure-sensitive copying paper of the present invention has a pressure-sensitive recording function and an ink jet recording function, and has a characteristic as a carbon-free pressure-sensitive copying paper on the surface of the support opposite to the microcapsule layer. Inkjet recording with excellent image density and image clarity is possible without impairing ink quality, ink drying is fast, and ink bleeding due to high humidity conditions and adhesion of water droplets is excellent. It has the suitability for recording, the suitability for high-speed printing, and the suitability for additional printing on a printing press.

Claims

The scope of the claims

1. At least ink jet recording is performed on carbonless pressure-sensitive copying paper that has a pressure-sensitive recording function and an ink-jet recording function that forms a color image by the reaction between an electron-donating color former and an electron-accepting developer. A carbonless pressure-sensitive copying paper characterized in that a cationic resin layer is provided on the surface of the support on the side and a layer containing microcapsules containing an electron-donating color former is provided on the other surface.

2. The coating amount of the cationic resin layer is, 0 as per side by dry weight. 1 to 2.0 is g / cm ^2, carbonless pressure-sensitive copying paper according to claim 1.

3. The cationic resin according to claim 1, wherein the cationic resin is at least one selected from the group consisting of a dimethylamine'epichlorohydrin addition polymer, an acrylamide / diallylamine salt copolymer, and a polyvinylamine copolymer. No carbon pressure sensitive copy paper.

4. The method according to claim 1, wherein the layer containing microcapsules containing the electron-donating color former contains microcapsules containing the electron-accepting color developer together with the microcapsules containing the electron-donor color former. Carbon pressure-sensitive copy paper.

5. A colorless image is formed by the reaction between an electron-donating color former and an electron-accepting color developer. In carbonless pressure-sensitive copying paper having a pressure-sensitive recording function and an ink-jet recording function, 1 per pulp solid content is used. A carbon-free pressure-sensitive copying paper characterized in that a support containing a 10% by weight of a cationic resin is provided on one side of a support with a layer containing an electron-donating color former-encapsulating microforce.

6. The cationic resin according to claim 5, wherein the cationic resin is at least one selected from the group consisting of a dimethylamine 'ebichlorohydrin addition polymer, an acrylamide' diarylamine salt copolymer and a polyvinylamine copolymer. Carbon-free pressure-sensitive copy paper as described.

7. The electron-donating color former-encapsulating microcapsule-containing layer contains an electron-donating color former-encapsulating microcapsule and an electron-accepting color developer-encapsulating microcapsule and a box. No carbon pressure-sensitive copy paper.

8. Form a color image by the reaction between an electron-donating color former and an electron-accepting color developer. In a carbonless pressure-sensitive copying paper having a pressure-sensitive recording function and an ink-jet recording function, an ink receiving layer containing a cationic resin and an inorganic pigment is provided on the surface of a support on which ink jet recording is performed, and the other surface is provided. A carbon-free pressure-sensitive copying paper characterized in that a microcapsule-containing layer containing an electron-donating color-forming agent is provided thereon.

9. The carbonless pressure-sensitive copying paper according to claim 8, wherein the inorganic pigment is an ultrafine inorganic pigment having an average primary particle diameter of 100 nm or less.

10. The cationic resin according to claim 8, wherein the cationic resin is at least one selected from the group consisting of a dimethylamine'epichlorohydrin addition polymer, an acrylamide-diallylamine salt copolymer, and a polyvinylamine copolymer. Carbonless pressure-sensitive copy paper.

11. The ink-receiving layer contains 10 to 50 wt% cationic resin, and the coating E amount is 0. 5 to 10 g / m ^2, carbonless pressure-sensitive copying paper according to claim 8.

12. The microcapsule-containing layer containing an electron-donating color former, the microcapsule containing an electron-donor color former, a microcapsule containing an electron-accepting developer, and a box. The carbonless pressure-sensitive copying paper described.

13. The side that performs ink jet recording on carbonless pressure-sensitive copying paper that has a pressure-sensitive recording function and an ink-jet recording function that form a color image by the reaction between an electron-donating color former and an electron-accepting developer. of the surface of the support, the surface treatment layer 5 wt% isopropyl alcohol solution used 10 seconds cup size of the JIS P8140 compliant is 20~ 60 g / m ² provided, the electron-donating color former encapsulated micro the other surface Carbon-free pressure-sensitive copying paper characterized by having a capsule containing layer.

14. Use of a 5% by weight aqueous solution of isopropyl alcohol according to JISP 8140 before providing a treatment layer on the surface of the support on which ink jet recording is performed, and a 10-second cob sizing degree of 60 to 120 g / m ^2. The pressure-sensitive copying paper described in.

15. The carbonless pressure-sensitive copying paper according to claim 13, wherein the surface treatment layer contains a cationic resin.

16. Whether the cationic resin is dimethylamine'ebichlorohydrin addition polymer, acrylamide / diallylamine salt copolymer or polyvinylamine copolymer 16. The monocarbon pressure-sensitive copying paper according to claim 15, which is at least one member selected from the group consisting of:

17. Inkjet recording is performed on a non-carbon pressure-sensitive copying paper that has a pressure-sensitive recording function and an ink-jet recording function that form a color image by the reaction between an electron-donating color former and an electron-accepting developer. the surface of the support side, is provided a pigment coating layer 5 wt% I Seo bromide pills aqueous alcohol using 10 seconds cup size of the JIS P8140 compliant is 20~ 80 g / m ^2, an electron donating the other surface A carbon-free pressure-sensitive copying paper characterized by having a microcapsule-containing layer containing a neutral coloring agent.

18. a Inkujietsu preparative recording JISP 8140 60 to 5 wt% I isopropyl alcohol solution used 10 seconds Cobb sizing degree of compliance 120 before providing the pigment coating layer in the support surface on the side performing g / m ^2, The pressure-sensitive copying paper according to claim 17.

19. The carbonless pressure-sensitive copying paper according to claim 17, wherein the pigment coating layer contains a cationic resin.

20. The cationic resin is at least one member selected from the group consisting of a dimethylamine′-ebichlorohydrin addition polymer, an acrylamide / diallylamine salt copolymer and a polyvinylamine copolymer. No-carbon pressure-sensitive copying paper described in.