WO1994026530A1

WO1994026530A1 - Ink jet recording sheet

Info

Publication number: WO1994026530A1
Application number: PCT/JP1994/000761
Authority: WO
Inventors: Toshihiko Matsushita; Kouji Idei; Hideaki Senoh; Yoshihiko Hibino; Kenji Momma
Original assignee: Mitsubishi Paper Mills Limited
Priority date: 1993-05-13
Filing date: 1994-05-11
Publication date: 1994-11-24
Also published as: EP0655346B1; EP0655346A4; DE69413179D1; DE69413179T2; EP0655346A1

Abstract

This invention provides an ink jet recording sheet having a high ink absorptivity, capable of providing an image of a high density and a good sharpness and recorded dots of a substantially perfect circularity, and having a high water-resistance. A component of an ink receiving layer of this sheet consists mainly of non-spherical cationic colloidal silica, and this ink receiving layer is composed of a layer of coating formed by contour painting a surface of a substrate, in which sheet a total quantity of charge of cations is specified, a polyvinyl amine copolymer-containing substrate being used. Preferably, the non-spherical cationic colloidal silica consists of acicular or columnar cationic colloidal silica.

Description

Description Inkjet record sheet [Technical field]

The present invention relates to an ink jet recording sheet, and more particularly, to an ink jet recording sheet which has no ink bleeding, has excellent ink absorbing properties, and has a recorded image. High density and sharpness, a recording dot close to a perfect circle is obtained, and the ink jet recording sheet of the fine coating type with excellent water resistance of the recording dot It is about.

(Background technology)

The ink jet recording method records fine images of ink and makes them adhere to a recording sheet such as paper, and records images, characters, etc., based on various operating principles. It is characterized by high speed, low noise, easy multi-coloring, great flexibility of recording pattern, and development-fixing is unnecessary. It is rapidly spreading in various applications as a recording device. Furthermore, an image formed by the multicolor ink jet method can obtain a record comparable to multicolor printing by the plate making method and printing by the color photographic method. Is possible. In applications where the number of copies required is small, it is being widely applied to the field of full-color image recording because it is cheaper than photographic technology.

Recording sheet used in this ink jet recording method Efforts have been made in terms of equipment and ink composition to use high-quality paper and coated paper used for normal printing and writing. However, with the improvement of the performance of ink jet recording devices and the expansion of applications, such as higher speed, higher definition, and full colorization of the devices, more advanced recording sheets are used. Characteristics have become required.

In other words, the recording sheet has a high density of recording dots, a bright and vivid color tone, and a shortage of ink dots due to rapid ink absorption. It is required that the ink does not flow out or bleed, that the recording dots do not spread in the horizontal direction more than necessary, and that the periphery is smooth and not blurred.

The form of the ink jet recording sheet is a plain paper type typified by so-called high-quality paper and bond paper, paper such as high-quality paper, synthetic paper, synthetic resin film, etc. These are roughly classified into coating types in which an ink receiving layer is provided on the surface of the support.

The coating Thailand-flops, 1 ~ 1 0 g / m 2 as low coating type, 1 0 ~ 2 0 g / m 2 about intercoat Engineering type, ² 0 g / m 2 or more high-coating There is a record sheet for each ink jet type.

In particular, it comes in recent years, low-coating coating amount of the lower limit in Thailand-flops 0. 5 ~ 5. O g / fine coating type of m ² is also the capital Ri name close to plain paper, aesthetically However, this type of fine coating is desired as it is also preferable for handling. However, in the case of a single color record, not only a single color record of yellow, yellow, cyan, black, but also a multi-color record with these colors superimposed, Since the ink adhesion amount is extremely large, the fine coating type has a relatively low size because the coating layer cannot absorb the ink completely. It has become necessary to use base paper to absorb some of the attached ink on the base paper itself of the support.

Japanese Patent Application Laid-Open No. Sho 60-63191 discloses an ink jet recording sheet having a high ink absorption and a good recording dot shape. . This publication is characterized in that the surface layer of the recording material (ink jet recording sheet) is a mixture of filler and fibrous material. Here, it is described that the material has a substrate made of a fibrous material and filler particles adhered so as to be very thinly dispersed on the surface of the substrate. However, the publication does not mention a state in which the filler material of the surface layer and the fibrous material are mixed, and a state in which the textile material forming the base material is exposed on the surface layer.

In order to you solve the problem of this are found, especially fairness 3 - 2 6 6 6 5 JP basis weight 6 0 g / m ² basis nice human size of of less than 4 seconds An example of an ink jet recording paper in which a coating layer containing fine silica and a water-soluble high molecular binder is provided on a base paper of JP-A No. 59-38 is disclosed. The 087 publication discloses an example of an ink jet recording material in which an ink absorbing layer is provided on a base material having a size of 0 to 10 seconds. Japanese Unexamined Patent Publication No. 59-95516 discloses an example of an ink jet recording paper in which base paper having a stigmatization degree of 0 to 5 seconds is impregnated with polyvinylpyrrolidone or the like. Have been.

In addition, the applicant's ink jet record sheet has a special There is Kaihei 5 — 2 2 1 1 15 issue. This publication discloses an ink jet recording sheet in which an ink receiving layer is provided on one side of a support and a back coat layer is provided on the back side, and the ink receiving layer is made of starch particles or It contains one or more of the modified starch particles or the specific ethylene vinyl acetate copolymer resin and a cationic dye fixing agent, and the fixing agent is cationized per unit area of the recording sheet. it is what is contained in the jar by the charged amount of 0. 2 ~ 4 0 me q . / m 2. The objectives are high image density, excellent ink absorption, reduction of bleeding in superimposed color areas, prevention of yellow discoloration, curl suppression, and the like. However, the ink-receiving layer disclosed in the publication is based on the definition of cation charge by the fixing agent and a specific material as an essential component, and uses specific particles and a unit weight per unit weight. There is no suggestion for the cation charge in the ink jet recording sheet.

Further, various proposals have been made to improve the water resistance of the dye. For example, Japanese Patent Application Laid-Open No. 56-84892 discloses a method of incorporating a polycationic polymer electrolyte on the surface, and Japanese Patent Application Laid-Open No. 55-150396 discloses an aqueous ink. A method of making the dyes and chelates in the fabric water resistant is disclosed. Further, in order to improve both the water fastness and the light fastness of the dye, Japanese Patent Application Laid-Open No. Sho 60-11389 discloses an ink jet device characterized by containing a basic oligomer. A test record sheet is disclosed. For example, Japanese Patent Application Laid-Open No. Sho 64-8085 discloses a method using a polyamine copolymer containing a cationic polymer or a salt thereof (polyvinylamine derivative). Let A recording material (inkjet recording sheet) with improved water resistance and light resistance has been disclosed. However, the polyvinylamine derivative is a polymer or a copolymer substantially containing no (meth) acrylic acid monomer unit.

As described above, when the ink-receiving layer has a low coating amount, a relatively low-size base paper is used, and the support itself absorbs a part of the adhesion ink. However, if the ink that could not be absorbed by the ink receiving layer was absorbed by the support itself, the recorded image would have low density and lacked sharpness. And In addition, as described above, the ink jet recording sheet in which the charge amount of cations is specified has a configuration in which a specific ink receiving layer material is used in combination. It differs from the ink jet recording sheet of the present invention of the fine paint type in terms of function and effect.

The purpose of the present invention is that the ink jet recording sheet is also a finely coated type ink jet recording sheet, and the ink does not bleed. Ink with excellent ink absorption, high density and sharpness of the recorded image, a recording dot close to a perfect circle, and excellent water resistance of the recording dot The purpose is to obtain a jet record sheet.

[Disclosure of the Invention]

The inventors of the present invention have conducted intensive studies in view of the above, and as a result, have found that there is no ink bleeding, ink absorption is excellent, the density of the recorded image is high, and a recording dot close to a perfect circle is obtained. In addition, an ink jet recording sheet with excellent water resistance of the recording dot is released. I came to tell. ;

That is, the ink jet recording sheet according to the first invention is an ink jet recording sheet in which an ink receiving layer is coated on a support. The receiving layer is a coating layer mainly composed of non-spherical cationic colloidal silica, and has a coating amount of 0.5 to 5 which is contour-coated along the surface of the support. It is a coating layer of 0 g / m ² .

The contour-coated layer is a layer in which the surface of the support is covered with a coverage of 70% or more.

The ink receiving layer is composed of a composition mainly composed of non-spherical cationic colloidal silica and a binder.

In the ink-receiving layer, the binder is 5 to 20 parts by weight based on 100 parts by weight of the non-spherical cationic colloidal silica.

The ink-receiving layer is obtained by applying an ink-receiving layer composition having a coating solution concentration of 4 to 20% by weight on a support.

The ink receiving layer is obtained by applying an ink receiving layer composition having a coating solution concentration of 4 to 10% by weight on a support in a sizeless manner.

The ink-receiving layer is obtained by applying the ink-receiving layer composition having a coating solution concentration of 10 to 20% by weight onto a support all over a rod.

The ink receiving layer is coated on a support with an ink receiving layer composition having a coating solution concentration of 10 to 20% by weight over a period of time. It is obtained. Non-spherical cationic colloidal silica is needle-like or columnar.

In addition, the ink jet recording sheet according to the second invention is an ink jet recording sheet comprising an ink receiving layer coated on a support. The receiving layer component is mainly composed of non-spherical cationic colloidal silica, and the ink receiving layer is contour-coated along the surface of the support.記録 5.0 g / m ² , and the recording sheet has a total force ionic charge of 0.5 020 meq./100 g.

The contour-coated coating layer is a coating layer in which the support surface is coated with a coverage of 70% or more.

The ink receiving layer has a binder of 5 to 20 parts by weight with respect to 100 parts by weight of the non-spherical cationic colloidal silica, and has an ink receiving layer of 4 to 2 parts by weight. It can be obtained by applying an ink receiving layer composition having a coating solution concentration of 0% by weight.

The ink-receiving layer is obtained by applying an ink-receiving layer composition having a coating solution concentration of 4 to 10% by weight on a support in a sizeless manner.

The ink-receiving layer is obtained by applying the ink-receiving layer composition having a coating solution concentration of 10 to 20% by weight onto a support all over a rod at a time.

Coating solution concentration where the ink receiving layer is 10 to 20% by weight The ink receiving layer composition of the present invention is obtained by coating the composition on a support with a trans-Fall coater.

Non-spherical cationic colloidal silica is needle-like or columnar.

Further, the ink jet recording sheet according to the third invention is an ink jet recording sheet comprising an ink receiving layer coated on a support, wherein the support comprises: N — Copolymerization reaction of vinylformamide and acrylonitrile to give a poly (vinylamine) copolymer having a molecular weight of at least 500,000 and a vinylamine molar ratio of at least 20 mol%. The ink receiving layer component mainly has a non-spherical cationic colloidal force, and the ink receiving layer extends along the surface of the support. This is a coating layer with a coating amount of 0.5 to 5.0 g / m ² that has been contour-coated.

The total charge of the ink jet recording sheet is from 0.5 to 20 meq. 100 g.

When the ink receiving layer has a binder content of 5 to 20 parts by weight based on 100 parts by weight of the non-spherical cationic colloidal silica.

The ink receiving layer is obtained by applying an ink receiving layer composition having a coating solution concentration of 4 to 20% by weight.

The ink receiving layer has a coating solution concentration of 4 to 10% by weight. It can be obtained by applying the ink receiving layer composition on a support by size pressing.

The ink-receiving layer can be obtained by applying an ink-receiving layer composition having a coating solution concentration of from 10 to 20% by weight onto a support with a rod coater.

The ink receiving layer is formed by applying an ink receiving layer composition having a coating solution concentration of 10 to 20% by weight on a support with a trans-Fallol coater. Is obtained.

Non-spherical cationic colloidal silica is needle-shaped or columnar.

Hereinafter, the ink jet recording sheet of the present invention will be described in detail.

The ink jet recording sheet of the present invention is a finely coated ink receiving layer contour-coated along the surface of the support, and specifies the ink receiving layer component. It is.

In the first ink jet recording sheet of the present invention, the ink receiving layer is a coating layer coated along the surface of the base paper. “Coated coating layer” is a coating layer surface coated with an ink-receiving layer component along a convex portion (mountain) or a concave portion (valley) of the base paper surface. The surface has a surface shape similar to the base paper surface.o

In general, “contour coating” refers to coating on the base paper using Air Knife Co., which is a thick coating that reflects the surface shape of the base paper. Coating layer is formed However, this is quoted in the ink jet recording sheet of the fine coating type of the present invention.

In other words, if we think of the “coating layer with contour coating” as an example, assuming that snow is piled up on a mountain range that can be seen far away, the mountain range is taken as the base paper surface and the mountain range is piled up along the mountain range. The snow scene that has been used as the ink receiving layer surface. If the amount of coating is small, pulp fibers are exposed on the surface of the ink receiving layer, as in the case of trees with no snow covered in places with little snow. If the amount of coating is large, the pulp fiber shape can be identified on the ink-receiving layer, as in the case where the amount of coating is large, as in the case of a lot of snow, where the contours of the mountains are recognized and the mountain is slightly piled up on the slope of the mountain. It can be seen that the ink receiving layer component slightly covers the recesses (valleys) between the pulp fibers. In addition, as the amount of snow increases, the slope of the mountain is filled with a lot of snow and the mountain range becomes uncertain. The valley is filled with the ink-receiving layer component, and the shape of the pulp fiber cannot be identified, resulting in a flattened ink-receiving layer surface. In this case, the ink jet recording sheet of the present invention is reminiscent of an ink jet recording sheet as a coated paper from a sheet approximating plain paper. It is out of range.

In the ink jet recording sheet of the present invention, the contour-coated coating layer is a coating layer in which the surface of the support is covered at a coverage of 70% or more. In order that the shape of the pulp fiber on the surface of the ink receiving layer on the base paper can be sufficiently identified. It is coated. The surface of the ink receiving layer is uniformly covered with non-spherical cationic colloidal silica along the surface of the pulp fiber, and is covered thinly according to the shape of the pulp fiber surface. ing. The surface coverage of the ink receiving layer surface is such that at least 70% of the pulp fiber surface of the ink receiving layer surface is covered, whereby the intended characteristics of the present invention are sufficiently exhibited. can do. It is preferably at least 80%, more preferably at least 90%.

The reason is that if the ink receiving layer surface is evenly covered, ink is given to the ink receiving layer surface using an ink jet printer. At this time, since the ink receiving layer surface is uniformly covered, the ink does not spread in the direction of the ink receiving layer surface, and a recording dot close to a perfect circle can be expressed. This is because excess ink penetrates from the coated surface in the thickness direction of the base paper. On the other hand, when the coverage of the ink receiving layer surface covering the pulp fibers is less than 70, the ink spreads more in the direction of the ink receiving layer surface, and as a result, the recording dot is reduced. However, the shape is out of the perfect circle. Furthermore, the penetration into the base paper becomes irregular, and ink bleeding appears.

In the present invention, it is preferable to form a continuous coating layer having a uniform coating layer thickness on the surface of the support as the contour-coated layer. This is defined as 100% coverage. The coating thickness is also related to the coating amount, but it is preferable that the coating thickness is essentially a thin but continuous coating layer. The coating thickness is about 0.3 to 3 μm. I However, it is not necessary for the contour-coated layer to be completely covered on the surface of the support, and it is preferable that the coverage be 70% or more. As a means for measuring the coverage, a scanning electron microscope can be used, and there is a method of calculating an area ratio by analyzing an image using the scanning electron microscope.

In the ink jet recording sheet of the present invention, a scanning electron microscope can be used as a means for measuring the coating ratio of the coating layer on the pulp fiber surface on the ink receiving layer surface. Then, image analysis is performed to calculate the area ratio.

The ink jet recording sheet according to the present invention provides a finely coated and plain paper by using an ink receiving layer as a coating layer contour-coated along the surface of the support. Features a type close to. Also, when this is recorded using an ink printer, a recording dot close to a perfect circle can be expressed. The injected ink is instantly absorbed by the non-spherical cation-based colloidal silica, which has good ink absorption, and the excess ink is in the cross-sectional direction of the coating layer. Penetrates in the thickness direction of the support. For this reason, a recording dot free of ink blur unevenness can be obtained.

The ink jet recording sheet of the present invention is mainly composed of a non-spherical cationic colloidal silica as an ink receiving layer component.

As the non-spherical cationic colloidal force used in the present invention, the surface of a non-spherical colloidal silica is coated with a metal oxide hydrate as a cation modifier, and the It has been denatured. The term non-spherical as used in the present invention means that it is not substantially spherical, and has various forms such as a needle, a column, a bead, a rod, a plate, a lump, a fiber, a spindle, and the like. There is also a fibrous form as a long-chain form obtained by consolidating these. Of these, needle-like or column-like ones are particularly preferred.

The non-spherical cationic colloidal silica used in the ink jet recording sheet of the present invention includes aluminum oxide hydrate and zirconium oxide aqueous solution. The colloidal silica coated with a cation denaturant consisting of metal oxide hydrates such as hydrates and tin oxide hydrates is preferably used, and in particular, aluminum oxide A cation modified with hydrate is preferably used.

As the method of cation change, the method described in US Patent No. 3,077,878, Japanese Patent Publication No. 47-26959, etc. may be used. You can do it.

The maximum minor axis of the non-spherical cationic colloidal silica used in the present invention is 50 nm for a pulp fiber forming a base paper having a fiber diameter of several 10 zm. Hereinafter, the length is preferably 30 nm or less, and the length of the colloidal silica is 30 O nm or less, preferably 10 O nm or less. Since the ratio of the fiber diameter of the pulp fiber to the particle diameter of the colloidal force is less than one-hundredth of a hundredths, the surface of the base paper can be treated with a small coating amount as described above. The surface of the pulp fiber can be coated uniformly and thinly. These non-spherical cationic colloidal silicas are usually those which are dispersed in the form of a colloid in water while maintaining the primary particle diameter.

In the non-spherical cationic colloidal silica used for the ink jet recording sheet of the present invention, the coating amount of the metal oxide hydrate as the cationic modifier is used. For this purpose, a range of 1 to 30% by weight in terms of metal oxide is useful for the silicate force (Sio2 conversion). If the coating amount of the cationic modifier is too low, such as 1% by weight, the water resistance of the ink-recorded image of the ink-jet recording sheet is remarkably deteriorated, and conversely, too much. In addition, the film properties of the coated surface become brittle and cause cracks, which is not preferable. The coating amount is preferably 2.5 to 25% by weight, and more preferably 5 to 20% by weight.

In addition, the dispersion of non-spherical cationic colloidal silica contains acid components such as acetic acid, citric acid, sulfuric acid, and phosphoric acid for the purpose of colloid stability. You may do it.

The ink jet recording sheet of the present invention is mainly composed of non-spherical cationic colloidal silica as an ink-receiving layer component. It is composed of a component consisting of cationic colloidal silica and a binder, and the binder is used in an amount of 5 to 20 parts by weight based on 100 parts by weight of the colloidal silica. What is mixed by weight, is it preferable? ~ 15 parts by weight.

The effect of the present invention can be exhibited with a small amount of the binder in the ink receiving layer coating solution because of the above-mentioned color filter. This is due to the binder effect of the force itself. Although there is a binder effect of the colloidal silica itself, if the binder amount is less than 5 parts by weight, it is insufficient and more than 20 parts by weight. It is not preferable because ink absorption is impaired by the binder and the binder.

In the ink jet recording sheet of the present invention, the ink receiving layer coating liquid preferably has a coating liquid concentration of 4 to 20% by weight. Here, when the concentration of the coating liquid is less than 4% by weight, it is difficult to apply a predetermined amount of coating on the support, and when the concentration is higher than 20% by weight, depending on the coating method, It is more than the target coating amount, which is not preferable because it is close to the coated paper type.

The method for coating the ink receiving layer using the ink receiving layer coating solution having the above specific coating solution concentration includes various blade coaters and roll coaters. One night, one night air, one night, one rod, one night, gate o-one night, one night, one night, a show It is possible to use various devices such as Todo Erco overnight, Graviaco overnight, Flexo gravure coater, size press, etc. on-machine or off-machine. You. Of these various types of copiers, size presses, rod copiers, translators and translators are preferred. Often used.

Also, after coating, the machine calender, temperature gradient

(TG) It may be finished using a calendar such as a calendar, a sono, a single calendar, and a soft calendar.

In particular, in the ink jet recording sheet of the present invention, When the ink receiving layer coating liquid composed of the above composition has a coating liquid concentration of 4 to 10% by weight, it is preferable to perform coating using a size press. Here, when the concentration of the coating liquid is less than 4% by weight, it is difficult to apply a predetermined amount of coating on the support, and when the concentration exceeds 10% by weight and the concentration is high, it exceeds the target amount of coating. Therefore, it is not preferable because it is close to the coated paper type.

In the ink jet recording sheet of the present invention, the ink receiving layer coating liquid composed of the above composition has a coating liquid concentration of 10 to 20% by weight. It is preferable to apply using a rod coater, a transformer, a nighttime recorder or an air knife coater. Here, when the concentration of the coating liquid is less than 10% by weight, it is difficult to apply a predetermined amount of coating on the support, and when the concentration exceeds 20% by weight and the concentration is high, the desired amount of coating is obtained. As described above, it is not preferable because it is close to a coated paper type.

As described above, in the ink jet recording sheet of the present invention, the ink receiving layer has been described as the surface state of the coating layer surface with the metaphor added thereto. The coating amount of the receiving layer is 0.5 to 5.0 g / m ² , preferably 1.0 to 4.0 O g / m ² . Within this range, the ink jet recording sheet of the present invention can be used as the ink jet recording sheet, and can be handled as a type close to plain paper. Here, when the coating amount of the ink receiving layer exceeds 5.0 g / m ² , an ink jet recording sheet of a type close to plain paper can be obtained. Absent. Conversely, the coating weight of Lee down click receiving layer 0 in. Less than 5 g / m ^2, Lee down click-receiving layer component covering uniformly support surface I can't do it and I don't like it.

In the ink jet recording sheet of the present invention, an ultrafine inorganic pigment can be used in addition to the non-spherical cationic colloidal silica. The followings can be exemplified as the ultrafine inorganic pigment.

For example, silica (colloidal silica), aluminum or aluminum hydrate (aluminasol, colloidal aluminum, cationic aluminum) Oxides or their hydrates, suspected mites, etc.), surface-treated cationic colloidal silica, aluminum silicate, magnesium silicate, magnesium carbonate, etc. No.

Furthermore, as the inorganic pigment that can be used in combination with the ultrafine inorganic pigment, any conventionally known inorganic pigment can be used. For example, light calcium carbonate, heavy calcium carbonate, potassium phosphate, sulfuric acid, calcium sulfate, barium sulfate, titanium dioxide, zinc oxide, zinc sulfide, carbonate Zinc, satin white, aluminum silicate, silica silicate, calcium silicate, synthetic amorphous silica, aluminum hydroxide, lithobon, zeolite , Hydrolyzed halo site, magnesium hydroxide, and the like.

Among these inorganic pigments, porous inorganic pigments are preferred, and examples thereof include porous synthetic amorphous silica, porous magnesium carbonate, and porous alumina. A large porous synthetic amorphous silica is preferred.

In addition, styrene plastic pigments and acrylic Organic pigments such as plastic pigments, polyethylene, microcapsules, urea resins, and melamine resins can also be used in combination with the ultrafine inorganic pigments.

Binders used with non-spherical cationic colloidal silica include, for example, polyvinyl alcohol, butyl acetate, oxidized starch, etherified starch, carboxymethylcell D— Cell mouths of cellulose, hydroxy, shetylseno-relose, etc.-cellulose derivatives, casein, gelatin, soybean protein, silyl-modified polyvinyl alcohol, etc .; maleic anhydride resin, styrene Conjugated copolymers latex such as butadiene copolymers, methinoacrylate acrylates, and benzene copolymers; acrylate esters and methacrylyl Acrylic polymer such as acid ester polymer or copolymer, acrylic acid and methacrylic acid polymer or copolymer, etc. Latex: Ethylene vinyl acetate Vinyl-based polymers such as copolymers Tex; a polymer modified with a functional group-containing monomer such as a carboxyl group of these various polymers; a tex; a melamine resin, a urea resin, etc. Aqueous binders such as thermosetting synthetic resin resins; polymethyl methacrylate, polyurethan resin, unsaturated polyester resin, vinyl chloride vinyl acetate Synthetic resin-based binders such as rimer, polyvinyl butyral, and alkyd resin can be mentioned, and at least one kind can be used.

Further, a thionionic resin added for the purpose of fixing a conventionally known dye can also be used in combination. Other additives include pigment dispersants, thickeners, flow improvers, defoamers, foam inhibitors, mold release agents, foaming agents, penetrants, coloring dyes, coloring pigments, and fluorescent brightening agents. Agents, ultraviolet absorbers, antioxidants, preservatives, anti-binders, water-proofing agents, wet paper strength agents, dry paper strength agents, and the like can also be appropriately compounded.

The second ink jet recording sheet of the present invention is a finely coated ink receiving layer that is contour-coated along the surface of the support, and includes a component of the ink receiving layer. Specified, and the total cation charge of the recording sheet is within a specific range per 100 g of the recording sheet.

The total amount of thione charge of the ink jet recording sheet of the present invention is 0.5 to 20 meq in accordance with the ink jet recording sheet of the fine coating type. Z 100 g, preferably 10 to 15 meq. Here, if the total thione charge is less than 0.5 meq.Z 100 g, it is not enough to achieve the purpose of the present invention, and the total thione charge is 20 meq./100 g. In the case of exceeding, the coating amount of the ink receiving layer also needs to be increased at the same time, and it is out of the category of the ink jet recording sheet of the fine coating type of the present invention. .

The total amount of thione charge is related to the fixing properties of the ink dye, and in the ink jet recording sheet of the fine coating type within the scope of the present invention, the ink charge is When the ink is injected by the printer, an anionic ink dye is fixed in the ink receiving layer, and the ink solvent is quickly transferred to the support. Can be absorbed inside. As a result, the image density is high, Inkjet recording of clear images is now possible. The ink-receiving layer component that contributes to the total amount of thione charge mainly includes the non-spherical cationic colloidal silica of the present invention, and also includes a cationic dye fixing agent and the like. There is. The total amount of thione charge within the scope of the present invention is 100 g of an ink jet recording sheet coated with an ink receiving layer containing these cationic materials. The total power of the thione charge. Further, in addition to the ink receiving layer components, a material comprising a strong thione material, for example, a basic pigment such as calcium carbonate, is internally added to the support of the recording sheet. In this way, the amount of charge from materials other than those in the ink receiving layer is added to the total amount of charge, and the total amount of ink in the ink jet recording sheet is calculated. The amount of charge is not limited in any way.

The total power of the ink jet recording sheet can be measured by the following method. First, the recording sheet including the base paper as the support and the ink-receiving layer coated on the base paper was collected, ion-exchanged water was added thereto, and the mixture was disintegrated. Collect the sample, adjust the pH to 4 to 5 by adding a buffer, then add an anionic substance for colloid titration, and filter to obtain a sample of a predetermined concentration. Measure with a colloid titration method using a microtiter plate.

The total thione charge is the cation charge of 100 g of the recording sheet, and is conveniently the sum of the cations of the support and the ink receiving layer. The total weight of the basis weight of the support and the coating weight of the ink-receiving layer was recorded on the ink jet recording system. It can be calculated as a value multiplied by a coefficient obtained by converting per 100 g. The unit is meq ./100 g. .

The third ink jet recording sheet of the present invention uses a support containing a specific polyvinylamine copolymer, and is coated with a fine outline coated along the surface of the support. It has an ink-receiving layer for coating.

In the ink jet recording sheet of the present invention, the support used is a copolymer of N-vinylformamide and acrylonitrile, and the vinylamine has a molar ratio of 2 The support contains a polyvinylamine copolymer having a molecular weight of at least 0 mol% and a molecular weight of at least 500,000. The ink jet recording sheet of the present invention is obtained by coating the ink receiving layer on the support using the support, and has excellent water resistance of the recorded image. ing.

The ink jet recording ink mainly comprises an aqueous ink containing a direct dye or an acid dye, and the anionic portion of the dye in the recording ink. The dye can be fixed by the reaction between the dye and a cationic substance such as a polyvinylamine copolymer used in the present invention. When the base paper (support) is made of a polyvinylamine copolymer as a cationic substance during the papermaking process, the polyvinylamine copolymer is strong against the pulp. Adsorbed and held in base paper (support). The dye of the recording ink thus recorded is formed by a polyvinylamine copolymer adsorbed on a support. As a result, the recorded image exhibits water resistance.

In the case of an ink jet recording sheet in which an ink receiving layer is provided on a support containing a polyvinylamine copolymer, an ink jet recording ink is used. When the ink is first applied to the ink receiving layer, the force is absorbed in the ink receiving layer, and the excess ink is absorbed in the thickness direction of the recording sheet, that is, in the support. The polyvinylamine copolymer contained and the dye of the ink come into contact with each other to fix the dye. Since the fixed dye is firmly fixed to the support, it does not elute even when external water is given. That is, a recorded image having water resistance can be obtained.

Here, even in the poly (vinylamine) copolymer obtained by copolymerization of N-vinylformamide and acrylonitrile used in the present invention, the vinylamine ratio is 20 mol. %, Sufficient water resistance cannot be obtained, and when the molecular weight is less than 500,000, the fixability of the polyvinylamine copolymer to the pulp and ink-receiving layers is insufficient. And the water resistance of the recorded image tends to be poor.

The polyvinylamine copolymer used in the present invention can be contained in an amount of 1% by weight or more, preferably 3% by weight or more, per pulp solid content of the support.

The poly (vinylamine) copolymer used in the present invention is exemplified by Japanese Patent Application Laid-Open (JP-A) Nos. Sho 64-49694 and Hei 4-111904. It is a copolymer.

Monomers for synthesizing polyvinylamine copolymers In addition to N-vinylformamide, for example, N_vinylacetamide, N-vinylpropionamide, N-vinylcarboxymethyl methacrylate, N-vinylvinylamide And ethyl propyl carboxylate.

Examples of monomers copolymerized with N-vinylformamide include acrylonitrile, alcohols having 1 to 4 carbon atoms, and (meth) acrylic acid. (Meth) acrylic acid ester, acrylamide, (meth) acrylic acid, and the like. Of these, particularly preferred are acrylonitrile and atalinoleamide.

Examples of the support used in the present invention include chemical pulp such as LBKP and NBKP, SGW, PGW, RMP, TMP, CTMP, CMP.CGP in addition to the above-mentioned polyvinylamine copolymer. Pulp, such as mechanical pulp, waste paper pulp, DIP, etc., and conventionally known pigments as binders, binders and size agents, fixing agents, yield improvers, cationizing agents, Base paper made by mixing one or more types of additives such as a paper strength agent and using various devices such as a fourdrinier paper machine, a circular web paper machine, and a twin wire paper machine.

More preferably, the base paper is a base paper whose surface is sized using a water-soluble polymer such as starch or polyvinyl alcohol. When the size-treated base paper is used, the coating and fixing properties of the ink receiving layer can be improved.

Even if such base paper is provided with an ink receiving layer as it is, For the purpose of controlling good and flattening, a calendar such as a machine calendar, a temperature gradient (TG) calendar, a soft calendar, etc. An ink receiving layer may be provided after using the die unit.

The ink jet recording ink according to the present invention is an aqueous ink comprising the following colorant, liquid medium, and other additives.

Examples of the coloring agent include water-soluble dyes such as direct dyes, acid dyes, basic dyes, reactive dyes, and food dyes.

Examples of the solvent for the aqueous ink include water and various water-soluble organic solvents such as methyl alcohol, ethyl alcohol, n-propynole alcohol, and isopropanol alcohol. C, alkyl alcohols having 1 to 4 carbon atoms such as n-butynol alcohol, sec-butynoleanol, tert-butyl alcohol, isobutyl alcohol; dimethylformamide, Amides such as dimethyl acetate amide; ketones or ketone alcohols such as acetate and diacetone alcohol; tetrahydrofuran, dioxane, etc. Ethers; polyethylene glycols, polyalkylene glycols such as polypropylene glycols; ethylene glycols; Propylene glycol, Chilean glycol, triethylene glycol, 1, 2, 6 — hexanitol, thioglycol, hexylene glycol Alkylene glycols such as ethylene glycol, ethylene glycol, etc .; 2 to 6 alkylene glycols; glycerin, ethylene glycol methyl ether, gel Lower alkyl ethers of polyhydric alcohols such as methyl alcohol methyl ether (or ethyl ether), triethylene glycol, monomethyl ether, etc. Are mentioned. Among these many water-soluble organic solvents, polyhydric alcohols such as ethylene glycol, triethylene glycol, etc., and methyl ether ethers And lower alkyl ethers of polyhydric alcohols such as triethylene glycol monoethyl ether.

Examples of the other additives include a pH adjuster, a metal sequestering agent, a fungicide, a viscosity adjuster, a surface tension adjuster, a wetting agent, a surfactant, and a sunscreen.

The ink jet recording sheet according to the present invention is not limited to the use as an ink jet recording sheet, but may be any ink sheet that is liquid at the time of recording. It can also be used as such a recording sheet.

For example, an ink sheet obtained by applying a heat-fusible ink mainly composed of a heat-fusible substance, a dye or the like on a thin support such as a resin film, high-density paper, or synthetic paper. An image receiving sheet for thermal transfer recording, which heats the ink from the back side and melts and transfers the ink, and an ink jet which heats and melts the heat-meltable ink into fine droplets and records the flight Record sheet, ink jet record sheet using an ink in which an oil-soluble dye is dissolved in a solvent, a photopolymerizable monomer, and a microphone containing a colorless or colored dye / pigment. An image receiving sheet corresponding to a photosensitive pressure-sensitive donor sheet using a mouth capsule is exemplified. The common feature of these recording sheets is that the ink is in a liquid state during recording. The liquid ink penetrates or spreads in the depth or horizontal direction of the ink receiving layer of the recording sheet before curing, solidifying or fixing. Since the various recording sheets described above require absorptivity in accordance with each system, the ink jet recording sheet of the present invention is combined with the various recording sheets described above. There is no restriction to use it.

Further, the ink jet recording sheet according to the present invention is used as a recording sheet for heating and fixing an electrophotographic recording method toner widely used in copiers and printers. Can also be used.

First, the ink jet recording sheet according to the present invention is an ink jet recording sheet having an ink receiving layer coated on a support. The ink-receiving layer is a coating layer mainly composed of non-spherical cationic colloidal silica, and has a coating amount of 0.5 which is contour-coated along the surface of the support. ~ 5. is a coating layer of O g / m ^2. When ink is applied to the ink receiving layer of the recording sheet, the ink does not spread in the surface direction, penetrates into the ink receiving layer, and excess ink flows in the thickness direction of the base paper. It is possible to obtain a recording dot shape close to a perfect circle by penetrating the ink jet recording sheet with high density and sharpness of the recorded image. O

Secondly, the ink jet recording sheet of the present invention is an ink jet recording sheet having an ink receiving layer provided on a support. In the jet recording sheet, the ink receiving layer component is mainly composed of non-spherical cationic colloidal silica, and the ink receiving layer extends along the surface of the support. coated amount is contoured coating Te 0. 5 ~ 5. O g / m 2 of the coating layer der is, and the recording total Gachio emissions charge amount force of sheet 0. 5 ~ 2 O meq. / in lOOg is there. When the ink is applied to the surface of the ink receiving layer of the recording sheet, the anionic ink is quickly fixed to the ink receiving layer (partly inside the base paper), and the surface of the ink receiving layer is fixed. It is presumed that the ink does not spread in the direction, and then the excess ink penetrates in the thickness direction of the base paper, resulting in a recording dot shape close to a perfect circle. This makes it possible to obtain an ink jet recording sheet with high density and sharpness of the recorded image.

Third, the ink jet recording sheet according to the present invention is an ink jet recording sheet comprising an ink receiving layer coated on a support. The support is subjected to a copolymerization reaction between N-vinylformamide and acrylonitrile, and has a molecular weight of at least 500,000 and a vinylamine molar ratio of at least 20 mol%. The ink-receiving layer component is mainly composed of non-spherical cationic colloidal silica, and the ink-receiving layer is composed of a non-spherical cationic colloidal silica. The layer is a coating layer having a coating amount of 0.5 to 5.0 g / m ² which is contour-coated along the surface of the support. When ink is applied to the ink receiving layer of the recording sheet, the anionic ink dye is quickly fixed to the ink receiving layer, and ink is directed toward the surface. Does not spread, then surplus ink is the thickness of the support (base paper) Penetrates in the opposite direction. The excess ink is brought into contact with the polyvinylamine copolymer in the support to fix the dye. It is presumed that by fixing this dye, excellent water resistance can be obtained.

[Best mode for carrying out the invention]

Hereinafter, examples of the present invention will be described, but the present invention is not limited to these examples. Further, “parts” and “%” shown in the examples are parts by weight and% by weight unless otherwise specified.

The ink jet recording sheets prepared in the following Examples and Comparative Examples were evaluated based on the following methods, and the results are shown in Tables 1 to 6 and 8, respectively.

[Ink absorption]

The ink absorptivity and the sharpness of the image are determined by the bleeding of the ink at the border of the solid-color solid printing area, for example, at the border of the red printing (magenta + yellow) and the green printing (cyan + yellow). The condition was visually determined. The case where the red printed portion and the green printed portion did not overlap and were separated was regarded as good characteristics, and the case where the overlap became large and became a black line was regarded as poor characteristics. A substance with poor ink absorption significantly deteriorates image quality (image clarity), so that even if other properties, for example, image density, are good, it has no meaning.

As evaluation criteria, A has good characteristics, B has good characteristics without practical problems, C has practical problems, and D has poor characteristics. [Image density]

The image density was measured using a reflection densitometer (Macbeth RD 918; manufactured by Macbeth) at the portion printed solid with black ink. The higher the numerical value is, the higher the image density is, and the better the image density is.

[Coverage]

The coverage (%) was determined by taking an X-ray image of the metal element of the material used on the pulp fiber surface of the ink jet recording sheet with a scanning electron microscope and using an image analyzer. The coverage on the surface of the support was measured as the area ratio.

[Dot shape factor]

Using an ink jet printer (July 720: manufactured by Sharp Corporation), a single-color dot consisting of black ink is printed and printed on an image analyzer. Therefore, the perimeter L of the dot and the area A of the dot were measured, and the dot shape factor C defined by Equation 1 below was calculated. Dot shape factor C The larger the force is, the larger the distance from the force is 1.0, indicating that the dot shape is irregular due to bleeding of the dot.

[Equation 1]

C 2 L ² Z (4 TT XA)

Here, C is the dot shape factor, L is the perimeter of the dot, and A is the area of the dot.

[Examples 1 to 5 and Comparative Examples 1 to 4]

Example 1

[Preparation of base paper] 3 parts of LBKP 83 with a freeness of 450 mlcfs and 8 parts of NBKP with a freeness of 48 O mlcs. 0.8 parts of cation starch, 0.4 parts of sulphate band and 0.110 parts of alkirketene dimer were added to the pulp slurry, and the pulp slurry was adjusted to pH 8.2. It was adjusted to, and papermaking dried Fourdrinier, and the Ma Thin mosquito les down Zehnder finished, to prepare a base paper having a basis weight of 8 5 g / m ^2. The stencil size of the prepared base paper was 25 seconds.

[Preparation of ink jet recording sheet]

The base paper was manufactured Ri by the above, as a Lee down click-receiving layer composition, needle-like co B A Darcy Li Ca shea Li mosquito (S i 0 ₂ conversion) paired Shi A 1 ₂ ◦ ₃ terms A 10% aqueous dispersion of needle-like cationic modified colloidal silica modified with about 6.2% by weight of aluminum oxide hydrate (particle size; width 1 0 to 20 nm X length 50 to 200 nm, cationic charge amount 0.41 meq./g) 100 parts, 60 parts of cationic resin as dye fixing agent % Aqueous solution (Polyix 61, cationic charge amount 6.9 meq./g, manufactured by Showa Polymer Co., Ltd.) Aqueous dispersion with 50% solid content and a solid concentration of 10% The solution is applied using a size press to a dry solid content of 0.5 g / m ² , dried, calendered and finished to make an ink jet recording sheet. Was made.

Example 2

Ink jet was prepared in the same manner as in Example 1 except that the amount of dry solid content in Example 1 was adjusted to 1.0 g / m ² using Rodco overnight. A seat record sheet was prepared. Example 3

The same procedure as in Example 1 was carried out except that the amount of the dry solid content in Example 1 was changed to 3.0 g / m ² by using a transfer filter. An ink jet recording sheet was prepared.

Example 4

The ink was prepared in the same manner as in Example 1 except that the dry solid content in Example 1 was applied using Air-Nifco Co., Ltd. to 5.0 g / m ² . A jet recording sheet was prepared. Comparative Example 1

The ink jet was prepared in the same manner as in Example 1 except that the dry solid content in Example 1 was applied using a size press so as to be 0.3 g / m ² . A recording sheet was made.

Comparative Example 2

Ink jet was prepared in the same manner as in Example 1 except that the dry solid content in Example 1 was adjusted to 5.5 g / m ² by using an air knife coater. A sheet recording sheet was prepared. Example 5

Instead of the needle-shaped cationic modified colloidal silica used in Example 1, a column-shaped colloidal silica was replaced with silica.

(S i 0 ₂ conversion) paired Shi A l ₂ 0 3 in terms of 2 9.5 wt% of oxide Al Mini ©厶水dihydrate in by Ri denatured columnar Ca Ji on-copolyester B A Dar Using a 10% aqueous dispersion of silica (particle size; width 4 O nmx length 100 to 30 O nm, cation charge 1.9 O meq./g), dry solid content the amount 3. 0 g / m ² and An ink jet recording sheet was prepared in the same manner as in Example 1 except that the coating was performed using a trans-fer roll coat overnight.

Comparative Example 3

Instead of the needle-like cationic modified colloidal silica force used in Example 1, a 40% aqueous dispersion of spherical colloidal silica (−300 ± 3 particle size) was used. 0 11 111, mosquitoes Ji on-charged amount one 0. 0 1 meq. / g ) 2 5 0 parts using, 3 the amount of dry solids. O g / m ² and Do that by power sale to preparative run- An ink jet recording sheet was prepared in the same manner as in Example 1 except that the coating was performed using a spherical roll.

Comparative Example 4

Instead of the needle-shaped cationic modified colloidal silica used in Example 1, a 30% aqueous dispersion of powdered silica (Nippsil E220A, Nihon Shiritsu) was used. . Li Ca Industries Ltd., average particle size 1 0 m, Kachio emissions charge amount -... 0 0 9 meq / g) 3 3 3 parts using, 3 the amount of dry solids 0 g / m ² and it Thus, an ink jet recording sheet was prepared in the same manner as in Example 1 except that the coating was performed using a transfer roll.

Table 1 shows the evaluation results of the ink jet recording sheets prepared in Examples 1 to 5 and Comparative Examples 1 to 4 described above. table 1

From the results shown in Table 1, the ink jet recording sheet of the present invention has a high coverage of the contour-coated layer, and has good ink absorption, image density and sharpness. In addition, the dot shape factor was small and showed a recording dot shape close to a perfect circle.

On the other hand, Comparative Examples 1 and 2 are cases where the coating amount of the ink receiving layer is out of the range.

Comparative Example 1 was inferior in ink absorption and clarity, and Comparative Example 2 showed good results, but was not preferable for handling as plain paper. Comparative Example 3 is an example using spherical colloidal silica, but not modified with cation Therefore, the image sharpness was poor, the coverage was low, and the dot shape factor was poor. In Comparative Example 4, the sharpness of the image was poor, the coverage was low, and the dot shape factor was poor due to the large particle size of the inorganic pigment used.

[Examples 6 to 11 and Comparative Examples 5 to 9]

Example 6

[Preparation of base paper]

It is composed of 3 parts of LBKP with a freeness of 45 O mlcfs and 8 parts of NBKP with a freeness of 480 mlcsί. 0.8 parts of cation starch, 0.4 parts of sulfuric acid compound and 0.110 parts of alkyl ketene dimer are added to the lubricating slurry, and the lubricating slurry is added. . was adjusted to 2, and papermaking dried Fourdrinier, and the Ma Thin mosquito les down Zehnder finished, to prepare a base paper having a basis weight of 8 5 g / m ^2. The stencil size of the prepared base paper was 25 seconds.

[Preparation of ink jet recording sheet]

The base paper was manufactured Ri by the above, as a Lee down click-receiving layer composition, needle-like co B A Darcy Li Ca shea Li mosquito (S i 0 ₂ conversion) paired Shi A 1 ₂ 0 ₃ in terms of A 10% aqueous dispersion of acicular cation-modified colloidal silica, modified with about 6.2% by weight of aluminum oxide hydrate (particle size; width: 10 to 10%) 200 nm X length 50-200 nm, charge amount of cation 0.41 raeq./g) 100 parts, 10% aqueous solution of polyvinyl alcohol as adhesive (PVA117, Kuraray Co., Ltd.) 300 parts, 60% aqueous solution of cationic resin as a dye fixing agent Fixation: 61, cationic charge: 6.9 meq./g, manufactured by Showa Polymer Co., Ltd.) An aqueous dispersion containing 50 parts as a main component and having a solid content of 10% was prepared by Rodco. One coat was used to apply a dry solid content of 1 g / m ² , dried, and calendered to produce an ink jet recording sheet.

Example 7

Ink jet was performed in the same manner as in Example 6, except that the dry solid content in Example 6 was applied using a size press so as to be 0.5 g / m ² . A recording sheet was prepared.

Example 8

The ink jet was prepared in the same manner as in Example 6, except that the dry solid content in Example 6 was applied using a load coater so as to be 2 g / m ² . A recording sheet was made.

Example 9

The aqueous dispersion used in Example 6 was applied to a solid concentration of 15%, and coated and dried using an air knife coater to a dry solid content of 5 g / m ² . After finishing the calendar, an ink jet recording sheet was prepared.

Example 10

The base paper prepared in Example 6, and the Lee down click-receiving layer composition, needle-like co B A Dodarushi Li Ca shea Li mosquito (S i 0 2 conversion calculation) paired Shi A 1 ₂ 0 3 in terms of Of a needle-shaped cationic modified colloidal silica modified with about 11% by weight of aluminum oxide hydrate at 10% aqueous solution (Snotex) UP — AK (1), manufactured by Nissan Chemical Industries, Inc., particle size; width: 10 to 20 nm X length Agglomerate of 50 to 200, cationic charge amount 0.10 meq./g) 100 parts, 10% aqueous solution of polyvinyl alcohol (PVA 1 170 parts, manufactured by Kuraray Co., Ltd.) 300 parts, 30% aqueous solution of cationic resin as dye fixing agent (Smilease resin 1001, cationic charge amount 3) 5 meq./g, manufactured by Sumitomo Chemical Co., Ltd.) An aqueous dispersion containing 100 parts as a main component and having a solids concentration of 10% was dried and solidified using a trans- fer filter. It was coated so as to have a mold weight of 2 g / m ² , dried, and calendered to produce an ink jet recording sheet. Example 1 1

The base paper prepared in Example 6, in as the click-receiving layer composition, 2 a columnar co B A Darcy Li Ca in Shi Li mosquito (S i 〇 ₂ equivalent) paired Shi A 1 ₂ 〇 ₃ terms A 10% aqueous dispersion of columnar cationic colloidal silica modified with 9.5% by weight of aluminum oxide hydrate (particle size; width 4 O nmx length 1 100 to 300 nm, cationic charge amount 1.9 Oraeq./g) 100 parts, 10% aqueous solution of polyvinyl alcohol as adhesive (PVA 117, 300 parts, 60% aqueous solution of cationic resin as dye fixing agent (Polyix 61, cationic charge 6.9 meq./g) , Showa high content made Kosha) 5 0 parts that Do a dry solids 5 g / m ² using an air Nai full co one te a solid concentration of 1 5% of the aqueous dispersion as a main component Coated, dried and finished with a calendar To prepare a click di We Tsu door record sheet.

Comparative Example 5 A 40% aqueous dispersion of spherical colloidal silica (primary particle diameter of 300 ± 30 nm, as the ink receiving layer composition) was added to the base paper prepared in Example 6. 250 l parts, 0.1% aqueous solution of poly alcohol (PVA 117, Kuraray Co., Ltd.) as adhesive, 300 parts 60% aqueous solution of cationic resin as dye fixing agent (polyix 61, cationic charge 6.9 meq./g, manufactured by Showa Kagaku Co., Ltd.) 50 part DOO lance off § a solid concentration of 1 0% water dispersion solution mainly composed of over Russia Ruko one evening coated on earthenware pots by that Do a dry solids 2 g / m ² using one, After drying, the calendar was finished to produce an ink jet recording sheet.

Comparative Example 6

The base paper prepared in Example 6, and the Lee down click-receiving layer composition, the co-B A Darcy Li mosquito spherical Shi Li Ka Shi pair (S i 0 2 conversion) A 1 ₂ 0 ₃ in terms of 1 30% aqueous dispersion of spherical cationic colloidal silica modified with 2.5% by weight of aluminum oxide hydrate (primary particle diameter 80 nm, cationic Charge amount (0.80 meq./g) 3 3 3 parts, 10% aqueous solution of polyvinyl alcohol as adhesive (PVA 117, manufactured by Kuraray Co., Ltd.) 300 parts, dye As a fixing agent, 50 parts of a 60% aqueous solution of cationic resin (Polyix 61, cationic charge amount 6.9 meq./g, manufactured by Showa Polymer Co., Ltd.) was used. An aqueous dispersion having a solid content of 10%, which is the main component, is applied to a dry solid overnight to obtain a dry solid content of 2 g / m ² , dried, and calendered. Finish to create an ink jet record sheet. It was. Comparative Example 7

A 10% aqueous dispersion of acicular colloidal silica (particle size; width: 10 to 2 O nmx length) was added to the base paper prepared in Example 1 as an ink receiving layer composition. Aggregate of 50 to 200, charge amount of cation: 0.02 meq./g) 100 parts, 10% aqueous solution of polyvinyl alcohol (PVA1) as adhesive 170 parts, manufactured by Kuraray Co., Ltd.) 300 parts, 30% aqueous solution of cationic resin as dye fixing agent (Sumirez resin 1001, cationic charge amount) 3.5 meq./g, manufactured by Sumitomo Chemical Co., Ltd.) An aqueous dispersion having a solids concentration of 10%, which is mainly composed of 100 parts, was prepared using a trans-fer roller. The ink was coated so as to have a dry solid content of 2 g / m ² , dried, and calendered to prepare an ink jet recording sheet.

Comparative Example 8

The base paper prepared in Example 6 was used as an ink receiving layer composition, as a 30% aqueous dispersion of powdered silica (Nippsil E220A, manufactured by Nippon Silicon Industries, average Particle size: 1.0 m, Cationic charge_0.09 meq./g) 33 parts, 10% aqueous solution of polyvinyl alcohol as adhesive (PVA 117, Claret 300 parts, 60% aqueous solution of cationic resin as dye fixing agent (Polyix 61, cationic charge 6.9 meq./g, Showa) the polymer Co., Ltd.) preparative 5 0 parts solids concentration 1 shall be the main component 0% aqueous dispersion lance off § over Russia over Turkey one evening dry solids 2 g / m ² by using an Coating, drying, calendering and ink jet recording sheet Was made.

Comparative Example 9

The aqueous dispersion used in Comparative Example 7 was adjusted to have a solid content of 15%, and was coated with an air knife coat to a dry solid content of 5 g / m ² , dried, and dried. Finished the ink jet recording sheet.

Table 2 shows the evaluation results of the ink jet recording sheets prepared in Examples 6 to 11 and Comparative Examples 5 to 9 described above.

Table 2 Related ink Ink rooster image clarity Clearness Dot or specific absorption (吸収) Shape factor Example 6 A 1. π A δ 1 1.12 Example 7 A 1.30 B 12 1.15 Example 8 A 1. HA, 1.10 Example 9 A 1.52 AS δ 1.08 Example 10 A 1. UA 85 1.13 Example 11 A 1. Π A 93 1.10

Image 5 B 1.08 C 6 {i.Π Comparative Example 6 B 1.15 c 69 1.21 删 7 A 1. Πc δ 5 1.21 Comparative Example 8 B ■ 1.12 c {9 1.36 Comparative Example 9 C 1.18 B 6 δ 1.31 According to the results in Table 2, in the ink jet recording sheets of Example 6 11 and Comparative Example 59, the recording sheets in the examples used non-spherical cationic colloidal silica. The coverage was within the range of the present invention, and both ink absorption, image density, and sharpness were good. Also, the dot shape factor was small, indicating a recording dot shape close to a perfect circle.

On the other hand, in Comparative Examples 5 and 6, since the spherical colloidal silica was used, the dot shape factor was large, and the recording dot shape was inferior. In Comparative Example 7, needle-like colloidal silica not modified with cation was used in place of the cation-modified needle-shaped colloidal silica of Example 10; Because of no denaturation, the image density and sharpness were poor. In Comparative Example 9, the coating amount was as large as 5 g / m ² , but the coverage was low due to the large particle size of the inorganic pigment used. In Comparative Example 8, the coating amount was 2 g / m ² , and the inorganic pigment used had a large particle size and a low coverage.

[Example 122 and Comparative Example 101]

Example 1 2

Lupus slurry consisting of 90 parts of LBKP with a freeness of 450 mlcsi and 10 parts of NBKP with a freeness of 480 m1 csf, 9 parts of kaolin, 0.8 parts of cation starch, The sulfuric acid band was adjusted to pH 8.2 by adding 0.4 parts of a sulfuric acid band and 0.10 parts of an alkyl keten dye. To prepare a base paper having a basis weight of 8 5 g / m ² and papermaking dried paper machine, followed by the composition of the fin click-receiving layer, needle-like co B A Dar re force Shi Li mosquito ( S i 0 ₂ conversion) paired Shi a 1 ₂ 0 s translated at about 6.2 wt% of Ri by the oxidation Aluminum Niu arm hydrate modified acicular mosquito thio emissions modified copolymer b a Darcy Li Ca 10% aqueous dispersion (particle size; width: 10 to 20 nm x length: 50 to 200 nm, electric charge of thione 0.41 meq./g) 100 parts, adhesive 50 parts of a 10% aqueous solution of polyvinyl alcohol (PVA 117, manufactured by Kuraray Co., Ltd.) and 60% aqueous solution of a cationic resin as a dye fixing agent (polystyrene) 601 mex./g, cationic charge amount 6.9 meq./g, manufactured by Showa Polymer Co., Ltd.) And dry to a dry solid content of 0.5 g / m ^{2 using} a An ink jet recording sheet was prepared by rendering the output.

Example 13

The ink receiving layer composition of Example 12 was coated with a size press so that the solid content concentration was 6%, and the amount of the dry solid content was 2 g / m ² . An ink jet recording sheet was prepared in the same manner as in Example 12 except for the above.

Example 14

Example 1 2 Lee down click-receiving layer composition was a solid content concentration of 1 0% with the size up Les scan the amount of dry solids 4. 5 g / ffl in earthenware pots by ² and that Do An ink jet recording sheet was prepared in the same manner as in Example 12 except that the ink was applied. Comparative Example 10

The ink receiving layer composition of Example 12 was adjusted to a solid content concentration of 3%, and the dry solid content was adjusted to 0.3 g / m ² using a size press. An ink jet recording sheet was prepared in the same manner as in Example 12 except that the coating was performed.

Comparative Example 1 1

The ink receiving layer composition of Example 12 was used at a solid content concentration of 12%, and a dry press was used so as to have an amount of 5.5 g / m ^{2 using a} size press. An ink jet recording sheet was prepared in the same manner as in Example 12 except that the coating was performed.

Example 15

Instead of Lee down click-receiving layer coating solution of Example 1 2, columnar co B A Da Le sheet against the re mosquitoes in Shi Li mosquito (S i 〇 ₂ equivalent) eight 1 ₂ 0 equivalent to ₃ 2 9 A 10% aqueous dispersion of columnar cationic colloidal silica modified with 5.5% by weight of aluminum oxide hydrate (particle size; width: 40 nm × length: 100 nm) ~ 30 O nm, cationic charge amount 1.9 O meq./g) 100 parts, 10% aqueous solution of polyvinyl alcohol as adhesive (PVA 117, 100 parts, 60% aqueous solution of cationic resin as dye fixing agent (Polyix 61, cationic charge amount 6.9 meq., Showa High Polymer) company, Ltd.) 1 6.7 parts applied to the jar by that Do a solid content concentration of 6% of the aqueous dispersion liquid fraction the size-flops be dried solid and have use the content ² g / m 2 as a main component of the Dry, dry, machine-calender finished and record the ink jet It was produced over door. Example 16

After paper-making in the same manner as in Example 12, the oxidized starch was applied to a size of 0.5 g / m ² by a size press, dried, and finished with a machine calendar. Thus, the size base paper used in Example 16 was used. Subsequently, the 6% aqueous dispersion of Example 15 was used, coated and dried under the same conditions, and calendered to prepare an ink jet recording sheet. At this time, the dry solid content was 2.5 g / m ² .

Example 17

Instead of the ink receiving layer coating liquid of Example 12, a 10% aqueous dispersion of the columnar cationic colloidal silica used in Example 15 (particle size; width 4O nmx length 100 to 30 O nm, cationic charge amount 1.90 meq./g) 100 parts, 10% aqueous solution of polyvinyl alcohol as adhesive (PVA 1150 parts, manufactured by Kuraray Co., Ltd.) 150 parts, power as a dye fixing agent. 60% aqueous solution of thionic resin (Polyix 61, Cationic charge 6) 9 meq./g, manufactured by Showa Polymer Co., Ltd. 16.7 parts of an aqueous dispersion having a solid content of 8% as a main component was dried using a size press to obtain a solid content of 2 g / m2. ^It was coated so as to become ² , dried, and finished with a single machine calendar to produce an ink jet recording sheet.

Comparative Example 1 2

The Ri generations columnar cationite down copolyester B A Dar Li mosquitoes used in Example 1 7, Shi pair co B A da Honoré sheet re mosquito spherical Shi Li mosquito (S i 0 ₂ conversion) A 1 2.5 wt 1 ₂ 0 ₃ basis 30% aqueous dispersion of spherical cationic colloidal silica modified with 1% aluminum oxide hydrate (primary particle size 8 O nm, cationic charge An ink jet recording sheet was produced in the same manner as in Example 17 except that 3.3 parts of 0.8 Omeq./g) were used. The dry solid content was 2.0 g / m ² .

Comparative Example 1 3

Instead of the columnar cationic colloidal silica used in Example 17, a needle-like colloidal silica 10% aqueous dispersion (particle size; width: 10 to 2) The same procedure as in Example 17 was carried out except that 100 parts of an aggregate having an O nmx length of 50 to 200 and a cationic charge amount of 0.02 meq./g) were used. An ink jet recording sheet was prepared. The dry solid content was 2.0 g / m ² .

Comparative Example 1 4

Instead of the columnar cationic colloidal silica used in Example 17, a 30% aqueous dispersion of powdered silica (Nippsil E22 OA, Japanese silica) was used. The same procedure as in Example 6 was carried out except that 33 parts of Rica Kogyo Co., Ltd., average particle diameter 1.Q am, cationic charge amount-0.09 meq./g) were used. A test record sheet was prepared. The dry solid content was 2.0 g / m ² .

Example 18

Instead of the ink receiving layer coating liquid of Example 12, a 10% aqueous dispersion of the columnar cationic colloidal silica used in Example 15 (particle size; width 4) was used. O nmx length 100 to 300 nm, cation charge amount 1.90 meq./g) 100 parts, adhesive 200 parts of a 10% aqueous solution of polyvinyl alcohol (PVA117, manufactured by Kuraray Co., Ltd.) and 60% aqueous solution of a cationic resin as a dye fixing agent (polystyrene) 66.1, Cation charge 6.9 meq./g, manufactured by Showa Polymer Co., Ltd.) 16.7 parts of an aqueous dispersion with a solid content of 10% The ink was coated to a dry solid content of 4.0 g / m using a dresser, dried, and calendered to produce an ink jet recording sheet.

Comparative Example 15

The 10% aqueous dispersion used in Example 18 was coated using an air knife coater, dried, and calendered to prepare an ink jet recording sheet. . The dry solid content was 6.0 g / m ² .

Table 3 shows the evaluation results of the ink jet recording sheets prepared in Examples 12 to 18 and Comparative Examples 10 to 15 described above.

Table 3

From the results shown in Table 3, the ink jet recording sheet of the present invention has a high coverage of the contour-coated layer, and has a high ink absorption, image density and sharpness. The recording dot shape was good, the dot shape factor was small, and the recording dot shape was close to a perfect circle. Examples 12 to 14 and Comparative Examples 10 to 11 are examples in which the same binder amount was used.However, in Comparative Example 10, a predetermined amount could not be applied because the concentration of the coating solution was low. It was bad. On the other hand, Comparative Example i1 was a good evaluation result, but was coated in a predetermined amount or more because of the high concentration of the coating liquid, and was not preferable for handling plain paper.

In Examples 15 and 16, the untreated base paper and the size-treated base paper were compared.However, using the size-treated base paper can increase the amount of coating even at the same coating liquid concentration, and variously. The characteristics were also good.

[Examples 19 to 25 and Comparative Examples 16 to 21]

Example 19

[Preparation of base paper]

It consists of 90 parts of LBKP with a freeness of 450 mlcsf and 10 parts of NBKP with a freeness of 450 mlcsf. Add 9 parts of kaolin, 0.8 parts of cation starch, 0.4 parts of band sulfate, and 0.10 parts of alkylketene dimer to Lupus Rally. Lupus la rie a p H 8. 2 to adjust, and papermaking in Nagamo抄paper machine, 0.5 after the g / m ² of oxidized starch and size flop Les scan, dried, Ma Shi linker les A base paper having a basis weight of 85 g / m ² was produced by performing a binder finish.

[Preparation of an ink jet recording sheet]

The base paper was manufactured Ri by the above, in as the composition of the click-receiving layer, needle-like co B A Dar Li Ka Shi pair shea re mosquito (S i 0 ₂ conversion calculation) A 1 ₂ 0 Approximately 6.2% by weight of oxidized aluminum Needle-shaped, denatured cation-modified cation porphyrin darcilica modified with medium hydrate 10% aqueous dispersion (particle size; width: 10 to 20 nm x length: 50 to 20 O nm, cation charge 0.41 meq./g) 100 parts, 10% aqueous solution of polyvinyl alcohol as adhesive (PVA 117, manufactured by Kuraray Co., Ltd.) 50 Part, 60% aqueous solution of cationic resin as dye fixing agent (Polyix 61, cation charge 6.9 meq./g, Showa Polymer Co., Ltd.) 16. 7 parts principal component to solid content concentration of 1 0% aqueous dispersion dry solids using a mouth Tsu DoCoMo Isseki scratch the 1.5 applied to earthenware pots by the g / m ^2, and dried, The calendar was finished to produce an ink jet recording sheet.

Example 20

The ink receiving layer composition of Example 19 was made to have a solid content concentration of 15%, and a rod coater was used so that the amount of the dry solid content was 2.5 g / m ² . An ink jet recording sheet was prepared in the same manner as in Example 19 except that the coating was performed.

Example 2 1

The ink receiving layer composition of Example 19 was adjusted to a solid content concentration of 20%, and the rod core was dried overnight so that the amount of the dried solid content was 5.0 g / m ² . An ink jet recording sheet was prepared in the same manner as in Example 19 except that the coating was performed.

Comparative Example 16

The ink receiving layer composition of Example 19 was set to a solid content concentration of 5%, and the amount of the dry solid content was adjusted to 0.3 g / m ² by using a rod-coater. Except for coating, the same as in Example 19 An ink jet recording sheet was prepared.

Comparative Example 1 7

The ink receiving layer composition of Example 19 was set to a solid content concentration of 25%, and the amount of the dry solid content was adjusted to be 6.5 g / m ² by rod rod overnight. An ink jet recording sheet was prepared in the same manner as in Example 19 except that the coating was performed using the ink jet recording method.

Example 22

The base paper prepared in Example 1 9, columnar co B A Darcy Li force Shi Li mosquito (S i 0 ₂ conversion) paired Shi A 1 ₂ 0 3 in terms of 2 9.5 wt% of oxide A Le Mi A 10% aqueous dispersion of columnar cationic colloidal silica denatured by sodium hydrate (particle size; width 4 O nm x length 100 to 30 O nm, Cation charge amount: 1.90 meq./g) 100 parts, 10% aqueous solution of polyvinyl alcohol as adhesive (PVA 117, manufactured by Kuraray Co., Ltd.) 10 0 parts, 60% aqueous solution of cationic resin as dye fixing agent (Polyix 61, cation charge 6.9 meq./g, Showa Polymer) 1 6.7 parts Lock DoCoMo one evening dry solids 2 with an a solid content concentration of 1 0% aqueous dispersion mainly composed of. 1 g / m ² and coated in earthenware pots by that Do, Dried and calendered to produce an ink jet record sheet It was.

Example 23

This was used as the base paper of Example 23 without sizing in Example 19. Subsequently, using the 10% aqueous dispersion of Example 22, coating and drying were performed under the same conditions, and a calendar finish was performed. Then, an ink jet recording sheet was prepared. At this time, the dry solid content was 3 g / m ² .

Example 2 4

A 10% aqueous dispersion of the columnar cationic colloidal silica used in Example 22 (particle diameter; width 4 O nmx length 10) was added to the base paper prepared in Example 19. 0 to 30 O nm, cationic charge amount 1.90 meq./g) 100 parts, 10% aqueous solution of polyvinyl alcohol as adhesive (PVA 117) 150 parts, 60% aqueous solution of cationic resin as dye fixing agent (Polyix 61, cationic charge amount 6.9 raeq. / g, manufactured by Showa Polymer Co., Ltd.) 16.7 parts of an aqueous dispersion having a solid content of 15% with a solid content of 15% was dried using a rod coater to obtain a solid content of 2.0 g / m2. coated on the jar by ² and that Do, dried, to prepare a Lee emissions click Fine-door recording sheet and mosquito-les-down Zehnder finish.

Comparative Example 1 8

Example 2 4 to Ri cash columnar cationite down copolyester B A Darcy Li mosquitoes used in spherical co-B A da Honoré Shi Li Ca shea Li mosquito (S i 0 ₂ conversion) paired Shi A 1 ₂ 0 equivalent to ₃ 1 2.5 wt% of Ca Ji on-resistance of the spherical denatured Ri by the oxidation Aluminum Niu arm hydrate co b a Darcy 3 0% aqueous dispersion of Li Ca (primary particle size 8 An ink jet recording sheet was prepared in the same manner as in Example 26, except that 33 parts of O nm and a cationic charge amount of 0.8 O meq./g) were used. At this time, the dry solid content was 2.0 g / m ² . Comparative Example 1 9

Instead of the columnar cationic colloidal silica used in Example 24, a needle-like colloidal silica 10% aqueous dispersion (particle size; width: 10 to 2) The same procedure as in Example 6 was carried out except that 100 parts of an aggregate having an O nmx length of 500 to 200 and a charge amount of cation (0.0211169.) Were used. The record sheet for the jet was prepared. At this time, the dry solid content was 2.0 g / m ² .

Comparative Example 20

Instead of the columnar cationic colloidal silica used in Example 24, a 30% aqueous dispersion of powdered silica (Nibushil E222A, Nippon Silica) was used. Ink cartridge was manufactured in the same manner as in Example 24, except that 33 3 parts of an average particle size of 1.0 μm, and a cationic charge of 0.09 meq./g) were used. An sheet of the record for the record was prepared. At this time, the dry solid content was 1.8 g / m ² .

Example 2 5

On the base paper prepared in Example 19, a 10% aqueous dispersion of the columnar cationic colloidal silica used in Example 24 (particle diameter; width 4 O nmx length 10) 0 to 30 O nm, cationic charge amount 1.90 meq./g) 100 parts, 10% aqueous solution of polyvinyl alcohol as adhesive (PVA 117) 200 parts, 60% aqueous solution of cationic resin as dye fixing agent (Polyix 61, cationic charge amount 6.9 meq.) / g, manufactured by Showa Polymer Co., Ltd.) 16.7 parts Solids concentration of 2 0% aqueous dispersion Lock DoCoMo one evening one dry solids using 4. 5 g / ni ² and applied to the power sale by that Do, dried, mosquitoes Le emissions Zehnder finish And created an ink jet recording sheet.

Comparative Example 2 1

The 20% aqueous dispersion used in Example 25 was applied and dried using an air-nafco overnight, calendered and finished to obtain an ink jet recording sheet. It was made. At this time, the dried solid content was 7.0 Og / m ² .

Table 4 shows the evaluation results of the ink jet recording sheets prepared in Examples 19 to 25 and Comparative Examples 16 to 21 described above.

Table 4

As can be seen from Table 4, the ink jet recording sheet of the present invention has a high coverage of the contour-coated layer, and has good ink absorption, image density and sharpness. In addition, the dot shape factor showed a recording dot shape close to a perfect circle with a small value of five. Examples 19 to 21 and Comparative Examples 16 to 17 are examples in which the same amount of binder was used.However, Comparative Example 16 was not able to apply a predetermined amount due to the low concentration of the coating solution, and was defective. there were. On the other hand, Comparative Example 17 was a good evaluation result, but because of the high concentration of the coating solution, it was applied in a predetermined amount or more, so that it was unfavorable for handling plain paper.

In Examples 22 and 23, the untreated base paper and the size-treated base paper were compared.However, using the size-treated base paper increased the coating amount even at the same coating liquid concentration, and various The characteristics were also good.

Examples 24 and Comparative Examples 18 to 20 are examples in which the materials used were changed. However, when materials other than the present invention were used, all were inferior.

Example 25 and Comparative Example 21 are examples in which the coating device was changed, but when produced using the air-nife coater used in Comparative Example 21, good evaluation results were obtained. Due to the high concentration of the coating solution, it was applied in a predetermined amount or more, which was not favorable for handling plain paper.

[Examples 26 to 32 and Comparative Examples 22 to 27]

Example 26

A nodule consisting of 90 parts of LBKP with a freeness of 450 mlcsf and 10 parts of NBKP with a freeness of 480 mlcsf. Add 9 parts of kaolin, 0.8 parts of cation starch, 0.4 parts of sulfuric acid compound, and 0.10 parts of alkyl ketene dimer to the lupus slurry. Was adjusted to pH 8.2. To prepare a base paper having a basis weight of 8 5 g / m ² and papermaking dried paper machine, followed by the composition of the fin click-receiving layer, needle-like co B A Darcy Li force Shi Li mosquito (S i 0 ₂ conversion) paired Shi a 1 ₂ 0 3 in terms of about 6.2 wt% of oxide Al mini © beam hydrate 'good Ri modified acicular cationite down-modified copolymer b a Dar Li 100% aqueous dispersion of mosquito (particle size; width 10 to 2 O nm x length 50 to 20 O nm, charge of thione 0.4 l meq./g) 100 parts, adhesion 50 parts of a 10% aqueous solution of polyvinyl alcohol (PVA117, manufactured by Kuraray Co., Ltd.) as the agent, and 60 parts of an aqueous solution of cationic resin (polyolefin as the dye fixing agent) Ixix, cation charge: 6.9 meq./. Showa Polymer Co., Ltd.) 16.7 parts of an aqueous dispersion having a solid content of 10% and a Nsu off § b Ruko one evening dry solids 1 using one. 5 g / m ² and coated in earthenware pots by that Do Followed by drying to produce a Lee emissions click di E Tsu door recording sheet and Ma Shi Lanka-les-down da one finish.

Example 2 7

The composition of the ink receiving layer of Example 26 was set to a solid content concentration of 15%, and the amount of the dry solid content was adjusted to 2.5 g / m ^{2 by} transfection. An ink jet recording sheet was prepared in the same manner as in Example 26, except that the coating was carried out using an alcohol filter. Example 2 8

The ink receiving layer composition of Example 26 was set to a solid content concentration of 20%, and the amount of the dry solid content was adjusted to 5.0 g / m ² by transfection. An ink jet recording sheet was prepared in the same manner as in Example 26, except that the coating was carried out using an overnight tool. Comparative Example 2 2

The ink receiving layer composition of Example 26 was made to have a solid content concentration of 5%, and the amount of the dry solid content was set to 0.3 g / m ² by transfection. An ink jet recording sheet was prepared in the same manner as in Example 26 except that the coating was performed using the same coating method. Comparative Example 2 3

The composition of the ink receiving layer of Example 26 was set to a solid content concentration of 25%, and the amount of the dry solid content was adjusted to 6.5 g / m ^{2 by} transfection. An ink jet recording sheet was prepared in the same manner as in Example 26, except that the coating was carried out using a coconut overnight. Example 2 9

Example 2 6 Ri Lee down instead of click-receiving layer coating solution, columnar co B A Darcy Li Ca shea Li mosquito (S i 〇 ₂ equivalent) to 2-to-Shi A 1 ₂ 0 3 in terms of 9.5 A 10% aqueous dispersion of columnar cationic colloidal silica modified by weight percent aluminum oxide hydrate (particle size; width 4 O nmx length 100-3 0 O nm, cationic charge amount 1.9 O meq./g) 100 parts, 10% aqueous solution of polyvinyl alcohol as adhesive (PVA 117, Claret 100 parts, 60% aqueous solution of cationic resin as dye fixing agent (Polyix 601, polythione charge 6.9 meq./g, 16.7 parts of an aqueous dispersion having a solid content of 10% and having a solid content of 10% was dried using a transfer filter to obtain a solid content of 1%. Coat to 3 g / m ² , dry, finish with a machine render An ink jet recording sheet was prepared. Example 30

After paper-making in the same manner as in Example 26, the oxidized starch was applied to 0.5 g / m ² by size pressing, dried, and calendered. The size base paper used for 30 was used. Subsequently, using the 10% aqueous dispersion of Example 29, coating and drying were performed under the same conditions, followed by calendering to prepare an ink jet recording sheet. At this time, the dry solid content was 2.1 g / m ² .

Example 3 1

Instead of the ink receiving layer coating solution of Example 26, a 10% aqueous dispersion of the columnar cationic colloidal silica used in Example 29 (particle size; width 4O nmx length 100 to 300 nm, cation charge amount 1.90 meq./g) 100 parts, 100% of polyvinyl alcohol as adhesive Aqueous solution (PVA 117, manufactured by Kuraray Co., Ltd.) 150 parts, 60% aqueous solution of cationic resin as dye fixing agent (Polyix 601, Polythione (Charge: 6.9 meq./g, manufactured by Showa Polymer Co., Ltd.) 16.7 parts of an aqueous dispersion having a solid content of 15% and a concentration of 15% It was applied to a dry solid content of 2.0 g / m ² using the above method, dried, and finished with a machine calender to prepare an ink jet recording sheet.

Comparative Example 2 4

Example 3 1 Ri generations of mosquitoes thio down copolyester B A Darcy Li force columnar used in spherical co-B A da Honoré Shi Li Ka Shi pair shea re mosquito (S i 0 ₂ conversion) A 1 1 2.5 wt in ₂ 0 ₃ basis 30% aqueous dispersion of spherical cationic colloidal silica modified with aluminum oxide hydrate (primary particle diameter 8 O nm, cationic charge 0 (8 O meq. / G) was used, and an ink jet recording sheet was prepared in the same manner as in Example 3.1. At this time, the dry solid content was 2.0 g / m ²

C, there is.

Comparative Example 2 5

Instead of the columnar cationic colloidal silica used in Example 31, a needle-like colloidal silica 10% aqueous dispersion (particle size; width: 10 to 2) was used. The same procedure as in Example 31 was performed except that 100 nm of an aggregate having a length of 0 nmx and a length of 500 to 200, and the cationic charge amount (0.02 meq./g) was used. An ink jet recording sheet was prepared. At this time, the dried solid content is 2.0 g / m ^{2, and} it is 7 holes.

Comparative Example 2 6

Instead of the columnar cationic colloidal silica used in Example 31, a 30% aqueous dispersion of powdered silica (Nippsil E22OA, Nihon Silica) was used. Ink cartridge was manufactured in the same manner as in Example 31 except that the average particle size was 1.0 μm, and the cation charge amount (0.09 meq./g) was 33 parts. A jet record sheet was prepared. At this time, the dry solid content was 1.8 g / m ² .

Example 3 2

Instead of the ink receiving layer coating liquid of Example 26, 10% of the columnar cationic colloidal silica used in Example 29 was used. Aqueous dispersion (particle size; width 400 nm x length 100 to 300 nm Cationic charge 1.90 meq./g) 100 parts, polyvinyl alcohol as adhesive 200 parts of a 10% aqueous solution of PVA (PVA117, manufactured by Kuraray Co., Ltd.), 60% aqueous solution of cationic resin as a dye fixing agent (Polyix 6) 0, Cationic charge 6.9 raeq./g, manufactured by Showa Polymer Co., Ltd.) 16.7 parts of an aqueous dispersion having a solid content of 20% and a solid concentration of 20% Using a roll of paper overnight, apply to dry solid content of 4.5 g / m ² , dry, machine render, and ink jet recording sheet Was made.

Comparative Example 2 7

Example 32 The 20% aqueous dispersion used in Example 2 was applied and dried using an air-nife coater, calendered, and subjected to an ink jet recording sheet. Was prepared. At this time, the dried solid content was 5.5 g / m ² .

Table 5 shows the evaluation results of the ink jet recording sheets prepared in Examples 26 to 32 and Comparative Examples 22 to 27 described above.

Table 5

From the results shown in Table 5, the ink jet recording sheet of the present invention has a high coverage of the contour-coated layer, and has good ink absorption, image density and sharpness. Low dot shape factor

25 It showed a recording dot shape very close to a perfect circle. In Examples 26 to 28 and Comparative Examples 22 to 23, the same amount of binder was used.However, in Comparative Example 22 the predetermined amount could not be applied due to the low concentration of the coating solution, and the results were poor. there were. On the other hand, Comparative Example 23 had good evaluation results, but because of the high concentration of the coating liquid, it was coated in a predetermined amount or more, which was not favorable for handling plain paper.

In Examples 29 and 30, the untreated base paper and the size-treated base paper were compared.However, using the size-treated base paper increased the coating amount even at the same coating liquid concentration, and various The characteristics were also good.

In Example 31 and Comparative Examples 24 to 26, the materials used were changed. However, when materials other than the present invention were used, all were inferior.

In Example 32 and Comparative Example 27, the coating apparatus was changed.However, when produced using the air knife coater used in Comparative Example 27, good evaluation results were obtained. Due to the high concentration of the coating solution, it was applied in a predetermined amount or more, and it was a favorable force for handling plain paper.

[Examples 33 to 39 and Comparative Examples 28 to 34]

Example 3 3

[Preparation of base paper]

90 parts of LBKP with a freeness of 450 m1 csf, and 10 parts of NBKP with a freeness of 480 mlcsf, ⁰ lup slurry, 9 parts of kaolin, 0.8 parts of cationic starch, Add 0.4 part of sulfuric acid band and 0.10 part of alkyl ketene dimer. In addition, no ,. The lupus rally was adjusted to pH 8.2 and paper-dried with a Fourdrinier paper machine to produce base paper having a basis weight of 85 g / m ² . The cationic charge of the base paper prepared in advance was measured and found to be 0.02 meq./100 g.

[Preparation of ink jet recording sheet]

As a composition of Lee down click-receiving layer, needle-like co B A Darcy Li force Shi Li mosquito (S i 0 ₂ conversion) paired Shi A 1 ₂ 0 3 in terms of at 7.0 wt% of oxide Al A 10% aqueous dispersion of acicular cationic colloidal silica denatured by sodium hydrate (particle size; width: 10 to 20 nm x length: 50 to 20) 0 nm, thione charge (0.46 meq./g) 100 parts, 10% aqueous solution of polyvinyl alcohol as adhesive (PVA117, manufactured by Kuraray Co., Ltd.) 50 parts, 60% aqueous solution of cationic resin as dye fixing agent (Polyix 61, cationic charge 6.9 meq./g, Showa Polymer Co., Ltd.) ) 16.7 parts of an aqueous dispersion having a solid content of 10% and having a solid content concentration of 10% was converted to a dry solid content of 0.5 g / m ² by using a Trans-Flor roll coater. Paint, dry, machine render and ink jet A test record sheet was prepared. As a result of measuring the total amount of zeon charge of the prepared ink jet record sheet by the colloid titration method, it was 0.557 meq. Z 100 g. Example 3 4

An ink was obtained in the same manner as in Example 33 except that the amount of the dried solid portion of the ink receiving layer in Example 33 was adjusted to 2.0 g / m ² . A jet recording sheet was prepared. Production As a result of measuring the total thione charge of the obtained ink sheet by the colloid titration method, it was found to be 2.30 meq./100 g.

Example 3 5

The amount of dry solids Lee down click-receiving layer that by the Example 3 3 4.5 except that coated the power sale by that Do and g / tn ² in the same manner as in Example 3 3 Lee down click A jet recording sheet was prepared. As a result of measuring the total thione charge of the prepared ink jet recording sheet by the colloid titration method, it was 5.00 meq./100 g.

Comparative Example 2 8

The ink was prepared in the same manner as in Example 33 except that the amount of the dry solid content of the ink receiving layer according to Example 33 was 0.3 g / m ² . A jet recording sheet was created. As a result of measuring the total thione charge of the prepared ink jet recording sheet by the colloid titration method, it was 0.35 meq. Z 100 g.

Comparative Example 2 9

Instead of the acicular cationic colloidal force used in Example 33, a spherical colloidal silica was used instead of silica.

(S i 0 ₂ conversion) paired Shi A 1 ₂ 0 ₃ in terms of in 1 2.5% in Weight% oxidizing Al Mini ©厶水Ri by the hydrate modified spherical force thio down copolyester B A Dal Example 29 was repeated except that 33 parts of a 30% aqueous dispersion of silica (primary particle diameter 80 nm, cationic charge amount 0.80 meq./g) was used. Ink Jets A recording sheet was prepared. As a result of measuring the total thione charge of the prepared ink jet record sheet by the colloid titration method, it was 0.75 meq.

Comparative Example 30

Instead of the acicular cationic colloidal force used in Example 34, a 10% aqueous dispersion of acicular colloidal silica (particle size; The same procedure as in Example 34 was carried out except that 100 parts of 2 O nmx aggregates having a length of 50 to 200 and a charge amount of cation (0.02! 1169.) Were used. An ink jet recording sheet was prepared. As a result of measuring the total thione charge of the prepared ink jet recording sheet by the colloid titration method, it was 1.30 meq./100 g.

Example 3 6

Example 3 Using the base paper prepared in Example 3 as a composition of the ink receiving layer, a columnar colloidal silica was used as the composition.

Columnar cationic colloid darica modified with 29.5% by weight of aluminum oxide hydrate in terms of Al ₂ O 3 (in terms of Si 02) 10% aqueous dispersion of (particle size; width

4 O nmx length 100 to 300 nm, cationic charge amount 1.90 meq./g) 100 parts, 10% aqueous solution of polyvinyl alcohol as adhesive (PVA 117, manufactured by Kuraray)

50 parts, 60% aqueous solution of cationic resin as a dye fixing agent (Polyix 61, cationic charge 6.9 meq./g, Showa Polymer Co., Ltd.) An aqueous dispersion containing 50 parts as a main component and having a solid content of 10% is dried and solidified using a rod coater. Coating was performed so as to obtain a coating weight of 1.0 g / m ² , dried, and machine-rendered to prepare an ink jet recording sheet. As a result of measuring the total thion charge of the prepared ink jet recording sheet by a colloid titration method, it was found to be 3.-4 Omeq.ZlOOg.

Comparative Example 3 1

Instead of the columnar cationic colloidal force used in Example 36, a 30% aqueous dispersion of powdered silica (Nippsil E22 OA, Ink jets were made in the same manner as in Example 36, except that 33 3 parts of an industrial product, average particle size 1.0 ^ 11, and cationic charge amount-0.09 11169.) were used. A recording sheet was made. As a result of measuring the total thione charge of the prepared ink jet recording sheet by the colloid titration method, it was 1.70 meq. Z 100 g.

Comparative Example 3 2

The base paper that had just been formed and dried in Example 33 was used as an ink jet recording sheet of Comparative Example 32 as it was. As a result of measuring the total thione charge of this ink jet recording sheet by the colloid titration method, it was 0.02 meq.

Example 3 7

[Preparation of base paper]

It consists of 90 parts of LBKP with a freeness of 450 mlcsf and 10 parts of NBKP with a freeness of 450 mlcsf. First, light calcium carbonate (TP-121) was used as a raw material. 10 parts, 0.8 parts of cation starch (Cat03210, manufactured by Oji National), 0.4 parts of sulfuric acid band, 0.4 parts of alkyl ketene dimer . (SPK - 9 0 3, manufactured by Arakawa chemical) 0 1 parts by adding to papermaking drying in Fourdrinier, and the Ma Shi Lanka les down loaders finish, a basis weight of 8 5 g / m ² Base paper was made. The cationic charge of the base paper prepared in advance was measured and found to be 3.50 meq./100 g.

[Preparation of ink jet recording sheet]

Same as Example 42 except that the same ink-receiving layer as that of Example 42 was used as the amount of dry solid content of 5.0 g / m ² using the base paper prepared as described above. In addition, an inkjet recording sheet was prepared. As a result of measuring the total thione charge of the produced ink jet recording sheet by the colloid titration method, it was 19.5 meq./100 g.

Comparative Example 3 3

An ink was obtained in the same manner as in Example 36 except that the amount of the dry solid content of the ink receiving layer in Example 36 was 5.5 g / m ² . A jet recording sheet was prepared. As a result of measuring the total thione charge of the prepared ink jet record sheet by the colloid titration method, it was found to be 2.1.10 meq./100 g.

Example 3 8

Using the base paper prepared in Example 3 7, and a set formed of Lee down click-receiving layer, Shi pairs pillars shaped co B A Da Le Shi Li Ca in Shi Li mosquito (S i 0 ₂ conversion) A 1 7.5 wt 1 ₂ 0 ₃ basis 10% aqueous dispersion of columnar cationic colloidal silica modified with 1% aluminum oxide hydrate (particle size; width 4 O nmx length 100-3 0 O nm, cation charge 1.13 meq./g) 100 parts, 10% aqueous solution of polyvinyl alcohol as adhesive (PVA 117, Kuraray Co., Ltd.) Made)

200 parts, 30% aqueous solution of cationic resin as a dye fixing agent (Smilez resin 1001, cation charge amount)

3.5 meq./, Showa Polymer Co., Ltd.) 3. A dry solid content of 3.0 g of an aqueous dispersion containing 3 parts as a main component and having a solid content of 10% using AirNifco Corporation. / m ² , dried, and machine-rendered to produce an ink jet recording sheet. As a result of measuring the total thione charge of the prepared ink jet recording sheet by a colloid titration method, it was found to be 7.25 meq. 100 g.

Example 3 9

The same ink-receiving layer composition as in Example 38 was used as an aqueous dispersion having a solid content concentration of 4% to obtain a dry solid content of 0.5 g / m ² using a size press. Coated, dried and finished with a machine render to produce an ink jet recording sheet. As a result of measuring the total ionic charge of the prepared ink record sheet by the π-ide titration method, it was 4.05 meq.

Comparative Example 3 4

The base paper that had just been formed and dried in Example 37 was used as an ink jet recording sheet of Comparative Example 34 as it was. This in As a result of measuring the total thion charge of the jet record sheet by the colloid titration method, it was 3.50 meq./100 g.

The ink jet recording sheets prepared in Examples 33 to 39 and Comparative Examples 28 to 34 were evaluated.

Table 6

From the results shown in Table 6, the ink jet recording sheet of the present invention has a high coverage of the contour-coated layer, a high ink absorption, Both image density and sharpness were good, and the dot shape factor was small, indicating a recording dot shape close to a perfect circle.

In the comparison of Examples 33 to 35 and Comparative Example 28, the same needle-like cationic colloidal silica was used, but the ink of Comparative Example 28 having a small coating amount was used. In the dot record sheet, the total amount of thione charge was out of the range of the present invention, the dot shape factor was large, and the ink absorption and clarity were both inferior. In the comparison between Example 33 and Comparative Example 29, the ink jet recording sheet of Comparative Example 29 using the same coating amount but using a material other than the present invention was a dot. The shape factor was large and the sharpness was poor.

In addition, in the comparison between Example 34 and Comparative Example 30, the ink jet recording sheet of Comparative Example 30 using the same coating amount but using a material other than the present invention had a dot shape. The coefficient was large, and the ink absorption and clarity were both poor. The ink jet recording sheet of Comparative Example 31 was a case where a powder silica other than the present invention was used, but was inferior in any of the characteristics.

In the comparison of the ink jet recording sheets of Example 37 and Comparative Example 33, the total amount of thione charge of the ink jet recording sheets of Example 37 was within the scope of the present invention. All of the properties were excellent. On the other hand, the ink jet recording sheet of Comparative Example 33 was a case where the coating amount was large, and accordingly, the total amount of thione charged amount was out of the range of the present invention. In terms of characteristics, it was a good evaluation result, but it was a favorable force for handling plain paper. In Comparative Examples 32 and 34, the base paper was treated as it was as an ink jet recording sheet, but all of the characteristics were inferior.

[Examples 40 to 44 and Comparative Examples 35 to 42]

Preparation Example 1

Polyvinylamine copolymer was synthesized by a known method, for example, a method according to Japanese Patent Application Laid-Open No. H11-11094. A reactor equipped with a stirrer, nitrogen inlet tube and cooling tube was charged with 4 g of raw material with a specific molar ratio of N-vinylformamide and acrylonitrile of 4 to 55, and 4 g of demineralized water. 35.9 g was charged. After the temperature was raised to 60 ° C with stirring in a nitrogen gas stream, 10% by weight of 2,2'-azobis-2_amidinoprono, aqueous dihydrochloride solution 0.12 g was added. The mixture was kept at 60 under stirring for 3 hours to obtain a copolymer. At this time, the monomer reaction rate was about 93%. Furthermore, an equivalent amount of concentrated hydrochloric acid was added to the formyl group in the copolymer, and the mixture was kept at 75 for 5 hours with stirring and hydrolyzed. The obtained copolymer solution was added to acetone, and the precipitated and vacuum-dried polyvinylamine copolymer was dissolved in deionized water. The weight average molecular weight of the polyvinylamine copolymer was about 80,000. The molar ratio of vinylamine is determined by the method of quantifying primary amine with copper (ethylene resin) tetraacetic acid as described in the Analytical Chemistry Handbook (approx. It was 0 mol%.

Preparation Example 2 A polyvinylamine copolymer was obtained in the same manner as in Preparation Example 1, except that the molar ratio of N-vinylformamide to acrylonitrile was changed to 24/78. Was. The weight average molecular weight of the polyvinylamine copolymer was about 80,000, and the molar ratio of buramine was 20 mol.

Preparation Example 3

Ν — Polyvinylamine was prepared in the same manner as in Preparation Example 1 except that the molar ratio of vinylformamide to acrylonitrile was changed to 24 278, and the polymerization time was changed to 1 hour. A copolymer was obtained. The weight average molecular weight of the polyvinylamine copolymer was about 30,000, and the molar ratio of buramine was 20 mol%.

Preparation Example 4

Ν—Polyvinylamine copolymer was obtained by the same method as in Preparation Example 1 except that the molar ratio of vinylformamide to acrylonitrile was changed to 12Ζ88. . The weight average molecular weight of the polyvinylamine copolymer was about 70,000, and the mole ratio of vinylamine was about 10 mol%.

[Preparation of base paper]

A pulp slurry consisting of 70 parts of LBKP with a freeness of 380 m1 csf and 30 parts of NBKP with 450 m1 cs 、 was used as a raw material with light calcium carbonate (trade name: TP12 1 , Okutama Kogyo Co., Ltd.) 10 parts, 0.6 parts of sulfuric acid band, 0.1 part of Alkylketene Dimer (trade name: SizePine K903, Arakawa Chemical Co., Ltd.), amphoteric starch (Product name: Cat 3210, manufactured by Oji National Co., Ltd.) The mixture was added, dried by a Fourdrinier machine, machine-finished, and a base paper having a basis weight of 85 g / m ² was produced.

[Base paper using polyvinylamine copolymer]

As shown in Table 7, the type and amount of the polyvinylamine copolymer were changed in the base paper blend prepared above, and a base paper using the polyvinylamine copolymer was prepared.

Table 7

Example 40

Using the base paper 2 prepared as described above, an ink receiving layer was coated to prepare an ink jet recording sheet.

As a composition of Lee down click-receiving layer, needle-like co B A Darcy Li force Shi Li mosquito (S i 0 ₂ conversion) paired Shi A 1 ₂ 0 3 in terms of at 7.0 wt% of oxide Al A 10% aqueous dispersion of acicular cationic colloidal silica denatured by sodium hydrate (particle size; width: 10 to 20 nm x length: 50 to 20) 0 nm, force 100 parts of thion charge (0.46 meq./g), 50 parts of a 10% aqueous solution of polyvinyl alcohol (PVA 117, manufactured by Kuraray Co., Ltd.) as an adhesive 60% aqueous solution of cationic resin as dye fixing agent (Polyix 61, cationic charge 6.9 meq./g, Showa Polymer Co., Ltd.) 16. An aqueous dispersion having a solid content of 10% and containing 7 parts as a main component is dried to a solid content of 3.0 g / m ² by using a transfer roll coater. This was coated, dried and machine-calendered to produce an ink jet recording sheet.

Example 4 1

Using the base paper 3 prepared as described above, an ink receiving layer was coated to prepare an ink jet recording sheet.

As a composition of Lee down click-receiving layer, columnar co B A Dar Li force Shi Li mosquito (S i 0 ₂ conversion) paired Shi A 1 ₂ 0 3 in terms of 2 9.5 wt% oxide Columnar cation-based colloids modified with aluminum hydrate 10% aqueous dispersion of force (particle size; width 4 O nm x length 100 to 30 O nm Charge amount: 1.900 meq./g) 100 parts, Aqueous solution of polyvinyl alcohol as adhesive (PVA 117, manufactured by Kuraray Co., Ltd.) 50 parts A 60% aqueous solution of cationic resin as a dye fixing agent (Polyix 61, cationic charge 6.9 meq./g, manufactured by Showa Polymer Co., Ltd.) 34 parts main component to solid content concentration of 1 0% aqueous dispersion dry solids using a size up Les scan the a 0. 5 g / ra ² and applied to the power sale by that Do, dried, Ma Create an ink jet recording sheet after finishing the sink render. Made.

Example 4 2

The size-flops of the scan that by the Example 4 1 and Lock DoCoMo one evening one, a coating amount of 1.0 except that the g / m ² in the same manner as in Example 4 1 Lee down click diヱ A seat record sheet was prepared.

Example 4 3

Example 41 The size press according to Example 1 was used as the air / niob / coil, the ink receiving layer coating liquid was 15%, and the coating amount was 5.0 g / m ² . An ink jet recording sheet was prepared in the same manner as in Example 41 except that this was performed.

Comparative Example 3 5

An ink jet recording sheet was prepared in the same manner as in Example 41, except that the coating amount in Example 41 was changed to 0.3 g / m ² .

Comparative Example 3 6

The size press according to Example 41 was an air knife coater, the ink receiving layer coating solution was 15%, and the coating amount was 5.5 g / m ² . An ink jet recording sheet was prepared in the same manner as in Example 41 except for the above.

Example 4 4

The base paper 4 produced as described above was used, and Example 40 was used except that the transfer device and the recording device according to the example 40 were replaced by the rod recording device. Similarly, an ink jet recording sheet was prepared.

Comparative Example 3 7 Example 4 Instead of the acicular cationic colloidal force used in Example 4, a spherical colloidal silica was used for the force (Si02 conversion). a l ₂ 0 3 in terms of 1 2.5% weight% oxidizing Al mini © beam hydrate force Ri denatured globular by the thio down copolyester b a Darcy 3 0% aqueous dispersion of Li mosquito ( An ink jet recording sheet was prepared in the same manner as in Example 44 except that 33 parts of a primary particle diameter of 80 nm and a cationic charge amount of 0.8 O meq./g) were used. It was made.

Comparative Example 3 8

Instead of the acicular cationic colloidal silica used in Example 44, a 10% aqueous dispersion of acicular colloidal silica (particle size; width: 10 to Aggregate of 2 O nmx length of 500 to 200, cationic charge amount-0.02 raeq./g) was used in the same manner as in Example 44 except that 100 parts of the same were used. An ink jet recording sheet was prepared.

Comparative Example 3 9

Instead of the acicular cationic colloidal force used in Example 4, a 30% aqueous dispersion of powdered silica (Nippsil E22OA, Nihon Shiritsu) was used. Rica Kogyo Co., Ltd., average particle diameter 1.0 im, cation charge-0.09 11) 69.)ヱ A kit recording sheet was prepared.

Comparative Example 40 to 42

Example 4 In the same manner as in Example 44, except that base paper 5, base paper 6, and base paper 1 were used instead of base paper 4 used in Ink jet recording sheets of Comparative Example 40, Comparative Example 41, and Comparative Example 42 were produced, respectively.

Table 8 shows the evaluation results of the ink jet recording sheets prepared in Examples 40 to 44 and Comparative Examples 35 to 42 described above. The method for evaluating water resistance is as follows.

[water resistant ]

The water resistance was determined by applying a drop of distilled water to the area where the letters and blue lines were printed with magenta ink, leaving it to dry, and visually assessing the degree of bleeding. As evaluation criteria, A shows good characteristics, B shows good results in practically acceptable range, and C shows bad results.

Table 8

As can be seen from Table 8, the ink jet recording sheet of the present invention has a high coverage of the contour-coated layer, and has good ink absorption, image density and sharpness. In addition, the dot shape factor was small, showing a recording dot shape close to a perfect circle, and was excellent in water resistance. In the comparison of Examples 41 to 43 and Comparative Examples 35 to 36, the same column-shaped cationic colloidal silica was used, but Comparative Example 35 with a small coating amount was used. The ink jet recording sheet had a large dot shape factor and poor clarity. On the other hand, in the ink jet recording sheet of Comparative Example 36, when the coating amount was increased, the results were good in terms of characteristics. That was not good.

In the comparison between Example 44 and Comparative Examples 37 to 39, the ink jet recording sheet of each Comparative Example using the same coating amount, but using a material other than the present invention, was found to be the same. The dot shape factor was large and the sharpness was poor.

Regarding the ink jet recording sheets of Comparative Examples 40 to 42, the base paper used was outside the scope of the present invention, and although the other properties were excellent, the water resistance was poor. Was.

[Industrial applicability]

The ink jet recording sheet of the present invention comprises an ink receiving layer component mainly composed of non-spherical cationic colloidal force, and is contour-coated on a support. In addition, the ink receiving layer is provided with the ink receiving layer, and further, by defining the total amount of thione charge, or by using a support containing a specific polyvinylamine copolymer. No ink bleeding, excellent ink absorption, high density and sharpness of the recorded image, a recording dot close to a perfect circle, and excellent water resistance This is the ink jet record sheet of the fine coating type.

Claims

The scope of the claims

1. In an ink jet recording sheet having an ink receiving layer coated on a support, the ink receiving layer is formed of a non-spherical cationic colloidal silica. And a coating layer having a coating amount of 0.5 to 5.0 g / m ² which is contour-coated along the surface of the support. Record record sheet.

2. The ink jet recording sheet according to claim 1, wherein the contour-coated coating layer is a coating layer in which the surface of a support is coated at a coverage of 70 or more.

3. The ink according to claim 1, wherein the ink receiving layer is composed of a composition mainly composed of a non-spherical cationic colloidal binder and a binder. Sheet record sheet.

4. The ink receiving layer according to claim 3, wherein the binder is 5 to 20 parts by weight based on 100 parts by weight of the non-spherical cationic colloidal silica. Ink jet record sheet

5. The ink receiving layer according to claim 1, wherein the ink receiving layer is obtained by applying an ink receiving layer composition having a coating solution concentration of 4 to 20% by weight on a support. Ink jet record sheet.

6. Claims obtained by applying the ink-receiving layer composition having a coating solution concentration of 4 to 10% by weight to an ink-receiving layer on a support in a sizeless manner. Ink jet record sheet according to clause 5.

7. The ink-receiving layer was obtained by applying an ink-receiving layer composition having a coating solution concentration of 10 to 20% by weight onto a support by rod coat over and over. The ink jet recording sheet according to claim 5.

8. The ink-receiving layer is coated with the ink-receiving layer composition having a coating solution concentration of 10 to 20% by weight on a support with a transfer fan at all times. An ink jet recording sheet according to claim 5, which is obtained as a result.

9. The ink jet recording sheet according to claim 1, wherein the non-spherical cationic colloidal silica is in the shape of a needle or a column.

100. The support is subjected to a copolymerization reaction of N-vinylformaldehyde and acrylonitrile, and has a molecular weight of 50,000 or more and a vinylamine mole ratio of 20 mol% or more. 2. The ink jet recording sheet according to claim 1, which contains a polyvinylamine copolymer.

1 1. In an ink jet recording sheet in which an ink receiving layer is coated on a support, the component of the ink receiving layer is a non-spherical cationic colloidal dye. The ink receiving layer is a coating layer having a coating amount of 0.5 to 5.0 Og / m ² , which is mainly composed of silica, and is contour-coated along the surface of the support; Inkjet record sheet with a total power of 0.5 to 20 meq. Z 100 g of thione charge on the record sheet.

1 2. The contour-coated coating layer is a coating layer in which the surface of a support is coated at a coverage of 70% or more. Ink jet record sheet described in section.

1 3. The ink according to claim 11, wherein the ink-receiving layer is composed of a composition mainly composed of a non-spherical cationic colloidal silica and a binder. Jet Record Record Sheet

1 4. Claim 1 wherein the ink receiving layer has a binder force of 5 to 20 parts by weight with respect to 100 parts by weight of non-spherical cationic colloidal silica. Inkjet record sheet described in item 1.

15. The ink-receiving layer according to claim 12, wherein the ink-receiving layer is obtained by applying an ink-receiving layer composition having a coating solution concentration of 4 to 20% by weight. Link jet record sheet.

16. The ink receiving layer is obtained by applying an ink receiving layer composition having a coating solution concentration of 4 to 10% by weight to a support in a sizeless manner. 15 Ink jet recording sheet described in section 5.

1 7. The ink-receiving layer was obtained by applying the ink-receiving layer composition having a coating solution concentration of 10 to 20% by weight onto a support at a time using a rodco. The ink jet recording sheet according to claim 15.

1 8. The ink-receiving layer was prepared by coating an ink-receiving layer composition having a coating solution concentration of 10 to 20% by weight on a support. An ink jet record sheet according to claim 15 obtained by coating.

1 9. Non-spherical cationic colloidal silica with needle-like or Is a pillar-shaped ink jet record described in claim 12

20. The support is subjected to a copolymerization reaction between N-butylformamide and acrylonitrile, and has a molecular weight of at least 50 ', and a vinylamine molar ratio of at least 20 mol%. 11. The ink jet recording sheet according to claim 11, which comprises a polyvinylamine copolymer.

2 1. In an ink jet recording sheet in which an ink-receiving layer is coated on a support, the support is composed of N-vinylformamide and acrylonitrile. And a vinylamine copolymer having a molecular weight of at least 500,000 and a vinylamine molar ratio of at least 20 mol%. The ink receiving layer component is mainly composed of non-spherical cationic colloidal silica, and the ink receiving layer is contour-coated along the surface of the support. ~ 5. Ink jet recording sheet with a coating layer of O g / m ² .

22. The ink jet recording according to claim 21, wherein the total power of the ink jet recording sheet is 0.5 to 20 meq. Sheet.

23. The ink jet printer according to claim 21, wherein the contour-coated coating layer is a coating layer in which the support surface is coated with a coverage of 70% or more. Record sheet.

2 4. The ink according to claim 21, wherein the ink-receiving layer is composed of a composition mainly composed of a non-spherical cationic colloidal resin and a binder. Record record sheet C

2 5. The ink receiving layer according to claim 2, wherein the binder is 5 to 20 parts by weight based on 100 parts by weight of the non-spherical cationic colloidal silica. Inkjet record sheet described in section 4.

26. The ink-receiving layer according to claim 21, wherein the ink-receiving layer is obtained by applying an ink-receiving layer composition having a coating solution concentration of 4 to 20% by weight. Ink jet record sheet.

2 7. Claims obtained by applying the ink receiving layer composition having a coating liquid concentration of 4 to 10% by weight to the support on the support in a sizeless manner. Inkjet record sheet according to paragraph 26.

2 8. The ink-receiving layer is obtained by coating the ink-receiving layer composition having a coating solution concentration of 10 to 20% by weight on a support at a time by rod-coating. An ink jet recording sheet according to claim 26, wherein

2 9. The ink-receiving layer is coated with an ink-receiving layer composition having a coating solution concentration of 10 to 20% by weight on a support in a single-stage process. The obtained ink jet recording sheet according to claim 26 obtained.

30. The ink jet sti recording sheet according to claim 21, wherein the non-spherical cationic colloidal silica is in the form of a needle or a column.