JP3307013B2 - Inkjet recording sheet - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an ink-jet recording sheet, and more particularly to an ink-jet recording sheet which is excellent in absorptivity of a water-based ink, gives a high-quality image, and is excellent in water resistance of a printed image.

[0002]

2. Description of the Related Art In recent years, ink jet recording systems have been used because of their low noise, high-speed recording, easy full-color and easy hard copy, and low cost. Applications to various facsimile machines and printers are rapidly spreading.

As a conventional ink jet recording sheet, a sheet made of ordinary paper or a sheet of paper or the like is used to quickly absorb ink to form clear ink dots in order to obtain a clear image. In addition, there are proposed a recording sheet provided with an ink receiving layer mainly composed of various pigments and an adhesive, or a recording sheet in which a porous pigment is formed in paper itself.

For example, JP-A-57-82085 discloses an ink-receiving layer comprising a water-soluble polymer adhesive using an inorganic pigment and an organic pigment together as a pigment.
JP-A-268682 discloses the provision of an ink receiving layer using a powdered silica and a polyvinyl alcohol copolymer having a silanol group as an adhesive.

On the other hand, with the improvement of the performance of the ink jet recording apparatus, as the recording speed has been increased and the full color printing has been advanced, higher quality characteristics have been required for the ink jet recording sheet. For example, quality characteristics required for an ink jet recording sheet to obtain a high-quality recorded image include: (1) fast ink absorption and large absorption capacity. (2) The diameter of the ink dots on the recording screen does not become larger than necessary. (3) When ink dots overlap, the ink that has adhered later does not flow out to the ink dot that has adhered earlier. (4) High color development of the ink. (5) The surface strength of the ink receiving layer is high. (6) The support has water resistance, and the ink does not cause unevenness or curling of the support. (7) The ink receiving layer has water resistance after image printing. (8) The ink receiving layer does not change over time. And the like.

Conventionally, in order to satisfy these requirements, a porous pigment or a water-soluble polymer excellent in ink absorbency has been used as a component of an ink receiving layer provided on an ink jet recording sheet, The use of latex for improvement and the use of water-resistant synthetic paper or plastic for the support itself have been implemented and studied.

However, those using paper as a support or using only a water-soluble polymer as an adhesive for an ink-receiving layer have poor water resistance and cause blurring or fading of a printed portion, or unevenness or curl. There is a drawback that it is easy to cause paper sizing trouble. On the other hand, when using synthetic paper or plastic film for the support, or using latex for the adhesive, the adhesiveness between the receiving layer and the support is weakened, and the drying and absorbing properties of the ink are poor. There were difficulties.

[0008]

The present invention relates to an ink jet recording sheet, and more particularly to a sheet having a high ink absorption speed.
A recording sheet with little ink dot bleed, sharp ink dot shapes, high quality printing and images with excellent ink coloring, and an ink receiving layer with excellent water and moisture resistance. And a full-color ink jet recording sheet.

[0009]

According to the present invention, there is provided an ink jet recording sheet having a support and an ink receiving layer mainly comprising a pigment and an adhesive, wherein the ink receiving layer mainly comprises a pigment and an amphoteric ion latex. Of fine-grained silica formed from an aqueous composition
Ink for inkjet recording characterized by containing
It is. Further, the present invention provides a method for preparing a pigment and a pigment on a support.
An ink jet provided with an ink receiving layer mainly composed of an adhesive.
In the recording sheet, the ink receiving layer is amphoteric with the pigment.
Formed from an aqueous composition based on ionic latex
And the aqueous composition of the ink receiving layer
For ink jet recording characterized by containing dong
It is a sheet. The present invention also provides a pigment and
Ink jet provided with ink receiving layer mainly composed of adhesive
In the ink jet recording sheet, the ink receiving layer is used in combination with the pigment.
Formed from aqueous composition mainly composed of ionic latex
And the cationic composition is contained in the aqueous composition of the ink receiving layer.
Ink jet recording characterized by including limers
Sheet. In addition, the present invention provides a method for preparing a pigment and
Ink provided with an ink receiving layer mainly composed of
In the ink jet recording sheet, the ink receiving layer is a pigment.
Formed from an aqueous composition mainly composed of zwitterionic latex
And the support is a plastic film or
An ink jet recording sheet characterized by being synthetic paper .

[0010]

In general, the resolution of a recorded image on an ink-jet recording sheet depends on the amount of ink absorbed. If the ink absorbency is increased more than necessary, the recorded image density will be reduced, and the sharpness and color development of the image will be reduced. The resolution decreases and the resolution deteriorates.
On the other hand, if the ink absorptivity is excessively suppressed, the image density becomes high, but there are disadvantages such as too thick or bleeding of print, deterioration of image quality due to uneven density, and long ink drying time. The present inventors have conducted various studies in order to solve the problems of the conventional ink jet recording sheet as described above. As a result, by forming an ink receiving layer composed of a specific aqueous composition on a support, excellent ink absorption and ink coloring properties, and sharp and high-quality images of ink dots can be obtained. It has been found for the first time that an ink jet recording sheet having excellent strength and water resistance can be obtained.

That is, the ink jet recording sheet of the present invention is characterized in that an ink receiving layer comprising an aqueous composition containing a pigment and a specific zwitterionic latex as main components is provided on a support. . Hereinafter, the present invention will be described in detail.

First, the zwitterionic latex used in the present invention has a core-shell composite structure shown in FIG. 1 and has basic physical properties as shown in Table 1. That is, the surface of the same particle has a zwitterionic functional group, the quaternary alkylamine group has a higher density than the carboxyl group, the particle size is 0.2 μm, the film is formed, the mechanical stability is excellent, and the average Specifically, it is a latex having a cationic colloid equivalent value.

The amphoteric ion latex will be further described below. That is, a synthetic rubber latex or a synthetic resin emulsion modified with a carboxyl group is used as a seed latex, and the seed latex is neutralized to have a pH of 6 or more.
When adding a monomer represented by the following general formula (Chemical Formula 1) or a mixture of the general formula (Chemical Formula 1) and an ethylenically unsaturated monomer copolymerizable with the general formula (Chemical Formula 1), From at least the colloid equivalent value (absolute value) of the seed latex,
The above monomer is added so as to have a large equivalent value, and an acid or a salt is added to a polymer obtained by polymerizing the seed latex and the added monomer using a radical polymerization initiator. A zwitterionic latex obtained by neutralizing or adding a quaternizing agent (for example, a general alkylating agent such as an alkyl halide, dimethyl sulfate, or diethyl sulfate) to form a quaternary ammonium salt; This is a polymer emulsion in which cationic properties are imparted to the surface of the emulsion particles at high density.

[0014]

Embedded image

(In the formula, R₁Is H or CH_Three, R
_TwoIs an alkylene group having 2 to 5 carbon atoms, R _ThreeAnd R_FourIs H
Or an alkyl group having 1 to 5 carbon atoms, A is -CO-O-
Or -CO-NH-;_2,R_3,R_FourIs a monomer
Selected within a range that is hardly soluble or insoluble in water
You. )

Here, the colloid equivalent value is a value obtained by the following method. That is, 95 ml of distilled water is placed in a beaker, 5 ml of a 1000 ppm solution of the sample is added thereto, the pH is adjusted to 4 with 1% HCl, and the mixture is stirred for about 1 minute. Next, 2-3 parts of toluidine blue indicator solution was added.
Add drops and titrate with N / 400 PVSK (polyvinyl potassium sulfate). The titration rate is 2 ml per minute,
The point at which the sample changes color from blue to red and the state is maintained for 10 seconds or more is defined as the end point of the reaction. In addition, the colloid equivalent value was calculated by the following equation (Equation 1).

[0017]

(Equation 1)

The reason why the monomer represented by the above general formula (Chemical Formula 1) is preferably used is that the monomer itself is hardly soluble or insoluble in water, so that the cation dissociation during the polymerization is prevented. Suppressed and easily supplied a stable polymer, the polymer formed to have an amino group in its structural formula is neutralized with an acid or salt, or quaternary ammonium chloride with a quaternizing agent And thereby imparting a high-density cationic property to the surface of the latex particles.

Specific examples of the monomer represented by the general formula (Formula 1) include, for example, diethylaminoethyl acrylate, diethylaminoethyl methacrylate, dipropylaminoethyl acrylate, dipropylaminoethyl methacrylate, dibutylaminoethyl Examples include methacrylate, t-butylaminoethyl (meth) acrylate, diethylaminopropyl methacrylamide, dipropylaminopropyl methacrylamide, dipropylaminopropyl acrylamide, dibutylaminopropyl methacrylamide, dibutylaminopropyl acrylamide, and the like.

Further, other ethylenically unsaturated monomers copolymerizable with the monomer represented by the general formula (Formula 1) include:
For example, hydrophobic monomers such as acrylates, methacrylates, acrylonitrile, styrene, vinyl acetate, or N, N'-methylenebisacrylamide, diallyl phthalate, divinylbenzene, (poly) ethylene glycol di (meth) acrylate, etc. Crosslinkable monomer.

The ethylenically unsaturated monomer copolymerizable with the general formula (Chemical Formula 1) may be appropriately determined according to the glass transition temperature and physical properties of the target latex. The amount is adjusted at about 0 to 40% by weight based on the monomer of 1). When an aqueous composition using this latex is used, it has a relatively low foaming property with little action as a surfactant, has a large self-adhesive performance with an inorganic pigment, and is stable in a wide pH range, It has the advantage that it has good compatibility with the cationic polymer and does not cause solvent shock. Furthermore, it has advantages such as excellent air permeability and excellent water resistance as compared with PVA-based binders. In addition, the point that the amphoteric ion latex as described above is particularly excellent is that it has good miscibility with various pigments, has less thickening as compared with adhesives conventionally used, and has strong adhesiveness with pigments. In particular, when a silica pigment is used, strong adhesiveness is exhibited.

Further, the distinctive feature of the amphoteric ion latex used in the present invention is exhibited when a synthetic resin-based material having a strong barrier property such as a plastic film or synthetic paper is used for the support. That is, the compatibility with the support as described above is improved, and as a result, a strong adhesive strength is obtained, no powder is dropped off of the receiving layer, the surface strength is improved, and the ink receiving layer is extremely excellent in water resistance. Was obtained.

Conventionally, an ink jet recording sheet using a pigment and an adhesive together includes a water-soluble polymer adhesive such as polyvinyl alcohol (PVA), modified PVA, hydroxyethylcellulose, CMC, a cellulose derivative, starch, and cationic starch. It has been used exclusively. When only these water-soluble polymers were used as the adhesive, not only the surface strength as in the present invention was not obtained, but also the water resistance after printing was poor.

Further, only an aqueous emulsion type polymer latex such as SBR, polyvinyl acetate, acrylic resin, styrene-acryl copolymer, ethylene-vinyl acetate polymer, polyvinyl butyral, polyurethane or the like is used as an adhesive. When used, the dry film, i.e., the ink receiving layer, becomes water resistant,
On the other hand, there is a problem in that the absorbability of the water-based ink is deteriorated, and the dried film undergoes a whitening phenomenon peculiar to latex, thereby lowering the resolution ability. On the other hand, when an amphoteric ion latex is used as an adhesive for an ink jet recording sheet as in the present invention, the difficulties peculiar to the latex are solved, and an extremely excellent water-resistance improving effect and water-based ink not found in the conventional latex system. It was found that the effect of improving the absorptivity was exhibited.

The reason why such an excellent effect can be obtained is not necessarily clear, but is presumed as follows. That is, the amphoteric ion latex used in the present invention has a cationic quaternary alkylamine group to improve the ink fixing effect, and furthermore, the interaction of the amphoteric ion causes the latex particles to have an electrical interaction. It is presumed that the resulting fine pores contribute to the improvement in ink absorbency.

The amount of the zwitterionic latex used in the present invention is 5 to 70 parts by weight per 100 parts by weight of the pigment.
Preferably it is adjusted in the range of 20 to 50 parts by weight. If the amount is more than 70 parts by weight, the ink absorbency is slow and the resolution of the image is deteriorated. If the amount is less than 5 parts by weight, the water resistance and the surface strength are reduced.

Next, as the pigment used in the present invention, various pigments used in the field of conventional coated paper can be used. Specific examples of the pigment include white carbon and finely divided silica. Porous pigments such as calcium, zeolite, magnesium aminosilicate, calcined siliceous earth, fine-grained magnesium carbonate, fine-grained alumina, sea urchin or spherical light calcium carbonate formed by aggregating multiple single particles, and talc, Minerals such as kaolin, clay, delamikaolin, heavy calcium carbonate, light calcium carbonate, magnesium carbonate, titanium dioxide, aluminum hydroxide, calcium hydroxide, magnesium hydroxide, magnesium silicate, calcium sulfate, sericite, bentonite, smectite, etc. Filler, polystyrene resin, urea resin, acrylic resin, melamine Resin, organic pigment fine particles such as benzoguanamine resins, and organic synthetic pigments such as fine hollow particles and the like, one of these pigments, or 2
It is also possible to appropriately select and use more than one species.

The present inventors have conducted various studies on the pigment constituting the ink receiving layer (aqueous composition), and as a result, have found that a more excellent effect can be obtained when fine silica is used as the pigment. Was. Conventionally, porous pigments are often used as the pigment for the receiving layer of an aqueous ink jet recording sheet.
There are various types such as the amount of ink absorbed differs depending on the shape, particle diameter, specific surface area, water absorption capacity and the like.

The finely divided silica used in the present invention is a white porous pigment, a pigment having a high oil absorbing property and a high specific surface area, and in particular, an amorphous silica having a secondary particle diameter of 15 μm or less. The effect is remarkable in the case. Among them, those having a particle diameter of 0.1 to 15 μm are desirable.
Those having a specific surface area of at least 200 m ² / g by the T method are particularly preferred. By the way, when the thickness exceeds 15 μm, the fixability of the aqueous ink is poor, and the resolution with the large ink dot diameter is poor. On the other hand, when the thickness is less than 0.1 μm, there are disadvantages such as that the fixability of the aqueous ink becomes slow and the ink drying time becomes long.

In the present invention, an aqueous composition comprising the above components is provided on a support as an ink receiving layer. As described above, the ink absorbing property and the ink fixing property can be improved by using an amphoteric ion latex in combination. Excellent in nature,
An ink jet recording sheet is provided, and particularly when a plastic film or synthetic paper is used as a support, the effect can be suitably obtained. In this case, the coating amount of the aqueous composition is 5 to 50 g / m ² in terms of dry weight, and preferably 1 to 50 g / m ² .
It is adjusted in the range of 0 to 30 g / m ² .

Next, the present inventors have conducted various studies on such an ink receiving layer (aqueous composition). As a result, the combined use of an amphoteric ionic latex and a water-soluble polymer makes it possible to obtain an ink receiving layer having better resolution. I found that I can get it. The reason for this is that the use of a water-soluble polymer greatly increases the ink absorption capacity, improves the ink absorption speed and drying properties, and provides an ink-receiving layer with better resolution.

Examples of the water-soluble polymer used in the present invention include polyvinyl alcohol, polyvinyl pyrrolidone, acetoacetylated polyvinyl alcohol, modified polyvinyl alcohol, polyvinyl methyl ether, polyvinyl pyridium halide, quaternized polyvinyl pyrrolidone, and polyvinyl butyral. Vinyl-based water-soluble polymers such as
Cellulose-based water-soluble polymers such as methylcellulose, ethylcellulose, methylethylcellulose, hydroxypropylcellulose, and CMC; synthetic water-soluble polymers such as polyethyleneimine and polyethylene oxide; poly (meth) acrylic acid or a copolymer thereof; Acrylic water-soluble polymers such as acid ester resins and acrylamide resins; modified starches such as cationic starch, amphoteric starch, esterified starch, and oxidized starch; natural water-soluble polymers such as gum arabic, sodium alginate, gelatin, and casein It has been found that more excellent effects can be obtained by using at least one or more water-soluble polymers selected from the above.

As for the water-soluble polymer used in the present invention, it has been found that more preferable results can be obtained when polyvinyl pyrrolidone is used among the above-mentioned water-soluble polymers. That is, when polyvinyl pyrrolidone was contained in the ink receiving layer, particularly excellent effects were obtained in terms of water-based ink absorption and ink drying properties, as compared with the case where other water-soluble polymers were used in combination. . In this case, the polyvinylpyrrolidone is a water-soluble basic polymer having a molecular weight of 100,000 to 1,000.
000, preferably 300,000 to 1,000,
000. Further, the polyvinyl pyrrolidone has good compatibility with the amphoteric ion latex used in the present invention.

The amount of the water-soluble polymer used is limited to the case where the water-soluble polymer is used in combination with the amphoteric ionic latex, and it is preferable to use the water-soluble polymer in the range of 5 to 70 parts by weight based on 100 parts by weight of the pigment. By the way, if it exceeds 70 parts by weight, the water resistance of the ink receiving layer and the printed image tends to deteriorate,
If the amount is less than 5 parts by weight, the degree of the improvement effect is small.

In addition to the water-soluble polymer, an adhesive used in a general coated paper field can be appropriately used as long as the effects of the present invention are not impaired. Such adhesives include, for example, SBR latex, conjugated diene-based polymer latex such as methyl methacrylate-butadiene copolymer, acryl resin such as phenolic resin, and polymer or copolymer of acrylic acid and methacrylic acid ester. Polymerized latex, vinyl-based polymer latex such as ethylene-vinyl acetate copolymer, and functional group-modified polymer latex with functional group-containing monomer such as carboxyl group of these various polymers, heat of melamine resin, urea resin, etc. Water-based adhesives of cured synthetic resins, synthetic resin-based adhesives such as polymethyl methacrylate, polyurethane resins, unsaturated polyester resins, vinyl chloride-vinyl acetate copolymers, polyvinyl butyral, and alkyd resins.
Species or two or more species are appropriately selected and used.

Further, in the present invention, when a cationic polymer is added to the ink-receiving layer in addition to the water-soluble polymer, the cationic polymer acts as an ink fixing agent to further improve the fixability and water resistance of an image after printing. It was found that it had an effect of improving. As the cationic polymer in this case,
There are quaternary ammonium salt derivatives of polyethyleneimine, acryl or methacrylate copolymers containing a quaternary ammonium group as a copolymer monomer, and specific examples thereof include poly (diallyldimethylammonium chloride) and polyethyleneimine hydrochloride. , Poly (2-acryloxyethyldimethylsulfonium chloride), poly (N-methyl-4-vinylpyridium chloride), poly (2-methacryloyloxyethyltrimethylammonium chloride) and the like.

The cationic polymer is added in an amount of 3 to 50 parts by weight, preferably 1 to 100 parts by weight of the pigment.
It is adjusted at about 0 to 30 parts by weight. Incidentally, if the amount is less than 3 parts by weight, it is difficult to obtain a desired effect. On the other hand, if it exceeds 50 parts by weight, the effect becomes saturated, and the bleeding of the printed image and the light resistance tend to be deteriorated.

Next, the present inventors have conducted intensive studies so that a high-resolution ink receiving layer having an excellent ink dot diameter can be formed in the ink receiving layer (aqueous composition) as described above. As a result, in an ink jet recording sheet provided with an ink receiving layer containing a pigment and an adhesive as a main component on a support, the ink receiving layer is formed of at least the following [upper layer] and [lower layer]. As a result, it has been found for the first time that an ink receiving layer exhibiting extremely high resolution is formed.

[Upper layer]: 10 to 35 parts by weight of zwitterionic latex and 20 to 20 parts of water-soluble polymer per 100 parts by weight of pigment
It is composed of an aqueous composition comprising 70 parts by weight and the amount of the amphoteric ion latex used is not more than a water-soluble polymer. [Lower layer]: An aqueous composition mainly composed of 40 to 70 parts by weight of amphoteric ion latex and 5 to 30 parts by weight of a water-soluble polymer per 100 parts by weight of pigment.

Hereinafter, the ink receiving layer will be described. First, in the present invention, a zwitterionic latex and a water-soluble polymer are used in combination. The reason for this is that, as described above, the use of a water-soluble polymer results in a larger ink absorption capacity than the case of using a zwitterionic latex alone. This is because an ink receiving layer having an even higher resolution can be obtained.

Examples of the water-soluble polymer used in the present invention include polyvinyl alcohol, polyvinyl pyrrolidone, acetoacetylated polyvinyl alcohol, modified polyvinyl alcohol, polyvinyl methyl ether, polyvinyl pyridium halide, quaternized polyvinyl pyrrolidone, and polyvinyl. Vinyl-based water-soluble polymers such as butyral,
Cellulose-based water-soluble polymers such as methylcellulose, ethylcellulose, methylethylcellulose, hydroxypropylcellulose, and CMC; synthetic water-soluble polymers such as polyethyleneimine and polyethylene oxide; poly (meth) acrylic acid or a copolymer thereof; Acrylic water-soluble polymers such as acid ester resins and acrylamide resins; modified starches such as cationic starch, amphoteric starch, esterified starch, and oxidized starch; natural water-soluble polymers such as gum arabic, sodium alginate, gelatin, and casein It has been found that more excellent effects can be obtained by using at least one or more water-soluble polymers selected from the above.

In particular, an important feature of the present invention is that at least an upper and lower two-layer ink receiving layer comprising a specific amount of the amphoteric ion latex and a water-soluble polymer is formed on a support, Further, the present invention is characterized in that the mixing ratio of the amphoteric ion latex and the water-soluble polymer in the aqueous composition constituting the upper and lower layers is different between the upper and lower layers, respectively. In addition, as long as the effects of the present invention are not impaired, the lower layer may be further divided into an intermediate layer and a lowermost layer whose constituent components are appropriately changed.

That is, the aqueous composition serving as the upper layer contains the pigment 10
10 to 35 parts by weight, preferably 20 to 30 parts by weight, of the zwitterionic latex to 0 part by weight, and 20 to 70 parts by weight of the water-soluble polymer, preferably about 2 times the weight of the zwitterionic latex. It is adjusted to be.
The aqueous composition serving as the lower layer is composed of 40 to 70 parts by weight, preferably 45 to 55 parts by weight, and 5 to 30 parts by weight of a water-soluble polymer, preferably 100 to 100 parts by weight of the pigment. Is adjusted so as to have a weight mixing ratio of about 1/2 times of the above. in this way,
The significance of changing the mixing ratio of the amphoteric ion latex and the water-soluble polymer in the upper and lower layers is as follows.

First, it was confirmed that by using a larger amount of the water-soluble polymer in the upper layer than in the amphoteric ion latex, the ink absorption in the surface layer was performed more quickly. This is because it has been found that the ink receiving layer can be excellent in terms of print drying property and ink absorption capacity.

Second, by increasing the amount of the amphoteric ion latex used in the lower layer to be greater than the amount of the water-soluble polymer, the adhesion to the support is improved, and as a result, the surface strength is increased, and It was confirmed to prevent powder dropping. Furthermore, it should be noted that by combining these upper and lower ink receiving layers, the merits of both are more remarkably exhibited, and the ink receiving layer, which is extremely superior to the case of a single layer, That is, they have found that an ink jet recording sheet having excellent ink absorbency, surface strength and water resistance can be obtained.

The amount of the amphoteric ion latex to be used will be described. In the case of the upper ink receiving layer, the amount exceeds 35 parts by weight with respect to 100 parts by weight of the pigment. When the amount is more than the above, the ink absorbency decreases, which is not preferable. On the other hand, when the amount is less than 10 parts by weight, the ink receiving layer has poor surface strength and water resistance. Further, in the case of the lower ink receiving layer, if it exceeds 70 parts by weight, no remarkable effect can be obtained, which is disadvantageous from an economical point of view. On the other hand, if it is less than 40 parts by weight, or if it is less than the amount of the water-soluble polymer used, the adhesion to the support is undesirably reduced.

Next, the amount of the water-soluble polymer specified will be described. In the case of the upper ink receiving layer, if the amount exceeds 70 parts by weight with respect to 100 parts by weight of the pigment, the present invention is desired. No effect is obtained, and the water resistance becomes poor. On the other hand, if the amount is less than 35 parts by weight, the ink absorption and the resolution become poor, which is not preferable. When the amount of the lower ink receiving layer exceeds 30 parts by weight, the adhesiveness to the support is weakened, and the water resistance of the ink receiving layer is further deteriorated. On the other hand, when the amount is less than 5 parts by weight, the ink absorbency decreases, which is not preferable.

In the present invention, if necessary, a thickener, a wetting agent, a thermal gelling agent, a defoaming agent, a defoaming agent, a foaming agent, and the like may be added to the aqueous composition in addition to these adhesives and pigments. Colorant, optical brightener, UV inhibitor, antioxidant, quencher, preservative, antistatic, crosslinker, dispersant, lubricant, plasticizer, pH adjuster, flow improver, solidification accelerator And various auxiliaries such as a waterproofing agent can be appropriately compounded.

The support used in the present invention includes:
Cloth, nonwoven fabric, wood, metal plate, glass plate, or paper such as high quality paper, medium paper, coated paper, art paper, cast coated paper and laminated paper, impregnated paper, nonwoven fabric such as polyethylene, polypropylene, polyethylene, Polyethylene terephthalate, polypropylene, diacetate, acrylic, polycarbonate, polyvinyl chloride, polyimide,
Any of resin-based films such as cellophane and celluloid, and synthetic paper can be used. However, in the case of the present invention, as described above, a plastic film or a synthetic paper such as polypropylene, in which the support itself has water resistance, can be a particularly preferred embodiment. Such a support is a preferable material from the viewpoint of suppressing unevenness and curling after printing, and is also preferable from the viewpoint of a water resistance effect of a printed image. Further, the thickness of the support is 10 to 200 μm.
Are suitable.

As described above, in the present invention, a specific different aqueous composition is divided into an upper layer and a lower layer to form a coating layer, which is provided on a support as an ink receiving layer. When paper is used, a desired effect can be obtained. In this case, the coating amount of the aqueous composition in the case of the upper ink receiving layer is ² to 25 g / m ² by dry weight, preferably 5 to 25 g / m ² .
１５15 g / m ² , while the lower ink receiving layer has a dry weight of 2-25 g / m ² , preferably 5
It is adjusted in the range of １５15 g / m ² . The coating amount of the entire upper and lower ink receiving layers is 5 to 50 g / m2 in dry weight.
² , preferably in the range of 10 to 30 g / m ² .

The coating apparatus for forming the ink receiving layer on the support includes, for example, a blade coater, an air knife coater, a roll coater, a reverse roll coater, a bar coater, a curtain coater, a die slot coater, a gravure coater, and a chaplex. Coater, brush coater, two-roll or metering blade type size press coater, gate roll coater, bill blade coater,
A coating device used in a normal coated paper manufacturing field, such as a short dwell coater, can be used as appropriate.

In the present invention, an antistatic treatment or a surface treatment for imparting writing characteristics (printing characteristics) is performed on the front and back surfaces of the recording surface, if necessary. An auxiliary agent such as an inhibitor may be added to improve the storability of the recorded image, or a pressure-sensitive adhesive layer may be provided on the back surface of the recording surface and bonded to a release sheet to finish the pressure-sensitive adhesive sheet.

[0053]

The present invention will be described in more detail with reference to the following examples, but it should be understood that the present invention is by no means restricted to such specific ranges. In the examples, "parts" and "%" indicate "parts by weight" and "% by weight", respectively, unless otherwise specified.

Example 1 [Preparation of aqueous composition] (Coating liquid 1) 100 parts of light calcium carbonate (trade name: Callite SA, secondary particle diameter: 3.0 μm / manufactured by Shiraishi Industry Co., Ltd.) Latex (trade name: Acostar C122 / manufactured by Mitsui Cyanamid) 46 parts ・ Dispersant (sodium polypyrophosphate) 0.5 part ・ Defoaming agent (trade name: Nopco 1407-K / manufactured by San Nopco) 0.03 parts or more Water was added to the composition, mixed and stirred to obtain an aqueous composition having a concentration of 25%.

[Preparation of Ink-Jet Recording Sheet] The above-mentioned coating liquid 1 was coated on a synthetic paper having a thickness of 80 μm [trade name: YUPO FP
G-80 / Oji Yuka Synthetic Paper Co., Ltd.]
/ M ^{2 was applied} and dried with a bar coater to obtain an ink jet recording sheet.

Example 2 [Preparation of Aqueous Composition] (Coating Liquid 2) 50 parts of light calcium carbonate (trade name: Callite SA, secondary particle diameter: 3.0 μm / manufactured by Shiraishi Industry Co., Ltd.) Fine alumina (Trade name: Alumina A, secondary particle diameter: 4.8 μm / manufactured by Mizusawa Chemical Industry Co., Ltd.) 50 parts ・ Amphoteric ion latex (trade name: Acostar C122 / manufactured by Mitsui Cyanamid Co.) 46 parts ・ Dispersant (sodium polypyrophosphate) 0.5 parts-Antifoaming agent (trade name: NOPCO 1407-K / manufactured by San Nopco) 0.03 parts Water was added to the above components and mixed with stirring to obtain an aqueous composition having a concentration of 25%.

[Preparation of Ink-Jet Recording Sheet] The above coating liquid 2 was coated on a synthetic paper having a thickness of 80 μm [trade name: YUPO FP
G-80 / Oji Yuka Synthetic Paper Co.] has a solid content of 20 g /
Coating and drying were performed with a bar coater so as to obtain m ² , thereby obtaining an ink jet recording sheet.

Example 3 [Preparation of Aqueous Composition] (Coating Liquid 3) 50 parts of light calcium carbonate (trade name: Callite SA, secondary particle diameter: 3.0 μm / manufactured by Shiraishi Industry Co., Ltd.) Silica (trade name: Syloid, secondary particle diameter: 12 μm / manufactured by Fuji Devison Chemical Co., Ltd.) 50 parts ・ Amphoteric ion latex (trade name: Acostar C122 / Mitsui Cyanamid Co., Ltd.) 46 parts ・ Dispersant (sodium polypyrophosphate) 0 0.5 parts-Antifoaming agent (trade name: NOPCO 1407-K / manufactured by San Nopco) 0.03 parts Water was added to the above components and mixed with stirring to obtain an aqueous composition having a concentration of 20%.

[Preparation of Ink-Jet Recording Sheet] The above-mentioned coating liquid 3 was coated with a synthetic paper having a thickness of 80 μm [trade name: YUPO FP
G-80 / Oji Yuka Synthetic Paper Co.] has a solid content of 20 g /
Coating and drying were performed with a bar coater so as to obtain m ^2, and an ink jet recording sheet was obtained.

Example 4 [Preparation of aqueous composition] (Coating liquid 4) 100 parts of colloidal silica (trade name: Syloid, secondary particle size: 12 μm / manufactured by Fuji Devison Chemical Co., Ltd.) Product name: Acostar C122 / manufactured by Mitsui Cyanamid) 46 parts ・ Dispersant (sodium polypyrophosphate) 0.5 part ・ Defoaming agent (product name: Nopco 1407-K / manufactured by San Nopco) 0.03 parts or more Was added and mixed with stirring to obtain an aqueous composition having a concentration of 20%.

[Preparation of Ink-Jet Recording Sheet] The above coating liquid 4 was coated with a synthetic paper having a thickness of 80 μm [trade name: YUPO FP
G-80 / Oji Yuka Synthetic Paper Co.] has a solid content of 20 g /
Coating and drying were performed with a bar coater so as to obtain m ² , thereby obtaining an ink jet recording sheet.

Example 5 [Preparation of aqueous composition] (Coating liquid 5) Fine silica (trade name: Fine Seal, secondary particle diameter: 3.7 μm, specific surface area by BET method: 280 m ² / g / 50 parts ・ Colloidal silica (trade name: Syloid, secondary particle diameter: 12 μm / Fuji Devison Chemical Co., Ltd.) 50 parts ・ Amphoteric ion latex (trade name: ACOSTAR C122 / Mitsui Cyanamid) 46 Part: dispersant (sodium polypyrophosphate) 0.5 part: antifoaming agent (trade name: NOPCO 1407-K / manufactured by San Nopco) 0.03 part Water is added to the above components, and the mixture is stirred with a concentration of 10 parts. % Of an aqueous composition was obtained.

[Preparation of Ink-Jet Recording Sheet] The above-mentioned coating liquid 5 was coated with a synthetic paper having a thickness of 80 μm [trade name: YUPO FP
G-80 / Oji Yuka Synthetic Paper Co.] has a solid content of 20 g /
Coating and drying were performed with a bar coater so as to obtain m ² , thereby obtaining an ink jet recording sheet.

Example 6 [Preparation of Aqueous Composition] (Coating Liquid 6) Fine silica (trade name: Fine Seal, secondary particle diameter: 3.7 μm, specific surface area by BET method: 280 m ² / g / Tokuyama Soda Co., Ltd.) 90 parts ・ Colloidal silica (trade name: Syloid, secondary particle size: 12 μm / Fuji Devison Chemical Co., Ltd.) 10 parts ・ Amphoteric ion latex (trade name: Acostar C122 / Mitsui Cyanamid) 50 Part: dispersant (sodium polypyrophosphate) 0.5 part: antifoaming agent (trade name: NOPCO 1407-K / manufactured by San Nopco) 0.03 part Water is added to the above components, and the mixture is stirred with a concentration of 10 parts. % Of an aqueous composition was obtained.

[Preparation of Ink-Jet Recording Sheet] The above coating liquid 6 was coated with a synthetic paper having a thickness of 80 μm [trade name: YUPO FP
G-80 / Oji Yuka Synthetic Paper Co.] has a solid content of 20 g /
Coating and drying were performed with a bar coater so as to obtain m ² , thereby obtaining an ink jet recording sheet.

Example 7 Polyvinyl pyrrolidone (trade name: Rubiscol K-90, molecular weight: 360,000 / BA) was added to the coating liquid 1 of Example 1.
An ink jet recording sheet was obtained in the same manner as in Example 1 except that the concentration was adjusted to 20% with a composition (coating liquid 7) to which 23 parts (manufactured by SF Corporation) was added.

Example 8 Polyvinylpyrrolidone (trade name: Rubiscol K-90, molecular weight: 360,000 / BA) was added to the coating solution 2 of Example 2.
An ink jet recording sheet was obtained in the same manner as in Example 2 except that the concentration was adjusted to 20% with a composition (coating liquid 8) containing 23 parts (manufactured by SF Corporation).

Example 9 Polyvinylpyrrolidone (trade name: Rubiscol K-90, molecular weight: 360,000 / BA) was added to the coating solution 3 of Example 3.
An ink jet recording sheet was obtained in the same manner as in Example 3 except that the concentration was adjusted to 18% with a composition (coating liquid 9) to which 23 parts (manufactured by SF Corporation) was added.

Example 10 The coating solution 4 of Example 4 was mixed with polyvinylpyrrolidone (trade name: Rubiscol K-90, molecular weight: 360,000 / BA).
An ink jet recording sheet was obtained in the same manner as in Example 4 except that the concentration was adjusted to 18% with a composition (coating liquid 10) containing 23 parts (manufactured by SF Corporation).

Example 11 The coating liquid 5 of Example 5 was mixed with polyvinylpyrrolidone (trade name: Rubiscol K-90, molecular weight: 360,000 / BA).
A sheet for inkjet recording was obtained in the same manner as in Example 5 except that the composition (coating liquid 11) was added to 23 parts (manufactured by SF Corporation).

Example 12 Polyvinyl pyrrolidone (trade name: Rubiscol K-90, molecular weight: 360,000 / BA) was added to the coating liquid 6 of Example 6.
An ink jet recording sheet was obtained in the same manner as in Example 6, except that the composition (coating liquid 12) was added to 25 parts (manufactured by SF Corporation).

Example 13 A cationic polymer (trade name: Sumireze Resin 1001 / manufactured by Sumitomo Chemical Co., Ltd.) was added to the coating liquid 7 of Example 7
Parts (trade name: KSR-100K / manufactured by Sanyo Chemical Industry Co., Ltd.)
In the same manner as in Example 7, an ink jet recording sheet was obtained.

Example 14 A cationic polymer (trade name: Sumireze Resin 1001 / manufactured by Sumitomo Chemical Co., Ltd.) was added to the composition of the coating liquid 8 of Example 8.
Parts (trade name: KSR-100K / manufactured by Sanyo Chemical Industry Co., Ltd.)
In the same manner as in Example 8, an ink jet recording sheet was obtained.

Example 15 A cationic polymer (trade name: Sumireze Resin 1001 / manufactured by Sumitomo Chemical Co., Ltd.) was added to the coating solution 9 of Example 9
And 20 parts (trade name: KSR-100K / manufactured by Sanyo Chemical Industry Co., Ltd.) at a concentration of 20%
In this manner, an ink jet recording sheet was obtained in the same manner as in Example 9, except that the composition was prepared as follows.

Example 16 A cationic polymer (trade name: Sumirezu Resin 1001 / manufactured by Sumitomo Chemical Co., Ltd.) was added to the coating liquid 10 of Example 10
Ink jet recording was carried out in the same manner as in Example 10, except that the concentration was adjusted to 20% with a composition (coating liquid 16) containing 10 parts and 20 parts (trade name: KSR-100K / manufactured by Sanyo Chemical Industries, Ltd.). Sheet was obtained.

Example 17 A cationic polymer (trade name: Sumireze Resin 1001 / manufactured by Sumitomo Chemical Co., Ltd.) was added to the composition of the coating liquid 11 of Example 11.
10 parts and 20 parts (trade name: KSR-100K / manufactured by Sanyo Chemical Industry Co., Ltd.) were added (coating liquid 17) to give a concentration of 2
An ink jet recording sheet was obtained in the same manner as in Example 11, except that the composition was adjusted to 0%.

Example 18 A cationic polymer (trade name: Sumireze Resin 1001 / manufactured by Sumitomo Chemical Co., Ltd.) was added to the coating liquid 12 in Example 12.
An ink jet recording sheet was obtained in the same manner as in Example 12, except that the concentration was 20% with the composition (coating liquid 18) to which 20 parts were added.

Example 19 [Preparation of aqueous composition] (Coating liquid 19) 90 parts of light calcium carbonate (trade name: Callite SA, secondary particle size: 3.0 μm / manufactured by Shiraishi Kogyo Co., Ltd.) Silica (trade name: Syloid, secondary particle size: 12 μm / manufactured by Fuji Devison Chemical Co., Ltd.) 10 parts ・ Amphoteric ion latex (trade name: Acostar C122 / Mitsui Cyanamid Co., Ltd.) 46 parts ・ Polyvinyl alcohol (trade name: PVA- R-1130 / manufactured by Kuraray Co., Ltd. 23 parts ・ Dispersant (sodium polypyrophosphate) 0.5 part ・ Defoaming agent (trade name: NOPCO 1407-K) 0.03 part Water is added to the above components and mixed and stirred. Thus, an aqueous composition having a concentration of 20% was obtained.

(Coating liquid 20) 90 parts of light calcium carbonate (trade name: Callite SA, secondary particle diameter: 3.0 μm / manufactured by Shiraishi Industry Co., Ltd.) colloidal silica (trade name: thyroid, secondary particles) Diameter: 12 μm / Fuji Devison Chemical Co., Ltd.) 10 parts ・ Amphoteric ion latex (trade name: Acostar C122 / Mitsui Cyanamid) 23 parts ・ Polyvinyl alcohol (trade name: PVA-R-1130 / Kuraray Co.) 46 parts -Dispersant (sodium polypyrophosphate) 0.5 part-Defoaming agent (trade name: NOPCO 1407-K) 0.03 part Water is added to the above components and mixed with stirring to obtain an aqueous composition having a concentration of 15%. I got

[Preparation of Inkjet Recording Sheet]
The coating liquid 19 was used as a lower ink receiving layer,
Synthetic paper having a thickness of 80 μm [trade name: YUPO FPG-80 /
8g / m on Oji Yuka Synthetic Paper ^TwoWill be
After coating and drying with a bar coater, the upper layer
As the ink-receiving layer, the coating liquid 20 was coated with a solid content of 10 g / m.^Two
Coat and dry with a bar coater so that
A jet recording sheet was obtained.

Example 20 [Preparation of Aqueous Composition] (Coating Liquid 21) 90 parts of light calcium carbonate (trade name: Callite SA, secondary particle diameter: 3.0 μm / manufactured by Shiraishi Industry Co., Ltd.) Silica (trade name: Syloid, secondary particle diameter: 12 μm / manufactured by Fuji Devison Chemical Co., Ltd.) 10 parts ・ Amphoteric ion latex (trade name: Acostar C122 / Mitsui Cyanamid) 46 parts ・ Polyvinyl pyrrolidone (trade name: rubiscol) K-90, molecular weight 360,000 / manufactured by BA SF) 23 parts ・ Dispersant (sodium polypyrophosphate) 0.5 part ・ Defoaming agent (trade name: NOPCO 1407-K) 0.03 part Was added and mixed and stirred to obtain an aqueous composition having a concentration of 20%.

(Coating liquid 22) 90 parts of light calcium carbonate (trade name: Callite SA, secondary particle size: 3.0 μm / manufactured by Shiraishi Industry Co., Ltd.) colloidal silica (trade name: Syloid, secondary particles) Diameter: 12 μm / manufactured by Fuji Devison Chemical Co., Ltd. 10 parts ・ Amphoteric ion latex (trade name: Acostar C122 / manufactured by Mitsui Cyanamid) 23 parts ・ Polyvinylpyrrolidone (trade name: Rubiscol K-90, molecular weight 360,000 / BA SF) 46 parts ・ Dispersant (sodium polypyrophosphate) 0.5 part ・ Defoaming agent (trade name: NOPCO 1407-K) 0.03 part Water is added to the above components, and the mixture is mixed and stirred to give a concentration of 20. % Of an aqueous composition was obtained.

[Preparation of Ink-Jet Recording Sheet] The coating liquid 21 was used as a lower ink receiving layer in Example 19
After coating and drying with a bar coater so that the solid content becomes 8 g / m ² on the same support as above, the coating liquid 22 becomes 10 g / m ² as the upper ink receiving layer thereon. Coating and drying were performed using a bar coater as described above to obtain an inkjet recording sheet.

Example 21 [Preparation of Aqueous Composition] (Coating Solution 23) 90 parts of light calcium carbonate (trade name: Callite SA, secondary particle size: 3.0 μm / manufactured by Shiraishi Industry Co., Ltd.) ・ Colloid Silica (trade name: Syloid, secondary particle diameter: 12 μm / manufactured by Fuji Devison Chemical Co., Ltd.) 10 parts ・ Amphoteric ion latex (trade name: Acostar C122 / Mitsui Cyanamid) 46 parts ・ Polyvinyl pyrrolidone (trade name: rubiscol) K-90, molecular weight 360,000 / manufactured by BA SF Co., Ltd. 23 parts Cationic polymer (trade name: Sumireze Resin 1001 / manufactured by Sumitomo Chemical Co., Ltd.) 20 parts Dispersant (sodium polypyrophosphate) 0.5 part Defoaming 0.03 parts of an agent (trade name: NOPCO 1407-K) Water was added to the above components, and mixed and stirred to obtain an aqueous composition having a concentration of 20%.

(Coating liquid 24) 90 parts of light calcium carbonate (trade name: Callite SA, secondary particle size: 3.0 μm / manufactured by Shiraishi Industry Co., Ltd.) colloidal silica (trade name: Syloid, secondary particles) Diameter: 12 μm / manufactured by Fuji Devison Chemical Co., Ltd. 10 parts ・ Amphoteric ion latex (trade name: Acostar C122 / manufactured by Mitsui Cyanamid) 23 parts ・ Polyvinylpyrrolidone (trade name: Rubiscol K-90, molecular weight 360,000 / BA SF) 46 parts ・ Cationic polymer (trade name: Sumireze Resin 1001 / Sumitomo Chemical Co., Ltd.) 20 parts ・ Dispersant (sodium polypyrophosphate) 0.5 part ・ Defoaming agent (trade name: Nopco 1407-K) Water was added to 0.03 parts or more of the components and mixed and stirred to obtain an aqueous composition having a concentration of 20%.

[Preparation of Ink-Jet Recording Sheet] The coating liquid 23 was used as a lower ink receiving layer in Example 19
After coating and drying with a bar coater so that the solid content is 8 g / m ² on the same support as above, the coating liquid 24 has a solid content of 10 g / m ² as an upper ink receiving layer thereon. Coating and drying were performed using a bar coater as described above to obtain an inkjet recording sheet.

Example 22 [Preparation of aqueous composition] (Coating liquid 25) 50 parts of fine alumina (trade name: alumina A, secondary particle size: 4.8 μm / manufactured by Mizusawa Chemical Industry Co., Ltd.) 50 colloidal silica (Trade name: thyroid, secondary particle diameter: 12 μm / manufactured by Fuji Devison Chemical Co., Ltd.) 50 parts ・ Amphoteric ion latex (trade name: Acostar C122 / manufactured by Mitsui Cyanamid) 46 parts ・ Polyvinylpyrrolidone (trade name: Rubiscol K) -90, molecular weight 360,000 / BA SF Co., Ltd. 23 parts Cationic polymer (trade name: Sumireze Resin 1001 / Sumitomo Chemical Co., Ltd.) 10 parts Cationic polymer (trade name: KSR-100K / Sanyo Chemical Industries, Ltd.) 20 parts ・ Dispersant (sodium polypyrophosphate) 0.5 part ・ Defoamer (trade name: NOPCO 1407-K) 0.03 part The added mixture was stirred, the concentration to obtain 20% of the aqueous composition.

(Coating liquid 26) 50 parts of fine alumina (trade name: alumina A, secondary particle diameter: 4.8 μm / manufactured by Mizusawa Chemical Industry Co., Ltd.) 50 colloidal silica (trade name: thyroid, secondary particle diameter) : 12 μm / Fuji Devison Chemical Co., Ltd.) 50 parts ・ Amphoteric ion latex (trade name: Acostar C122 / Mitsui Cyanamid) 23 parts ・ Polyvinylpyrrolidone (trade name: Luviscol K-90, molecular weight 360,000 / BA SF Company) 46 parts ・ Cationic polymer (trade name: Sumireze Resin 1001 / Sumitomo Chemical Co., Ltd.) 10 parts ・ Cationic polymer (trade name: KSR-100K / Sanyo Kasei Kogyo Co., Ltd.) 20 parts ・ Dispersant (polypyrophosphate) Soda) 0.5 part ・ Antifoaming agent (trade name: NOPCO 1407-K) 0.03 part Water is added to the above composition, mixed and stirred, and the concentration is 2 % Of to obtain an aqueous composition.

[Preparation of Ink-Jet Recording Sheet] The coating liquid 25 was used as a lower ink receiving layer in Example 19
After coating and drying with a bar coater so that the solid content becomes 8 g / m ² on the same support as above, the coating liquid 26 becomes a solid content of 10 g / m ² as an upper ink receiving layer thereon. Coating and drying were performed using a bar coater as described above to obtain an inkjet recording sheet.

Example 23 [Preparation of Aqueous Composition] (Coating Liquid 27) Fine silica (trade name: Fine Seal, secondary particle diameter: 3.7 μm, specific surface area by BET method: 280 m ² / g / Tokuyama Soda Co., Ltd.) 90 parts ・ Colloidal silica (trade name: Syloid, secondary particle size: 12 μm / Fuji Devison Chemical Co., Ltd.) 10 parts ・ Amphoteric ion latex (trade name: Acostar C122 / Mitsui Sianamid) 46 Part ・ Polyvinylpyrrolidone (trade name: Rubiscol K-90, molecular weight: 360,000 / manufactured by BA SF) 23 parts ・ Cationic polymer (trade name: Sumireze Resin 1001 / Sumitomo Chemical Co., Ltd.) 10 parts ・ Cationic polymer ( Trade name: KSR-100K / manufactured by Sanyo Chemical Industries, Ltd.) 20 parts ・ Dispersant (polysodium pyrophosphate) 0.5 part ・ Defoaming agent (trade name: NOPCO 1) 407-K) 0.03 parts Water was added to the above components and mixed and stirred to obtain an aqueous composition having a concentration of 20%.

(Coating Liquid 28) 90 parts of fine silica (trade name: Fine Seal, secondary particle diameter: 3.7 μm, specific surface area by BET method: 280 m ² / g / manufactured by Tokuyama Soda Co., Ltd.) 90 parts Silica (trade name: Syloid, secondary particle size: 12 μm / manufactured by Fuji Devison Chemical Co., Ltd.) 10 parts ・ Amphoteric ion latex (trade name: Acostar C122 / manufactured by Mitsui Cyanamid) 23 parts K-90, molecular weight: 360,000 / manufactured by BA SF) 46 parts ・ Cationic polymer (trade name: Sumireze Resin 1001 / Sumitomo Chemical Co., Ltd.) 10 parts ・ Cationic polymer (trade name: KSR-100K / Sanyo Chemical Industries) 20 parts ・ Dispersant (sodium polypyrophosphate) 0.5 part ・ Defoaming agent (trade name: NOPCO 1407-K) 0.03 parts or more Water was added to mixture stirred component concentration to obtain 20% of the aqueous composition.

[Preparation of Ink-Jet Recording Sheet] The coating liquid 27 was used as a lower ink receiving layer in Example 19
After coating and drying with a bar coater so that the solid content is 8 g / m ² on the same support as above, the coating liquid 28 is applied thereon as an upper ink receiving layer to have a solid content of 10 g / m ^2. Coating and drying were performed using a bar coater as described above to obtain an inkjet recording sheet.

Example 24 [Preparation of aqueous composition] (Coating liquid 29) 50 parts of light calcium carbonate (trade name: Callite SA, secondary particle size: 3.0 μm / manufactured by Shiraishi Kogyo Co., Ltd.) (Trade name: Fine Seal, secondary particle diameter: 3.7 μm, specific surface area by BET method: 280 m ² / g / manufactured by Tokuyama Soda Co., Ltd.) 50 parts ・ Amphoteric ion latex (trade name: ACOSTAR C122 / Mitsui Cyanamid Co., Ltd.) 46 parts ・ Polyvinylpyrrolidone (trade name: Rubiscol K-90, molecular weight 360,000 / manufactured by BA SF) 23 parts ・ Cationic polymer (trade name: Sumireze Resin 1001 / Sumitomo Chemical Co., Ltd.) 10 parts ・ Cationic 20 parts of polymer (trade name: KSR-100K / manufactured by Sanyo Chemical Industries, Ltd.) 0.5 part of dispersant (sodium polypyrophosphate)-Defoamer (trade name: NOPCO 14) 07-K) 0.03 parts Water was added to the above components and mixed and stirred to obtain an aqueous composition having a concentration of 20%.

(Coating liquid 30) 70 parts of fine silica (trade name: fine seal, secondary particle diameter: 3.7 μm, specific surface area by BET method: 280 m ² / g / manufactured by Tokuyama Soda Co., Ltd.) Silica (trade name: Syloid, secondary particle size: 12 μm / manufactured by Fuji Devison Chemical Co., Ltd.) 30 parts ・ Amphoteric ion latex (trade name: Acostar C122 / manufactured by Mitsui Cyanamid) 23 parts K-90, molecular weight: 360,000 / manufactured by BA SF) 46 parts ・ Cationic polymer (trade name: Sumireze Resin 1001 / Sumitomo Chemical Co., Ltd.) 10 parts ・ Cationic polymer (trade name: KSR-100K / Sanyo Chemical Industries) 20 parts ・ Dispersant (sodium polypyrophosphate) 0.5 part ・ Defoaming agent (trade name: NOPCO 1407-K) 0.03 parts or more Water was added to mixture stirred component concentration to obtain 20% of the aqueous composition.

[Preparation of Ink-Jet Recording Sheet] The coating liquid 29 was used as the lower ink receiving layer in Example 19
After coating and drying with a bar coater so that the solid content becomes 8 g / m ² on the same support as above, the coating liquid 30 becomes 10 g / m ² as an upper ink receiving layer thereon. Coating and drying were performed using a bar coater as described above to obtain an inkjet recording sheet.

Example 25 In Example 23, the amount of the amphoteric ion latex in the coating liquid 28 was changed from 23 parts to 35
In the same manner as in Example 23, except that the blending amount of polyvinylpyrrolidone was changed from 46 parts to 35 parts, a sheet for inkjet recording was obtained.

Example 26 In Example 23, the amount of the amphoteric ion latex in the coating liquid 28 was changed from 23 parts to 10
In the same manner as in Example 23, except that the blending amount of polyvinylpyrrolidone was changed from 46 parts to 50 parts, an inkjet recording sheet was obtained.

Example 27 In Example 23, the coating amount of the amphoteric ion latex in the coating solution 27 was changed from 46 parts to 60
And the amount of polyvinylpyrrolidone was changed from 23 parts to 10 parts, and an ink jet recording sheet was obtained in the same manner as in Example 23.

Example 28 In Example 23, the amount of the amphoteric ion latex in the coating liquid 27 was changed from 46 parts to 40
In the same manner as in Example 23, except that the amount of polyvinylpyrrolidone was changed from 23 parts to 30 parts, a sheet for inkjet recording was obtained.

Comparative Example 1 An ink jet recording sheet was prepared using acidic high-quality paper (trade name: Kinno, 81.4 g / m ² / manufactured by Nippon Paper).

Comparative Example 2 An ink jet recording sheet was prepared using neutral high-quality paper (trade name: Kinrishi, 64.0 g / m ² / manufactured by Mitsubishi Paper Mills).

Comparative Example 3 An ink jet recording sheet was prepared using coated paper which had been smeared under the following conditions. A coating solution comprising 70 parts of kaolin, 20 parts of heavy calcium carbonate, and 10 parts of satin white as a pigment, and 3 parts of phosphorylated ester starch (solid content) and 11 parts of SBR latex (solid content) as an adhesive. Was prepared and the coating liquid was adjusted to 50 g / m
Dry weight on both sides of base paper consisting of ² is 25g per side
/ M ² . "

Comparative Example 4 A commercially available synthetic paper (trade name: YUPO FPG-80 / Oji Yuka Synthetic Paper) was used as an ink jet recording sheet.

Comparative Example 5 In the aqueous composition of Coating Liquid 5 used in Example 5, except that the amphoteric ionic latex was changed to an aqueous polyurethane resin (trade name: Hydran AP-40 / manufactured by Dainippon Ink and Chemicals, Inc.) In the same manner as in Example 5, an inkjet recording sheet was obtained.

Comparative Example 6 In the aqueous composition of the coating liquid 11 used in Example 17,
An ink jet recording sheet was obtained in the same manner as in Example 17, except that the amphoteric ion latex was changed to an aqueous vinyl acetate-ethylene copolymer (trade name: Sumika Flexs 752 / Sumitomo Chemical Industries, Ltd.).

Comparative Example 7 In the aqueous composition of coating liquid 17 used in Example 17,
The amount of the amphoteric ion latex was changed from 46 parts to 0 part, and the amount of the polyvinylpyrrolidone was changed from 23 parts to 4 parts.
An ink jet recording sheet was obtained in the same manner as in Example 17, except that the amount was changed to 0.

Comparative Example 8 Ink jet recording was carried out in the same manner as in Example 23 except that the amount of the amphoteric ionic latex was changed to 0 part in the aqueous compositions of the coating liquids 27 and 28 used in Example 23. I got a sheet.

The ink jet recording sheet obtained as described above was subjected to an evaluation test according to the following method.
Table 3 shows the obtained results. In addition, about each Example and the comparative example, the sheet for inkjet recording (recording layer)
About the pigment, adhesive, and cationic polymer blending,
It is summarized in Table 2 for easy understanding. For evaluation printing printers, Sharp Corporation (IO-735)
X) and Canon (PIXEL-JET)
Both are black, yellow, cyan and magenta
After a printed image was formed on a recording sheet using the colors, the evaluation was performed. The evaluation method and evaluation criteria in this case are shown below.

(Ink Absorption Time) After printing with a printer, the recorded matter was allowed to stand at room temperature, and the ink drying time (second) was measured until the ink did not adhere even when the recording portion was touched with a finger. However, those which did not adhere to the ink immediately after printing with the finger immediately after the printing with the finger were dried quickly, and those which took 180 seconds or more were evaluated as x.

(Surface strength) After a cellophane tape was stuck to the ink receiving layer and brought into close contact with the ink receiving layer, 90
The film was manually peeled off at an angle of ° to evaluate the state in which the ink receiving layer was transferred to the cellophane tape. A: No transfer of the ink receiving layer is observed. O: Transfer of the ink receiving layer is slightly observed. Δ: Part of the ink receiving layer is transferred, but there is no practical problem. ×: A large amount of the ink receiving layer is transferred.

(Printing Blurring / Sludge) The blurring and the degree of blurring of the recorded image were visually evaluated. ◎: No bleeding / sludge ○: Slight bleeding / sludge is observed △: Smearing / sludge is recognized, but there is no practical problem ×: Smearing / sludge is large

(Printing Color Development) The color and sharpness of the recorded image were visually evaluated. ◎: Excellent color and color development, no color fading. ○: Slight color and color fading. △: Slight lack of color and color development, but no practical problem. ×: Lack of color and color development (printing. Image is whitened: latex whitening phenomenon occurs)

(Water Resistance of Receptive Layer) Water was applied to the ink receiving layer, and the state of peeling of the receiving layer when water was wiped off at a constant finger pressure was evaluated. ◎: There is no peeling of the ink receiving layer. ：: The ink receiving layer is slightly peeled. Δ: Part of the ink receiving layer is peeled off, but there is no practical problem. X: A large amount of the ink receiving layer is peeled.

(Water resistance of printed image)
When the recorded matter was soaked in water (30 minutes) and then dried at room temperature, the bleeding of the recorded image and the degree of change in coloring were evaluated visually. A: No change is observed in the image. ：: The image is slightly discolored. Δ: The image is slightly discolored, but there is no practical problem. X: The image is discolored.

(Comprehensive Evaluation) The above evaluations were collectively evaluated. ◎: Very good. ：: Excellent. Δ: Slightly inferior, but no practical problem. ×: poor

[0116]

[Table 1]

[0117]

[Table 2]

[Remarks]: Each symbol in Table 2 is as follows. A: Light calcium carbonate (trade name: Callite SA) B: Fine alumina (trade name: alumina A) C: Fine silica (trade name: Fine Seal X-37) D: Colloidal silica (trade name: Silodo # 620) A: Zwitterionic latex (trade name: Acostar C12)
2) A : Polyvinyl alcohol (trade name: PVA-R-11)
30) C: Polyvinylpyrrolidone (PVP) (trade name: Rubis)
Cole K-90) d: Other adhesives (aqueous vinyl acetate-ethylene copolymer)
Body (trade name: Sumikaflex 752) or water-based poly
Urethane resin (product name: water-based polyurethane resin (product
Name: Hydran AP-40)) α: Cationic polymer (trade name: Sumireze resin)
1001) β: Cationic polymer (trade name: KSR-100K)

[0119]

[Table 3]

[0120]

As is evident from the results in Table 3, the ink jet recording sheet obtained according to the example of the present invention has excellent ink absorbency, shows a sharp high-resolution image, and further has the conventional synthetic properties. The ink jet recording sheet was excellent in the surface strength and water resistance of the ink receiving layer as compared with the recording sheet coated on a support such as a film.

[Brief description of the drawings]

FIG. 1 is a schematic structural view of a zwitterionic latex used in an ink receiving layer of the present invention.

[Explanation of symbols]

 1: Quaternary alkylamine group (cationic) 2: Carboxyl group (anionic)

──────────────────────────────────────────────────続 き Continuation of front page (56) References JP-A-59-112094 (JP, A) JP-A-59-142216 (JP, A) JP-A-60-89395 (JP, A) JP-A-2- 229296 (JP, A) JP-A-4-50394 (JP, A) (58) Fields investigated (Int. Cl. ⁷ , DB name) B41M 5/00

Claims (12)

(57) [Claims] 1. An ink jet recording sheet comprising a support and an ink receiving layer mainly comprising a pigment and an adhesive, wherein the ink receiving layer is formed from an aqueous composition mainly comprising a pigment and an amphoteric ionic latex. And receive ink
An ink jet recording sheet comprising fine silica as a pigment of a container . 2. A composition comprising a pigment and an adhesive as main components on a support.
Ink-jet recording sheet provided with an ink receiving layer
Wherein the ink receiving layer comprises a pigment and a zwitterionic latex.
Formed from an aqueous composition mainly composed of
The aqueous composition of the container contains polyvinylpyrrolidone.
And a sheet for inkjet recording. 3. A composition comprising a pigment and an adhesive as main components on a support.
Ink-jet recording sheet provided with an ink receiving layer
Wherein the ink receiving layer comprises a pigment and a zwitterionic latex.
Formed from an aqueous composition mainly composed of
The aqueous composition of the container contains a cationic polymer.
And a sheet for inkjet recording. 4. A pigment containing a pigment and an adhesive as main components on a support.
Ink-jet recording sheet provided with an ink receiving layer
Wherein the ink receiving layer comprises a pigment and a zwitterionic latex.
And a support formed from an aqueous composition mainly composed of
Is plastic film or synthetic paper
Characteristic inkjet recording sheet. 5. The ink jet recording sheet according to claim 4, wherein the ink receiving layer is formed of two or more layers, and the lowermost layer is an aqueous composition containing more amphoteric ion latex than other layers. 6. The ink jet recording sheet according to claim 5, wherein the ink receiving layer is formed of at least an upper layer and a lower layer, and the upper layer and the lower layer are made of an aqueous composition satisfying the following conditions. [Upper layer]: an aqueous composition comprising 10 to 35 parts by weight of amphoteric ion latex and 20 to 70 parts by weight of a water-soluble polymer with respect to 100 parts by weight of a pigment, and the amount of the amphoteric ion latex used is not more than a water-soluble polymer. Consists of [Lower layer]: An aqueous composition mainly composed of 40 to 70 parts by weight of amphoteric ion latex and 5 to 30 parts by weight of a water-soluble polymer per 100 parts by weight of pigment. 7. The ink jet recording sheet according to any one of claims 2 to 6 which contains fine silica as pigment in the ink-receiving layer. 8. The ink jet recording sheet according to claim 1, wherein the aqueous composition of the ink receiving layer contains a water-soluble polymer. 9. The ink jet recording sheet according to claim 8, wherein polyvinyl pyrrolidone is contained as a water-soluble polymer in the ink receiving layer. 10. The ink-receiving layer according to claim 1, wherein the aqueous composition contains a cationic polymer.
Item 7. The ink jet recording sheet according to item 1 . 11. The support-jet recording sheet according to any one of claims 1, 2, 3 is a plastic film or a synthetic paper. 12. The ink-receiving layer according to claim 1, wherein the ink-receiving layer comprises an aqueous composition containing 10 to 70 parts by weight of amphoteric ion latex and 5 to 70 parts by weight of a water-soluble polymer per 100 parts by weight of pigment . The inkjet recording sheet according to any one of the preceding claims.