JP2003001928A - Ink jet recording material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain an ink jet recording material, the ink absorbency and printing density of which are favorable, which is excellent in white paper lustrous properties, especially in scratch resistance and dark fading properties. SOLUTION: In the ink jet recording material, in which at least one ink accepting layer is provided on a support, the oxygen transmission degree prescribed by the constant pressure method of JIS K 7126 of which is 10 cm<3> /cm<2> per 24 hours under 1 atm. or less, the ink accepting layer includes a gas phase method silica and a hydrophilic binder and, after being provided with the ink accepting layer, the material is surface-treated with a calender having a metal roll. Preferably, the ink accepting layer includes fine thermoplastic organic polymer particles having the lowest film-forming temperature of 40 to 160 deg.C and the surface treatment is performed through the contact of the metal roll, the surface temperature of which is set to be higher than the lowest film-forming temperature of the fine thermoplastic organic polymer particle and lower than 250 deg.C, of the calender with the ink accepting layer.

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 material having a good ink absorbency and a high gloss on a white paper portion, and more particularly to an ink jet recording material excellent in scratch resistance and dark fading of a printed image.

[0002]

2. Description of the Related Art As a recording material used in an ink jet recording method, a pigment called amorphous silica or the like is formed on a support called ordinary paper or ink jet recording paper, and a porous material made of a water-soluble binder such as polyvinyl alcohol is used. A recording material provided with the ink absorption layer is known.

For example, JP-A-55-51583 and JP-A-5-51583.
No. 6-157, No. 57-107879, No. 57-10.
No. 7880, No. 59-230787, No. 62-160.
No. 277, No. 62-184879, No. 62-1833.
No. 82 and No. 64-11877, there are proposed recording materials obtained by coating a paper support with a silicon-containing pigment such as silica together with an aqueous binder.

Further, Japanese Patent Publication No. 3-56552 and Japanese Patent Laid-Open No. Hei 2
No. 188287, No. 8-132728, No. 10
81064, 10-119423, 10
-175365, 10-203006, 10-
217601, Doppei 11-20300, Doppei 11-
Nos. 20306 and 11-34481 disclose recording materials using synthetic silica fine particles prepared by a vapor phase method (hereinafter referred to as vapor phase silica). However, it has been difficult to achieve both ink absorbency and white paper gloss.

Further, JP-A-62-174183, JP-A-2-276670, JP-A-5-32037 and JP-A-6-199034 disclose recording materials using alumina or alumina hydrate. ing. However, the white paper gloss was good, but the ink absorbency was insufficient.

Further, a proposal of providing a gloss developing layer on the ink receiving layer is disclosed in JP-A-3-215080 and JP-A-7-8.
9220, JP-A-7-117335, JP-A-2000
No. 37944, for example. These gloss-developing layers are colloidal silica, and the ink absorbency is likely to decrease, and it is difficult to obtain a delicate image if the surface pores are increased in order to improve the ink passing speed.

Japanese Unexamined Patent Publication No. 6-55829 discloses a recording sheet having a silica porous layer as a lower layer and an alumina or alumina hydrate-containing layer as an upper layer.
No. 6 discloses a recording material having a water-absorbing pigment-containing layer as the lower layer and pseudo-boehmite as the outermost layer. However, the pigments used for these lower layers have an average particle diameter of several μm or more and are coarse, and when trying to obtain sufficient surface gloss, the coating amount of alumina or alumina hydrate in the upper layer is increased. Since it was necessary to do so, the ink absorbency was lowered, and both glossiness and ink absorbency could not be sufficiently satisfied.

Further, in recent years, with the demand for photo-like recording sheets, the glossiness has become more and more important, and polyolefin resin-coated paper (paper having both sides laminated with a polyolefin resin such as polyethylene) or polyester is used. A recording material has been proposed in which an ink receiving layer mainly composed of vapor phase silica is coated on a water resistant support such as a film.

Although the paper support which has been generally used conventionally has a role as an ink absorbing layer, the water-resistant support such as the above-mentioned polyolefin resin coated paper is a paper support. Unlike the above, since it cannot absorb ink, the ink absorbability of the ink receiving layer provided on the support is important, and it is necessary to increase the porosity of the ink receiving layer. Therefore, it was necessary to increase the coating amount of the vapor phase method silica and further reduce the ratio of the binder to the vapor phase method silica, and the scratch resistance tended to decrease.

When inorganic fine particles such as vapor-phase method silica are used, fading of a printed image due to trace gases in the atmosphere such as ozone and NOx, that is, so-called dark fading, is apt to decrease.
In particular, a porous recording material provided with an ink receiving layer using inorganic fine particles on a water-resistant support has a problem that a printed image is greatly discolored during storage after printing. That is, the inorganic fine particles easily adsorb a trace gas in the atmosphere such as ozone and NOx,
It is expected that image fading will be accelerated because the water resistant support will impede air movement.

As a solution to the scratch resistance, Japanese Patent Publication No. 63-65.
No. 036, 63-65038 and the like add filler particles having a large particle size of 3 μm or more to the surface of the ink receiving layer.
Although the use of a spherical fine particle polymer of μm has been proposed,
The gloss of the white paper part is reduced. Japanese Patent Application Laid-Open No. 11-321080 proposes to add a matting agent having a dispersity of 2 or less to the uppermost layer of the void layer, but as a preferred embodiment, a matte having a thickness of 2 μm or more larger than the dry film thickness of the uppermost layer. It is described that an agent is used, and the gloss tends to decrease in order to obtain sufficient scratch resistance. Generally, the void-type inkjet recording material has low gloss as compared with a so-called swelling inkjet recording material whose ink receiving layer is mainly composed of a hydrophilic binder that absorbs an ink solvent,
Since addition of a coarse matting agent further reduces the amount, improvement has been desired.

To solve the dark fading property, JP-A-61-1772
No. 79 discloses that a nitrogen-containing heterocyclic mercapto compound is used. JP-A-7-314882 discloses compounds such as dithiocarbamic acid and thiocyanic acid, and JP-A-8-25796 discloses iodo compounds. And a thiourea compound or the like are combined to prevent discoloration due to a trace gas in the atmosphere. However, the effect of improving the image storability is not sufficient, the ink absorbability is significantly reduced, the white background is discolored, and the compound itself is toxic, so that it is not sufficiently satisfactory. There wasn't.

Further, in Japanese Unexamined Patent Publication No. 6-155894, an ink receiving layer is provided on a support containing wood pulp and a pigment as main components, and calendering is performed to make the dot shape of the ink uniform and improve the background stain. Was proposed, and Japanese Patent Laid-Open No. 7-
In Japanese Patent No. 17125, an ink fixing layer mainly composed of cationic colloid particles is provided on the outermost surface layer of a recording sheet, and calendering is performed with a heating metal roll and a synthetic resin roll to prevent unevenness in ink absorption and thickening of the dot diameter. A proposal has been made, and in JP-A-11-268405, a coating layer containing a pigment and an adhesive is provided on a substrate, specific silica fine particles are contained in the outermost layer of the coating layer, and treated by a thermal calendar. It has been proposed to improve gloss and surface strength by doing so. However, none of the proposals has a specific example in which an ink receiving layer containing vapor phase silica, alumina, or alumina hydrate is provided on a water-resistant support and calendering is performed, and calendering improves the dark fading property. There is no mention of the fact that it does not improve the scratch resistance.

Further, in JP-A-2000-280603, an ink jet recording sheet having a support provided with an ink receiving layer containing inorganic fine particles such as fumed silica and a layer mainly containing thermoplastic organic polymer fine particles is provided. It has been proposed to improve the water resistance and the image storability by heating after printing on the paper, but the heating after printing is troublesome, and the sharpness of the printed image decreases, and problems such as stains with ink Is likely to occur. Further, the proposal does not mention the improvement of ink absorbency, gloss on white paper, scratch resistance, and gas resistance by calendering before printing.

Conventionally, water-based dyes have been exclusively used as coloring materials used in ink jet recording inks, but they have the drawbacks of poor light resistance and water resistance, and have excellent color tone and vividness, and excellent light resistance and water resistance. Pigment inks have come into use. However, pigment ink needs to disperse water-insoluble pigment particles and keep it stable.Due to the dryness and scratch resistance of the ink, pigment particles that are larger in size than dyes are the pore size in the ink receiving layer. Easily affected by
Pigment inks generally have low ink absorbency.

[0016]

SUMMARY OF THE INVENTION An object of the present invention is to provide an ink jet recording material having good ink absorbency, glossiness on a white paper portion, and dark fading property, and particularly scratch resistance and darkness of printed image. Provided is an inkjet recording material having excellent color fading properties.

[0017]

As a result of sincerity examination, it was found that the above object of the present invention can be basically achieved by the following means.

(1) The oxygen permeability defined by the isobaric method of JIS-K-7126 is 10 cm ³ / cm ² · 24 h · atm.
In the inkjet recording material having at least one ink-receiving layer on a support, the ink-receiving layer contains at least one of fumed silica, alumina, or alumina hydrate and a hydrophilic binder. And
An inkjet recording material, which is surface-treated with a calendar having a metal roll after providing an ink receiving layer.

(2) The ink receiving layer contains the thermoplastic organic polymer fine particles having a minimum film forming temperature of 40 ° C. to 160 ° C., and the surface temperature of the metal roll of the calender has the minimum temperature of the thermoplastic organic polymer fine particles. 2. The inkjet recording material as described in 1 above, which is subjected to a surface treatment by contacting with an ink receiving layer at a film temperature of 250 ° C. or higher.

(3) A protective layer is laminated on the ink receiving layer, and the protective layer contains colloidal silica, a hydrophilic binder, and thermoplastic organic polymer fine particles having a minimum film forming temperature of 40 ° C to 160 ° C. 2. The inkjet recording material as described in 1 above, wherein the surface treatment of the metal roll of the calender is carried out by contacting with a protective layer at a surface temperature of at least the minimum film forming temperature of the thermoplastic organic polymer fine particles and 250 ° C. or less.

[0021]

BEST MODE FOR CARRYING OUT THE INVENTION The present invention will be described in detail below.
The oxygen permeability defined by the isobaric method of JIS-K-7126 used in the present invention is 10 cm ³ / cm ² · 24 h · atm.
As the support which is the following, films of polyethylene, polypropylene, polyvinyl chloride, diacetate resin, triacetate resin, cellophane, acrylic resin, polyethylene terephthalate, polyethylene naphthalate, etc.,
It is selected from resin-coated paper, resin-impregnated paper and the like, and resin-coated paper is preferably used from the viewpoint of handleability and cost. The thickness of these supports is preferably about 50 to 250 μm.

The oxygen permeability of the support of the present invention is JIS-K.
It is obtained by the method specified in the isobaric method of -7126, oxygen gas is made to flow on one side of the support at about atmospheric pressure, and nitrogen carrier gas is circulated on the other side, and the permeated oxygen is measured by an oxygen detector. It can be obtained. In the present invention, the unit of oxygen permeability is cm ³ / cm ² · 24h · atm.

The base paper constituting the resin-coated paper preferably used in the present invention is not particularly limited, and commonly used paper can be used, but more preferably, it is smooth as used for a photographic support. Raw base paper is preferred. As the pulp constituting the raw paper, one kind or a mixture of two or more kinds of natural pulp, recycled pulp, synthetic pulp and the like is used. This base paper has a sizing agent, a paper strengthening agent, a filler, an antistatic agent, an optical brightening agent, which is generally used in papermaking,
Additives such as dyes are blended.

Further, a surface sizing agent, a surface paper strength agent, a fluorescent whitening agent, an antistatic agent, a dye, an anchoring agent and the like may be applied on the surface.

As the resin for the resin-coated paper, a polyolefin resin or a resin curable with an electron beam can be used.
The polyolefin resin is a homopolymer of olefins such as low-density polyethylene, high-density polyethylene, polypropylene, polybutene, and polypentene, or a copolymer of two or more olefins such as ethylene-propylene copolymer and a mixture thereof. Various densities and melt viscosity indexes (melt indexes) can be used alone or in combination. The amount of resin is selected so that the oxygen permeability is 10 cm ³ / cm ² · 24 h · atm or less, but it is 8 g / m ² or more on one side from the viewpoint of preventing wrinkles and water resistance after printing, and 10 to 50 g / m ² is preferred.

In the resin of the resin-coated paper, white pigments such as titanium oxide, zinc oxide, talc and calcium carbonate, fatty acid amides such as stearic acid amide and arachidic acid amide, zinc stearate, calcium stearate, stearic acid. Aluminum, fatty acid metal salts such as magnesium stearate, antioxidants such as Irganox 1010 and Irganox 1076, blue pigments and dyes such as Cobalt Blue, Ultramarine Blue, Cecilian Blue, Phthalocyanine Blue, Cobalt Violet, Fast Violet, Manganese Purple It is preferable to add various additives such as magenta pigments and dyes, fluorescent whitening agents, and ultraviolet absorbers in an appropriate combination.

The vapor-phase process silica used in the ink receiving layer of the present invention is also called a dry process and is generally produced by a flame hydrolysis method. Specifically, a method of burning silicon tetrachloride with hydrogen and oxygen is generally known, but instead of silicon tetrachloride, silanes such as methyltrichlorosilane and trichlorosilane may be used alone or in the form of silicon tetrachloride. It can be used as a mixture with. Vapor phase silica is commercially available as Aerosil from Nippon Aerosil Co., Ltd. and QS type from Tokuyama Corp., and can be obtained. In general, vapor-phase method silica is aggregated into secondary particles having appropriate voids, and has a particle size of 50 to 300 n.
It is preferable that the particles are pulverized and dispersed by an ultrasonic wave, a high pressure homogenizer, an opposed collision type jet pulverizer or the like until the secondary particles of about m are obtained because the ink absorption and the gloss are good.

Alumina and alumina hydrate contained in the ink receiving layer of the present invention are aluminum oxide and hydrates thereof, which may be crystalline or amorphous, and may be amorphous, spherical, plate-like or the like. Those having a morphology are used. Either of them may be used, or they may be used in combination. In particular, the use of a plate-shaped alumina hydrate having an aspect ratio of 2 or more, preferably 3 to 7 is preferable because the glossiness and the ink absorption are improved.

As the alumina of the present invention, γ-alumina which is a γ-type crystal of aluminum oxide is preferable, and δ is particularly preferable.
Group crystals are preferred. γ-alumina has 1 primary particle
It is possible to reduce the particle size to about 0 nm, but normally, secondary particle crystals of several thousands to tens of thousands nm are ultrasonically treated, a high pressure homogenizer, an opposed collision type jet crusher, etc.
Those crushed to about 00 nm can be preferably used.

The alumina hydrate of the present invention is Al ₂ O ₃ .nH
It is represented by a constitutive formula of 2O (n = 1 to 3). When n is 1, it represents an alumina hydrate having a boehmite structure, and when n is more than 1 and less than 3, it is an alumina hydrate having a pseudo-boehmite structure. It can be obtained by a known production method such as hydrolysis of aluminum alkoxide such as aluminum isopropoxide, neutralization of aluminum salt with alkali, and hydrolysis of aluminate.

The average particle size of the primary particles of the fumed silica, alumina, and alumina hydrate of the present invention means that the dispersed particles exist within a certain area by observation with an electron microscope.
The diameter of a circle equal to the projected area of each individual particle was determined as the particle size of the particle. The average particle size of the primary particles of the vapor-phase method silica used in the present invention is 5 to 50 nm, preferably 5 to 50 nm.
It is 30 nm. The average particle diameter of the primary particles of the tabular alumina hydrate of the present invention, that is, the average particle diameter of the flat plate is 5 to 5.
It is 0 nm, preferably 10 to 30 nm. The average thickness of the tabular alumina hydrate is obtained by observing the cut surface of the sheet coated with the alumina hydrate on the film, and the aspect ratio of the alumina hydrate is obtained by the ratio of the average particle diameter to the average thickness. To be The average particle size of the secondary particles of the vapor phase silica or tabular alumina hydrate of the present invention can be obtained by measuring the dilute dispersion with a laser diffraction / scattering particle size distribution analyzer.

In the present invention, the total amount of fumed silica, alumina, or alumina hydrate used in the ink receiving layer is in the range of 8-40 g / m ² , preferably 10-3.
It is 0 g / m ² . If the amount is less than 8 g / m ² , the ink absorbency is poor, and if the amount is more than 40 g / m ² , the strength of the ink receiving layer is weakened and cracks are likely to occur on the surface.

The vapor phase silica used in the ink receiving layer B of the present invention has a content of 3 to 20 g / m ² , preferably 5 to 1
It is 5 g / m ² . Outside the above range, the effect of having two or more ink receiving layers is difficult to obtain.

In the present invention, the range of the total amount of alumina or aluminum hydrate used in the ink receiving layer D is 0.
It is 5 to 18 g / m ² , and preferably 1 to 14 g / m ² . When it is less than 0.5 g / m ² , gloss of the surface of the recording material is hard to appear, and when it is more than 18 g / m ² , the ink absorbency is lowered. Alumina and alumina hydrate may be used in combination.

In the present invention, the total weight of the fumed silica of the ink receiving layer C and the alumina or alumina hydrate of the ink receiving layer D is 12 to 35 g / m ² , preferably 15 to 30 g / m 2. ^{Is 2} . If it is less than 12 g / m ² , sufficient ink absorbency cannot be obtained, and if it is more than 35 g / m ² , the cost becomes high and the strength of the ink receiving layer is lowered, which tends to cause a problem during production or use.

In the present invention, the oxygen permeability defined by the isobaric method of JIS-K-7126 is 10 (cm ³ / cm ² · 24h).
Atm) or less, and after providing an ink receiving layer containing vapor phase silica, alumina, or alumina hydrate and a hydrophilic binder on a support, the surface is treated with a calendar having a metal roll to produce a white paper. In addition to improving the gloss of the area, the dark fading property of the image is improved. The dark fading property is improved because the hydrophilic binder of the ink receiving layer and the vapor-phase method silica are rearranged by the calendar treatment, and the voids on the surface are appropriately filled, so that gases such as ozone become difficult to pass through and oxygen permeation. Degree is 10 (cm ³ / cm ² · 24h · at
It is speculated that the support having a thickness of m or less prevents ozone and the like from passing through from the surface opposite to the ink receiving layer surface. In particular, the surface treatment of the metal roll at a surface temperature of 50 to 250 ° C., preferably 80 to 200 ° C. further improves the glossiness and dark fading of the white paper, and the scratch resistance is improved by the hydrophilic property of the ink receiving layer. It is presumed that the conductive binder softens due to heat, covers the surface of the vapor-phase grown silica, and fills large voids on the surface. A protective layer may be provided on the ink receiving layer to improve the scratch resistance, and calendering may be performed.

In the present invention, the ink receiving layer is preferably composed of two or more layers, and each layer contains fumed silica. More preferably, by making the average particle size of the primary particles of the vapor phase silica of the lower ink receiving layer A closer to the support smaller than the average particle size of the vapor phase silica used for the upper ink receiving layer B, The ink absorbability is improved, and especially when the pigment ink is used, the ink fixability is improved. When vapor phase method silica having a coarse particle size is used for the upper layer, the glossiness of the white paper portion is likely to decrease, but it is possible to suppress the deterioration of ink absorbency by a calendar process and improve the glossiness and dark fading property of the white paper portion. Preferably, the average particle size of the primary particles of the vapor phase silica of the ink receiving layer A is 5 to 30 nm, and the average particle size of the primary particles of the vapor phase silica of the ink receiving layer B is 10 to 40 nm. In order to improve the scratch resistance, a protective layer may be provided on the ink receiving layer B and calendered.

In the present invention, preferably, the ink receiving layer is composed of two or more layers, vapor phase silica is used for the lower ink receiving layer C near the support, and alumina or alumina hydrate is used for the upper ink receiving layer D. It has a good surface gloss by being calendered and has improved dark fading. The ink printed on the surface layer is quickly absorbed by the lower layer, and there is no bleeding or beading. An image is obtained. In particular, even when a pigment ink is used, the ink absorbency is good, and high print density and color developability can be obtained. When the average particle diameter of the primary particles of vapor-phase method silica of the lower layer is larger than 50 nm, it is difficult to improve the glossiness even by calendering, and the ink absorption of the lower layer is too fast, so the coloring agent or adhesive in the ink is fixed on the upper layer. Since it is difficult to do so, the printed part is easily scratched, the gloss of the printed part is reduced, and the print density becomes low and the color becomes dull. On the contrary, if the average particle size of the primary particles of the vapor-phase method silica of the lower layer is too small, ink is likely to accumulate in the upper layer and bleeding or beading easily occurs, and stains on the back surface of the recording material occur in continuous printing. It will be easier. The average particle diameter of the preferable primary particles of the vapor-phase grown silica of the lower layer is 5 to 30 nm. Further, by using alumina or alumina hydrate, which is easily positively charged, in the upper ink receiving layer D, the fixability of the acid dye, direct dye and pigment in the ink is improved, and high print density and color developability are obtained. To be If the average particle size of the primary particles of alumina or alumina hydrate of the upper layer is larger than 50 nm, the gloss of the surface will be reduced, and the transparency of the ink receiving layer will be inferior, and the printing density will be difficult to appear because the colorant sinks. On the other hand, if it is smaller than 5 nm, the ink absorbency is likely to be lowered, and a problem is likely to occur especially in the pigment ink. The preferable average particle size of primary particles is 8 to 3
It is 0 nm. To improve scratch resistance, a protective layer may be provided on the ink receiving layer and calendered.

In the present invention, the ink receiving layer preferably contains thermoplastic organic polymer fine particles having a minimum film forming temperature of 40 ° C. to 160 ° C., and the calender metal roll has a surface temperature of the minimum amount of thermoplastic organic polymer fine particles. By subjecting to surface treatment by contacting with an ink receiving layer at a film temperature of 250 ° C. or more, an inkjet recording material having good white paper gloss and ink absorbency, scratch resistance and dark fading of printed images can be obtained. To be In particular, when the ink receiving layer is two or more layers, the upper ink receiving layer B or the ink receiving layer D contains the above-mentioned thermoplastic organic polymer fine particles so that the lower ink receiving layer mainly has ink absorbability, It is preferable that the surface treatment of the upper ink receiving layer with a calender is easy to obtain the effects of improving gloss, scratch resistance, and dark fading of the white paper. The content of the thermoplastic organic polymer fine particles is 30% by mass or less, and preferably 5 to 20% by mass of the total solid content of the ink receiving layer to be added. If the amount is too large, the ink absorbency tends to decrease, and if it is too small, the effect of improving the glossiness decreases.

In the present invention, a protective layer preferably containing thermoplastic organic polymer fine particles, more preferably colloidal silica, a hydrophilic binder, and a thermoplastic resin having a minimum film forming temperature of 40 ° C. to 160 ° C. on the ink receiving layer. By providing a protective layer containing organic polymer fine particles and contacting the metal roll of the calendar with the protective layer in a state where the surface temperature is at least the minimum film forming temperature of the thermoplastic organic polymer fine particles to 250 ° C. or less, calendering is performed. White paper gloss and ink absorption are good,
An inkjet recording material excellent in scratch resistance and dark fading of a printed image can be obtained. The content of colloidal silica is generally 20 to 80% by mass, preferably 30 to 75% by mass, based on the total solid content of the protective layer, mainly from the balance of ink absorption and glossiness. From the balance of properties, the hydrophilic binder is 5 to 30% by mass, preferably 8 to 25% by mass of the protective layer.
From the viewpoint of the balance between the glossiness of the white paper portion and the dark fading property, the content of the thermoplastic organic polymer fine particles is 50% by mass or less, preferably 5 to 40% by mass of the protective layer.

The colloidal silica used in the protective layer of the present invention can be obtained, for example, by metathesis of sodium silicate with an acid or the like, or by heat aging the silica sol obtained through the ion exchange resin layer. The average particle size of general primary particles of colloidal silica is about 5 to 100 nm, and it is preferable to form secondary particles having an average particle size of about 10 to 500 nm from the viewpoint of ink absorbability. Examples of commercially available spherical products include Nissan Chemical Co., Ltd., Snowtex 20, etc., Catalyst Chemical Industry Co., Ltd., Cataloid USB, etc., and chain products include Nissan Chemical Co., Ltd., Snowtex UP, etc., pearl necklace. For example, Snowtex PS-M manufactured by Nissan Chemical Co., Ltd. can be used.

The thermoplastic organic polymer fine particles preferably used in the ink receiving layer and the protective layer in the present invention include, for example, polystyrene, polymethylstyrene, polymethoxystyrene, polychlorostyrene, polyvinyl chloride, polyvinylcyclohexane and polyethylene. Polymers such as polypropylene, polybutadiene, polyvinylidene chloride, polymethacrylate, polychloroacrylate, and polymethylmethacrylate, and their copolymers and styrene-butadiene copolymers are listed, and the minimum film formation temperature is 4
The thing of 0-160 degreeC is selected. If the minimum film forming temperature of these organic polymer fine particles is lower than 40 ° C., a film is formed when the ink receiving layer or the protective layer is dried, and the ink absorbability is deteriorated. When the temperature is higher than 160 ° C, the organic polymer fine particles are difficult to melt by the usual heat treatment, and thus the effect of improving the glossiness and the dark fading property is difficult to be obtained, and the voids of the ink receiving layer and the protective layer contained therein remain, so that the printed image is obtained. Becomes whitish and unclear. These thermoplastic organic polymer fine particles usually have a diameter of 0.01 to 50 μm, preferably 0.1 to 20 μm.
The one with μm is used. If it is too small, the ink absorbency is likely to decrease, so that it is difficult to carry out the calendar treatment, and if it is too large, the print image quality is likely to deteriorate.

In the present invention, preferably, the minimum film forming temperature of 40 ° C. to 1 is applied to either or both of the ink receiving layer and the protective layer.
Surface treatment is performed by contacting the metal roll of the calender containing the thermoplastic organic polymer fine particles at 60 ° C. with the ink receiving layer in a state where the surface temperature is not less than the minimum film forming temperature of the thermoplastic organic polymer fine particles and not more than 250 ° C. The reason why an inkjet recording material having good scratch resistance and dark fading of printed images can be obtained is presumed as follows. That is, the thermoplastic organic polymer fine particles are heated by the metal roll of the calender,
It is melted moderately to form a film on the surface of vapor-phase method silica of the ink receiving layer or colloidal silica of the protective layer, and covering the surface improves scratch resistance and reduces the gas adsorption capacity of the silica surface. In addition, since the voids on the surface of the ink receiving layer or the protective layer are appropriately reduced, the gas permeability is lowered and the dark fading property of the printed image is also improved.

The minimum film formation temperature of the thermoplastic organic polymer fine particles used in the present invention means the lowest temperature required for the polymer fine particles to bind to each other to form a film. It can be measured by the temperature gradient plate method described in Souichi Muroi).

The ink receiving layer and the protective layer of the present invention include
It has a binder to maintain its properties as a film. As this binder, various known binders can be used, but a hydrophilic binder having high transparency and high ink permeability can be preferably used. In using the hydrophilic binder, it is important that the hydrophilic binder does not swell and block the voids at the initial penetration of the ink. From this viewpoint, a hydrophilic binder having a low swelling property at around room temperature is preferable. Used. For example, polyvinyl alcohol, vinyl acetate, oxidized starch, etherified starch, carboxymethyl cellulose, casein, gelatin, etc., and particularly preferred hydrophilic binders are completely or partially saponified polyvinyl alcohol or cation-modified polyvinyl alcohol.

Among the polyvinyl alcohols, those partially or completely saponified with a saponification degree of 80% or more are particularly preferable. Polyvinyl alcohol having an average degree of polymerization of 500 to 5000 is preferable.

As the cation-modified polyvinyl alcohol, for example, as described in JP-A-61-10483, primary to tertiary amino groups and quaternary ammonium groups are added to the main chain or side chain of polyvinyl alcohol. It is a polyvinyl alcohol.

Further, other hydrophilic binders can be used in combination, but it is preferably 20% by weight or less based on polyvinyl alcohol.

The ink receiving layer A of the present invention may contain inorganic fine particles other than vapor-phase grown silica in an amount of about 30% by mass or less of the vapor-phase grown silica. Further, the ink receiving layer B may also contain other inorganic fine particles in an amount of about 30% by mass or less of alumina and alumina hydrate.

In the present invention, in each layer of the ink receiving layer,
The ratio of the mass of vapor grown silica, alumina and hydrated alumina to the mass of hydrophilic binder is generally 60:40.
The range is from 92: 8. Preferably 70: 30-9
It is 0:10. When the ratio of the inorganic fine particles to the hydrophilic binder is increased, the ink absorbability is improved, but the transparency is lowered, cracks are likely to occur during drying, the surface strength is lowered, and the powder is likely to fall off. On the contrary, when the ratio of the inorganic fine particles is lowered, the transparency and surface strength of the ink receiving layer are improved, but the ink absorbency is lowered.

As the calendar having the metal roll of the present invention, a super calendar, a gloss calendar, a machine calendar, a soft calendar or the like is used. By passing the recording material through a nip between a metal roll and another roll, the gloss of the surface of the ink receiving layer is improved by pressure, shearing force and heat. As a metal roll, a roll made of steel or the like is usually used to form a protective layer by spraying nickel, chromium, ceramics or the like, and the surface is polished to have a mirror gloss. As the other roll to be combined with the metal roll, a metal roll, an elastic roll, or the like is used, but the elastic roll is preferable from the viewpoint of the gloss uniformity of the surface of the ink receiving layer or the protective layer. As the elastic roll, a roll obtained by rolling cotton, wool, pulp or the like around an iron core and subjecting it to high pressure processing and polishing, a synthetic resin roll such as urethane resin, epoxy resin or polyimide resin, or an aramid fiber roll is used. In the present invention, the calender may be treated without heating the metal roll, but heating is preferable because the glossiness is further improved and the scratch resistance is improved. If the calender is operated continuously, the surface temperature will be about 30 ° C. without forcibly heating the metal roll, so the surface temperature of a general metal roll is 30 to 300 ° C.
0-250 degreeC is preferable. Especially, the minimum film formation temperature is 5
The thermoplastic organic polymer fine particles at 0 to 160 ° C. are added to the ink receiving layer, the protective layer, or both, so that the surface of the metal roll is at least the minimum film forming temperature of the thermoplastic organic polymer fine particles,
The treatment at 250 ° C. or lower is preferable because it improves the white paper glossiness with little influence on the ink absorbency. When the surface temperature of the metal roll is higher than 250 ° C, the thermoplastic organic polymer fine particles are easily melted completely and fill the minute voids on the surface of the ink receiving layer or the protective layer, so that the ink absorbability is greatly reduced The rigidity of the body tends to decrease, and
When the temperature is lower than ℃, the effect of improving the glossiness of the white paper part by the thermoplastic organic polymer fine particles becomes small. Further, by appropriately selecting the surface temperature of the metal roll so as not to be significantly higher than the softening temperature of the water resistant support, roll contamination by the support can be prevented. Depending on the calendering speed and the nip linear pressure, it is preferably 60 than the softening temperature of the surface material of the support.
Do not rise above ℃. The linear pressure of the nip between the metal roll and the other roll during the calendar treatment of the present invention is 20.
0 kg / cm or less, preferably 10 to 150 kg
/ Cm. If the linear pressure at the nip is too low, the effect of improving the glossiness and the dark fading property is difficult to be obtained, and the glossiness of the white paper portion tends to be uneven. If it is too high, the ink absorbency tends to decrease, the rigidity of the recording material decreases, and the texture deteriorates. The preferable nip line pressure changes depending on the processing speed, but the line pressure is 10 to 2
Processing speed of 20 at least 1 nip of 00 kg / cm
Treatment at m / min or higher is preferred. More preferably, the surface temperature of the metal roll is 80 to 200 ° C., and the linear pressure is 20 to
It is desirable to process at 150 kg / cm and a processing speed of 50 m / min or more. There is no particular upper limit to the processing speed, but it is 500 m / min or less in terms of quality stability and workability.

In the ink jet recording material of the present invention, the haze value of the laminated ink receiving layer defined by JIS-K-7105 is preferably 40% or less, more preferably 30% or less. When it is higher than 40%, the print density is lowered and the color developability is also lowered.

The ink receiving layer of each layer of the present invention preferably contains a cationic compound for the purpose of improving water resistance.
Examples of the cationic compound include cationic polymers and water-soluble metal compounds. When used in combination with vapor phase silica, the cationic polymer tends to lower the transparency, and the water-soluble metal compound, on the contrary, improves the transparency. It is presumed that this is to suppress fine cracks generated in the ink receiving layer.

Examples of the cationic compound used in the present invention include cationic polymers and water-soluble metal compounds. Examples of the cationic polymer include polyethyleneimine, polydiallylamine, polyallylamine, JP-A-59-20696, JP-A-59-33176, and JP-A-59-33176.
9-33177, 59-155088, 60-
11389, 60-49990 and 60-838.
No. 82, No. 60-109894, No. 62-19849.
No. 3, No. 63-49478, No. 63-115780.
No. 63-280681, JP-A-1-40371.
Polymers having a primary to tertiary amino group and a quaternary ammonium salt group described in JP-A Nos. 6-234268, 7-125411, 10-193776, etc. are preferably used. The molecular weight of these cationic polymers is
About 5,000 to 100,000 is preferable.

The amount of these cationic polymers used is 1 to 10% by mass, preferably 2 to 10% by mass based on the above-mentioned inorganic fine particles.
It is 7 mass%.

Examples of the water-soluble metal compound used in the present invention include water-soluble polyvalent metal salts. Examples thereof include water-soluble salts of metals selected from calcium, barium, manganese, copper, cobalt, nickel, aluminum, iron, zinc, zirconium, chromium, magnesium, tungsten and molybdenum. Specifically, for example, calcium acetate, calcium chloride, calcium formate, calcium sulfate, barium acetate, barium sulfate, barium phosphate, manganese chloride, manganese acetate, manganese formate dihydrate, manganese ammonium sulfate hexahydrate, chloride chloride. Dicopper, ammonium chloride copper (II) dihydrate, copper sulfate, cobalt chloride,
Cobalt thiocyanate, cobalt sulfate, nickel sulfate hexahydrate, nickel chloride hexahydrate, nickel acetate tetrahydrate, nickel ammonium ammonium hexahydrate, nickel amidosulfate tetrahydrate, aluminum sulfate, aluminum sulfite, Aluminum thiosulfate, polyaluminum chloride, aluminum nitrate nonahydrate, aluminum chloride hexahydrate,
Ferrous bromide, ferrous chloride, ferric chloride, ferrous sulfate, ferric sulfate, zinc bromide, zinc chloride, zinc nitrate hexahydrate, zinc sulfate, zirconium acetate, zirconium chloride, chloride Zirconium oxide octahydrate, zirconium hydroxychloride, chromium acetate, chromium sulfate, magnesium sulfate, magnesium chloride hexahydrate, magnesium citrate nonahydrate, sodium phosphotungstate, sodium citrate tungsten, 12 tungstophosphate n Hydrate, 12 tungstosilicic acid 26 hydrate, molybdenum chloride, 12 molybdophosphoric acid n hydrate and the like can be mentioned. Of these, zirconium compounds having high transparency and high water resistance improving effect are preferable.

Further, as the cationic compound, an inorganic type compound is used.
Basic polyhydric acid, an aluminum-containing cationic polymer
Aluminum compounds can be mentioned. Basic polyhydration
The aluminum compound has the following main formulas 1 and 2
Or 3 and, for example, [Al₆(OH)₁₅]³⁺, [A
l₈(OH)₂₀]⁴⁺, [Al₁₃(OH)₃₄]⁵⁺, [Al
_{twenty one}(OH)₆₀]³⁺Basic, macromolecular polynuclear contractions such as
Water-soluble polyaluminum hydroxide containing stable mixed ions
It is Ni.

[Al ₂ (OH) _n Cl _6-n ] _m ··· Formula 1 [Al (OH) ₃ ] _n AlCl ₃ · · Formula 2 Al _n (OH) _m Cl _(3n-m) 0 <m < 3n ... Equation 3

These are water treatment agents under the name of polyaluminum chloride (PAC) from Taki Chemical Co., Ltd., under the name of polyaluminum hydroxide (Paho) from Asada Chemical Co., Ltd. It is marketed by Riken Green under the name Purachem WT and from other manufacturers for the same purpose, and various grades are easily available. In the present invention, these commercially available products can be used as they are,
Some have an inappropriately low pH, and in that case, the pH can be adjusted appropriately before use.

In the present invention, the content of the water-soluble metal compound in the ink receiving layer is 0.1 g / m ^{2 to} 10 g /
m ^2, preferably from ^{0.2g / m 2 ~5g / m 2} .

Two or more of the above-mentioned cationic compounds can be used in combination. For example, a cationic polymer and a water-soluble metal compound may be used together.

The ink receiving layer in the present invention preferably contains various oil droplets in order to improve the brittleness of the film, but such oil droplets have a solubility in water at room temperature of 0.01% by weight. Polymerization of the following hydrophobic high-boiling organic solvents (eg, liquid paraffin, dioctyl phthalate, tricresyl phosphate, silicone oil, etc.) and polymer particles (eg, styrene, butyl acrylate, divinylbenzene, butyl methacrylate, hydroxyethyl methacrylate, etc.) Particles obtained by polymerizing at least one type of volatile monomer may be contained. Such oil droplets are preferably 10 to 50% by weight with respect to the hydrophilic binder.
It can be used in the range of.

In the present invention, the ink receiving layer may be hardened with a suitable hardener for the purpose of improving water resistance and dot reproducibility. Specific examples of the hardener include aldehyde compounds such as formaldehyde and glutaraldehyde, ketone compounds such as diacetyl and chloropentanedione, and bis (2-chloroethylurea) -2-hydroxy-4,6-dichloro-1. , 3,5 triazine, a compound having a reactive halogen as described in US Pat. No. 3,288,775, divinyl sulfone, a compound having a reactive olefin as described in US Pat. No. 3,635,718, US N-methylol compounds as described in US Pat. No. 2,732,316, US Pat. No. 3,103,43
Isocyanates such as those described in US Pat.
No. 7,280, 2,983,611, aziridine compounds, US Pat. No. 3,100,704, carbodiimide compounds, US Pat. No. 3,093.
There are epoxy compounds as described in No. 1,537, halogen carboxaldehydes such as mucochloric acid, dioxane derivatives such as dihydroxydioxane, and inorganic hardeners such as chromium alum, zirconium sulfate, boric acid and borate. They may be used alone or in combination of two or more. The amount of the hardener added is 0.01 to 10 relative to 100 g of the water-soluble polymer constituting the ink receiving layer.
g is preferable, and more preferably 0.1 to 5 g.

In the present invention, the ink receiving layer of each layer further includes a coloring agent, a coloring pigment, a fixing agent for the ink dye, an ultraviolet absorber, an antioxidant, in addition to the surfactant and the hardener.
Various known additives such as a pigment dispersant, a defoaming agent, a leveling agent, a preservative, a fluorescent whitening agent, a viscosity stabilizer, and a pH adjusting agent may be added.

In the present invention, the coating method of each layer constituting the ink receiving layer and the protective layer may be a known coating method. For example, there are a slide bead method, a curtain method, an extrusion method, an air knife method, a roll coating method, a ked bar coating method and the like.

In the present invention, the characteristics required for each layer are efficiently obtained by applying the respective layers constituting the ink receiving layer and the protective layer such as those of the slide bead system almost simultaneously without providing a drying step. It is also preferable in terms of efficiency. That is, it is expected that by laminating each layer in a wet state, the components contained in each layer are less likely to penetrate into the lower layer, so that the component constitution of each layer is well maintained even after drying.

When the coating liquid for the ink receiving layer is applied to the film support or the resin-coated paper, corona discharge treatment, flame treatment, ultraviolet irradiation treatment, plasma treatment or the like is preferably carried out prior to coating.

In the present invention, particularly when a film or resin-coated paper is used for the support, it is preferable to provide a primer layer mainly containing a natural polymer compound or a synthetic resin on the surface on which the ink receiving layer is provided. The transparency of the ink receiving layer is further improved by coating the ink receiving layer containing the inorganic fine particles of the present invention on the primer layer, then cooling and drying at a relatively low temperature.

The primer layer provided on the support is mainly composed of natural polymer compounds such as gelatin and casein and synthetic resins. Examples of the synthetic resin include acrylic resin, polyester resin, vinylidene chloride, vinyl chloride resin, vinyl acetate resin, polystyrene, polyamide resin, and polyurethane resin.

The above-mentioned primer layer is formed on the support by 0.01
It is provided with a film thickness (dry film thickness) of ˜5 μm. It is preferably in the range of 0.05 to 5 μm.

The water-resistant support of the present invention has a writing property,
Various back coat layers can be coated for antistatic properties, transport properties, curl prevention properties, and the like. The back coat layer may contain an inorganic antistatic agent, an organic antistatic agent, a hydrophilic binder, a latex, a pigment, a curing agent, a surfactant and the like in an appropriate combination.

[0072]

The present invention will be described in detail below with reference to examples, but the contents of the present invention are not limited to the examples.
In addition, part and% show a mass part and the mass%.

Example 1 <Preparation of Polyolefin Resin Coated Paper Support> A 1: 1 mixture of a bleached hardwood kraft pulp (LBKP) and a bleached softwood sulfite pulp (NBSP) was beaten to 300 ml with Canadian Standard Freeness to produce pulp. A slurry was prepared. Alkyl ketene dimer as a sizing agent to 0.5% by weight of pulp, polyacrylamide as a strength agent to 1.0% by weight of pulp, cationized starch to 2.0% by weight of pulp, and polyamide epichlorohydrin resin. 0.5% by mass of pulp was added and diluted with water to obtain a 1% slurry. This slurry was made into paper by a Fourdrinier paper machine so as to have a basis weight of 170 g / m ² , dried and conditioned to obtain a base paper for polyolefin resin-coated paper. Low density polyethylene with density of 0.918 g / cm ^{3 on} paper
320% of a polyethylene resin composition in which 10% by mass of anatase-type titanium is uniformly dispersed in 0% by mass of resin
It was melted at 0 ° C., extrusion-coated so as to have a thickness of 35 μm at 200 m / min, and extrusion-coated using a cooling roller having a micro-roughened surface. Density 0.9 on the other side
A blended resin composition of 70 parts by mass of 62 g / cm ³ high-density polyethylene resin and 30 parts by mass of low-density polyethylene resin having a density of 0.918 was similarly melted at 320 ° C. to give a thickness of 30.
It was extrusion-coated to have a thickness of μm, and was extrusion-coated using a roughened cooling roll. The obtained polyolefin resin-coated paper has an oxygen permeability of 2.1 (cm ³ / cm ² · 24h) defined by the isobaric method of JIS-K-7126.
・ Atm).

After the high frequency corona discharge treatment was applied to the surface of the above polyolefin resin-coated paper, an undercoat layer having the following composition was coated and dried so that gelatin was 50 mg / m ² to prepare a support.

[0075] <Undercoat layer> 100 parts of lime-processed gelatin Sulfosuccinic acid-2-ethylhexyl ester salt 2 parts Chrome Alum 10 copies

Coating solutions for ink receiving layers A and B having the following compositions were simultaneously coated on the above-mentioned support with a slide bead coating apparatus and dried. A coating liquid for the ink receiving layer A for the lower layer and the ink receiving layer B for the upper layer, which are close to the support having the following composition, was prepared by dispersing inorganic fine particles with a high-pressure homogenizer so that the solid content concentration was 9% by mass. These coating solutions were applied and dried so that the vapor phase silica in the ink receiving layer A was 16 g / m ^{2 in} solid and the vapor phase silica in the ink receiving layer B was 6 g / m ² . The obtained coated product was calendered at a surface temperature of 150 ° C. using a calender made of a combination of a metal roll and a urethane rubber roll with a nip pressure of 80 kg / cm and a speed of 100.
The recording material for inkjet of Example 1 was obtained by passing m / min.

[0077] <Composition of ink receiving layer A> 100 parts of vapor phase silica   (Average primary particle size 7 nm) Dimethyldiallylammonium chloride homopolymer 4 parts Boric acid 4 parts Polyvinyl alcohol 20 parts   (Saponification degree 88%, average degree of polymerization 3500) Surfactant 0.3 parts Zirconium acetate 2 parts

[0078] <Composition of ink receiving layer B> 100 parts of vapor phase silica   (Average primary particle size 12 nm) Dimethyldiallylammonium chloride homopolymer 4 parts Boric acid 4 parts Polyvinyl alcohol 15 parts   (Saponification degree 88%, average degree of polymerization 3500) Surfactant 0.3 parts 20 parts of thermoplastic organic polymer particles   (Mitsui Chemicals; Chemipearl S200, minimum film formation temperature 85 ° C) Zirconium acetate 2 parts

The drying conditions after coating are shown below. 3 at 5 ° C
After cooling for 0 seconds, the total solid content concentration is 90% by mass at 45 ° C.
It was dried at 10% RH and then at 35 ° C. 10% RH.

The following evaluation was carried out on the ink jet recording material prepared as described above. The results are shown in Table 2.

<Ink Absorption> GO with a commercially available inkjet printer (NOVAJET manufactured by ENCAD)
Cyan, magenta, and yellow single color 100% with ink,
Prints 300% of each triplet color, and immediately after printing, PPC
The paper was overlaid on the printing portion and lightly pressed, and the degree of the amount of ink transferred to the P-PC paper was visually observed. The overall evaluation was made based on the following criteria. ◯: No transfer is performed. Δ: Transfer a little. X: Transfer is large and cannot be actually used.

<Printing Density> The printing density of the solid black portion printed in the same manner as the ink absorption evaluation was measured with a Macbeth reflection densitometer and shown as an average value of five measurements.

<Dark fading property> Cyan, magenta, and yellow single color 100% printing was performed using an inkjet printer (PM-770C manufactured by Seiko Epson Corp.), and the density of the printed portion was exposed after exposing the wall surface of the dark room at room temperature for 60 days. The residual image rate (concentration after exposure / concentration before exposure) was determined and the lowest residual rate for each color was displayed.

<Glossiness of blank portion of white paper> The glossiness of blank portion of the recording material before printing was observed by oblique light and evaluated according to the following criteria. 5: It has a higher glossy feeling than a color photograph. 4: There is a glossy feeling similar to that of a color photograph. 3: There is a glossy feeling similar to that of art paper. 2: There is a glossy feeling similar to that of coated paper. 1: It has a shining gloss equivalent to that of high-quality paper.

<Scratch resistance> Two recording materials are stacked with the ink receiving layer side facing upward, a metal weight having a mass of 100 g is placed on the recording material, the lower recording material is slowly pulled out, and then the lower recording material is printed. The degree of scratches on the surface was evaluated according to the following criteria. ⊚: No scratches were generated. ○: Thin scratches are seen, but no problem. Δ: Scratches are observed and is the lower limit of actual use. X: Many scratches were generated, and practical use is impossible.

Examples 2 to 4 Examples 2 to 4 were carried out except that the number of thermoplastic organic polymer fine particles added to the ink receiving layer B, the metal roll surface temperature of the calender and the nip pressure were changed as shown in Table 1. In the same manner as in Example 1, inkjet recording materials of Examples 2 to 4 were obtained. The evaluation results are shown in Table 2.

Example 5 The same as Example 1 except that the thermoplastic organic polymer fine particles of the ink receiving layer B in Example 1 were replaced by those having a minimum film forming temperature of 105 ° C. (Chemipearl M200, manufactured by Mitsui Chemicals, Inc.). Thus, an inkjet recording material of Example 5 was obtained. The evaluation results are shown in Table 2.

Example 6 Inkjet recording material of Example 6 was carried out in the same manner as in Example 1 except that the fumed silica in the ink receiving layer B was changed to that having an average primary particle diameter of 20 nm. Got
The evaluation results are shown in Table 2.

Example 7 An ink jet recording material of Example 7 was obtained in the same manner as in Example 1 except that the ink receiving layer B in Example 1 was replaced with the ink receiving layer D having the following composition. The results are shown in Table 2.

[0090] <Composition of ink receiving layer D> 100 copies of pseudo-boehmite   (Average primary particle size 15nm, aspect ratio 5) Nitric acid 1 part 1 part boric acid Polyvinyl alcohol 15 parts   (Saponification degree 88%, average degree of polymerization 3500) Surfactant 0.3 parts 20 parts of thermoplastic organic polymer particles   (Mitsui Chemicals; Chemipearl S200, minimum film formation temperature 85 ° C) Zirconium acetate 2 parts

Example 8 Example 7 was repeated except that the pseudo-boehmite of the ink receiving layer D was replaced by γ-alumina having an average primary particle size of 13 nm (Aerosil Aluminum Oxide C, manufactured by Nippon Aerosil Co., Ltd.).
An ink jet recording material of Example 8 was obtained in the same manner as in. The evaluation results are shown in Table 2.

Example 9 In Example 1, the plastic organic polymer fine particles in the ink receiving layer B were removed, and a solid protective layer of the following composition was formed on the ink receiving layer B in a solid state.
An inkjet recording material of Example 9 was obtained in the same manner as in Example 1 except that g / m ² was applied. The evaluation results are shown in Table 2.

[0093] <Protective layer composition> 100 parts of colloidal silica (Nissan Chemical Co .; Snowtex PS-L, secondary particle average particle size 160 nm) Polyvinyl alcohol 15 parts   (Saponification degree 88%, average degree of polymerization 3500) 30 parts of thermoplastic organic polymer particles   (Mitsui Chemicals; Chemipearl S200, minimum film formation temperature 85 ° C) Surfactant 0.3 parts

Example 10 Except that the thermoplastic organic polymer fine particles in the ink receiving layer D in Example 7 were removed and the same protective layer as in Example 9 was coated on the ink receiving layer D as a solid at 3 g / m ^2. An ink jet recording material of Example 10 was obtained in the same manner as in Example 7. The evaluation results are shown in Table 2.

Example 11 The same as Example 1 except that the ink receiving layer in Example 1 was a single layer containing only the composition of the ink receiving layer B, and vapor-phase method silica was applied so as to have a solid content of 22 g / m ² and dried. Example 11
A recording material for inkjet of was obtained. The evaluation results are shown in Table 2.

Example 12 An ink jet recording material of Example 12 was obtained in the same manner as in Example 1 except that the thermoplastic organic polymer fine particles in the ink receiving layer B were omitted. The evaluation results are shown in Table 2.

Example 13 Ink jet recording of Example 13 was carried out in the same manner as in Example 1 except that the thermoplastic organic polymer fine particles of the ink receiving layer B were removed and the surface temperature of the metal roll was changed to 40 ° C. Got the material. The evaluation results are shown in Table 2.

Comparative Example 1 An ink jet recording material of Comparative Example 1 was obtained in the same manner as in Example 1 except that the thermoplastic organic polymer fine particles in the ink receiving layer B were removed and calendering was not carried out. It was The evaluation results are shown in Table 2.

Comparative Example 2 An ink jet recording material of Comparative Example 2 was obtained in the same manner as in Example 11 except that the thermoplastic organic polymer fine particles in the ink receiving layer were removed and calendering was not performed. The evaluation results are shown in Table 2.

Comparative Example 3 In place of the vapor phase silica used in the ink receiving layers A and B in Example 1, wet synthetic silica (Nips manufactured by Nippon Silica Industry Co., Ltd.) was used.
An inkjet recording material of Comparative Example 3 was obtained in the same manner as in Example 1 except that il E-1011 average particle diameter 2 μm) was used. The evaluation results are shown in Table 2.

Comparative Example 4 An ink jet recording material of Comparative Example 4 was obtained in the same manner as in Example 11 except that calendering was not performed after the ink receiving layer was provided. The evaluation results are shown in Table 2.

Comparative Example 5 The base material of the polyolefin resin-coated paper used in Example 12 was coated with the undercoat layer coating solution having the following composition so that the solid content was 13 g / m ² , and dried, which was used as a support. An inkjet recording material of Comparative Example 5 was obtained in the same manner as in Example 12 except for the above. The oxygen permeability of the support specified by JIS-K-7126 isobaric method is 24 (cm ³ / cm ² · 24h ·
was atm).

[0103] <Undercoat composition> Amorphous synthetic silica 80 parts   (Average primary particle size 15 nm, average secondary particle size 4.5 μm) Zeolite 20 parts   (Average particle size 1.5μm) Polyvinyl alcohol 20 parts   (Saponification degree 88%, average degree of polymerization 3500)

[0104]

[Table 1] (Note 1) The minimum film forming temperature is the minimum film forming temperature of the thermoplastic organic polymer fine particles contained in the ink receiving layer or the protective layer, and the unit is ° C. (Note 2) The number of added parts is the number of added parts of the thermoplastic organic polymer fine particles contained in the ink receiving layer or the protective layer, and the unit is part by mass. (Note 3) The treatment temperature is the surface temperature of the metal roll of the calender, and the unit is ° C.

[0105]

[Table 2] ────────────────────────────────────            Ink print density Dark fading White paper scratch resistance            Absorbent gloss ──────────────────────────────────── Example 1 ○ 2.12 88 4.5 ◎ to ○ Example 2 ○ 2.16 84 4.5 ○ Example 3 ○ to △ 2.04 91 5 ◎ Example 4 ○ 2.00 83 4 ○ Example 5 ○ 2.04 83 4.5 ○ Example 6 ○ 2.05 86 4 ◎ to ○ Example 7 ○ 2.14 87 5 ○ Example 8 ○ to △ 2.06 86 4.5 ○ Example 9 ○ 2.14 92 5 ◎ Example 10 ○ 2.15 89 5 ◎ Example 11 ○ to △ 2.05 86 4 ○ Example 12 ○ 2.10 80 4 ○ Example 13 ○ 2.08 77 3.5 △ ──────────────────────────────────── Comparative Example 1 ○ 2.04 73 3 △ Comparative Example 2 ○ to △ 2.00 74 2.5 △ Comparative Example 3 ○ 1.75 79 1.5 ○ to △ Comparative Example 4 ○ 1.61 73 2.0 2.0 △ Comparative Example 5 ○ 2.02 74 3 ○ ────────────────────────────────────

Results: Examples 1 to 13 of the present invention showed good characteristics. Examples 1 to 11 using the thermoplastic organic polymer fine particles of the present invention also had good dark fading properties. In particular, Examples 9 and 10 having the protective layer of the present invention showed excellent glossiness and scratch resistance on the blank portion. In Example 12 in which the thermoplastic organic polymer fine particles in the ink receiving layer were removed from Example 1, the dark fading property was lower than that in Example 1, and the glossiness and scratch resistance of the white paper part were slightly lowered. In Example 13, in which the surface temperature of the metal roll of the calender was 40 ° C., the glossiness and scratch resistance of the white paper portion were lowered, but the level was not a problem in actual use. In Comparative Example 1 in which the thermoplastic organic polymer fine particles in the ink receiving layer were removed and calendar processing was not performed in Example 1, dark fading is
The glossiness and scratch resistance of the white paper part decreased, which was the lower limit of actual use.
In Comparative Example 2 in which the thermoplastic organic polymer fine particles in the ink receiving layer were removed from the ink receiving layer in Example 11 and calendar processing was not performed, the dark fading property, the glossiness of the white paper portion and the scratch resistance were greatly reduced. Comparative Example 3
In the case of using wet silica in place of the vapor phase method silica of the ink receiving layer of Example 1, the print density and the glossiness of the white paper portion were greatly reduced, and it was not practically usable. Comparative Example 4 is the case in which the calendering was not performed in Example 11, but the print density was significantly reduced, and the glossiness of the white paper portion and the dark fading property were reduced. Comparative Example 5 has an oxygen permeability of 24 (cm ³ / cm ² · 24h).
-Atm) is used, but in Example 12
The dark fading property was lower than that of the above, and the glossiness of the white paper part was also lowered due to the influence of the smoothness of the support.

[0107]

As is apparent from the above results, according to the present invention, the ink absorbency and the print density are good, and the glossiness of the blank portion is
An ink jet recording material having excellent scratch resistance and dark fading can be obtained.

─────────────────────────────────────────────────── ─── Continuation of front page (51) Int.Cl. ⁷ Identification symbol FI theme code (reference) B29L 9:00 B29L 31:00 31:00 B41J 3/04 101Y F term (reference) 2C056 FC06 2H086 BA15 BA33 BA35 BA41 4F201 AC03 AG01 AG03 AH53 AH81 AR06 AR12 BA07 BC02 BC03 BC13 BR02 BR06 BR21 BT02

Claims (11)

[Claims] 1. An inkjet recording in which at least one ink receiving layer is provided on a support having an oxygen permeability of 10 cm ³ / cm ² · 24 h · atm or less as defined by the isobaric method of JIS-K-7126. In the material, the ink receiving layer contains at least one of fumed silica, alumina, or alumina hydrate and a hydrophilic binder, and after the ink receiving layer is provided, a surface treatment is performed with a calendar having a metal roll. An inkjet recording material characterized by the following. 2. The ink receptive layer comprises at least two layers, an ink receptive layer (A) near the support and an ink receptive layer (B) far from the support, both of which contain fumed silica. The inkjet recording material according to claim 1, wherein the recording material is an inkjet recording material. 3. The ink receiving layer comprises at least two layers, an ink receiving layer (C) close to the support and an ink receiving layer (D) far from the support, and the ink receiving layer C contains fumed silica. 2. The ink jet recording material according to claim 1, wherein the ink receiving layer D contains alumina or alumina hydrate. 4. The average particle size of the primary particles of vapor phase silica of the ink receiving layer A is smaller than the average particle size of the primary particles of vapor phase silica of the ink receiving layer B. The recording material for ink jet according to. 5. The ink jet recording material according to claim 3, wherein the alumina hydrate of the ink receiving layer D is a tabular alumina hydrate having an aspect ratio of 3 to 7. 6. The inkjet according to claim 1, wherein the surface of the metal roll of the calender is brought into contact with the ink receiving layer for surface treatment when the surface temperature is 50 to 250 ° C. Recording material. 7. The minimum film forming temperature of the ink receiving layer is 40.
C. to 160.degree. C., containing the thermoplastic organic polymer fine particles, and the surface temperature of the metal roll of the calender is not less than the minimum film forming temperature of the thermoplastic organic polymer fine particles and not more than 250.degree. The inkjet recording material according to any one of claims 1 to 6, which is treated. 8. A protective layer is laminated on the ink receiving layer, and the protective layer comprises colloidal silica, a hydrophilic binder,
And a thermoplastic organic polymer fine particle having a minimum film forming temperature of 40 ° C. to 160 ° C., and the metal roll of the calender is protected at a surface temperature of the thermoplastic organic polymer fine particle at a minimum film forming temperature of 250 ° C. or more. The inkjet recording material according to any one of claims 1 to 6, which is brought into contact with the layer for surface treatment. 9. The surface treatment by the calender is linear pressure 1
The inkjet recording material according to any one of claims 1 to 8, wherein the speed is 20 m / min or more with at least one nip of 0 to 200 kg / cm. 10. The ink jet recording material according to claim 1, wherein the support is a resin-coated paper. 11. The ink jet recording material according to claim 1, wherein each layer constituting the ink receiving layer and a protective layer are simultaneously coated.