JPH10291361A - Medium to be recorded by ink jet - Google Patents

Abstract

PROBLEM TO BE SOLVED: To eliminate trouble of overlap feeding at the time of printing by preventing a blocking in a medium to be recorded ink jet, wherein a dye receiv ing layer contains interlayer compound which receives and holds water soluble dye by an intercalation reaction. SOLUTION: The medium 10 to be recorded by ink jet comprises a dye receiving layer 1 formed of interlayer compound for receiving and holding water soluble dye by an intercalation reaction and binder resin. In this case, the layer 1 contains two types of nylon particles having different mean particle sizes in such a manner that weight ratio of the particles having larger mean particle size to the particles having smaller mean particle size (content of the particles having large mean particle size/content of the particles having small mean particle size) is larger than 1/2.

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 medium having a dye receiving layer for fixing and holding a dye by an intercalation reaction. More specifically, the present invention relates to an inkjet recording medium that has a high ink absorption rate, can provide a high-resolution image with little ink bleeding, has excellent transportability during printing, and can improve the storage durability of an image.

[0002]

2. Description of the Related Art Image information and character code information produced by a personal computer or a word processor are
As one of the methods for outputting to a recording medium such as paper or an OHP film, an aqueous ink containing a water-soluble dye is ejected onto a recording medium from a recording nozzle driven by electric field, heat, pressure or the like as a driving source. An ink-jet recording system for forming is used.

[0003] This ink jet recording method has the advantages that noise during recording is low, running cost is low, an image can be formed on plain paper, and no waste such as ink ribbon is involved. In offices and homes, its use has been expanding in recent years.

Meanwhile, in an image fixed on a recording medium by an ink jet recording method, a water-soluble dye constituting the image is generally held on the recording medium by van der Waals force or hydrogen bonding. For this reason, when a solvent such as water having a high affinity for the water-soluble dye comes into contact with the image, there is a problem that the water-soluble dye constituting the image is eluted into the solvent and the image is blurred. Also,
Even when the recording medium is supplied with thermal energy or water vapor sufficient to cancel the van der Waals force and hydrogen bonding between the water-soluble dye constituting the image and the recording medium, the dye moves and blurs the image. There is a problem that occurs. Furthermore,
When a water-soluble dye constituting an image is exposed to a high-energy light such as ultraviolet light, there is also a problem that the image itself is discolored, discolored or reduced in density due to decomposition of the dye itself.

Therefore, in order to improve the fixing property (for example, water resistance) and light resistance of an image in such an ink jet recording system, an intercalation is added to a dye receiving layer (that is, a dye receiving layer) of a recording medium. It has been proposed to mix an interlayer compound capable of retaining a water-soluble dye by a reaction together with a binder resin such as a polyvinylpyrrolidone resin, a polyvinyl butyral resin, a hydroxypropylcellulose resin or a polyvinyl alcohol resin (JP-A-7-68925). No.). According to this dye receiving layer, the water-soluble dye is firmly held between the interlayer compounds. Therefore, an image composed of the dye held here has greatly improved fixability, prevents fading, discoloration, and a decrease in image density during image storage, and improves storage durability.

[0006]

However, in the conventional method using an interlayer compound in the dye receiving layer, a solvent having low volatility contained in the ink remains in the dye receiving layer.
The stickiness after printing is large, and there is a problem that the prints cannot be stacked unless left for a long time.

Further, if a plurality of recording media are superposed before printing, adhesion (blocking) occurs between the recording media. For this reason, if the recording medium is set on the paper feed tray of the printer, a double feed trouble that a plurality of blocking recording media are simultaneously fed at the time of printing has also been a problem.

An object of the present invention is to solve the above-mentioned problems of the prior art, in which an interlayer compound for receiving and retaining a water-soluble dye by an intercalation reaction is contained in a dye receiving layer to fix an image and maintain an image. An object of the present invention is to prevent blocking in an ink-jet recording medium in which storage durability is improved at the time of printing, and to eliminate a double feed trouble at the time of printing. It is another object of the present invention to improve ink absorbability so that a higher resolution image with less ink bleeding can be obtained.

[0009]

Means for Solving the Problems The present inventors have found that the above object can be achieved by blending two kinds of nylon particles having different average particle diameters in a specific ratio in a dye receiving layer. It was completed.

That is, the present invention relates to an ink jet recording medium having a dye receiving layer formed of an interlayer compound for receiving and retaining a water-soluble dye by an intercalation reaction and a binder resin, wherein the dye receiving layer has an average particle size. The weight ratio of the larger average particle size nylon particle to the smaller average particle size nylon particle containing two types of nylon particles having different diameters (content of the average particle size larger nylon particle / average particle size) (A content of small-diameter nylon particles) is more than 1/2.

In particular, in a mode in which the dye receiving layer is formed on a substrate, in this ink jet recording medium, the nylon particles are spherical, and the nylon particles having a larger average particle size have an average particle size of 25 μm or more and 45 μm or less. And the average particle size of the nylon particles is smaller than 1 μm 2
The present invention provides an aspect of less than 5 μm and an aspect in which the content of nylon particles in the dye-receiving layer is 0.02 to 10% by weight based on the water-absorbing resin constituting the dye-receiving layer.

In addition, the ink jet recording apparatus has a dye receiving layer formed of an interlayer compound that receives and holds a water-soluble dye by an intercalation reaction, and a binder resin, and is provided on the dye receiving layer with an ink absorbing resin that absorbs aqueous ink. The present invention provides an ink jet recording medium having an ink absorbing layer formed, wherein at least one of the dye receiving layer and the ink absorbing layer contains two kinds of nylon particles as described above.

According to the ink jet recording medium of the present invention, the dye receiving layer or the ink absorbing layer contains nylon particles. The nylon particles are compatible with the aqueous ink but do not penetrate the aqueous ink, and thus do not prevent the water-soluble dye in the aqueous ink from being accepted by the interlayer compound. Therefore, the inkjet recording medium of the present invention can form a high-resolution image with a high ink absorption speed and little ink bleeding.

Further, nylon particles have a low coefficient of friction and have self-lubricating properties. In particular, this property
This is remarkable when the nylon particles are spherical. Therefore, according to the present invention, it is possible to prevent double feed during printing and to improve transportability in the printer.

Further, in the present invention, as the nylon particles,
Since two types of nylon particles having different average particle sizes are used in a specific ratio, it is possible to prevent blocking and further improve the transportability in the printer.

[0016]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in detail.

FIG. 1 is a sectional view of an ink jet recording medium of the present invention. In FIG.
Has a structure in which a dye receiving layer 1 is formed on a substrate 2.

The dye receiving layer 1 comprises an interlayer compound for receiving and retaining a water-soluble dye by an intercalation reaction and a binder resin, and further contains two types of nylon particles having different average particle sizes. The weight ratio of the larger diameter nylon particles to the smaller average particle size nylon particles (content of large average particle size nylon particles / content of small average particle size nylon particles) is greater than 1/2. It is characterized by becoming.

Here, the shape of the nylon particles is preferably spherical from the viewpoint of improving the transportability of the recording medium for inkjet in a printer. The nylon particles having a larger average particle diameter have an average particle diameter of 25 μm or more and 45 μm or less, and the nylon particles having a smaller average particle diameter have an average particle diameter of 1 μm.
It is preferable to set it to m or more and less than 25 μm.

In the present invention, the two kinds of nylon particles having different particle sizes are used for the following reasons.

Nylon particles having a large average particle size, for example,
When spherical nylon particles having an average particle diameter of 25 μm or more and 45 μm or less are used, irregularities are formed on the surface of the inkjet recording medium due to the effect of the particle diameter. Therefore, when a plurality of inkjet recording media are superimposed, the dye receiving layer which is the surface of one inkjet recording medium, and the back surface of another inkjet recording medium overlaid on the dye receiving layer. Between them so that they do not come into full contact. Therefore, it is possible to prevent the superposed ink jet recording media from sticking to each other. However, in order to prevent sticking sufficiently using only the nylon particles having a large particle diameter, a large amount of the nylon particles must be added to the dye receiving layer. When added in a large amount to the dye receiving layer, the light scattering property is increased and the transparency of the dye receiving layer is impaired. For this reason, it is not preferable to add nylon particles having a large particle diameter to the dye receiving layer in an amount sufficient to prevent sticking.
In particular, when high transparency is required for an inkjet recording medium such as an OHP, the amount of added nylon particles is significantly limited, and it is difficult to prevent sticking.

On the other hand, when nylon particles having a small average particle diameter, for example, spherical nylon particles having an average particle diameter of 1 μm or more and less than 25 μm are used, the effect of the particle diameter is small, and therefore the average particle diameter is large. Although the effect of preventing sticking is smaller than that of nylon particles, the increase in light scattering with respect to the added amount is smaller than that of nylon particles having a large average particle size, so that transparency is not easily impaired.

Therefore, in the present invention, nylon particles having a large average particle size and nylon particles having a small average particle size are mixed, and the gap between the nylon particles having a large average particle size is filled with the nylon particles having a small average particle size. By doing so, it is possible to achieve both sticking prevention and transparency.
In this case, as the particle size of the two kinds of large and small nylon particles, as described above, the larger nylon particles have an average particle size from the viewpoint of the balance between the anti-sticking effect and the light scattering property depending on the particle diameter. The average particle diameter of the smaller nylon particles is preferably 25 μm or more and 45 μm or less, and the average diameter of the smaller nylon particles is preferably 1 μm or more and less than 25 μm.

In the present invention, when two kinds of nylon particles having different average particle sizes are used, the weight of the nylon particles having the larger average particle size and the nylon particles having the smaller average particle size is increased. The ratio, that is, (content of nylon particles having a large average particle size / content of nylon particles having a small average particle size) is made larger than 1/2. If the proportion of the nylon particles having a larger average particle diameter is smaller than this, the effect of preventing sticking becomes small, and it becomes difficult to sufficiently improve the transportability of the inkjet recording medium in the printer.

The content ratio of the nylon particles including the large particles and the small particles in the dye receiving layer depends on the water-absorbing resin constituting the dye-receiving layer (this water-absorbing resin will be described later). On the other hand, the content is preferably set to 0.02 to 10% by weight. When the content ratio of the nylon particles is less than 0.02% by weight, stickiness is large before printing, and blocking between recording media easily occurs.
A plurality of inkjet recording media set in a paper feed tray of a printer are stuck together, and a double feeding trouble in which two or more media are simultaneously fed is likely to occur. After printing, sticking or set-off is likely to occur when touching with a finger or storing a plurality of sheets in a pile. Conversely, if the content is more than 10% by weight, the transparency decreases, and O
It is not preferable as a recording medium requiring transparency such as HP.

On the other hand, as the interlayer compound constituting the dye receiving layer 1 together with such nylon particles, those having a layered structure and capable of receiving and holding a water-soluble dye by an intercalation reaction are used. Preferred examples of such an interlayer compound include a layered inorganic polymer having exchangeable ions capable of ion exchange with a water-soluble dye between hydrophilic layers of the interlayer compound.

Here, the exchangeable ion of the layered inorganic polymer means, when the water-soluble dye is a water-soluble cationic dye,
When the water-soluble dye is a water-soluble anionic dye, it is an exchangeable anion such as a carboxyl anion. These exchangeable cations or exchangeable anions themselves will be described later in detail.

Examples of the layered inorganic polymer having exchangeable cations (hereinafter, referred to as cation exchangeable intercalation compound) include natural or synthetic layered silicates or their calcined products. A montmorillonite group mineral that is a kind of clay mineral and has a 3-octahedral smectite structure and is represented by the following formula (1) can be preferably used.

[0029]

(X, Y) _2-3 Z ₄ O ₁₀ (OH) ₂ .mH ₂ O. (W _1/3 ) (1) (where X is Al, Fe (III), Mn (III) ) Or C
o (III), where Y is Mg, Fe (II), Ni, Zn
Or Li, Z is Si or Al, W is K, N
a or Ca, H ₂ O is interlayer water, and m represents an integer. Specifically, depending on the combination of X and Y and the number of substitutions, montmorillonite, magnesia montmorillonite, iron montmorillonite, iron magnesia montmorillonite, beidellite, aluminian beidellite, nontronite, aluminian nontronite, saponite, aluminum Natural products and synthetic products such as nian saponite, hectorite and sauconite can be exemplified. Further, those in which the OH group in the above formula (1) is substituted with fluorine can also be used.

In addition to the montmorillonite group mineral of the formula (1), mica group minerals such as sodium silicic mica, sodium teniolite and lithium teniolite can be used as the cation exchangeable intercalation compound.

As in the case of the synthetic clay mineral, examples of the cation-exchangeable interlayer compound having a layered structure and having exchangeable cations include acidic salts such as zirconium phosphate and layered hydrous titanium oxide. Since they have optical concealability or a unique color, they can be preferably used when transparency, glossiness and whiteness are not simultaneously required for the dye receiving layer 1.

As the cation-exchangeable intercalation compound, fine powder having a pure white color such as a synthetic silicon salt containing no contaminants can also be mentioned. Since the fine powder crystal itself is optically transparent, it is possible to form a dye-receiving layer that realizes high saturation comparable to silver halide photography.

The exchangeable cations between the layers of the cation exchangeable intercalation compound include inorganic cations which are easily solvated in a high dielectric constant medium such as water or alcohol, for example, Li ⁺ , N 2
Examples thereof include alkali metal ions such as a ⁺ and K ⁺ , alkaline earth metal ions such as Mg ²⁺ , and H ⁺ (in this case, so-called clay acid). Of the alkaline earth metal ions, Ca ²⁺ and Ba ²⁺ tend to provide an interlayer that is less likely to solvate than the other inorganic ions described above.

In addition, between the layers of the cation-exchange intercalation compound, a part of the exchangeable inorganic cations of the above-mentioned cation-exchange intercalation compound may be used to increase the interlayer distance (pillar effect) or to make the interlayer partially hydrophobic. May be substituted with an organic cation having the effect of converting This makes it possible to improve the dispersibility of the cation-exchange intercalation compound in the binder and further improve the swellability in a non-aqueous solvent such as alcohol. As such an organic cation, a quaternary ammonium ion or a phosphonium ion such as an alkylphosphonium ion or an arylphosphonium ion can be preferably used. Here, in the case of a quaternary ammonium ion, at least three of the four alkyl groups each preferably have 4 or more carbon atoms, and more preferably 8 or more carbon atoms. When the number of long-chain alkyls is small, the pillar effect is not sufficient, and it is difficult to sufficiently increase the interlayer distance between the fixing seats (= exchangeable inorganic cations). For example, n-octyltrimethylammonium ion is not preferred because even if it occupies most of the fixing seat, the interlayer distance does not increase more than about 4 angstroms and gives an excessively hydrophobic layer.

On the other hand, the layered inorganic polymer having exchangeable anions (hereinafter referred to as anion-exchange intercalation compound) used in the present invention is a kind of 0: 1 type clay mineral, and is an AlO ₆ octahedral sheet. Preferably, a layered hydrotalcite group mineral consisting of A typical example of such a hydrotalcite group mineral is the formula (2)

[0036]

Embedded image A natural hydrotalcite represented by Mg ₆ Al ₂ (OH) ₁₆ .CO ₃ .4H ₂ O (2) can be exemplified.

Although the composition is slightly different from that of the natural hydrotalcite of the formula (2), synthetic hydrotalcite is also commercially available and can be used. Although the fine powder of this synthetic hydrotalcite does not contain any contaminants and presents a pure white color, the crystal itself is optically transparent. It is possible to form the dye receiving layer 1 that realizes saturation.

Examples of the anion-exchange intercalation compounds other than the above-mentioned hydrotalcite group minerals include hydrated oxides such as titanium, zirconium, lanthanum and bismuth, and hydroxide phosphates. Since they have an optical hiding property or a unique color, they can be used when transparency, glossiness and whiteness are not simultaneously required for the dye receiving layer 1.

As the exchangeable anion between the anion exchangeable intercalation compounds, an inorganic anion which is easily solvated in a high dielectric constant medium such as water or alcohol, for example, NO ₃ ⁻ , S
O ₄ ²⁻ , CIO ₄ ⁻ , Fe (CN) ₆ ⁴⁻ , heteropolyphosphate ions and hydrophilic organic anions such as lower carboxylate ions can be used. Note that higher carboxylate ions tend to provide interlayers that are more difficult to solvate than the aforementioned anions.

In addition, between the layers of the anion-exchange interlayer compound, a part of the exchangeable inorganic anions of the above-mentioned anion-exchange interlayer compound may be used to increase the interlayer distance (pillar effect) or to partially hydrophobicize the interlayer. May be substituted with an organic anion having the effect of converting This makes it possible to improve the dispersibility of the anion-exchangeable intercalation compound in the binder and further improve the swellability in a non-aqueous solvent such as alcohol. Examples of such an organic anion include a carboxylate anion, a sulfonate anion, an ester anion, and a phosphate anion.

Such an anion usually has an alkyl group or an anikel group, but when the number of carbon atoms is small, the pillar effect is not sufficient, and the interlayer distance of the fixing seat (= exchangeable inorganic ion) is reduced. On the other hand, it is difficult to sufficiently expand the carbon atoms. Conversely, if the number of carbon atoms is too large, the substitution becomes difficult.

In the present invention, a general thermoplastic resin can be used as the binder resin forming the dye receiving layer 1, but the interlayer compound is easily dispersed, and
It is preferable to use a water-absorbent resin that easily permeates water, alcohol, and the like, which are solvents of the aqueous ink. Preferred examples of such a binder resin include polyvinyl butyral, hydroxypropyl cellulose, vinyl pyrrolidone-vinyl acetate copolymer, polyvinyl alcohol, and polyvinyl acetal.

When the weight ratio of the above-mentioned intercalation compound to the binder resin is too small, the amount of the water-soluble dye retained by the intercalation reaction is reduced to cause blurring of the image. The amount of the binder resin decreases, the adhesiveness and dispersibility of the dye receiving layer decrease,
Further, since the flexibility is also reduced, preferably 1: 0.1 to
The ratio is 1: 2, more preferably 1: 0.2 to 1: 1.5.

In the present invention, if necessary, various additives (for example, a crosslinking agent, a plasticizer, an ultraviolet absorber, a fluorescent whitening agent, and the like) used in the conventional dye receiving layer may be added to the dye receiving layer 1. Other hydrophilic resins) can be blended.

The thickness of the dye receiving layer 1 is usually 2 to 40 μm.
Is preferable, and 4 to 15 μm is more preferable.

The substrate 2 can be arbitrarily selected from paper, synthetic paper, plastic paper, metal plate, metal foil, plastic film on which aluminum or the like is vapor-deposited. Can be.
When the recording medium for inkjet is used for an application such as OHP, a light-transmissive substrate 2 is used.

The ink jet recording medium 10 having the layer configuration shown in FIG. 1 has been described above. As the ink jet recording medium of the present invention, as in the ink jet recording medium 11 shown in FIG. An ink absorbing layer 3 may be further provided on the dye receiving layer 1 of the recording medium for inkjet 10 shown in FIG.

The ink absorbing layer 3 temporarily receives the attached ink and transmits the ink to the dye receiving layer 1.
It can be composed of an ink-absorbing resin that absorbs an aqueous ink composed of a water-soluble dye. Therefore, the ink absorbing layer 3 can be formed from, for example, hydroxypropyl cellulose resin, polyvinyl alcohol resin, gelatin, hydratable polyvinyl acetal resin, polyvinyl pyrrolidone resin, and the like. In addition, the ink absorbing layer 3 includes
Further, various additives (for example, a cross-linking agent, a plasticizer, an ultraviolet absorber, a fluorescent brightener, other hydrophilic resins, and the like) can be added.

When both the dye receiving layer 1 and the ink absorbing layer 3 are provided as in the case of the ink jet recording medium 11 shown in FIG. 2, the ink jet recording medium 10 shown in FIG. Like the dye receiving layer 1, the dye receiving layer 1 contains two types of nylon particles having different average particle diameters,
And the weight ratio of the nylon particles having a larger average particle size to the nylon particles having a smaller average particle size (content of nylon particles having larger average particle size / content of nylon particles having smaller average particle size)
Can be greater than 1/2. In addition, two kinds of nylon particles having different particle diameters may be similarly contained in the ink absorbing layer 3 instead of the dye receiving layer 1, or both the dye receiving layer 1 and the ink absorbing layer 3 may have different particle diameters. Nylon particles may be contained.

When the nylon particles are contained in either the dye receiving layer 1 or the ink absorbing layer 3 or when both the layers contain the nylon particles, the nylon particles to be contained have a shape. It is preferable that the nylon particles having a larger average particle size have a mean particle size of 25 μm or more.
It is preferable that the average particle diameter of the nylon particles having a smaller average particle diameter of 5 μm or less is 1 μm or more and less than 25 μm.

The content ratio of nylon particles in the dye-receiving layer or ink-absorbing layer is preferably 0.02 to 10% by weight based on the water-absorbing resin constituting the dye-receiving layer or ink-absorbing layer.

When the thickness of the ink absorbing layer 3 is too large, the ratio of the dye fixed to the dye receiving layer 1 is reduced and the dye fixing property is deteriorated, so that it is usually 5 μm or less, preferably 3 μm.
The following is assumed.

As described above, the present invention has been described with respect to an ink jet recording medium having the layer structure shown in FIGS. 1 and 2, but the dye receiving layer or the ink absorbing layer contains nylon particles having different particle diameters as described above. The present invention can take various aspects as long as it is possible. For example, as shown in the recording medium 12 for inkjet shown in FIG.
The substrate itself may have a function as a substrate, and providing a substrate separately from the dye receiving layer 1 may be omitted.

The recording medium for ink-jet recording of the present invention comprises:
It can be prepared by an ordinary method. For example, two kinds of nylon particles having different particle diameters, an intercalation compound, a binder resin, and a solvent are dispersed as required, and the resulting dispersion is applied to the substrate 2 and dried to obtain a layer structure shown in FIG. Can be obtained. Furthermore,
When the ink absorbing layer 3 is provided on the dye receiving layer 1, the ink absorbing layer 3 can be prepared by applying the ink absorbing resin composition on the dye receiving layer 1 and drying.

The recording medium for ink jet of the present invention comprises:
It can be used in the same manner as a conventional inkjet recording medium.

[0056]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention will be specifically described below based on embodiments.

Examples 1 to 9 and Comparative Examples 1 to 4 (Preparation of Inkjet Recording Medium) A 125 μm thick transparent polyester film (Lumirror T-60, manufactured by Toray Industries, Inc.) was prepared as a substrate.

Table 1 and Table 2 were added to 100 parts by weight of the water-absorbent resin.
The spherical nylon particles shown in (1) were added and dispersed, and 100 parts by weight of hydrotalcite treated with an organic acid as an intercalation compound (hydrotalcite obtained by adsorbing 10 mg equivalent of malic acid) was added with stirring, and the mixture was added with a bead mill. Dispersion processing was performed for 5 hours. The obtained dispersion is applied to the above-mentioned transparent polyester film having a thickness of 125 μm (Lumilar T
-60, manufactured by Toray Industries Co., Ltd.), coated with a wire bar so as to have a thickness of 6 μm, dried at 100 ° C. for 1 minute, and then subjected to inkjet recording in which a dye receiving layer is formed on a substrate. A medium was produced (Examples 1, 2, 9 and Comparative Examples 1 to 1).
4).

After forming the dye receiving layer on the substrate in the same manner as described above, the spherical nylon particles shown in Tables 1 and 2 were further treated with ethyl alcohol: hydroxypropyl cellulose resin =
A 9: 1 (weight ratio) liquid mixture was added and dispersed, and the resulting mixture was applied on a dye receiving layer with a wire bar so as to have a thickness of 1.5 μm to form an ink absorbing layer. Ink-jet recording media in which a dye receiving layer and an ink absorbing layer were sequentially formed on a material were produced (Examples 3 to 3).
8).

[0060]

[Table 1] Example Layer composition Compounding ratio of spherical nylon particles (parts by weight) 1 Base dye receiving layer Resin: 40μ particles: 10μ particles = 100: 0.5: 0.5 2 Base dye receiving layer resin: 40μ particles: 20μ particles = 100: 0.5 : 0.5 3 Base dye receiving layer Resin: 40μ particle: 10μ particle = 100: 0.5: 0.5 ink absorbing layer (without nylon particles) 4 Base dye receiving layer resin: 40μ particle: 20μ particle = 100: 0.5: 0.5 ink absorption Layer (without nylon particles) 5 Substrate Dye receiving layer (without nylon particles) Ink absorbing layer Resin: 40μ particles: 20μ particles = 100: 0.5: 0.5 6 Base Dye receiving layer (without nylon particles) Ink absorbing layer Resin: 40μ Particle: 10μ particle = 100: 0.5: 0.5 7 Base dye receiving layer Resin: 40μ particle: 10μ particle = 100: 0.5: 0.5 ink absorption layer Resin: 40μ particle: 10μ particle = 100: 0.5: 0.58 Base dye reception layer resin: 40 [mu particles: 20 [mu] particle = 100: 0.5: 0.5 ink absorbing layer resin: 40 [mu particles 20μ particle = 100: 0.5: 0.5 9 Substrate dye-receiving layer resin: 40 [mu particles: 10 [mu] particle = 100: 10.0: 10.0 (Table 1 Note) 40 [mu particles ... Olga sole 2002, ES4 (average particle size 40 [mu] m), Japan Rilsan Co., Ltd. 20μ particles: Olgasol 2002, D (average particle size: 20 μm), Nippon Rilsan Co., Ltd. 10μ particles: Olgasol 2002, EXD (average particle size: 10 μm), Nippon Rilsan Co., Ltd.

[0061]

[Table 2] Comparative Example Layer Composition Mixing ratio of spherical nylon particles (parts by weight) 1 Base dye receiving layer Resin: 40μ particles: 6μ particles = 100: 0.5: 1.0 2 Base dye receiving layer Resin: 40μ particles: 10μ particles = 100: 0.5 : 1.0 3 Base dye-receiving layer Resin: 40μ particles = 100: 0.5 4 Base dye-receiving layer (without nylon particles) (Table 2 Note) 40μ particles: Orgasol 2002, ES4 (average particle size 40μm), Nippon Rilsan Co., Ltd. 10μ particles manufactured by the company: Olgasol 2002, EXD (average particle size: 10 μm), manufactured by Nippon Rilsan Co., Ltd. 6μ particles: Olgasol 2002, ULD (average particle size: 6 μm), manufactured by Nippon Rilsan Co., Ltd.

Evaluation A test pattern image was formed on each of the ink-jet recording media obtained using an ink-jet recording system printer (HP1200C, manufactured by HP), and (1) transportability, (2) ink absorption, and (3) Dye receiving layer water resistance, (4) ink fixability, (5)
The print density and (6) film transparency were tested and evaluated as follows. In this case, solid printing was performed for each of three colors of Y (yellow), M (magenta), and C (cyan) as test patterns. Table 3 shows the results.

(1) Conveyability When forming an image under a constant environmental condition (15 ° C., 25%), 20 recording media are stacked and set on a paper feed tray to improve the conveyability in continuous printing. It was visually observed and evaluated according to the following evaluation criteria. Transportability evaluation criteria 〇: When continuous printing of 20 sheets was possible ×: When double running occurred during printing and continuous printing of 20 sheets was not possible

(2) Ink Absorption When an image is formed on an ink-jet recording medium in the manner described above, it is visually observed whether or not the ink penetrates into and is absorbed by the recording medium. The evaluation was performed according to evaluation criteria. Ink absorption evaluation criteria 〇: Ink penetrates into recording medium and absorbed ×: Ink does not penetrate into recording medium

(3) Dye-Receiving Layer Water Resistance After forming an image, the entire recording medium is immersed in water for 10 minutes, and the recording medium changes so that it cannot be used (eg, peeling, dissolution and disappearance). Whether or not to perform was visually observed and evaluated according to the following evaluation criteria. Water resistance evaluation criterion 〇: When the recording medium did not change so that it could not be used ×: When the recording medium changed so that it could not be used

(4) Ink fixability The image changes during the above-mentioned water resistance test (for example, flowing out,
Whether or not bleeding was observed was visually observed and evaluated according to the following evaluation criteria. Fixability evaluation criterion 〇: When the image is almost maintained Δ: When the dye runs out within the usable range of the image ×: When the image is changed to an unusable level

(5) Print Density The reflection density of a high-density image portion obtained by solid printing with each ink was measured with a Macbeth densitometer (TR924). From the viewpoint of print saturation, Y. M. Each concentration of C is preferably 2.2 or more.

(6) Film Transparency The light transmittance of the unprinted area with respect to the transparent polyester film before coating the dye receiving layer was measured by a spectrophotometer (U.S.A., manufactured by Hitachi, Ltd.).
-3400). From the viewpoint of projection quality as an OHP, it is desirable that the transmittance is 95% or more.

[0069]

[Table 3]

From Table 3, Examples 1 to 8 show (1) transportability,
It can be seen that good results were obtained for (2) ink absorption, (3) water resistance of the dye receiving layer, (4) ink fixability, (5) print density, and (6) film transparency. Further, in the dye receiving layer, the transparency was relatively low in Example 9 in which the total compounding ratio of the two types of nylon particles was 20 parts by weight with respect to 100 parts by weight of the resin, but in the other evaluation items, Good results are obtained, and it can be seen that the medium is a good recording medium except for applications requiring transparency such as OHP.

On the other hand, in the case where the dye receiving layer contains only 1/2 of the nylon particles having a large particle diameter (particle diameter of 40 μm) of the nylon particles having a small particle diameter (particle diameter of 6 μm or 10 μm) (Comparative Example) 1, Comparative Example 2) or when no nylon particles were contained (Comparative Example 4), the transportability was extremely poor, and nylon particles having a large particle size were contained, but nylon particles having a large particle size were included. It can be seen that good transportability cannot be obtained when no nylon particles are contained (Comparative Example 3).

[0072]

According to the present invention, an interlayer compound for receiving and retaining a water-soluble dye by an intercalation reaction is contained in a dye receiving layer to improve the fixing property of an image and the storage durability during image storage. In the recording medium for inkjet, blocking can be prevented, and a double feed trouble at the time of printing can be eliminated.

Further, the ink absorbency is improved, and a high-resolution image with little ink bleeding can be obtained.

[Brief description of the drawings]

FIG. 1 is a sectional view of an inkjet recording medium of the present invention.

FIG. 2 is a sectional view of an inkjet recording medium of the present invention.

FIG. 3 is a sectional view of an inkjet recording medium of the present invention.

[Explanation of symbols]

DESCRIPTION OF SYMBOLS 1 ... Dye receiving layer 2 ... Base material 3 ... Ink absorption layer 10 ...
Inkjet recording medium 11 ... Inkjet recording medium 12 ... Inkjet recording medium

Claims (14)

[Claims] 1. An ink jet recording medium having a dye receiving layer formed from an interlayer compound for receiving and retaining a water-soluble dye by an intercalation reaction and a binder resin, wherein the dye receiving layer has a different average particle size. Weight ratio of nylon particles having a larger average particle size and smaller average particle size (content of nylon particles having larger average particle size / nylon having smaller average particle size) (Content of particles) is more than 1/2. 2. The ink jet recording medium according to claim 1, wherein the dye receiving layer is formed on a substrate. 3. The method according to claim 1, wherein the nylon particles are spherical, and the nylon particles having a larger average particle size have an average particle size of 25 μm or more and 45 μm or more.
The nylon particles having a smaller average particle diameter of 1 μm or less and an average particle diameter of 1 μm or more and less than 25 μm.
The recording medium for inkjet according to the above. 4. The ink jet according to claim 1, wherein the content of the nylon particles in the dye-receiving layer is 0.02 to 10% by weight based on the water-absorbing resin constituting the dye-receiving layer. Recording medium. 5. A dye-receiving layer formed from an interlayer compound for receiving and retaining a water-soluble dye by an intercalation reaction and a binder resin, and an ink-absorbing resin absorbing water-based ink is provided on the dye-receiving layer. In an inkjet recording medium having the formed ink absorbing layer,
At least one of the dye-receiving layer and the ink-absorbing layer contains two types of nylon particles having different average particle sizes, and the weight ratio of the nylon particles having the larger average particle size to the nylon particles having the smaller average particle size ( Recording medium for ink-jet recording, wherein the content of nylon particles having a large average particle diameter / the content of nylon particles having a small average particle diameter is larger than 1/2. 6. The ink jet recording medium according to claim 5, wherein the dye receiving layer is formed on a substrate. 7. The nylon particles are spherical, and the nylon particles having a larger average particle size have an average particle size of 25 μm or more and 45 μm or more.
The nylon particles having an average particle diameter of 1 μm or less and less than 25 μm.
The recording medium for inkjet according to the above. 8. The content of nylon particles in the dye-receiving layer or ink-absorbing layer is 0.02 to 10% by weight based on the water-absorbing resin constituting the dye-receiving layer or ink-absorbing layer.
The inkjet recording medium according to any one of claims 5 to 7. 9. The ink jet recording medium according to claim 1, wherein the interlayer compound is a layered inorganic polymer having exchangeable cations. 10. The inkjet recording medium according to claim 9, wherein the layered inorganic polymer having exchangeable cations is a montmorillonite group mineral. 11. The montmorillonite group mineral is represented by the formula (1): ## STR1 ## (X, Y) _2-3 Z ₄ O ₁₀ (OH) ₂ .mH ₂ O. (W _1/3 ) (1) , X is Al, Fe (III), Mn (III) or C
o (III), where Y is Mg, Fe (II), Ni, Zn
Or Li, Z is Si or Al, W is K, N
a or Ca, H ₂ O is interlayer water, and m represents an integer. The recording medium for inkjet according to claim 10, wherein 12. The inkjet recording medium according to claim 1, wherein the interlayer compound is a layered inorganic polymer having exchangeable anions. 13. The ink jet recording medium according to claim 12, wherein the layered inorganic polymer having exchangeable anions is a hydrotalcite group mineral. 14. The inkjet recording material according to claim 13, wherein the hydrotalcite group mineral is represented by the following formula (2): Mg ₆ Al ₂ (OH) ₁₆ .CO ₃ .4H ₂ O (2) Medium.